Zhang Wanning, Ai Jing, Ouyang Tianwei, Yu Lu, Liu Aokun, Han Lu, Duan Yingying, Tian Changlin, Chu Chaoyang, Ma Yanhang, Che Shunai, Fang Yuxi
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, State Key Laboratory of Metal Matrix Composites, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
Sinopec Shanghai Research Institute of Petrochemical Technology, 1658 Pudong Beilu, Shanghai 201208, China.
J Am Chem Soc. 2024 Oct 2. doi: 10.1021/jacs.4c08445.
The formation of multicarbon products from CO electroreduction is challenging on materials other than Cu-based catalysts. Ag has been known to be a typical metal catalyst, producing CO in CO electroreduction. The formation of C products by Ag has never been reported because the carbon-carbon (C-C) coupling is an unfavorable process due to the high reaction barrier energy of *OCCO. Here, we propose that the chirality-induced spin polarization of chiral nanostructured Ag films (CNAFs) can promote the formation of triplet OCCO by regulating its parallel electron spin alignment, and the helical lattice distortion of nanostructures can decrease the reaction energy of *OCCO, which triggers C-C coupling and promotes subsequent *OCCO hydrogenation to facilitate the generation of C products. The CNAFs with helically lattice-distorted nanoflakes were fabricated via electrodeposition using phenylalanine as the symmetry-breaking agent. C products (CH, CH, CH, CHOH, and CHCOOH) with a Faradaic efficiency of ∼4.7% and a current density of ∼22 mA/cm were generated in KHCO electrolytes under 12.5 atm of CO (g). Our findings propose that the chiral nanostructured materials can regulate the multifunctionality of catalytic performance in the catalytic reactions with triplet intermediates and products.
在非铜基催化剂的材料上，通过CO电还原形成多碳产物具有挑战性。已知Ag是一种典型的金属催化剂，在CO电还原中产生CO。由于OCCO的反应势垒能量高，C-C偶联是一个不利过程，因此从未有过Ag形成C产物的报道。在此，我们提出，手性纳米结构Ag膜（CNAFs）的手性诱导自旋极化可以通过调节其平行电子自旋排列来促进三重态OCCO的形成，并且纳米结构的螺旋晶格畸变可以降低OCCO的反应能量，从而触发C-C偶联并促进随后的*OCCO氢化，以促进C产物的生成。通过使用苯丙氨酸作为对称破缺剂的电沉积方法制备了具有螺旋晶格畸变纳米片的CNAFs。在12.5 atm的CO（g）下，在KHCO电解液中产生了法拉第效率约为4.7%、电流密度约为22 mA/cm的C产物（CH、CH、CH、CHOH和CHCOOH）。我们的研究结果表明，手性纳米结构材料可以在具有三重态中间体和产物的催化反应中调节催化性能的多功能性。
