近日，华东理工大学Chunzhong Li及其研究组提出了路易斯碱配体重塑界面氢键网络促进二氧化碳电解。该研究于2024年6月22日发表于《国家科学评论》杂志。

据悉，催化剂和电解液对CO₂电解性能的影响很大。尽管在催化剂方面取得了长足的进步，但定制电解质成分和了解它们在催化剂界面上的功能仍然具有很大的挑战性。

研究小组报道了乙二胺四乙酸(EDTA)及其类似物，与金属阳离子具有强的刘易斯酸碱相互作用，被选择作为电解质添加剂来重塑催化剂-电解质界面以促进CO₂的电解。机理研究表明，EDTA分子在EDTA^4-—K⁺强刘易斯酸碱相互作用的偏置电位下向界面区动态组装，结果，界面H₂O之间原有的氢键网络被干扰，在通电界面处形成了一个氢键间隙层。

EDTA重塑的K⁺溶剂化结构促进*CO₂质子化为*COOH，抑制*H₂O解离为*H，从而促进CO₂和H₂O共电解生成碳基产物。当电解质中加入5 mM的EDTA时，在电流密度为工业界的500 mA cm^-2时，CO在银纳米颗粒催化剂上的法拉第效率从57.0%提高到90.0%。更重要的是，刘易斯碱配体重塑界面允许一系列催化剂(Ag, Zn, Pd, Bi, Sn和Cu)，在H型和流型电解池中提供显著提高的碳基产物选择性。

附：英文原文

Title: Lewis-base ligand-reshaped interfacial hydrogen-bond network boosts CO2 electrolysis

Author: Ge, Wangxin, Tao, Haolan, Dong, Lei, Fan, Yu, Niu, Yanpu, Zhu, Yihua, Lian, Cheng, Liu, Honglai, Jiang, Hongliang, Li, Chunzhong

Issue&Volume: 2024-06-22

Abstract: Both the catalyst and electrolyte strongly impact the performance of CO2 electrolysis. Despite substantial progress in catalysts, it remains highly challenging to tailor electrolyte compositions and understand their functions at the catalyst interface. Here, we report that the ethylenediaminetetraacetic acid (EDTA) and its analogs, featuring strong Lewis acid-base interaction with metal cations, are selected as electrolyte additives to reshape the catalyst-electrolyte interface for promoting CO2 electrolysis. Mechanistic studies reveal that EDTA molecules are dynamically assembled toward interface region in response to bias potential due to strong Lewis acid-base interaction of EDTA4–-K+. As a result, the original hydrogen-bond network among interfacial H2O is disrupted, and a hydrogen-bond gap layer at the electrified interface is established. The EDTA-reshaped K+ solvation structure promotes the protonation of *CO2 to *COOH and suppressing *H2O dissociation to *H, thereby boosting the co-electrolysis of CO2 and H2O toward carbon-based products. In particular, when 5 mM of EDTA is added into the electrolytes, the faradaic efficiency of CO on the commercial Ag nanoparticle catalyst is increased from 57.0% to 90.0% at an industry-relevant current density of 500 mA cm2. More importantly, the Lewis-base ligand-reshaped interface allows a range of catalysts (Ag, Zn, Pd, Bi, Sn, and Cu) to deliver substantially increased selectivity of carbon-based products in both H-type and flow-type electrolysis cells.

DOI: 10.1093/nsr/nwae218

Source: https://academic.oup.com/nsr/advance-article/doi/10.1093/nsr/nwae218/7697572searchresult=1&login=false