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Plasmonic Heterostructure Functionalized with a Carbene-Linked

Molecular Catalyst for Sustainable and Selective Carbon Dioxide
Reduction
Hwiseok Jun, Shinyoung Choi, Joong Bum Lee, and Yoon Sung Nam*
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ABSTRACT: Hybridization of homogeneous catalytic sites with a photoelectrode

is an attractive approach to highly selective and tunable photocatalysis using
heterogeneous platforms. However, weak and unclear surface chemistry often leads
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to the dissociation and irregular orientation of catalytic centers, restricting long-

term usability with high selectivity. Well-defined and robust ligands that can persist
under harsh photocatalytic conditions are essential for the success of hybrid-type
photocatalysis. Here, we introduce N-heterocyclic carbene as a durable linker for
the immobilization of a Rubpy complex-based CO2 reduction site (cis-dichloro-
(4,4′-diphosphonato-Rubpy)(p-cymene) (RuCY)) on a p-type gallium nitride/
gold nanoparticle (p-GaN/AuNP) heterostructure. The p-GaN/AuNPs/RuCY
photocathode was coupled with a hematite photoanode to drive photoelectrochemical CO2 reduction along with water oxidation.
Highly selective CO2 reduction into formates, up to 98.2%, was achieved utilizing plasmonic hot electrons accumulated on AuNPs.
The turnover frequency was 1.46 min−1 with a faradic efficiency of 96.8% under visible light illumination (243 mW·cm−2). This work
demonstrates that the N-heterocyclic carbene-mediated surface functionalization with homogeneous catalytic sites is a promising
approach to increase the sustainability and usability of hybrid catalysts.
KEYWORDS: CO2 reduction, heterogenization, N-heterocyclic carbenes, photocatalysis, surface plasmon resonance

■ INTRODUCTION
High demand for clean, renewable energy resources has led to
an intensive study of efficient and sustainable photocatalysis, in
which sunlight drives the chemical transformation to produce
value-added products.1 A variety of molecular catalysts (e.g.,
complexes of cobalt,2 iridium,3 palladium, 4 rhenium, 5
ruthenium,6 etc.) have been studied as highly selective reactive
species because their catalytic activities are tunable by the
molecular manipulation of specified single reactive sites.7,8
However, homogeneous catalysis possesses demerits of slow
charge transfer rates9,10 and difficulty in the separation of the
reaction mixtures,11 which hinder their practical applications.
Consequently, with a conventional experimental setup, their
catalytic activity is generally limited to only 15−30 of turnover
number for tens of hours.12 Elevated pressure (50−150 bar) or
excess organic solvents (90%) has been adopted to upgrade the
performance.13,14
As another class of catalysts, metal−semiconductor-based
photoelectrodes have also been used because photoelectrodes
offer strong light absorption throughout the visible and
infrared regimes by band gap engineering15−17 and chemical
compatibility with a broad spectrum of solutions.18 Despite
such advantages, the inability to control the surface reactivity
to selective reaction pathways may limit the versatility of
heterogeneous photoelectrodes. The catalytic activity is
determined by the intrinsic properties of materials, which
makes it very challenging to optimize the catalytic perform-
ance.19,20 As a means to resolve the limitations, recent studies
on grafting molecular catalytic sites to a solid photoelectrode,
making a hybrid-type photoelectrode, have inspired researchers
in the field to harness both the tunable selectivity of molecular
catalysts and efficient light-harvesting and charge transfer of
photoelectrodes.21−23 Indeed, introducing a cocatalyst is
expected to be a promising strategy to achieve high selectivity
and catalytic activity because the specific catalytic site plays the
roles of (1) improving selectivity, (2) lowering overpotential,
(3) promoting charge separation, (4) enhancing CO 2
interaction, and (5) suppressing undesired reactions.24,25
Therefore, the hybrid-type photoelectrode exhibits synergistic
effects on ameliorations in the catalytic activity by instantly
transferring a high flux of photoinduced charge carriers to
molecular catalysts,26−28 increasing the ease of recovery and
reusability29 and securing high reaction selectivity toward the
desired product.30,31 However, there is the Achilles’ heel of the
Received: May 27, 2020
Accepted: July 8, 2020
Published: July 8, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsami.0c09517

33817 ACS Appl. Mater. Interfaces 2020, 12, 33817−33826
ACS Applied Materials & Interfaces
hybrid-type photoelectrode, which is the labile linkage
chemistry that cannot persist under harsh photocatalytic
conditions.32 Therefore, robust and sustainable immobilization
chemistry is essentially required to achieve high performance
of hybrid-type photoelectrodes for solar-to-chemical con-
version reactions.
N-heterocyclic carbene (NHC) ligands can functionalize a
metallic gold surface by generating a self-assembled monolayer.
NHC has almost double binding energy than that of Au ion,
∼343 kJ·mol−1, compared to thiol (170 kJ·mol−1), which is
widely used as a ligand for metal and semiconductor
nanoparticles.33 The bond strengths on the surface of metallic
Au, according to the previous studies,34,35 also imply that the
NHC moiety (149 kJ·mol−1) is a more plausible species than
thiol (126 kJ·mol−1) for stable immobilization of small
molecules. The high binding energy between Au and NHC
originates from the chemical properties of the filled sp2 orbital
of CNHC being a strong σ-donor and the empty p orbital of
CNHC being an acceptor for π back-donation.36 There have
been examples that manipulate the reactivity of metal catalysts
using NHC as a surface ligand.37−40 However, despite the high
energy benefits, it is exceptionally rare to use NHC as a linker
between two components that play different roles in hybrid-
type catalysts for intentionally controlled product alteration
and improved reactivity. The ultrastable and unreactive
properties of NHC against thermal, chemical, and electrical
stresses, therefore, led us to consider it as a new linker suitable
for the surface functionalization of plasmonic heterostructures
with molecular catalytic sites.40,41
Herein, we report the photoelectrochemical (PEC) reduc-
tion of carbon dioxide (CO2) into formates by ruthenium
complexes hybridized with a plasmonic p-GaN/gold nano-
particle (AuNP) heterojunction photoelectrode (Figure 1). We
Figure 1. Schematic illustration of the photoelectrochemical α-
Fe2O3/fluorinated tin oxide (FTO)∥p-GaN/AuNPs/RuCY full
reaction (a) and immobilization of RuCY on the surface of AuNPs
via NHC ligand (b).
aim to demonstrate that NHC is a promising candidate for
surface functionalization to develop sustainable hybrid-type
photocatalysts. The water oxidation reaction is driven at a
counter α-Fe2O3 (hematite) electrode consuming hot holes
that originate from the d-band of plasmonic AuNPs. The p-
GaN/AuNP heterojunction generates a Schottky barrier for
hot hole collection. The entire Z-scheme band structure is
described in Figure S1. Due to the shape of the band structure,
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holes are extracted to p-GaN and electrons are accumulated in
AuNPs and then spontaneously transferred to a CO2 reduction
catalytic site. cis-Dichloro-(4,4′-diphosphonato-Rubpy)(p-cym-
ene) (RuCY), a molecular catalyst for selective conversion of
CO2 to formates,42 was directly immobilized onto the surface
of AuNPs via NHC. The generated NHC-RuCY monolayer
could reduce the overpotential43 and surface resistance44 for
efficient hot electron transfer to convert CO2 at a smaller
reduction potential (−1.0 VRHE) than bare p-GaN/AuNP
photoelectrode (−1.8 VRHE).45 The immobilization of RuCY
and passivation of the gold surface via NHC ligands resulted in
successful alteration of the major product from CO generated
at the surface of AuNPs to the desired product, formates,
generated at RuCY. The full PEC reactions exhibited excellent
faradic efficiency (FE) (96.8%) and high selectivity (up to
98.2%).
■
RESULTS AND DISCUSSION
Plasmonic p-GaN/AuNP Heterostructure for Efficient
Hot Hole Collection. Hot electrons generated from metal−
semiconductor heterostructures have been extensively studied
for photocatalytic applications.42,46−50 The removal of hot
holes from the metal d-band to p-type semiconductors through
the heterojunction can affect the relaxation mechanism of hot
electrons in the metal sp-band, which can lead to the improved
performances of metal−semiconductor heterostructures.51,52
On the contrary, only a few studies have been reported on hot
hole collection to drive a catalytic reaction.45,53,54 The driving
force can be greater if hot holes are generated from the d-band
that has a large density of states.52,55,56 The strong oxidation
power of the holes can drive an oxidation reaction effectively
when transferred to the appropriate catalytic site compared to
the sp-band holes that have a relatively small energy.
Plasmonic gold nanostructures have an interband transition
threshold of ∼1.8 eV, and photons with energies below the
threshold only contribute to intraband transition (excitation at
the sp-band) producing hot electrons to overcome the barrier
height of the Schottky junction for n-type semiconductor.57,58
However, even if photons with energies higher than 1.8 eV are
received, very few hot electrons are transferred to the n-type
semiconductor because the d-band of Au is located more than
2 eV below the Fermi level (Figure S2a).58 However, the
excited d-band holes at the p-GaN/AuNP interface can be
easily transferred to p-GaN due to high energy over the barrier
height (Figure S2b).
As an sp-band-active plasmonic light-harvesting material,
therefore, we prepared a p-GaN/AuNP heterostructure by
depositing atomic Au layers onto an epitaxial p-GaN wafer on
sapphire using electron-beam evaporation (Figure S3a). The
bare p-GaN substrate is transparent and has no significant
absorption in the visible regime (>400 nm) (Figure 2a). The
fringes in the absorption spectra originate from Fabry−Pérot
interference, which is due to the high refractive index of GaN
substrate.59,60 Therefore, interference or undesired effects by
the p-GaN substrate are negligible under visible light
illumination. A broad absorption peak appeared around 700
nm after the deposition of Au layers with a thickness of 1.5 nm.
When the p-GaN/Au substrate was annealed at 300 °C, the
absorption maximum was blue-shifted to 570 nm, indicating
the formation of plasmonic AuNPs. The scanning electron
microscopy (SEM) image of p-GaN/AuNPs exhibits the
formation of AuNPs on the surface of p-GaN (Figure 2b), and
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Figure 2. Absorption spectra of photocathodes in the fabrication
process (a) and SEM image of the p-GaN/AuNPs (b).
their average diameter was ∼15.5 nm with 7.84 standard
deviation (Figure S3b).
RuCY Immobilization via N-Heterocyclic Carbene
Chemistry. RuCY is a ruthenium bipyridine complex that
serves as a molecular catalyst to selectively convert CO2 into
formates with high selectivity (∼95%) as reported in our
previous study.42 RuCY follows a proton-involving reaction
mechanism with an active [Ru−H]+ (ruthenium hydride
complex) form. NHC-functionalized RuCY (denoted as
“NHC-RuCY”) was prepared as described in the Experimental
Section and used for immobilization onto AuNPs via Au−
NHC linkages. The terminal groups of bipyridine were
transformed to possess propargyl moieties (−CCH) for
click conjugation with azide groups (−N3) in N,N′-diisopropyl
benzimidazolium carbenes, resulting in a highly stable triazole
bridge. Isopropyl groups at carbene-nitrogens are known to be
an optimal substituent to strengthen Au−CNHC binding with
no hindrance by bulkiness.43 The prepared NHC-RuCY was
self-assembled at the surface of AuNPs on p-GaN, as
confirmed by X-ray photoelectron spectroscopy (XPS) analysis
for Ru 3d and N 1s scans (Figure S3c).
To obtain evidence for strong and sustainable immobiliza-
tion of NHC-RuCY onto AuNPs, we carried out an
electrochemical analysis to examine the surface stabilization
effect of NHC ligand (Figure S4). Cyclic voltammetry was
performed in the range of −1.2 to +0.45 VRHE, which does not
cause the delamination of AuNPs from the substrate. The
changes of the largest current density at −1.2 VRHE in both
bare AuNPs and NHC-RuCY-modified AuNPs were limited to
<10% (from −1.08 to −1.13 μA and from −0.71 to −0.78 μA,
respectively) during 30 cycles of analysis. However, the
cysteamine-modified AuNPs exhibited over 40% of the
difference (from −0.44 to −0.74 μA). The result indicates
that the NHC-modified surface is much more stable than the
thiol-modified surface.
Next, we determined whether NHC can replace the thiol
ligand of cysteamine prelinked to AuNPs through a conven-
tional Au−S bond. The ligand exchange by NHC-RuCY was
analyzed using XPS (Figure S5). In the N 1s scan, the
population of nitrogen atoms increased because NHC-RuCY
has seven nitrogen atoms, while cysteamine has only one
nitrogen atom. The total counts of nitrogen atoms did not
increase seven times because of the larger surface coverage of
benzimidazolium carbene compared to cysteamine. No
significant sulfur 2p peak remained in the NHC-RuCY-treated
sample, indicating the complete elimination of cysteamine. The
Ru 3d scan also confirmed that the counts of carbon atoms
increased as the ruthenium signal was generated. The results
support the successful immobilization of NHC-RuCY on the
surface of AuNPs.
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Photoelectrochemical Analysis of p-GaN/AuNPs/
RuCY Photocathode. We determined the photovoltages of
the prepared heterostructures using a Pt foil as a counter
electrode under AM 1.5 illumination with a long-pass filter
(>400 nm). AuNPs on the p-GaN effectively absorb visible
light over 400 nm and produced hot carriers through the
interband transition. The p-GaN/AuNP heterostructure
exhibited a photovoltage of ∼720 mV, which was much higher
than the photovoltage generated at Au/TiO2 (∼200 mV)42
and over 55-fold higher than bare p-GaN (13 mV) (Figure 3a).
Figure 3. Open-circuit voltages of the bare p-GaN (black line (a)), p-
GaN/AuNPs (blue line (a)), and p-GaN/AuNPs/RuCY (red line
(b)). Two graphic panels are used because of different relaxation
kinetics.
The high photovoltage suggests that hot hole collection from
the p-GaN/AuNP heterostructure can more efficiently drive
photocatalytic reactions than hot electron extraction.61,62 After
the light was turned off, the photovoltage decreased slowly
because of efficient carrier separation with a low recombination
rate at the p-GaN/AuNP junction. The photovoltage of p-
GaN/AuNPs/RuCY increased linearly in the early stage of
light illumination (Figure S6). RuCY reduces protons to
construct a [Ru−H] complex, while the self-consumption of
hot electrons occurs at the photoelectrode.63 The photovoltage
was eventually saturated to ∼600 mV (Figure 3b).
We also examined the redox properties of each photo-
electrode using cyclic voltammetry. In the CO2-free buffer, p-
GaN/AuNPs exhibited a high photocurrent density of around
20 μA·cm−2 (Figure S7). However, the immobilization of
RuCY decreased the photocurrent density to 5 μA·cm−2, which
might result from the passivation of AuNPs by the self-
assembled RuCY monolayer in the absence of substances for
RuCY. p-GaN/AuNPs and p-GaN/AuNPs/RuCY exhibited
different reduction peaks and onset potential values in the
CO2-saturated buffer (Figure 4a). A weak reduction peak was
observed at −0.41 VRHE with an onset potential of +0.12 VRHE
for p-GaN/AuNPs/RuCY, while p-GaN/AuNPs exhibited a
peak at −0.87 VRHE with an onset potential of −0.06 VRHE.
Interestingly, the photocurrent density of p-GaN/AuNPs at
−1.2 VRHE significantly decreased from 20 μA·cm−2, in the
CO2-free buffer, to 3 μA·cm−2, in the CO2-saturated buffer,
and p-GaN/AuNPs/RuCY exhibited over 1.5 times larger
photocurrent density at −0.4 VRHE than p-GaN/AuNPs
(Figure 4b). The surface of AuNPs cannot easily convert
protons to molecular hydrogen in the presence of CO2 because
the molar concentration of protons was only 0.2 mM, while the
saturated molar concentration of CO2 was 41 mM in acetate
buffer at pH 3.7. The small reduction peak originated from
CO2 conversion into CO at the surface of AuNPs. p-GaN/
AuNPs produced CO as the major product with two-tenth of
H2 as a side product (Figure 4c). On the other hand, the
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Figure 4. Linear-sweep voltammograms (a) and chronoamperograms
at −0.4 VRHE (b) of p-GaN/AuNPs (blue lines) and p-GaN/AuNPs/
RuCY (red lines) in CO2-saturated acetate buffer (pH 3.7). The scan
rate was 50 mV·s−1 in (a). (c) Product analysis of photo-
electrochemical CO2 reduction with p-GaN/AuNPs and p-GaN/
AuNPs/RuCY. External bias: −0.4 VRHE; counter electrode: Pt foil;
light source: solar simulator AM 1.5 with a 400 nm undercut filter.
NHC-RuCY monolayer successfully altered the major product
from CO to formates even with a higher total amount of
products. The different reactivity might result from the
reduced work function of gold43 and the decreased resistance
at the electrode/electrolyte interface44 by the self-assembled
NHC-RuCY monolayer, promoting electron transfer for the
reaction.
To determine whether p-GaN/AuNPs/RuCY is a more
effective electron injecting electrode than nonfunctionalized p-
GaN/AuNPs, we employed electrochemical impedance spec-
troscopy (EIS) with an equivalent circuit (Figure 5a,b), where
Figure 5. Layouts of p-GaN/AuNPs (a) and p-GaN/AuNPs/RuCY
(b) for impedance spectroscopy with their equivalent circuits used to
fit the parameters, where “el” and “inter” indicate the electrode and
the electrode/electrolyte interface, respectively. Nyquist plots of p-
GaN/AuNPs and p-GaN/AuNPs/RuCY electrodes in a CO2-
saturated solution in the dark or under light illumination (c) and
under light illumination with or without the dissolved CO2 (d).
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R is a resistor and CPE is a constant phase element. The entire
Nyquist plots with detailed fitted parameters are described in
Table S1 and Figure S8. Notably, the plots in Figure 5c,d
indicate that both CO2 and NHC-RuCY increased the
interface resistance (Rinter) because CO2 has a higher reduction
potential than hydrogen, and the NHC-RuCY monolayer
blocks the direct contact of electrolyte with the highly
conductive Au surface. Besides, the resistance inside the
electrodes (Rel) increased in the dark when NHC-RuCY was
immobilized (entries 5 and 7 compared to entries 1 and 3,
respectively), which supports the work function-reducing effect
of surface functionalization.43 Moreover, the NHC-RuCY
monolayer also significantly decreased Rinter when p-GaN/
AuNPs/RuCY was exposed to the incident light. In the dark, p-
GaN/AuNPs/RuCY exhibited a very high Rinter of 3225 kΩ
(entry 7) while p-GaN/AuNPs showed only 674 kΩ (entry 3).
In contrast, Rinter of p-GaN/AuNPs/RuCY became even
smaller (237 kΩ, entry 8) than that of p-GaN/AuNPs (288
kΩ, entry 4) under light illumination. Since materials with a
small work function generally exhibit a low threshold voltage
and high electron mobility toward the electrolyte solution, the
NHC-RuCY monolayer on the surface of AuNPs promotes
electron transfer through the surface, and, consistently, RuCY
immobilized via NHC ligands in this work takes on the role of
efficiently delivering electrons to CO2 and suppressing the
undesired reaction that occurs directly at the Au surface.
Plasmon-Driven Photoelectrochemical CO2 Reduc-
tion and Water Oxidation. The p-GaN/AuNPs/RuCY
photocathode was coupled to a hematite (α-Fe2O3) nanowire
photoanode to conduct PEC full reaction, i.e., CO2 reduction
at the photocathode and water oxidation at the photoanode.
The hematite nanowires were grown on the surface of FTO-
coated glass according to a well-known hydrothermal method
(Figure S9a),64 and their water oxidation activity was analyzed
before the full reaction. The additional sintering of hematite
nanowires on the FTO substrate for Sn-doping was also
performed at 800 °C for 20 min to promote catalytic activity.64
The sintering process increased the current density from 1.7 to
121 μA·cm−2 (Figure S9b) while decreasing the oxidation
potential from +1.7 to +0.9 VRHE (Figure S9c).
The catalytic performance was examined at pH 6 under four
different external biases from −1.45 to −0.4 VRHE (Table 1 and
Figure 6a). The calibration data for product quantification are
presented in Figure S10, and it was confirmed through the
isotope-labeling study using 13CO2 that the source of formate
was carbon dioxide (Figure S11). The formate selectivity
decreased as side reactions, especially, the generation of
methanol that is a six-electron-requiring product increased
when a more negative potential was applied. The PEC full
reaction exhibited the maximum performance at −1.05 VRHE,
which is a faradic efficiency of 96.8% with a formate selectivity
of 91.8%. However, faradic efficiencies significantly decreased
above −1.05 VRHE (62.4% at −0.85 VRHE and 42.1% at −0.4
VRHE) despite very high formate selectivity (92.5 and 98.2%,
respectively). Thus, in the following experiments, the photo-
electrochemical reactions were conducted at −1.05 VRHE to
minimize the loss of electrical energy.
Chronoamperometry analysis indicates that the photo-
current depends on the externally added gaseous CO2. The
α-Fe2O3/FTO∥p-GaN/AuNPs/RuCY full reaction exhibited a
photocurrent density of ∼40 μA·cm−2 in the CO2-saturated
buffer though the photocurrent gradually increased (Figure
6b). In contrast to Figure 4b, where a Pt foil was used as a
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Table 1. Photoelectrochemical CO2 Reduction with Water Oxidation at Various External Biasesa
entry ext. bias/V (vs RHE) current/μA CO/nmol MeOH/nmol HCOO−/nmol formate selectivity/% FE/%b
1 −0.4 2.36 <10c
<1c
223 98.2 42.3
2 −0.85 8.83 <10c 33 1141 92.5 62.4
3 −1.05 15.11 60 71 3010 91.8 96.8
4 −1.45 19.74 119 181 3633 84.6 97.0
a
Results based on the average values from three independent reaction batches. Reaction conditions: electrolyte = 0.2 M phosphate buffer at pH 6
with CO2 saturation; reaction time = 12 h; and light intensity = 243 mW·cm−2 (Xe lamp, >400 nm). bFaradic efficiency was calculated by taking
the number of electrons required for each product. cConcentrations indistinguishable from noises in the spectrum.

Figure 6. Product selectivity with faradic efficiency at four different external biases for 12 h reactions (a) and photocurrent density (b) of α-Fe2O3/
FTO∥p-GaN/AuNPs/RuCY full reaction. The number of Ru atoms on the surface of p-GaN/AuNP substrates monitored during the reaction (c)
and stable i−t graph during 20 h of the reaction (d) at −1.05 VRHE.

counter electrode, the hematite photoanode exhibited slower
kinetics of water oxidation. After 5 min of standing by, the
steady-state photocurrent density was 61 μA·cm−2 (Figure
S12). Once the light was turned off, interestingly, the
photocurrent decayed in multistep kinetics exhibiting a 5−6
min delayed complete recovery to zero since shallow traps and
deep traps of the photoelectrode can hold the hot carriers for
up to thousands of seconds.65 The delayed current decay
occurred only in the p-GaN/AuNPs/RuCY electrode (Figure
S12).
Next, we examined the robustness of the NHC ligand and
the long-term stability of the hybrid photocathode. The
number of RuCY on the electrode was determined using
inductively coupled plasma mass spectrometry (ICP-MS)
(Figure 6c). The average amount of the immobilized NHC-
RuCY was 3.36 nmol, and no significant changes were
observed while thiol-linked RuCY molecules were detached
gradually, and physisorbed RuCY molecules were eliminated
within 2 h (Figure S13). The hollow point of HS-RuCY at 20 h
indicates the detached amount of Ru in the reaction solution.
The stable binding property of the NHC ligand on gold or
transition metal surfaces comes from the unordinary electronic
structure that allows the carbon atom to be divalent with a
highly directional sp2-hybridization,66 while thiol-based mono-
layers are prone to degrade because of their air and thermal
instability. The compared XPS survey scans also support the
chemical consistency before and after the reaction with no
significant difference in the ratio of Au, C, N, and Ru signals
(Figure S14). Due to the strong affinity and stability of NHC
on Au surface, simultaneous CO2 reduction and water
oxidation reaction were successfully conducted for at least 20
h without a decrease of the catalytic activity (Figure 6d).
We also confirmed the long-term stable catalytic activity by
quantitatively analyzing CO2-derived products and O2 evolved
at the photocathode and photoanode, respectively. The
product generated at the photocathode was mainly formates,
alongside small proportions (<3%) of methanol and CO
(Figure 7a). According to the calculation based on the number
of RuCY (∼3.36 nmol per a photocathode), the hybrid catalyst
exhibited a high turnover number of 1757 for 20 h, which
corresponds to a turnover frequency of 1.46 min−1 to produce
formates, while a similar photoelectrochemical configuration in
Figure 7. Photoelectrochemical CO2 reduction at p-GaN/AuNPs/
RuCY (a) and water oxidation at α-Fe2O3/FTO (b) in the CO2-
saturated buffer (0.2 M phosphate, pH 6) under visible light
illumination (>400 nm). External bias was −1.05 VRHE, and the
loaded amount of RuCY was 3.36 nmol.

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the most recent study using polymeric molecular catalytic site
exhibited an overall turnover number of 25 in 5 h with a faradic
efficiency of 85%.67 As the counter electrode, the α-Fe2O3/
FTO photoanode produced gaseous O2 by half the amount of
CO2 conversion products (Figure 7b). Because the faradic
efficiency of this reaction condition was 96.8%, the 2:1 ratio of
formate to oxygen was reasonable.
■
CONCLUSIONS
We presented the first example of the hybrid photocathode
design using carbene-based functionalization of a metal−
semiconductor heterostructure with molecular catalytic sites.
This work demonstrated that the p-GaN/AuNPs/RuCY
hybrid photocathode can efficiently collect plasmon-induced
hot holes via the Schottky barrier junction of p-GaN and
AuNPs and drive highly selective CO2 reduction for formate
production with simultaneous water oxidation by a hematite
photoanode under visible light illumination. The successful
immobilization of RuCY to the plasmonic photoelectrode was
achieved using strong and stable NHC chemistry. Due to the
work function lowering effect of AuNPs by the NHC
monolayer and resistance-reducing effect of the interface by
redox-active surface functionalization, ∼97% of the overall
faradic efficiency was obtained at the external bias of −1.05 V
(vs reversible hydrogen electrode (RHE)). The NHC ligand
provided a long-term stable surface layer to maintain the
catalytic activity over 20 h. We believe that the high selectivity
and stability of the carbene-linked hybrid electrode can lead to
advances in the field of solar-to-chemical conversion and
artificial photosynthesis.
■
EXPERIMENTAL SECTION
Synthesis of 5-Azido-1,3-diisopropylbenzimidazolium Io-
dide (Scheme S1). A mixture of 6-bromo-1H-benzimidazole (2.54
mmol), sodium azide (5.08 mmol), sodium ascorbate (0.13 mmol),
copper iodide (0.25 mmol), and ethylenediamine ligand (0.38 mmol)
was placed in a 50 mL round-bottomed flask containing 10 mL of
ethanol−water (7:3) solution. The reaction mixture was degassed and
purged with argon gas, and then stirred under a reflux condition for 3
h. After the designated time, the reaction mixture was allowed to cool
to room temperature, and the crude mixture was purified by
extraction with ethyl acetate and short flash column chromatography
to remove unreacted residue and impurities. Then, 6-azido-1H-
benzimidazole (1.57 mmol) and cesium carbonate (2.35 mmol) were
added to a 100 mL round-bottomed flask. Acetonitrile (25 mL) was
added to the flask followed by the addition of 2-iodopropane (4.71
mmol). The reaction mixture was heated to a reflux condition at 85−
90 °C and stirred overnight. The volatile chemicals were removed in
vacuo, and the residual solid was then extracted three times from the
ethyl acetate/water mixed solution. The combined organic layer was
then dried with anhydrous magnesium sulfate and then filtered over a
glass filter. The filtrate was concentrated under reduced pressure, and
the resultant viscous compound was added to a thick-walled sealed
tube. Neat 2-iodopropane (2 mL, 20 mmol) was then added to the
flask. The flask was tightly sealed with a Teflon screw cap and stirred
at 90−100 °C for 96 h. After the designated reaction time, the flask
was cooled to room temperature and the volatile 2-iodopropane was
removed in vacuo. Acetonitrile was added to dissolve the solid
completely. Around 30 mL of diethyl ether was then added to the
solution and stirred until precipitation ceased. The precipitate was
triturated by diethyl ether to give the product for the next step.
1
H NMR (dimethyl sulfoxide (DMSO)-d6, 300 MHz): δ 9.40 (s,
1H), 7.77 (d, 1H), 6.99 (d, 1H), 6.93 (s, 1H), 4.90 (m, 2H), 1.58 (d,
6H), 1.17 (d, 6H) (Figure S15).
Synthesis of cis-Dichloro-(4,4′-bis-propargylamido-Rubpy)-
(p-cymene) (Scheme S2). Oxalyl chloride (6 mmol, 3 equiv) and
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4,4′-dicarboxyl-2,2′-bipyridyl (2 mmol, 1 equiv) were dissolved in 10
mL of dichloromethane, and three drops of dimethylformamide
(DMF) was added to the solution. After 30 min, the solvent and
volatile components were removed by a rotary evaporator. Then, the
crude solid was redissolved in dichloromethane, and propargylamine
(2.2 equiv) and diisopropylethylamine (DIPEA, 3 equiv) were added
to the solution. The reaction mixture was stirred for over 12 h. After
the designated time of reaction, the mixture solution was quickly
filtered through a short silica gel column by negative pressure to
eliminate unreacted propargylamine, DIPEA, and DIPEA−H+ salt.
The residual solution was concentrated under reduced pressure and
dissolved in acetonitrile. Dichloro-(p-cymene)ruthenium(II) dimer
(2.1 equiv) was suspended in the solution. The heterogeneous
suspension was bubbled by Ar for 20 min, and then, the mixture was
refluxed for 4 h. After the designated time, the pot was placed in a
refrigerator at 4 °C for over 6−12 h to precipitate enough of the
suspended brown product. The precipitate was filtered and washed
three times with cold acetonitrile. The obtained solid was dried in a
vacuum oven at 40 °C for over 6 h to give cis-dichloro-(4,4′-bis-
propargylamido-Rubpy)(p-cymene).
1
H NMR (CDCl3, 300 MHz): δ 10.54 (d, 2H), 9.87 (t, 2H), 9.24
(d, 2H), 8.29 (m, 2H), 5.82 (d, 2H), 5.67 (d, 2H), 4.30 (s, 4H), 2.62
(m, 1H), 2.32 (s, 3H), 2.23 (s, 2H), 1.05 (d, 6H) (Figure S16).
Synthesis of cis-Dichloro-(4,4′-bis-(diisopropyl benzimida-
zolium-triazolyl)amido-Rubpy)(p-cymene) (NHC-RuCY Precur-
sor) (Scheme S3). The azide-terminated carbene precursor (100 mg,
0.27 mmol) and propargyl RuCY (84 mg, 0.14 mmol) were dissolved
in tetrahydrofuran (THF) (6 mL) and water (6 mL). CuSO4 (4% w/v
aqueous solution, 1.84 mL, 0.294 mmol) was added followed by the
dropwise addition of a freshly prepared sodium ascorbate solution (1
M aqueous solution, 0.59 mL). The reaction mixture was stirred at
room temperature for 2 h. After removal of THF under vacuum,
chloroform (10 mL) and conc. NH3 (3 mL) were added to the
solution, which was allowed to stir for an additional 30 min at room
temperature to quench all of the Cu(I) by complexation of
[Cu(NH3)6]. The aqueous phase was discarded and the organic
phase was washed twice with water and once with brine and then
dried with anhydrous MgSO4. The product was obtained after the
filtration of MgSO4 and the following solvent evaporation. The
residual solid was redissolved in DMSO (30 mg·mL−1), and 50 mL of
acetonitrile was slowly added to the solution using a dropping funnel
for over 1 h. The precipitate was washed with acetonitrile two more
times and dried in a vacuum oven at 40 °C for over 6 h.
1
H NMR (DMSO-d6, 300 MHz): δ 9.38 (s, 2H), 8.32 (s, 2H), 7.88
(d, 2H), 7.74 (d, 2H), 7.27 (s, 2H), 7.00 (d, 2H), 6.95 (s, 2H), 6.94
(d, 2H), 6.17 (m, 2H), 6.05 (m, 2H), 4.88 (m, 4H), 4.20 (d, 4H),
2.73 (m, 1H), 2.27 (s, 3H), 1.58 (m, 12 H), 1.22 (d, 6H), 1.15 (m,
12H). High-resolution mass spectrometry (HR-MS) (electrospray
ionization (ESI), m/z, [M − 2I]2+): calcd molecular weight (M.W.)
556.1873, found M.W. 556.1844 (Figure S17).
After the preparation of NHC-RuCY precursors, the active NHC-
RuCY was obtained by dissolving in THF, followed by slow addition
of 1.1 equiv potassium tert-butoxide (t-BuOK) in an ice bath. The
reaction was stirred for 30 min, and then, THF was evaporated under
reduced pressure. The resulting solid was redissolved in DMSO and
used for surface modification. The solution (5 mg·mL−1 in DMSO) of
activated NHC-RuCY was placed in a 24-well plate carrying the p-
GaN/AuNPs substrates. Then, the molecular catalyst was immobi-
lized onto the surface of AuNPs during shaking incubation at room
temperature for over 12 h.
Synthesis of 4,4′-Dithiazolidine-2,2′-bipyridine (Scheme
S4). A suspension of 4,4′-dicarboxaldehyde-2,2′-bipyridine (500 mg,
2.356 mmol) in 30 mL of absolute ethanol was slightly heated to
obtain a clear solution. Another 10 mL of ethanol solution of
cysteamine hydrochloride (802 mg, 7.068 mmol) was neutralized by
addition of trimethylamine (1.03 mL, 7.421 mmol) and was then
added to the bipyridine solution. The mixture solution was refluxed
for 6 h and cooled to room temperature. After the cooled mixture was
filtered to remove undissolved substances, the solvent was removed by
a rotary evaporator. The residual solid was redissolved in 50 mL of a
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ACS Applied Materials & Interfaces
1:1 mixed solution of water and dichloromethane, and the organic
layer was extracted three times. The collected organic solution was
dried by anhydrous magnesium sulfate, filtered, and concentrated by a
rotary evaporator. Fifty milliliters of a 1:1 mixed solution of ethanol
and diethyl ether was added to the residue, and the mixture was
heated until the solution become clear. Standing still for 1 h at room
temperature for slow cooling gave a pale-yellow precipitate, and the
solid was washed with cold diethyl ether three times.
1
H NMR (CDCl3, 300 MHz): δ 8.64 (d, 2H), 8.50 (s, 2H), 7.41
(d, 2H), 5.66 (s, 2H), 3.48 (m, 2H), 3.28 (m, 2H), 3.11 (m, 4H)
(Figure S18).
Synthesis of 4,4′-Bis(methylaminoethanethiol)Rubpy(p-
cymene) (Thiol-RuCY) (Scheme S5). The resulting powder in
Scheme S4 (100 mg, 0.303 mmol) and dichloro(p-cymene)-
ruthenium(II) dimer (92.6 mg, 0.151 mmol) were suspended in 30
mL of pure acetonitrile, and the heterogeneous suspension was
bubbled by Ar gas for 20 min. The mixture was refluxed for 4 h, and
the suspension became dark during the reaction. After the designated
time, the reaction pot was placed in a refrigerator overnight to
precipitate the brown solid. The resulting solid was washed with cold
diethyl ether three times and dried in a vacuum oven at 40 °C for 6 h
to give dithiazolidine-Rubpy(p-cymene). Then, the thiazolidine-
terminated RuCY was dissolved in 30 mL of 0.5 M K2CO3 solution.
Sodium borohydride (90.8 mg, 2.4 mmol) in 3 mL of 0.25 M NaOH
solution was then added to the mixture. The solution was stirred for 2
h while maintaining the temperature under 20 °C and cooled to 0−4
°C in an ice bath. Glacial acetic acid was added to the reaction
mixture until the final pH become 5. After a quick filtration through a
3 cm layer of celite to remove residual salt, the mixture was poured
into 50 mL of tetrahydrofuran, and a dark brown solid was
precipitated. The supernatant solution was decanted, and the
precipitate was resuspended and triturated using diethyl ether to
give the thiol-terminated RuCY.
1
H NMR (DMSO-d6, 300 MHz): δ 8.62 (d, 2H), 8.44 (s, 2H),
7.46 (d, 2H), 6.31 (d, 2H), 6.07 (d, 2H), 5.70 (d, 4H), 3.58 (m, 2H),
3.20 (m, 4H), 2.98 (m, 4H), 2.59 (m, 1H), 2.16 (s, 3H), 0.95 (d,
6H). HR-MS (ESI, m/z, [M − Cl]+): calcd M.W. 605.1113, found
M.W. 605.1091 (Figure S19).
Preparation of the p-GaN/AuNP Photoelectrodes. The
known procedure in the literature45 was followed with slight
modification for the actual experimental environment. The plasmonic
p-GaN/Au photoelectrode was prepared via electron-beam evapo-
ration of the atomic Au layer onto commercial p-type gallium nitride
substrates epitaxially grown on sapphire (Pam-Xiamen, c-axis 0001).
First, the p-GaN substrates were thoroughly cleaned with 0.02% (v/v)
of NH4OH solution and copious amounts of deionized water. Then,
the substrates were dried in an oven at 60 °C for 1 h. A film of Au
with 1.5 nm thickness was deposited on the p-GaN surface by physical
vapor deposition under a pressure of 1 × 10−7 Torr. The Au film was
then annealed in an ambient condition at 300 °C (heating rate: 10
°C·min−1) for 1 h to construct the spherical geometry of gold
nanoparticles, as well as to ensure the stable adhesion between gold
and p-GaN interface.
Hematite (α-Fe2O3) Nanowires on FTO Substrate as a
Photoanode. The α-Fe2O3/FTO photoanode was prepared
according to a hydrothermal method as previously reported68 with
slight modification. Fluorinated tin oxide (FTO) substrates were
washed three times in an ultrasonicator with a 1:1:1 mixture solution
of deionized water, 2-propanol, and acetone. After rinsing the
substrates with copious amounts of deionized water, they are dried in
air at 100 °C for 1 h. A 50 mL poly(tetrafluoroethylene) (PTFE) liner
was filled with 25 mL of an aqueous solution containing ferric
chloride (FeCl3, 0.15 M), sodium nitrate (NaNO3, 1 M), and 131 μL
of hydrochloric acid (37 wt % HCl). The washed FTO substrates
were put into the PTFE liner leaning against the wall with the
conducting face down. The autoclave was placed in an oven at a
temperature of 100 °C and taken out after 4 h. After the autoclave was
cooled to room temperature, the substrates covered with uniform iron
oxyhydroxide (FeOOH) nanowires were rinsed with deionized water
and subsequently annealed at 550 °C (heating rate: 10 °C·min−1) for
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2 h. During the heat treatment, the FeOOH nanowires were
converted into hematite nanowires without deterioration of the
nanowire structures. To further reduce the defects of the hematite
nanowires and Sn-doping, the second sintering process64 was carried
out at 800 °C for an additional 20 min.
Photoelectrochemical Analysis of the Half-Reaction and
the Full Reaction at p-GaN/AuNPs/RuCY Photocathode. The
half-reaction and the full reaction were conducted to analyze
electrochemical behaviors of p-GaN/AuNPs/RuCY in three-electrode
configurations with Ag/AgCl electrode as the reference electrode in
0.2 M acetate buffer (pH 3.7) and 0.2 M phosphate buffer (pH 6),
respectively. Pt foil was used as a counter electrode for the half-
reaction, and α-Fe2O3/FTO photoanode was used for the PEC full
reaction. The photocurrent was obtained under 1 sun AM 1.5
illumination (>400 nm) using a solar simulator (Asahi Spectra, HAL-
320). The electronic potentials were converted into the reversible
hydrogen electrode (RHE) scale using the following equation: E(RHE)
= E(Ag/AgCl) + (0.059 × pH) + E(Ag/AgCl)0, where E(Ag/AgCl)0 = 0.197 V
at 25 °C.
Formate Production by the Plasmon-Driven Photoelec-
trochemical CO 2 Reduction with Simultaneous Water
Oxidation. The photoelectrochemical CO2 reduction and water
oxidation reactions were conducted in a three-electrode system to
elucidate the catalytic activity of p-GaN/AuNPs/RuCY at a certain
electric potential. The aqueous solution was a 0.2 M KH2PO4/
Na2HPO4 buffer, and the pH of the solution was adjusted to 6.0
because RuCY significantly loses its reactivity with carbon dioxide
above this pH, as described previously.42 The electrolyte solutions
were degassed under reduced pressure and N2 bubbling, and then, the
solution was saturated with CO2 by bubbling at a slightly positive
pressure for 1 h. All three electrodes, p-GaN/AuNPs/RuCY, α-
Fe2O3/FTO, and Ag/AgCl, were put in a 10 mL vial containing 4 mL
of the electrolyte solution, and the gas phase was purged with Ar,
while the vial was tightly sealed with a rubber septum and paraffin
seal-tape. The vial was placed in front of a xenon lamp (XLS300-OFR,
SPECTRO), and the light was irradiated for designated periods of
time with a 400 nm long-pass filter. Formate ions were protonated by
addition of sulfuric acid (10 vol % 1.0 M H2SO4) and extracted as
formic acid by ethyl acetate three times.69 Chemical species in the
aqueous and gas phases were determined, respectively, by gas
chromatography (GC) (YL6500 GC) (aqueous phase: detector =
pulsed discharge ionization detector (PDD); carrier gas = helium;
flow rate = 1.0 mL·min−1; temperature conditions = 40 °C for 3 min,
then elevated to 200 °C at a rate of 30 °C·min−1; column for PDD =
Agilent Technologies, HP-FFAP, 30 m × 0.53 mm, 1.00 μm. Gas
phase: detector = thermal conductivity detector (TCD); carrier gas =
argon; flow rate = 10.0 mL·min−1; temperature condition = isocratic
90 °C; column for TCD = SUPELCO Analytical, Mol Sieve 5A, 6 ft ×
1/8 in.).
Isotope-Labeled Study for Photoelectrochemical Formate
Production. Two phosphate buffer solutions were bubbled with
12
CO2 and 13CO2, respectively. The 13CO2 gas was generated by
addition of 1.0 M sulfuric acid into a Ba13CO3-containing flask.14
After 20 h of light illumination, the formate ions were protonated and
extracted by ethyl acetate. Then, gas chromatography-mass spectrom-
etry (GC-MS) analysis (EI mode, ISQ QD300, Thermo Fisher
Scientific) was conducted to determine whether the formic acid was
labeled with 13C.
Calculation of Faradic Efficiency. The faradic efficiency (FE) of
the photoelectrochemical CO2 reduction for each product was
calculated as follows
FE (%) = 100 × (Ni × F × Pm)/(I × t )
where Ni is the number of electrons required to produce a particular
product, F is the Faraday constant (96 485 C·mol−1, 1 C = 1 A·s), Pm
is the determined molarity of the product, I is the average current
during the reaction time, and t is the reaction time (12 h = 43 200 s).
The number of electrons involved with the reduction reactions is
two for H2, CO, and formate and six for methanol. The molarity of
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ACS Appl. Mater. Interfaces 2020, 12, 33817−33826
ACS Applied Materials & Interfaces
the products was determined by calibrating the GC using a serial
dilution of each standard reagent in known concentrations.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.0c09517.
Detailed methods, characterizations, and additional data
of solar-to-chemical conversion (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Yoon Sung Nam − Department of Materials Science and
Engineering and KAIST Institute for NanoCentury, Korea
Advanced Institute of Science and Technology, Daejeon 34141,
Republic of Korea; orcid.org/0000-0002-7302-6928;
Email: yoonsung@kaist.ac.kr
Authors
Hwiseok Jun − Department of Materials Science and
Engineering, Korea Advanced Institute of Science and
Technology, Daejeon 34141, Republic of Korea; orcid.org/
0000-0002-1266-001X
Shinyoung Choi − Department of Materials Science and
Engineering, Korea Advanced Institute of Science and
Technology, Daejeon 34141, Republic of Korea; orcid.org/
0000-0001-6220-1180
Joong Bum Lee − Department of Materials Science and
Engineering, Korea Advanced Institute of Science and
Technology, Daejeon 34141, Republic of Korea; orcid.org/
0000-0001-7751-1720
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.0c09517
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the Basic Science Research
Program and Nano·Material Technology Development Pro-
gram through the National Research Foundation of Korea
(NRF) funded by the Ministry of Science and ICT (NRF-
2020R1A2C2004168, NRF-2017M3A7B4052797, and NRF-
2017M3A7B4042235).
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