双金属片
化学
纳米团簇
密度泛函理论
催化作用
星团(航天器)
铜
结晶学
兴奋剂
单晶
配体(生物化学)
卤化物
法拉第效率
晶体结构
纳米技术
电极
无机化学
物理化学
电化学
计算化学
材料科学
有机化学
光电子学
程序设计语言
计算机科学
生物化学
受体
作者
Guocheng Deng,Hyewon Yun,Megalamane S. Bootharaju,Fang Sun,Kangjae Lee,Xiaolin Liu,Seungwoo Yoo,Qing Tang,Yun Jeong Hwang,Taeghwan Hyeon
摘要
Unraveling the atomistic synergistic effects of nanoalloys on the electrocatalytic CO2 reduction reaction (eCO2RR), especially in the presence of copper, is of paramount importance. However, this endeavor encounters significant challenges due to the lack of the crystallographically determined atomic-level structure of appropriate monometallic and bimetallic analogues. Herein, we report a one-pot synthesis and structure characterization of a AuCu nanoalloy cluster catalyst, [Au15Cu4(DPPM)6Cl4(C≡CR)1]2+ (denoted as Au15Cu4). Single-crystal X-ray diffraction analysis reveals that Au15Cu4 comprises two interpenetrating incomplete, centered icosahedra (Au9Cu2 and Au8Cu3) and is protected by six DPPM, four halide, and one alkynyl ligand. The Au15Cu4 cluster and its closest monometal structural analogue, [Au18(DPPM)6Br4]2+ (denoted as Au18), as model systems, enable the elucidation of the atomistic synergistic effects of Au and Cu on eCO2RR. The results reveal that Au15Cu4 is an excellent eCO2RR catalyst in a gas diffusion electrode-based membrane electrode assembly (MEA) cell, exhibiting a high CO Faradaic efficiency (FECO) of >90%, and this efficiency is substantially higher than that of the undoped Au18 (FECO: 60% at -3.75 V). Au15Cu4 exhibits an industrial-level CO partial current density of up to -413 mA/cm2 at -3.75 V with the gas CO2-fed MEA, which is 2-fold higher than that of Au18. The density functional theory (DFT) calculations demonstrate that the synergistic effects are induced by Cu doping, where the exposed pair of AuCu dual sites was suggested for launching the eCO2RR process. Besides, DFT simulations reveal that these special dual sites synergistically coordinate a moderate shift in the d-state, thus enhancing its overall catalytic performance.
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