Zisheng Zhang

All Publications

• Off-Equilibrium Reactivity of Boron-Enriched Metal Diboride Surfaces in Electroreduction Conditions ACS CATALYSIS Zhang, Z., Abild-Pedersen, F. 2025

  View details for DOI 10.1021/acscatal.5c04054

  View details for Web of Science ID 001526334700001

• Structure Sensitivity and Catalyst Restructuring for CO₂ Electro-reduction on Copper NATURE COMMUNICATIONS Cheng, D., Nguyen, K. C., Sumaria, V., Wei, Z., Zhang, Z., Gee, W., Li, Y., Morales-Guio, C. G., Heyde, M., Roldan Cuenya, B., Alexandrova, A. N., Sautet, P. 2025; 16 (1): 4064

  Abstract

  Cu is the most promising metal catalyst for CO2 electroreduction (CO2RR) to multi-carbon products, yet the structure sensitivity of the reaction and the stability versus restructuring of the catalyst surface under reaction conditions remain controversial. Here, atomic scale simulations of surface energies and reaction pathway kinetics supported by experimental evidence unveil that CO2RR does not take place on perfect planar Cu(111) and Cu(100) surfaces but rather on steps or kinks. These planar surfaces tend to restructure in reaction conditions to the active stepped surfaces, with the strong binding of CO on defective sites acting as a thermodynamic driving force. Notably, we identify that the square motifs adjacent to defects, not the defects themselves, as the active sites for CO2RR via synergistic effect. We evaluate these mechanisms against experiments of CO2RR on ultra-high vacuum-prepared ultraclean Cu surfaces, uncovering the crucial role of step-edge orientation in steering selectivity. Overall, our study refines the structural sensitivity of CO2RR on Cu at the atomic level, highlights the self-activation mechanism and elucidates the origin of in situ restructuring of Cu surfaces during the reaction.

  View details for DOI 10.1038/s41467-025-59267-3

  View details for Web of Science ID 001479703200027

  View details for PubMedID 40307245

  View details for PubMedCentralID PMC12043938

• Reorganizing the Pt Surface Water Structure for Highly Efficient Alkaline Hydrogen Oxidation Reaction. Journal of the American Chemical Society Wan, C., Zhang, Z., Wang, S., Sun, Q., Liu, E., Pu, H., Zhang, A., Chen, Z., Shah, A. H., Fu, X., Alexandrova, A. N., Jia, Q., Huang, Y., Duan, X. 2025

  Abstract

  The hydrogen oxidation reaction (HOR) in alkaline electrolytes exhibits markedly slower kinetics than that in acidic electrolytes. This poses a critical challenge for alkaline exchange membrane fuel cells (AEMFCs). The slower kinetics in alkaline electrolytes is often attributed to the more sluggish Volmer step (hydrogen desorption). It has been shown that the alkaline HOR activity on the Pt surface can be considerably enhanced by the presence of oxophilic transition metals (TMs) and surface-adsorbed hydroxyl groups on TMs (TM-OHad), although the exact role of TM-OHad remains a topic of active debates. Herein, using single-atom Rh-tailored Pt nanowires as a model system, we demonstrate that hydroxyl groups adsorbed on the Rh sites (Rh-OHad) can profoundly reorganize the Pt surface water structure to deliver a record-setting alkaline HOR performance. In situ surface characterizations, together with theoretical studies, reveal that surface Rh-OHad could promote the oxygen-down water (H2O↓) that favors more hydrogen bond with Pt surface adsorbed hydrogen (H2O↓···Had-Pt) than the hydrogen-down water (OH2↓). The H2O↓ further serves as the bridge to facilitate the formation of an energetically favorable six-membered-ring transition structure with neighboring Pt-Had and Rh-OHad, thus reducing the Volmer step activation energy and boosting HOR kinetics.

  View details for DOI 10.1021/jacs.5c00775

  View details for PubMedID 40130907

• GOCIA: a grand canonical global optimizer for clusters, interfaces, and adsorbates. Physical chemistry chemical physics : PCCP Zhang, Z., Gee, W., Lavroff, R. H., Alexandrova, A. N. 2024

  Abstract

  Restructuring of surfaces and interfaces plays a key role in the activation and/or deactivation of a wide spectrum of heterogeneous catalysts and functional materials. The statistical ensemble representation can provide unique atomistic insights into this fluxional and metastable realm, but constructing the ensemble is very challenging, especially for the systems with off-stoichiometric reconstruction and varying coverage of mixed adsorbates. Here, we report GOCIA, a versatile global optimizer for exploring the chemical space of these systems. It features the grand canonical genetic algorithm (GCGA), which bases the target function on the grand potential and evolves across the compositional space, as well as many useful functionalities, with implementation details explained. GOCIA has been applied to various systems in catalysis, from clusters to surfaces and from thermal to electrocatalysis.

  View details for DOI 10.1039/d4cp03801k

  View details for PubMedID 39687986

• Cu-Supported ZnO under Conditions of CO2Reduction to Methanol: Why 0.2 ML Coverage? The journal of physical chemistry letters Lavroff, R. H., Cummings, E., Sawant, K., Zhang, Z., Sautet, P., Alexandrova, A. N. 2024: 11745-11752

  Abstract

  By hydrogenating carbon dioxide to value-added products such as methanol, heterogeneous catalysts can lower greenhouse gas emissions and generate alternative liquid fuels. The most common commercial catalyst for the reduction of CO2 to methanol is Cu/ZnO/Al2O3, where ZnO improves conversion and selectivity toward methanol. The structure of this catalyst is thought to be Zn oxy(hydroxyl) overlayers on the nanometer scale on Cu. In the presence of CO2 and H2 under reaction conditions, the Cu substrate itself can be restructured and/or partially oxidized at its interface with ZnO, or the Zn might be reduced, possibly completely to a CuZn alloy, making the exact structure and stoichiometry of the active site a topic of active debate. In this study, we examine Zn3 clusters on Cu(100) and Cu(111), as a subnano model of the catalyst. We use a grand canonical genetic algorithm to sample the system structure and stoichiometry under catalytic conditions: T of 550 K, initial partial pressures of H2 of 4.5 atm and CO2 of 0.5 atm, and 1% conversion. We uncover a strong dependence of the catalyst stoichiometry on the surface coverage. At the optimal 0.2 ML surface coverage, chains of Zn(OH) form on both Cu surfaces. On Cu(100), the catalyst has many thermally accessible metastable minima, whereas on Cu(111), it does not. No oxidation or reconstruction of the Cu is found. However, at a lower coverage of Zn, Zn3 clusters take on a metallic form on Cu(100), and slightly oxidized Zn3O on Cu(111), while the surface uptakes H to form a variety of low hydrides of Cu. We thus hypothesize that the 0.2 ML Zn coverage is optimal, as found experimentally, because of the stronger yet incomplete oxidation afforded by Zn at this coverage.

  View details for DOI 10.1021/acs.jpclett.4c02908

  View details for PubMedID 39547933

• Synthesis and characterization of low-dimensional N-heterocyclic carbene lattices SCIENCE Qie, B., Wang, Z., Jiang, J., Zhang, Z., Jacobse, P. H., Lu, J., Li, X., Liu, F., Alexandrova, A. N., Louie, S. G., Crommie, M. F., Fischer, F. R. 2024; 384 (6698): 895-901

  Abstract

  The covalent interaction of N-heterocyclic carbenes (NHCs) with transition metal atoms gives rise to distinctive frontier molecular orbitals (FMOs). These emergent electronic states have spurred the widespread adoption of NHC ligands in chemical catalysis and functional materials. Although formation of carbene-metal complexes in self-assembled monolayers on surfaces has been explored, design and electronic structure characterization of extended low-dimensional NHC-metal lattices remains elusive. Here we demonstrate a modular approach to engineering one-dimensional (1D) metal-organic chains and two-dimensional (2D) Kagome lattices using the FMOs of NHC-Au-NHC junctions to create low-dimensional molecular networks exhibiting intrinsic metallicity. Scanning tunneling spectroscopy and first-principles density functional theory reveal the contribution of C-Au-C π-bonding states to dispersive bands that imbue 1D- and 2D-NHC lattices with exceptionally small work functions.

  View details for DOI 10.1126/science.adm9814

  View details for Web of Science ID 001253631400002

  View details for PubMedID 38781380

• Tracking Active Phase Behavior on Boron Nitride during the Oxidative Dehydrogenation of Propane Using Operando X-ray Raman Spectroscopy. Journal of the American Chemical Society Cendejas, M. C., Paredes Mellone, O. A., Kurumbail, U., Zhang, Z., Jansen, J. H., Ibrahim, F., Dong, S., Vinson, J., Alexandrova, A. N., Sokaras, D., Bare, S. R., Hermans, I. 2023

  Abstract

  Hexagonal boron nitride (hBN) is a highly selective catalyst for the oxidative dehydrogenation of propane (ODHP) to propylene. Using a variety of ex situ characterization techniques, the activity of the catalyst has been attributed to the formation of an amorphous boron oxyhydroxide surface layer. The ODHP reaction mechanism proceeds via a combination of surface mediated and gas phase propagated radical reactions with the relative importance of both depending on the surface-to-void-volume ratio. Here we demonstrate the unique capability of operando X-ray Raman spectroscopy (XRS) to investigate the oxyfunctionalization of the catalyst under reaction conditions (1 mm outer diameter reactor, 500 to 550 °C, P = 30 kPa C3H8, 15 kPa O2, 56 kPa He). We probe the effect of a water cofeed on the surface of the activated catalyst and find that water removes boron oxyhydroxide from the surface, resulting in a lower reaction rate when the surface reaction dominates and an enhanced reaction rate when the gas phase contribution dominates. Computational description of the surface transformations at an atomic-level combined with high precision XRS spectra simulations with the OCEAN code rationalize the experimental observations. This work establishes XRS as a powerful technique for the investigation of light element-containing catalysts under working conditions.

  View details for DOI 10.1021/jacs.3c08679

  View details for PubMedID 37931025

• Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO(2)reduction NATURE ENERGY Zhang, X., Wang, Y., Gu, M., Wang, M., Zhang, Z., Pan, W., Jiang, Z., Zheng, H., Lucero, M., Wang, H., Sterbinsky, G. E., Ma, Q., Wang, Y., Feng, Z., Li, J., Dai, H., Liang, Y. 2020

  View details for DOI 10.1038/s41560-020-0667-9

  View details for Web of Science ID 000558156800001