State Key Laboratory of High-Efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China.
Int J Mol Sci. 2023 Aug 11;24(16):12680. doi: 10.3390/ijms241612680.
Ethylene is an ideal CO product in an electrocatalytic CO reduction reaction (CORR) with high economic value. This paper synthesised Al-doped octahedral CuO (Al-CuO) nanocrystal by a simple wet chemical method. The selectivity of CORR products was improved by doping Al onto the surface of octahedral CuO. The Al-CuO was used as an efficient electrocatalyst for CORR with selective ethylene production. The Al-CuO exhibited a high % Faradic efficiency (FE) of 44.9% at -1.23 V (vs. RHE) in CO saturated 0.1 M KHCO electrolyte. Charge transfer from the Al atom to the Cu atom occurs after Al doping in CuO, optimizing the electronic structure and facilitating CORR to ethylene production. The DFT calculation showed that the Al-CuO catalyst could effectively reduce the adsorption energy of the *CHCOH intermediate and promote the mass transfer of charges, thus improving the FE. After Al doping into CuO, the center of d orbitals shift positively, which makes the d-band closer to the Fermi level. Furthermore, the density of electronic states increases due to the interaction between Cu atoms and intermediates, thus accelerating the electrochemical CO reduction process. This work proved that the metal doping strategy can effectively improve the catalytic properties of CuO, thus providing a useful way for CO cycling and green production of CH.
乙烯是电催化 CO 还原反应（CORR）中具有高经济价值的理想 CO 产物。本文通过简单的湿化学方法合成了掺铝八面体 CuO（Al-CuO）纳米晶体。通过在八面体 CuO 表面掺杂 Al，提高了 CORR 产物的选择性。Al-CuO 用作 CORR 的高效电催化剂，可选择性地生产乙烯。Al-CuO 在 CO 饱和的 0.1 M KHCO 电解质中，在-1.23 V（相对于 RHE）下表现出高的法拉第效率（FE）为 44.9%。Al 掺杂到 CuO 后，Al 原子向 Cu 原子转移电荷，优化了电子结构，有利于 CORR 生成乙烯。DFT 计算表明，Al-CuO 催化剂可以有效地降低*CHCOH 中间体的吸附能，并促进电荷的转移，从而提高 FE。Al 掺杂到 CuO 后，d 轨道中心正移，使 d 带更接近费米能级。此外，由于 Cu 原子与中间体之间的相互作用，电子态密度增加，从而加速了电化学 CO 还原过程。这项工作证明了金属掺杂策略可以有效地提高 CuO 的催化性能，为 CO 循环和 CH 的绿色生产提供了一种有用的方法。
