广东工业大学何军团队报道了二维锆基金属-有机框架/氧化铋纳米棒复合材料电催化二氧化碳还原成甲酸酯。2024年4月10日出版的《结构化学》。

电催化二氧化碳还原反应（eCO₂RR）是将二氧化碳可持续转化为增值产品的最有前途的技术之一。尽管金属有机框架（MOFs）可以被极大地功能化以产生CO₂RR的活性位点，但低的本征电导率总是使MOFs不适合用于eCO₂RR。此外，与多核金属中心簇的组装相比，如何从连接体的功能角度调节MOFs的eCO₂RR活性的研究远远落后。

该工作将无毒的氧化铋（Bi₂O₃）掺入由Zr-氧代簇合物和三嗪为中心的，具有不同官能团（LX=1～5）的3-c连接体建立的一系列二维MOFs（ZrLX）中，得到复合材料ZrLX/Bi₂O₃。为了研究连接体上的功能如何远程调节MOFs的eCO₂RR性能，在三嗪核心或苯甲酸盐末端安装了给电子/吸电子基团。

研究发现，ZrL₂/Bi₂O₃（在三嗪核上功能化的F）表现出最佳的eCO₂RR性能，在1.07VvsRHE具有96.73%的最高法拉第效率，最大的电活性表面（Cdl=4.23mF cm^-2）和最高的电导率（5.54×10⁷ S cm^-1），突出了调节连接体功能，因此电子结构作为调节eCO₂RR的替代方式。

附：英文原文

Title: 2D Zirconium-based metal-organic framework/bismuth(III) oxide nanorods composite for electrocatalytic CO2-to-formate reduction

Author: Dong-Ling Kuang, Song Chen, Shaoru Chen, Yong-Jie Liao, Ning Li, Lai-Hon Chung, Jun He

Issue&Volume: 2024-04-10

Abstract: Electrocatalytic carbon dioxide reduction reaction (eCO2RR) represents one of the most promising technologies for sustainable conversion of CO2 to value-added products. Although metal-organic frameworks (MOFs) can be vastly functionalized to create active sites for CO2RR, low intrinsic electrical conductivity always make MOFs unfavorable candidates for eCO2RR. Besides, studies on how to regulate eCO2RR activity of MOFs from linkers’ functionalities viewpoint lag far behind when compared with assembly of multinuclear metal-centered clusters. In this work, non-toxic bismuth(III) oxide (Bi2O3) was incorporated into a series of 2D MOFs (ZrLX) established from Zr-oxo clusters and triazine-centered 3-c linkers with different functionalities (LX = 1～5) to give composites ZrLX/Bi2O3. To investigate how functionalities on linkers distantly tune the eCO2RR performance of MOFs, electron-donating/withdrawing groups were installed at triazine core or benzoate terminals. It was found that ZrL2/Bi2O3 (F functionalized on triazine core) exhibits the best eCO2RR performance with highest Faradaic efficiency of 96.73% at 1.07 V vs. RHE, largest electroactive surface (Cdl = 4.23 mF cm2) and highest electrical conductivity (5.54 × 107 S cm1), highlighting tuning linker functionalities and hence electronic structure as an alternative way to regulate eCO2RR.

DOI: 10.1016/j.cjsc.2024.100301

Source: http://cjsc.ac.cn/cms/issues/598