文献类型：期刊文献

英文题名：Electrochemical conversion of CO2 to syngas with a stable H2/CO ratio in a wide potential range over ligand-engineered metal-organic frameworks

作者：Cao, Lin[1];Wu, Xuefeng[1];Liu, Yuanwei[1];Mao, Fangxin[1];Shi, Yingli[1];Li, Jiayu[2];Zhu, Minghui[2];Dai, Sheng[3];Chen, Aiping[1];Liu, Peng Fei[1];Yang, Hua Gui[1]

机构：[1]East China Univ Sci & Technol, Shanghai Engn Res Ctr Hierarch Nanomat, Sch Mat Sci & Engn, Key Lab Ultrafine Mat,Minist Educ, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem Engn, Key Lab Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Sch Chem & Mol Engn, Inst Fine Chem,Key Lab Adv Mat, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2022

卷号：10

期号：18

起止页码：9954

外文期刊名：JOURNAL OF MATERIALS CHEMISTRY A

收录：;EI(收录号：20221912069874);WOS:【SCI-EXPANDED(收录号:WOS:000778329600001)】；

基金：This work was financially supported by the International (Regional) Cooperation and Exchange Projects of the National Natural Science Foundation of China (51920105003), the National Natural Science Funds for Distinguished Young Scholars (51725201), the Innovation Program of Shanghai Municipal Education Commission (E00014), the National Natural Science Foundation of China (51902105 and 52103340), the Shanghai Engineering Research Center of Hierarchical Nanomaterials (18DZ2252400), the Science and Technology Commission of Shanghai Municipality (21DZ1207101 and 19YF1411600), and the Fundamental Research Funds for the Central Universities (JKD01211519). The authors also thank the Frontiers Science Center for Materiobiology and Dynamic Chemistry. The authors also thank the crew of the 1W1B beamline of the Beijing Synchrotron Radiation Facility (BSRF) for their constructive assistance with the XAFS measurements and data analyses. Additional support was provided by the Feringa Nobel Prize Scientist Joint Research Center.

语种：英文

外文关键词：Electrocatalysts - Ligands - Light absorption - Metal-Organic Frameworks - Molar ratio - Potassium hydroxide

摘要：The efficient electrochemical conversion of CO2 to value-added chemicals is a promising approach to mitigate the current energy and environmental challenges. In this work, a ligand-engineering strategy was reported to be applied to stabilize CO2 adsorption in metal-organic frameworks (MOFs). Zn-based MOFs (Zn-MOFs) related to two different carboxyl functional ligands, i.e., 1,3,5-benzenetricarboxylic acid (Zn-BTC) and 1,4-benzenedicarboxylate (Zn-BDC), were investigated for the CO2 reduction reaction (CO2RR) in a flow cell electrolyzer. Zn-BTC exhibits a stable H-2/CO ratio (approximate to 1 : 2) up to a high current density (-300 mA cm(-2)) in a wide potential range (-0.96 to -1.96 V vs. RHE) in 1 M KOH. The molar H-2/CO ratio is steady in both neutral and alkaline electrolytes. Ex situ experimental results indicate that the carboxyl groups in Zn-BTC are more durable than those in Zn-BDC, which also enhances the absorption of CO2. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy elucidates that carboxyl groups can stabilize CO2RR intermediates. This work not only verifies the significance of the carboxyl groups in sustaining molecular structures but also offers valuable understandings in electrocatalyst design.