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Abstract Cu is the most promising metal catalyst for CO₂electroreduction (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. 

Abstract Aldehyde‐assisted water electrolysis offers an attractive pathway for energy‐saving bipolar hydrogen production with combined faradaic efficiency (FE) of 200% while converting formaldehyde into value‐added formate. Herein we report the design and synthesis of noble metal‐free Cu₆Sn₅alloy as a highly effective electrocatalyst for formaldehyde electro‐oxidative dehydrogenation, demonstrating a geometric current density of 915 ± 46 mA cm⁻²at 0.4 V versus reversible hydrogen electrode, outperforming many noble metal electrocatalysts reported previously. The formaldehyde‐assisted water electrolyzer delivers 100 mA cm⁻²at a low cell voltage of 0.124 V, and a current density of 486 ± 20 mA cm⁻²at a cell voltage of 0.6 V without any iR compensation and exhibits nearly 200% faradaic efficiency for bipolar hydrogen production at 100 mA cm⁻²in 88 h long‐term operation. Density functional theory calculations further confirm the notably lowered barriers for dehydrogenation and Tafel steps on the Cu₆Sn₅ surface compared to Cu, underscoring its potential as a highly active catalyst. 

Abstract CO₂electroreduction (CO₂R) operating in acidic media circumvents the problems of carbonate formation and CO₂crossover in neutral/alkaline electrolyzers. Alkali cations have been universally recognized as indispensable components for acidic CO₂R, while they cause the inevitable issue of salt precipitation. It is therefore desirable to realize alkali‐cation‐free CO₂R in pure acid. However, without alkali cations, stabilizing *CO₂intermediates by catalyst itself at the acidic interface poses as a challenge. Herein, we first demonstrate that a carbon nanotube‐supported molecularly dispersed cobalt phthalocyanine (CoPc@CNT) catalyst provides the Co single‐atom active site with energetically localizeddstates to strengthen the adsorbate‐surface interactions, which stabilizes *CO₂intermediates at the acidic interface (pH=1). As a result, we realize CO₂conversion to CO in pure acid with a faradaic efficiency of 60 % at pH=2 in flow cell. Furthermore, CO₂is successfully converted in cation exchanged membrane‐based electrode assembly with a faradaic efficiency of 73 %. For CoPc@CNT, acidic conditions also promote the intrinsic activity of CO₂R compared to alkaline conditions, since the potential‐limiting step, *CO₂to *COOH, is pH‐dependent. This work provides a new understanding for the stabilization of reaction intermediates and facilitates the designs of catalysts and devices for acidic CO₂R. 

Abstract The dynamic restructuring of Cu surfaces in electroreduction conditions is of fundamental interest in electrocatalysis. We decode the structural dynamics of a Cu(111) electrode under reduction conditions by joint first‐principles calculations and operando electrochemical scanning tunneling microscopy (ECSTM) experiments. Combining global optimization and grand canonical density functional theory, we unravel the potential‐ and pH‐dependent restructuring of Cu(111) in acidic electrolyte. At reductive potential, Cu(111) is covered by a high density of H atoms and, below a threshold potential, Cu adatoms are formed on the surface in a (4×4) superstructure, a restructuring unfavorable in vacuum. The strong H adsorption is the driving force for the restructuring, itself induced by the electrode potential. On the restructured surface, barriers for hydrogen evolution reaction steps are low. Restructuring in electroreduction conditions creates highly active Cu adatom sites not present on Cu(111). 

Abstract Hydrazine‐assisted water electrolysis offers a feasible path for low‐voltage green hydrogen production. Herein, the design and synthesis of ultrathin RhRu_0.5‐alloy wavy nanowires as bifunctional electrocatalysts for both the anodic hydrazine oxidation reaction (HzOR) and the cathodic hydrogen evolution reaction (HER) is reported. It is shown that the RhRu_0.5‐alloy wavy nanowires can achieve complete electrooxidation of hydrazine with a low overpotential and high mass activity, as well as improved performance for the HER. The resulting RhRu_0.5bifunctional electrocatalysts enable, high performance hydrazine‐assisted water electrolysis delivering a current density of 100 mA cm⁻²at an ultralow cell voltage of 54 mV and a high current density of 853 mA cm⁻²at a cell voltage of 0.6 V. The RhRu_0.5 electrocatalysts further demonstrate a stable operation at a high current density of 100 mA cm⁻²for 80 hours of testing period with little irreversible degradation. The overall performance greatly exceeds that of the previously reported hydrazine‐assisted water electrolyzers, offering a pathway for efficiently converting hazardous hydrazine into molecular hydrogen. 

Ru decorated Ag nanoparticles are designed as highly effective bifunctional electrocatalysts for hydrazine oxidation and hydrogen evolution reactions, enabling a hydrazine assisted water electrolyser with greatly increased current density.