Jia Yufei, Ding Yunxuan, Song Tao, Xu Yunlong, Li Yaqing, Duan Lele, Li Fei, Sun Licheng, Fan Ke
State Key Laboratory of Fine Chemicals, Institute of Artificial Photosynthesis, DUT-KTH Joint Education and Research Centre on Molecular Devices, Institute for Energy Science and Technology, Dalian University of Technology, Dalian, 116024, P. R. China.
Center of Artificial Photosynthesis for Solar Fuels, Department of Chemistry, School of Science, Westlake University, Hangzhou, 310024, P. R. China.
Adv Sci (Weinh). 2023 Oct;10(28):e2303726. doi: 10.1002/advs.202303726. Epub 2023 Aug 2.
The recognition of the surface reconstruction of the catalysts during electrochemical CO reduction (CO2RR) is essential for exploring and comprehending active sites. Although the superior performance of Cu-Zn bimetallic sites toward multicarbon C products has been established, the dynamic surface reconstruction has not been fully understood. Herein, Zn-doped Cu O nano-octahedrons are used to investigate the effect of the dynamic stability by the leaching and redeposition on CO2RR. Correlative characterizations confirm the Zn leaching from Zn-doped Cu O, which is redeposited at the surface of the catalysts, leading to dynamic stability and abundant Cu-Zn bimetallic sites at the surface. The reconstructed Zn-doped Cu O catalysts achieve a high Faradaic efficiency (FE) of C products (77% at -1.1 V versus reversible hydrogen electrode (RHE)). Additionally, similar dynamic stability is also discovered in Al-doped Cu O for CO2RR, proving its universality in amphoteric metal-doped catalysts. Mechanism analyses reveal that the OHC-CHO pathway can be the C-C coupling processes on bare Cu O and Zn-doped Cu O, and the introduction of Zn to Cu can efficiently lower the energy barrier for CO2RR to C H . This research provides profound insight into unraveling surface dynamic reconstruction of amphoteric metal-containing electrocatalysts and can guide rational design of the high-performance electrocatalysts for CO2RR.
认识电化学CO还原（CO2RR）过程中催化剂的表面重构对于探索和理解活性位点至关重要。尽管已经证实了Cu-Zn双金属位点对多碳C产物具有优异性能，但动态表面重构尚未得到充分理解。在此，使用Zn掺杂的CuO纳米八面体来研究浸出和再沉积对CO2RR的动态稳定性的影响。相关表征证实了Zn从Zn掺杂的CuO中浸出，并重新沉积在催化剂表面，从而导致表面的动态稳定性和丰富的Cu-Zn双金属位点。重构的Zn掺杂CuO催化剂实现了C产物的高法拉第效率（FE）（相对于可逆氢电极（RHE）在-1.1 V时为77%）。此外，在用于CO2RR的Al掺杂CuO中也发现了类似的动态稳定性，证明了其在两性金属掺杂催化剂中的普遍性。机理分析表明，OHC-CHO途径可能是裸CuO和Zn掺杂CuO上的C-C偶联过程，并且将Zn引入Cu可以有效降低CO2RR生成C2H4的能垒。这项研究为揭示含两性金属的电催化剂的表面动态重构提供了深刻见解，并可指导用于CO2RR的高性能电催化剂的合理设计。
