Kim Dongha, Park Sungjin, Lee Junwoo, Chen Yiqing, Li Feng, Kim Jiheon, Bai Yang, Huang Jianan Erick, Liu Shijie, Jung Eui Dae, Lee Byoung-Hoon, Papangelakis Panagiotis, Ni Weiyan, Alkayyali Tartela, Miao Rui Kai, Li Peihao, Liang Yongxiang, Shayesteh Zeraati Ali, Dorakhan Roham, Meira Debora Motta, Chen Yanna, Sinton David, Zhong Mingjiang, Sargent Edward H
The Edward S. Rogers Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario M5S 1A4, Canada.
Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06520, United States.
J Am Chem Soc. 2024 Oct 9;146(40):27701-27712. doi: 10.1021/jacs.4c09230. Epub 2024 Sep 27.
The electrochemical reduction of CO in acidic media offers the advantage of high carbon utilization, but achieving high selectivity to C products at a low overpotential remains a challenge. We identified the chemical instability of oxide-derived Cu catalysts as a reason that advances in neutral/alkaline electrolysis do not translate to acidic conditions. In acid, Cu ions leach from Cu oxides, leading to the deactivation of the C-active sites of Cu nanoparticles. This prompted us to design acid-stable Cu cluster precatalysts that are reduced in situ to active Cu nanoparticles in strong acid. Operando Raman and X-ray spectroscopy indicated that the bonding between the Cu cluster precatalyst ligand and in situ formed Cu nanoparticles preserves a high density of undercoordinated Cu sites, resulting in a CH Faradaic efficiency of 62% at a low overpotential. The result is a 1.4-fold increase in energy efficiency compared with previous acidic CO-to-C electrocatalytic systems.
在酸性介质中对CO进行电化学还原具有高碳利用率的优势，但在低过电位下实现对含碳产物的高选择性仍然是一项挑战。我们发现氧化物衍生的Cu催化剂的化学不稳定性是中性/碱性电解的进展无法转化到酸性条件的一个原因。在酸性条件下，Cu离子从Cu氧化物中浸出，导致Cu纳米颗粒的C活性位点失活。这促使我们设计在强酸中原位还原为活性Cu纳米颗粒的酸稳定型Cu簇前催化剂。原位拉曼光谱和X射线光谱表明，Cu簇前催化剂配体与原位形成的Cu纳米颗粒之间的键合保留了高密度的低配位Cu位点，从而在低过电位下实现了62%的CH法拉第效率。与之前的酸性CO到C的电催化系统相比，能量效率提高了1.4倍。
