Recent advances in understanding and

design of efficient hydrogen evolution

electrocatalysts for water splitting: A
comprehensive review Bashir
Adegbemiga Yusuf
Visit to download the full and correct content document:
https://ebookmass.com/product/recent-advances-in-understanding-and-design-of-effic
ient-hydrogen-evolution-electrocatalysts-for-water-splitting-a-comprehensive-review-b
ashir-adegbemiga-yusuf/
 Advances in Colloid and Interface Science 311 (2023) 102811

Contents lists available at ScienceDirect

Advances in Colloid and Interface Science

journal homepage: www.elsevier.com/locate/cis

Historical perspective

Recent advances in understanding and design of efficient hydrogen

evolution electrocatalysts for water splitting: A comprehensive review
Bashir Adegbemiga Yusuf a, b, Waleed Yaseen a, Meng Xie a, *, Rabi Sanusi Zayyan e,
Atika Ibrahim Muhammad c, Rosalynn Nankya d, Jimin Xie a, Yuanguo Xu a, b, *
a
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China
b
School of Materials Science & Engineering, Jiangsu University, Zhenjiang 212013, China
c
The University of Manchester, UK
d
Rice University, Houston, Texas 77005, USA
e
Department of Basic and Applied Sciences, College of Science and Technology, Hassan Usman, Katsina Polytechnic. Katsina state, Nigeria

A R T I C L E I N F O A B S T R A C T

Keywords: An unsustainable reliance on fossil fuels is the primary cause of the vast majority of greenhouse gas emissions,
Intrinsic effect which in turn lead to climate change. Green hydrogen (H2), which may be generated by electrolyzing water with
HER renewable power sources, is a possible substitute for fossil fuels. On the other hand, the increasing intricacy of
Water-splitting reaction
hydrogen evolution electrocatalysts that are presently being explored makes it more challenging to integrate
Extrinsic effect
Catalyst fabrication
catalytic theories, catalytic fabrication procedures, and characterization techniques. This review will initially
Electrocatalysis present the thermodynamics, kinetics, and associated electrical and structural characteristics for HER electro­
catalysts before highlighting design approaches for the electrocatalysts. Secondly, an in-depth discussion
regarding the rational design, synthesis, mechanistic insight, and performance improvement of electrocatalysts is
centered on both the intrinsic and extrinsic influences. Thirdly, the most recent technological advances in
electrocatalytic water-splitting approaches are described. Finally, the difficulties and possibilities associated with
generating extremely effective HER electrocatalysts for water-splitting applications are discussed.

1. Introduction
The agreement for the sustainable advancement of society is to
change the energy system and improve the amount of renewable energy
in the overall structure due to the deepening of the conventional energy
crisis and the rising prominence of environmental issues. The generation
and use of hydrogen energy from renewable sources has emerged as one
of the most important future directions for the global development goal
[1–4]. H2 energy is considered the energy source of the future due to its
exceptional characteristics of zero pollution, great effectiveness,
numerous supplies, and a vast array of applications. In particular, the
generation of hydrogen through water electrolysis using renewable
power is recognized as one of the most promising approaches due to its
extremely low pollutant output, zero carbon dioxide emissions, and
environmental friendliness [5–8].
The hydrogen evolution reaction (HER), which is one of the half-
reactions in the process of electrocatalytic water splitting, has gotten a
lot of attention in the past few decades, leading to the discovery and
design of many active catalysts [9–19]. As a result, it is not hard to find
out through detailed research that catalysts with great performance tend
to have high intrinsic performance, a large surface area, and rapid
electron transfer. This means that improving these characteristics should
be a primary target during the design and preparation of the catalyst.
Based on the intrinsic impacts and extrinsic aids of the catalysts them­
selves, the fabrication approaches of catalysts can be tailored to the
aforementioned characteristics (Fig. 1). The implementation of the
fabrication approach of intrinsic or extrinsic impacts does not often in­
fluence the structural or electrical performance of the catalytic materials
individually, but rather enhances both concurrently. For instance, the
nano-structuring impact and narrow size distribution have been shown
to be effective for increasing both the interfacial area (due to the
structural impact) and the number of catalytically active sites that are
inherently exposed (electronic impact), leading to an increase in elec­
trocatalytic effectiveness [20].
To further maximize the inherent overall catalytic efficiency, cata­
lytic materials with all essential components cohesively bonded were

* Corresponding authors at: School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China.
E-mail addresses: xuyuanguo0402@163.com, xuyg@ujs.edu.cn (Y. Xu).

https://doi.org/10.1016/j.cis.2022.102811
Received in revised form 10 October 2022;
Available online 19 November 2022
0001-8686/© 2022 Elsevier B.V. All rights reserved.
B.A. Yusuf et al.
developed in accordance with the concepts of catalyst configuration.
These components, which optimized the electronic characteristics of the
catalyst, included phase modification, surface chemistry, and hetero-
atomic infusion defects. Even though there are various exceptional
studies pertinent to HER [21–31], there is not yet a thorough review that
takes into account all of the internal and external effects, such as alloy-
impact, strain-impact, and support-effect, for HER. Herein, this article
provides a summary of current breakthroughs in the intrinsic impact and
the extrinsic influence of enhanced electrocatalytic materials toward
HER. These electrocatalytic materials include those centered on noble-
metal and transition-metal nanomaterials. First, we begin with a
concise discussion of the reaction mechanism of HER, followed by a
discussion of both conventional and cutting-edge descriptors for
hydrogen evolution reactions. The subsequent step involves an in-depth
discussion of the rational design, fabrication, mechanistic insight, and
continuous improvement of electrocatalytic materials. In the following
section, current developments in the technological advancements of
proton exchange membranes and anion exchange membrane fuel cell
systems are further presented in a concise manner. Finally, the diffi­
culties and prospects of the hydrogen evolution reaction are discussed.
We anticipate that this review will provide useful guidance and new
perspectives on the development and application of improved electro­
catalytic materials for water-splitting approaches.
Defects-impact
Alloys and
HER
confinement H + (aq) + e-
effect
H*
Doping, strain
and promoter-
effect
Interface, field,
and nano-
structuring
Fig. 1. Diverse impacts on the hydrogen evolution reaction catalysts.
2
Advances in Colloid and Interface Science 311 (2023) 102811
2. Fundamental mechanistic concepts of hydrogen evolution
reactions
2.1. Catalytic pathways for hydrogen evolution reactions
The generation of H2 through the HER process in an alkaline solution
and the invention of an alternative to renewable fuels for diverse energy
technologies are presently the subjects of intense research. Owing to an
additional phase of electrocatalytic water dissociation, the reaction rate
of this procedure is sluggish. Therefore, current catalysts operate well in
an acidic condition but underperform in an alkaline solution.
According to theoretical investigations, two parameters influence the
effectiveness of the catalysts in an alkaline solution. These parameters
are the disintegration of H2O and the binding energy of H2. As a result,
any catalysts with a higher potential to split H2 molecules with a high
adsorption potential and generate a H2 molecule will improve the HER
catalytic reaction in a basic environment [32]. In regards to the reaction
effectiveness, very few electrocatalytic materials competent with plat­
inum in an alkaline medium have been described. Hence, it is necessary
to verify the fundamentals of electrode kinetic parameters and to
investigate the response process. This will lay the groundwork for future
researchers to investigate novel and effective electrocatalysts [33].
Various mechanisms govern the catalytic processes, as indicated in
Figs. 2 and 3. In an acidic solution, the reaction follows the Volmer
mechanism, which involves the combination of an e− from the electrode
interface with a H+ from the electrolyte. The Tafel mechanism is another
combination of the present H-atom with the nearby one. The Heyrovsky
mechanism refers to the combination of another H+ from the electrolyte
and an e− from the interface of the electrode. In an alkaline
Mul-site
Funconalizaon
1/2H2(g)
Compound and
phase
transformaons
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Alkaline medium Acidic medium

Step 1 Step 2 Step 3

Step 1 Step 2 Step 3

e- Adsorpon e- Desorpon e- Recombinaon

e- Adsorpon e- Desorpon e- Recombinaon Volmer Reacon Heyrovsky Reacon
Volmer Reacon Heyrovsky Reacon Tafel Reacon Tafel Reacon

e-
e-

Electrode deposited Electrode deposited

catalyst surface area catalyst surface area

e-
e-

Fig. 2. Schematic representations of the Volmer-Heyrovsky and Volmer-Tafel reactions taking place on the surface of a catalyst in both acidic and basic
environments.

The actual reaction process is considerably more complex than these

Overall
representaon H--H
- + -- -+-
+H+ + e-
2M
H H2O+ + e-
+H+ + e-
Tafel step
M OH+
H2O+ + e- M accelerate the reaction mechanism of alkaline hydrogen evolution. Ac­
Volmer step H--H
OH- -- +--
+H+ + e- M one of the most perplexing questions in the alkaline hydrogen evolution
H2O+ + e-
Heyrovsky step
OH-
Fig. 3. Overall schematic illustrations of the Volmer-Heyrovsky and Volmer-
Tafel reactions.
environment, however, H+ are missing from electrolytes. The reaction
therefore begins with the breakdown of a H2O molecule, a process
known as the Volmer mechanism. Subsequently, either the Tafel or
Heyrovsky mechanism is utilized to produce H2. The excessive H2O
dissociation phase in the basic electrolyte suggests that the same cata­
lytic material performs less efficiently in an alkaline environment than
in an acidic environment [34]. Furthermore, the approach can describe
the HER process on the interface of the catalyst-deposited electrode. The
HER in the alkaline solution is considered a combination of three basic
steps: one chemical and two electrochemical. The first phase consists of
a chemical reduction of H2O to produce an H2 molecule, which is sub­
sequently deposited on the interface of the electrode by the Volmer
mechanism. The deposited H2 then undergoes an electrochemical phase
to generate hydrogen, followed by the Heyrovsky process or a chemical
process, i.e., the Tafel response [35].
Additionally, the Tafel slope measurements illustrate the HER pro­
cess by defining the potential difference (PD) needed to change the
current density. When the Volmer or discharging response is rapid and
the chemical dissociation is the rate-determining phase, the b = 29 mV/
dec is determined by the formula b = 2.3RT/2F = 0.029 V/dec @ 25 ◦ C.
Therefore, if the electrochemical dissociation, or Heyrovsky process, is
the rate-determining phase and the discharging response is quick, the b
= 39 mV/dec and determined by b = 2.3RT/2F = 0.039 V/dec @ 25 ◦ C.
Lastly, assuming the discharging response is slow, b = 116 mV/dec can
be calculated as b = 2.3RT/2F = 0.116 V/dec @ 25 ◦ C.
phases suggest. Current perspectives, such as the water-splitting hy­
pothesis [36,37], the H2 binding energy theory [38,39], and the surface
H2O and/or anion transport principle [40], have typically addressed the
H2 crucial themes in the system of alkaline hydrogen evolution reaction, as
to whether water dissociation or H2-adsorption is the key component to
cording to water-splitting theory, the function of the hydroxide (OH) is
H2
process. Current findings have shown that OH* deposition neither
contributes to nor impacts the Volmer stage of the alkaline hydrogen
evolution process nor its effectiveness [41,42]. Koper and coworker
described a bi-functional pathway using OHads in alkaline HER processes
[43]. They demonstrate a volcano-like link between the rate of alkaline
H2 development and the OH binding potential. The authors also discover
that platinum with ruthenium at the phase’s border is 65-times more
effective for HER than uncoated platinum. Models of electrochemical
H2O dissolution demonstrate that the activation energy corresponds
with the OHads strength, even when the deposited OH is not an outcome
precursor, resulting in a computed volcano slope that corresponds to the
experimental plot (Fig. 4 a-d). Similarly, Jia and coworkers show that
OHads (water)-alkali M+ (where M+ represents metal cation) derivates
perform catalytic roles in the alkaline hydrogen evolution process and
the hydrogen oxidation approach reaction mechanism [44]. This is
supported by the observation that increasing the abundance of OHads at
the surface benefits the HER/HOR, whereas increasing the intensity of
alkali M+ only improves the hydrogen evolution process, and altering
the specificity of alkali M+ influences both the hydrogen evolution
process and the hydrogen oxidation approach, respectively. According
to the hard-soft acid-base principle, the formation of OHads (water)-al­
kali M+ in the double-layer region facilitates the withdrawal of OHads
into the mass and the generation of OH (water)-alkali M+, which then
promotes the HER (Fig. 4e, f).
Despite current debate about the possible role of precipitated hy­
droxide in the hydrogen evolution process in alkaline environments,
hydrogen binding energy theory has been demonstrated to be the most
accurate description of hydrogen evolution reaction performance. Since
the reaction pathways for HER in basic and acidic solutions are similar,
some researchers think that the factors that control HER performance
are the same in all pH media and mostly depend on how hydrogen and

3
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

(caption on next page)

4
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 4. (a) A schematic diagram depicting the process of measuring and decorating HER performance. (b) The reaction energy chart illustrates the reaction
mechanism of the HER reaction. (c) Theoretical (black line) and experimental (blue dots) HER process kinetics on Pt (553), Pt (553 with Mo*, Re*, Ru*, Rh*, and Ag*
deposited at phase, and Pt (111) vs the DFT predicted OHads energy at 0 Vs. RHE. (d) A chart illustrating a 3D model of the HER active volcano. Reproduced with
permission [43]. Copyright 2017, Nature Publishing Group. (e) Schematic depiction of the catalytic functions of OHads in the reaction mechanism of alkaline HER/
HOR. (f) HER/HOR polarization curves of a polycrystalline platinum electrode in 0.1 M solutions of sodium hydroxide, potassium hydroxide, and lithium hydroxide
that are saturated with H2. Reproduced with permission [44]. Copyright 2019, American Chemical Society. (g) A comparative study of the Hupd characteristic peaks
of polycrystalline platinum in electrolytes of varying pH. (h) pH of the solution in relation to HBE for both Pt (110) and Pt (100). (i) HER on Pt across the entire pH
spectrum of solutions. (j) The overpotential of the HER of Pt in all electrolytes with a pH buffer. Reproduced with permission. ref Copyright 2015, Nature Publishing
Group. (k) Cyclic voltammetry was employed to measure the interaction of Pt(111) with a buffered solution with pH=10 adjusted by a submonolayer quantity of Ni
(OH)2. (l) Measurements of cyclic voltammetry and laser-induced temperature jumps at pH=13. (m) Coulostatic potential transients created by laser for the Pt(111)
electrode. (n) Laser-induced coulostatic potential transients acquired for the Ni(OH)2-coated Pt(111) electrode. (o) H2 evolution and reaction mechanism on Pt(111)
in the presence of Ni(OH)2. Reproduced with permission [47]. Copyright 2017, Nature Publishing Group.

the targeted catalyst interact [45,46]. Yan and colleagues discovered a
link between HOR/HER activities and empirically observed HBE for
polycrystalline Pt tested in many buffer solutions over a broad pH scale
of 0–13 [38]. The HOR/HER performance measured by the rotating disc
electrode technique decreases with increasing pH, whereas the HBE
measured by cyclic voltammograms grows linearly with increasing pH.
Attributing the HOR/HER processes to the HBE yields a monotonically
decreasing HOR/HER interaction with the HBE, providing excellent
evidence for the theory that HBE is the only response descriptor for the
HOR/HER operation (Fig. 4g-j). This indicates that the HBE dependency
hypothesis is not always applicable to all situations. In the meantime, a
significant amount of work has been put into the development of useful
compounds (poly-crystalline and stepped single-crystal platinum). It is
quite unlikely that the Hupd spectra are indirectly related to the *OH,
and it is important to note that the influence of oxygenated molecules
adsorbed must also be properly considered. To put it differently, the
deposited OH may interact with the reactive substrate at the same
interface locations and/or enhance its uptake capacity, which will ulti­
mately have an effect on the reaction mechanisms of the HER. In addi­
tion, the electrochemical surface architecture at the atomic level must be
considered (for instance, the potential of zero total charge). Koper and
colleagues reported direct experimental proof of the adsorption of a
modest quantity of nickel (II) hydroxide on platinum (111) [47]. They
hypothesized that the influence of the potential of zero total charge on
the activation threshold of Hads is the energy loss caused by the rear­
rangement of interfacial water in order to support electron transport via
the electrocatalytic double-layer support. Specifically, HER and the
Hads region occur in an alkaline environment away from the potential of
zero total charge. In an alkaline condition, the interfacial H2O network
at the HER and the Hads region potentials interacts significantly with the
good interfacial electromagnetic field, resulting in a more complex and
rigorous rearrangement during the flow of charges via the electro­
catalytic double-layer support (Fig. 4k-o).
2.2. The thermodynamics and reaction kinetics of the hydrogen evolution
reaction
2.2.1. The thermodynamics of the HER process
The hydrogen evolution process can proceed in two possible ways:
through a Volmer-Tafel or a Volmer-Heyrovsky pathway. Hads and
hydrogen synthesis are thus two sequential steps in the conversion of
hydrogen ions to hydrogen molecules. The complexity of the targeted
catalyst for starting the process is often assessed using two equivalent
theoretical descriptors, Hads energy and the Gibbs free energy for
adsorbing H-atoms (ΔGH*). The Nernst effect is an additional parameter
that contributes to the HER mechanism. This potential represents the
likelihood of thermodynamic equilibrium occurring throughout the
electrochemical process. HER activation under equilibrium conditions
occurs infrequently in real-world contexts. This indicates that the vast
majority of electrochemical processes must surpass a preset activation
energy barrier. The magnitude of the energy barrier that must be
overcome is significantly affected by the nature of the contact at which
the reaction occurs. Therefore, electrochemical reactions often demand
a larger quantity of energy than thermodynamics predicts.
2.2.2. The kinetics of the HER process
The overpotential (η): is the most important criterion for evaluating
the HER performance of an electrocatalyst. A catalyst that is suitable for
the hydrogen evolution process must be able to reduce the over­
potential, as a minimal overpotential value is the cause of strong cata­
lytic performance. The theoretic estimate of the cell potential for the
total water splitting pathway is 1.23 V (0 V for HER). Due to impedi­
ments, the HER requires additional capacity to generate responses. Extra
potential, also known as overpotential, is a critical component in esti­
mating the catalyst’s effectiveness. Typically, the overpotential values of
various electrocatalysts are correlated at a constant current density
level, such as 100 mA/cm2 and/or 10 mA/cm2. The ideal HER electro­
catalyst must be able to catalyze the electrochemical process at a po­
tential of 100 mV or lower.
The Tafel slope (b) and exchange current density (j0): Re-plotting the
polarisation data into Tafel slope plotlines (overpotential" versus "lg|
current density|) allows the deduction of two key variables from the
Tafel slope system (η = a + b lg|j|), namely the Tafel slope (b) and the
exchange current density (j0). Both of these variables may be found in
the Tafel calculations.
The Tafel formula depicts the direct proportionality involving
overpotential and lg|j|, where g stands for overpotential, a denotes for
the Tafel constant, b stands for the Tafel slope, and j stands for current
density. It should be noted that a linear correlation is developed when
the overpotential is greater than or equal to 59 mV. Typically, the Tafel
slope is designed to evaluate catalytic performance and potential
hydrogen evolution process pathways. When the gradient of the Tafel
curve is less steep, optimizing the current density needs a considerable
low overpotential, indicating a rapid charge transport reaction
mechanism.
When g is considered to be 0, the exchange current density, denoted
by j0, is calculated as the result. This result is dependent on the inherent
catalytic properties of the electrode material itself when parameters are
in steady state. If the exchange current density is significantly high, then
the electron transport rate will be higher, and the reaction efficiency will
be even better. In summary, the ideal characteristics of an effective
electrocatalytic material are a small overpotential (η), a reduced Tafel
slope (b), and a significant exchange current density (j0).
Electrochemically active surface area (ECSA): In order to evaluate
the effectiveness of various nanosized electrocatalysts, it is important to
calculate the electrochemically active surface area (ECSA). The equiv­
alent cross-sectional region of a nanosized electrode is typically more
than the geometrical region of the equivalent planar electrode. The
ECSA of the hydrogen evolution reaction electrocatalytic materials can
typically be evaluated utilizing two distinct methodologies: the
Coulombic charge of a predominant surface Faradaic reaction including
H2 underpotential accumulation, underpotential accumulation of cop­
per, carbo monoxide stripping, and oxidation/reduction of interface
metal; and the electrical double-layer capacitance. Both methodologies
are described in more detail below (Cdl). Furthermore, the approach
based on the evaluation of Cdl is relatively often employed to obtain the

5
B.A. Yusuf et al.
ECSAs of all various types of HER electrocatalytic materials because
almost all electrocatalytic materials exhibit the characteristics of Cdl
when subjected to cyclic voltammetry scans.
Cdl is calculated in the same manner as catalytic evaluation, by
spinning the electrodes in non-Faradaic regions (i.e., at the potential
areas where no charge transport response happens but adsorption-
desorption mechanisms can exist). The variation in non-Faradaic cur­
rent density (j) while cycling at different sweep rates (m) should be
directly proportional to the scan rate, resulting in the electrical double-
layer capacitances per the slopes (Cdl = j/m).
Faradaic efficiency (FE): is an additional criterion for assessing the
performance of an electrocatalytic material. This is modified so that an
assessment can be made on the number of electrons involved in the
intended reaction rather than the reaction product. Faradaic efficiency is
the ratio of empirically detected hydrogen to hypothetical hydrogen
calculated from current density at 100 percent faradaic yield. This is the
ratio between the empirically produced quantity of hydrogen and the
predicted quantity of hydrogen in the HER system. The quantity of
generated hydrogen can be estimated using gas chromatography (GC) or
the H2O displacement approach. The conceptual modelling of hydrogen
is performed under the conditions of potentiostatic or galvanostatic
electrolytic set-ups, and comparing it to an experimental result allows
the calculation of the faradaic efficiency. In the hydrogen evolution
process, 100 percent faradaic efficiency is typically recorded, and a
higher faradaic efficiency indicates increased HER mechanism sensi­
tivity in alkaline conditions.
The turnover frequency (TOF): is a metric that describes the quantity
of reactants that are transformed into the specific product at each cat­
alytic domain in a given amount of time by the catalytic material. At the
moment, the system which is mostly aimed at the HER electrocatalytic
TOF values is primarily based on TOF = jA/4nF, where A denotes the
region of the working electrode and n illustrates the electroactive ma­
terial number of moles, which is aimed from the interface area of the
electrocatalyst. However, it is not possible to find precise TOF values for
the majority of the solid-state catalytic materials, particularly for the few
developing complexes. The explanation for this is that not all of the
atoms on the catalytic material’s interface are equally accessible or
catalytically activated at the same time. In addition, bubbles are
generated by the hydrogen evolution process on the interface of the
electrode, which results in a higher overpotential due to the degradation
of the electronic conductivity. Even if the TOF values are inaccurate,
they can still be used when attempting to compare the catalytic per­
formance of multiple catalysts, particularly in the context of identical
systems [48].
Hydrogen bonding energy (HBE): The optimum electrocatalytic
material for HER is one that demonstrates an HBE that is neither too
strong nor underly weak. The hydrogen evolution process demonstrates
that the initial protons diffuse and then are attached to the interface of
the electrocatalytic material. Ultimately, the proton is converted to
hydrogen. Instead, the low HBE value suggests that there is a relatively
low concentration of deposited protons on the electrocatalytic material.
When the HBE concentration is high, the catalysts deteriorate into a
poisonous state due to the constant coverage of the catalytically active
sites by deposited hydrogen ions. Since the value of the SHE is assumed
to be 0, the magnitude of ΔGH* must also be assumed to be zero for an
ideal HER electrocatalytic material. When attempting to demonstrate
the effectiveness of HER, the current density is another highly significant
factor to consider. Therefore, electrocatalytic materials that are some­
what close to the peak of the Sabatier volcano curves are the ones that
demonstrate enhanced performance for the hydrogen evolution process
[49].
The relationship between the electrochemical active surface area and
the kinetics of the HER process: The relationship between the electro­
chemical active surface area and the kinetics of the HER process, namely
two intermediates (*H and *OH), determines the HER catalytic perfor­
mance in alkaline medium [50–52]. In contrast to the complex multi-
6
Advances in Colloid and Interface Science 311 (2023) 102811
step processes of the oxygen evolution reaction, HER performance
may therefore be simply modified [51,53]. In basic medium, cobalt-
based oxides are excellent materials for the oxygen evolution reaction,
whereas pure TM-oxides are ineffective for the HER owing to their un­
favorable H2 adsorption/desorption energy values [52,54,55]. Owing to
the generation of O 2p ligand vacancies from the robust bonding be­
tween the three-dimensional transition metals and O 2p states, high-
valence TM-ions (such as Fe4+, Cu3+, Co4+, and Ni3+) exhibit signifi­
cant metallic characteristics, suggesting their possible participation in
hydrogen desorption [54]. Moreover, oxygen vacancies in oxides
enhance the adsorption of H2O [56]. Motivated by these ideals, Shao
and colleagues established two important criteria for fabricating excel­
lent HER electrocatalytic materials based on bulk TM-oxides: (1)
exceptional electrochemical active surface area with district catalytic
active centers for the two-step HER process and (2) short reaction routes
[54]. To demonstrate the fabrication approach, the study utilized A-site-
ordered perovskite oxides RBaCo2O5.5+δ (R = gadolinium, samarium,
and lanthanum). By precisely manipulating the amount and dispersion
of oxygen vacancies at pyramidal Co3+ sites and octahedral Co4+ sites, a
near-ideal reaction route and relative-optimal synergistic interactions
could be established for the HER process (Fig. 5a, b). Significantly, both
catalytic active sites were incorporated concurrently into the structured
perovskite oxide lattice. Thus, the optimum sample (Gd0.5La0.5)
BaCo2O5.75 significantly surpassed the standard platinum/C catalyst.
Chen and colleagues also investigated double perovskite oxides as HER
catalytic materials in basic environments. The authors discovered that
the orthorhombic double perovskite PrBaCo2O5+δ (δ ≈ 0.52) demon­
strated superior HER activity compared to the cubic Pr0.5Ba0.5CoO3 and
tetragonal PrBaCo2O5+δ (δ ≈ 0.76). The significant level of structural
misfit, increased electrochemically active surface area, lattice-oxygen
species, and reduced charge-transfer resistance all contribute to the
robust performance. Additionally, the occurrence of the redox pair
Co3+/Co4+ is favorable for the HER kinetic process [57].
Remarkably, 4d and 5d TMs with greater valence can also serve as
HER catalytic active sites. For instance, Luo and colleagues, for instance,
described the synthesis of IrMo nanomaterials as excellent bifunctional
electrocatalysts for HER and hydrogen oxidation processes in alkaline
conditions [58]. Notably, improved IrMo0.59 demonstrated the best
catalytic performance, nearly 10 times that of conventional platinum/C
and its equivalent iridium. Simulations based on DFT revealed that the
initial phase of the HER reaction (H2O + e− + * → OH− + H* (the
Volmer reaction, electrochemical adsorption, ≈120 mV dec− 1))
preferred to take place at the molybdenum site of IrMo. H2O-adsorbed
molybdenum may substantially improve the interface concentrations of
*H2O and *OH molecules, with *OH species participating actively in the
HER kinetic process. Furthermore, Gibbs free energy values were
determined for the various reactive intermediates of the HER kinetic
process of iridium and Ir3Mo(H2O), displaying that the H2O-adsorption/
dissociation procedures were more advantageous for IrMo(H2O) than for
iridium, suggesting the synergistic impact of molybdenum(H2O) and
iridium on the reported HER kinetic process (Fig. 5c-h).
2.3. The conventional hydrogen evolution reaction descriptors
2.3.1. The hydrogen adsorption Gibbs free energy (ΔGH*)
The ΔGH* is a concise expression for bonding strength that is
frequently employed in the determination of the hydrogen evolution
performance of the electrocatalytic reactive sites [59–62]. In accordance
with the Sabatier hypothesis [63], for the reaction pathways to be able
to be induced and the byproducts to be easily removed, the electro­
catalytic reactive sites must maintain a bonding strength that is
adequate for the essential intermediates [64]. This bond must neither be
too weak nor too robust. Platinum is acknowledged for demonstrating
the superior efficacy of HER and its ability to achieve higher response
rates with low overpotential (η). Platinum is placed quite close to the
volcano chart’s peak and exhibits an almost thermally independent
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 5. (a) Crystal structure of the oxygen vacancies and A-site ordered double perovskites. (b) Calculated free energies at the various steps of the alkaline HER
process on RBaCo2O5.5+δ (δ = 0, 0.25, and 0.5). Reproduced with permission [54]. Copyright 2019, Wiley-VCH. (c) HER polarization curves. (d) The Tafel of IrMo0.59
NPs, Ir NPs, and Pt/C catalysts in Ar-saturated 0.1 M KOH with a scan rate of 10 mV s− 1 at the rotating speed of 1600 rpm. (e, f) The geometric configurations of
Ir3Mo1(H2O) (a) and Ir (b) (111) surface. (g) Calculated free energy diagram of the series of reaction intermediates of the HER process of Ir and Ir3Mo1(H2O). (h)
Schematic diagram showing the HER mechanism of Ir3Mo1(H2O). Reproduced with permission [58]. Copyright 2020, American Chemical Society.

ΔGH*. Consequently, platinum is commonly utilized as a standard. If the
catalyst is positioned to the left of platinum (ΔGH* less than 0), the initial
Volmer phase is straightforward, but H-atom desorption is challenging.
This hampers the subsequent Heyrovsky or Tafel processes, which ulti­
mately causes the electrocatalyst contact to be poisonous. In contrast,
Roger Parson reported the relationship that exists between the exchange
current for electrochemical HER and the capability of the electrode to
bind H-atoms [65]. The author observed that when the catalyst is
positioned on the right side of the platinum (ΔGH* greater than 0), the
hydrogen molecule binding ability is quite poor. Therefore, a greater

7
B.A. Yusuf et al.
amount of energy is needed to activate the Volmer phase, which de­
creases the overall efficiency of the catalytic process (Fig. 6a). The
volcano plot can reveal which kinds of catalytic materials are most
effective for a particular category of catalysts. Nevertheless, as shown in
(Fig. 6b), despite the fact that molybdenum disulfide reaches a value
close to the ideal ΔGH* the exchange current density of molybdenum
disulfide is quite low. This is because the volcano plot is totally depen­
dent on a thermodynamic descriptor, whereas the precise reaction
process is quantitatively dictated by other kinetic characteristics. The
active volcano plot does not shift to the left-side or right-side but rather
upward and downward, indicating that the descriptor can still identify
the bonding characteristics of the optimal HER catalytic material despite
the variation of phases [66].
2.3.2. The d-band center theory
The composition of the metal species is the primary factor that de­
termines the inherent performance of a specific catalyst. As a result of
this, metal-based descriptors have been established to evaluate the
interaction between the features of the active site and the catalytic
performance [67,68]. Electronic interaction between catalysts and
adsorption processes is the origin of the vast majority of catalytic effi­
ciency, such as the activation of reactants and the adsorption of in­
termediates. Therefore, certain hypothetical characteristics of metal
catalytic materials have been provided for the scalability relationship to
the adsorption intensity of chemical components and precursors on the
metal interface. These hypothetical parameters include the d-band
center [69], filling (eg) [70], and valence-and conduction-band [71].
The d-band theory was utilized in order to provide an explanation for
the genesis of electrocatalytic performance, as can be seen in (Fig. 6c).
After catalyst-H bonding, the valence orbital d2z of electrocatalysts can
cleave into bonding and anti-bonding orbitals, denoted by the symbols
(σ) and (σ*), respectively. The greater the d-band position of a metal
nanomaterial, the greater the anti-bonding (σ*) orbital was filled by
fewer electrons. This increased H-adsorption on the catalytic active
interface, resulting in a lower H-adsorption free energy (ΔG*H). As a
consequence of this, the energy of the anti-bonding state, also known as
(E*σ), which was shown to be in a linear proportion to ΔG*H, emerged as
an effective descriptor for the HER mechanism (Fig. 6d) [72]. Based on
this scalability correlation, the optimum HER effectiveness (ΔG*H = 0)
on the volcano plot was matched to the ideal d-band center of the metal
ion pivot. This ensured that the H-adsorption was neither excessively
strong nor excessively weak.
In a similar manner, as can be seen in (Fig. 6e, f), the descriptor that
originated from the d-band concept was also extended to the interaction
between the M-atom (where M is a metal) catalyst and the intermediary
hydroxyl species, which served as the most important precursor.
Because more electrons were able to occupy the (σ*) orbital as a function
of catalyst-hydroxyl coupling, the amount of hydroxyl-adsorption was
lowered when the energy intensity of the d-band center moved in the
direction of a lower value [68]. Consequently, specific volcano plots
connected with descriptors have been constructed in order to supply
useful insights for the effective computational assessment and experi­
mentation [73,74]. In addition, Zeng and colleagues have established a
unified descriptor, φ, which can allow access to the catalytic properties
of the hydrogen evolution process with the basic characteristics of active
centers, namely the electronegativity of M-atoms, the amount and
quantity of coordinating atoms of catalytic active sites, and the number
of total reactive centers. For the classification and regulation of M ion
centers, it is important that the optimal electronic configuration be
found in the active ion and that it be close to or higher than the
maximum level of the volcano (Fig. 6g, h) [68].
2.3.3. The valence band model
The valence band model is appropriate for non-metallic carbon-
based material composites if the d-band center concept is directed to­
wards M-atoms of catalytic active sites. Qiao and coworkers studied the
8
Advances in Colloid and Interface Science 311 (2023) 102811
sources of the diverse Hads responses observed in doped-graphene
nanomaterials [75]. As demonstrated in (Fig. 6i, j, k), the ΔGH* values
of all tested models exhibit a consistent trend in relation to Evar (Evar,
signifies the difference between the minimum valence orbital energy of
(Cs) catalytic active sites and the maximum valence orbital intensity of
the as-doped graphene aggregate). In addition, the author demonstrates
how the valence band (v) of the activated atom interacts with the
deposited H* to form the bonding (v-σ) and anti-bonding (v-σ) * phases
that constitute the basis for this interaction. Lower catalytic active site
valence orbitals may promote (v-σ) state filling, hence strengthening the
bond between H* and catalytic active Cs and reducing ΔGH*. This
equates to the smallest number of ΔGH*. and, thus, the maximum pre­
dicted hydrogen evolution reaction performance.
2.3.4. Ionic electronegativity
Pauling and co-workers were the first to introduce the idea of elec­
tronegativity (abbreviated as EN) [76], which is regarded as a chemical
attribute that characterizes an atoms or functional chemical units’
propensity to draw electrons towards itself. The atomic number and the
separation between its valence electrons and ionic centers always have
an impact on the EN [77]. In order to systematically explain the bond
ionic/covalent proportion and the transition metal ionic ENs with
varying coordination numbers, oxidation states, and spinning states in
the complex oxide-based compounds, several scalings of ionic electro­
negativity and bridge electronegativity have been created [78–81]. In
fact, according to the bond valence sum (BVS) model, the inherent
chemical electron orbitals for the majority of materials, particularly for
the transition metal ions, are never unitary. Thus, it stands to reason that
the electronegativity values of transition metal compounds perovskite
oxide-based should be better determined by the bond valence, which has
a strong correlation with the chemical reaction strengths [82–84].
In order to anticipate the hydrogen evolution reaction performances
of Co-based perovskite materials, Zhou and colleagues use coordination
theories to present A-site ionic electronegativity (AIE) as an effective
integrative descriptor [85]. In comparison to earlier descriptors based
on B-sites of perovskite materials, the authors employ adjacent combi­
nations of active B-sites to quickly and logically screen effective
perovskite materials for the hydrogen evolution process. The authors
show that AIE, as a single unified interactive descriptor, has the highest
prediction accuracy for distinguishing an extremely hydrogen evolution-
efficient oxide-based material from more than ten distinct Co-based
perovskite materials (produced under the same conditions). This is
done specifically by correlating structural or thermodynamic variables
(such as A-site ionic radius and A-O bond length) (Fig. 6l-p). Further­
more, Bai and colleagues reported that bond valence sums (BVS)
increased ionic electronegativity (EN) scales for effectively integrating
the double perovskite materials La2CuMO6-x (Metal = titanium, man­
ganese, ruthenium) with a heterogeneous bonding propensity [86]. In
order to correlate structural and physical properties, the coordinated B-
site sub-assembled deformation and the metal oxygen bonded covalency
percentage are also considered. The authors hypothesized that both the
d(metal)-p(oxygen) orbital hybridization and the metal-oxygen bond
covalency could be regulated by adopting the metal cation with the
suitable ionic electronegativity values (Fig. 7a-d). Moreover, this engi­
neering concept is applicable to MXenes and transition M-disulfide
(bond electronegativity) as well. Thygesen and coworkers discovered
that the thicknesses of the covalently bonded MXene mono-shells have a
significant impact and may be used to adjust the functionality of MXenes
for the hydrogen evolution reaction by utilizing the free energy of Hads
as a major descriptor (Fig. 7e-g) [87]. In addition, Liu and colleagues
have described a generalized hydrogen evolution reaction performance
design technique for transition M-disulfides, atom valence electron
numbers and bond electronegativity [88]. By identifying the electron
transport potential, these variables are used to predict catalytic perfor­
mance. According to the findings of the authors, the charge transport
efficiency of the centralized model next to adsorption sites is a factor
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 6. (a) The graphical illustration showing that the deposited atoms follow a Langmuir isotherm involves exchange current at an H2 electrode and the standard
free energy of H-adsorption on the electrode interface. Reproduced with permission [65]. Copyright 1958, Royal Society of Chemistry. (b) HER volcanic scheme
involving metals and molybdenum disulfide. Reproduced with permission [66]. Copyright 2017, American Association for the Advancement of Science. (c) The
orbital hybridization between the d-band of the M-catalyst and the s-band of the H-atom (σ = bonding, and σ* = antibonding phase orbital). (d) The linear rela­
tionship between Gibbs free energy (ΔGH*) and the condition of anti-bonding (σ*). Reproduced with permission [72]. Copyright 2019, Wiley-VCH. (e) Orbital
hybridization between an M-atom and a hydroxyl adsorbate. EF represents the Fermi level. (f) The anti-bonding orbital Eanti-bonding center and the descriptor r φ Vs.
ΔGOH*. (g) The relative adsorption free energies of OOH and O compared to those of OH on each individual transition metal atom supported by graphene. (h)
Hydrogen evolution reaction: hypothetical overpotential in comparison to adsorption free energies denoted by ΔGH* for each and every single transition metal atom
supported by graphene. Reproduced with permission [68]. Copyright 2018, Nature Publishing Group. (i) Analysis of the abundance of nonmetallic heteroatoms in
graphene matrix. (j) The HER at equilibrium potential models (ΔGH*) diagram. (k) The connection between (ΔGH*) and Evar for different models. Reproduced with
permission [75]. Copyright 2022, American Chemical Society. (l) Graphical representation of values of ionic radius and ionic electronegativity. (m) Doping lan­
thanides and alkaline-earth metal cations into solitary perovskites centered on Co. (n) A-site ionic electronegativity. (o) A-site ionic radius for single and double
perovskites. (p) Molecular orbital theory predicting inductive interactions and electron exchange exchanges between A-and B-sites in perovskites. Reproduced with
permission [85]. Copyright 2019, Nature Publishing Group.

9
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 7. Graphical representations of heat images of EN variations between M and oxygen elements (a) Metal-oxygen bond covalency percentages. (b) Heat images of
various elemental EN levels with both 6-fold coordination and BVS-modified charge state. (c) Relationship graphs of EN variations, and bond covalency percentages.
(d) for the four EN levels. Reproduced with permission [86]. Copyright 2022, Elsevier B.V. (e, f) Negative plot of carbide and nitride MXene overpotentials versus
hydrogen adsorption free energy (ΔGH*). (g) The graphical representation of ΔGH* versus ΔGH plot for MXenes. The circled data points represent compounds with |Δ
GH| greater than or equal to 0.1 eV and hence the potential to operate as excellent hydrogen evolution materials. Reproduced with permission [87]. Copyright 2017,
American Chemical Society. (h) Graphical representation of bond electronegativity as a HER Descriptor. (i) HER hypothetical overpotential vs adsorption free en­
ergies ΔGH* for all TMs doped in molybdenum disulfide with varied defect configurations. (j) Conceptual, experimental, and estimated by descriptor overpotentials
for HER relative to the descriptor Ψ. Reproduced with permission [88]. Copyright 2020, American Chemical Society. (k) The generalized adsorption energies of *OH
above and (l) the coordination numbers of the locations to which the adsorbate is attached. Reproduced with permission [92]. Copyright 2014, Wiley-VCH.

that defines the level of catalytic characteristics (Fig. 7h-j). zeroth order to represent the electronic framework whereby an atom is
situated. In the majority of face-centered cubic crystals, maximal coor­
2.3.5. Generalized coordination number dination is achieved when each atom is surrounded by its twelve closest
In chemistry, coordination numbers are employed as an estimation of neighbors. Coordination numbers lower than twelve are characteristic of

10
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

interfaces and relate to atoms with a propensity to establish interactions HER operations and degradability of over 700 binary interfacial alloys,
that address the lack of interaction [89,90]. According to the bond-order as depicted in (Fig. 8a-f) [62], and discovered that bismuth-platinum
preservation concept [91], there is indeed a proportional correlation alloy could be a reasonable alternative with even superior electro­
between the poor coordination of interface states and their responsive­ catalytic performance than conventional platinum. The quest for robust
ness to the generation of strong bonds. To illustrate this relationship, the HER noble metal-based alloy catalytic materials with diverse morphol­
E-ads of hydroxyl above were represented by the 2 kinds of coordination ogies has made significant advancements over the last decade. Using the
numbers for a variety of adsorbent centers on platinum38, platinum79, noble metal platinum-based alloy as an illustration, we will now explore
platinum201, and extending interfaces (Fig. 7k, l) [92]. the alloying impact on the results of the hydrogen evolution process. By
Typical coordination numbers (cn) and their first-order generaliza­ relocating the platinum d-band centers, alloying platinum with 3d-TMs
tion, which we shall refer to as "generalized coordination numbers" (iron, cobalt, nickel, copper, and titanium) considerably improves the
(CN), represent the patterns in (Fig. 6k, l). To determine the generalized catalytic efficiency of platinum-based alloyed nanostructures. The
coordination number (CN) of an atom (i) having ni (closest neighbors), calculated electronegativity of platinum and TMs such as copper, nickel,
the neighbors’ normal coordination numbers are recorded and weighed iron, titanium, and cobalt are 2.20, 1.90, 1.91, 1.83, 1.88, and 1.30 eV,
Equation (1): respectively, creating an electron transport route from TMs to platinum,
∑ni ( / ) giving rise to the massive negative charges on platinum’s interface,
CN(i) = j=1
cn(j)nj cnmax (1) which will undoubtedly enhance the H2 evolution reaction performance.
Dai and coworkers devised a simple approach to intercalate intermittent
As a result, rather than accounting for each neighbor of atom (i) with
H-atoms into palladium-copper alloy nanomaterials in order to improve
a value of 1, as is customary, nj/cnmax is used instead (cnmax being equal
HER activity [96]. Owing to the suitable Hads free energy and the
to 12 for a face-centered cubic crystal). The generalized coordination
reduced metal dispersibility, the resulting palladium-copper-hydride
number of the interface metal atom for the topmost location on a (111)
catalyst possesses good HER durability. The enhancement of Hads in­
interface is CN = (9 X 6 + 12 x 3)/12 = 7:50. (as there are 6 and 3
tensity on as-fabricated palladium-copper-hydride nanostructures is
neighbors in the initial and secondary shell, respectively, with typical
mostly attributable to the copper-doped precursor and interaction with
coordination numbers of 9 and 12. Furthermore, Table 1 provides a
an intermediate H-atom, which serve to decrease the H* coupling and
summary of several exemplary theoretical descriptors utilized for HER.
increase the HER performance (Fig. 8g-k), In addition to the affordable
cost, considerable enhancements in catalytic performance and
3. Enhancement of HER electrocatalysts
morphological durability revealed the viability of incorporating an
additional TM into a binary equivalent nanomaterial. For instance,
3.1. Intrinsic impact
platinum-silver-cobalt, platinum-rhodium-cobalt, and platinum-nickel-
cobalt. Cheng and coworkers fabricated nanomaterials with a reduced
3.1.1. Alloying
platinum concentration, a hollowed core, and exposed interfaces [97].
It has been demonstrated that alloying noble metals with 3d TMs
The synthesis of hollowed platinum-nickel-copper nanomaterials is a
increases their inherent activity while decreasing their consumption. In
result of atom migration and a galvanic replacement interaction
these instances, the chemical composition of the different metallic in­
involving copper-nickel nanoparticles and platinum atoms that were
terfaces can be altered by modifying the maximum interface d-band
generated in-situ. Incessant activation through etching and calcination
energy and spacing as a result of total overall strain and binding site
removes unwanted copper and nickel from the interface, leading to an
impacts through multiple atomic bond configurations and d-spacing
abundance of platinum. Owing to the advantages of alloy-based impact,
modification, thereby optimizing the Hads uptake capacity to boost HER
hollowed and porous architecture, the resultant catalytic material ex­
performance [93–95]. Nrskov and co-workers initially achieved a robust
hibits exceptional HER electrochemical characteristics (Fig. 8l, m, n).
evaluation system density functional theory to effectively analyze the
3.1.2. Chemical compounds and phase transformation
Table 1 In the areas of the hydrogen evolution process, TM compounds,
Some exemplary theoretical descriptors for HER.
including S2− , C−2 2, N− 3, and P− 3-based precursors, as well as their
Descriptor Category Trends of catalytic Applicable distinctive phase transitions, have garnered considerable interest. Some
performances TM dichalcogenides (TMDs), such as molybdenum disulfide [98–101],
ΔGH* Electronic ΔGH* < 0 a relatively All catalyst rhenium disulfide [102], and nickel disulfide [103], as rapidly evolving
descriptor strong H molecule 2-dimensional TMDs, have received great attention due to their excep­
binding ability;
tional physical and chemical characteristics. Experimentation and den­
ΔGH* > 0 a relatively
weak H molecule sity functional theory (DFT) simulations show that the majority of
binding ability extremely active catalytic sites in TM sulphides are localized at the
d-band center theory Electronic Downward/upward Metal and metal limiting edges, whereas the bulk activation is weak. This is the case for
descriptor shift of the d-band alloy/oxide all of the TM sulphides. Molybdenum disulfide is a good example since it
center. Weakening/
enhancing the metal-
has a tiny size and/or numerous defects, both of which are favorable to
H bond strength the active edge being exposed to its full potential. In addition to merely
Valence band theory Electronic Increase/decrease of Nonmetallic exposing a significant number of defect sites, the focus was also placed
descriptor the filling of the carbon materials on designing unsaturated sulphur edges and exceptionally low interlayer
bonding states
conductivity [104]. In its natural state, molybdenum disulfide is capable
enhancing/
weakening the of forming three distinct crystalline phases. These frameworks are
metal-H bond designated as the rhombic hexahedron 3R phase, the hexagon shaped
strength 2H phase, and the tetrahedron 1T-phase, and they differ in terms of the
Ionic Electronic AIE-activity volcano Cobalt-based layer thickness and the interaction of the molybdenum atoms. In the 2H
electronegativity descriptor plot perovskites
regional Ψ-ΔGH* volcano plot transition metal
phase, the d-orbital will split into the defective phases, leaving an energy
electronegativity φ disulfide band gap of approximately 1 eV (Fig. 9a-f) [105]. In the 1T-phase, the d-
Generalized Structural GCN-activity Metals and metal orbitals will disintegrate, which results in the emergence of six electrons
coordination descriptor volcano plot alloys single-atom occupying the e2g orbital [106]. Metallic characteristics are produced by
number electrocatalysts
only partially filling the orbitals, whereas semiconducting

11
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 8. (a) HER volcano plot for a variety of pure metals and metal overlayers. Geometrical representations of interfacial alloys at solute coverages for which
computations are performed. (b) pure metal. (c) An alloy layer with solute saturation= 1/3 ML (d) An alloy layer with solute saturation= 2/3 ML. (e) 1 ML of solute
atoms that form a coating. (f) H2 evolution after every phase of BiPt interfacial alloy formation on a fluorine-doped tin-oxide layer. Reproduced with permission [62].
Copyright 2006, Nature Publishing Group. (g) Schematic representation of the PdCu0.2H0.43 nanomaterial synthesis. (h) Atomic-scale HAADF-STEM and elemental
EDS images of PdCu0.2H0.43/C. (insert) HRTEM images and FFT patterns matching to PdCu0.2H0.43/C and Pd/C. (i) Linear sweep voltammetry plots. (j) DFT
structures of Pd (111), Pd-H (111), PdCu0.2 (111), and PdCu0.2-H (111) interfaces. (k) A diagram illustrating the HER’s free energy on various Pd-based catalyst
interfaces. Reproduced with permission [96]. Copyright 2022, American Chemical Society. (l) Graphical representation of the formation of trimetallic hollow PtNiCu
nanomaterials with exposed and Pt-enriched interfaces. (m) TEM images with distinctive magnifications. (n) LSV curves and Tafel plots (inset) of S-PtNiCu, H-PtNiCu-
AAT, H-PtNiCu nanomaterials, and commercial Pt/C catalysts. Reproduced with permission [97]. Copyright 2020, American Chemical Society.

characteristics are produced by completely filling the orbitals (2H).
In comparison to the HER reaction that occurs on semiconducting
2H-molybdenum disulfide, the hydrogen evolution reaction that occurs
on metallic 1T-molybdenum disulfide maintains exceptional kinetics
due to the efficient electron transport and abundance of catalytically
active sites on the surface and edges [39,104]. In contrast, the 1T-molyb­
denum disulfide phase exhibits thermodynamic metastability and easily
converts into the 2H-molybdenum disulfide phase, especially during
calcination procedures. Therefore, research into the method of stabi­
lizing 1T-molybdenum disulfide and the development of durable nano­
materials will be advantageous to the process of boosting the catalytic
performance. It is possible to incorporate the necessary dopants into the
1T-system in order to resolve this issue and achieve the required results.
M-dopants and non-metal dopants are the two most frequently
employed types of phase-induced doping agents. M-dopants, which
often serve as electron donors, maintain high electron states in the d-
orbital of molybdenum ions through their own oxidation states of (4+
and 3+), thereby optimizing 1T-molybdenum disulfide (Fig. 9g-m)
[107].
In relation to hydrogen evolution reactions, interest in TM phos­
phides (TMPs) has increased as a result of their low resistivity, greater
mechanical properties, and exceptional thermal durability compared to
other TM nanomaterials [108–114]. The effect that TMPs have on H2
evolution reactions is highly dependent on their composition. Owing to
the significant contact between precipitated H2 and the transition metal
interface, most metals (for example, nickel) have low H2 evolution
performance. When P permeates the crystalline phase of a metal, its
incorporation can disperse the M-atoms while maintaining the metal’s
intrinsic electrical characteristics, hence reducing the free energy of
Hads, which is favorable to Hdes [114–123]. M-phosphides, as compared
to M-sulphides, are present in their bulk state and are reactive. In this
research direction, certain novel approaches, like the doping of hetero

12
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

(caption on next page)

13
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 9. The stacking of bilayer MoS2 interlayers. (a, b) Schematic depictions of 2H (a) and 3R (b) stacking, respectively. (c, d) HAADF-STEM images of 2H and 3R
bilayer MoS2 in planar view, respectively. (d, e) High-resolution HAADF-STEM images of bilayer 2H and 3R MoS2. Reproduced with permission [105]. Copyright
2022, Springer Nature Limited. (g) Schematic representation of the CoS2@1T-MoS2 fabrication. (h) SEM image, (i, j) magnification of the selected locations and
associated lattice diagram. (k) LSV plot in acid (0.5 M H2SO4). (l) Heterostructure deformation charge density of CoS2@1T-MoS2. (m) Hydrogen absorption free-
energy (ΔGH) illustration. Reproduced with permission [107]. Copyright 2019, Elsevier B.V. (n) Schematic depiction of the synthesis of Ni-doped FeP/C nano­
materials. (o) FESEM and TEM images. (p) LSV curves. (q) XPS spectra of Fe 2p, Fe 2p3/2 and P 2p. Reproduced with permission [124]. Copyright 2019, American
Association for the Advancement of Science. (r) HAADF-STEM image. (s) TEM image. (t) STEM-EDX elemental mapping of wrinkled Rh2P nanomaterials. (u) LSV
plots and (v) Free energy pathways (ΔG) for HER. Reproduced with permission [126]. Copyright 2018, Wiley-VCH.

atoms, were implemented to expedite HER reactivity. Lou and co­ [124]. X-Ray photoelectron spectroscopy surface analysis revealed that
workers fabricated a symmetrical hollow nanostructure of nickel-doped the positive shift for P 2p and the negative shift for Fe 2p spectra indicate
iron phosphide nanomaterials using a carbon-conjugated technique the presence of electron transport from phosphorus atom to iron atom,

Fig. 10. (a) A schematic representation of the fabrication procedure of the Ni-GF/VC nanomaterials. (b, c) SEM images. (d) The iR-corrected LSV curves. (e)
Computed ΔGH* for HER. (f) The overall DOS configurations of (100) and (111) surfaces. (g) the computed ΔGH* of the Ni-deposition VC catalyst at different Hads
sites for HER. (h, i) Schematic illustration and free energy chart for the suggested HER route on the Ni-GF/VC catalyst interface in alkaline conditions. Reproduced
with permission [138]. Copyright 2020, Wiley-VCH. (j) Schematic representation of the fabrication procedures and the predicted Hads and Hdes for various TMC@NG
electrocatalysts. (k) Diagrams of free energy derived from DFT simulations of HER performance on several TMC@NG model electrocatalysts. (l) A volcano plot
representing the HER activities on TMC@NG model electrocatalysts. (m) Schematic illustration of HER mechanism pathways in alkaline media. Reproduced with
permission [143]. Copyright 2022, Wiley-VCH.

14
B.A. Yusuf et al.
and nickel doping iron phosphide results in the generation of higher
levels for catalytically effective phosphides, which remarkably optimize
the electrical properties and consequently result in outstanding HER
performance (Fig. 9n-q). Numerous studies have shown that platinum-
group, rhodium-group, and ruthenium-group noble metal P-based cat­
alysts [125–129] exhibit exceptional HER performances comparable to
or even superior to conventional Pt/C. For example, Guo and coworkers
established a novel category of crumpled ultrathin Rh2P nanomaterials
for improving HER reactivity [126]. These nanomaterials are extremely
fine and wrinkled. According to the results of theoretical calculations,
the P-3p band orbital, which has a robust porous layer effect, makes Rh-
4d band more conducive to enhanced proton-electron charge transfer
and advantageous to the HER mechanism (Fig. 9r-v).
Due to its distinctive "Pt-like functionality," transition metal carbide
(TMC) has been identified as one of the most viable options to substitute
platinum-based electrocatalytic materials [130–134]. The bonding be­
tween the d-orbitals of a TM and the s-orbital/p-orbital of a C-atom in
the associated carbide-based materials greatly broadens the d-band of a
TM within a TMC. The d-band configuration of a transition metal car­
bide is remarkably comparable to that of platinum metal [135]. Typi­
cally, doping with active TMs and non-metallic elements (such as iron
[136], cobalt [137], nickel [138], nitrogen [139], phosphorous [140],
boron [141], and sulphur [142]) has a considerable impact on the
abundance of electrons at the M-sites, leading to a downshift of the d-
band centers and a weakening of hydrogen-binding towards enhancing
TMCs. Nickel adsorption on vanadium carbide catalytic material shown
increased hydrogen evolution performance and reduced overpotential in
basic solution. Li and coworkers have observed nickel activation of
transition metal carbides (M = vanadium) by adsorption of Ni-atoms on
the nickel-transition metal carbide interface [138]. The authors found
the lowest ΔGH* values for nickel atom deposition on the (100) and
(111) surfaces of vanadium carbide catalytic materials. This indicates
that nickel atom deposition on vanadium carbide is the most active
process. Due to the fact that the electronic characteristics of the nickel-
deposited vanadium carbide catalytic material around the Fermi level
are much higher than those of the pure vanadium carbide and nickel-
doped vanadium carbide nanomaterials, its exceptional electronic
conductance can be assumed (Fig. 10a-e). Moreover, a relatively large
density levels of carbon and vanadium on the adsorbent surface for
(100) and (111) of the nickel deposited vanadium carbide catalytic
materials compared to those of the pure vanadium carbide and nickel-
doped vanadium carbide nanomaterials at the Fermi level suggests
that both carbon and vanadium sites are induced in the nickel deposited
vanadium nanomaterial along with a significant increase in charge
density (Fig. 10f-i). Yang and coworkers presented a generalized
"balancing effect" technique involving the introduction of N-doped
graphene (NG) to reduce the interplay of transition metal carbides (M =
vanadium) with H* [143]. The DFT binding energies for H2 indicate that
the TMCs combined with N-doped graphene are thermoneutral. Due to
the dissimilar activities of TMCs and N-doped graphene, incomplete
electrons are transferred from the TMC interface to the N-doped gra­
phene interface, leading to the optimization of the electronic configu­
ration of the as-fabricated electrocatalysts. These improved electronic
architectures achieve an equilibrium between Hads and Hdes, resulting
in exponentially increased HER rates (Fig. 10j-m).
3.1.3. Defects effect
The term "defect" was originally identified by Latham and coworkers
in 1897 as a deficiency or omission of something fundamental to
wholeness [144]. In modern scientific nomenclature, defects are de­
viations from the diffraction pattern in complete crystals [145]. Ac­
cording to their arrangement, defects in crystalline nanomaterials can be
divided into bulk and interface defects. In order to change the electronic
composition and surface characteristics of electrocatalytic materials,
interface defects, such as point, line, and plane defects, have been
intensively used. In electrocatalytic processes, point defects (including
15
Advances in Colloid and Interface Science 311 (2023) 102811
vacancy, interstitial, anti-site, and replacement defects), which deviate
from the usual crystallographic configuration in the nodes or neigh­
boring states, are highly efficient and widely employed. Recent studies
have found that defects are advantageous for generating electrocatalytic
materials with distinctive electronic configurations and for altering their
interface nano-environments in order to improve their effectiveness.
Oxygen vacancies [146,147] in metal oxides and sulphur vacancies
[148–151] in 2-dimensional transition metal dichalcogenides (TMDs)
materials are two examples of the frequent point defects known as va­
cancy defects. By adjusting the density of vacancies, the ΔGH* might be
made to function optimally, using the sulphur vacancies as an example.
Additionally, the formation of sulphur vacancies causes the leftover
electrons to preferentially migrate to the nearby M-atoms, resulting in
an electron-rich area on the M-atoms. More specifically, the delocalized
electrons surrounding M-atoms support higher H2 affinity and enhance
Hads on interfaces, increasing the number of charge carriers on the inert
lattice. Voiry and colleagues investigated the hydrogen evolution per­
formance of defective multidimensional molybdenum disulfide across a
broad range of interface S vacancy ratios [149]. The authors discovered
that the HER process on defective molybdenum disulfide is classified
into 2 phases, correlating to (i) "point" defects at small concentrations of
interface sulphur-vacancies and (ii) under-organized molybdenum areas
induced by S-atom extraction at increased concentrations of interface
defects (Fig. 11a-f).
Linear defects (consisting of dislocations and stepping-phases) are
regular structural breakdowns that form along a path close to the
dislocated-atoms. For instance, Chen and co-workers used the thermal
shock approach at a non-equilibrium high temperature in order to create
numerous dislocations in platinum nanostructures that they referred to
as Dr-Pt (Fig. 11g-j) [152]. During the crystallization process, disloca­
tions that are generated by thermomechanical stresses crystallize
interactively at a rapid processing temperature. This process takes place
in a matter of milliseconds (Fig. 11k, l, m). According to the author’s
findings, the efficiency of the hydrogen evolution process can be greatly
improved by the addition of abundant dislocations. A crystal is
frequently divided into several smaller subdomains by certain surfaces,
which have stronger atomic configuration stability and extreme atom
distortion adjacent to the surfaces between the subdomains. These de­
fects include twin defects, layered defects, stacking defects and grain
boundary-defects. Grain boundary-defects are typical examples of
interface defects found in polycrystalline-based materials that are ul­
trathin or 2-dimensional. Recent research has demonstrated that the
occurrence of grain boundary defects can increase the electrocatalytic
performance of metallic materials [153,154]. For instance, Liu and co­
workers generated wafer-sized nanostructured ultrathin films with
extremely high grain boundary densities (Fig. 11n, o). Owing to the
existence of grain boundaries, domains on the normally hydrogen evo­
lution inert particle surface of the molybdenum disulfide were activated,
leading to a better hydrogen evolution efficiency in acidic media in the
final nano-grain layer (Fig. 11p, q) [155].
Bulk defects are crystal defects in the 3D region, such as cracks,
pores, unwanted inclusions, as well as other components that are typi­
cally generated during treatment and synthesis procedures. Porous
structures, the most common type of metal bulk defect, contain a huge
quantity of pore structures. The pore structure is distinctly visible in
high-angle annular dark field scanning transmission electron micro­
scopy (HAADF-STEM) images owing to the darker contrast of porous
locations, which have fewer atoms. For instance, Yang and colleagues,
for instance, demonstrated the fabrication of mesoporous copper
nanoribbons using in-situ electrochemical reduction of copper-based
MOFs (Fig. 12a, b, c) [156]. The HAADF-STEM image displayed a
dense distribution of mesopores across the nanoribbons (Fig. 12d), as
numerous dark pores were observed on the bright copper nanoribbons.
The evidence could be obtained further from the HAADF-STEM image,
which displayed pores distinctly. For instance, the intensity profile was
derived from a HAADF-STEM image to corroborate the pores (Fig. 12e).
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 11. (a-d) Evolution of the various layers of MoS2 and transmission electron microscopy (TEM) studies of as-fabricated MoS2. (e) Graphical representation of TOF
progression of HER as a function of S concentration at the interface. (f) HRTEM image of ultrathin layer of S vacancies (red cycles). Reproduced with permission
[149]. Copyright 2019, American Chemical Society. (g, h) Schematic representation of the synthesis of dislocation-rich Pt nanoparticles via environmental HTS. (i)
Modifications of the Pt d-band upon compression. (j) HRTEM images of several T-marked dislocations (IFFT patterns). Reproduced with permission [152]. Copyright
2021, Wiley-VCH. (k, l, m) Analysis of 10 nm Pt particles by molecular dynamics simulation during fast heating and cooling to a high temperature. (n, o) Fabrication
of TMD nanograin films on wafers. (p) HAADF-STEM image of MoS2 grains and grain boundaries. (q) A schematic representation of MoS2 illustrates the principal
types of catalytically active sites for the HER process. Reproduced with permission [155]. Copyright 2020, Nature Publishing Group.

16
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 12. Synthesis and characterization of Cu nanoribbons. (a) Schematic representation of the fabrication of Cu-MOFs and the in-situ electroreduction to porous Cu
nanoribbons. (b) SEM images. (c) TEM images. (d) HAADF-STEM images of Cu nanoribbons. (e) The corresponding intensity profile along the line as shown in (d).
Reproduced with permission [156]. Copyright 2021, Wiley-VCH. (f) Ratio of area normalized CDB spectra of calcined C3N4 with respect to area normalized CDB
spectra of 420 ◦ C calcined C3N4. (g) Doppler broadening shape parameter, S-parameter, for differently calcined C3N4 samples. Reproduced with permission [157].
Copyright 2018, American Chemical Society. (h) AFM image of three kinds of defects after controlled steam treatment during the CVD process. Reproduced with
permission [158]. Copyright 2018, Elsevier.

Periodic fluctuations in intensity suggest the presence of mesopores. The
N2 adsorption-desorption could be studied to get more knowledge about
the distribution of pore sizes. Furthermore, Giri and colleagues, for
instance, fabricated g-C3N4 containing N defects via pyrolysis. At an
increased heat-treatment of 570 ◦ C, it can be observed that the ratio
curve has a broad dip around the momentum value pL = 10 ×10− 3,
signifying increased bulk defects (Fig. 12f) [157]. In addition, the in­
crease in the system’s S-parameter related to the annihilation of low-
and-high-momentum positrons illustrates the increased bulk defect
density (Fig. 12g). Finally, Dong and colleagues regulated the steam
during the chemical vapor deposition process, which designed the basal
interface of bulk molybdenum disulphides with bulk defects in the form
of nano-channels (1-dimensional), triangular pits (2-dimensional), and
hexagonal voids (3-dimensional) (Fig. 12h) [158]. In addition, the
electrocatalytic performance of steam-etched MoS2 flake was improved,
and the slope of the Tafel curve was decreased by 49%.
3.1.4. The confinement effect
The confinement effect is the process in which the anomalous
dispersion of localized outer electrons and the comparatively confined
geometry of the reaction zone both impede the mobility of molecules
and favor specific catalytic reactions. These two factors combine to
create the confinement impact. In particular, confinement effects can be
classified into the following 3 groups: spatial confinement effects, cover
confinement effects, and lattice confinement effects. Spatial confine­
ment effects frequently require the use of hierarchical porous carbon-
based materials or metal organic frameworks (MOFs), the microparti­
cles of which efficiently regulate the size distribution of the targeted
particles. Hu and colleagues successfully fabricated a highly porous
electrocatalytic material (designated Co@HMNC) oriented on nitrogen-
doped graphitic carbon containing cobalt nanoparticles spatially
enclosed in the as-fabricated honeycomb-like macro-porous framework
(Fig. 13a, b) [159]. Cobalt particles with a dimension of 10–11 nano­
meters were homogeneously encapsulated in a carbonaceous porous
structure through the " metal organic frameworks in-situ extraction and

17
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 13. (a) Schematic representation for the fabrication of Co@HMNC. (b) Different magnification of SEM images of the Co@HMNC. Reproduced with permission
[159]. Copyright 2021, Wiley-VCH. (c) SEM image. (d) HAADF-STEM image (yellow circles with dots represent Se-dopants). (e) Enlargement of the dot pattern in
d and the related simulation image. (f) Theoretical studies of Co/Se co-doped MoS2 nanofoam (Co/Se-MoS2-NF). Reproduced with permission [161]. Copyright 2020,
Nature Publishing Group. (g) Fabrication approach to NiCu/C. (h) STEM image. (i) HAADF-STEM image of Ni0.25Cu0.75/C electrocatalyst. (j) LSV curves. (k) The
respective ΔGH* per each nanoalloy. (l) DFT studies showing the most energetically advantageous catalytic active sites in NiCu nanoalloys. Reproduced with
permission [167]. Copyright 2020, American Chemical Society.

confined formation of MOF" technique. The "ships in a bottle" spatial
confinement is primarily responsible for the quickening of threefold
mobility and quick reaction response. In addition, the tiny size and
increased distribution of particles bound to MOFs boost their electro­
catalytic performance [160].
The term "lattice confinement effect of single-atoms" refers to atoms
that are either doped with another substance or bound in the coordi­
nation sphere of the catalytic lattice (host frameworks). While this is
occurring, the agglomeration of active species can be efficiently mini­
mized via the confinement of single-atoms to the host framework matrix.
In addition, the electronic structures that are produced as a result of
interactions between single atoms and their host substrates have the

18
B.A. Yusuf et al.
potential to improve the electrochemical performance and reaction
mechanisms of nanomaterials [161–163]. Deng and coworkers reported
the fabrication of a molybdenum disulfide nanofoam electrocatalyst that
co-confines Se on the interface and Co in the interior core and exhibits an
exceptionally high current density [161]. In contrast to producing a new
layer of molybdenum diselenide or adhering to the interface, the study
revealed that the selenium-atoms are covalently deposited into the
molybdenum disulfide lattice (Fig. 13c, d, e). Furthermore, DFT analyses
reveal a cohesiveness between the stimulating impact of confining co­
balt in the core molybdenum-layer and the strengthening impact of
confining selenium in the interfacial sulphur-layer, which facilitates the
creation of both in-plane and perimeter active sites and improves the
Hads free energy (Fig. 13f).
The term "cover-confinement effects of metals" refers to particles of
metals [164] or metal-alloys [165,166] that are enclosed in a substance.
Owing to their stability and chemical inertness, carbon compounds,
including graphene-based nanomaterials, carbon nanowires, and carbon
nanotubes, offer electrochemically active M-catalysts with efficient and
compact shielding against hostile circumstances. Consequently, this sort
of catalyst enables the utilization of resistant but volatile non-noble
metals in extreme environments. In addition, the differential in work
function allows electrons to flow from the M-atoms to the cover, which
optimizes the electron configuration or work function on the cover’s
outermost layer, facilitating their catalytic performance and so initiating
the interaction. Noveron and colleagues describe the simple fabrication
of bimetallic nickel-copper nanomaterials enclosed in carbon, which
permits the methodical regulation of the morphology and mechanical
characteristics, hence yielding excellent catalytic performance for HER
processes (Fig. 13g) [167]. To manipulate the morphological and elec­
trochemical properties of the as-fabricated nanomaterials, the Ni:Cu
proportion was altered. Based on theoretical findings, it was observed
that the local defects of the crystalline matrix at the nanoparticle
interface were closely linked with the downshift of the d-band and the
reduction of the interaction affinity of the substrate reactive agents,
which enhances the charge carrier transport rates of the catalyst active
sites on the interface and optimizes kinetics (Fig. 13h-l).
3.1.5. Multi-site functionalization
Organic chemistry is where the functionalization effect idea first
appeared. Currently, the field of catalysis makes extensive use of this
idea. The catalytic performance may be impacted by the capture re­
actants, substrate outputs, and electronic configuration of the sur­
rounding adsorption sites due to the steric and electronic influences of
the existing or novel functional groups generated after the synthesis, in
addition to the electrostatic influence of electrons. Due to their excellent
thermal conductivity and well-structured porous frameworks that sup­
port mass transport, carbon-based materials have been thoroughly
studied. However, owing to the excellent degree of surface modification,
carbon compounds cannot typically offer efficient stabilization for direct
attachment of other functional M-based nanomaterials. It is generally
accepted that adding functional groups to the intermediates improves
the electrochemical performance of the nanocomposite while also
exposing numerous active sites [168–170]. Typical functional groups
consist of hydroxyl, methyl, carbonyl, carboxyl, amino, phosphate,
halogen, and sulfhydryl, among others. Sun and coworkers reported the
synthesis of functionalized carbon-supported ruthenium nanostructured
electrocatalytic materials containing abundant Ru-N(O)-C moieties for
the purpose of accelerating the HER process [171]. The binding reaction
of the Ru-N(O)-C moieties, and consequently the spatial and electronic
configurations of the ruthenium species, are effectively modified by
calcination. The ideal nanostructures as-fabricated electrocatalysts
exhibit a high specific performance (Fig. 14a-e). Furthermore, Lin and
colleagues reported a novel platinum single-atom and clustered nano­
catalyst on functionalized multiwalled carbon nanotubes (represented
as Pt/f-MWCNTs) that was deposited using photo-deposition without
the use of a caustic reactant. f-MWCNTs effectively serve the functions of
19
Advances in Colloid and Interface Science 311 (2023) 102811
photo-electron producers to reduce Pt cations during irradiation;
transport of attaching Pt-atoms; and conductors linking diverse active
sites throughout the entire carbon matrix (Fig. 14f, g, h) [172]. Moreso,
XAS suggests that a platinum-atom in the f-MWCNTs scaffold was likely
coupled with 4 oxygen-atoms of OOH. The large density of vacant d-
orbitals of platinum in Pt/f-MWCNTs proved advantageous for the
pairing with the hydrogen 1s orbital. In addition, negatively charged
OOH surrounding the platinum-sites can decrease the hydrogen ion
concentration polarization, hence enhancing the performance and
durability (Fig. 14i).
3.2. Extrinsic effect
3.2.1. Effect of strain
It has been demonstrated that adjusting surface strain is an effective
method for modulating the interface electrical characteristics and,
consequently, the catalytic efficiency of M-catalysts [152,173–180]. The
strain impact on the atomic scale can result in the modification of lattice
characteristics, the modification of the intrinsic atomic spacing, and the
modification of the energy state of bonding electrons, thus drastically
lowering the energy state threshold of the hydrogen evolution process.
The term "lattice-mismatch" refers to the occurrence that occurs when
two different types of crystals have lattice parameters that are incon­
sistent with one another. Dealloying [181–183] and epitaxial [184–186]
evolutions are two of the most popular synthetic methods that are used
for lattice mismatches. Dealloying, also termed as selective corrosion, is
the process of selectively removing one or more active functionalities
(also referred to as base components) from an alloy using chemicals or
electrochemical approaches based on the distinctions in the chemical
characteristics of the various elements that make up the alloy materials.
The remaining variables, which are also known as noble components,
will automatically form three-dimensional intermittent porosity through
atomic dispersion and agglomeration. Dealloying can cause strain as
well as other impacts, which can either lessen the load distribution of
catalysts containing noble metals or boost the efficiency of HER elec­
trocatalysts. Huang and coworkers reported that the fabrication of
Iridium ditelluride hollowed nanomaterials with metal iridium shells
(D-IrTe2 HNSs) occurred when the voltage applied during the electro­
lytic dealloying was moderate (Fig. 15a-e). The development of defects
(cavities, twins, and GBs) as a response to this electrolytic dealloying
increases the lattice-strain of the regenerated Iridium ditelluride-hollow
nanoshuttles. In addition, D-IrTe2 hollow nanoshuttles exhibit excellent
electrocatalytic efficiency and defect-rich properties (Fig. 15f, g) [187].
Vapor deposition is a technique that has been used for quite some time in
the formation of functional heterojunctions through multimodal
epitaxy. Tungsten disulfide [186] restricted epitaxy emerges in an
interconnected porous graphene-based material that is defined by a
nano-crystalline lattice structure. Additionally, the spherical shape
imparted by the highly porous graphite causes the forming tungsten
disulfide nanomaterial to create strain and sulphur-vacancy evenly.
According to the results of density functional theory, the strain signifi­
cantly contributes to the increase in HER performance.
Two-dimensional materials offer natural benefits (flexibility,
strength, and strain sensitivity) for modulating their fundamental
chemical or physical characteristics via strain impacts. Thus, there have
been extensive theoretical [188,189] and practical [190] studies into
the effects of strain on the electrical architecture of 2-dimensional ma­
terials. This section is classified into two groups based on the source of
strain: those strained on flexible substrates and those strained on rigid
substrates. Cheng and coworkers observed that the interface strain
resulting from the stiff composite microflower-like frameworks (inter­
face)-molybdenum disulfide nanomaterials (substrates) efficiently re­
duces aggregation (nanosheets), which adds to higher performance
[191]. In comparison to hard substrates, flexible substrates not only
serve as templates but also offer prospective commercial applications,
especially in harsh situations. On the basis of experimental studies and
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 14. (a) Schematic depiction of Ru/NC heterostructure fabrication. The grey balls denote C-atoms, the blue balls indicate N-atoms, the red balls symbolize O-
atoms, the cyan balls represent Cl-atoms, and the gold balls illustrate Ru-atoms. (b) HAADF-STEM image (inset: the FFT pattern matching to a particular Ru
nanoparticle). (c) HAADF-STEM image. (d) the matching EDS elemental mappings. (e) Schematic depiction of the alkaline HER process on the Ru/NC-400 elec­
trocatalyst. Reproduced with permission [171]. Copyright 2021, Wiley-VCH. (f) Schematic representation of Pt/f-MWCNTs fabrication. (g) HAADF-STEM image. (h,
i) XAFS of the Pt/f-MWCNTs. Reproduced with permission [172]. Copyright 2019, Elsevier Ltd.

20
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 15. (a) Schematic representation electrochemical dealloying-induced fabrication of IrTe2 HNSs with metal Ir- shell and IrOx surface (D-IrTe2). (b, c, d) HAADF-
STEM images. (e) Matching EDS line scans of D-IrTe2. (f) Schematic representation of defect-rich frameworks and HAADF-STEM images of D-IrTe2. (g) EXAFS
patterns of D-IrTe2 HNSs. Reproduced with permission [187]. Copyright 2020, Wiley-VCH. (h) Schematic representation of the crumpling mechanism of MoS2 film.
(I, j) LSV and Tafel curves of the film before and after the crumpling. Reproduced with permission [192]. Copyright 2020, American Chemical Society. (k, l) XAFs
patterns of NixMo1-xO2. Reproduced with permission [209]. Copyright 2020, American Chemical Society.

21
B.A. Yusuf et al.
theoretical estimations, Cao and coworkers investigated the impact of
titanium-coated flexible polymer-based substrates on the hydrogen
evolution processes of defective molybdenum disulfide. (Fig. 15h) de­
picts the transport of a monolayer molybdenum disulfide layer to the
surface of a titanium film anisotropically formed on a 100 nm-diameter
pre-strained polymer substrate, followed by the relaxation of the
polymer-based substrate’s strain. It is established that a change in
chemical characteristics and the formation of an intermediate tunnelling
resistance are responsible for the significant increase in performance
following the relaxation of the polymer-based substrate (Fig. 15i, j)
[192].
3.2.2. Heteroatom-doping effect
Hetero-atom doping continually and effectively modifies the elec­
tronic properties and hydrogen evolution performance of an electro­
catalyst without altering its chemical components [193–205].
Consequently, hetero-atom doping is an efficient and extensively
employed method for optimizing HER function. Doping with TMs such
as iron [206], cobalt [207,208], nickel [209], zinc [210], and molyb­
denum [211] may alter the local electronic state and optimize neigh­
boring atoms’ spacing together with coordination numbers at catalyst
interface sites. The doping-agents and strain impacts that are brought
about by the presence of TMs have the ability to modify the ΔGH*. For
instance, Meng and coworkers reported the fabrication of nickel-atom-
doped molybdenum dioxide exhibits high hydrogen evolution catalytic
efficiency and high acidic environment durability [209]. Evaluations
using X-ray absorption near edge structure and extended X-ray absorp­
tion fine structure show that nickel-atoms in molybdenum dioxide are
doped by replacement molybdenum-atoms (Fig. 15k, l). The electron
depletion of nearby oxygen-sites brought about by nickel-doping results
in the deposition of hydrogen on oxygen-sites, hence enhancing the
interface hydrogen saturation.
3.2.3. Metal doping
It has been established that utilization of metal-doping can expedite
the HER mechanism by increasing the number of catalytic active sites
[212], enhancing conductivity [213], and optimizing electronic struc­
ture [214]. Several technologies, such as self-assembly solution
impregnation [215], chemical vapor deposition (CVD) [216], plasma
[217], hydrothermal techniques [218], electrochemical depositions
[219], and photoreductions [220], are currently available for efficient
doping. Fig. 16a depicts 2 kinds of doping based on the atomic config­
urations of the doped metal atoms: substitutional and interstitial doping
[221]. Numerous TMs have been documented for substitutional doping
in TMDCs, including cobalt, iron, vanadium, chromium, palladium, and
rhenium. Theoretically, Abild-Pedersen and colleagues calculated the
ΔGH* on several species of TM-doped molybdenum disulfide using DFT,
enabling a reasonable architecture for a novel molybdenum disulfide-
type catalyst to enhance or decrease the interaction of crucial in­
termediates (Fig. 16b) [222]. Experiments revealed, however, that this
doping not only influences the interaction strength of doped metal atoms
but also substantially modifies their coordination environment, which
typically introduces sulfur vacancies and local phase changes in transi­
tion metal dichalcogenide-based electrocatalysts [223]. Using the CVD
method, Fan and colleagues created 2 geometries of metal-doped mo­
lybdenum disulfide nanostructures [224]. As demonstrated in Fig. 16c,
iron-and cobalt-based configurations are typically followed by vacancy
formation. 3CoMo-Vs exhibit the best performances: a modest over­
potential at the current density of 10 mA cm− 2 (η10 = 75 mV vs. RHE), a
small Tafel slope of 57 mV dec− 1, and time-dependent stability (η10
declines by only 10 mV after 1000 cycles), as depicted in Fig. 16d. Xing
and colleagues produced substitutional doping of palladium in the mo­
lybdenum disulfide basal plane via a solvothermal approach in which
sulfur vacancies were concurrently injected to induce a local phase
change (Fig. 16e). The exchange current density of 1% palladium-MoS2
is 805 μA cm− 2 and the overpotential is 78 mV (Fig. 16f) [215]. This is
22
Advances in Colloid and Interface Science 311 (2023) 102811
comparable to the activity of platinum/C catalysts. In addition, the
structural durability of these substituted electrocatalysts with high co­
ordination numbers is exceptional.
Interstitial doping, in contrast to the previously described substitu­
tion, is placed on top of the basal plane as opposed to being contained
within the crystalline structure. As interstitial dopant atoms in TMDCs
for HER, platinum, rhodium, lead, bismuth, palladium, tin, niobium,
molybdenum, and copper are currently employed [216,219,225,226].
Using electrochemical underpotential deposition, Xia and colleagues
generated a range of atomically scattered platinum, rhodium, copper,
lead, bismuth, and tin atoms on the molybdenum disulfide interface
(Fig. 16g) [225]. Furthermore, Chhowalla and colleagues demonstrated
interstitial doped 2H-Nb1.35S2 using the chemical vapor deposition
technique, which produced an extraordinarily high current density in
HER (1000 mA cm− 2 at ~ 370 mV and 5000 mA cm− 2 at ~ 420 mV)
[216]. In relation to the previous heteroatom doping, Liu and colleagues
employed a cold H2 plasma technique to generate molybdenum-single-
atom doped molybdenum disulfide (homo-atomic doping), attaining a
boost in HER performance with a small Tafel slope of 36.4 mV dec− 1 and
a large current density of 400 mA cm− 2 at ~ 260 mV, as shown in
(Fig. 16h, i, j), as a result of an increase in H2 interaction [226].
3.2.4. Non-metal doping
Non-metal doping also demonstrates different characteristics and
higher hydrogen evolution performance in comparison to M-doping.
Contrary to M-doped strategies, non-metal doping also results in
amorphous phase or structural deformation with a large number of
activated sites, which can alter ΔGH* or the intensity of energy state
compatibility. In recent years, a large number of researchers have
concentrated their efforts on the regulation of the HER reaction mech­
anism and the enhancement of their electrocatalytic performances
through the incorporation of non-metal elements (such as nitrogen
[227], oxygen [228], boron [229], sulfur [230–232], and phosphorous
[233]) in TMs-based HER electrocatalytic materials. For instance, Zhang
and coworkers utilized a solvothermal ion-exchange strategy in order to
synthesize sulfur-atoms that were subsequently doped into CoSe2
nanomaterials [232]. Simulations using density functional theory un­
equivocally establish that the addition of sulfur enhances ΔGH* closer to
the ideal value and noticeably lowers the energy barrier of the Heyr­
ovsky reaction for sulfur-CoSe2-activated HER, which ultimately results
in an improvement in HER efficiency (Fig. 17a-e). Non-metal doping,
particularly co-doping (dual) and tri-doping approaches, can efficiently
adjust the electronic characteristics of near-atoms, hence enhancing the
catalytic efficacy of the as-targeted nanomaterials. Zhu and coworkers
synthesized molybdenum disulfide nanostructures with phosphorus and
oxygen dual doping [228]. To accomplish accelerated electron trans­
port, molybdenum disulfide nanosheets are specifically interacted with
each other by P-O bonds generated by phosphorus and oxygen dual-
doping. Additionally, by preventing additional molybdenum disulfide
aggregation and re-stacking, the as-fabricated P-O linkages can increase
the number of accessible catalytic active sites (Fig. 17f-j). Furthermore,
Li and colleagues reported a simple and inexpensive method for fabri­
cating novel 3D-Co nanostructures-enclosed and extremely high boron
and nitrogen co-doped hierarchical structures of nanoporous nanowires
(denoted as Co@BNPCFs) by carbonizing the 3D Co(AC)2-HBBA-PVP-
DMF precursor frameworks woven through spin coating [234]. After
modifying calcination temperatures, the ideal Co@BNPCFs-800 displays
optimum activity. In conclusion, DFT analysis findings have demon­
strated that the pyridinic-N, pyrrolic-N, graphitic-N, and B-C have the
same electronic configuration and excellently enhance the electro­
chemical performance (Fig. 17k, l). Zhao and colleagues used a simple
extraction technique to create a unique defects-designed tri-doped-
intertwined asphaltene (DE-TDAP) as an M-free nanomaterial with a
lower Gibbs free energy of HER precursors [235]. The DE-TDAP nano­
composite, which is endowed with N, S, and O, performs well for the
hydrogen evolution process. Owing to defects-modifying and tri-doping
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

(caption on next page)

23
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 16. Metal-doping strategy of 2D-TMDCs for HER. (a) Schematic representation of metal-doping in TMDCs by substitutional (left) and interstitial (right).
Reproduced with permission [221]. Copyright 2022, Royal Society of Chemistry. (b) Range of ΔGH* on each transition metal-doped MoS2. Reproduced with
permission [222]. Copyright 2015, Royal Society of Chemistry. (c) Two configurations of metal-doped MoS2 structures, in which the sulfur vacancies (SVs) are
marked in blue circles and the H-bonded S atoms in red circles. (d) The matching η10-Tafel slope in 0.5 M H2SO4 for the HER catalysts in (c). Reproduced with
permission [224]. Copyright 2020, Springer Nature. (e) Substitutional doping of Pd in the MoS2 basal plane and (f) the polarization curves of the resultant catalysts.
Reproduced with permission [215]. Copyright 2018, Springer Nature. (g) Schematic representation of single-atom doping on TMDC surfaces by electrochemical
deposition. Reproduced with permission [225]. Copyright 2020, Springer Nature. (h) Schematic representation of cold hydrogen-plasma interstitial Mo atom doping
on MoS2. (i) Polarization curves and (j) Tafel plots of the pristine ML-MoS2, Mo SAs/ML-MoS2, and Pt samples in H2SO4 (0.5 M) and KOH (1.0 M). Reproduced with
permission [226]. Copyright 2020, American Chemical Society.

intertwined, this unique DE-TDAP exhibits excellent HER performance
in the basic medium (Fig. 17m, n). Furthermore, Table 2 provides a
summary of several exemplary advantages of metal and non-metal
doping in enhancing the electrocatalytic performance of HER.
3.2.5. Promoter effect
The promoter influence is the modification of catalyst efficiency
(physicochemical characteristics) driven by the inclusion of promoters.
Conventionally, owing to their superior electronic configuration,
platinum-based nanomaterials are the most effective and distinctive
catalysts for the hydrogen evolution process in both acidic and alkaline
conditions. Furthermore, the reaction mechanism of the Volmer reaction
of alkaline hydrogen evolution reaction is sluggish, attributed mostly to
the absence of an ideal active center for chelating the H-O-H covalent
linkage. Consequently, the catalytic performance of platinum in an
alkaline environment is 2 to 3 orders of magnitude less than in an acidic
environment. To increase the alkaline HER effectiveness, an approach
involving the fabrication of an electrocatalyst with one constituent as a
water dissolution promoter and the other responsible for H+ removal
and hydrogen generation was employed. Nevertheless, H+ can be ach­
ieved directly from aqueous systems in acidic environments. Thus,
promoters frequently play additional crucial roles in the electrocatalysis
procedure. Titanium carbide MXenes-based [250] and nitrogen-doped
graphdiyne (NGDY) [251], for instance, act as promoters to increase
charge transport, resulting in extremely effective hydrogen evolution
catalytic performance [252–259]. Moreover, promoters may encourage
the creation of catalytically active sites [250,251,260–262]. Based on
studies and DFT computations, Bar-Sadan and coworkers postulated that
utilizing replacement dopants promotes molybdenum diselenide and
transition metal dichalcogenide-like performance by increasing the
creation of active selenium-vacancies as opposed to enhancing their
intrinsic performance [260].
Additionally, certain promoters enhance the electronic characteris­
tics of the active sites, thereby boosting catalytic performance.
Furthermore, Mai and colleagues have reported the fabrication of het­
erogeneous nanomaterials including molybdenum dioxide and nickel
nanoparticles enclosed in nitrogen-doped carbon shells [261]. Accord­
ing to density functional theory calculations, the nitrogen-doped carbon
sheet functions as an active Hads site as well. The intrinsic MoO2-Ni
species operate as efficient promoters to synergistically enhance the Hads
and Hdes strengths on the carbon surface, hence enhancing the perfor­
mance of the catalytic active sites.
Some studies have demonstrated that oxides and hydroxides can act
as efficient promoters for the breakdown of the O-H bond, thus
enhancing the activity of the hydrogen evolution reaction. For example,
Sun and colleagues described a platinum/nickel(HCO3)2 nanostructure
electrocatalyst used in alkaline environments [258]. Fig. 18a shows the
TEM image of 20% platinum/nickel(HCO3)2 (platinum mass ratio is
20% wt%), suggesting that platinum NPs were evenly dispersed over
nickel(HCO3)2. As depicted in Fig. 18b, the 20% platinum/nickel
(HCO3)2 nanostructure electrocatalyst displayed higher HER perfor­
mance compared to platinum NPs with similar platinum loading,
demonstrating the crucial role of nickel(HCO3)2 in boosting the catalytic
performance of platinum in an alkaline environment. The authors have
postulated a potential hydrogen evolution reaction mechanism for
platinum/nickel(HCO3)2 in alkaline environments (Fig. 18c). Nickel
(HCO3)2 can provide catalytic active centers for the adsorption and
dissociation of H2O species to create hydrogen intermediates, whereas
platinum nanoparticles are considered to be the active core for the
adsorption and recombination of hydrogen intermediates. As a result,
platinum/nickel(HCO3)2 could accelerate the Volmer phase (the disso­
lution of H2O), reduce the Tafel slope, and significantly improve HER
performance. Furthermore, the significance of the interplay between
platinum and nickel(HCO3)2 was demonstrated by the superior dura­
bility of 20% platinum/nickel(HCO3)2 over 20% platinum+nickel
(HCO3)2. XANES and EXAFS measurements have shown that platinum
and nickel(HCO3)2 have a strong electronic interaction. The synergistic
relationship between platinum and nickel(HCO3)2 may prevent
agglomeration of platinum nanoparticles, thereby increasing their
robustness over time. Such collective effects endow the platinum/nickel
(HCO3)2 nanostructures with higher catalytic performance and alkaline
medium durability compared to conventional platinum/C.
In addition to nickel(HCO3)2, it is increasingly common to fabricate
heterostructures that bind platinum-based elements with nickel(OH)2
for enhancing the catalytic performance of platinum metal-dependent
electrocatalysts through synergistic interaction. Jin and colleagues
synthesized a platinum nanostructure with two-dimensional nickel
(OH)2 (depicted as platinum@2D-Ni(OH)2) and investigated its catalytic
functions. In alkaline conditions, the platinum@2D-Ni(OH)2 nano­
structure electrocatalyst outperformed pure platinum and nickel(OH)2.
Their density functional theory findings demonstrated the synergistic
interaction of platinum nanomaterials and two-dimensional-Ni(OH)2 in
increasing HER activity. Markovic and colleagues observed an increase
in HER activity in alkaline conditions after treating pristine platinum
interfaces and platinum-island/Pt(111) interfaces with Ni(OH)2 clusters
[263]. The authors hypothesized that the Ni(OH)2 edges aided the H2O
dissolution process in the formation of H-intermediates, which were
then deposited on the surrounding platinum interfaces and reassembled
to form hydrogen. Tang and colleagues developed a robust hetero­
structure catalyst for HER in alkaline conditions by forming 1-dimen­
sional ultrathin platinum nanowires (NWs) on the interface of two-
dimensional single-layered Ni(OH)2 (platinum NWs/SL-Ni(OH)2), with
NWs lengths ranging from 10 to nanometers and widths of approxi­
mately 1.8 nanometers (Fig. 18d) [264]. When compared to conven­
tional platinum/C, the platinum NWs/SL-Ni(OH)2 heterostructures
demonstrated improved HER performance in 1.0 M KOH and 0.1 M KOH
environments, as shown in Fig. 18e, f. In 1.0 M KOH and 0.1 M KOH, its
mass current density was 4.35 times greater than that of conventional
platinum/C and 4.50 times compared to conventional platinum/C,
respectively. In addition, it was discovered that the Ni(OH)2 nano­
composites significantly enhanced the HER durability in both alkaline
and basic environments. After a 4,000-second measurement, platinum
NPs/SL-Ni(OH)2 retains 85.4% and 90.3% of its original performance in
1.0 M and 0.1 M KOH, respectively. The improved durability can be
related to the anisotropy of ultrathin Ni(OH)2 nanocomposites, which
inhibited mechanical ripening and disintegration during the time-
dependent HER operation.
Zhang and colleagues studied the ensemble effect of Co(OH)2 het­
erostructures on HER performance in an alkaline environment [265]. On
a titanium mesh, the authors fabricated a heterostructure of nanoscale
platinum dioxide (nanoparticles) supported by Co(OH)F NWs (repre­
sented by platinum dioxide-Co(OH)F NA/TM) (Fig. 18g). The

24
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 17. (a) Schematic illustration of the S-doping technique for fabricating S-CoSe2 NSs. (b) HRTEM image. (c) The nanopore region. (d) STEM-EDX elemental
mapping images. (e) DFT calculations of S-CoSe2. Reproduced with permission [232]. Copyright 2020, American Chemical Society. (f) Schematic diagram of the
fabrication pathways for O, P-MoS2 and O-MoS2 with distinct structures. (g, h) TEM images of O-MoS2. (I, j) SEM image and matching element mapping images of O,
P-MoS2. Reproduced with permission [228]. Copyright 2019, Wiley-VCH. (k) Schematic depiction of the network fabrication methods for Co@BNPCF. (l) SEM image
of Co@BNPCFs-800 networks. Reproduced with permission [234]. Copyright 2022, Elsevier B.V. (m) Schematic depiction of the catalyst DE-TDAP synthesis method.
(n) STEM image and matching elemental mapping dispersion. Reproduced with permission [235]. Copyright 2021, Elsevier Ltd.

substantially overlapping lattice fringes of platinum dioxide and Co(OH) which is comparable to that of conventional platinum/C (20 wt%) in 0.1
F are depicted in Fig. 18h, indicating the atomic interaction between M KOH (Fig. 18i). In addition, the platinum dioxide-Co(OH)F NA/TM
platinum dioxide and Co(OH)F. This electrocatalyst has a platinum Tafel slope exhibited the lowest value of 63 mV dec− 1. The surfaces of
loading of 54 g cm− 2 and an overpotential need of 39 mV at 4 mA cm− 2, platinum dioxide-Co(OH)F, as demonstrated by density functional

25
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Table 2 are numerous ways to categorize nanomaterials, and they can be sepa­
Advantages of metal and non-metal doping in enhancing the electrocatalytic rated into 3D→2D [202,282–285], 1D [286–288] and 0D [289–292]
performance of HER. nanostructured materials depending on their structural complexity. Ma
Dopant Content Role Application Ref and coworkers fabricated a new hybrid electrocatalyst using graphdiyne
Metal 17.83% Enabled significant Hydrogen [236]
and copper/nickel bimetallic phosphide composite nanostructures via a
Iron electron interaction evolution straightforward technique with regulated multistage architectures
between the metal and [293]. Owing to the distinct 3D-structural features of the as-fabricated
carbon nitride and created nanomaterials, the excellent electrocatalytic efficiency of these nano­
electronic structures
materials has been significantly enhanced and improved. In addition to
encouraging electron
mobility along the 2D enhancing the nanomaterial’s structural design, the multistage nano­
nanomaterial plane structure and atomic heterostructure expedited charge transport oper­
Palladium 1.2% To modify the mode of Hydrogen [237] ations. Furthermore, the DFT simulations revealed that the incorporated
electron excitation; to evolution GDY greatly enhances performance and creates distinct catalytic active
quicken the hydrogen
evolution kinetics
sites for the as-fabricated nanostructured materials (Fig. 19a-e). In cat­
Nickel 0.5% To enhance the number of Hydrogen [238] alysts’ approach to nano-structuring, the size impact is crucial. If the
(wt) catalytic active sites; to evolution; tiny crystals are well distributed, the active nanomaterial becomes more
promote electron transfer pollutant effective, and thus, the catalytic performance increases. To increase
removal
reactivity, the nano-size of the catalysts is regulated while preserving
Cobalt 1%(wt) To generate Co-N catalytic Hydrogen [239]
active sites; to reduce the evolution; reactivity and preventing agglomeration. Additionally, size effects may
bandgap pollutant result in some remarkable reaction phenomena. For instance, whenever
removal the particle size is below a specific threshold, the electron degree adja­
Copper 3 mol% To create catalytically Hydrogen [240] cent to the M Fermi level shifts from a quasi-continuous to a distinct
active sites evolution
degree, resulting in the presence of intermittent HOMO and LUMO,
Molybdenum 1.25 Increase the Hydrogen [241]
mmol electrochemically active evolution causing a greater energy band gap and an exponential change in the
area, and adjusts the interface energy. The reduction in particle sizes alters the atom mobility
electronic structure and electron energy distribution at the interface of nanomaterials,
Selenium 5 wt% Increase active edges and Hydrogen [242]
resulting in an increase in the interface atoms’ catalytic performance.
are well dispersed in the evolution
highly conductive Jiang and colleagues showed in their latest research that cobalt phos­
graphene networks phide/C (CoP/C-3) nanoparticles with a size of 9.2 nanometers exhibit
Zinc 3 wt% Increase active sites, Hydrogen [243] greater inherent HER-performance than cobalt phosphide (CoP/C-1)
optimize electron transfers evolution particles with a size of 3.3 nanometers. This difference is related to the
as well as a stable frame
significant oxidation of smaller cobalt phosphide nanoparticles when
structure
Non-Metal exposed to the air. According to X-ray photoelectron spectroscopy
Oxygen 9.91 To facilitate the separation Hydrogen [244] measurements, the majority of the cobalt in 9.2 nanometer nm cobalt
mol% of e− and h+ pairs evolution phosphide (CoP/C-3) nanoparticles persists in a quasi-metallic config­
Sulphur 0.56 wt Increase the density of Hydrogen [245]
uration, which is favorable to the Hdes [294].
% active areas evolution
Boron 15.4 at. Superior electrical Hydrogen [141]
% conductivity, rapid evolution 3.2.7. Interface effect
electron transfer kinetics, The term "interface effect" refers to the interaction that occurs be­
and optimum hydrogen tween two distinct types of active nanomaterials as a result of strong
intermediate adsorption
coordination, electronic coupling, or synergy, all of which have the
Phosphorous 1.11 at. Significantly enhanced Hydrogen [246]
% charge carrier density evolution potential to generate more catalytic active sites than the individual
within C3N4 components separately [107,171,295–312]. Due to the complex elec­
Carbon 1.18 at. Boost the conductivity and Hydrogen [247] tronic arrangement of these electrocatalytic materials, research into the
% the electron transfer evolution
concept describing the structural performance correlation of electro­
capability of the catalyst
Iodine 0.25 Enhanced hydrogen Hydrogen [248]
catalytic materials remains a challenging undertaking. However, this
atom % absorption and improved evolution complexity also introduces a number of structural components that can
HER kinetics be modified in a direction that is advantageous. For instance, the
Fluorine 0.82% Induce the valence state Hydrogen [249] fabrication of active nanomaterials that have an increased energy sur­
and electrical structure for evolution
face structure, such as molybdenum sulfide-cobalt sulfide [12], molyb­
increased HER activity
denum carbide-molybdenum diselenide [313], ruthenium-molybdenum
nitride [314], Mo2CTx-1-2HMoS2 [315], Co9S8/MoS2-NF [316], CoP/
theory, not only stimulate the deposition and dissolution of H2O species MoO2-MF [317,318], and so on, can optimize the electronic properties
but also accommodate the BE of H* to a favorable value (Fig. 18j), at the interaction sites, thereby lowering the activation energy barrier
thereby accelerating the kinetics of the HER mechanism and decreasing for the reaction route that results in H2 production. For instance, Liu and
the Tafel slope. Furthermore, after 50 h of potentiometric measurement, coworkers reported the design of an interfacial electrocatalyst (SA Co-D
platinum dioxide-Co(OH)F NA/TM showed a slight decrease in HER 1T molybdenum disulfide) that was covalently coupled with a deformed
performance. Yang and colleagues recently developed a platinum-Co 1T-molybdenum disulfide nanostructure [319]. Both the atomically
(OH)2/CC heterostructure electrocatalyst with a modest platinum distinct cobalt particles scattered across the D-1T molybdenum disulfide
loading of 5.7% wt., which exhibited exceptional catalytic HER activity matrix and the apparent interaction between 2H molybdenum disulfide
and durability owing to the synergistic interaction of heavily utilized and SA Co-D-1T molybdenum disulfide are confirmed by HAADF-STEM
platinum and Co(OH)2 [266]. analysis. DFT studies demonstrate that the interplay between the cobalt
atom and the sulphur atom of the D-1T molybdenum disulfide substrate
3.2.6. Nano-structuring optimizes the H-binding mechanism at the surface, resulting in
Nanomaterials have significant application potential in energy stor­ enhanced catalytic performance (Fig. 19f-j).
age and conversion technologies as electrocatalysts [267–281]. There

26
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 18. (a) TEM image of 20% Pt/Ni(HCO3)2 heterostructure. (b) Geometric LSV curves of various catalysts in 1.0 M KOH. (c) Schematic representation of a possible
HER mechanism to reveal the enhanced activity of Pt/Ni(HCO3)2 heterostructures in alkaline environment. Reproduced with permission [258]. Copyright 2019,
Wiley-VCH. (d) TEM images of Pt NWs/SL-Ni(OH)2, scale bar in 100. (e) LSV curves of catalysts in 1.0 M KOH and (f) in 0.1 M KOH at room temperature. Reproduced
with permission [264]. Copyright 2015, Springer Nature. (g) Schematic representation of water adsorption, water activation, and H2 generation procedures for PtO2-
Co(OH)F NA/TM. (h) HRTEM image of PtO2-Co(OH)F. (i) LSV curves of catalysts in 0.1 M KOH. (j) Calculated free energies of H2O adsorption and dissociation on
PtO2(111) and the interface between PtO2 and Co(OH)F. Reproduced with permission [265]. Copyright 2018, the Royal Society of Chemistry.

3.2.8. Field-assisted effect due to their monoatomic-scale characteristics-induced electrostatic in­

Electrocatalysis that takes place as a result of a field is known as field-
assisted electrocatalysis. It is a potential approach since it allows for a
greater amount of flexibility when designing an electrochemical reac­
tion. Noticeable advancements in HER and OER have been achieved
with the aid of diverse fields, such as the electric field, magnetic field,
light, and strain. For instance, the electrocatalytic hydrogen evolution
reaction of molybdenum sulfide nanomaterials can be significantly
enhanced by utilizing a reverse voltage output of 5 V @ − 100 mA/cm2
[320]. Its overpotential is reduced from 240 to 38 mV. Furthermore,
improvement in alkaline water electrolysis is obtained by applying a
mild magnetic field (less than or equal to 450 mT) to a strongly magnetic
electrocatalytic anode [321]. Its current density increases by more than
a factor of a hundred. In addition, the hydrogen evolution function of
β-PdHx increases evenly from 0 to 4.5 percent as the applied strain rises
[322]. Following irradiation with infrared radiation, the current density
of gold-molybdenum sulfide for HER increases by nearly thrice [323].
These findings provide conclusive evidence that the application of a field
during electrocatalysis presents significant prospects for achieving even
greater enhancements in catalytic performance. In addition, this method
has the advantages of being simple, dynamical, uninterrupted, repeat­
able, and ubiquitous in terms of control.
Despite impressive accomplishments, these studies remain dispersed.
The underlying techniques and concepts increase electron infusion from
electrodes to catalytic centers, resulting in metal borders or 1T phase
[324]. In contrast, the conductivities of low-dimensional semi­
conducting nanomaterials demonstrate substantial gate configuration
teractions. Thus, extensive evidence indicates that the on and off fre­
quencies of field-effect transistors (FETs) constructed with two-
dimensional transition metal dichalcogenides exceed 106 [325–328].
According to the aforementioned studies, scientists have just lately
discovered that low-dimensional semiconducting electrocatalytic ma­
terials are responsive to an extrinsic electric field [320,329]. The impact
of a gate electric field on a hydrogen evolution process with a back-gated
two-dimensional molybdenum sulfide working electrode was thor­
oughly investigated by Mai and coworkers [320]. A diagrammatic rep­
resentation of the test design is shown in (Fig. 20a). The catalytic unit
and associated FET can be thought of as sharing a single molybdenum
sulfide nanosheet. A gold pad connects the molybdenum disulfide
nanosheet, acting as a functional electrode. The entire device is encased
in a shell of (C5O2H8)n coat to prevent gold from participating in elec­
trocatalysis, with the exception of revealing a clearly defined basal plane
of molybdenum disulfide for electrocatalytic processes. A M-oxide-
semiconductor heterojunction is created by the 3-electrode membrane
reactor on a silicon dioxide/silicon (≤0.005 Ω cm/1) precursor. In
electrocatalysis, it acts as a gate electrode by producing a lateral electric
field. As illustrated in (Fig. 20b, c), an overpotential of 240 mV is needed
to achieve a current density of 100 mA/cm2 when there is no gate
electric field present, and the Tafel slope that corresponds to this over­
potential is 200 mV/dec. Overpotential and Tafel slope both progres­
sively drop as the gate voltage is increased from 0 to 5V. This is coupled
with an increase in molybdenum disulfide ’s conductance (Fig. 20d). At
a gate voltage of 5V, the electrochemical unit only requires an

27
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 19. (a) Schematic representation of the CuNiPx-GDY nanomaterials fabrication method. (b, c, d) SEM images. (e) DFT calculations (the five probable active sites
in CuNiPx-GDY structural models). Reproduced with permission [293]. Copyright 2022, Elsevier Inc. (f) Schematic illustration of the SA Co-D 1T MoS2 synthesis
procedure. (g) Aberration-corrected HAADF-STEM image of SA Co-D 1T MoS2, demonstrating the clear junction between SA Co-D 1T MoS2 (dark cyan) and pure 2H
MoS2 (wine). Inset: HRTEM and EELS spectrum of SA Co-D 1T MoS2. (h, I, j) Theoretical estimation of SA Co-D 1T MoS2 for HER. Reproduced with permission [319].
Copyright 2019, Nature Publishing Group.

overpotential of 38 mV to generate a current density of 100 mA/cm2,
which is practically identical to that of platinum (25 mV). As shown in
Fig. 20e, f, g, the energy band model provides an in-depth explanation
for the electric field-tuned hydrogen evolution process. By capacitive
induction, electrons amass in the molybdenum disulfide network in
response to a positive gate voltage, causing a shift of the Fermi level
toward the bandgap. Due to the fact that molybdenum disulfide is an n-
type semiconductor [330], its conductivity is enhanced and the gold-
molybdenum disulfide interface barrier is decreased. A new examina­
tion of first-principles computations [331]supports this theory and
illustrates that an electric field can effectively modify the Schottky
barrier type and amplitude between gold and molybdenum disulfide.
Consequently, the charge infusion within a mild electric field can be
regulated over a wide spectrum. Additionally, an improvement in con­
ductivity aids in reducing iR degradation. An enhanced electrocatalysis
of molybdenum disulfide for HER is ultimately activated by a positive
back gate voltage.
The presence of a magnetic field can also speed up electrochemical
reactions. Magnetohydrodynamics, magnetothermal, Kelvin force, spin
selectivity, and Maxwell stress effects are all examples of magnetic

28
B.A. Yusuf et al. Advances in Colloid and Interface Science 311 (2023) 102811

Fig. 20. (a) Schematic representation of a three-electrode microreactor with a back-gated MoS2 working electrode for HER. (b) LSV plots of HER for various back
gate voltages. (c) The matching Tafel curves. (d) The electrical conductivity of a MoS2 nanomaterial as a function of back gate voltage. (e) The typical condition of a
device with a closed circuit and no gate voltage. (f) The energy band of the device when the gate voltage bias is positive, and (g) when the gate voltage bias is
negative. Reproduced with permission [320]. Copyright 2017, John Wiley and Sons, Inc. (h) The schematic depiction of MoS2 flake lateral stitching and vertical
stacking formation. (i) Schematic representation of electron transport. Reproduced with permission [333]. Copyright 2020, American Chemical Society. (j) TEM
images of Co2P hollow nanoparticles generated in various magnetic fields. (k) Magnetic field versus size plot. Reproduced with permission [334]. Copyright 2019,
Elsevier Ltd.

effects that can occur during electrochemical processes [321,332]. For
instance, Marian Chatenet and coworkers reported a method for
reducing hydrogen evolution overpotential caused by the magneto­
thermal effect, in which the performance of hydrogen evolution re­
actions was enhanced by iron carbide-nickel core-shell nanomaterials in
an increased-frequency interchanging magnetic field [332]. Conse­
quently, HER performance may be enhanced (ΔE = 150 mV at 40.1 mT)
in an alkaline solution. While the improvement of the OER mechanism is
comparable to enhancing the cell temperature to 200 ◦ C in the oxygen
evolution process, the reaction mechanism in the hydrogen evolution
reaction shows just a minor increase, which serves as a benchmark for
the utilization of magnetic fields in the hydrogen evolution reaction
area. However, according to an alternative HER support mechanism,
Wang and coworkers reported that the extrinsic vertical magnetism
could easily transfer electrons from the glassy carbon electrodes to the
catalytic active center for activating HER, thus accomplishing magnetic

29
Another random document with
no related content on Scribd:
roots of the conscience and the will. Teufelsdröckh’s mental progress
out of the mood of the “Everlasting No” is a succession of practical
determinations as to the conduct of his own spirit, each
determination coming as an inspired effort of the will, altering his
demeanour from that moment, and the last bringing him into a final
condition of freedom and self-mastery. The effort of the will does
indeed diffuse a corresponding change through the intellect; but it is
as if on the principle, “Henceforth such and such a view of things
shall be my view,”—which is but a variation of the Scriptural
principle that it is by doing the law that one comes to know the
gospel.
The Leith Walk incident, accordingly, is to be taken as the
equivalent in Carlyle’s case to that first step out of the “Everlasting
No” of which he makes so much in the biography of Teufelsdröckh. It
was not by any means his complete conversion or emancipation, but
it was a beginning. It was, to use his own words, a change at least “in
the temper of his misery,” and a change for the better, inasmuch as it
substituted indignation and defiance for what had been mere fear
and whimpering. His mood thenceforth, though still miserable
enough, was to be less abject and more stern. On the whole, if this
construction of the Leith Walk incident of June 1821 does not make
so much of it as Mr. Froude’s does, it leaves enough of reason for any
Edinburgh youth, when he next chances to be in that straggling
thoroughfare between Edinburgh and Leith, to pause near the
middle of it, and look about him. The spot must have been just below
Pilrig Street, which was Carlyle’s starting-point from his lodgings in
Moray Street (now Spey Street) on his way to Leith.
There was, at all events, no very obvious change in Carlyle’s
mood and demeanour in Edinburgh in the latter part of 1821. His
own report in the Reminiscences is still of the dreariness of his life,
his gruff humours, and gloomy prognostications. But, corroborated
though this report is in the main by contemporary letters, it would be
a mistake, I believe, to accept it absolutely, or without such
abatements as mere reflection on the circumstances will easily
suggest. It is impossible to suppose that Carlyle, at this period of his
life or at any other, can have been all unhappy, even when he thought
himself most unhappy. There must have been ardours and glows of
soul, great joys and exhilarations, corresponding to the complexity of
nervous endowment that could descend to such depths of sadness.
From himself we learn, in particular, how the society of Irving,
whether in their Annandale meetings, or in Irving’s visits to
Edinburgh, had always an effect upon his spirits like that of sunrising
upon night or fog. Irving’s letters must have had a similar effect:
such a letter, for example, as that from Glasgow in which Irving had
written, “I am beginning to see the dawn of the day when you shall be
plucked by the literary world from my solitary, and therefore more
clear, admiration,” and had added this interesting note respecting
Dr. Chalmers: “Our honest Demosthenes, or shall I call him
Chrysostom?—Boanerges would fit him better!—seems to have
caught some glimpse of your inner man, though he had few
opportunities; for he never ceases to be inquiring after you.”[37]
Whether such letters brought Carlyle exhilaration or not, there
must have been exhilaration for him, or at least roused interest, on
Irving’s own account, in the news, which came late in 1821, that
Irving was not to be tied much longer to the great Glasgow
Demosthenes and his very difficult congregation. After two years and
a half of the Glasgow assistantship to Dr. Chalmers, there had come
that invitation to the pastorship of the Scotch Church, Hatton
Garden, London, which Irving received as exultingly, as he
afterwards said, as if it had been a call to the Archbishopric of
Canterbury. He passed through Edinburgh on his way to London to
offer himself on probation to the little colony of London Scots that
thought he might suit them for their minister; and Carlyle was the
last person he saw before leaving Scotland. The scene of their parting
was the coffee-room of the old Black Bull Hotel in Leith Street, then
the great starting-place for the Edinburgh coaches. It was “a dim
night, November or December, between nine and ten,” Carlyle tells
us; but Mrs. Oliphant’s Life of Irving helps us to the more precise
dating of December 1821, a day or two before Christmas. They had
their talk in the coffee-room; and Carlyle, on going, gave Irving a
bundle of cigars, that he might try one or two of them in the tedium
of his journey next day on the top of the coach. Who smoked the
cigars no one ever knew; for Irving, in the hurry of starting next
morning, forgot to take them with him, and left them lying in a stall
in the coffee-room.
 That meeting at the Black Bull in Leith Street, however, was to
be remembered by both. Irving had gone to London to set the
Thames on fire; Carlyle remained in Edinburgh for his mathematical
teaching, his private German readings, his hackwork for Brewster’s
Edinburgh Encyclopædia, and the chances of continued
contributorship to the New Edinburgh Review. Thus the year 1821
ended, and the year 1822 began.
 PART III.—1822–1828
By Carlyle’s own account, and still more distinctly by the
evidence of other records, the beginning of the year 1822 was marked
by a break in his hitherto cloudy sky. How much of this is to be
attributed to the continuance of the change of mental mood which
has to be dated from June 1821, and associated with the Leith Walk
revelation of that month, one can hardly say. One finds causes of an
external kind that must have contributed to the result.
One was the Charles Buller engagement. Carlyle’s dating of this
very important event in his life is rather hazy. In his Reminiscences
he gives us to understand that, after his parting with Irving at the
Black Bull in Edinburgh, just before the Christmas of 1821, he lost
sight of Irving altogether for a while, and was chagrined by Irving’s
silence. He thought their correspondence had come to an end;
accounted for the fact as well as he could by remembering in what a
turmoil of new occupation Irving was then involved in London; and
only came to know how faithful his friend had been to him all the
while when the Buller tutorship at £200 a year emerged, “in the
spring and summer of 1822,” as the product of Irving’s London
exertions in his behalf. In reading this account, one fancies Irving
already established in London, In fact, however, as Mrs. Oliphant’s
Life of Irving makes clear, Irving’s journey from the Black Bull to
London in December 1821 had been on a trial visit only. He was back
in Glasgow early in February 1822,—whence, on the 9th of that
month, he wrote a long letter to his “dear and lovely pupil,” Miss
Jane Welsh, sending it under cover to his friend “T. C.” in Edinburgh,
because he was not sure but she might be then in Edinburgh too; and
it was not till July 1822, and after some difficult negotiation, that
Irving, ordained by his native Presbytery of Annan, took his farewell
of Glasgow and the West of Scotland, and settled in London
definitely. The good turn he had done Carlyle in the matter of the
Buller tutorship must have been done, therefore, in his preliminary
London visit of January 1822, within a month after his parting from
Carlyle at the Black Bull, and before Carlyle’s cigars, if Irving had
taken them with him, could have been smoked out. It must have
been in those January weeks of his probationary preachings before
the Hatton Garden people that Irving, moving about as a new
Scottish lion in the drawing-room of the English Stracheys of the
India House, was introduced to Mrs. Strachey’s sister, Mrs. Buller,
and, after some meetings with that lady, helped her in a “domestic
intricacy.” This was that her eldest son, Charles Buller, a very clever
and high-spirited boy, of about fifteen years of age, “fresh from
Harrow,” but too young to go to Cambridge, was somewhat
troublesome, and she and her husband were at a loss what to do with
him. Irving’s advice had been to send the boy for a session or two to
the University of Edinburgh, and to secure for him there the private
tutorship of a certain young literary man, Mr. Thomas Carlyle, whom
Irving knew thoroughly and could highly recommend. Mrs. Buller
must have been a rapid lady, for the thing was arranged almost at
once. Carlyle had been communicated with; and he had accepted the
tutorship on the terms stipulated by Irving. It must have been on an
early day in the spring of 1822 that he made that call at the house of
the Rev. Dr. Fleming in George Square, to receive his new pupil,
Charles Buller, with Charles’s younger brother Arthur, on their
arrival in Edinburgh, and had that first walk with them by the foot of
Salisbury Crags, and up the High Street from Holyrood, of which
there is such pleasant mention in the Reminiscences. Dr. Fleming, a
fellow-contributor with Carlyle to Brewster’s Encyclopædia, and a
much respected clergyman of Edinburgh, had interested himself
greatly in Irving’s London prospects, and had tried to smooth the
way for him by letters to London friends; and it was in his house in
George Square that the two English boys were to board,—Carlyle
coming to them daily from his lodgings in Moray Street. He had
already, before the arrival of the boys, he tells us, entered Charles
Buller in Dunbar’s “third Greek class” in the University. The
information agrees with the University records; for in the
matriculation-book of the session 1821–22 I find one of the very
latest matriculations to have been that of “Charles Buller, Cornwall,”
and I find him to have been all but the last student enrolled for that
session in Dunbar’s senior class. This of itself would imply that
Carlyle’s tutorship of the boys must have begun in February 1822;
for, as the University session ends in the beginning of April, it would
have hardly been worth while to enroll the young Buller in a class
after February. The tutorship was a settled thing, therefore, while
Irving was still in Glasgow, and it had been going on for some
months before Irving’s permanent removal to London. Carlyle
himself seems to have become aware of the haziness of his dating of
the transaction; for he inserts, by way of afterthought, a dim
recollection of one or two sights of Irving somewhere shortly after
the Black Bull parting, and of talks with him about the Buller family
while the tutorship was in its infancy. Anyhow, the Buller tutorship,
with its £200 a year, was “a most important thing” to Carlyle in “the
economies and practical departments” of his life at the time; and he
owed it “wholly to Irving.” The two boys, Charles Buller especially,
took to their new tutor cordially at once, and he cordially to them;
and there were no difficulties. In the classics, indeed, and especially
in Greek, Charles Buller, fresh from his Harrow training, was
Carlyle’s superior; but Carlyle could do his duty for both the boys by
getting up their Latin and Greek lessons along with them, teaching
them as much mathematics as they would learn, and guiding them
generally into solid reading, inquiry, and reflection.
Another gleam of sunshine in Carlyle’s life early in 1822, or what
ought to have been such, was the correspondence with Haddington.
Since the visit of the previous June that had gradually established
itself, till it had become constant, in the form of “weekly or oftener
sending books, etc., etc.,” with occasional runs down to Haddington
in person, or sights of Miss Welsh, with her mother, in Edinburgh.
How far matters had gone by this time does not distinctly appear;
but there is some significance in the fact that Irving, writing from
Glasgow to Miss Welsh immediately after his return from the trial-
preachings before the Hatton Garden congregation in London, had
sent the letter through “T. C.” The impression made by that letter, as
it may be read in Mrs. Oliphant’s Life of Irving, certainly is that
Irving’s own feelings in the Haddington quarter were still of so
tender a kind that the advancing relations of “T. C.” to the “dear and
lovely pupil” were not indifferent to him. Doubtless there were
obstacles yet in the way of any definite engagement between Carlyle
and the young lady who was heiress of Craigenputtock,—criticisms of
relatives and others who “saw only the outside of the thing”; but the
young lady “had faith in her own insight,” as she afterwards told Miss
Jewsbury, and was likely to act for herself. Meanwhile, to be “aiding
and directing her studies,” and have a kind of home at Haddington
when he chose to go there on a Saturday, was surely a tinge of gold
upon the silver of the Buller tutorship.
Moreover, Carlyle’s occupations of a literary kind were
becoming more numerous and congenial. “I was already getting my
head a little up,” he says, “translating Legendre’s Geometry for
Brewster; my outlook somewhat cheerfuller.” All through the
preceding year, it appears from private letters, he had been exerting
himself indefatigably to find literary work. Thus, in a letter of date
March 1821 to an old college friend: “I have had about twenty plans
this winter in the way of authorship: they have all failed. I have about
twenty more to try; and, if it does but please the Director of all things
to continue the moderate share of health now restored to me, I will
make the doors of human society fly open before me yet,
notwithstanding. My petards will not burst, or make only noise when
they do. I must mix them better, plant them more judiciously; they
shall burst, and do execution too.”[38] Again, in a letter of the very
next month: “I am moving on, weary and heavy-laden, with very
fickle health, and many discomforts,—still looking forward to the
future (brave future!) for all the accommodation and enjoyment that
render life an object of desire. Then shall I no longer play a candle-
snuffer’s part in the great drama; or, if I do, my salary will be
raised.”[39] From Mr. Froude we learn that one of the burst petards of
1821 had been the proposal to a London publishing firm of a
complete translation of Schiller’s Works. That offer having been
declined, with the twenty others of which Carlyle speaks, the only
obvious increase of his literary engagements at the time of the
beginning of the Buller tutorship in 1822 consisted, it would appear,
in that connection with the New Edinburgh Review of which
mention has been already made, and in the translation of Legendre
which he had undertaken for Brewster. But there was more in the
background. There is significance in the fact that his second
contribution to the New Edinburgh, published in April 1822, when
the Buller tutorship had just begun, was an article on Goethe’s Faust.
The German readings which had been going on since 1819 had
influenced him greatly; and he was now absorbed in a passion for
German Literature. Schiller, Goethe, and Jean Paul were the
demigods of his intellectual worship, the authors in whose works,
rather than in those of any of the same century in France or Britain,
he found suitable nutriment for his own spirit. He had proposed, we
see, to translate the whole of Schiller. Of his studies in Goethe and
their effects we have a striking commemoration in the passage of his
Reminiscences where he tells of that “windless, Scotch-misty,
Saturday night,” apparently just about our present date, when,
having finished the reading of Wilhelm Meister, he walked through
the deserted streets of Edinburgh in a state of agitation over the
wonders he had found in that book. Henceforth, accordingly, he had
a portion of his literary career definitely marked out for him.
Whatever else he was to be, there was work enough before him for a
while in translation from the German and in commentary on the
great German writers for the behoof of the British public. There were
but three or four men in Britain competent for that business, and he
was one of them.
The translation of Legendre’s Geometry for Brewster deserves a
passing notice. Though not published till 1824,—when it appeared,
from the press of Oliver and Boyd of Edinburgh, as an octavo of
nearly 400 pages, with the title Elements of Geometry and
Trigonometry; with Notes. Translated from the French of A. M.
Legendre, Member of the Institute, etc. Edited by David Brewster,
LL.D., etc. With Notes and Additions, and an Introductory Essay on
Proportion,—it was begun by Carlyle in 1822, and continued to
occupy him through the whole of that year. His authorship of this
Translation remained such a secret, or had been so forgotten, that
the late Professor De Morgan, specially learned though he was in the
bibliography of mathematics, did not know the fact, and would
hardly believe it, till I procured him the evidence. It was one day in
or about 1860, if I remember rightly, and in the common room of
University College, London, that De Morgan, in the course of the
chats on all things and sundry which I used to have with him there,
adverted to the Legendre book. He knew, he said, that Brewster
himself could not have done the translation; but he had always been
under the impression that the person employed by Brewster had
been a certain Galbraith, a noted teacher of mathematics in
Edinburgh. Recently, however, he had heard Carlyle named as the
man; and, being very doubtful on the point, he wanted very much to
be certain. To back my own statement, I undertook to obtain an
affidavit from head-quarters. “Tell De Morgan,” said Carlyle, when I
next saw him, “that every word of the book is mine, and that I got
£50 for the job from Brewster; which was then of some consideration
to me.” He went on to speak, very much as he does in the
Reminiscences, of the prefixed little Essay on Proportion, retaining a
fond recollection of that section of the book,—begun and finished, he
says, on “a happy forenoon (Sunday, I fear)” in his Edinburgh
lodgings, and never seen again since he had revised the proof. De
Morgan, who had some correspondence on the subject with Carlyle
after I had conveyed Carlyle’s message, paid it a compliment
afterwards in his Budget of Paradoxes, by calling it “as good a
substitute for the Fifth Book of Euclid as could be given in speech”;
and a glance at the Essay in the volume itself will confirm the
opinion. It fills but eight printed pages, and consists of but four
definitions and three theorems, wound up with these concluding
sentences:—“By means of these theorems, and their corollaries, it is
easy to demonstrate, or even to discover, all the most important facts
connected with the Doctrine of Proportion. The facts given here will
enable the student to go through these Elements [Legendre’s]
without any obstruction on that head.”
The Translation of Legendre, with this Essay on Proportion, was
Carlyle’s farewell to Mathematics. To the end of his life, however, he
would talk with great relish of mathematical matters. Once, in the
vicinity of Sloane Street, when I mentioned to him a geometrical
theorem which Dr. Chalmers had confided to me, with the
information that he had been working at it all his life and had never
accomplished the solution, Carlyle became so eager that he made me
stop and draw a diagram of the theorem for him on the pavement.
Having thus picked up the notion of it, he branched out, in the most
interesting manner, as we walked on, into talk and anecdote about
mathematics and mathematicians, with references especially to
Leslie, West, Robert Simson, and Pappus. A marked similarity of
character between Carlyle and Chalmers was discernible in the fact
that they both avowed a strong personal preference for the old pure
geometry over the more potent modern analytics. “In geometry, sir,
you are dealing with the ipsissima corpora,” Chalmers used to say;
and Carlyle’s feeling seems to have been something of the same kind.
There was a variation of Carlyle’s Edinburgh existence, not
altogether disagreeable, when the seniors of the Buller family
followed the two boys, and made Edinburgh for some time their
residence. They took up house in India Street, giving dinners and
seeing a good deal of company; and Carlyle, while continuing his
lessons to young Charles and Arthur, was thus a good deal in India
Street, observing new society, and becoming acquainted with Mr.
Buller senior, the sprightly Mrs. Buller, and their third and youngest
child, Reginald. As he makes this advent of the Bullers to Edinburgh
to have been “towards the autumn” in 1822, we are able to connect it
with another advent.
It was on the 15th of August 1822, after several weeks of
enormous expectation, that George IV. arrived in Edinburgh,
welcomed so memorably on board his yacht before landing by Sir
Walter Scott; and thence to the 29th, when his Majesty took his
departure, all Edinburgh was in that paroxysm of loyal excitement
and Celtic heraldry and hubbub of which Sir Walter was the soul and
manager, and a full account of which is to be found in his Life by
Lockhart. It is hardly a surprise to know that what the veteran Scott,
with his great jovial heart, his Toryism, and his love of symbols, thus
plunged into and enjoyed with such passionate avidity, tasking all his
energies for a fortnight to make the business a triumphant success,
the moody young Carlyle, then a Radical to the core, fled from in
unmitigated disgust. He tells us in his Reminiscences how, on seeing
the placard by the magistrates of Edinburgh, a day or two before the
King’s arrival, requesting all the citizens to appear in the streets well-
dressed on the day of his Majesty’s entry, the men in “black coats and
white duck trousers,” he could stand it no longer, and resolved to be
absent from the approaching “efflorescence of the flunkeyisms.” The
tutorial duties with the Bullers being naturally in abeyance at such a
time, and rooms in Edinburgh being so scarce that the use of
Carlyle’s in Moray Street was a welcome gift to his merchant friends,
Graham and Hope, who were to arrive from Glasgow for the
spectacle, he himself was off for a run in Annandale and Galloway
before his Majesty made his appearance; and he did not return till all
the hubbub of the fortnight was “comfortably rolled away.” I have
heard him describe this flight of his from George IV., and from the
horrors of that fortnight of feastings, processionings, huzzaings, and
bagpipings, round his Majesty in Edinburgh, at more length and in
greater detail than in the passage incidentally given to the subject in
the Reminiscences; and one of the details may be worth relating:—
On the first stage out of Edinburgh he put up for the night at some
village inn. Even at that distance the “efflorescence of the
flunkeyisms” from which he had fled seemed to pursue him; for the
talk of the people at the inn, and the very papers that were lying
about, were of nothing but George IV. and the Royal Visit. Taking
refuge at last in his bedroom, he was fighting there with his habitual
enemy, sleeplessness, when, as if to make sleep absolutely impossible
for that night, there came upon his ear from the next room, from
which he was separated only by a thin partition, the moanings and
groanings of a woman, in distress with toothache or some other pain.
The “oh! oh!” from the next room had become louder and louder,
and threatened to be incessant through the whole night, so that each
repetition of it became more and more insufferable. At last, having
knocked to solicit attention, he addressed the invisible sufferer
through the partition thus: “For God’s sake, woman, be articulate. If
anything can be done for you, be it even to ride ten miles in the dark
for a doctor, tell me, and I’ll do it; if not, endeavour to compose
yourself.” There ensued a dead silence, and he was troubled no more.
The Edinburgh University records show that “Charles Buller,
Cornwall,” matriculated again for the session 1822–3 (one of the very
earliest students to matriculate that year, for he stands as No. 8 in a
total of 2071 matriculations), and that he attended the 2nd Latin
class, under Professor James Pillans, who had succeeded Christison
as Humanity Professor in 1820. A later name in the matriculation list
(No. 836) is that of “Arthur Buller,” who had not attended the
University with his brother in the previous year, but now joined him
in the 2nd Latin class, and also took out Dunbar’s 2nd Greek class. In
the same matriculation list of 1823–3 (No. 21), as entering the
University for the first time, and attending Pillans’s 2nd Latin class
with the two Bullers, appears “John Carlyle, Dumfriesshire.” This
was Carlyle’s younger brother, the future Dr. John Carlyle, translator
of Dante, and the only other of the family who received a University
education. He had been for some time a teacher in Annan School, in
succession to his brother; and, as he was to choose the medical
profession, his present attendance in the Arts classes was but
preliminary to attendance in the medical classes in the sessions
immediately to follow. He lodged, as the Reminiscences tell us, with
his brother, in the rooms in Moray Street, Pilrig Street.
The winter of 1822–3 was passed by Carlyle in the Edinburgh
routine of his daily walks from those rooms to the house of the
Bullers in India Street, his tutorship of the two young Bullers and
other intercourse with the Buller family and their guests, and his
own German and other readings and literary efforts and schemings.
It was in that winter, and not at the earlier date hazily assigned in the
Reminiscences, that the cessation of correspondence with Irving
became a matter of secret vexation to him. The good Irving, now in
the full whirl of his activity with the Hatton Garden congregation and
of the London notoriety to which that led, was too busy to write; and
it was only by rumour, or by letters from others, that Carlyle heard of
Irving’s extraordinary doings and extraordinary successes in the
metropolis, of the crowds that were flocking to hear him in the little
Scotch chapel, and of the stir he and his preachings were making in
the London fashionable world. “People have their envies, their pitiful
self-comparisons,” says Carlyle, admitting that the real joy he felt at
the vast and sudden effulgence of his friend into a fame
commensurate with his powers was tempered by a sense of the
contrast between himself, still toiling obscurely in Edinburgh, a
“poor, suffering, handcuffed wretch,” and the other Annandale
fellow, now so free and glorious among the grandees on the Thames.
There was, he adds, just a speck of another feeling. Would Irving be
able to keep his head in the blaze of such enormous London
popularity? Had he strength enough to guide and manage himself in
that huge element with anything like the steadiness that had
characterised the behaviour of the more massive and more simple-
hearted Chalmers in Glasgow? This feeling, he seems to hint, was
increased rather than lessened when Irving’s first publication came
into his hands,—the famous Orations and Arguments for Judgment
to Come, by which, early in 1823, the cooler and more critical world
was enabled to judge of the real substance of those pulpit-discourses
which were so amazing the Londoners. Meanwhile, as Irving himself
was still silent, Carlyle could only plod on at his own work. It seems
to have been late in 1822, or early in 1823, that, having closed his
contributions to Brewster’s Encyclopædia, and got the Legendre
translation off his hands, he set himself to his Life of Schiller.
If, however, the Life of Schiller was begun in Edinburgh, it was
not finished there. The University session of 1822–3 over, and the
spring and summer of 1823 having come, the Bullers, with that
aptitude for change of residence which characterises retired Indians
and people with plenty of money, had removed to the mansion of
Kinnaird in Perthshire, situated on the river Tay, some miles to the
north of Dunkeld. Carlyle and his tutorship of young Charles and
Arthur Buller had, accordingly, been transferred thither. He must
have been there early in June 1823; for a letter of his is extant, dated
from Kinnaird House on the 17th of that month, in which he
describes his first sight of Dunkeld and its old cathedral, with
Dunsinane Hill, and the position of old Birnam Wood in the
neighbourhood, and his thoughts in those spots of “the immortal
link-boy” that had made them famous. The same letter gives an
interesting glimpse of his own mood in the first month of his Tayside
residence with the Bullers. “Some time hence,” he says to his
correspondent, Thomas Mitchell, “when you are seated in your
peaceful manse,—you at one side of the parlour fire, Mrs. M. at the
other, and two or three little M.’s, fine chubby urchins, hopping
about the carpet,—you will suddenly observe the door fly open, and a
tall, meagre, careworn figure stalk forward, his grave countenance
lightened by unusual smiles in the certainty of meeting a cordial
welcome. This knight of the rueful visage will, in fact, mingle with the
group for a season, and be merry as the merriest, though his looks
are sinister. I warn you to make provision for such emergencies. In
process of time I too must have my own peculiar hearth; wayward as
my destiny has hitherto been, perplexed and solitary as my path of
life still is, I never cease to reckon on yet paying scot and lot on my
own footing.”[40] From the Reminiscences, where we learn that he
was at this time persevering with his Life of Schiller, we have his
later recollection of those summer and autumn months, and on into
late autumn, in Kinnaird House:—
“I was nightly working at the thing in a serious, sad, and totally solitary, way.
My two rooms were in the old mansion of Kinnaird, some three or four hundred
yards from the new, and on a lower level, overshadowed with wood. Thither I
always retired directly after tea, and for most part had the edifice all to myself,—
good candles, good wood fire, place dry enough, tolerably clean, and such silence
and total absence of company, good or bad, as I never experienced before or since.
I remember still the grand sough of those woods, or, perhaps, in the stillest times,
the distant ripple of the Tay. Nothing else to converse with but this and my own
thoughts, which never for a moment pretended to be joyful, and were sometimes
pathetically sad. I was in the miserablest dyspeptic health, uncertain whether I
ought not to quit on that account, and at times almost resolving to do it; dumb, far
away from all my loved ones. My poor Schiller, nothing considerable of a work
even to my own judgment, had to be steadily persisted in, as the only protection
and resource in this inarticulate huge wilderness, actual and symbolical.”[41]
It was in October 1823 that the first part of Schiller’s Life and
Writings appeared, without the author’s name, in the then
celebrated London Magazine of Messrs. Taylor and Hessey. It was
the most important of the metropolitan magazines of that time,
counting among its contributors, since its foundation in 1820, such
writers as Charles Lamb, Hazlitt, Allan Cunningham, the Rev. Henry
Francis Cary, Hamilton Reynolds, Bryan Waller Procter, Thomas
Noon Talfourd, young Thomas Hood, and De Quincey. The
admission of Carlyle into such company, the opening of such a
London connection at last, ought to have been some gratification to
him in his recluse life at Kinnaird; and, doubtless, it was, to a far
greater extent than he could remember when he wrote the
Reminiscences. He does vaguely mention there that, though his own
judgment of the merits of his performance was not very high, he had
compliments from the editor of the magazine,—i.e., we must
suppose, from Messrs. Taylor and Hessey, who were their own
editors, unless indeed young Thomas Hood, who was a kind of
assistant editor, was the medium of the communication. What is
more important is that the Life of Schiller, if not all in the editor’s
hands complete when the first part appeared, must have been
reported as complete, or as approaching completeness, in Carlyle’s
own hands at Kinnaird. This, accordingly, fixes October 1823, or
thereabouts, as the date of his passing on from Schiller to the new
work which he had prescribed for himself as a sequel, viz. the
Translation of the Wilhelm Meister. It must have been in one of
those nocturnal sittings in the late autumn of 1823 in the old
mansion of Kinnaird, amid “the grand sough of those woods”
outside, when his Schiller manuscript lay finished beside him, and he
had Goethe before him, that there happened that “Tragedy of the
Night-Moth” which he has commemorated in one of his metrical
fragments—
 “’Tis placid midnight; stars are keeping
Their meek and silent course in heaven;
Save pale recluse, for knowledge seeking,
All mortal things to sleep are given.

But see! a wandering night-moth enters,

Allured by taper gleaming bright;
A while keeps hovering round, then ventures
On Goethe’s mystic page to light.

With awe she views the candle blazing

A universe of fire it seems
To moth-savante with rapture gazing,
Or fount whence life and motion streams.

What passions in her small heart whirling,

Hopes boundless, adoration, dread?
At length, her tiny pinions twirling,
She darts, and,—puff!—the moth is dead.”

Carlyle’s own distinct statement in the Reminiscences is that

Irving had encouraged him in the Life of Schiller, and had “prepared
the way” for it in the London Magazine. How is this to be reconciled
with his repeated references to the total cessation of correspondence
between himself and Irving from the date of Irving’s definite
settlement in London to that week, “late in autumn 1823,” when
Irving, having married Miss Martin of Kirkcaldy, was on his
marriage-jaunt with her in Scotland, and generously determined to
pass near Kinnaird, so as to pick up his old friend and have a day or
two of his society? One might have thought that it was in this
renewed meeting of the two friends in Irving’s honeymoon jaunt that
there came from Irving the suggestion of the London Magazine as a
place for the Schiller, or the intimation that he had already arranged
for it and knew it would be welcome there. This supposition,
however, will not cohere with the date of Irving’s marriage. It took
place at Kirkcaldy on the 13th of October 1823, after the number of
the London Magazine containing the first part of the Schiller had
been out for a fortnight; and Irving’s marriage-tour in Scotland
lasted through the rest of that month and the whole of November.
There must, therefore, have been renewed correspondence between
Irving and Carlyle, with arrangements about the Schiller, some while
before October 1823, though Carlyle’s memory had become hazy
about that matter too. It is pleasant to be sure of the main fact,—
which is that it was to the ever-friendly Irving that Carlyle owed this
second great service of his introduction to the London Magazine,
just as he had already owed him the Buller tutorship.
The winter of 1823–4 seems to have been passed wholly at
Kinnaird. At least, there was no re-appearance of the Bullers in
Edinburgh that winter, and no re-attendance that winter of Charles
Buller or his brother Arthur in any of the classes of Edinburgh
University. What we gather from the Reminiscences is that, towards
the end of the winter, the Bullers had begun to weary of Kinnaird life,
and indeed of life in Scotland, and were meditating a return to
England, possibly for ultimate settlement in Cornwall, but certainly
with a view to London as their intermediate head-quarters. He hints
also that they had by this time been a good deal exercised by the
moodiness and miserable bad health of the strange tutor they had
with them, and whom they respected and admired so much. Might it
not be the best arrangement that he should go for a month or two to
his native Annandale to recruit his health, and then rejoin them in
London, there again to take charge of his pupils?
Taking leave of Kinnaird with that understanding, Carlyle, it
appears, rode, either directly thence or very soon afterwards from his
father’s house at Mainhill, all the way to Edinburgh, to consult a
doctor about his dyspepsia. Was it chronic, and incurable except by
regimen? or could it be removed by medical treatment? “It is all
tobacco, sir; give up tobacco,” was the physician’s answer; on which
Carlyle’s comment is that, having instantly and absolutely followed
the advice, and persevered for “long months” in total abstinence
from tobacco, without the slightest sign of improvement, he came to
the conclusion that he might as well have ridden sixty miles in the
opposite direction, and poured his sorrows into the “long hairy ear of
the first jackass” he met, as have made that ride to Edinburgh to
consult the great authority. This story of the tobacco consultation
was a favourite one with Carlyle in later days. I have heard it from
him several times, with two additions to what appears in the
Reminiscences. One was that, the doctor having asked him whether
he could give up tobacco, “Give it up, sir?” he replied; “I can cut off
my left hand with an axe, if that should be necessary!” The other was
an account of his months of probation of the new no-tobacco
regimen. The account took the form of a recollection of himself as
staggering for months from tree-trunk to tree-trunk in a
metaphorical wood, tobaccoless and dreary, without one symptom of
benefit from his self-denial, till at last, sinking at the foot of one of
the tree-trunks, and seeing a long clay and a tobacco-pouch
providentially lying on the turf, he exclaimed “I will endure this
diabolical farce and delusion no longer,” and had a good smoke then
and there once more, in signal of reverting for ever to his old
comfort. Tobacco and a very little good brandy, he used to say to the
end of his life, were the only two drugs in the whole pharmacopœia
that he had found of any real utility to the distressed human
organism.[42]
It was during the two or three spring months of 1824, spent at
Mainhill in Dumfriesshire, under the care of that “best of nurses and
of hostesses,” his mother, that the Translation of Wilhelm Meister
was finished. It was in the June of the same year that, having revised
the proofs of the three volumes of that book for Messrs. Oliver and
Boyd of Edinburgh, who had agreed to be the publishers, as they
were also of his translation of Legendre’s Geometry, and having run
up to Edinburgh himself with the last proofs and the preface, and
received from Messrs. Oliver and Boyd £180 for the labour, and
having taken a farewell at Haddington the purport of which may be
guessed, he embarked in the Leith smack that was to carry him to
London. He was then in his twenty-ninth year, and it was his first
visit to the Great Babylon. The second part of his Life of Schiller had
appeared in the number of the London Magazine for January 1824;
but the rest had still to be published, and would probably appear in
the magazine when he was himself in London and had formed
personal acquaintance with the editorial powers. Copies of the
Wilhelm Meister from the press of Messrs. Oliver and Boyd would
follow him from Edinburgh; and it would thus be as the anonymous
author of the Life of Schiller and of the Translation of Wilhelm
Meister that he would first step into London literary society. For the
rest, his prospects were utterly undefined. Whether he should
remain in London permanently, or return to Scotland, depended on
events not yet calculable. All that was certain was that the Buller
tutorship would still be his anchorage for a time in London, as it had
been for the last two years in Scotland, and that he had Irving’s
house for his London home so long as he might choose. It was, in
fact, to Irving’s house in Myddelton Terrace, Islington, where Irving
and his wife were living as a newly-married couple, that Carlyle was
to steer himself after the Leith smack had landed him in London
river.

From this point there is a break of two years and four months in
Carlyle’s life, during which he had nothing to do with Edinburgh. The
incidents of that interval may be filled in briefly thus:—
Nine Months in London and Birmingham (June 1824–March
1825).—Residing with the Irvings at Islington, or in lodgings near
them, Carlyle in those months made his first acquaintance with
London, and with various persons in it of greater or less note.
Introduced at once to the Stracheys, and to the then celebrated Mr.
and Mrs. Basil Montagu of Bedford Square, it was through them, or
otherwise directly or indirectly through Irving, that he saw
something of Coleridge, Charles Lamb, Allan Cunningham, Bryan
Waller Procter, Crabb Robinson, and others of literary name, besides
such commercial London Scots of Irving’s congregation as Sir Peter
Laurie, Mr. William Hamilton, and Mr. Dinwiddie, and the young
English manufacturing chemist, Mr. Badams of Birmingham. After
Mrs. Strachey and the queenly Mrs. Basil Montagu, his most valued
new friends in this list, he tells us, were Procter, Allan Cunningham,
and Badams. This last, indeed, under pretext of putting him on a
regimen that would cure his dyspepsia, lured him away to
Birmingham for three months; which three months of residence with
Badams in Birmingham, and of rambles with Badams hither and
thither in Warwickshire and sights of Joe Parkes and other
Birmingham notabilities, have to be interpolated therefore in the
general bulk of the London visit. There was also a trip to Dover, in
the company of the Stracheys and the Irvings, with a run of some of
the party, Carlyle one of them, to Paris, for ten days of Parisian sight-
seeing. Altogether, the London visit had been so successful that,
when the tutorial engagement with the Bullers came to an end in the
course of it,—which it did from the impossibility of an adjustment of
Carlyle’s views with Mrs. Buller’s ever-changing plans,—the notion
among his friends was that he could not do better than remain in
London and take his chances as a London man of letters. The
concluding portions of his Schiller had appeared in the London
Magazine during the first months of his visit; and before the end of
1825 the five portions into which the work had been cut up for
magazine purposes had been gathered together, and published by
Messrs. Taylor and Hessey in the form of an octavo volume, with the
title The Life of Friedrich Schiller, bringing the author £100. It was
during his stay in London also that he received his first
communication from Goethe, in the form of a brief letter of thanks
for a copy of the Translation of Wilhelm Meister which had been
sent to Weimar some months before. But, though things seemed thus
to conspire in favour of the detention of Carlyle in London, he had
made up his mind to the contrary; and in March 1825 he turned his
back upon the great city, and was on his way once more to his native
Dumfriesshire.
Nineteen Months of Dumfriesshire Farm-life (March 1825–
October 1826):—For about two months Carlyle was at his father’s
farmhouse of Mainhill, near Ecclefechan, resting from his return-
tour through England, and preparing for the adventure which he had
planned. This was an attempt at tenant-farming on his own account
in that neighbourhood. A letter of his to Mrs. Basil Montagu, of date
May 20, 1825, is still from Mainhill; but on the 26th of that month he
entered on the possession of the adjacent little farm of Hoddam Hill,
which he had taken on lease from his father’s landlord, General
Sharpe,—“a neat, compact little farm, rent £100,” with “a
prettyishlooking cottage.” Here for a whole year he lived, nominally a
tenant-farmer, as his father was, and close to his father, but in reality
entrusting the practical farm-work to his brother Alick, while he
himself, with his mother or one of his sisters for his housekeeper,
delved a little for amusement, rode about for health, and pursued his
studies and literary tasks,—chiefly his projected translation of
Specimens of German Romance for the bookseller Tait of
Edinburgh. There were letters to and from his London friends; there
was once a sight in Annan of poor Irving, whose London troubles and
aberrations were by this time matters of public notoriety; there were
visits to and from neighbours; but, on the whole, the year was one of
industrious loneliness. Though he tells us but little of it, what he does
tell us enables us to see that it was a most important and memorable
year in his recollection. Perhaps in all Carlyle’s life no other year is so
important intrinsically. “I call that year idyllic,” he tells us, “in spite
of its russet coat.” This is general; but he gives us vital particulars. It
was the time, he distinctly says, of his complete spiritual triumph, his
attainment once and for ever to that state of clear and high serenity,
as to all the essentials of religion and moral belief, which enabled
him to understand in his own case “what the old Christian people
meant by conversion,” and which he described afterwards, in the
Teufelsdröckh manner, as the reaching of the harbour of the
“Everlasting Yes” at last. The word happiness was no favourite one in
Carlyle’s vocabulary, with reference to himself at least; but he does
not refuse even this word in describing his new mental condition
through the year at Hoddam Hill. What he felt, he says, was the
attainment of “a constant inward happiness that was quite royal and
supreme, in which all temporal evil was transient and insignificant.”
Even his bodily health seemed to be improving; and the effect
extended itself most manifestly to his temper and disposition
towards others. “My thoughts were very peaceable,” he says, “full of
pity and humanity as they had never been before.” In short, he was
no longer the moody, defiant, mainly despondent and sarcastic
Carlyle he had been, or had seemed to be to superficial observers,
through the past Edinburgh days, but a calmer, wiser, and more self-
possessed Carlyle, with depths of tenderness under all his strength
and fearlessness,—the Carlyle that he was to be recognised as being
by all who knew him through the next twenty years of his life, and
that indeed he continued to be essentially to the very end. To what
agency does he attribute this “immense victory,” as he calls it, which
he had thus permanently gained over his own spirit in this thirtieth
year of his age, passed at Hoddam Hill? “Pious musings,
communings silent and spontaneous with Fact and Nature in those
poor Annandale localities,”—these, including the sound on Sundays
of the Hoddam kirk-bell coming to him touchingly from the plain
below, “like the departing voice of eighteen centuries,” are
mentioned as accounting for much, but not for all. “I then felt, and
still feel, endlessly indebted to Goethe in the business. He, in his
fashion, I perceived, had travelled the steep rocky road before me,
the first of the moderns.” Not to be forgotten either, as that which
tinged the year to perfection in its “idyllic” character, was the flitting
across the scene of the presence that was dearest to him. His pledged
bride, no longer at Haddington, but residing with her relatives in
Nithsdale, made her first visit to his family in this year; they rode