在Ni单原子催化剂中的N,S协调促进CO2RR向HCOOH
Zengxuan Chen1, Shoufu Cao1, Jiao Li1
1School of Materials Science and Engineering, China University of Petroleum, Qingdao, Shandong 266580, P. R. China. wangzhaojie@upc.edu.cn.
在--4 (NiN4) 单原子催化剂中的硫替代增强了二氧化碳减排 (CO2RR) 形成. NiN2S2表现出卓越的性能,突出了N,S协调,以实现高效的电催化.
科学领域:
- 电化学和催化剂的应用
- 材料科学 材料科学 材料科学
- 环境化学环境化学
背景情况:
- 基于碳的单原子催化剂 (SAC) 对于CO2减少反应 (CO2RR) 是非常有效的,因为它们最大限度地利用了原子和可调节的活性点.
- 活性部位的协调环境对于SACs的内在催化活性至关重要.
- -协调 (NiN4) 是一个常见的动机,但其在CO2RR中的性能可以进一步优化.
研究的目的:
- 研究将硫 (S) 原子纳入NiN4协调环境对CO2RR性能的影响.
- 阐明不同Ni-N4-x催化剂的CO2RR机制.
- 为了确定一个最佳的催化剂,以高效的形式 (HCOOH) 生产.
主要方法:
- 对NiN4,NiN3S1和NiN2单原子催化剂的计算研究.
- 电子结构的分析,重点是Ni d轨道的占用和可用的轨道.
- 系统地阐明二电子CO2RR路径用于CO和HCOOH生成.
主要成果:
- 将S原子引入NiN4协调 (NiNxS4-x) 导致结构稳定性和催化活性的增强.
- 硫的替代产生了额外的轨道在-1.60 eV左右,并改变了Ni d轨道的占用,促进了中间体的质子化.
- NiN2S2表现为HCOOH生成最有利的性能,限制潜力为-0.24 V,显著超过NiN4 (-1.14 V) 和NiN3S1 (-0.50 V).
结论:
- NiN2S2被确定为CO2RR的高性能电催化剂,以产生HCOOH.
- N,S 协调是调整原子分散电催化剂性能的一个有效策略.
- 这项研究表明,S原子替代对CO2RR活性和选择性的显著影响.
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