在晶体催化剂中增强的性相互作用促进了CO2到CH4的高度选择性电还原
Lei Zhang1, Xiao-Xin Li2, Zhong-Ling Lang3
1Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, P. R. China.
Journal of the American Chemical Society
|March 2, 2021
概括
这项研究揭示了具有铜性相互作用的铜催化剂如何增强电化学二氧化碳降解到甲. 这些催化剂对甲生产具有很高的选择性,为高效的二氧化碳转化提供了新的设计策略.
科学领域:
- 电化学
- 材料科学
- 催化剂
背景情况:
- 基于铜的催化剂对于电化学二氧化碳降解反应 (CO2RR) 对碳化合物至关重要.
- 对于优化CO2RR性能来说,了解Cu (I) 催化剂内在性相互作用的作用具有挑战性,但至关重要.
研究的目的:
- 合成和研究基于铜的新型协调聚合物 (NNU-32和NNU-33S) 用于二氧化碳的电减.
- 阐明分子内性相互作用对电催化机制和甲选择性的影响.
- 在现场探索动态晶体结构的转变及其对催化活性的影响.
主要方法:
- 合成基于铜的协调聚合物 (NNU-32和NNU-33S).
- 将催化剂集成到二氧化碳流电池中进行电催化测试.
- 在现场描述动态晶体结构的转变.
- 密度函数理论 (DFT) 计算以分析反应机制和能量.
主要成果:
- 由于固有的性相互作用,NNU-32和NNU-33 ((S) 对二氧化碳转化具有很高的选择性.
- 从NNU-33 ((S) 转变为NNU-33 ((H) 的动态晶体结构,增强了性相互作用.
- 在 -0.9 V (391 mA cm-2) 时实现了82%的CH4选择性,为晶体催化剂设定了新的基准.
- DFT的计算证实,性相互作用通过降低速率决定阶段的激活能量来促进二氧化碳的降电到CH4.
结论:
- 在Cu(I) 催化剂中的内在性相互作用显著增强了电催化二氧化碳转化为甲的过程.
- 可以利用动态晶体结构的转换来加强这些相互作用并提高催化剂的性能.
- 这项工作为开发高效转化二氧化碳成有价值产品的先进晶体催化剂提供了基础知识和设计策略.
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