从纯酸盐减少通过调双金属位点在氧活性共价有机框架中高效的氨电合成
Zedong Zhang1, Miao Wang1, Hao-Ran Xing1
1State Key Laboratory of Coordination Chemistry, MOE Key Laboratory of Mesoscopic Chemistry, MOE Key Laboratory of High Performance Polymer Materials and Technology, Jiangsu Key Laboratory of Advanced Organic Materials, Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu, 210023, P.R. China.
本研究介绍了用于合成氨的电催化酸盐还原反应 (NITRR) 的新型金属化共价有机框架. 优化的NiTP-CoTAPP MCOF催化剂显示出高效率和产量,克服了动力限制.
科学领域:
- 材料科学 材料科学 材料科学
- 电化学 电化学 电化学
- 催化剂是一种催化剂.
背景情况:
- 电催化降解反应 (NITRR) 是氨合成的一个有前途的途径.
- 由于复杂的质子合电子转移和缓慢的动力学,现有的方法面临挑战.
- 开发高效的电催化剂对于实际生产氨至关重要.
研究的目的:
- 为增强NITRR合成和研究金属化共价有机框架 (MCOFs).
- 为了确定一个最优的MCOF催化剂,克服动力限制,提高氨产量.
- 用实验和计算方法阐明催化机制.
主要方法:
- 一系列NiTP-MTAPPMCOFs (M = 2H,Co,Cu,Fe) 的合成,具有双重氧化还原活性中心.
- 对NITRR的电催化性能评估,包括法拉第效率和产率.
- 密度函数理论 (DFT) 计算分析反应路径和能量障碍.
主要成果:
- NiTP-CoTAPP MCOF表现出最高的法拉第效率 (~85.6%) 和收益率 (160.2 mmol h−1 g−1 cat.) 在 -0.8 V.
- [NiS4]和CoN4位点之间的协同作用促进了活性的产生,并抑制了的进化.
- DFT的计算显示,在CoN4-NiS4系统中,对于确定速率的步骤 (*NO → *HNO) 的能量障碍降低了.
结论:
- NiTP-CoTAPP MCOF是一种有效的电催化剂,通过NITRR合成氨.
- 双重氧化还原活性中心和优化的吸附/脱附特性是高性能的关键.
- 这项工作为设计高效电催化氨生产的先进MCOF提供了洞察力.
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