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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 The electrochemical hydrogenation (e‐hydrogenation) of unsaturated compounds like imines or carbonyls presents a benign reduction method. It enables direct use of electrons as reducing agent, water as proton source, while bypassing the need for elevated temperatures or pressures. In this contribution, we discuss the active species in electrocatalytic reductive amination with the transformation of acetone and methylamine as model reaction. Surprisingly, lead impurities in the ppm‐range proved to possess a significant effect in e‐hydrogenation. Accordingly, the influence of applied potential and cathode material in presence of 1 ppm Pb was investigated. Finally, we transferred the insights to the reduction of acetone manifesting comparable observations as for imine reduction. The results suggest that previous studies on electrochemical reduction in the presence of lead electrodes should be re‐evaluated. 

Copper electrodes corrode using mixtures of acetone and methylamine even under reductive potential conditions. Simulations explain this dynamical process from a microscopic perspective through the formation of a surface Cu–amine complex. 

Abstract Addressing sustainable energy storage remains crucial for transitioning to renewable sources. While Li‐ion batteries have made significant contributions, enhancing their capacity through alternative materials remains a key challenge. Micro‐sized silicon is a promising anode material due to its tenfold higher theoretical capacity compared to conventional graphite. However, its substantial volumetric expansion during cycling impedes practical application due to mechanical failure and rapid capacity fading. A novel approach is proposed to mitigate this issue by incorporating trace amounts of aluminum into the micro‐sized silicon electrode using ball milling. Density functional theory (DFT) is employed to establish a theoretical framework elucidating how grain boundary sliding, a key mechanism involved in preventing mechanical failure is facilitated by the presence of trace aluminum at grain boundaries. This, in turn, reduces stress accumulation within the material, reducing the likelihood of failure. To validate the theoretical predictions, capacity retention experiments are conducted on undoped and Al‐doped micro‐sized silicon samples. The results demonstrate significantly reduced capacity fading in the doped sample, corroborating the theoretical framework and showcasing the potential of aluminum doping for improved Li‐ion battery performance.