Jiang Minghang, Han Linkai, Peng Peng, Hu Yi, Xiong Yan, Mi Chunxia, Tie Zuoxiu, Xiang Zhonghua, Jin Zhong
MOE Key Laboratory of Mesoscopic Chemistry, MOE Key Laboratory of High Performance Polymer Materials and Technology, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210023, China.
Shenzhen Research Institute of Nanjing University, Shenzhen 518063, China.
Nano Lett. 2022 Jan 12;22(1):372-379. doi: 10.1021/acs.nanolett.1c04009. Epub 2021 Dec 22.
Developing high-performance nitrogen reduction reaction (NRR) electrocatalysts is an ongoing challenge. Herein, we report a pyrolysis-free synthetic method for introducing ordered quasi-phthalocyanine N-coordinated transition metal (Ti, Cu, or Co) centers into a conjugated two-dimensional (2D) covalent organic framework (COF) for enhanced NRR performance. Detailed experiments and characterizations revealed that the NRR activity of Ti-COF was clearly better than that of Cu-COF and Co-COF, because of the superior abilities of Ti metal centers in activating inert N molecules and suppressing the hydrogen evolution reaction (HER). The resulting Ti-COF exhibits a high NH yield of 26.89 μg h mg and a Faradaic efficiency of 34.62% for NRR. Density functional theory (DFT) calculations verify that Ti-COF can effectively adsorb and activate N molecules and inhibit HER compared with Cu-COF, Co-COF, and pristine COF catalysts. This work opens a new avenue for developing 2D-COF materials that contain abundant coordinated transition metal centers toward electrocatalytic NRR.
开发高性能的氮还原反应（NRR）电催化剂是一项持续存在的挑战。在此，我们报告了一种无需热解的合成方法，可将有序的准酞菁氮配位过渡金属（Ti、Cu或Co）中心引入共轭二维（2D）共价有机框架（COF）中，以提高NRR性能。详细的实验和表征表明，Ti-COF的NRR活性明显优于Cu-COF和Co-COF，这是因为Ti金属中心在活化惰性N分子和抑制析氢反应（HER）方面具有卓越能力。所得的Ti-COF在NRR方面表现出26.89 μg h mg的高NH产率和34.62%的法拉第效率。密度泛函理论（DFT）计算证实，与Cu-COF、Co-COF和原始COF催化剂相比，Ti-COF能够有效吸附和活化N分子并抑制HER。这项工作为开发含有丰富配位过渡金属中心的二维COF材料用于电催化NRR开辟了一条新途径。
