Accepted Article: Chemistry-Sustainability-Energy-Materials

Chemistry–Sustainability–Energy–Materials
Accepted Article
Title: Plasmonic photocatalysts for sunlight-driven reduction of CO2:

Detail, development and perspective
Authors: Trong-On Do, Nhu-Nang Vu, and Serge Kaliaguine
This manuscript has been accepted after peer review and appears as an
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published online in Early View as soon as possible and may be different
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the VoR from the journal website shown below when it is published
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content of this Accepted Article.
To be cited as: ChemSusChem 10.1002/cssc.202000905
Link to VoR: https://doi.org/10.1002/cssc.202000905
01/2020
ChemSusChem 10.1002/cssc.202000905
REVIEW
Plasmonic photocatalysts for sunlight-driven reduction of CO2:
Detail, development and perspective
Nhu-Nang Vu, Serge Kaliaguine, Trong-On Do*
Accepted Manuscript
1
This article is protected by copyright. All rights reserved.
REVIEW
* Prof. Trong-On Do
Department of Chemical Engineering
Laval University
1065 Avenue de la Médecine, Québec (Québec), G1V 0A6, Canada
E-mail: Trong-on.do@gch.ulaval.ca
[3]
Abstract: The plasmonic photocatalysis is among the most efficient with an absorption efficiency up to 42.3% [4]. The LSPR
Accepted Manuscript
processes for the photoreduction of CO2 into valuable fuels. The simultaneously generates highly energetic electrons and
formation of localized surface plasmon resonance (LSPR), energy facilitates their fast and efficient transfer to the nearby
transfer, and surface reaction are the significant steps in this process. semiconductor whose efficiency can reach 45% [5]. Moreover, the
LSPR has essential roles in the performance of plasmonic distinctive designed architecture can minimize many limitations of
photocatalysts as it promotes an excellent, broad wavelength range conventional photocatalysts for improving the CO2 photoreduction
[3a-c, 3h, 6]
light absorption, simultaneously facilitating an efficient energy transfer . The efficiency of the plasmonic CO2 photoreduction is,
to semiconductors. The LSPR transfers energy to a semiconductor therefore, able to surpass the highest one of the photocatalysis
through various mechanisms which have both advantages and (5%) achieved for solar water splitting [7] and become competitive
disadvantages. This work points out four critical features for to other efficient technological approaches such as CO 2
plasmonic photocatalyst design such as plasmonic materials, size, photoelectrochemical reduction and CO2 electrochemical
and shape of plasmonic nanoparticles (PNPs) and the contact reduction.
between PNPs and semiconductor. Various developed plasmonic Many prominent review papers on the plasmonic photocatalysts
photocatalysts, as well as their photocatalytic performance in CO 2 have been published over the last several years [2b, 3a-c, 3e, 6, 8].
photoreduction, are reviewed and discussed. Finally, our perspectives Some of them focus on rational structural designs with precise
of advanced architectures and structural engineering for plasmonic manipulation to maximize solar energy harvesting and enhance
photocatalyst design are put forward with high expectations to achieve photocatalytic activity. For example, studies on six rational
an efficient CO2 photoreduction shortly. nanostructure designs of single active plasmonic photocatalysts
for enhanced photocatalysis were summarized and discussed in
the review of Yamashita’s group [8a]. A very recent paper of Kumar
et al. reviewed an interesting plasmonic photocatalyst system
1. Introduction constructed by interfacing plasmonic particles with ferroelectrics
[8e]
. Scientific understanding of the enhanced charge carrier
The rapid increase in the atmospheric CO2 concentration injection of this system was given along with numerous examples
associated with the massive consumption of fossil fuels is causing of state-of-art ferroelectric-plasmonic photocatalysts developed.
a series of disastrous environmental problems such as global Several other reviews direct attention to particular plasmonic
warming and climate change [1]. Therefore, finding effective photocatalysts, their structure, and fabrication. Au-ZnO plasmonic
strategies for decreasing CO2 concentration is urgently needed. photocatalyst has been intensively studied for light-driven
Recycling CO2 via photochemical reduction is among the most hydrogen production and pollutant degradation due to its
promising approaches for not only reduction of CO2 emission but interesting structure-electronic properties. The recent work of
the production of alternative energy sources [2]. In this process, Kavitha and co-workers provided insight into the correlation
photocatalysts convert solar energy into chemical energy to between crucial structure-relating features of this photocatalyst
reduce CO2 to valuable compounds with high-energy content such as charge carrier dynamic, LSPR effect, surface
such as methane, methanol, ethanol, etc. The photocatalytic functionalization, etc., in relevance to the photocatalysis [8f]. This
system is simple to design with low cost, high flexibility, and work also summarized strategies for the preparation of the Au-
reusability. Additionally, solar energy is abundant and carbon-free, ZnO plasmonic photocatalyst, simultaneously giving a
thus avoiding CO2 emission. In recent work, we have pointed out comprehensive discussion on key challenges and issues
several critical aspects of CO2 photoreduction, including band remained. Notably, a significant number of review papers
structure, charge separation, surface reaction, and materials [2l]. concentrate on the development of plasmonic photocatalysts for
Notably, various structural engineering strategies (e.g., band certain applications, attracting particular attention. For instance,
structure, geometrical, and heterostructure engineering) for the the development and achievement of plasmonic photocatalysts
construction of an efficient photocatalytic system have been for the H2 production were systematically reviewed by Reddy and
reviewed [2l]. colleagues [8c]. In another work, Zhou et al. highlighted advances
Constructing localized surface plasmon resonance (LSPR) in the synthesis and photocatalytic properties of plasmonic
material/photocatalyst heterostructure is a highly attractive photocatalysts for diverse applications in mineralization of organic
approach owing to the benefits of this photocatalytic system. Such pollutants, organic synthesis, and water splitting [8d]. The
a system is built by depositing plasmonic nanostructures onto a plasmonic photocatalysts have been widely investigated for the
semiconductor. The adequately designed architecture allows the application of the CO2 photoreduction in recent years. However,
formation of localized surface plasmon resonance (LSPR), which systematic documentation on structure, significant processes,
induces a wide-wavelength range and excellent light absorption
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2. Major processes of CO2 photoreduction on
the plasmonic photocatalyst
Nhu-Nang Vu obtained his B.S. in Chemistry
from Hanoi University of Sciences, Viet Nam,
CO2 photoreduction on a plasmonic photocatalyst includes three
in 2014. Then he entered Université Laval,
essential processes: formation of localized surface plasmon
Canada and completed his M.S. degree in
resonance (LSPR) on plasmonic nanoparticles (PNPs), energy
Chemical Engineering, in 2016. He is
currently working for his Ph.D. degree under
transfer to nearby semiconductor and surface reactions.
the directorship of Prof. Trong-On Do and co-
directorship of Prof. Serge Kaliaguine. His
2.1. Formation of localized surface plasmon resonance
current research interest is developing (LSPR)
photocatalysts for water splitting and CO2
photoreduction using solar energy. LSPR is described as the collective oscillation of the free
Accepted Manuscript
electrons in plasmonic nanoparticles (PNPs) in response to light
((Author Portrait)) irradiation [3b, 3d, 6a, 8b, 9]. LSPR formed by PNPs with spherical
Professor Serge Kaliaguine obtained his shape is the simplest and most widely studied model in the
Ph.D. degree in Chemical Engineering from plasmonic field. Under light irradiation, the electric field will
Institut de Génie Chimique of Toulouse displace free electrons relative to the nuclei, inducing a large
(France) in 1967. From that time he has been electric dipole, as shown in Figure 1. Simultaneously, the
teaching at the Department of Chemical Coulomb attraction between nuclei and electron gives rise to a
Engineering, Université Laval, Québec, restoring force, resulting in a resonant oscillation of electrons.
Canada. He worked for more than 40 years When the PNPs are considerably smaller than the wavelength of
in catalysis and surface science research. He light, the LSPR will occur. This effect is described by the quasi-
published over 500 papers in refereed static approximation where the interaction of light with a spherical
journals (over 25000 citations) and received PNP is governed by electrostatics rather than electrodynamics [3e,
several prestigious awards. These include 9]
. The LSPR improves the light absorption efficiency as it
Le Prix Urgel-Archambaut (ACFAS); The Canadian Catalysis
((Author Award (CIC);
Portrait)) increases the cross-section absorption by several orders of
The Catalysis Lectureship Award (CCF); The Century of Achievements magnitude compared to the physical cross-section absorption [3b,
Award (CSChE). 10]
. It also creates a powerful electric field at the PNP outer surface
which is much stronger than the initial electric field of the incident
light [3e, 9, 11]. This phenomenon is called the near-field
Trong-On Do is a full professor in the
enhancement, which is significantly advantageous for charge
Department of Chemical Engineering,
carrier generation and transfer to the neighboring semiconductor
Université Laval, Canada. He obtained his
[3a, 3b, 8b, 12]
M.S. degree in 1986 and Ph.D. degree in
.
1989 from University of P. and M. Curie
(Paris 6, France). He moved to Laval
University in 1990 and then spent two years
at Kanagawa Academy of Science and
technology (1997-1999) before rejoining
Laval University as professor. He worked for
more than 30 years in the field of zeolite-
based materials including controlled-size nano-zeolites and hybrid
((Author Portrait))
zeolite/mesoporous molecular sieve materials. His current research
interests focus on the design and synthesis of innovative and smart
Figure 1. Schematic of plasmon oscillation for a sphere, showing the
materials and their applications in heterogeneous photocatalysis and
displacement of the conduction electron cloud relative to the nuclei. Reproduced
renewable energy. He has published over 160 papers and review articles in with permission from ref [9].
refereed journals and holds 5 international patents. He is the recipient of the
2014/2015 Canadian Catalysis Lectureship Award (CCLA).
Near-field enhancement, plasmonic resonance frequency, and
the LSPR light absorption are crucial features of the LSPR
and photocatalytic performance of plasmonic photocatalysts for needed to be concerned. The near-field enhancement is
this application has been still limited to date. This review is, significantly dependent on the light energy and the distance from
therefore, aimed to fill this gap. In this work, a brief fundamental the PNP surface [3e, 9, 11].
of LSPR and detailed mechanism of electron-hole transfer
between plasmonic nanostructures and semiconductors will be
provided. Additionally, critical features including plasmonic
materials, size, and shape of plasmonic nanoparticles, and
structural design for efficient CO2 reduction, will be discussed.
Furthermore, recent studies of CO2 photoreduction over
plasmonic photocatalysts will be summarized.
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Radiative decay Non-radiative decay of CO2 due to their lower Fermi level, thus playing the role as co-
catalyst. Revealing the role of PNPs is, therefore, critical. These
techniques provide near-field mapping image of multiple PNP-
Hot electrons
decorated systems, coupled with the corresponding topography
images, can indicate which NPs have the LSPR. The role of
individual NP in the plasmonic photocatalysts is thus determined.
hv Ef On the other hand, the near-field mapping image displays the
near-field intensity and near-field distribution, allowing the
determination of plasmonic hot spots for highly efficient
photocatalytic reactions.
d-band
2.2. Energy transfer in plasmonic photocatalyst
Accepted Manuscript
Figure 2. Radiative and non-radiative decays of LSPR via re-emitted photons
and excitation of hot electrons, respectively. Reproduced with permission from
In the plasmonic photocatalyst, LSPR of PNPs can transfer
ref [3b]. energy to a nearby semiconductor through several manners such
as hot electron injection, near field enhancement, and other
mechanisms [3b, 3e, 6a, 8b, 15, 20]. Hot electron and near field
The incident light with reliable power intensifies the electric dipole, enhancement are the two most proposed mechanisms for
improving the near field enhancement. The near-field interpreting the charge transfer in CO2 photoreduction. These
enhancement is, however, limited in a specific nearby region of mechanisms are mainly differentiated by the form of energy
the PNP surface. When moving away from the PNPs surface, it is transferred.
strongly impaired due to the rapid decline of the electric dipole.
This limitation is, therefore, critical for engineering interfacial 2.2.1. Hot electron injection
contact between PNPs and semiconductors (to be discussed in
later sections). The plasmonic resonance frequency is After taking place on a femtosecond time scale, LSPR can decay
characteristic of the absorption wavelength of PNPs which can be radiatively via re-emitted photons or non-radiatively via the
estimated using the Drude model [3e, 13]. It was found that the excitation of hot electrons, as shown in Figure 2 [3a, 3b].
plasmonic resonance frequency is reversely proportional to the The hot electrons are excited during the non-radiative decay
dielectric constant of the surrounding medium. It means that the primarily through the intraband within the conduction band or
plasmonic resonance frequency decreases with an increase in through the interband resulting from transitions between other
the dielectric constant of the surrounding medium. The absorption bands (for example, d-band) and the conduction band. Note that,
wavelength of PNPs is thus red-shifted. This estimation is for specific PNPs such as Au and Ag, owing to their considerably
particularly valuable for enhancing the sunlight absorption of low level of their d-band below Fermi level, intraband excitation of
PNPs. Nonetheless, the estimation via the Drude model is not hot electrons is preferred to interband excitation [3b, 6a]. The
accurate for PNPs whose LSPR is affected by intraband transition generated hot electrons are then injected into the conduction
[13a]
. The Drude model is also not adequate for estimating the band (CB) of the nearby semiconductor while leaving holes in
absorption wavelength of PNPs with various particle sizes. The PNPs, as shown in Figure 3 [21]. The rate of electron injection to
discrete dipole approximation method is more accurate for this the adjacent semiconductor can be measured by several different
estimation [14]. The LSPR absorption is determined by two techniques such as femtosecond transient absorption
essential parameters: The cross-section light absorption (Cabs) spectroscopy, femtosecond tunable spectroscopy, and open-
and the cross-section light scattering (Cscat). These two circuit voltage decay (OCVD) [22].
parameters are exponentially proportional to the radius of
spherical PNPs (r) [3e, 11, 15]. For small particles where r is much
Hot electron
smaller than the light wavelength (λ), Cscat is negligible. For large
particles where r is comparably large to λ, Cscat becomes e-
significant compared to Cabs. The quantitative determination of the hν
e-
LSPR
ratio Cscat/Cabs is, therefore, essential for determining the CB

efficiency of the LSPR absorption. Ef
To determine the LSPR formation of plasmonic photocatalysts, h+
measuring the light absorption using UV-Vis spectroscopy is
currently the most common method. The LSPR absorption is VB PNP
easily distinguishable from the physical absorption by an intense
and distinct absorption peak. Since near-field enhancement is a
characteristic phenomenon of the LSPR, near-field detection is a Semiconductor
practical confirmation approach. Up till now, there have been
various techniques employed for this detection, such as scanning
Figure 3. Plasmonic-mediated hot electron injection from PNP to CB of the
near-field optical microscopy [16], cathodoluminescence semiconductor. Reproduced with permission from ref [21].
microscopy [17], electron energy-loss spectroscopy [18],
photoemission electron microscopy (PEEM) [19]. In several
plasmonic photocatalysts, PNPs can trap generated electrons Similar to conventional electron transfer, the injection of the hot
from the excited semiconductor to conduct the surface reduction electron is governed by the PNP-semiconductor interfacial
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contact and band alignment [2l, 3b, 3g, 15]. When metal PNPs are to the size and shape of PNPs and their interfacial contact with
brought in touch with an n-type semiconductor, an interfacial the semiconductor.
energy barrier called the Motts-Schottky barrier is formed. For
injection, the energies of generated electrons must surpass this
barrier. Another factor in the hot electron injection is the timescale e-
requirement. The lifetime of hot electron ranges from 10-100 ps, CB
ELSPR
which are extremely short compared to that of excited electrons VB
in semiconductors [23]. Therefore, structural design with proper h+
interfacial contact is needed, which can enable a fast electron
injection to the semiconductor to avoid the decay, simultaneously hν
preventing electron back-injection to enhance injection efficiency.
Moreover, for plasmonic photocatalysts, the hot electron injection
e-
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is dependent on the electron momentum-direction, which relates
to the contact morphology of PNPs and semiconductor [3b]. The
hot electrons can be injected into semiconductors only if their
h+
momentum-direction mainly points toward those semiconductors. PNP
Other factors as size and shape of PNPs have a substantial
impact on LSPR, thus indirectly influencing the hot electron
injection. The full effect of all these factors will be discussed in the Semiconductor
next sections. Apart from conventional factors, the hot electron
injection can be influenced by the hybridization of the unoccupied
Figure 4. Schematic illustration of electron-hole excitation in the semiconductor
states for several particular plasmonic systems. In a recent due to near field enhancement.
computational study, Long et al. showed that the hybridization of
the unoccupied states in the plasmonic metal and semiconductor
is significantly crucial for the injection of hot electrons [24]. For the near field enhancement mechanism, charge carriers are
Nonetheless, the effect of this factor requires further experimental selectively generated on the surface of the semiconductor rather
investigation. than in bulk due to the limitation of the near-field enhancement on
Although this process induces hot electrons with reasonably high the vicinity of the PNP surface [6a]. This shortens the travel
energy for the photocatalytic reaction, it can give rise to an pathway of charge carriers to the active sites, thus decreasing the
adverse effect on the photocatalytic activity. Lin et al. probability of charge-carrier recombination. Besides, the near
demonstrated that the hot electron injection from Au PNPs field enhancement can inhibit the electron-hole recombination in
accelerated the recombination of electrons generated in TiO 2 the nearby semiconductor, simultaneously accelerating the
under UV light, thus leading to a decline of photoactivity [25]. The charge carrier transfer [27].
reason is that hot electrons injected by LSPR may compensate
for and even surpass those transferred from TiO2 to the Au NPs. 2.2.3. Other mechanisms
Therefore, a proper light source is needed.
Plasmon-induced direct electron injection: Plasmon-induced
2.2.2. Resonance energy transfer (RET) mechanism via near direct electron injection (DEI) occurs when the dimension of PNPs
field enhancement is comparable to the electronic mean free path [3b, 20, 28]. In this
process, LSPR decays through another ultrafast dephasing
The near field enhancement mechanism results from the channel, known as chemical interface damping (CID). The
interaction of a semiconductor with the strong LSPR-induced interaction between PNPs and semiconductor induces dephasing
electric fields localized nearby the PNPs [3b, 6a, 8b, 23]. As mentioned through direct excitation of resonant electrons into the unoccupied
above, the large electric dipole generated upon light irradiation states located in the interface (interfacial states), as illustrated in
results in an enhanced electric field at the surface of PNPs. This Figure 5. These electrons then move out of the interfacial region
electric field increases the photoresponse and the electron-hole to initiate the redox reactions. This direct injection process has
generation within the nearby semiconductor. When near-field been experimentally demonstrated in several studies [28a, 29].
energy is higher than the bandgap of the adjacent semiconductor, Charge carrier transfer strongly depends on the electronic
it enables local electron excitation, leading to the formation of structure of the interfacial contact between PNP and the
electron-hole pair as shown in Figure 4. Since the electron-hole semiconductor. Also, the energy of excited electrons at interfacial
formation is proportional to the intensity of the electric field, its rate states should be higher than CB of the semiconductor to facilitate
can be significantly increased by several orders of magnitudes the electron transfer out of the interfacial region. The most
compared to that of regular light absorption [6a, 8b]. highlighted point of this mechanism is that charge carrier transfer
Measurement of photoluminescence emission is the typical overcomes issues of conventional hot electron injection such as
technique to support the near field enhancement mechanism [26]. the momentum-direction and timescale requirements in the PNP-
Based on this mechanism, three main factors can affect the semiconductor system.
energy transfer: the electric field of the incident light, the overlap
between LSPR and optical transitions of the nearby
semiconductor, and the near-field covered volume [2, 8, 11, 29]. The
energy of the near field is significantly dependent on the electric
field of the incident light while the latter two factors strongly relate
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removal cathodically charges PNPs, leading to the formation of
new (quasi) Fermi level (Ef’) which is raised above the dark Fermi
level (Ef) [35]. Figure 6 shows an example of the
charging/discharging mechanism of Au PNP. When CO 2 is
adsorbed on the PNP surface, hot electrons from the raised Fermi
levels of PNP are injected into the adsorbed CO 2 molecule,
simultaneously making the discharging of PNP and the CO2
reduction. In this process, the charging degree of PNP strongly
depends on the hole removal and the light source [35]. High photon
energy and light intensity induce more plasmon-resonant
excitation with a higher energy level of hot electrons while the
efficient hole removal lowers the electron loss due to the back-
Accepted Manuscript
recombination, resulting in a higher degree of charging with a
larger magnitude of the Ef’ rise. The adsorption of CO2 on to the
Figure 5. Schematic illustration of direct electron injection from a plasmonic
surface of PNP is also essential for the charging/discharging
nanoparticle (PNP) to a semiconductor via chemical interface damping (CID).
Reproduced with permission from ref [3b]. mechanism, similarly to the DEI mechanism above. Moreover, Yu
et al. showed that the CO2 adsorption promotes induced
shrinkage of its HOMO – LUMO gap (HOMO’ – LUMO’ as the new
CO2 as an adsorbate that can replace the semiconductor in the gap) (Figure 6) [35a]. This shrinkage coupled with the Ef’ rise,
DEI mechanism. The hot electrons can coherently scatter into facilitates an excellent efficiency of electron injection in the
unoccupied states of CO2 molecules adsorbed onto the PNP adsorbed CO2 molecules. The most resemblance of the
surface [30]. This possibly triggers the vibrational activation of CO2 charging/discharging and DEI mechanisms are the direct electron
molecules for further bond dissociation and/or reduction injection to adsorbed CO2. This effectively restricts energy loss of
processes, which resembles recent studies [31]. The adsorption of the hot electron compared to the conventional charge transfer
CO2 on the surface of PNP, which is determined by several factors through semiconductor channels, thus can enhance the CO 2
such as plasmonic materials and reaction media, strongly reduction.
influences the electron scattering. In the chemisorption, the
hybridizations of CO2 electronic states with those of PNP induces
mixed-electronic states which have a partial character of PNP,
thus being delocalized into the PNP to some extent [32]. Electrons
are, therefore, easy to scatter into the unoccupied states. By
contrast, in physio-sorption, the electronic states of PNP and
adsorbate are mostly isolated, hindering the electron scattering
[32]
.
RET mechanism via dipole-dipole coupling: The dipole-dipole
coupling (DDC) mechanism is similar to the Förster resonance
energy transfer (FRET), where the plasmonic dipole replaces the
fluorescent donor [3b, 3d, 3g, 15]. In this process, LSPR energy is
transferred to the nearby semiconductor by coupling the
plasmonic dipole of PNPs and the electron-hole pair dipole in the
semiconductor. This RET directly excites electron-hole pairs in
the semiconductor non-radiatively through the relaxation of the
plasmonic dipole. Wu et al. experimentally investigated the DDC
mechanism in metal-insulator-semiconductor core-shell–shell
nanostructures using transient absorption spectroscopy to
monitor the energy transfer behavior [33]. This mechanism has
also been unified in a predictive model using a density matrix
approach in another computational study [34]. Figure 6. The charging/discharging mechanism of Au PNP in the presence of
In the DDC mechanism, RET is dependent on two factors: the isopropyl alcohol (IPA) as a hole scavenger. Reproduced with permission from
ref [35a].
dephasing time and the distance between the PNPs and the
semiconductor [33-34]. The occurrence of RET is more significant if
the dephasing time of PNPs is longer than that of the
semiconductor, while RET efficiency is higher at a decreased Structure of plasmonic photocatalysts not only influences specific
distance between the PNPs and semiconductors. Notably, RET is aspects of the LSPR energy transfer of each mechanism but also
found to be capable of generating electron-hole pairs at an energy determines the mechanism activated and then the location of the
below the bandgap of semiconductor [33]. This is highly surface reaction processes, which include the CO2 reduction and
advantageous for the massive increase in the light absorption of oxidation of electron donor. In plasmonic systems comprising only
the wide-bandgap semiconductors in coupling with PNPs, leading PNPs, the DEI (with CO2 as the adsorbate) and PNP
to a significant enhancement of solar conversion efficiency. charging/discharging mechanisms are dominant so that the
PNP charging/discharging: Under light illumination, the plasmon- surface reaction processes occur on the surface of the same PNP.
resonant excitation of electrons coupled with simultaneous hole Bringing PNPs in direct contact with a semiconductor additionally
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advances the LSPR energy transfer via the hot electron injection, The surface reactions on plasmonic photocatalysts are similar to
near field enhancement, DEI, and DDC mechanisms. An electron that on the conventional photocatalysts, including two essential
acceptor can replace the semiconductor in the plasmonic parallel processes: reduction and oxidation. The reduction begins
photocatalysts, but this replacement allows the activation of only from the surface adsorption and activation of CO2 followed by the
hot electron injection and DEI mechanisms. Two or more single-electron reduction to form the anion radicals CO2•–. It then
mechanisms of LSPR energy transfer can simultaneously occur proceeds through a series of elemental steps that involve the
in plasmonic photocomposites with appropriate structure. As such, transfer of generated electrons, protons, hydrogen radicals, the
the CO2 reduction can take place on the semiconductor surface cleavage of C-O, and the creation of C-H bond, resulting in the
or both semiconductor and PNP surfaces. This simultaneous formation of numerous intermediates and final products. The
occurring multiplies the efficiency of the LSPR energy transfer, surface adsorption and activation steps significantly determine
enhancing the photocatalytic reaction. Long et al. experimentally the entire efficiency of CO2 reduction. Detail of this process has
demonstrated the coupling of the hot electron injection and near been comprehensively discussed in our recent work [2l]. Up till now,
Accepted Manuscript
field enhancement mechanisms in the plasmonic system the effect of the LSPR on the surface CO2 reduction is limited. The
constructed by exposing Au PNPs on the [001] facets of anatase fast electron transfer, as a result of the LSPR, can conduct a
TiO2 nanosheets [36]. This coupling significantly increased the simultaneous reduction of various CO2 molecules, leading to the
electron-hole formation rate, resulting in a 64-fold improved accumulation of intermediates which promotes C-C coupling to
efficiency of the photocatalytic reaction. The mechanistic form 2C products [35a]. It is plausible that the LSPR may have other
determination of the energy transfer processes is necessary for significant effects on the surface CO2 reduction because of the
the structural engineering of plasmonic photocatalysts and/or the near-field enhancement and the local heat. The relax of hot
control of the reaction media to enhance the LSPR energy carriers can locally heat the PNPs and the semiconductor surface,
transfer and the CO2 reduction. The surface study of the facilitating the thermal activation of adsorbed CO 2 molecules [38].
plasmonic photocatalyst during the CO2 reduction indicates the The local heat can also increase kinetic energy, speeding up the
location of the surface reactions, coupled with characterization CO2 reaction. Nonetheless, there is some evidence
techniques of each mechanism as mentioned above, can reveal demonstrating that these effects may be negligible. For instance,
the exact energy transfer processes. For the surface study, it has been reported that the difference between the local
several techniques have been employed such as transient temperature at the NP surface and the temperature of the medium
absorption measurement, scanning tunneling microscopy [37]. is slightly under the continuous-wave light illumination [39]. Clear
Besides, from the perspective of timescale, the LSPR energy evidence, characterization, and computational model of these
transfer is completed instantaneously while the surface reactions effects are, therefore, needed in further studies. At plasmonic hot
are relatively slow, thus making the CO2 photoreduction spots, the enhanced electric field can polarize CO 2 molecules,
ineffective. The use of sacrificial electron donors is an efficient simultaneously decreasing the activation energy, thus facilitating
strategy for this timescale drawback. It consumes holes and the chemical adsorption and then reduction of CO2 [40]. Also, the
prolongs the lifetime of hot electron enough for subsequent strong electric field can support the bond dissociation of the CO2
transfer and CO2 surface reduction. Another excellent strategy is molecules, simultaneously stabilizing key intermediates [40-41]. The
the use of rational architectures coupled with structural selectivity of formed products is, therefore, shifted. Notably, the
engineering, which promotes an efficient charge separation to LSPR-induced electric field can couple with an intrinsic inner
prolong the charge carrier lifetime. Also, they can enrich the effect electric field (IEF) created by particular semiconductors (field-field
of LSPR, simultaneously promoting advanced LSPR energy coupling) to effectively activate CO2 molecules. Zhao et al.
transfers, thus further enhancing the charge generation and experimentally proved that the field-field coupling in either Au- or
separation. On the other hand, rational architectures allow Ag- loaded ZnO nanosheet systems greatly intensified the
effective adsorption and activation of CO2 molecules, thereby surface polarization of ZnO nanosheets, charging negatively CO 2
speeding up their surface reduction with the generated electrons. molecules and making their O=C=O bonds bent [42]. The LSPR-
induced electric field can also promote the polarization and
2.2.4. Surface reactions subsequent dissociation of methane C-H bonds on the ZnO
surface, triggering the radical coupling reaction of activated
After the step of LSPR energy transfer, generated electrons and methane molecules to form 2C hydrocarbon products [42-43]. These
holes migrates to the surface active sites for the surface reactions. studies provide a smart strategy employing plasmon to achieve
For PNP-semiconductor plasmonic systems, the charge carriers an efficient and selective photoreduction of CO 2 into desired
continue to migrate in the semiconductor structure before products.
reaching the active sites. During this migration, the charge The oxidation involves the reaction of generated holes with
carriers can suffer unexpected processes of bulk and surface sacrificial electron donors to conserve the charge balance. On the
recombination which relates to undesired structural defects of the other hand, this process prevents the accumulation of generated
semiconductor [2l]. The charge carrier migration is also influenced holes inside the photocatalyst that can cause the back-
by surface band bending caused by the contact of the recombination of electrons-holes. The sacrificial electron donors
semiconductor with external media [2l]. These factors hinder the are a crucial component of this process. Small oxidation potential
charge carrier transfer toward the active sites to initiate the coupled with strong bind to the photocatalyst surface of the
surface reactions. For plasmonic systems comprising only PNPs, sacrificial electron donors makes their reaction with generated
PNPs play a dual role as charge generator and active sites for the holes highly favorable. Moreover, their presence reduces the
surface reactions, thus limiting the disadvantages of the charge kinetic limitation of the oxidation, advancing this process to
migration. effectively remove the generated holes [2b, 44]. The use of sacrificial
electron donors is consequently requisite for plasmonic
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photocatalysts because of the extremely short lifetime of the the sunlight spectrum, which distributes over a very long range
generated hot electrons. Currently, H2O is among the most widely of wavelengths from 200 nm to 2600 nm [2l]. By contrast, NPs
used sacrificial electron donor for the plasmonic CO 2 of metals such as Pt and Pd exhibit broad light absorption from
photoreduction [45]. It is abundant and able to play simultaneous the UV to the short wavelength of visible light, but their LSPR is
roles as the electron donor, H source, and reaction media. The significantly weak [48c, 48d].
use of water, however, increases the competition of H 2O
reduction, which decreases the efficiency and selectivity of the
CO2 photoreduction. This is due to the preferential adsorption of
H2O on the photocatalyst surface and its more negative reduction
potential compared to those of CO2 [2l]. On the other hand,
hydroxyl radicals (•OH) as an intermediate of the sequential water
oxidation possibly oxidize intermediates of the CO 2 reduction,
interrupting this process [2l, 46]. Utilizing co-catalyst can effectively
Accepted Manuscript
suppress H2O reduction, simultaneously increasing the CO2
reduction. Other employed sacrificial electron donors are
methanol [22f], i-propanol [35a] and triethylamine (TEA) [47]. Besides,
there are numerous other efficient sacrificial electron donors such
as ethanol, triethanolamine (TEOA), and ascorbic acid which can
use for the plasmonic CO2 photoreduction. The significant
advantages of these compounds are the high selectivity toward
the oxidation compared to water. Hence, they are highly
recommended for the oxidation reaction of the plasmonic
photocatalysts. Nonetheless, their oxidation induced by holes
may generate products that are considered as CO 2 reduction
products, owing to rich carbon content [44a]. Isotope labeling of
13
CO2 is, therefore, imperative to determine the exact pathway of
the products derived and quantify the CO2 reduction efficiency.
3. Critical features in the development of

plasmonic photocatalysts for CO2
photoreduction
Plasmonic materials, size and shape of PNPs, and contact Figure 7. (a) Light absorption of plasmonic metals (Al, Ag, Au, and Cu) and
between PNPs and semiconductors are essential features of the plasmonic conducting oxides (RuO2, AZO, and ITO) with the sunlight spectrum
development of plasmonic photocatalysts. These features have a plotted in the background. (b) Fermi level (EF), conduction band (Ec), valence
significant effect on the plasmonic properties of PNPs, governing band (Ev) and bandgap (Eg) of several metals, conducting oxides and wide-
bandgap semiconductors. Reproduced with permission from ref [3a].
the vital processes of the LSPR formation and LSPR energy
transfer. Moreover, they affect specific steps of the CO2 surface
reduction, thus determining the entire efficiency of the CO2
NPs of conducting oxides and semiconductors doped intrinsically
photoreduction.
display broader LSPR absorption, which simultaneously shifts to
longer-wavelength regions (Figure 7a), as compared to
3.1. Plasmonic materials
plasmonic metals. This is mainly because of their higher optical
losses [50]. Notably, the free carrier concentration of these
Choosing a plasmonic material is crucial for the development of a
materials can be tuned by altering the doping-element level,
plasmonic photocatalyst. Currently, there have been three typical
resulting in tunable light absorption. Conducting transition-metal
classes of plasmonic materials including plasmonic metals (Al, Ag,
nitrides, especially TiN, are new materials for plasmonic
Au, Cu, Pt, Pd, etc.), conducting oxides (RuO2, aluminum-doped
applications [51]. TiN NPs have a similar absorption efficiency as
zinc oxide (AZO) and iodine-doped titanium dioxide (ITO)) and
Au, but it exhibits a near-field enhancement along a broader
conducting transitional metal nitrides (TiN, ZrN, HfN, and TaN) [3a,
48] wavelength region, which can extend to 1600 nm as seen in
. Besides, several semiconductors and metal oxides doped
Figure 8 [51-52]. This near field enhancement covers a significant
extrinsically can have plasmonic properties such as Cu‐deficient
part of the sunlight spectrum.
chalcogenides (Cu2−xE, E=S, Se, Te) and O‐deficient transition‐
The electronic properties of plasmonic materials are the second
metal oxides (e.g., WO3-x and MoO3-x) [49]. Plasmonic properties
essential factor. Alignment of the Fermi level of the PNPs with the
are the first essential factor. A powerful LSPR advances the
bands of the semiconductor strongly affects the height of the
energy transfer process while a broad light absorption enhances
semiconductor–PNP energy barrier, and the density of available
solar energy harvesting. Possessing a relatively high carrier
states in the conduction band, which affects the efficiency of the
concentration, Al, Ag, Au, and Cu metal NPs exhibit strong LSPR
carrier injection process [33a]. The effect of Fermi level alignment
with sharp and intense LSPR peaks, as shown in Figure 7a [3a].
will be discussed in more detail in a later section. Generally,
Notably, Ag, Au, and Cu metals have a natural response to visible
proper alignment with the CB of semiconductors will favor an
light. Their LSPR is, however, significantly narrow compared to
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REVIEW
a b
Accepted Manuscript
c d
Figure 8. (a,b) Near-field intensity efficiencies, showing the field enhancement at the surface of the plasmonic particle, calculated for spherical Au and TiN
nanoparticles based on Mie coefficients; (c,d) Absorption efficiency, which is an efficient indicator for electromagnetic-to-heat energy conversion, for spherical Au
and TiN nanoparticles with various radius. Reproduced with permission from ref [51].
efficient charge carrier injection. Most of PNPs have lower Fermi Currently, Au and Ag are among the most common plasmonic
level than popular semiconductors (Figure 7b), requiring materials for photocatalytic reduction of CO2 due to the strong
photoexcited hot electrons with sufficient energy to enable their plasmonic properties. Nonetheless, their narrow LSPR absorption
injection to the semiconductor. The lower Fermi level can allow significantly limits the solar energy harvesting [2l]. Tailoring size
an opposite electron transfer from excited semiconductor to PNPs, and shape of their nanostructures are the most common
decreasing the plasmonic process efficiency, as mentioned above. strategies to promote light absorption. Pd and Pt nanostructures
Conducting oxides and transition metal nitrides have comparable have been widely used as co-catalysts rather than plasmonic
Fermi levels to CB of semiconductors, thus can favor an efficient components due to their weak LSPR. They are also vigorously
carrier injection to the semiconductors. active for H2 production – the most prominent side reaction that
The active surface toward CO2 adsorption and reduction is the competes and decreases the CO2 reduction. New light absorption
third crucial factor. It can simultaneously promote the direct CO 2 architectures have been recently developed that allowed Pt
reduction via PNP charging/discharging and DEI mechanisms, nanostructures to absorb the scattered light in the near field of the
and the CO2 reduction initiated by other common mechanisms dielectric surface of SiO2 support, thereby improving the LSPR
(e.g., hot electron injection), enhancing the entire efficiency. and shifting the LSPR absorption to longer wavelength region [56].
Metals such as Pt and Pd are highly active for CO 2 reduction as This development opens a promising approach not only to use
their surface actively promotes the chemical adsorption of CO 2 plasmonic nanostructures with weak LSPR but also to enhance
molecules [2k, 53]. The conducting oxides and semiconductors the LSPR absorption of other nanostructures for the CO 2
doped intrinsically present structural defects (e.g., oxygen photoreduction. On the other hand, alloying Pt and Pd into Au or
vacancies) that maintain a strong and stable CO2 adsorption since Ag could be another efficient approach to enhance
oxygen atoms of CO2 heal the vacancies, thus lowering the simultaneously the LSPR as well as the efficiency of the CO2
activation energy for CO2 reduction [37d, 54]. A selective surface reduction since the formed alloy PNPs possess full advantages of
toward the CO2 reduction can also suppress side reactions, each component [2l]. This is priceless for the design of the
simultaneously increasing the selectivity of desired products. Cu photocatalysts comprising only PNPs. Additionally, alloying can
surface is particularly favorable for binding CO as an essential induce a decline in the height of the Schottky barrier created at
intermediate of CO2 reduction rather than binding hydrogen [55]. the PNP-semiconductor interface that promotes a high transfer
The CO2 reduction is, therefore, more selective than H2 rate of the hot electron from PNPs to nearby semiconductors as
production while using Cu. Additionally, Cu has been mentioned in part below [57]. Moreover, alloying can tailor the
demonstrated to be highly selective for the CO2 reduction into surface nature of the formed alloy PNPs, making them more
hydrocarbon [2k]. Pt, Pd, and Au metals exhibit good selectivity for active and selective toward the CO2 reduction.
the CO2 reduction into CH4 while Ag metal exhibits good Alloying one metal with a proper proportion to another one is,
selectivity for CO production [2k, 53]. however, still a significant challenge due to several obstacles
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REVIEW
such as dissimilarities of used metal precursors and aggregation separation is consequently improved with a long lifetime of charge
of PNPs at high-temperature treatment. Conducting oxides carriers. Whereas, large Au PNPs induce a pronounced back
possess substantial advantages in term of light absorption, band transfer of electrons due to a large number of DOS. Wang et al.
alignment, and CO2 adsorption, but their photocatalytic activity is also proved that moderate Au PNPs not only promote the
rather low. This is because structural defects can become formation of charge carriers with sufficiently high energy but also
combination centers for the photogenerated electrons and holes induce a strong interaction with semiconductors, boosting the
[49]
. Control of defects via structural engineering is an effective charge transfer [64]. Determining the effect of PNP size on the hot-
strategy to enhance their photocatalytic performance. By contrast, electron generation and injection is, therefore, critical for the
TiN has been demonstrated to have good activity in photocatalytic development of plasmonic photocatalysts.
applications due to their efficient light absorption resulting from Besides, varying size can alter the nature of PNPs. As the particle
the LSPR [58]. Nonetheless, TiN has not been yet reported active size gets too large, PNPs can act as electron-hole recombination
for CO2 photoreduction. Moreover, the preparation of TiN requires sink, leading to a decrease of charge separation. They can also
Accepted Manuscript
rough conditions of synthesis, which is a big obstacle for structural hinder the exposed surface of a semiconductor to CO2 molecules,
engineering to enhance its photocatalytic performance. causing degradation of photoreaction. By contrast, bringing the
size of PNPs down too small can completely damp the plasmon,
3.2. Size of plasmonic nanoparticles making their plasmonic behavior disappear, simultaneously
converting them into NP co-catalyst.
Size has significant effects on the plasmonic absorption of the Regarding the mentioned effects, optimization of PNP size is
PNPs. An increase in particle size results in a broadening of LSPR critical to enhancing sunlight absorption as well as electron
peak due to the rise in the contribution of multipolar excitations [14, transfer of plasmonic photocatalysts for CO2 photoreduction. For
59] current CO2 photoreduction, most of the plasmonic photocatalyst
. It also gives rise to the domination of radiative decay such as
light scattering [18, 52-53]. For example, the plasmonic absorption has been commonly prepared by direct deposition of metal PNPs
wavelength of Au PNPs goes from 520 to 540 nm with an increase on the semiconductor surface via photo-deposition or chemical
in the ratio Cscat/Cabs from 0 to 0.65 as the size increases from 20 reduction [8c]. Notably, metal PNPs are usually formed with the
to 80 nm [14]. Because the light scattering is a faster process than shape of a sphere in these two approaches. The significant
the absorption process that requires interaction with lattice advantage of these two processes is that PNPs are uniformly
phonons, its domination causes a reduction of the light absorption dispersed on the semiconductor surface with good contact, thus
efficiency [59b]. The light scattering of PNPs can, however, be promoting the transfer of charge carriers. For the photo-
beneficial for improving light absorption of several plasmonic deposition process, the size of metal PNPs can be well controlled
structures containing large and uniform PNPs. The reason is that by the intensity of irradiated light and the concentration of metal
PNPs can act as nano-mirrors which scatter photons non- precursors. Incomplete reduction of the metal precursor, however,
absorbed by the semiconductor on the first pass through the results in the formation of impurities (e.g., metal oxide),
composite structure [60]. It, therefore, increases the average decreasing plasmonic properties of metal PNPs. For the chemical
photon path length in plasmonic nanostructures and reduction process, utilization of reducing agents (e.g., H 2, N2H4)
semiconductor composite, producing an increased rate of promotes a complete reduction of metal precursor to metal
electron-hole pair formation. nanoparticles, thus eliminating impurities. Nonetheless, the
The size of PNPs is critical for the hot electron generation and limitation of this process is size control due to the aggregation of
injection. Nonetheless, there exist different conclusions, giving PNPs during the chemical reduction. Synthesis of size-uniform
rise to a controversy on the influence of PNP size. Some studies PNPs followed by their surface loading on a semiconductor can
reported a positive effect of the particle-size increase on the be an effective strategy to address the issues of two those
electron generation and injection. As the size increases, the local approaches. The following step should be thoroughly carried out
electric field around PNPs is enhanced, resulting in an increased to obtain good contact with the semiconductor that facilitates
amount of hot electrons generated [61]. Also, according to Quian charge carrier transfer. Besides, other strategies of synthesizing
et al., large PNPs promotes an efficient electron injection to the photocatalysts containing well-dispersed uniform co-catalyst NPs
nearby semiconductor, whereas small PNPs lead to a low can apply for this preparation [2l].
injection efficiency of the hot electrons [12a]. Moreover, it was found
that the size of PNPs can tune the reduction potential of hot 3.3. Shapes of plasmonic nanoparticles
electrons injected [12a]. Accordingly, the large size of Au PNPs
allows an electron accumulation on the CB of TiO2 which The shape of PNPs significantly influences the number and
manipulates the reduction potential of those electrons. Meanwhile, location of the LSPR absorption peak. This is due to the difference
the buildup of hot electrons injected from small Au PNPs is in the number of resonant directions, which is varied with the PNP
insufficient to raise their reduction potential. By contrast, some shape [3e, 3f, 65]. For plasmonic nanospheres, the plasmonic
studies demonstrated that the particle-size decrease improves resonance of electron cloud is identical in all directions, resulting
the electron generation and injection. The recent theoretical in a single LSPR absorption peak (Figure 9a, b). Meanwhile,
calculation showed that small PNPs produce hot electrons in large plasmonic nanorods exhibit two LSPR absorption peaks
proportions [62]. In other words, the hot-electron generation rate corresponding to plasmonic resonance in longitudinal and
increases as the size of PNPs decreases. Notably, Teranishi et al. transverse directions (Figure 9c, d). Notably, the longitudinal
indicated that the decrease in the size of Au PNPs diminishes LSPR absorption of the plasmonic nanorods is broader and much
density states (DOS), thus increasing the entropic driving force for higher in intensity, simultaneously locating at a longer wavelength
the hot electron injection from Au PNPs to TiO 2, simultaneously than that of the plasmonic nanospheres. Similarly to plasmonic
reducing that for the back electron transfer [63]. The charge nanorods, PNPs with other shapes such as triangle, cube,
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REVIEW
(a) (b)
Accepted Manuscript
(c) (d)
Figure 9. Schematic illustration of plasmonic resonance and typical LSPR absorption peak for (a,b) plasmonic nanospheres; (c, d) plasmonic nanorods. Reproduced
with permission from ref [65b].
pentagon, and ellipsoid also display multiple-peak and red-shifted indirect strategy, including the first synthesis of non-spherical
LSPR absorption due to their plasmonic resonance in multiple PNPs followed by their loading on the semiconductor surface. The
directions [3e, 3f, 65-66]. Because of these advantages, the efficiency synthesis of non-spherical PNPs such as Au and Ag have been
of sunlight absorption is significantly enhanced. Nishijima et al. summarized in many excellent reviews [70]. However, the surface
showed that Au nanorods deposited on the TiO2 surface produced dispersion of PNPs and PNP-semiconductor interfacial contact
an enhanced long-wavelength absorption where incident photon- are significant challenges of this strategy. A non-uniform load of
to-photocurrent efficiency (IPCE) reached 8.4 % at 1000 nm while PNPs can cover the semiconductor surface, hindering the
being immersed in an electron-donor solution [67]. adsorption of CO2 while an undesirable PNP-semiconductor
The shape of PNPs also affects the near field enhancement. contact can hamper the charge carrier transfer. The approach of
Compared to spherical shape with the same volume, PNPs with loading or coating semiconductor on the surface of PNPs can
other shapes produce a significantly enhanced near field at the eliminate these challenges. The dielectric material coating is
location of abrupt shape change [3e, 49]. For example, spherical currently one of the most effective methods for loading or coating
PNPs decorated TiO2 provide an enhancement of near field in the semiconductor on the surface of PNPs [71]. The size or layer
order of 5 times, compared to the applied field, while this value is thickness of the semiconductor should be controlled to avoid the
determined to be 15 times in the case of plasmonic nanorods [68]. coverage that hinders the light absorption of PNPs.
The strong near-field can simultaneously enable processes of
LSPR energy transfer such as hot electron injection, near field 3.4. Contact between plasmonic nanoparticles and
enhancement, and even DDC, thus effectively enhancing electron semiconductor
generation and injection. By theoretical analysis, Kumarasinghe
et al. demonstrated that electron generation and injection of The contact between PNPs and semiconductors is an essential
plasmonic nanorods were several orders of magnitude higher factor for plasmonic photocatalysts. The form of PNP-
than those of spheres of similar volume due to stronger near semiconductor contact determines the mechanism of the LSPR
field enhancement [69]. energy transfer in plasmonic photocatalysts. Direct contact can
Plasmonic systems comprising non-spherical PNPs and enable a simultaneous energy transfer through both
semiconductors or substrate have been usually prepared via an
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Accepted Manuscript
Figure 10. Schematic of hot-carrier generation and collection over (a) Schottky and (b) Ohmic barriers. Band diagram schematics of (c) Au-TiO2 Schottky and (d)
Au-Ti-TiO2 Ohmic systems. Reproduced with permission from ref [73b].
mechanisms of hot electron injection and resonance energy than that of semiconductor, Ohmic contact is formed [73]. In the
transfers such as near field enhancement and DDC. For Ohmic contact, the height of the energy barrier is zero. This
example, Hou et al. demonstrated that near field enhancement contact is frequent for plasmonic photocatalysts containing
and hot electron injection occurred concurrently in an Au-TiO2 conducting transitional metal nitrides.
plasmonic photocatalyst with direct contact under visible light [45a]. Because of the energy barrier, the hot injection of the two contact
Meanwhile, resonance energy transfers are usually dominant in types is different. In the Schottky device (Figure 10a, c), where
the indirect contact between PNPs and the semiconductor with the Schottky barrier is present, only the high-energy electrons will
the presence of an interlayer. For instance, Zhao et al. identified have sufficient kinetic energy to overcome this barrier, thus
that near field enhancement was dominant in a photocomposite hindering the electron collection. The hot electron injection is
of Au NPs decorated TiO 2 with an Al2O3 insulating interlayer [72]. exclusively from hot electrons excited through intraband
Nonetheless, when the resonance energy transfers are unable excitation of metal PNPs [52c, 73b]. Despite that, the Schottky barrier
to occur due to the lack of spectral overlap between LSPR is valuable to prevent the back injection of electrons from
absorption and semiconductor absorption tail, the presence of an semiconductor to PNPs, thus leading to enhanced charge
interlayer makes the photocatalytic property disappear. The direct separation [74]. Meanwhile, Ohmic device has no energy barrier,
contact is therefore preferable in plasmonic photocatalyst design. allowing even low-energy electrons excited through interband
In plasmonic photocatalysts with direct contact of the PNP and excitation of metal PNPs, thus producing an enhanced collection
the semiconductor, the interfacial energy barrier strongly affects of hot electrons (Figure 10b, d), as compared to Schottky device
[52c, 73b]
the injection of hot electrons from PNPs to the semiconductor. . However, the absence of an energy barrier can give rise
Currently, there are two essential types of PNP-semiconductor to the back injection of hot electrons from semiconductor to PNPs,
contact, including Schottky and Ohmic contacts. Schottky contact causing a decrease in the photoactivity of plasmonic
is formed when PNPs are brought into contact with an n-type photocatalysts. Fortunately, the band bending resulting from
semiconductor whose Fermi level is higher than that of the PNPs Schottky contact is negligible for the semiconductors with a
[73]
. Upon contact, the Fermi level of PNPs is shifted to be equal nanosize dimension [2l, 75]. In other words, the height of the
to that of semiconductors, leading to an upward bending of CB Schottky barrier can be varied by reducing the semiconductor size.
and VB of the semiconductor at the interface. This bending This aspect is particularly valuable in nanostructure engineering
creates an energy barrier, which is the so-called Schottky barrier. to enhance the hot electron collection as well as the charge carrier
As mentioned above, the height of the Schottky barrier is separation of plasmonic photocatalysts.
strongly influenced by the alignment between Fermi levels of
PNPs and semiconductor [33a]. The Schottky contact is mostly
observed in plasmonic photocatalysts using plasmonic metals. By
contrast, when the Fermi level of PNPs is comparable to or higher
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REVIEW
photoreduction to CO with a yield rate of 1237 μmol g −1 h−1, ~ 29
folds higher than that of TiO2 NWs under visible light. In another
work, BiVO4 was brought in contact with TiO2 to form 1D/2D/2D
Au/TiO2/BiVO4 nanocomposites that exhibited exceptional visible-
light photocatalytic activities for CO2 reduction [45e]. The presence
of BiVO4 coupled with LSPR of Au promoted a higher rate of
electron generation, resulting in 30-fold and 60-fold
enhancements of photocatalytic efficiency compared to the BiVO 4
nanoflakes and the previously-reported BiVO4 nanoparticles,
respectively. Very recently, Kumar et al. reported the synthesis of
trimetallic Pt-nanodots (Pt NDs, 3–4 nm) and TiO2 (4–5 nm)
coated Au nanoparticles (Pt@TiO2–Au NPs) with spherical
Accepted Manuscript
dendritic shape, robust structure, and high colloidal stability for
CO2 photoreduction in the aqueous medium at room temperature
Figure 11. Shift of LSPR absorption with the increase in the embedded area of
[45c]
. The photocatalytic efficiency of Pt@TiO2–Au NPs was 312-
the Ag nanosphere into Mica shell (the surface area touching Mica). fold increased compared to bare Au PNPs where HCOOH was
Reproduced with permission from ref [76]. significantly formed with a chemical yield, and quantum yield of
3.12 and 1.84%, respectively. This is due to the high rate of hot
electrons transfer to Pt NDs, the increase in the surface area, and
Apart from electronic properties, the morphology of PNP- the broadening of the light absorption even to NIR.
semiconductor contact is another important factor. In plasmonic
photocatalysts, PNPs can be partially (or fully) enclosed into the
semiconductor. This embed changes the electric constant of the (a) (b)
surrounding medium, resulting in a red-shift of LSPR absorption
(Figure 11) [76-77]. Embedding PNPs into the semiconductor also
increases the portion of hot electrons in momentum space toward
the semiconductor, thus enhancing the hot electron injection [71b,
78]
. Regarding these advantages, the Janus structure has been
proposed as an efficient structure for broadband light absorption
and hot electron injection [79].
(c) (d) (e)

4. Plasmonic photocatalysts for the sunlight-
driven conversion of CO2
Au- and Ag-based photocatalysts are among the most studied

plasmonic photocatalysts for CO2 photoreduction. In an effort of
enhancing photocatalytic performance, alloy-based plasmonic
photocatalysts are also developed where PNPs (Au and Ag) are
coupled to each other or with another metal (e.g., Pt, Cu, and Pd).
Moreover, plasmonic Al and Cu NPs were recently used to
Figure 12. (a) TEM and (b) high-resolution TEM (inset) images of Au/TiO2 yolk-
prepare plasmonic photocatalysts with efficient performance. All shell hollow spheres. CH4 (c) and C2H6 (d) production amounts and their
of them are summarized in Table 1. production rates (e) of Au/TiO2 in comparison with P25 and TiO2 with a hollow
sphere structure. Reproduced with permission from ref [45d].
4.1. Gold-based plasmonic photocatalysts
Up to date, Au-TiO2 is among the most popular plasmonic Tu et al. prepared Au/TiO2 yolk-shell hollow spheres for the
photocomposite system which has been widely used for light- photocatalytic reduction of CO 2 [45d]. The LSPR of Au PNPs
driven conversion of CO2. According to Hou et al., LSPR of Au created an enhanced near field between them and TiO 2 that
NPs deposited on top of TiO2 resulted in a strong local electric boosted the generation and transfer of electrons to the surface of
field near the surface of Au PNPs that significantly improved the TiO2 upon the visible light absorption. Moreover, the yolk-shell
visible light absorption and increased the rate of electron-hole structure prevented the aggregation of Au NPs and detachment
generation [45a]. Photocatalytic activity of Au-TiO2 photocomposite of Au from the TiO2. Therefore, the CO2 photoreduction toward
was consequently 24-fold higher compared to pure TiO2 for CO2 CH4 is superior compared to the photocatalysts without Au
photoreduction in the visible range (532 nm). Coupling Au NPs (Figure 12). Notably, the rational yolk-shell structure promotes
with rational nanostructures of TiO2 is an exciting approach to the explosive accumulation of •CH3 radicals on the TiO2 surface,
enhance the efficiency of CO2 photoreduction. Tahir and his group which preferentially favors a dimerization process to generate C2H6. In
deposited Au NPs on TiO2 nanowires (NWs) and used this the same manner, Jiao et al. designed three-dimensionally
composite for CO2 reduction [45b]. The presence of Au NPs ordered macroporous (3DOM) TiO2-supported Au nanoparticles
significantly enhanced the visible light absorption and charge for application in carbon dioxide (CO2) photoreduction [80].
separation promoted by LSPR, resulting in an efficient CO 2 Because of the slow photon effect induced by a hollow structure
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Table 1. List of several plasmonic photocatalysts developed for CO2 photoreduction
Main Other
Photocatalyst Light source Plasmonic NPs Max yield Max yield Ref
product products
Green laser
Accepted Manuscript
Au-TiO2 350 mW/cm2 Au CH4 22.4[b] - - [45a]
(λ=532 nm)
300W Xe lamp
Au-3DOM TiO2 Au CH4 23.1[a] - [80]
(λ>420 nm)
Au-TiO2 NWs 35 W Xe car lamp Au CO 1237[a] CH3OH 12.65[a] [45b]
Pt@TiO2–Au Xe lamp HCOOH

[45c]
Au - - -
nanodendrites 5.71 W/cm 2
CH3OH
CH4 2.52[a]
Au@TiO2 yolk-shell 300W Xe lamp Au C2H6 1.67[a] [45d]
[45e]
Au/TiO2/BiVO4 300W Xe lamp Au CH4 - CO -
Au/g-C3N4 300W Xe lamp Au CO 13.17[c] CH4 3.10[c] [45f]
Au/g-C3N4 8W Hg lamp Au CO 77.5[c] CH4 38.5[c] [61]
300W Xe lamp
Au/ PPF-3 Au HCOOH 42.7[a] - - [81]
(λ>400 nm)
C2H6 27.0[a]
[42]
Au-ZnO Nanosheets 300W Xe lamp Au CO -
CH4 21.0[a]
Au NR@ZnO 300W Xe lamp Au CO 32.4[a] CH4 17.12[a] [82]
Xe lamp
[22f]
RGO/Au nanoparticles Au HCOOH - - -
5.71 W/cm2
LA-251 Xe lamp
Pt/Au-SiO2 0.6 W/cm2 Au CO 122.1[f] CH4 55.3[f] [83]
(300<λ<800 nm)
300W Xe lamp CH4 -

[35a]
Au NPs Au - -
2
300 mW/cm C2H6 -
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500W Xe lamp
Ag/TiO2 nanowire films Ag CH3OH 8.3[d] - - [84]
(λ>420 nm)
500W Xe lamp
Ag/TiO2 Ag CH3OH 405.2[c] - - [45g]
(λ>400 nm)
300W Xe lamp
Ag-TiO2 hollow-sphere Ag CH4 1.5[a] - - [85]
(λ>420 nm)
500W Xe lamp
24.4[c] 2.98[c] [86]
Accepted Manuscript
Ag-AgIO3 Ag CH4 CO
(λ>400 nm)
500W Xe lamp
Ag-Ag2SO3 Ag CH4 12.05[c] CO 4.94[c] [87]
(400<λ<800 nm)
Xe lamp
Ag@LixTiO2 nanocubes 100 mW/cm2 Ag CH4 42[c] - - [88]
(λ=420 nm)
300W Xe lamp
Ag/AgX (X=Ci, Br) Ag CH4 37.7[a] - - [89]
(λ>400 nm)
15W daylight lamp

Ag-AgCl/C3N4 Ag CH4 1.2[a] - - [90]
(400<λ<650 nm)
300W Xe lamp
Ag-CeO2 Ag CH4 100[a] CH3OH 35[a] [45h]
(λ>420 nm)
300W Xe lamp
Ag⊂Re3-MOF (400<λ<700 nm) Ag CO - - - [47]
Ag-NT-MnOx
300W Xe lamp
(NT: N-self doped TiO2 Ag CH3OH 0.53[a] - - [91]
(λ>400 nm)
microsheets)
Ag-MgO-TiO2 300W Xe lamp

Ag CH4 0.86[a] CH3OH 0.06[a] [92]
nanofibrous
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Ag-ZrO2 500W Xe lamp Ag CO 0.66[a] - - [93]
Ag-ZnO Nanosheets 300W Xe lamp Ag CO 25.0[a] CH4 - [42]
Accepted Manuscript
Xe lamp
Pd-Au/Al2O3 Au-Pd CH4 930.3[a] - - [94]
(λ>420 nm)
Pd-Au/TiO2 300W Xe lamp Au-Pd CH4 48.2[a] CO - [95]
1000 W Xe lamp
Au-Cu alloys/TiO2 Au-Cu CH4 2000[a] - - [45i]
AM 1.5 filter
Au3Cu@STO/TiO2 Hydro
300W Xe lamp Au-Cu CH4 3770[a] 725.4[a] [96]
nanotube arrays carbons
35W HID Xe lamp

Au-Ag/TiO2 nanowires Au-Ag CO 1813[a] - - [97]
20 mW cm−2
Pd-ZnO Nanosheets 300W Xe lamp Pd CH4 18.0[a] CO - [42]
500W Xe lamp
Cu/TiO2 Cu CH3OH 1.8[e] - - [98]
(λ>420 nm)
Al@Cu2O antenna Supercontinuum fiber laser

Al CO 360[e] - - [99]
heterostructures (400<λ<850 nm)
Ni modified Ni-Ge
300W Xe lamp Ni CO 9.3[a] CH4 3.5[a] [100]
hydroxide
(-) Parameters which were not mentioned in studies
[a] μmol g−1 h−1; [b] μmol m−2 g−1; [c] μmol g−1; [d] μmol cm−2; [e] μmol cm−2 h−1, [f] μmol g−1 min−1
coupled with LSPR of Au NPs, 3DOM Au-TiO2 photocomposite and used this composite for CO2 photoreduction [45f]. As the LSPR
exhibited a significantly high catalytic activity for the photocatalytic effect of Au NPs promoted hot electrons generation and visible
reduction of CO2 with H2O to CH4 under visible illumination. light absorption, Au-g-C3N4 photocatalyst exhibited a high
Au PNPs have also been brought in contact with other production rate of CH4, which was more than nine times that of
semiconductors. Li and co-workers deposited Au PNPs on g-C3N4 pure g-C3N4. Chen et al. reported the synthesis of thin porphyrin
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REVIEW
paddle-wheel framework-3 (PPF-3) nanosheets anchored with Au dependence of electron transfer on the light sources provides an
NPs, which exhibited a superior photocatalytic activity for effective strategy of using plasmonic photocatalysts for the
CO2 reduction to HCOOH [81]. The formation rate of HCOOH was controlled chemical bond formation and further the selectivity
determined to be 42.7 μmol g−1 h−1, being 4-fold higher than over toward desired products in CO2 photoreduction.
the pristine sample. As mentioned earlier, loading Au NPs on the
ZnO NSs created a field-field coupling that promoted an effective
solar-driven CO2 conversion with a 10-fold enhanced conversion (a)
efficiency and a selectivity toward hydrocarbons of 80% [42]. The
highest product yield reached up to 75.0 μmol g−1 h−1,
corresponding to a QE of 1.03% at Au loading content of 4.6%.
Surprisingly, C2H6 was largely generated (27.0 μmol g−1 h−1) in
addition to CH4 (27.0 μmol g−1 h−1). Very recently, Au-ZnO
Accepted Manuscript
plasmonic system with core (Au nanorod)-shell (ZnO) structure
was developed, which also produced high yields of CO and CH4 CH4
in the solar-driven CO2 reduction [82]. The Au nanorod core with
the LSPR effect not only extended the light absorption but also
contributed to the formation of CH4 generation. (b)
The combination of Au PNPs and an electron acceptor (e.g.,
graphene materials) produces a highly active photocomposite for
the CO2 photoreduction. Kumar et al. reported the preparation of
reduced graphene oxide-coated gold nanoparticles (RGO–Au
NPs) which reduced efficiently CO2 into HCOOH with excellent
selectivity (>90%) under visible-light [22f]. The quantum yield of the
reduction was 1.52%, superior to that of Pt-coated Au NPs C2H6
(1.14%). The excellent performance of RGO–Au NPs resulted
from the LSPR of Au PNPs and especially, the presence of RGO
layers. The LSPR induced an efficient generation of hot electrons
and their injection to RGO while the RGO presence promoted an
Figure 13. Mechanism for plasmon-assisted CO2 reduction into CH4 (a) and
ultrafast and efficient transport of these electrons to CO 2 reduction C2H6 under higher light intensity (b). RDS: Rate determining step. Reproduced
sites. Notably, the electron transport efficiency of RGO–Au NPs with permission from ref [35a].
was determined to be about 8.7 times higher than that of the Au
NPs.
Au PNPs have been used to reduce CO2 in the absence of the 4.2. Silver-based plasmonic photocatalysts
semiconductors and electron acceptors. Song et al. reported the
synthesis of Pt deposited Au NPs supported on SiO2 layer (Pt– Ag-based plasmonic photocatalysts are the second most used
Au/SiO2) for CO2 photoreduction through dry reforming of photocomposites for CO2 reduction. Liu et al. reported an
methane reaction [83]. Pt NPs acted as electron trappers and enhancement in photocatalytic reduction of CO2 with H2O using
active sites for CO2 reduction. LSPR created by Au NPs plasmonic Ag NPs deposited on TiO2 nanowire films (Ag/TiO2
effectively excited a high concentration of hot electrons, NWFs) [84]. Ag/TiO2 NWFs exhibited visible-light-harvesting
simultaneously reducing the activation energies for CO 2 reduction properties and effective charge separation due to the LSPR of Ag
∼30% below thermal activation energies upon the light irradiation. NPS coupled with the unique nano-wire structure of the TiO2 film.
Consequently, Pt–Au/SiO2 produced an enhanced CO2 Consequently, the activity of Ag/TiO2 NWFs was greatly
photoreduction rate, reaching 46.6 μmol g–1 min–1, which was 2.4 enhanced with CH3OH yield reaching 8.3 μmol cm−2 after 3 hours
times higher than that of the thermocatalytic reaction. Recently, reaction, corresponding to the energy efficiency of about 0.012
Yu et al. reported a multi-electron, multi-proton reduction of CO2 under UV-Visible light. In another work, Ag-loaded TiO2 (Ag/TiO2)
into CH4 and C2 hydrocarbons (e.g., ethane) using plasmonic Au nanocomposites were prepared using the microwave-assisted
PNP photocatalyst [35a]. The mechanism of this CO2 chemical reduction method [45g]. The optimal Ag content was
photoreduction is shown in Figure 13. The plasmonic excitation found to be 2.5% that enhanced the CH4 formation rate by nearly
of Au PNPs causes a hot electron to be transferred to adsorbed 9.4 times compared to the pure TiO2. Methanol yield was 405.3
CO2 to form an anion radical CO2•–. After this rate-determining μmol g−1 after 3 hours reaction, corresponding to the energy
step (RDS), this formed CO2•– proceeds through a series of hot- efficiency of 0.5%. Very recently, Do’s group studied CO 2
electron and proton transfer steps to generate CH4. When the light photoreduction of CO2 over Ag NPs anchored cubic phase LixTiO2
intensity and energy increase, more than one electron transfer [88]
. Ag NPs exhibited important roles for enhancing the efficiency
can take place within the surface residence time of adsorbed CO2 of CO2 conversion as well as the selectivity toward CH4 under
molecules, resulting in the simultaneous formation of two anion both UV and visible lights (Figure 14). Under UV light, Ag NPs
radicals CO2•–. The C-C coupling of these formed anion radicals acted as co-catalysts that trapped generated electrons from
followed by a series of hot-electron and proton transfer steps LixTiO2 to catalyze CO2 reduction. The yield of CH4 reached 49
results in the formation of C2H6. One of the most highlighted μmol g-1 after 10h of reaction, which was 8.2 and 1.5 times higher
points of this study is the plasmon-induced PNP charging, as than that of cubic TiO2 (6 μmol g-1) and Li0.075TiO2 (33 μmol g-1).
mentioned above, which allows an efficient electron transfer to Under visible light, Ag NPs induced a strong LSPR, coupled with
adsorbed CO2 molecules for their activation. Moreover, the oxygen defect sites on the Li0.075TiO2 lattice surface, promoting
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Accepted Manuscript
Figure 14. Mechanisms for the photoreduction of CO2 to CH4 on Ag@LixTiO2 photocomposite under (A) UV and (B) visible light irradiations. Reproduced with
permission from ref [88].
the charge separation, simultaneously prolonging the MnOx (0.37 μmol h−1 g−1). Similarly, co-loading Ag and MgO NPs
photocatalysts lifetime over a long period. CH4 yields of 42 and onto TiO2 nanofibrous exerted a great activity and selectivity of
34 μmol g-1 were respectively obtained after 10h under visible the CO2 photoreduction into CH4 [92]. The LSPR effect of Au NPs
lights of 420 and 620 nm. broadened the light absorption, simultaneously increasing the
Ag PNPs loaded on other semiconductors have also been studied local reaction temperature. MgO NPs acted as basic sites to
for CO2 photoreduction. He et al. reported the synthesis, enhance surface adsorption of CO2 molecules. The as-prepared
characteristics, and application of Ag supported AgIO3 (Ag/AgIO3) photocatalysts produced the highest CH4 production rate of
photocomposite for CO2 reduction with H2O [86]. Under visible light 0.86 μmol h−1 g−1 with an apparent quantum yield of 0.091%.
irradiation, Ag/AgIO3 photocomposite reduced CO2 to CH4 and
CO with considerably high turnover numbers (TON) of 1367 and
167, respectively. The estimated quantum yield for this CO2
reduction was about 0.19%. Ag/AgIO3 photocomposite displayed
a higher photocatalytic in comparison to N-TiO2, as shown in
Figure 15. The enhancement of photoactivity of
Ag/AgIO3 photocomposite is contributed to the LSPR induced by Ag
PNPs. Similarly, plasmonic Ag NPs supported Ag2SO3 was also
synthesized by Wang et al. [87]. At the optimum molar ratio of
Ag0/Ag+ of 5 %, Ag/Ag2SO3 photocomposite exhibited the highest
activity in CO2 photoreduction to CH4 and CO with a quantum
yield of 0.126 %, and energy returned on energy invested of
0.156 %. Choi et al. covalently attached Re I(CO)3(BPYDC)Cl,
BPYDC = 2,2′-bipyridine-5,5′-dicarboxylate, to a zirconium UiO-
67 and coated on Ag nanocubes (Ag⊂Re3-MOF) for CO2
photoreduction under visible light [47]. The CO2-to-CO
photoreduction was determined to be 7-fold enhancement due to
the intensified near field created by Ag nanocubes.
The method of co-loading Ag PNPs and another co-catalyst offers
an effective strategy to improve the CO2 photoreduction. Akple et
al. co-loaded Ag and MnOx NPs onto the exposed [101] and [001] Figure 15. Time dependence of CH4 and CO yields over
facets of N-self-doped anatase TiO2 microsheets (NT), Ag/AgIO3 photocomposite and N-TiO2 under visible light. The inset shows the
respectively, via the photodeposition [91]. This co-loading induced time dependence of CH4 and CO yields over AgIO3 under UV-vis light.
Reproduced with permission from ref [86].
a spatial separation of electron-hole pairs. Also, the near field
enhancement created by the LSPR of Ag NPs significantly
accelerated the charge transfer, improving further the charge
The LSPR of Ag PNPs can create a local heat that assists the
separation efficiency. As a result, the prepared photocatalyst with
CO2 photoreduction. Zhang and colleagues showed that, for the
co-loading of Ag and MnOx NPs exhibited an enhanced CO2
CO2 photoreduction in the presence of H2 on Ag loaded ZrO2
photoreduction into CH3OH (0.53 μmol h−1 g−1), in comparison
photocatalyst (Ag-ZrO2), the local heat created by the LSPR of Ag
with photocatalysts loaded alone with Ag (0.35 μmol h−1 g−1) and
NPs effectively activated H2 molecules to form H species
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REVIEW
supplying to the CO2 reduction on ZrO2 surface sites [93]. CO was (a) (b)
efficiently generated at a rate of 0.66 μmol h−1 g−1 with
approximately zero-order kinetics. Ag-ZrO2 could also induce CO2
photoreduction to CO at a limited rate with the addition of Mg2+
using moisture. Many other Ag-based plasmonic photocatalysts Au-Cu
recently developed for CO2 photoreduction are summarized in alloy NP
Table 1.
TiO2
4.3. Alloy-based plasmonic photocatalyst
Alloying another metal into Au or Ag PNPs is an efficient approach

to enhance photocatalytic performance as well as the selectivity
(c)
Accepted Manuscript
toward desired products of plasmonic photocatalysts.
Neatu et al. reported that alloying adequate proportions of Cu into
Au NPs loaded on TiO2 created an extremely efficient
photocatalyst for the sunlight reduction of CO 2 to CH4 in the
presence of H2O [45i]. Au-Cu/TiO2 exhibited a remarkable rate of
CH4 formation, reaching above 2000 μmol g−1 h−1 with an
excellent selectivity of up to 97% over H2. The CH4 formation rate
of Au-Cu/TiO2 was determined to be 50 times higher than non-
loaded TiO2 and nearly 8 and11 times higher than those of single
Cu and Au loaded TiO2 materials, respectively. The excellent
photocatalytic performance resulted from the synergy of
enhanced light absorption and electron generation promoted by Figure 16. (a) TEM image of Au-Cu/TiO2 (Au/Cu ratio 1:2), (b) High-resolution
LSPR of Au and high selectivity toward CO2 reduction of Cu. The TEM image of one Au–Cu alloy nanoparticle (NP) and (c) Charge transfer and
superb contact of Au and Cu atoms in alloys NPs facilitated a fast product distribution on Au-Cu/TiO2 photocatalyst under visible light. The bottom
electron transfer from Au atoms to Cu atoms rather than CB of part presents a plausible route for methane generation in the CO 2
photoreduction. Reproduced with permission from ref [45i].
TiO2, thus eliminating H2 formation which occurs mainly on TiO2
surface (Figure 16). Alloying Cu into Au NPs loaded on
SrTiO3/TiO2 coaxial nanotube arrays was also found to improve
4.4. Other plasmonic photocatalysts
the CO2 photoreduction to CO and hydrocarbons in the presence
of hydrous hydrazine (N2H4) [96]. Under the UV/Vis-light
Cu- and Al-based plasmonic photocatalysts have been recently
illumination using diluted CO2 (33%), Au3Cu@STO/TiO2
reported for CO2 photoreduction. Liu et al. reported a simple
nanotube arrays photocatalyst generated CO and hydrocarbon at
strategy to fabricate plasmonic Cu modified TiO2 flower films for
very high yield rates of 3.77 mmol g -1 h-1 and 725.4 µmol g-1 h-1,
CO2 photoreduction to methanol [98]. In the presence of Cu NPs,
respectively, which were much higher than those of STO/TiO 2
visible light absorption and the Raman scattering of TiO 2 were
nanotube arrays using single Au and Cu NPs. Nonetheless, the
significantly enhanced by the Cu NPs due to their LSPR
role of Au was determined to be preferable for electron transfer
absorption, as shown in Figure 17A. Also, this LSPR increased
from STO/TiO2 to Cu atoms rather than light harvester and
the energy of trapped electrons, allowing them to react with
electron generation even though the LSPR gave rise to visible
adsorbed CO2 molecules efficiently. Moreover, Cu NPs effectively
light absorption. In another work, Liu et al. alloyed Au into Pd
suppressed the electron-hole recombination, simultaneously
PNPs supported on Al2O3 to improve catalytic performance in CO2
improving the charge transfer efficiency. Consequently, a high
reduction under visible light [94]. The LSPR of Au concurrently
yield rate of CH3OH was obtained, reaching 1.8 μmol cm−2 h−1,
promoted the light absorption in the visible light region and
which was 6.0 times higher than that over a pure TiO2 film (Figure
facilitated the electron-hole separation. Additionally, the presence
17B).
of Au changed the electronic structure of Pd to an electron-
deficient one, which favored the stability of the photocatalysts.
Consequently, a high CH4 yield of 930.3 μmol g−1 min−1 was
obtained over Pd90Au10/Al2O3 photocatalyst under visible light.
Owing to the excellent plasmonic properties generated, coupling
Au and Ag in alloy structures can result in a significant
enhancement of CO2 photoreduction. Tahir et al. reported that Au-
Ag alloy NPs loaded TiO2 NWs exhibited an improvement of
visible light absorption compared to that of single Au and Ag NPs
loaded TiO2 NWs as the LSPR peak became broader in
wavelength and higher in intensity [97]. On the other hand, Au-Ag
alloy NPs can act as both plasmonic NPs and electron sink
depending on their particle size, allowing an effective charge
generation and separation. As a result, CO was formed at a
remarkable rate of 1813 μmol g−1 h−1, which was 73-fold
increased compared to the bare TiO2 NWs under visible light.
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REVIEW
g−1 h−1, respectively, under visible light. Notably, CO can be
A formed at a rate of 3.8 μmol g−1 h−1 even under infrared light
irradiation.
Accepted Manuscript
B
Figure 18. Structure and mechanism of plasmon-induced carrier-assisted CO2

reduction over Al@Cu2O antenna-reactor geometry. (a) Energy band diagram
of Al@Cu2O for plasmon-mediated carrier generation for injection into the
unoccupied state of CO2 for C–O bond activation. (b) Schematic of plasmon-
induced carrier-driven CO2 reduction on Al@Cu2O Reproduced with permission
Figure 17. (A) UV–vis diffuse reflection absorption of 0.5 Cu/TiO2 film, inset is from ref [99].
LSPR absorption of the Cu NPs in the reaction solution. (B) The CH3OH
production rate of photocatalytic reduction of CO2 under UV and visible light
irradiation for 3 h (λ > 420 nm). Reproduced with permission from ref [98].
5. Approaches of plasmonic photocatalyst
design for CO2 photoreduction
Robatjazi et al. reported earth-abundant aluminum embedded in
cuprous oxide antenna-reactor heterostructures that reduced CO2 To date, numerous plasmonic photocatalysts have been made for
more effectively and selectively compared to conventional CO2 photoreduction. Their structural design has mostly followed
thermal reduction [99]. This unique geometry efficiently harnessed several common architectures in which PNPs are loaded on
the plasmon resonance of Al to supply energetic hot-carriers, semiconductor thin film and 1D/2D nanostructures such as
simultaneously increasing optical absorption in cuprous oxide for nanowires or nanosheets, according to studies discussed above.
selective CO2 reduction to CO under visible light. The CO There are still many other advanced plasmonic architectures that
formation rate was determined to be about 360 µmol cm–2 h–1, have occasionally been studied for CO2 photoreduction yet. On
corresponding to a quantum efficiency of 0.35%. Mechanism of the other hand, structure engineering has seldom been reported
CO2 photoreduction over Al@Cu2O antenna-reactor geometry is in the plasmonic photocatalyst design. Several advanced
shown in Figure 18. This study provides a sustainable route to architectures and structure engineering strategies with
high-value chemicals and promotes the practical potential of corresponding advantages are provided in this section. Their
plasmon-mediated chemical transformations. implementation is highly desirable for an efficient photoreduction
The LSPR of Ni NPs is rarely reported for photocatalytic of CO2.
applications. Nonetheless, Xin et al. recently synthesized Ni
modified low-crystalline Ni–Ge containing hydroxide with Lewis 5.1. Advanced architectures for plasmonic photocatalyst
acid sites for CO2 photoreduction [100]. The LSPR of Ni NPs design
resulted in wide-spectrum light absorption extended even to near
IR region. Coupling with Lewis acid sites that activated C O Semiconductor hollow sphere is one of the advanced designs with
bonds to decrease the kinetic barriers of CO 2 reduction, the enhanced light scattering. A hollow sphere introduces slow
prepared photocatalyst exhibited an efficient reduction of CO 2 photons by multiple scattering of incident light within the hollow
with CO and CH4 formation rates of 9.3 μmol g−1 h−1 and 3.5 μmol cavity that can significantly improve the LSPR absorption of PNPs
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(a) (b)
Accepted Manuscript
Figure 19. Light scattering of (a) Au/TiO2 yolk-shell structure and TiO2 hollow structure, and (b) 3D‐array and disordered Au–TiO2 yolk-shell structure. Reproduced
with permission from ref [101].
and thus leads to the production of more electrons [102]. For produced a high photoconversion efficiency reaching 0.52%
example, Zhang et al. showed that light absorption of under simulated sunlight illumination [57b]. Photoconversion
plasmonic Au NPs loaded hierarchical hollow porous efficiency can even reach more than 1% while depositing Au NPs
TiO2 spheres was increased by 21% compared to non-hollow on TiO2 dendritic nanorod arrays [106]. This enhancement is mainly
structure [103]. Notably, multiple-shell hollow spheres and ordered due to the introduction of single-crystalline branches and
assembly of hollow spheres can multiply the light scattering, backbones that act as excellent transport corridors for injected
further enhancing the LSPR absorption (Figure 19) [10a, 80, 101-102]. electrons. Additionally, the branched nanostructure allows PNPs
On the other hand, due to porous structure with closely packed to have much higher light absorption compared to PNPs coated
interpenetrating networks, this structure exposes a very high onto non-branched nanoarrays. The oriented nanostructure also
specific surface area with numerous active sites for CO 2 reduction, suffers from the stability issue caused by the breakage of 1D
and an efficient of charge carrier transfer [102]. Its porous structure nanostructures with small diameter and thin structure [2l].
coupled with a hollow cavity allows effective capture and Increasing diameter can reduce the structural damage and
adsorption of CO2. Only a few plasmonic photocatalysts based on improve the stability of 1D nanostructures.
hollow structure have been utilized for CO2 photoreduction to date Core-shell structure composed of PNP core and semiconductor
[45d, 80, 104]
. The primary issue of hollow spheres is their stability that shell is considered as one of the most efficient architectures of
relates to the hollow shell. A thin shell enables an enhanced plasmonic photocatalysts. This structure provides an intimate
charge transfer with faster mobility, but it makes hollow spheres PNP-semiconductor contact, simultaneously maximizing the
fragile. A thick shell, however, increases charge recombination portion of hot electrons in momentum space toward the
though it improves the stability. Controlling shell thickness is, semiconductor, thus facilitating an efficient injection of hot
therefore, critical for the design of the hollow spheres. The layer- electrons [78b]. Simultaneously, the core-shell structure spatially
by-layer coating is a practical approach for shell thickness control confines semiconductor shell to the intensified near-electric field
and uniform deposition of PNPs onto the hollow sphere surface created by PNPs, which effectively promotes the LSPR energy
[10a]
. transfer via processes of near field enhancement and DDC [47]. As
Oriented nanostructures (e.g., nanorod, nanowire, and nanotube multiple LSPR energy transfer occurs, a superior rate of electron
arrays) is another advanced architecture to enhance the LSPR generation is achieved while a thin semiconductor shell allows a
energy transfer, especially the hot electron injection. The fast charge migration to active sites, thus inducing an excellent
vertically oriented topology of this architecture facilitates a fast photocatalytic performance. Similar to embedding PNPs into the
and directed electron diffusion along with the 1D structure, thus semiconductor, coating the semiconductor shell onto the PNP
enhancing the hot electron injection as well as electron lifetime. In results in a red-shift of LSPR wavelength, leading to an extension
other words, the timescale requirement of hot electrons is of light absorption over the visible light region. For example, the
therefore reduced or eliminated. For example, Au NPs coated on Ag@Cu2O core-shell NPs exhibited an enhanced visible light
the tips of ZnO nanorod arrays induced an efficient charge absorption and an efficient multiple LSPR energy transfer from Ag
generation and transfer, making a significant photoconversion to Cu2O [77]. Consequently, their photocatalytic activity under
efficiency of 0.48% [105]. Au NPs grafted TiO2 nanowire arrays visible light was comparable to that of pure Cu2O produced upon
resulted in a longer electron lifetime of two orders of magnitude, UV-light. Notably, the LSPR absorption shows stronger red-shift
enabling an enhanced photocatalytic performance [22c]. The as the shell thickness increases [77]. As the shell gets thicker, it,
hollow cavity of nanotube arrays improves the LSPR absorption however, resists the light absorption of PNPs, simultaneously
and CO2 capture, similar to the hollow structure mentioned above. increasing the charge recombination due to the more extended
A better injection of hot electrons can be achieved by depositing travel pathway of electrons to active sites. Shell thickness control
PNPs on three dimensional (3D) branched nanostructures. is critical in the core-shell structure design. The core-shell
Decorating Au NPs on 3D branched ZnO nanowire arrays structure also has other advantages such as nanosize with a high
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Accepted Manuscript
Figure 20. (a) Schematic illustration of anisotropic TiO2 growth on Au nanorods, (b) SEM image of the as-prepared Au-TiO2 nanodumbbells. Reproduced with
permission from ref [109].
surface exposure of semiconductor, and wide application range simultaneously excellent electron acceptors and active catalysts
of the synthesis for a variety of PNP shapes [107]. The high surface for CO2 absorption and reduction [109]. They can also effectively
exposure of semiconductor gives rise to more interaction with CO 2 cling to the surface of various PNPs through anchoring groups.
molecules. It also allows easy utilization of structural engineering PNP-MC will be, therefore, a newly efficient structure for CO2
to further enhance the CO2 photoreduction. Interestingly, photoreduction. In PNP-MC, the electron transfer process
according to Han et al., for Au NR@ZnO core-shell system, the significantly depends on the anchoring groups of MCs as well as
Au NR core is predominant for the hydrocarbon generation while the contact and distance between MCs and PNPs [2l]. The proper
the ZnO shell is the main part for the formation of CO in the CO2 structure design is needed to achieve the highest photocatalytic
photoreduction [82]. Moreover, adjusting either amount of the core performance.
or the shell thickness can tune the hydrocarbon generation. This Graphene-based plasmonic photocomposite: Graphene (G) and
is a critical point in the design of core-shell plasmonic its derivatives such as reduced graphene oxides (RGO) are
photocatalysts for a selective photoreduction of CO 2. Despite excellent materials in photocatalysis. The integration of graphene
major advantages, few plasmonic photocatalysts with core-shell materials with semiconductors was shown to facilitate a fast and
structure have been yet developed for CO2 photoreduction [22f, 47]. efficient electron transfer with low charge recombination [2l].
On the other hand, literature still reports a controversy that the Additionally, the high electronic conductivity of graphene
core-shell photocatalysts are unsatisfied with the charge refilling materials allows more electrons to reach to reductive sites where
as the shell blocks the access of holes to their reaction partner [71a, CO2 molecules are readily absorbed, leading to a more effective
71d]
. Resolving this issue requires further works. reduction of CO2 [2l]. Recently, PNPs integrated RGO in core-shell
The effort in addressing this issue led to the formation of structure have been reported for CO2 photoreduction with an
nanodumbbell as an evolutionary version in which the excellent photocatalytic activity resulted from the significantly
semiconductor is separately grown on the tips of nanorods [71a, 71d]. efficient electron transfer between PNPs and RGO [22f]. This result
Figure 20 shows the Au-TiO2 nanodumbbell structure formed by reveals the high potential of the PNP-graphene integration for the
the anisotropic TiO2 growth on Au nanorods as an example. The CO2 photoreduction.
nanodumbbells have a strong plasmonic interaction with the Among all advanced architectures above, oriented nanostructure
semiconductor, favoring an efficient charge generation and arrays and graphene-based plasmonic photocomposite are
transfer similar to the core-shell structure. Additionally, spatial considered to be more competitive as they allow practical
separation allows electrons and holes to be fully accessed by approaches of designing, offering a great chance of large-scale
reactant molecules, resulting in higher photocatalytic application. The oriented nanostructure arrays are an effective
performance. The plasmonic nanodumbbell is, therefore, a highly integration of 1D oriented structure and hollow structure that
desirable architecture for efficient CO2 photoreduction. The simultaneously enhance LSPR light absorption, charge
spatial-separated growth approach is also promising to design separation and transfer, and CO2 adsorption. PNPs can be
plasmonic architectures of PNPs with other shapes for CO2 selectively deposited on this architecture through simple
photoreduction. approaches (e.g., photo-deposition, ionic layer adsorption, and
Plasmonic nanoparticles sensitized metal-based molecular thermal-reduction). For the graphene-based plasmonic
complex (PNP-MC): PNPs are determined to be efficient photocomposite, graphene materials with typical functional
photosensitizers in addition to molecular and semiconductor groups favor a facile deposition of PNPs with an improved surface
quantum dot (QD) chromophores [22a, 24, 108]. This is due to the dispersion and intimate interface contact. Significantly, their
enhanced light absorption and the extremely rapid injection of hot excellent flexibility can enable their integration with PNPs in
electrons to molecular chromophores as the results of LSPR. various nanostructures such as core-shell, hollow structure, etc.
Nonetheless, there has been no report of plasmonic Nonetheless, graphene materials have an inherent disadvantage
photosensitized systems for CO2 photoreduction up till now. On of light-shielding effect toward the light, which decreases the light
the other hand, metal-based molecular complexes (MCs) are absorption of the plasmonic photocatalysts, leading to low
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photocatalytic activity. Controlling dosage of the graphene structural defects such as bulk vacancies can act as
materials in the photocatalyst system is among the simplest recombination centers that reduce the photocatalytic activity,
strategy which can relieve the light-shielding effect [110]. Reducing controlling defect type production is needed.
the dosage can, however, result in a loss of charge transfer Porous structure engineering: Making semiconductor structure
interface, also causing the decline of the photocatalytic activity. porous is an effective strategy as it enlarges the surface area,
Structure regulation of graphene material sheets (e.g. reducing providing more reductive sites for CO2 not only on the external
sheet size, etching in-plane holes) is a good option [111]. For this surface but inside the pores. Also, it provides rapid transport of
strategy, unnecessary filter-like portions are removed, allowing CO2 molecules, promoting high-efficient CO2 adsorption and
light to reach PNPs. Significantly, reducing sheet size is beneficial reduction [2l]. This strategy can be typically useful for the
for the attachment of graphene material sheets onto PNPs while construction of the plasmonic core-shell structure. The porous
etching in-plane holes enlarges the surface area of the layer of the semiconductor improves the access of reactant
photocatalyst system and accelerates the mass transfer. There molecules to react with holes in the PNPs, thus satisfying the
Accepted Manuscript
exist unfortunately several disadvantages. The structure charge refilling requirement and improving the photocatalytic
regulation can either damage or destroy the graphene structure, activity. The synthesis of porous materials and porous shell of the
causing loss of valuable properties. Moreover, the unavoidable core-shell structure has been extensively studied and discussed
exposure to light of graphene materials makes this strategy in several excellent reviews [107, 113].
fundamentally ineffective to reduce the light-shielding effect. Co-catalyst/photocatalyst heterostructure engineering: A co-
Developing rational designs by exploiting the excellent flexibility catalyst efficiently traps, and stores generated electrons,
of graphene materials is the most competitive strategy as it not promoting the charge separation [2k, 2l]. It also facilitates the
only minimizes the light-shielding effect but also induces protons transfer and promotes CO2 chemical adsorption [2k, 2l].
advanced features for enhanced photocatalytic performance. As Therefore, loading co-catalysts on the surface of plasmonic
mentioned above, the core-shell structure with PNPs (core) photocatalysts is highly desirable to enhance the CO 2
integrated to graphene materials (shell) is an excellent design for photoreduction. Up to date, there have been various simple
graphene-based plasmonic photocomposite [22f]. This structure methods for surface deposition of co-catalysts such as photo-
with a thin-graphene shell can effectively eliminate the light- deposition and impregnation. The component and structure of co-
shielding effect, simultaneously maximizing the LSPR mediated catalysts can be varied to obtain further enhancement of
electron transfer through a substantial intimate interface of PNP- photocatalytic activity.
graphene [22f, 112]. The deposition of PNPs onto the outer surface
of graphene hollow spheres creates another rational design that
maximizes the exposure of PNPs to light. Moreover, this 6. Conclusion
deposition is facilitated by functional groups of the graphene
materials. The development of rational designs, however, The plasmonic photocatalyst is among the most efficient
involves complex preparation procedures in parallel with hard photocatalytic systems for the photoreduction of CO2 into valuable
techniques, thus limited to large scale synthesis. fuels owing to its high solar utilization efficiency and the significant
improvement of the limitations compared to conventional
5.2. Advanced structure engineering for enhancing CO2 photocatalysts. A significant CO2 photoreduction process over
photoreduction of plasmonic photocatalyst plasmonic photocatalysts includes three steps: the formation of
localized surface plasmon resonance (LSPR), energy transfer,
Based on discussions over major processes and essential and surface CO2 reduction. LSPR has essential roles in the
features of plasmonic photocatalysts, many structure engineering performance of plasmonic photocatalysts since it promotes a wide
strategies can be used to improve their photocatalytic wavelength range and excellent light absorption, simultaneously
performance for CO2 photoreduction. facilitating an efficient energy transfer to semiconductors. In the
Semiconductor defect engineering: This strategy can significantly next step, the LSPR transfers energy to semiconductor through
enhance the charge generation and transfer by LSPR as well as four main mechanisms: hot electron injection, near-field
the CO2 reduction of plasmonic photocatalysts. The presence of enhancement, plasmon-induced direct electron injection, dipole-
defects in the semiconductor structure results in a reduction of dipole coupling, and PNP charging/discharging mechanisms.
bandgap corresponding to an extension of light absorption spectral Each mechanism has both advantages and disadvantages, which
range [2l]. This extension is improving the spectral overlap between are critical for structure design. This work also reviews, in detail,
LSPR absorption and semiconductor absorption tail, promoting four critical features for plasmonic photocatalyst design, including
the RETs concurrently to hot electron injection. As a result, hot plasmonic materials, size, and shape of PNPs and the contact
electrons are efficiently generated. Structural defects such as between PNPs and semiconductor. The optical and electronic
oxygen vacancies facilitate the charge separation process by properties of plasmonic materials strongly affect the light
allowing electrons to be trapped there, preventing the charge absorption, further solar utilization efficiency, and the formation of
recombination [2l]. They also play the role of absorption sites that contact type between them and semiconductor. The size and
strengthen and stabilize the absorption of CO 2 molecules, thus shape of PNPs directly contribute to LSPR and the energy
decreasing the activation energy of CO2 reduction [54]. As the transfer mechanism. The type and morphology of PNP-
electrons and CO2 molecules are readily trapped at the defect semiconductor contact play a decisive role in the LSPR energy
sites, the photoreduction of CO2 is significantly enhanced. transfer. In the next part, this work summarizes recently
Structural defects can be quickly produced via doping (e.g., metal developed plasmonic photocatalysts as well as their
and non-metal doping) and reduction of semiconductors using photocatalytic performance in CO2 photoreduction. Among
active reductive materials (e.g., H2, NaBH4). However, as various plasmonic systems, plasmonic photocatalysts based Au
23
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26
REVIEW
Entry for the Table of Contents
Accepted Manuscript
This article provides detail of the plasmonic CO 2 photoreduction, including significant steps. Four critical features for plasmonic
photocatalyst design such as plasmonic materials, size, and shape of plasmonic nanoparticles (PNPs) and the contact between PNPs
and semiconductor, are emphasized in-depth discussion. Furthermore, our perspectives of advanced architectures and structural
engineering for plasmonic photocatalyst design are put forward for the future achievement of an efficient CO 2 photoreduction.
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Chemistry–Sustainability–Energy–Materials

Title: Plasmonic photocatalysts for sunlight-driven reduction of CO2­:

Authors: Trong-On Do, Nhu-Nang Vu, and Serge Kaliaguine

To be cited as: ChemSusChem 10.1002/cssc.202000905

Link to VoR: https://doi.org/10.1002/cssc.202000905

ratio Cscat/Cabs is, therefore, essential for determining the CB

3. Critical features in the development of

(c) (d) (e)

Au- and Ag-based photocatalysts are among the most studied

Table 1. List of several plasmonic photocatalysts developed for CO2 photoreduction

Au-TiO2 NWs 35 W Xe car lamp Au CO 1237[a] CH3OH 12.65[a] [45b]

Pt@TiO2–Au Xe lamp HCOOH

Au/g-C3N4 300W Xe lamp Au CO 13.17[c] CH4 3.10[c] [45f]

Au/g-C3N4 8W Hg lamp Au CO 77.5[c] CH4 38.5[c] [61]

Au NR@ZnO 300W Xe lamp Au CO 32.4[a] CH4 17.12[a] [82]

Pt/Au-SiO2 0.6 W/cm2 Au CO 122.1[f] CH4 55.3[f] [83]

300W Xe lamp CH4 -

Ag@LixTiO2 nanocubes 100 mW/cm2 Ag CH4 42[c] - - [88]

15W daylight lamp

Ag⊂Re3-MOF (400<λ<700 nm) Ag CO - - - [47]

Ag-MgO-TiO2 300W Xe lamp

Ag-ZrO2 500W Xe lamp Ag CO 0.66[a] - - [93]

Ag-ZnO Nanosheets 300W Xe lamp Ag CO 25.0[a] CH4 - [42]

Pd-Au/TiO2 300W Xe lamp Au-Pd CH4 48.2[a] CO - [95]

35W HID Xe lamp

Pd-ZnO Nanosheets 300W Xe lamp Pd CH4 18.0[a] CO - [42]

Al@Cu2O antenna Supercontinuum fiber laser

(-) Parameters which were not mentioned in studies

Alloying another metal into Au or Ag PNPs is an efficient approach

Figure 18. Structure and mechanism of plasmon-induced carrier-assisted CO2

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Title: Plasmonic photocatalysts for sunlight-driven reduction of CO2: