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RuP2-based hybrids derived from MOFs: highly

Cite this: J. Mater. Chem. A, 2021, 9,
12276
efficient pH-universal electrocatalysts for the
hydrogen evolution reaction†
Ji-Sen Li, *a Meng-Jie Huang,a Yu-Wei Zhou,a Xiao-Nan Chen,a Shuang Yang,a
Ji-Yu Zhu,a Guo-Dong Liu,a Ling-Juan Ma,b Sheng-Hao Caia and Ji-Yuan Hana

Received 3rd March 2021
Accepted 30th April 2021
DOI: 10.1039/d1ta01868j
rsc.li/materials-a
Rational design of efficient, low-cost, and durable electrocatalysts for the hydrogen evolution reaction
(HER) in various pH media is highly desirable but remains challenging. Herein, for the first time, we
present a novel hybrid of ruthenium diphosphide encapsulated in P-doped porous carbon (denoted as
RuP2@PC) utilizing metal–organic frameworks (MOFs) as templates by a multi-step strategy.
Unexpectedly, benefitting from the synergistic contribution of highly dispersed ultrafine RuP2
nanoparticles, porous carbon skeleton, and P-dopant, the as-synthesized RuP2@PC exhibits exceptional
catalytic activity and superior durability as pH-universal electrocatalysts for the HER. Particularly, a low
overpotential of 78.9 mV to deliver a current density of 10 mA cm
2 and a small Tafel slope of 36.7 mV
dec
1 can be achieved in 1.0 M KOH toward the HER. Such outstanding electrocatalytic properties
exceed those of commercial Pt/C and rank the catalyst among the best HER electrocatalysts reported
until now. Importantly, this work paves a new route in elaborately fabricating efficient and stable
electrocatalysts based on MOFs for energy-related fields.

from satisfactory in comparison to Pt, especially in alkaline or

Introduction
In view of increasing global energy demand and environmental
concerns, it is of great urgency to develop renewable and eco-
friendly energy conversion technologies. Hydrogen with high
energy density and zero-carbon emission is regarded as
a promising clean replacement for fossil fuels.1,2 Electrocatalytic
water splitting for hydrogen generation as one of the most
appealing approaches has attracted much attention so far.3–6
Although platinum (Pt)-based nanomaterials are the state-of-
the-art electrocatalysts for the hydrogen evolution reaction
(HER), their large-scale implementation is signicantly
hindered due to the high cost and natural scarcity.7,8 Therefore,
searching for high-performance and low-cost catalysts for the
HER is urgently needed.
To this end, plentiful transition-metal-based catalysts have
been intensively designed and explored to boost catalytic
activities toward the HER.3 Among them, transition-metal
phosphides (TMPs) have received considerable interest owing
to their distinguished electrocatalytic properties for the HER.9–18
Despite great progress, their catalytic performances are still far
a
Department of Chemistry and Chemical Engineering, Jining University, Qufu, 273155,
P. R. China. E-mail: senjili@sina.com
b
College of Chemistry and Chemical Engineering, Qufu Normal University, Qufu,
273165, P. R. China
† Electronic supplementary information (ESI) available.
10.1039/d1ta01868j
neutral media. Recently, ruthenium (Ru) and Ru-based TMP
materials have shown outstanding catalytic HER perfor-
mances,19–33 which are comparable or even superior to
commercial Pt/C catalyst. Nevertheless, the price of Ru is much
lower than that of Pt.34 Regrettably, metal-based nanoparticles
(NPs) are prone to growing into large bulk counterparts during
high-temperature thermal treatment,35 and falling off from the
surface of the electrode during the operational process, further
resulting in a dramatic decrease of catalytic activity toward the
HER. Consequently, great efforts have been devoted to devel-
oping rational and controllable synthetic approaches to fabri-
cate ultrane Ru-based catalysts with high performance and
remarkable stability.
Metal–organic frameworks (MOFs), as fascinating porous
materials composed of metal ions and organic ligands, have
been chosen as ideal templates/precursors to prepare porous
carbon-based materials by means of the pyrolysis process.36–39
Remarkably, the resultant porous carbon structures have many
prominent advantages as follows: (1) the large surface area is
benecial to anchor NPs and maximize the dispersion degree of
NPs, thereby enhancing the electroactivity; (2) the 3D hierar-
chical porous architecture can provide numerous exposed
active sites, shorten ion diffusion length, expedite the charge
transfer throughout the electrolytic process, and increase the
accessibility to the electroactive sites, further yielding remark-
See DOI:
able catalytic behavior. Meanwhile, the connement effect of
hierarchical pores can effectively suppress the aggregation of

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Paper
NPs during thermal treatment.40,41 However, to the best of our
knowledge, the design of innovative coupled hybrids of Ru-
based TMPs and porous carbon nanomaterials as advanced
pH-universal catalysts still remains a great challenge and has
rarely been reported.
Encouraged by the above-mentioned considerations, we
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present an ingenious and feasible fabrication of ultrane P-rich
RuP2 NPs encapsulated in P-doped porous carbon (designated
as RuP2@PC) using MOFs as both metal and carbon sources
simultaneously. As far as we know, the constructed hybrid
framework is achieved for the rst time. When evaluated as
electrocatalysts toward the HER in basic, acidic and neutral
solutions, respectively, the resultant RuP2@PC exhibits
extraordinary catalytic performance with Pt-like activity and
excellent long-term durability due to the unique compositional
and structural features. In particular, it only demands a small
overpotential of 78.9 mV for 10 mA cm
2 and a low Tafel slope
of 36.7 mV dec
1 for the HER in basic solution, which outper-
forms the commercial Pt/C catalyst and most recently reported
electrocatalysts toward the HER.
Experimental section
Chemicals
Cupric acetate monohydrate (Cu(CH3COO)2$H2O, 98%), tri-
mesic acid (C6H3(CO2H)3, 98%), ruthenium chloride hydrate
(RuCl3$xH2O, 99.99% metal basis), diammonium hydrogen
phosphate ((NH4)2HPO4), and iron chloride hexahydrate
(FeCl3$6H2O, 99%) were purchased from Macklin Biochemical
Co., Ltd (Shanghai, China). Commercial Pt/C (20 wt%) was ob-
tained from Johnson Matthey. Naon (5.0 wt%) was supplied by
Sigma-Aldrich. All chemicals were used as received without
further purication.
Synthesis of samples
Cu-BTC. The Cu-BTC MOF was prepared using the previously
reported strategy.11 In a typical procedure, 0.6 g of Cu(CH3-
COO)2$H2O was dispersed in 120 mL of ultrapuried water and
stirred for 1 h. 120 mL of an ethanol solution of trimesic acid
(0.422 g) was added into the above solution. Aer continuous
stirring for 24 h, Cu-BTC was obtained by centrifuging and
washing with ethanol several times before being dried overnight.
CuRu-BTC. 100 mg of the as-prepared Cu-BTC was added
into 80 mL of a mixed solution containing ultrapuried water/
ethanol (Vwater : Vethanol ¼ 1 : 1) and vigorously stirred to get
a uniform solution. Then, 40 mL of RuCl3$xH2O solution (10 mg
mL
1) was added into the above suspension and continuously
stirred for 24 h. Finally, the sample (denoted as RuCu-BTC) was
obtained through centrifugation, washing with ethanol several
times, and drying at 80  C.
As control experiments, RuCu-BTC (0.2 mg and 0.6 mg)
samples were also prepared under the same conditions except
that the volumes of RuCl3$xH2O solution were 20 mL and 60 mL,
respectively.
RuP2@PC. The resultant RuCu-BTC was heated to 600  C for
5 h under Ar, and is denoted as Ru–Cu@PC. Subsequently, Ru–
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Cu@PC was etched with FeCl3 solution (0.1 M) for 12 h in order
to remove accessible Cu species (named Ru@PC). Finally, the
as-prepared Ru@PC and (NH4)2HPO4 (100 mg) were put at the
center and upstream side of the tube furnace, respectively. Aer
heating at 800  C for 2 h in an Ar atmosphere, the RuP2@PC
sample was obtained. Besides, RuP2@PC samples (0.2 mg and
0.6 mg) were also fabricated by an identical method using
RuCu-BTC (0.2 and 0.6 mg) as precursors, respectively.
PC. The PC sample was synthesized utilizing only Cu-BTC
MOFs as templates using a similar strategy.
Instruments
Scanning electron microscopy (SEM) images were taken on
a JSM-7800F. Transmission electron microscopy (TEM), high-
resolution (HR) TEM, STEM, and energy-dispersive X-ray spec-
troscopy (EDX) elemental mapping images were obtained on
a JEOL-2100F. Powder X-ray diffraction (PXRD) was carried out
on a D/max 2500/PC diffractometer with Cu Ka radiation
(0.154060 nm, Japan). X-ray photon spectroscopy (XPS, PHI
5000 Versa) was used to probe surface elements and chemical
states. Surface area was assessed on a Micromeritics ASAP 2050
Brunauer–Emmett–Teller (BET) analyzer. The corresponding
pore size distribution was estimated by the NLDFT approach.
Electrochemical measurements
The electrochemical performance was studied on an electro-
chemical station (CHI-660E) using a three-electrode cell with
graphite rod as the counter electrode. The reference electrodes
were Hg/HgO (1.0 M KOH) electrode in 1.0 M KOH, saturated
calomel electrode (SCE) in 0.5 M H2SO4, and Ag/AgCl (saturated
KCl solution) electrode in 1.0 M PBS, respectively. Notably, the
reference electrode was calibrated via a reversible hydrogen
electrode (RHE) in a H2-saturated electrolyte with Pt foil as the
counter electrode and working electrode, respectively (Fig. S1–
S3, ESI†). In 1.0 M KOH, ERHE ¼ 0.924 V + EHg/HgO; in 0.5 M
H2SO4, ERHE ¼ 0.258 V + ESCE; in 1.0 M PBS, ERHE ¼ 0.5807 V +
EAg/AgCl. To fabricate the working electrode, 2 mg of the pre-
synthesized sample was homogeneously dispersed in
a mixture of 970 mL ethanol solution and 30 mL Naon solution
(5 wt%) by continuous sonication for 30 min. Then, 5 mL of the
ink was dropped onto a glassy carbon electrode surface (0.14 mg
cm
2). For comparison, commercial Pt/C was also prepared
under similar conditions. Cyclic voltammetry (CV) at 100 mV
s
1 and linear sweep voltammetry (LSV) at 2 mV s
1 were per-
formed, respectively. Herein, all these potentials have been
corrected with 95% iR drop compensation and then trans-
formed to the RHE. The double-layer capacitance (Cdl) was
evaluated from CV curves at 20–100 mV s
1 in the non-faradaic
region.
Results and discussion
The RuP2@PC nanocomposite was synthesized using MOFs as
precursors through a multi-step process, as is schematically
depicted in Scheme 1. First, the Cu-BTC MOF is obtained by
a solution method, wherein Cu2+ and trimesic acid are chosen
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Scheme 1 Schematic illustration of the synthetic procedure of
RuP2@PC.
as the metal source and organic ligand, respectively. Next, Cu2+
of Cu-BTC is partially replaced by Ru3+ through a facile cation
exchange method, thus leading to the formation of RuCu-BTC.
Subsequently, the RuCu-BTC hybrid is transformed into Ru–
Cu@PC during the heating treatment in an Ar atmosphere.
Finally, the RuP2@PC sample can be obtained by etching with
FeCl3 solution, followed by phosphating treatment using
(NH4)2HPO4 as the phosphorus source.
As shown in Fig. S4 (ESI†), the powder X-ray diffraction
(PXRD) pattern of the obtained Cu-BTC MOF is consistent with
that of the simulated HKUST, implying good crystallinity.10 In
Fig. S5 (ESI†), the scanning electron microscopy (SEM) and
transmission electron microscopy (TEM) images show that the
Cu-BTC MOF is composed of abundant irregular nanoparticles.
When a certain amount of Ru3+ is introduced by an ion-
exchange strategy, the RuCu-BTC MOF can be generated. The
initial structure and morphology are mostly retained compared
to those of Cu-BTC MOF (Fig. S4 and S6, ESI†), evidencing that
the introduction of Ru3+ has not affected the crystalline
framework of MOF.42 Impressively, some nanoparticles with
open mouths can be clearly observed, which may be associated
with the release of Cu2+. Aer annealing–etching–phosphating
treatments, the RuP2@PC composite is successfully fabricated.
The structure of the resultant RuP2@PC was investigated by
PXRD, as displayed in Fig. 1a. The characteristic diffraction
peaks are well assigned to the orthorhombic RuP2 phase (JCPDS
34-0333). Additionally, the broad and weak peaks at 24.8 and
43.2 belong to amorphous carbon. The morphology of
RuP2@PC is examined by SEM and TEM, respectively. As dis-
played in Fig. 1b and c, RuP2@PC perfectly inherits the initial
morphology.43 Furthermore, plenty of macro/mesopores labeled
with yellow circles can be intuitively observed originating from
the removal of Cu particles, which is favorable to the exposure
12278 | J. Mater. Chem. A, 2021, 9, 12276–12282
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Fig. 1 (a) PXRD pattern, (b and c) SEM, (d and e) TEM, (f) HRTEM, and
(g) STEM and EDX elemental mapping images for C, P, and Ru in
RuP2@PC.
of more active sites and accelerates electron transport. The TEM
image in Fig. 1d distinctly reveals that numerous ultrasmall
RuP2 NPs are uniformly decorated on the carbon framework.
The mean particle size of RuP2 NPs is calculated to be about
6.8 nm. Furthermore, it is found that the RuP2 NPs are encap-
sulated by carbon layers (Fig. 1e), which can prevent the
oxidation and aggregation of RuP2 NPs.20,35 In Fig. 1f, the high-
resolution TEM (HRTEM) image shows the well-dened lattice
fringes with an interplanar spacing of 0.386 nm, attributable to
the (110) plane of orthorhombic RuP2. The STEM and energy-
dispersive X-ray spectroscopy (EDX) elemental mapping
images (Fig. 1g) reveal that the C, P, and Ru elements are
homogeneously distributed on the entire RuP2@PC matrix. As
revealed by an inductively coupled plasma atomic emission
spectrometer (ICP-AES), the content of Ru is around 14.6 wt%.
The Brunauer–Emmett–Teller (BET) surface area of RuP2@PC is
determined to be 719.5 cm3 g
1 according to the N2 sorption
isotherm, as indicated in Fig. S7a (ESI†). Moreover, the corre-
sponding pore size distribution calculated using the NLDFT
method in Fig. S7b (ESI†) strongly proves the existence of
a hierarchical porous structure, which can enable active sites to
closely contact with the electrolyte, thereby boosting the elec-
trocatalytic HER performance.35
For comparison, the PC was also synthesized without adding
RuCl3 under similar conditions. The morphological and struc-
tural information of the PC were also analyzed by SEM, TEM,
and PXRD, respectively, as shown in Fig. S8 and S9 (ESI†).
X-ray photoelectron spectroscopy (XPS) measurements were
carried out to probe the surface electronic interactions and
chemical states. As indicated in Fig. 2a, the peaks of C, P, O, and
Ru are clearly observed in the XPS full spectrum of RuP2@PC,
which is in agreement with the result of EDX elemental
mapping. In Fig. 2b, the C 1s + Ru 3d spectrum can be tted into
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Fig. 2 (a) XPS survey spectrum. High-resolution XPS scans of (b) C 1s +
Ru 3d, (c) P 2p, and (d) Ru 3p for RuP2@PC, respectively.
ve peaks, assignable to C–C/C]C (284.8 eV), C–P (286.1 eV),
O–C]O (289.3 eV), Ru 3d3/2 (284.6 eV), and Ru 3d5/2 (280.7 3 V),
respectively.21 In the XPS spectrum of P 2p shown in Fig. 2c, the
binding energies at 129.5 and 130.3 eV are attributed to P 2p3/2
and P 2p1/2 in the RuP2. Notably, the binding energy of P 2p3/2 is
lower than that of elemental P (130.1 eV), implying that the P
atom in RuP2 possesses a partial negative charge.10 The P–C
peak at 133.5 eV reveals the successful incorporation of P into
the porous carbon skeleton. The additional peak at 134.5 eV
may be ascribed to amorphous phosphate stemming from the
surface oxidation.4,28 In the Ru 3p high-resolution spectrum
(Fig. 2d), the peaks located at 461.9 and 484.1 eV correspond to
Ru 3p3/2 and Ru 3p1/2.22 Compared to that of metallic Ru (461.5
eV), the Ru 3p3/2 peak is positively shied by 0.4 eV, suggesting
the generation of positively charged Ru species. The other two
peaks at 464.6 and 485.9 eV can be assigned to the Ru oxide
species.17 The above results strongly conrm that some of the
electrons could be transferred from Ru to P and then to the
neighboring C, thereby resulting in enhanced HER
performance.19,44
The electrocatalytic HER performances of the as-prepared
products were assessed in N2 saturated 1.0 M KOH using
a typical three-electrode system. For comparison, the electro-
catalytic behavior of commercial Pt/C (20 wt%) was also evalu-
ated as a benchmark. The linear sweep voltammetry (LSV)
curves in Fig. 3a indicate that the resultant RuP2@PC shows
extraordinary hydrogen evolution performance, outperforming
the commercial Pt/C catalyst. The onset overpotential (h) at
a current density of 1 mA cm
2 follows the trend of RuP2@PC
(33.6 mV) < Pt/C (42.1 mV) < PC (379.4 mV). Amazingly, the
obtained RuP2@PC only requires a small overpotential (h10) of
78.9 mV to deliver the current density of 10 mA cm
2 as shown
in Fig. 3b, which exceeds commercial Pt/C (120.7 mV) and is far
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Fig. 3 (a) LSV curves of different samples in 1.0 M KOH, respectively.
(b) Corresponding overpotentials (@10 mA cm
2 and 20 mA cm
2), (c)
Tafel plots. (d) Cdl of PC and RuP2@PC based on current density versus
scan rate. (e) LSV curves of RuP2@PC initial and after 1000 cycles. (f)
Chronopotentiometry measurement of RuP2@PC at 10 mA cm
2.
better than that of PC (550.1 mV). Besides, to investigate the
intrinsic electroactivity of catalysts toward the HER, the corre-
sponding Tafel plots were studied. Unexpectedly, the Tafel slope
value of 36.7 mV dec
1 for RuP2@PC is lower than those of
commercial Pt/C (44.3 mV dec
1) and PC (127.8 mV dec
1),
suggesting that RuP2@PC exhibits the most favorable kinetics
for the HER via the Volmer–Tafel mechanism (Fig. 3c and Note
S1, ESI†).4,22 The exchange current density (j0) of RuP2@PC is
calculated to be 0.124 mA cm
2, which is higher than that of Pt/
C (0.118 mA cm
2), revealing prominent intrinsic electro-
catalytic activity. Such remarkable catalytic HER performance of
RuP2@PC surpasses that of most non-noble and Ru-based
catalysts recently reported, as listed in Table S1 (ESI†).20,37–39,44
To further examine the effective electrochemically active surface
areas (ECSAs), the double-layer capacitance (Cdl) is measured by
cyclic voltammetry (CV) tests from 24 mV to 124 mV (Fig. S10,
ESI†). As exhibited in Fig. 3d, RuP2@PC presents a Cdl value of
15.1 mF cm
2, which is 1.72 times higher than that of PC (8.8
mF cm
2). This may be attributed to the fact that the 3D porous
skeleton is conducive to high exposure of RuP2 electroactive
sites. Furthermore, on the basis of the LSV curves normalized by
ECSAs (Fig. S11, ESI†), the resultant RuP2@PC electrocatalyst
still exhibits outstanding catalytic behavior toward the HER.
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Moreover, the electrochemical impedance spectroscopy (EIS)
evidences that RuP2@PC has smaller charge transfer resistance
relative to PC (Fig. S12, ESI†), implying faster electron transfer.
Additionally, the turnover frequency (TOF) is determined to be
4.9 s
1 at 62.1 mV in 1.0 M KOH (Fig. S13, ESI†). As shown in
Fig. S14 and S15 (ESI†), the faradaic efficiency of RuP2@PC for
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the HER is calculated to be 97.8%. All in all, the high intrinsic
electrocatalytic performance and abundant electroactive sites
are responsible for the superior HER performance of RuP2@PC.
In terms of the practical applications of electrocatalysts,
long-term stability is of great importance. In Fig. 3e, it can be
found that the LSV curve of RuP2@PC almost remains
unchanged aer 1000 cycles in comparison with the initial one,
unambiguously manifesting the excellent durability. Mean-
while, the chronopotentiometry measurement was also carried
out to estimate the stability of the RuP2@PC electrode. During
continuous operation for 10 h at an overpotential of 78.9 mV,
merely 18% current density decay could be observed in Fig. 3f,
reconrming the remarkable electrocatalytic durability. More
importantly, the morphology and structure can still be
preserved aer the hydrogen evolution test (Fig. S16 and S17,
ESI†), providing evidence for the robust stability of the
RuP2@PC electrocatalyst throughout the catalytic HER process.
To optimize the electrocatalytic behavior for the HER alka-
line media, a series of RuP2@PC prepared with different
amounts of RuCl3 (0.2 and 0.6 mg) were also assessed as control
samples. As displayed in Fig. 4, it is worth pointing out that the
highest catalytic performance toward the HER could be ach-
ieved for RuP2@PC when the amount of RuCl3 was 0.4 mg in
view of the lowest h10, and the smallest Tafel slope. Hence,
RuP2@PC indicates that the catalyst was synthesized with
0.4 mg of RuCl3 unless specied.
Additionally, the inuence of Cu species on the electro-
catalytic performance toward the HER was also investigated. As
illustrated in Fig. S18 (ESI†), the PXRD pattern of Cu3P/
RuP2@PC matches well with the orthorhombic RuP2 phase
(JCPDS 34-0333), hexagonal Cu3P phase (JCPDS 71-2261), and
amorphous carbon. The SEM and TEM images in Fig. 5a and
b illustrate that Cu3P/RuP2@PC consists of larger-sized Cu3P
NPs and smaller-sized RuP2 NPs, which are randomly dispersed
in the PC architecture. Based on the LSV curves, corresponding
Tafel plots in Fig. 5c and d and EIS plots in Fig. S19 (ESI†), the
RuP2@PC hybrid presents much better electrocatalytic perfor-
mance for the HER in comparison to Cu3P/RuP2@PC.
Fig. 4 (a) LSV curves and (b) corresponding Tafel plots of RuP2@PC
synthesized with different amounts of RuCl3.
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Fig. 5 (a) SEM and (b) TEM images of Cu3P/RuP2@PC. (c) LSV curves of
Cu3P/RuP2@PC and RuP2@PC. (d) Corresponding Tafel plots.
Consequently, this result signicantly suggests that the Cu3P
NPs are inert to the HER. That is, the removal of Cu species
plays a crucial role in enhancing the catalytic hydrogen
production, which is benecial to the formation of rich meso/
macropores and exposure of more RuP2 sites.11,39
As is well known, it is of great signicance that an electro-
catalyst functions well in pH-universal ranges for the HER.
Hence, the electrocatalytic activities of RuP2@PC, PC and
commercial Pt/C were further studied in both acidic and neutral
media. Impressively, RuP2@PC shows outstanding electro-
catalytic properties for the HER in 0.5 M H2SO4 and 1.0 M PBS
solutions, as exhibited in Fig. 6a and d. The as-prepared
RuP2@PC merely needs h10 of 77.2 mV and 179.6 mV, respec-
tively. The values are considerably lower than those of PC
(409.6 mV and 805.5 mV), but slightly higher than those of the
benchmark Pt/C (39.1 mV and 148.4 mV). Also, the corre-
sponding values of Tafel slope for RuP2@PC are 41.2 mV dec
1,
indicative of a Volmer–Heyrovsky mechanism (Note S1, ESI†),
and 85.6 mV dec
1 as shown in Fig. 6b and e, respectively,
surpassing those of PC. As exhibited in Fig. S20 (ESI†), the
smaller charge-transfer resistance of RuP2@PC can accelerate
charge transfer, further leading to outstanding HER activity. In
addition, the TOF values of RuP2@PC in 0.5 M H2SO4, and 1.0 M
PBS solutions are 6.2 s
1 at 52.2 mV, and 6.1 s
1 at 79.4 mV
(Fig. S21, ESI†). It is noteworthy that the electroactivity of
RuP2@PC is comparable to, or even better than that of most
reported HER catalysts (Table S1, ESI†).19,33–35,40 Besides, the
long-term stability of the RuP2@PC electrode under both acidic
and neutral conditions was also examined by successive CVs
(Fig. 6c and f), and chronopotentiometry test (Fig. S22, ESI†).
And the morphology and elemental composition distribution
could still be preserved aer the HER test, as shown in Fig. S23–
S25 (ESI†). All these results undoubtedly demonstrate that the
RuP2@PC is a stable pH-universal catalyst for the HER.
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Fig. 6 LSV curves of different catalysts in (a) 0.5 M H2SO4 and (d) 1.0 M
PBS. (b and e) Corresponding Tafel plots. LSV curves of RuP2@PC initial
and after 1000 CV scanning in (c) 0.5 M H2SO4 and (f) 1.0 M PBS.
Considering the characteristic structure and composition of
RuP2@PC, as demonstrated in Scheme 2, the superefficient
electrocatalytic performance of RuP2@PC toward the HER can
be ascribed to the following reasons. (1) In general, P-rich RuP2
NPs with Pt-like activity have been regarded as a highly efficient
catalyst for the HER.19,20 Particularly, highly dispersed ultra-
small RuP2 NPs are benecial to increase the utilization effi-
ciency of RuP2 active sites.24 (2) The 3D hierarchical porous
structure can not only provide a large surface area to stabilize
Scheme 2 Schematic illustration of the merits of RuP2@PC as
advanced electrocatalysts toward the HER in an alkaline electrolyte.
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and disperse nanoparticles, but expose more active sites.30 More
importantly, the hierarchical pores benet charge transport and
mass transfer, further boosting the reaction kinetics.39 (3) The P
dopant may change the electron density and modulate the
electronic structure of the neighboring carbon and offer extra
catalytic sites.19,35 Meanwhile, the carbon layer can effectively
prevent the RuP2 NPs from being corroded and aggregating
during the electrolysis process, contributing to the long-term
stability.22 Overall, the above-mentioned advantages jointly
endow the as-synthesized RuP2@PC with unparalleled catalytic
performance toward the HER over the full pH range.
Conclusions
In summary, we have reported the ingenious design of RuP2
nanoparticles encapsulated in a P-doped porous carbon hybrid
using MOFs as templates. When employed as electrocatalysts
for the HER under alkaline, acidic, and neutral conditions,
respectively, RuP2@PC shows excellent catalytic activity and
better long-term stability due to the advanced structural merits.
Impressively, the exceptional catalytic HER performance of
RuP2@PC in alkaline media is superior to that of the
commercial Pt/C catalyst. The present ndings pave a new route
to fabricate cost-effective and highly durable pH-universal
electrocatalysts toward hydrogen production.
Author contributions
Ji-Sen Li and Meng-Jie Huang designed this project and elabo-
rated on this concept. Meng-Jie Huang, Yu-Wei Zhou, and Xiao-
Nan Chen synthesized the catalysts and performed the elec-
trochemical and material characterization experiments. Shuang
Yang, Guo-Dong Liu, and Ji-Yu Zhu participated in the material
characterization part. Ling-Juan Ma, Sheng-Hao Cai, and Ji-
Yuan Han analyzed the obtained data. Ji-Sen Li and Meng-Jie
Huang wrote the manuscript. All the authors contributed to
the interpretation of the data and the revision of this manu-
script. This project is coordinated by Ji-Sen Li.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was nancially supported by the National Natural
Science Foundation of China (No. 21971086) and the Natural
Science Foundation of Shandong Province (No. ZR2019MB013
and ZR2019MB047).
Notes and references
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