pubs.acs.org/JACS Article
In Situ Raman Spectroscopic Insight of Hydrogen Spillover in
Electrocatalytic Hydrogenation
Yan Liu, Ze-Yu Zhang, Jie Wei,* Yan Liu, Hua Zhang,* and Jian-Feng Li*
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ABSTRACT: Given the crucial role of adsorbed hydrogen species (*H) in
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electrochemical hydrogenation reactions, manipulating hydrogen spillover to
facilitate the generation and migration of *H is highly necessary. However,
the strong coupling between hydrogen activation sites and hydrogenation
sites, together with the coexistence of protons and water molecules in
practical electrocatalytic systems, renders a grand challenge for the in situ
monitoring of hydrogen spillover. Herein, using single-atom Ru-doped Cu as
a model catalyst, the spectroscopic visualization of hydrogen spillover under
electrochemical conditions was realized by in situ surface-enhanced Raman
spectroscopy. Taking para-nitrothiophenol as the probe molecule, we
elucidated that the hydrogen spillover distance was facet-dependent, with
Cu(111) being more active for electrocatalytic hydrogenation than Cu(100).
Notably, electrochemical hydrogen spillover distances were tunable with the
variation of applied potentials, which increased, ranging from 0.8 to 2.6 nm as the potentials shifted negatively. Moreover, by
leveraging the hydrogen spillover effect to increase the hydrogen coverage on the Cu(111) surface, we found that the rate-
determining step of nitrate electroreduction could be altered, resulting in a significant enhancement of catalytic performance.
■ INTRODUCTION
The electrochemical hydrogenation (ECH) reaction, driven by
ideal model catalysts to gain more profound insight about the
hydrogen spillover mechanism in complex reaction net-
renewable electricity using clean water as the hydrogen source, works.33,34 For instance, isolated Pd atoms on the Cu surface
is emerging as an appealing approach to produce high-value- significantly lowered the energy barrier of H2 dissociation and
added chemicals.1−6 Typically, the dissociation of H2O to form adsorption, allowing for reactive hydrogen to diffuse across the
surface-adsorbed hydrogen species (*H) and the subsequent Cu surface and thus achieving highly selective hydrogenation
consumption of *H are significantly essential for the ECH of styrene and acetylene.30 Similarly, highly diluted Pd single
process.7−13 Therefore, the precise manipulation of hydrogen atoms on Cu supports demonstrated the facet-dependent
spillover, which involves the transfer of H species from metal hydrogen spillover, where the hydrogen atoms spilled from Pd
sites onto the catalyst support, is highly necessary to facilitate were readily utilized for the semihydrogenation of alkynes.31
the generation and migration of *H, thereby enhancing the Despite these advances, direct observation of hydrogen
catalytic performance.14−22 However, in most traditional spillover under reaction conditions, which is crucial for
supported metal catalysts, the complex metal−support inter- clarifying reaction mechanisms and guiding catalyst design,
face and the extremely closed active sites for hydrogen remains a formidable challenge, particularly in electrocatalytic
activation and hydrogenation render great challenge to systems.35−39 The interplay among protons (H+), water
separately investigate the process of hydrogen generation, molecules, and adsorbed hydrogen species (H*) in electro-
migration, and utilization.23,24 Such a lack of well-defined catalytic reactions makes it difficult to unambiguously
structures with spatially separated active sites has severely distinguish the contribution of spilled hydrogen from other
hindered the in-depth understanding and stoichiometric hydrogen sources.40−43 Therefore, the development of ultra-
evaluation of the hydrogen spillover effect.25−27 sensitive in situ characterization techniques applicable to
In recent years, the emergence of single-atom catalysts
(SACs), where the metal atoms are isolated and dispersed on
supports, has provided new opportunities for probing the Received: January 6, 2026
hydrogen spillover effect.28,29 Owing to the isolated nature of Revised: March 7, 2026
noble metal atoms, SACs inherently separate the sites for Accepted: March 11, 2026
hydrogen dissociation from those for hydrogenation, thereby Published: March 16, 2026
achieving a structural “decoupling” of the spillover proc-
ess.17,30−32 Consequently, SACs have been widely applied as
© 2026 American Chemical Society https://doi.org/10.1021/jacs.6c00294
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Figure 1. SEM images of (a) Ru1/Cu(111) and (b) Ru1/Cu(100). HAADF-STEM and corresponding EDS mapping of (c) Ru1/Cu(111) and (d)
Ru1/Cu(100). Ru K-edge (e) XANES and (f) EXAFS spectra of Ru1/Cu(111) and Ru1/Cu(100). (g) CV curves of Ru1/Cu(111) and Ru1/
Cu(100) in 1 M KOH. (h) Pb UPD for Ru1/Cu(111) and Ru1/Cu(100). (i) In situ Cu K-edge XAFS for Ru-doped octahedral Cu2O.
aqueous environments is highly desired to acquire fundamental constructing a Raman-enhanced coupled nanostructure
insight, including the migration distance and the molecular composed of SHINs and single-atom Ru-doped Cu with
mechanism of hydrogen spillover in electrocatalytic reac-
specific facets (denoted as Ru1/Cu(111) and Ru1/Cu(100),
tions.44−50
Shell-isolated nanoparticle-enhanced Raman spectroscopy respectively). Taking para-nitrothiophenol (pNTP) as the
(SHINERS), as a new generation of spectroscopy, possesses probe molecule, we observed that the electrocatalytic hydro-
extremely high sensitivity and wide universality for in situ genation on Cu(111) was more favorable than on (100) facets,
monitoring of the catalytic reaction.51−53 In SHINERS, Au
nanoparticles with the Raman enhancement effect are encased spectroscopically evidencing that the hydrogen spillover
in ultrathin silica to form shell-isolated nanoparticles (SHINs), distance on Cu surfaces was facet-dependent. Moreover,
simultaneously isolating the interference of the Au core.54−57 electrochemical hydrogen spillover distances were tunable
Moreover, SHINERS could easily eliminate the interference with the variation of applied potentials, which increased,
from the signal of bulk water since only species close to the
surface could be enhanced, making it particularly well-suited ranging from 0.8 to 2.6 nm as the potentials shifted negatively.
for in situ study of electrocatalytic reactions in aqueous Furthermore, we found that leveraging the hydrogen spillover
solution.58,59 Thus, it is appealing to combine SHINERS and effect to enhance hydrogen coverage on Cu(111) could alter
site-isolated SACs to elucidate the underlying mechanism of
the rate-determining step in nitrate (NO3−) electroreduction,
hydrogen spillover in electrocatalytic reactions.
Herein, we realized the spectroscopic visualization of significantly improving the catalytic activity toward NH3
hydrogen spillover under electrochemical conditions by production.
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Figure 2. (a) Scheme of in situ SHINERS study on the hydrogenation of pNTP. (b) Distribution of the electromagnetic field simulated by the 3D-
FDTD method. (c) Cross-sectional SEM and (d) typical SEM images of Ru1/Cu(111) assembled with SHINs. (e) HAADF-STEM and
corresponding EDS mapping of Ru1/Cu(111) assembled with SHINs. In situ Raman spectra of hydrogenation of pNTP on (f) Ru1/Cu(111) and
(g) Cu(111). (h) Conversion of pNTP over Ru1/Cu(111) and Ru1/Cu(100).
■ RESULTS
Design of Ru1/Cu(111) and Ru1/Cu(100) Catalysts
structure (XANES) of the two catalysts were located between
Ru foil and RuO2, indicating the oxidation state of Ru species
in the two catalysts (Figure 1e). Figure 1f depicts the Ru K-
Octahedral Cu2O with {111} facets and cubic Cu2O with edge extended X-ray absorption fine structure (EXAFS)
{100} facets were initially synthesized by a wet chemical spectra of Ru1/Cu(111) and Ru1/Cu(100). The peaks at
method (Figure S1).60,61 The introduction of Ru single atoms 1.53 Å were ascribed to Ru−O bonds, which were originated
was achieved by immersing Cu2O into a RuCl3 solution before from the inevitable oxidation of catalysts after exposure to the
an electroreduction process to reduce Cu2O into Cu air.62 Notably, the peaks at 2.21 Å of the two catalysts were
nanoparticles with well-defined shapes. As shown in Figure assigned to Ru−Cu bonds, which were distinct from that of Ru
1a,b, the scanning electron microscopy (SEM) images of Ru1/ foil (2.39 Å). The absence of the Ru−Ru bond verified the
Cu(111) and Ru1/Cu(100) showed that the facets were well- atomic dispersion of Ru in the two catalysts. The fitting results
preserved after the galvanic process, with a slightly increased and the wavelet transform (WT)-EXAFS analysis also
surface roughness. The uniform distribution of Ru was identified the presence of Ru−Cu coordination in Ru1/
demonstrated by high-angle annular dark-field scanning Cu(111) and Ru1/Cu(100) (Figures S3 and S4, and Table
transmission electron microscopy (HAADF-STEM) combined S1).
with energy-dispersive X-ray spectroscopy (EDS) mapping To acquire more facet features of the Ru1/Cu(111) and
(Figure 1c,d). As displayed in Figure S2, the X-ray diffraction Ru1/Cu(100) catalysts, we investigated the electrochemical
(XRD) patterns of Ru1/Cu(111) and Ru1/Cu(100) matched adsorption of OH− and lead underpotential deposition (UPD),
well with the metallic Cu without the observation of residual respectively. Figure 1g shows the cyclic voltammetry (CV)
Cu2O phase after the electroreduction. To verify the chemical curves of the two catalysts in 1 M KOH. The peaks of OH−
state and coordination structure of Ru species, we conducted adsorption appeared at ∼0.42 and ∼0.33 V vs reversible
Ru K-edge X-ray absorption fine structure (XAFS) measure- hydrogen electrode (RHE) for Ru1/Cu(111) and Ru1/
ments for Ru1/Cu(111) and Ru1/Cu(100). The energy Cu(100), respectively, demonstrating the facet-dependent
adsorption edge profiles in the X-ray absorption near edge OH− adsorption behavior.61 In addition, the reduction peaks
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Figure 3. (a) Hydrogen spillover distance over Ru1/Cu(111) and Ru1/Cu(100) at different applied potentials. The in situ Raman spectra of pNTP
hydrogenation over (b) Ru1/Cu(111) and (c) Ru1/Cu(100) at different site densities of Ru. (d) Conversion of pNTP and (e) hydrogen spillover
distance at different site densities of Ru. (f) Scheme of hydrogen spillover on the surface of Ru1/Cu(111) and Ru1/Cu(100).
of Pb UPD for Ru1/Cu(111) and Ru1/Cu(100) were observed the plasmonic nanogap between the SHINs and the underlying
at −0.034 and −0.055 V vs RHE, respectively, further implying catalysts via the three-dimensional finite difference time
that Ru1/Cu(111) and Ru1/Cu(100) inherited the surface domain (3D-FDTD) method. The Raman signals of adsorbed
features of cubic and octahedral Cu, respectively.63 More species on the catalysts could be magnified by 106, enabling in
importantly, we carried out in situ Cu K-edge XAFS to probe situ Raman investigation into the hydrogenation reaction. The
the dynamic structure revolution during the electroreduction cross-sectional SEM images clearly illustrated the multilayer
of Ru-doped Cu2O (Figures 1h and S5 and S6). It is obvious structure of SHINs-assembled Ru1/Cu(111) and Ru1/Cu-
that Cu2O was gradually reduced to metallic Cu with the (100) nanocomposites (Figures 2c and S8). As shown in SEM
increased applied potentials. Specifically, at the applied images, HAADF-STEM images, and EDS mapping results, the
potential of −0.6 V vs RHE, the disappearance of the Cu−O monolayer SHINs were uniformly distributed on the surface of
bond demonstrated the complete reduction of the oxide, which Ru1/Cu(111) and Ru1/Cu(100) (Figures 2d,2e and S9).
was consistent with the XRD result. Compared with catalysts alone and the physical mixture of
In Situ SERS Study of the Facet-Dependent Hydrogenation catalysts and SHINs, the Raman signal of pNTP was
on Ru1/Cu(111) and Ru1/Cu(100) significantly magnified on SHINs-assembled catalysts, enabling
The reduction of pNTP to para-aminothiophenol (pATP) the in situ Raman investigation into the hydrogenation process
generally serves as a probe reaction with the conversion of the (Figure S10).
nitro group to an amino group once in contact with surface- To investigate the facet-dependent hydrogenation of pNTP,
adsorbed H, enabling molecular-level visualization of the we initially conducted in situ Raman measurements at different
hydrogen spillover process.45−47 The electrochemical hydro- applied potentials. The Raman peaks at 1337 and 1571 cm−1
genation of pNTP to para-aminothiophenol (pATP) was were ascribed to the symmetric nitro stretching vibration and
employed as a model reaction to assess the facet-dependent the phenyl ring modes of pNTP, respectively (Figure 2f,g).64
hydrogenation on Ru1/Cu(111) and Ru1/Cu(100). Given the As the potentials shifted negatively, the Raman peaks at 1571
SHINERS as an ultrasensitive spectroscopy technique to cm−1 gradually shifted to 1594 cm−1, which was assigned to the
investigate the catalytic reactions, we fabricated SHINs on the benzene ring mode of pATP, indicating that pNTP was
surface of the catalysts to monitor the hydrogenation process. gradually hydrogenated to pATP. As displayed in Figures 2f
Figure 2a illustrates the schemes of the hydrogenation reaction and S11a, the emergence of pATP for Ru1/Cu(111) and Ru1/
over Ru1/Cu(111) assembled with SHINs. Ru1/Cu(111) and Cu(100) was observed at the potential of −0.1 V vs RHE. In
Ru1/Cu(100) were initially deposited on the glass carbon comparison, the counterparts without Ru incorporation were
electrodes as the working electrode, respectively, followed by denoted as Cu(111) and Cu(100), respectively (Figure S12).
immersion in the solution of pNTP to adsorb the pNTP. The signals of pATP for Cu(111) and Cu(100) appeared until
Then, a monolayer of SHINs was prepared on the surface of the potential shifted to as negative as −0.4 V vs RHE,
electrodes via a universal method (Figure S7). Figure 2b shows demonstrating that bare Cu could hardly activate H2O at low
the distribution of the electromagnetic (EM) field generated in potentials (Figures 2g and S11b). As such, the hydrogenation
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Figure 4. (a) Free energy diagram of the *H generation over Ru1/Cu(111) and Cu(111). (b) Free energy diagram of the *H generation over Ru1/
Cu(100) and Cu(100). Free energy diagram of the hydrogen spillover over (c) Ru1/Cu(111) and (d) Ru1/Cu(100). The yellow, purple, red, and
white spheres represent Cu, Ru, O, and H atoms, respectively. The asterisk represents an adsorption site.
of pNTP on Ru1/Cu(111) and Ru1/Cu(100) below the 1.8 nm, much higher than that on Cu(100) (0.8 nm),
potential of −0.3 V vs RHE could be attributed to the spillover highlighting the superior hydrogen migration capability of the
hydrogenation with *H species generated on Ru sites and then Cu(111) facet. With the negative shift of potentials, the
spilled over Cu facets. Notably, the signal of pNTP on Ru1/ hydrogen spillover distance initially extended and then
Cu(111) completely disappeared at −0.6 V vs RHE, whereas remained stable at higher potentials. Notably, at the potential
residual pNTP was still observed on Ru1/Cu(100). The more of −0.3 V vs RHE, the H spillover distance on Cu(111) facet
favorable hydrogenation of pNTP over Ru1/Cu(111) than was estimated to be 2.4 nm, which was longer than that on
Ru1/Cu(100) implied the superior hydrogen spillover on Ru1/ Cu(100) facet (1.9 nm). Previous studies have shown that,
Cu(111). Figure 2h displays the conversion of pNTP under nonelectrochemical conditions, hydrogen can migrate
calculated by the integrated areas of the peaks at 1337 cm−1. over hundreds of nanometers across the Cu(100) surface.31
Obviously, the conversion over Ru1/Cu(111) was higher than This discrepancy might be caused by the consumption of the
that over Ru1/Cu(100), especially under the low potentials surface-adsorbed hydrogen species by water molecules or
(−0.1 ∼ −0.3 V vs RHE), further revealing that the hydrogen protons under electrochemical conditions. To verify the
spillover effect under electrocatalytic hydrogenation was more reliability of the quantified hydrogen spillover distance, we
profound on the Cu(111) facet than the Cu(100) facet. further regulated the site density of Ru atoms to investigate the
To further clarify the facet effect on hydrogen spillover, we conversion of pNTP (Table S2). When the spillover distance
conducted a series of control experiments. As shown in Figure was smaller than half of the average distance between adjacent
S13, the coverage of adsorbed pNTP on the catalyst’s surface Ru atoms, the pNTP conversion would increase with the
had no significant impact on the hydrogenation process. growing Ru site density until approaching 100%. As shown in
Besides, the plasmon-induced hot electrons are not sufficient Figure 3b,3c, in situ Raman spectra of the hydrogenation
for driving the conversion of pNTP to pATP due to the fast process on Ru1/Cu(111) and Ru1/Cu(100) with different ns
charge-carrier recombination, implying that the hydrogenation values were collected at −0.3 V vs RHE after 30 min reaction.
of pNTP originated from an electrochemical process (Figure As expected, the Raman peak associated with the −NO2 group
S14). Then, we estimated the spillover distance over different of pNTP gradually decreased with increasing ns values for the
Cu facets based on the conversion of pNTP and the site two catalysts. Notably, Ru1/Cu(111) exhibited a higher pNTP
density of Ru atoms (ns, Ru atoms per 100 nm2). As displayed conversion than Ru1/Cu(100) when ns was below 33,
in Figure 3a, at a low potential of −0.1 V vs RHE, the suggesting a broader hydrogenation range on the Cu(111)
hydrogen spillover distance on Cu(111) was measured to be surface (Figure 3d). Based on the conversion and the
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Figure 5. (a) Current density of Ru1/Cu(111) and Cu(111) in 0.5 M Na2SO4 containing 0.1 M KNO3. (b) Yield rate of NH3 on Ru1/Cu(111)
and Cu(111). (c) Scheme of hydrogen spillover for NO3− electroreduction. (d) EPR spectra of electrocatalysts under different conditions. The
DEMS results of (e) Ru1/Cu(111) and (f) Cu(111). (g) Free energy diagram of the NO3− reduction. The yellow, blue, red, and white spheres
represent Cu, N, O, and H atoms, respectively. The asterisk represents an adsorption site.
corresponding ns value, the hydrogen spillover distance for Density Functional Theory (DFT) Calculations
Ru1/Cu(111) was estimated to be 2.0−2.4 nm, which is larger DFT calculations were conducted to acquire deeper insight
than that for Ru1/Cu(100) (1.6−1.8 nm) (Figure 3e). In
into the facet-dependent H spillover. As displayed in Figure
addition, the two catalysts with a sufficient surface Ru site
density to supply abundant *H both exhibited a fast kinetic of 4a,b, in terms of the barrier for H2O dissociation, the Ru sites
pNTP hydrogenation (Figure S15). In this regard, the facet- on Ru1/Cu(111) and Ru1/Cu(100) were more active in
dependent hydrogenation of pNTP observed at lower Ru generating *H than the Cu sites on Cu(111) and Cu(100). In
densities was primarily governed by the hydrogen spillover this case, the doping of Ru would accelerate the generation of
distance. These results demonstrated that the Cu(111) facet *H. We further calculated the free energy of hydrogen spillover
facilitated hydrogen spillover more than Cu(100).31 over Ru1/Cu(111) and Ru1/Cu(100) to evaluate the spill
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ability of *H, respectively (Figure 4c,d). It is worth noting that mediates (Figures S20 and S21). In addition, the energy barrier
the kinetic barrier for *H spillover on Ru1/Cu(111) was 0.59 of PDS (*NH3 → * + NH3) in the *H-mediated pathway was
eV (Figure 4c), which was much lower than that on Ru1/ 0.30 eV, which was lower than that in the PCET pathway,
Cu(100) (Figures 4d and S16). As such, the abundant Cu manifesting the superiority of the *H-mediated pathway in the
hollow sites on Ru1/Cu(111) supported the migration of *H electroreduction of NO3−. As such, under the effect of *H
from the Ru sites, which was conducive to the hydrogenation spillover, the rate-determining step of nitrate electroreduction
of pNTP. was altered, giving rise to a significant enhancement of catalytic
Catalytic Performance toward NO3− Electroreduction performance.
To further elucidate the hydrogen spillover effect on the
electrocatalytic reaction, we investigated the catalytic perform-
■ CONCLUSION
In summary, we revealed the facet-dependent and potential-
ance of Ru1/Cu(111) and Cu(111) toward nitrate electro-
dependent hydrogen spillover during the electrochemical
reduction, which is a promising pathway for renewable
hydrogenation process using the SHINERS. As the potentials
ammonia production. As shown in Figure 5a, the current
shifted negatively, the electrochemical hydrogen spillover
densities of Ru1/Cu(111) in the electrolyte containing 1 M
distances increased, ranging from 0.8 to 2.6 nm for Cu(111)
KNO3 were much larger than those of Cu(111), implying the and (100) facets. In addition, we found that leveraging the
superior activity of Ru1/Cu(111). Then, we evaluated the hydrogen spillover effect to increase the hydrogen coverage on
performance of Ru1/Cu(111) with different site densities of the Cu(111) surface could alter the rate-determining step of
Ru. The production of NH3 in the electrolyte was quantified nitrate electroreduction, resulting in a significant enhancement
by the indophenol blue method (Figure S17). As displayed in of catalytic performance. This work provides a profound
Figure 5b, compared with Cu(111), the samples modified by understanding of hydrogen spillover under electrochemical
Ru all exhibited a higher yield rate of NH3. Notably, as the ns conditions and guides the rational design of electrocatalysts
of Ru increased, the yield rate of NH3 initially increased but with the hydrogen spillover concept.
then decreased. This phenomenon indicated that the moderate
Ru content could supply appropriate *H to match the
hydrogenation of nitrate, whereas excessive Ru would provide
superfluous *H to bind together, generating undesired H2
■ ASSOCIATED CONTENT
* Supporting Information
sı
(Figures 5c and S18). Given the crucial role of *H in the NO3− The Supporting Information is available free of charge at
electroreduction, we conducted electron paramagnetic reso- https://pubs.acs.org/doi/10.1021/jacs.6c00294.
nance (EPR) measurements to probe the generation of *H Experimental procedures, characterization of pristine
using 5,5-dimethyl-1-pyrroline N-oxide (DMPO) as a *H Cu2O, XRD of Ru1/Cu(111) and Ru1/Cu(100), EXAFS
trapping reagent. As displayed in Figure 5d, at the potential of fitting results, SEM and TEM of SHINs-assembled Ru1/
−0.3 V vs RHE, Ru1/Cu(111) showed stronger DMPO-H Cu(100), in situ Raman of pNTP hydrogenation on
signals in the electrolyte without NO3− relative to Cu(111), SHINs-assembled Ru1/Cu(100), concentration−absorb-
demonstrating that the introduction of Ru promoted the H2O ance curve of NH4+, and the structure models of
dissociation to produce abundant *H.32 After the addition of intermediates for Cu(111) (PDF)
NO3−, the DMPO-H signals of Ru1/Cu(111) were undetect-
able, revealing that the generated *H was rapidly consumed to
boost the hydrogenation of NO3−.
To understand the reaction pathways of NO3− electro-
■ AUTHOR INFORMATION
Corresponding Authors
reduction, we performed electrochemical online differential Jie Wei − College of Energy, College of Materials, State Key
electrochemical mass spectrometry (DEMS) for Ru1/Cu(111) Laboratory of Physical Chemistry of Solid Surfaces, College of
and Cu(111). The signal of the *NO2 intermediate was not Chemistry and Chemical Engineering, School of Life Sciences,
detected for the two samples, implying the effective conversion College of Physical Science and Technology, Discipline of
of NO2− during the reaction process (Figure 5e,f). It is worth Intelligent Instrument and Equipment, iChEM, Fujian Key
noting that the signal of *NH2OH was observed only in Laboratory of Advanced Materials, Xiamen University,
Cu(111), verifying that the NO3− electroreduction for Xiamen 361005, China; Innovation Laboratory for Sciences
Cu(111) experienced the pathway containing *NH2OH and Technologies of Energy Materials of Fujian Province
intermediates. In the case of Ru1/Cu(111), the absence of (IKKEM), Xiamen 361102, China; orcid.org/0009-
the *NH2OH signal indicated that Ru1/Cu(111) circumvented 0003-5437-6345; Email: weij@xmu.edu.cn
the NH2OH pathway due to the sufficient supply of *H. To Hua Zhang − College of Energy, College of Materials, State
get a theoretical insight into the role of *H in NO3− Key Laboratory of Physical Chemistry of Solid Surfaces,
electroreduction, we conducted DFT calculations based on College of Chemistry and Chemical Engineering, School of
the typical proton-coupled electron transfer (PCET) pathway Life Sciences, College of Physical Science and Technology,
and *H-mediated pathway for Cu(111), respectively. As Discipline of Intelligent Instrument and Equipment, iChEM,
displayed in Figures 5g and S19, the step from *NO to Fujian Key Laboratory of Advanced Materials, Xiamen
*NOH with an energy barrier of 0.36 eV served as the University, Xiamen 361005, China; Innovation Laboratory
potential-determining step (PDS) in the PCET pathway, for Sciences and Technologies of Energy Materials of Fujian
indicating the unfavorable generation of NH3. Surprisingly, in Province (IKKEM), Xiamen 361102, China; orcid.org/
the *H-mediated pathway, the *NO intermediate sponta- 0000-0001-9588-9030; Email: zhanghua@xmu.edu.cn
neously transformed into *NH with a quite negative free Jian-Feng Li − College of Energy, College of Materials, State
energy change (−1.58 eV), which was attributed to the Key Laboratory of Physical Chemistry of Solid Surfaces,
spontaneous binding of *H with nitrogen-containing inter- College of Chemistry and Chemical Engineering, School of
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Life Sciences, College of Physical Science and Technology, (4) Li, M.; Wu, Y.; Zhao, B.-H.; Cheng, C.; Zhao, J.; Liu, C.; Zhang,
Discipline of Intelligent Instrument and Equipment, iChEM, B. Electrosynthesis of amino acids from NO and α-keto acids using
Fujian Key Laboratory of Advanced Materials, Xiamen two decoupled flow reactors. Nat. Catal. 2023, 6, 906−915.
University, Xiamen 361005, China; Innovation Laboratory (5) Xiong, H. C.; Yu, P. P.; Chen, K. D.; Lu, S. K.; Hu, Q. K.;
Cheng, T.; Xu, B. J.; Lu, Q. Urea synthesis via electrocatalytic
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Chemistry, Chemical Engineering and Environment, Minnan (6) Kang, H.; Zhu, L.; Li, S. Y.; Yu, S. W.; Niu, Y. M.; Zhang, B. S.;
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Key Laboratory of Physical Chemistry of Solid Surfaces, spillover-bridged Volmer/Tafel processes enabling ampere-level
College of Chemistry and Chemical Engineering, School of current density alkaline hydrogen evolution reaction under low
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University, Xiamen 361005, China phenomenon of electrocatalytic hydrogen evolution. Nat. Commun.
2021, 12, No. 3502.
Yan Liu − School of Chemistry and Materials Science, Anhui (11) Fan, H.; Yang, Q. Q.; Fang, S. R.; Xu, Y. N.; Lv, Y.; Lin, H. Y.;
Normal University, Wuhu 241000, China Lin, M. Y.; Liu, J. K.; Wu, Y. X.; Yuan, H. Y.; Dai, S.; Liu, P. F.; Yang,
Complete contact information is available at: H. G. Operando stable palladium hydride nanoclusters anchored on
https://pubs.acs.org/10.1021/jacs.6c00294 tungsten carbides mediate reverse hydrogen spillover for hydrogen
evolution. Angew. Chem., Int. Ed. 2024, 63, No. e202412080.
Notes (12) Bao, D.; Huang, L.; Gao, Y.; Davey, K.; Zheng, Y.; Qiao, S. Z.
Dynamic creation of a local acid-like environment for hydrogen
The authors declare no competing financial interest. evolution reaction in natural seawater. J. Am. Chem. Soc. 2024, 146,
■ ACKNOWLEDGMENTS
This work was supported by NSFC (52571257, 22302184,
34711−34719.
(13) Chen, J.; Chen, C.; Qin, M.; Li, B.; Lin, B.; Mao, Q.; Yang, H.;
Liu, B.; Wang, Y. Reversible hydrogen spillover in Ru-WO3‑x enhances
hydrogen evolution activity in neutral pH water splitting. Nat.
22361132532, 22525042, T2293692, U25A20558 and Commun. 2022, 13, No. 5382.
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