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Heteroatom Doping Restructures Interfacial H2O to Resolve
Mechanistic Contradictions in CO2 Electroreduction
Lingyue Liu,∇ Haihui Lan,∇ Li Li, Weijue Wang, Yuhang Jin, Guoqin Liu, Yuhang Liu, Wenqiang Yang,
Ming Zhao, Jie Ding, Hongbin Yang,* Yanqiang Huang,* and Xinliang Feng*
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ABSTRACT: Interfacial H2O is increasingly recognized as an
active participant in electrocatalysis, yet a central challenge
remains: how to deliberately and predictably program its
microscopic structure to steer proton-coupled electron transfer
(PCET) and selectivity. Here we introduce nonmetal doping as a
materials-encoded handle to tune interfacial hydration on a model
SnO2 catalyst without changing its bulk phase. Across N, P and S
dopants, S uniquely stabilizes a disordered, predominantly H-down
hydration motif at the catalyst-electrolyte boundary, which
promotes H2O activation and directional proton delivery,
accelerating PCET toward formate formation. Notably, this
enhancement arises despite weaker binding of CO2-derived
intermediates, revealing a solution-structure-controlled selectivity
lever that can override conventional binding-energy-based expectations. By establishing a causal link between a doping-defined
hydration motif and reaction kinetics, this work elevates interfacial H2O from a “context” to a designable variable, and suggests a
broadly applicable strategy for optimizing PCET-governed transformations via interfacial solvation engineering.
■ INTRODUCTION
Electrocatalytic reactions occur at the delicate interface
regulation has provided compelling precedents, for example,
engineering cation solvation structures or interfacial hydrogen-
between catalyst surfaces and electrolyte solvents, where the bond networks can reshape local proton availability and
structure and dynamics of interfacial H2O layers have long reaction barriers (Figure 1b); however, these approaches
been regarded as spectators.1−3 Yet recent studies have begun predominantly rely on electrolyte-side tuning or external
to unravel a more active role of these H2O layers in shaping modifiers, whereas catalyst-side hydration programming
reactivity and selectivity.4−6 In the case of carbon dioxide encoded by the catalyst lattice itself remains far less
explored.16−21 These studies collectively support a view in
electroreduction (CO2RR), while catalyst composition and
which H2O can actively modulate transition-state stabilization
intermediate adsorption energies have traditionally been
depending on its orientation and degree of order.22,23
considered the primary descriptors for product selectivity,
However, compared with electrolyte-side solvation engineering
growing evidence suggests that interfacial solvation structure
or adsorbate/additive-mediated interfacial restructuring, a
can tip the balance between competing pathways.7−9
dopant-identity-defined, catalyst-encoded strategy that stabil-
A key conceptual shift is that interfacial H2O is not merely a
izes a measurable hydration motif (connectivity-disrupted yet
background medium: ordered hydration layers stabilized by
orientation-biased, H-down-rich) and links it quantitatively to
extended hydrogen-bond networks can impede elementary
PCET-controlled CO2RR kinetics is still underdeveloped,
proton-coupled electron transfer (PCET), whereas disordered
motivating the present study.24,25 We hypothesize that
hydration, particularly with a high H-down population, may
heteroatom doping offers a practical route to encode local
facilitate PCET-driven pathways (Figure 1a).10−15 Yet,
electrostatics and hydrogen-bonding propensity at the surface,
mechanistic interpretations of CO2RR still predominantly
rely on static surface descriptors such as intermediate binding
energies or metal oxidation states, which often fail to reconcile Received: April 23, 2026
predicted trends with experimentally observed selectivity. This Revised: July 14, 2026
mismatch points to interfacial solvation, and especially the Accepted: July 15, 2026
microscopic structure of interfacial H2O, as an independent
variable that must be considered alongside adsorbate
energetics. Electrolyte- and additive-driven microenvironment
© XXXX The Authors. Published by
American Chemical Society https://doi.org/10.1021/jacs.6c08293
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Figure 1. Modulating interfacial H2O structure through nonmetal doping in electrocatalysis. (a) Schematic illustration showing the transition from ordered to disordered H2O layers at the catalyst-electrolyte interface. While ordered H2O forms a robust hydrogen-bond network that stabilizes water molecules, disordered H2O exhibits enhanced molecular dynamics, facilitating H2O dissociation and proton-coupled electron transfer (PCET) by lowering the activation energy barrier. (b) Representative strategy of regulating interfacial H2O structure using hydrated alkali metal cations (Na+, K+, Cs+). Varying cation hydration energies and sizes affect the outer Helmholtz plane and influence H2O orientation and dissociation energetics. (c) Conceptual design of nonmetal heteroatom doping (N, S, P) into the catalyst lattice to directly perturb the interfacial H2O network. Beyond electronic modulation of the active site, these heteroatoms serve as polar interaction centers that restructure the local hydrogen-bonding environment, thereby promoting interfacial H2O disordering and lowering the barrier for H2O activation in electrocatalytic reactions.
Figure 2. Structural and electronic modulation of SnO2 by nonmetal dopants and their impact on CO2 electroreduction. (a) High-resolution XPS spectra confirming the formation of Sn−N, Sn−S, and Sn−P bonds in N-, S-, and P-doped SnO2, respectively, along with signals from oxidized species (e.g., N−O, S−O, P−O). (b) Sn L3-edge XANES spectra showing a progressive redshift and decreased white line intensity from pristine to P-doped SnO2, indicative of reduced Sn oxidation states and modified electronic environments induced by heteroatom coordination. (c) Partial current densities for HCOOH production as a function of applied potential, highlighting enhanced CO2RR performance for doped catalysts, particularly S-SnO2. (d) Stability test of S-SnO2 in a flow-cell electrolyzer at −1.0 V vs RHE, revealing stable formate Faradaic efficiency (FEHCOOH,
90%) and constant current density over 50 h of continuous operation, insect shows the photograph of the flow-cell setup used in the electrolysis experiments.
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thereby stabilizing distinct hydration motifs (including (−0.7 to −1.2 V vs RHE). As shown in Figure S6, S-SnO2 disordered, H-down-rich domains) that are favorable for exhibits the highest formate selectivity, maintaining FEHCOOH > PCET (Figure 1c).26,27 90% over the full potential window. In contrast, P-SnO2 shows Here, using S-doped SnO2 (S-SnO2) as a model system, we only moderate selectivity (∼70−80%), while N-SnO2 and show that heteroatom-modified surfaces can stabilize a unique SnO2 suffer from pronounced selectivity loss at more negative population of disordered interfacial H2O with predominant H- potentials due to increased hydrogen evolution and minor down orientation, as supported by AIMD simulations and CO/CH4 formation. The corresponding partial current operando spectroscopic signatures. More importantly, we densities for HCOOH (jHCOOH) follow the trend: SnO2 < establish a testable mechanistic framework in which a N-SnO2 < P-SnO2 < S-SnO2 (Figure 2c). Control experiments doping-encoded hydration motif regulates H2O activation varying N, S, and P doping concentration (Figures S7−S10) and directional proton delivery, thereby setting the effective show that while the formate activity dependence on barrier for the CO2-to-formate pathway beyond conventional concentration is nonmonotonic (e.g., for P), S remains the binding-energy descriptors. Combining operando measure- most effective across all tested ranges, underscoring a dopant- ments, AIMD-derived hydration statistics, isotopic labeling species-specific programming of interfacial water. Specifically, and kinetic isotope effect analyses, we demonstrate that the S-SnO2 reaches 60 mA cm−2 at −1.2 V vs RHE, representing microstructural H2 O environment can dictate CO 2RR more than a 4-fold increase over SnO2, confirming substantial selectivity even when CO2-derived intermediates bind more enhancement in intrinsic activity. Under continuous operation, weakly. This framework provides a falsifiable prediction and a S-SnO2 also demonstrates remarkable stability, maintaining broadly applicable design handle for PCET-governed electro- both FEHCOOH > 90% and a stable current density of ∼130 mA catalysis: programming interfacial solvation can rationalize and cm−2 for 80 h in the flow cell without observable degradation potentially overturn selectivity trends inferred solely from (Figure 2d), underscoring its robustness under operationally adsorbate-binding energetics. relevant conditions. Notably, although P-SnO2 shows the
■ RESULTS AND DISCUSSION To establish a model platform for dissecting the role of strongest electronic perturbation/oxidation-state shift (Figure 2b), it does not deliver the highest formate activity (Figure 2c), indicating that electronic descriptors alone do not
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igure 4d), shows that S-SnO2 exhibits intensified high- transfer pathways, both governed by the catalyst’s surface frequency O−H vibrations, consistent with strengthened electronic structure, it is equally critical to systematically H2O−surface interactions and a perturbed hydrogen-bond investigate how the catalyst’s surface electronic structure network.16,42 Complementary radial distribution functions modulates the electrochemical interface microenvironment, (RDFs), further reveal broadened first-shell features and particularly its influence on the PCET step. strongly damped medium-range oscillations in both Sn−H To further elucidate how interfacial H2O governs CO2RR and Sn−O correlations on S-SnO2, consistent with a kinetics and selectivity, we analyzed the O−H stretching region connectivity-disrupted interfacial solvation shell relative to (3080−3640 cm−1) of operando ATR-SEIRAS spectra (Figures SnO2, N-SnO2, and P-SnO2 (Figure 4e,f).43−45 Importantly, we 4a,b and S25).39,40 Rather than treating “ordered” and do not infer molecular orientation solely from ν OH “disordered” H2O as a purely qualitative binary assignment, deconvolution because ATR-SEIRAS intensities are governed F https://doi.org/10.1021/jacs.6c08293 J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
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by the surface-selection rule and depend strongly on dipole reorganized interfacial H2O specifically favors the PCET orientation (approximately cos2 θ).46 Instead, the H-down-rich pathway for CO2-to-formate conversion, while rendering the orientational bias on S-SnO2 is supported independently by sequence of steps required for H−H bond formation AIMD-derived two-dimensional angular distribution maps kinetically unfavorable. (cos θ1 − cos θ2, Figures 4g and S26), which quantify an asymmetric configuration with one O−H preferentially aligned toward the surface while the other is directed away. Together, ■ CONCLUSION In this study, we establish a solvation-structure-directed the hydration-shell connectivity disruption (RDF/VDOS) and paradigm for CO2 electroreduction by systematically engineer- orientational bias (cos θ maps) identify the S-SnO2 interface as ing the interfacial environment of SnO2 catalysts through connectivity-disrupted but orientation-biased (H-down-rich), nonmetal heteroatom doping. Integrating operando spectros- providing a structural basis for enhanced directional proton copy, ab initio molecular dynamics simulations, and electro- delivery and accelerated PCET. The energetic implications of chemical kinetics, we demonstrate that sulfur doping uniquely this solvent reorganization were further probed by DFT promotes disordered yet H-down-oriented H2O configurations calculations. Among all samples, S-SnO2 exhibits the most at the catalyst-electrolyte interface. This restructured hydration exergonic H2O adsorption energy (−0.97 eV, Figure S27) and layer lowers the barrier for interfacial H2O dissociation and a shortened S···H−O hydrogen bond distance of 1.91 Å enables efficient proton-coupled electron transfer (PCET), (Figure S28), forming a compact prereactive geometry thereby overriding conventional activity trends based on conducive to H2O activation. Most notably, the calculated intermediate adsorption energies or surface oxidation states. H2O dissociation barrier on S-SnO2 is nearly negligible (0.009 Notably, although P-SnO2 exhibits the strongest electronic eV, Figure S29), orders of magnitude lower than those of N- perturbation and intermediate binding affinity, it fails to deliver SnO2 (1.11 eV) and pristine SnO2 (1.32 eV). This nearly superior catalytic performance, highlighting the decisive role of barrierless dissociation process highlights the kinetic advantage interfacial H2O dynamics in governing reaction pathways. Our of the S-induced interfacial environment in promoting surface findings underscore that solvation structure, its orientation, hydroxyl generation and mobile proton supply during CO2RR. disorder, and reactivity, can serve as a tunable vector to To directly connect dopant-regulated interfacial H2O modulate electrochemical selectivity and kinetics. This insight structures with CO2 reduction kinetics, we evaluated CO2RR opens a new direction for electrocatalyst design, where performance and proton-transfer sensitivity for all four dynamic solvent−catalyst interactions are actively harnessed catalysts (Figure 5). Under CO2-saturated conditions (Figure alongside conventional surface engineering. 5a), S-SnO2 delivers the largest cathodic current density together with the smallest Tafel slope (155.7 mV dec−1, Figure 5b), indicating a distinct kinetic regime in which the barrier for the rate-determining step is substantially lowered. The low ■ ASSOCIATED CONTENT Data Availability Statement slope is consistent with a fast initial electron-transfer step All experimental and spectroscopic data are included in followed by a chemical protonation of *OCHO/*COOH Supporting Information. Source data are provided with this intermediates. H/D isotope substitution further reveals that paper. SnO2, N-SnO2 and P-SnO2 exhibit pronounced decreases in * sı Supporting Information CO2RR current density as the D2O fraction increases (Figure The Supporting Information is available free of charge at 5c), evidencing a strong kinetic isotope effect and highlighting https://pubs.acs.org/doi/10.1021/jacs.6c08293. their reliance on bulk proton supply. In contrast, S-SnO2 shows only a modest, gradual decline in current upon D2O addition, Schematic illustration of the fabrication procedures for implying that proton delivery is buffered by the preorganized heteroatom-doped S-SnO2 catalysts; powder X-ray H-down interfacial H2O network rather than limited by proton diffraction patterns of SnO2 and heteroatom-doped diffusion from the bulk. This interfacial robustness is also samples; elemental mapping of pristine and heteroatom- reflected in the product distribution: at −0.8 V vs RHE, the doped SnO2 catalysts; kinetic isotope effect (KIE) formate Faradaic efficiencies of SnO2, N-SnO2 and P-SnO2 analysis using H2O/D2O electrolytes (PDF) decrease noticeably with increasing D2O content, whereas S- SnO2 maintains both the highest FEHCOOH and the smallest isotope-induced variation (Figure 5d). Together with the structural and dynamical descriptors of the S-modified H2O ■ AUTHOR INFORMATION Corresponding Authors layer, these electrochemical trends support a scenario in which Hongbin Yang − School of Materials Science and Engineering, S-SnO2 sustains CO2RR through a solvent-organized, inter- Suzhou University of Science and Technology, Suzhou face-confined proton-transfer pathway that efficiently feeds 215009, China; Email: yanghb@mail.usts.edu.cn PCET to CO2-derived intermediates. Yanqiang Huang − State Key Laboratory of Catalysis, Dalian To verify that this dopant effect is selective for CO2RR Institute of Chemical Physics, Chinese Academy of Sciences, rather than a general acceleration of proton-involving Dalian 116023, China; University of Chinese Academy of reactions, we also evaluated HER in Ar-saturated electrolyte Sciences, Beijing 100049, China; orcid.org/0000-0002- (Figures S30−S31).47,48 In this case, S-SnO2 exhibits the 7556-317X; Email: yqhuang@dicp.ac.cn lowest HER current density despite its proton-rich interface, Xinliang Feng − Max Planck Institute of Microstructure and the isotope effect follows the opposite trend: HER activity Physics, Halle (Saale) 06120, Germany; Faculty of on SnO2, N-SnO2 and P-SnO2 is more strongly suppressed in Chemistry and Food Chemistry & Center for Advancing D2O than on S-SnO2. These control experiments corroborate Electronics Dresden (CFAED), Technische Universität that S-doping does not simply increase proton availability but Dresden, Dresden 01062, Germany; Email: Xinliang.feng@ reshapes the electrochemical double layer so that the mpi-halle.mpg.de G https://doi.org/10.1021/jacs.6c08293 J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
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