Advanced electrocatalysts capable of bifunctional catalysis for formic acid oxidation (FAOR) and hydrogen evolution reaction (HER) have garnered significant attention due to their exceptional energy efficiency. In this research, we have meticulously designed a PdCu bimetallene characterized by numerous crystalline/amorphous (c/a) interfaces and robust d–sp orbital hybridization, achieved by integrating the p-block metalloid boron within the PdCu matrix (B-PdCu-c/a). The B-PdCu-c/a bimetallene revealed a multitude of surface atoms and unsaturated defect sites, offering abundant catalytic active sites and an optimized electronic structure. The B₂-PdCu-c/a exhibited the best performance in FAOR and HER, achieving a mass activity of 1106 mA mg_cat^–1 and an overpotential of 52 mV, respectively. Significantly, the two-electrode configuration of B₂-PdCu-c/a∥B₂-PdCu-c/a attained a low cell voltage of 0.19 V at 10 mA cm^–2 during formic acid-assisted overall water splitting. Density functional theory (DFT) calculations indicated that c/a interface engineering and d–sp orbital hybridization synergistically optimized the electronic configuration of pristine PdCu bimetallene. This led to an elevation of the d-band center and an accumulation of charge at the c/a interface, which enhanced the adsorption of intermediates, facilitated C–H bond cleavage, and balanced the adsorption–desorption of hydrogen, thereby improving electrocatalytic activities for FAOR and HER, respectively. This study not only presents a viable strategy for effectively tuning the electronic configuration of bimetallene but also offers valuable insights into the development of electrocatalysts.

中文翻译：

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结晶/非晶界面工程和 d-sp 轨道杂交协同提高 PdCu 双金属烯的电催化性能，实现甲酸辅助的整体水分解


能够进行甲酸氧化 （FAOR） 和析氢反应 （HER） 双功能催化的先进电催化剂因其卓越的能源效率而受到广泛关注。在这项研究中，我们精心设计了一种 PdCu 双金属烯，其特征是具有许多结晶/非晶 （c/a） 界面和稳健的 d-sp 轨道杂化，这是通过在 PdCu 基体 （B-PdCu-c/a） 中整合 p 区准金属硼来实现的。B-PdCu-c/a 双金属烯揭示了大量的表面原子和不饱和缺陷位点，提供了丰富的催化活性位点和优化的电子结构。B 2-PdCu-c/a 在 FAOR 和 HER 中表现出最佳性能，质量活性分别为 1106 mA mg_cat^–1 和 52 mV。值得注意的是，在甲酸辅助的整体水分解过程中，B 2-PdCu-c/a∥B_2-PdCu-c/a 的双电极构型在 10 mA cm^–2 时达到了 0.19 V 的低电池电压。密度泛函理论 （DFT） 计算表明，c/a 界面工程和 d-sp 轨道杂化协同优化了原始 PdCu 双金属烯的电子构型。这导致 d 带中心升高，电荷在 c/a 界面积累，增强了中间体的吸附，促进了 C-H 键的裂解，平衡了氢的吸附-解吸，从而分别提高了 FAOR 和 HER 的电催化活性。这项研究不仅提出了一种有效调节双金属烯电子构型的可行策略，而且还为电催化剂的发展提供了有价值的见解。