Letter

http://pubs.acs.org/journal/aelccp

Direct H2S Decomposition by Plasmonic

Photocatalysis: Efficient Remediation plus
Sustainable Hydrogen Production
Minghe Lou, Junwei Lucas Bao, Linan Zhou, Gopal Narmada Naidu, Hossein Robatjazi,*
Aaron I. Bayles, Henry O. Everitt,* Peter Nordlander,* Emily A. Carter,* and Naomi J. Halas*
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ABSTRACT: Plasmonic metal nanostructures have garnered rapidly increasing

interest as heterogeneous photocatalysts, facilitating chemical bond activation and
overcoming the high energy demands of conventional thermal catalysis. Here we
report the highly efficient plasmonic photocatalysis of the direct decomposition of
hydrogen sulfide into hydrogen and sulfur, an alternative to the industrial Claus
process. Under visible light illumination and with no external heat source, up to a
20-fold reactivity enhancement compared to thermocatalysis can be observed. The
substantially enhanced reactivity can be attributed to plasmon-mediated hot carriers
(HCs) that modify the reaction energetics. With a shift in the rate-determining step
of the reaction, a new reaction pathway is made possible with a lower apparent
reaction barrier. Light-driven one-step decomposition of hydrogen sulfide
represents an exciting opportunity for simultaneous high-efficiency hydrogen production and low-temperature sulfur
recovery, important in many industrial processes.

H ydrogen sulfide (H2S) is a key byproduct of the

hydrodesulfurization process in oil and gas refineries
and the petrochemical industry (R-SH + H2 → RH +
H2S), contributing to the majority of the sulfur supply
worldwide.1 As a toxic and corrosive gas, H2S is listed as an
extremely hazardous substance by the United States (U.S.)
Environment Protection Agency, causing irreversible harmful
effects to humans at concentrations as low as 20 ppm in
ambient air.2 The U.S. National Emission Inventory reports
annual H2S emissions of ∼9800 tons in the U.S. alone.3 Hence,
H2S decomposition is critical for reducing sulfur emissions,
while also potentially producing hydrogen (H2), a high-value
product. The traditionally established technology for H2S
decomposition is the energy-intensive two-step Claus process:
H2S first is partially oxidized in the air into SO2 in combustion
chambers at temperatures >1100 K (thermal stage), followed
by a catalytic reaction of H2S with SO2 (Claus reaction) to
produce S2 and H2O.4 The produced S2 can further polymerize
or transform into other more stable forms of sulfur, such as S8.
In contrast, direct decomposition of H2S into H2 and sulfur
(2H2S(g) → 2H2(g) + S2(g)) is a potentially attractive way to
address the high overall energy cost of the Claus process5 and
simultaneously obtain clean H2 during sulfur recovery.6,7 This
approach can be implemented for H2 production from other,
nonpetrochemical H2S-containing resources, such as chemical
and animal wastes and sewer gases. The produced H2 can also
be fed back into the hydrodesulfurization reaction, forming a
closed loop and mitigating the need for an external H2 supply
(which, in current industrial practice, typically originates from
a CO2-emitting source). However, the direct decomposition of
H2S is a highly endothermic process (with a reaction enthalpy
of +169.4 kJ/mol)8 with limited thermodynamic conversion at
temperatures below 1000 K.6 Aside from thermocatalytic
efforts for direct H2S decomposition,9,10 there have been
attempts to achieve faster kinetic rates at milder temperatures
using electrocatalytic,11,12 photocatalytic,13−19 plasma-in-
duced,20 and microwave-assisted approaches.21,22 Chemical
looping23,24 has also been implemented to circumvent the
thermodynamic limitation of this reaction. While these studies
represent valuable progress toward the direct decomposition of
H2S at milder temperatures, difficulties with scale-up due to
the energy source or the catalyst are still major challenges.
Here we demonstrate highly efficient, visible-light-driven,
heterogeneous photocatalysis for the direct decomposition of
Received: August 3, 2022
Accepted: September 14, 2022

© XXXX American Chemical Society https://doi.org/10.1021/acsenergylett.2c01755

3666 ACS Energy Lett. 2022, 7, 3666−3674
ACS Energy Letters http://pubs.acs.org/journal/aelccp Letter

Figure 1. Optical characterization of the photocatalyst and its catalytic properties. (a) Transmission electron microscope (TEM) image of 5−
10 nm Au NPs dispersed in chloroform (scale bar: 5 nm). (b) TEM image of SiO2-supported Au NPs (scale bar: 10 nm). (c) Measured (solid
line) and Monte Carlo simulated (dashed line) diffuse reflectance spectra of SiO2-supported Au NPs. (d) H2S turnover frequency at different
surface temperatures in thermocatalytic (528−773 K) and photocatalytic (white light laser, 400−900 nm, 4.0−10.0 W/cm2 without external
heating, surface temperature monitored with IR camera) H2S decomposition. Error bars represent standard deviations of three parallel
measurements under the same conditions, using samples from the same batch. Solid lines are the linear fitting of the data points with R2 =
0.993 and 0.97 for thermocatalysis and photocatalysis, respectively.

H2S into H2 and sulfur using SiO2-supported gold (Au)
nanoparticles (NPs) as the plasmonic photocatalyst. Plasmonic
metal nanostructures constitute a transformative approach for
enhancing catalysis at substantially milder operating temper-
atures than traditional processes by taking advantage of the
strong interactions between metal NPs and light.25 Illumina-
tion of plasmonic metal NPs can excite collective electronic
oscillations, known as localized surface plasmons.26 Decay of
localized surface plasmons generates energetic HCs that
facilitate surface reactions through nonthermal bond activation
mechanisms or through the excitation of phonons, producing
heat.26,27
Compared to traditional thermocatalysis, hot-carrier-medi-
ated plasmonic photocatalysis has been reported to be capable
of enhancing both reactivity and selectivity,28,29 making it an
attractive and more sustainable alternative to traditional
phonon-driven chemistry.30 Recent studies also show that
nonthermal bond activation in plasmonic photocatalysis is
different from photocatalytic redox chemistry on semi-
conductors that involves charge transfer to adsorbate(s),
because the net result of HC generation in photoexcited
metal nanostructures is energy transfer.25 This feature of
plasmonic photocatalysts results in a positive dependence of
quantum efficiency on photon flux and operating temper-
ature,27 allowing for higher reaction rates under illumination
and a broader scope of chemical reactions that can be enabled
with light. The use of light for promoting heterogeneous
catalysis on plasmonic NPs has been demonstrated recently for
several high-impact chemical reactions, including, but not
limited to, CO2 reduction,28,31,32 methane dry reforming,33,34
C−F bond activation,35 and olefin epoxidation.36
In this work we report the direct illumination of a SiO2-
supported Au NP catalyst resulting in surface temperature
increases of up to 500 °C (at ∼13 W cm−2), producing up to a
20-fold increase in reactivity compared to thermocatalysis at
similar surface temperatures. H2 was produced at a rate of up
to 5 μmol H2 s−1 per gram of catalyst (turnover frequency
TOF = 0.28 s−1 and external quantum yield EQY = 1.8%;
Figure S1) in photocatalysis, which is on par with or better
than most previously reported results, albeit without the need
to use a basic solution and additional reagents (Table S1). The
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use of only visible light, with no external heating, to drive a
one-step H2S decomposition process allows for relatively
straightforward future scale-up using renewable solar energy or
highly efficient solid-state lighting systems (e.g., LEDs).37
The photocatalyst, consisting of Au NPs (5−10 nm
diameter; Figure 1a and Figure S2), was synthesized colloidally
using a previously reported method with slight modifications
(see the Supporting Information for details) and supported on
powdery SiO2 at a 2% weight percentage using a wet
impregnation method (Figure 1b) to increase its stability.38
The extinction spectrum of the NPs dispersed in chloroform
shows a dipolar plasmon peak at ∼512 nm, consistent with
spectra simulated using the finite difference time domain
(FDTD) method (Figure S2D). The ensemble absorption
spectrum of the NPs on the support measured by diffuse
reflectance spectrometry and reproduced using Monte Carlo
simulations also shows a strong dipolar plasmon peak with a
slight red shift to ∼516 nm due to the increase in the
surrounding dielectric environment of the NPs (Figure 1c).
Polycrystalline X-ray diffraction (PXRD) of the supported
catalyst Au/SiO2 shows characteristic peaks of SiO2 and Au
(Figure S3). The broadened peaks indicate that both the Au
and SiO2 are on the nanoscale. X-ray photoelectron spectros-
copy (XPS) analysis of the catalyst indicates a surface Au:Si
atomic ratio of 1:109 (Figure S4). A Brunauer−Emmett−
Teller (BET) analysis of the adsorption isotherm of the
catalyst gives a surface area of 196.4 m2/g (Figure S5).
When the as-prepared catalyst was used for H 2 S
decomposition, a reduction of the apparent activation barrier
from 0.61 eV for thermocatalysis to 0.32 eV for photocatalysis
was observed (Figure 1d) (see the Supporting Information for
experimental details of photocatalysis and thermocatalysis
measurements). Such a significant change in apparent
activation barrier indicates a nontrivial involvement of HCs
in the photocatalytic process, as has been reported in several
previous studies.33,35,39 The photocatalytic process also
exhibits 1−2 orders of magnitude higher reactivity than
thermocatalysis at the same temperature (Figure 1d), depend-
ing on the optical intensity and power used. A set of
photocatalysis experiments was performed to understand these
properties further.
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Figure 2. Photocatalytic behavior of the Au/SiO2 photocatalyst. Photocatalytic H2S turnover frequency from H2S decomposition (blue) and
the corresponding light-induced surface temperature of the catalyst (red) as a function of incident laser power density (a, 525 ± 25 nm
illumination) and illumination wavelength (b, 8.8 W/cm2 from each 50 nm filtered bandwidth of the light source). The estimated
photothermal contributions (black curves) were obtained by inserting the maximum surface temperature at each data point into the
Arrhenius fit of the thermocatalytic process in Figure 1d. The dashed line in (b) corresponds to the extinction spectrum of the Au NPs. All
measurements were performed under a 10 sccm H2S flow. Error bars represent the standard deviations of three parallel measurements under
the same conditions using samples from the same batch. Solid lines are included as visual guides.

Photocatalytic reaction rates as a function of incident power
show a pseudolinear power dependence with a TOF as high as
∼0.28 s−1 at an incident light intensity of ∼13 W/cm2 (Figure
2a, blue). Due to the small thermal conductivity of H2S40 and
the low flow rates applied over an Au-NP-based catalyst known
for efficient photothermal heating, the light-induced maximum
surface temperature of the sample pellet reaches ∼773 K
(Figure 2a, red). It should be mentioned that the assessments
of temperature homogeneity based on the previously proposed
empirical model41 and our calculations (see the Supporting
Information for details) suggested the influence of collective
heating, where a light-induced local temperature increase on an
individual nanoparticle is assumed to be similar to that of its
surroundings, as resolved by the camera. The wavelength-
dependent reactivity was also measured from 450 to 675 nm
(Figure 2b, blue) and followed the extinction spectrum of the
catalyst (Figure 2b, dashed), with a maximum reactivity near
the dipolar plasmon wavelength of the Au NPs (525 nm).
Figure 2b also displays wavelength-dependent catalyst
heating (red) that qualitatively follows the trend of the
reactivity response (blue). Despite the significant photo-
thermal heating produced, these data clearly show that there
is a difference in reactivity at excitation wavelengths that
induce similar surface temperatures. For example, illumination
in the wavelength range between 575 and 625 nm results in a
substantially lower photocatalytic reactivity than illumination
in the 450−500 nm wavelength range, despite similar surface
temperatures. This observation strongly suggests that non-
thermal effects are contributing to the reaction pathway, even
at these elevated temperatures, and that photothermal catalyst
heating is only a minor contributor to the overall reactivity.42
To provide insight into the relative contributions of thermal
and nonthermal effects to the photocatalytic reaction, we
estimated the photocatalytic reactivities associated with
photothermal heating alone by inserting the maximum surface
temperatures under illumination into the Arrhenius expression
for thermocatalytic reactivity that would have been measured
in the dark at elevated temperatures (Figure 2a,b, black). By
assuming a uniform light-induced temperature profile within
the bulk of the catalyst and using the maximum surface
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temperature increase to estimate photothermal reactivity, we
overestimate the actual photothermal heating of photocatalysis.
Even so, the photothermal contribution is found to account for
less than 10% of the total photocatalytic TOF. This result
strongly supports the contribution of nonthermal plasmonic
effects (HC injection and near-field enhancement)25,43 as the
predominant bond activation mechanism for this process.
To understand how plasmonically generated HCs efficiently
catalyze this highly endothermic reaction, quantum mechanical
simulations were performed. The optimized geometries and
energies of the key structures along minimum energy paths
(MEPs) were calculated, assuming the steps
H 2S(g) + * H 2S* (1)
H 2S* + * HS* + H* (2)
HS* + * S* + H* (3)
2H* H 2(g) + 2* (4)
2S* S2* + * (5)
S2* S2(g) + * (6)
where * denotes active sites on the Au surface. These involve
the adsorption of gaseous H2S (step 1), the sequential scission
of two H−S bonds (steps 2 and 3), the associative desorption
of gaseous H2 (step 4), and the formation (step 5) and
desorption (step 6) of S2, as generally accepted for H2S
decomposition on metal catalysts.7,8,44−47 The reaction
initiates via the adsorption of H2S molecules on the
photocatalyst surface with an adsorption energy of 0.60 eV
(Figure 3a), matching well with experimental values of 0.4−0.5
eV.48 Both previous work47,49 and our optimizations (Figure
S6) show that the physisorbed H2S molecules attach to the
Au(111) surface with an S atom on top of an Au atom.
Subsequent scissions of the two H−S bonds then are facilitated
by a polarization of the Au surface through interaction with the
adsorbed H2S, generating adsorbed H*, HS*, and S* species.
The associative desorption of these species yields H2 and S2 as
the final products.
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Figure 3. emb-CASPT2 energy curves for ground and excited states along the MEPs. (a) Ground-state potential energy diagram of H2S
decomposition on Au(111) constructed using the optimized MEPs. (b, c) emb-CASPT2 energy curves for ground and excited states along
the MEPs for HS* scission ((b) 0 to ∼3 Å along the reaction coordinate s; the 1.18 eV barrier at s = 4.8 Å is for (unnecessary) *S migration
(see text)), S2 formation ((c) 0−4.8 Å along s), and S2 desorption ((c) s = 4.8−10.5 Å). Blue and orange dashed curves are possible excited
state trajectories.

The potential energy diagram obtained from the optimized
MEP geometries (Figures S6−S9) calculated using plane-wave
density functional theory (PW-DFT; see the Supporting
Information for details) indicates three key steps with high
activation barriers in the ground state (Figure 3a). These steps
are the scission of the second H−S bond (step 3) and the
formation and desorption of S2 (steps 5 and 6). In steps 5 and
6, the energies labeled are the barriers normalized to forming
or desorbing “half” of an S2 molecule, so that the actual barrier
is twice the labeled value. Although step 3 has a lower barrier
compared to the other two steps, previous studies have shown
that S-covered Au surfaces may increase the activation barrier
of step 3.47 Based on these analyses, steps 3, 5, and 6 are likely
to compete to be the rate-determining step (RDS) for the
ground state.
The accuracy of this theory has been proven in numerous
previous studies on different systems,33,39,50−52 but we still see
a discrepancy between the measured (0.61 eV) and calculated
(>1.36 eV) reaction barriers, regardless of the RDS. We ascribe
this discrepancy mainly to the nature of small Au NPs and the
idealized Au(111) model we applied. For Au NPs between 2
and 10 nm, the terraces, corners, or step edges dominate their
catalytic reactivity, giving rise to a lower barrier than that for an
Au(111) surface.53,54 Small Au NPs have also been reported to
be prone to surface reconstruction under various reaction
conditions.55,56 Although our model Au(111) surface does not
provide an accurate estimation of the ground-state barrier for
thermocatalysis, it is still practical to use for comparison
between the ground and excited states.
Potential energies along the MEPs of nine excited states S1−
S9 for steps 3 (Figure 3b), 5, and 6 (Figure 3c, with both
singlet states S1−S9 and triplet states T1−T9 presented
because S2(g) is a ground state triplet) were calculated with
embedded correlated wave function (ECW) theory using
complete active space second-order perturbation theory (emb-
3669
CASPT2).51 Previous work has shown that HCs generated
during plasmonic photocatalysis can transfer energy to
adsorbed species on the catalyst surface by exciting them
into electronic or vibronic excited states.35,36,39,57 In the Au/
SiO2 catalysts, the insulating SiO2 support can confine the
energetic HCs on the Au NPs, making it more likely for the
plasmon-mediated decomposition of H2S to happen on the Au
surface instead of the SiO2 surface.
The emb-CASPT2 ground-state activation barrier of step 3
(reaction coordinate 0.70−1.05 Å in Figure 3b) was calculated
to be 1.36 eV without zero-point-energy corrections. However,
the HS* at reaction coordinate 0.70 Å can absorb, for instance,
∼1.68 eV of energy from a plasmon decay and jump to the
ninth excited state (S9). At reaction coordinate ∼0.96 Å, the
potential energy surface (PES) crosses to S2 or S3 non-
adiabatically, and the reaction trajectory then follows the
excited state MEPs adiabatically until it reaches the transition
state at 1.39 Å for S3 or 1.99 Å for S2. The PES then crosses
again to either S2 or S1 nonadiabatically at 2.58 Å or before,
before jumping back to the ground state near 4 Å. These
reaction trajectories can lower the activation barrier of the H−
S* bond-breaking step to 0.30−0.56 eV. Note that the PES
between 3.8 and 5.8 Å corresponds to S* migration from a
hexagonal-close-packed (hcp) site to a face-centered-cubic site
on Au (111) (Figure S7), which is a possible pathway but does
not appear to be necessary for the following steps of S2
formation and desorption to occur.
Similarly, the activation barriers of steps 5 and 6 also can be
reduced to ∼0.40−0.45 eV (Figure 3c). In this case, the two
S* (occupying two hcp sites but slightly shifted toward the
bridge sites, as shown in Figure S9) could gain 1.4 eV of energy
from the plasmon decay, jumping to S9 at 0 Å. Because S9 is
nearly degenerate with T4 (the notation Tn denotes a triplet
state), an intersystem crossing facilitated by spin−orbit
coupling may occur and the reaction trajectory then may go
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Figure 4. Photoinduced changes in the kinetics of H2S decomposition. (a) Measurements of turnover frequencies as a function of H2S partial
pressure for photocatalysis under different incident power densities (triangles, solid lines) and dark thermocatalysis under external heating
(cubes, dashed lines). Photocatalysis and thermocatalysis measurements for a given maximum surface temperature share the same color.
Error bars represent the standard deviations of three parallel measurements under the same condition using samples from the same batch.
(b) Illustration of photo- and thermocatalytic H2S decomposition on the Au surface. We consider H−S bond scission in HS* to be the rate-
determining step (RDS) in the thermocatalytic process. Plasmon-induced hot electrons can facilitate the H−S bond scission in HS* while
shifting the RDS to the associative desorption of S2 in photocatalysis, thus resulting in a substantial enhancement in the reaction rates
relative to pure thermocatalysis. (c) Schematic showing the role of plasmon-induced hot electrons for activating the H−S bond in HS*
surface intermediates. HCs with sufficient energy can deposit energy into the adsorbate, resulting in electronic and/or vibrational excitation
of the adsorbate, which subsequently evolves along the reaction coordinate, thus effectively lowering the energy barrier for bond activation.

along the PES of T4 until crossing nonadiabatically to T2/T3
at 1.60 Å. The reaction can go either along T2/T3 to give an
∼0.45 eV RDS barrier (more specifically, the dashed blue
curve shows a small barrier of ∼0.17 eV at 0.8 Å and two
consecutive RDS barriers, both of which are ∼0.45 eV) or
spin-cross to T0 at ∼2.8 Å to experience an ∼0.20 eV barrier
(dashed orange curve) until the final formation of adsorbed S2
at 4.80 Å.
In the desorption step, at 4.80 Å, T0 and S0 are nearly
degenerate with only a 0.13 eV energy gap, making ground-
state spin crossover possible. The HC excitation therefore can
populate the system directly from S0 to S9 by the transfer of
1.69 eV of energy to the adsorbed S2, which can travel along
the S9 PES by acquiring 0.40 eV of thermal energy, then hop
back to the triplet manifold at 5.30 Å. At 7.30 Å, the trajectory
could cross back to T5 and finally deexcite to T0 at the
desorption limit of 10.40 Å (the dashed blue line shows this
possible path). Although this analysis suggests that it might be
possible to lower the barriers of S2 formation and desorption
via additional excitations (see vertical arrows in Figure 3c), the
linear power dependence suggests that this photocatalysis only
involves a single excitation, namely that which lowers the
barrier for the second H−S bond scission.
Whether these excited state pathways are feasible also
depends on the surface coverages of the adsorbed species
involved. For example, although the activation barrier can be
lowered to ∼0.41 eV for step 2 (Figure S6), the surface
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coverage of H2S* is low because the scission of the first H−S
bond is faster than scission of the second H−S bond. This
results in a lower probability of H2S* species being excited
compared to other species with higher surface coverages, such
as S* and HS*.
Both our photocatalytic reactivity measurements (see also
Figures S10−S13) and our quantum mechanical calculations
point to a substantial contribution from nonthermal effects in
the observed light-activated direct H2S decomposition. To
ascertain which elementary step is benefiting most from this
mechanism, a kinetic study of photocatalysis and thermocatal-
ysis was performed. We measured the apparent reaction order
for H2S under photocatalytic and thermocatalytic conditions
by measuring the reaction rate as a function of H2S partial
pressure (Figure 4a). The steady-state measurements of the
reaction order for thermocatalytic H2S decomposition exhibit a
slight temperature-dependent behavior that decreases from 0.8
to 0.6 with increasing temperature from 573 to 673 K. In
contrast, we observe a near zeroth-order dependence of the
reaction rate on H2S in photocatalysis (measured under 4.4
W/cm2), that remained statistically unchanged (−0.10 to 0.10)
with increasing illumination intensities up to 7.2 W/cm2.
Given that the light-induced maximum surface temperature
within the intensities used is less than 673 K, the substantial
photon-induced changes to the reaction order compared to
that of thermocatalysis provide additional definitive proof that
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nonthermal effects dominate this high-temperature photo-
catalytic reaction.
Light-induced changes in the reaction order directly
correlate with changes in coverages of surface species
(intermediates) involved in the RDS. Previous studies
suggested that nonthermal photoexcitation of adsorbate−
surface states mediated by HCs can promote reactivity in
light-driven catalysis by modifying nanoparticle surface cover-
ages of the adsorbed species, shifting the reaction
RDS.35,39,58,59
To understand the observed photoinduced changes to the
reaction order, we performed a microkinetic analysis, deriving
rate expressions using a quasi-equilibrium approximation to
calculate the reaction orders (nH2S) (see the Supporting
Information for details). We considered three scenarios,
assuming the RDS was the H−S bond scission in HS*, the
formation of S2*, or the desorption of S2*. Equations 7−9
account for changes to the reaction orders as a function of
adsorbate surface coverage, where [i*] is the surface coverage
of adsorbate i. If the scission of the H−S bond in HS* is the
RDS,
n H 2S = 1 2[H 2S*] 2[HS*] (7)
and HS* will be the dominant species. If the formation of
adsorbed S2* is the RDS,
n H 2S = 2 2[H 2S*] 2[HS*] 2[S*] (8)
and S* will be the dominant species. If the desorption of
gaseous S2 is the RDS,
n H 2S = 2 [H 2S*] [HS*] [S*] 2[S*2 ]
(9)
and S2* will be the dominant species.
For the thermocatalytic reaction (Figure 4a, dashed curves),
we observe temperature- and coverage-dependent reaction
orders. Inserting the measured reaction orders into eqs 7−9
gives a free site coverage [*] ranging from 0.9 to 0.4 if one
assumes [*] = 1 − [D*], where D represents the dominant
species in each case. The measured thermocatalytic reaction
order of ∼0.8 for H2S at 573 K indicates that free active sites
are relatively abundant. Increasing the temperature by 100 K
slightly decreased the reaction order for H2S, indicating there
are fewer available free sites for gaseous H2S. This observed
decrease in the reaction order suggests that the kinetics of H−
S bond scission in HS* benefit slightly more from the
temperature increase than the other steps, leading to an
increase in [S*] and [S2*] coverage on the surface. The
comparable surface coverages of the intermediate species and
the relatively close energy barriers for these three steps in the
ground state suggest that, for the thermocatalytic reaction, the
reaction rate on the Au surface is controlled by competing
RDSs.
For the photocatalytic reaction (Figure 4a, solid curves) we
observe near-zero reaction orders over the same temperature
range, confirming that illumination substantially alters the
kinetics and energetics of the elementary reaction steps.
Directing light energy into the photoexcitation of adsorbate−
metal states is known to induce nonthermal dissociation and
desorption that may modify the coverage of surface species and
thus the reaction pathway.25,29,33,39,59,60 For H2S photo-
decomposition, nonthermal energy transfer from plasmon-
mediated HCs into unoccupied orbitals of HS* could induce
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Letter
electronic and/or vibrational excitation of the adsorbate along
the reaction coordinate that subsequently lowers the energy
barrier for the H−S* bond scission more than the other
elementary reaction steps, shifting the RDS toward S2
formation and desorption (Figure 4b,c). This shift in the
RDS causes an increase in the surface coverage of S* and S2*,
which leaves only limited free sites for gaseous H2S, leading to
the near-zero reaction order. According to our experiments
(Figure 4a), this occurs even at illumination intensities as low
as 4.4 W cm−2, for which the light-induced surface temperature
(∼550 K) is lower than the lowest surface temperature for
thermocatalysis (573 K).
In conclusion, we demonstrated the direct and efficient
decomposition of H2S using visible light and no external
heating, on SiO2-supported Au NP plasmonic photocatalysts.
Reaction rates up to 20 times higher than thermocatalysis at
nominally the same surface temperatures were obtained. We
thoroughly examined the plasmon-induced nonthermal effects
responsible for this enhanced reactivity, showing that photo-
generated HCs can accelerate the second H−S bond scission.
Our results clearly point to light-driven catalysis resulting in a
shift in the RDS to S2* formation and desorption, away from
the competing RDSs observed for thermocatalysis, substan-
tially decreasing the apparent reaction barrier. This light-based
direct decomposition reaction represents an exciting oppor-
tunity for improving desulfurization processes and developing
heterogeneous approaches for sustainable sulfur chemistry and
hydrogen production. The continuous drop in the cost of
renewable electricity over the past decade and the increasingly
improving efficiency of the LED technology has also made
cheap renewable photons available, allowing for future
sustainable production of value-added chemicals and fuels
through photocatalytic and photochemistry approaches.37
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsenergylett.2c01755.
Synthesis details, details of the optical and Monte Carlo
simulations, microkinetic analysis, and details of the
quantum mechanical studies, including all atomic
structures used in the quantum mechanical simulations
(PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Hossein Robatjazi − Department of Chemistry, Rice
University, Houston, Texas 77005, United States; Laboratory
of Nanophotonics, Rice University, Houston, Texas 77005,
United States; Syzygy Plasmonics Inc., Houston, Texas
77054, United States; orcid.org/0000-0002-5101-263X;
Email: hr10@rice.edu
Henry O. Everitt − Department of Electrical and Computer
Engineering and Laboratory of Nanophotonics, Rice
University, Houston, Texas 77005, United States; U.S. Army
DEVCOM Army Research Laboratory, Houston, Texas
77005, United States; orcid.org/0000-0002-8141-3768;
Email: he5@rice.edu
Peter Nordlander − Department of Electrical and Computer
Engineering, Laboratory of Nanophotonics, and Department
of Physics and Astronomy, Rice University, Houston, Texas
https://doi.org/10.1021/acsenergylett.2c01755
ACS Energy Lett. 2022, 7, 3666−3674
ACS Energy Letters http://pubs.acs.org/journal/aelccp
77005, United States; orcid.org/0000-0002-1633-2937;
Email: nordlander@rice.edu
Emily A. Carter − Department of Mechanical and Aerospace
Engineering and the Andlinger Center for Energy and the
Environment, Princeton University, Princeton, New Jersey
08544, United States; orcid.org/0000-0001-7330-7554;
Email: eac@princeton.edu
Naomi J. Halas − Department of Chemistry, Rice University,
Houston, Texas 77005, United States; Department of
Electrical and Computer Engineering and Laboratory of
Nanophotonics, Rice University, Houston, Texas 77005,
United States; orcid.org/0000-0002-8461-8494;
Email: halas@rice.edu
Authors
Minghe Lou − Department of Chemistry, Rice University,
Houston, Texas 77005, United States; Laboratory of
Nanophotonics, Rice University, Houston, Texas 77005,
United States
Junwei Lucas Bao − Department of Mechanical and
Aerospace Engineering and the Andlinger Center for Energy
and the Environment, Princeton University, Princeton, New
Jersey 08544, United States; Department of Chemistry,
Boston College, Chestnut Hill, Massachusetts 02467, United
States; orcid.org/0000-0002-4967-663X
Linan Zhou − Department of Chemistry, Rice University,
Houston, Texas 77005, United States; Laboratory of
Nanophotonics, Rice University, Houston, Texas 77005,
United States
Gopal Narmada Naidu − Department of Electrical and
Computer Engineering and Laboratory of Nanophotonics,
Rice University, Houston, Texas 77005, United States
Aaron I. Bayles − Department of Chemistry, Rice University,
Houston, Texas 77005, United States; Laboratory of
Nanophotonics, Rice University, Houston, Texas 77005,
United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsenergylett.2c01755
Author Contributions
M.L., L.Z., and N.J.H. designed the experiments. M.L.
conducted the synthesis and experiments. G.N.N. and P.N.
performed the optical simulations. J.L.B. and E.A.C. designed
and performed the quantum mechanics calculations. H.R.
assisted in analyzing and interpreting the data. H.O.E. assisted
in designing the experiments. A.I.B. performed the BET and
XRD measurements and part of the TEM imaging of the
samples. The manuscript was written with contributions from
all authors.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We gratefully acknowledge support from the Robert A. Welch
Foundation under Grants C-1220 (N.J.H.) and C-1222 (P.N.)
and support from the Air Force Office of Scientific Research
(FA9550-15-1-0022) and the Defense Threat Reduction
Agency (HDTRA 1-16-1-0042). We also thank the Rice
Shared Equipment Authority for use of electron microscopy,
Raman, XRD, XPS, and BET.
3672
Letter
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