电子结构对酸盐降解的作用:一个周期性的旅程
O Quinn Carvalho1,2, Rylee Marks1, Hoan K K Nguyen1
1School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, Oregon 97331, United States.
Journal of the American Chemical Society
|August 4, 2022
概括
电催化利用可再生能源将废物酸盐转化为氨. 催化剂通过平衡演变和酸盐还原反应,对生产具有特殊的选择性.
科学领域:
- 电化学
- 催化剂
- 绿色化学
背景情况:
- 电催化为氨合成提供了一个可持续的途径,利用水源而不是甲.
- 优化化反应 (NO3RR) 的催化剂需要平衡演变反应 (HER) 活性和NO3RR选择性.
- 实现氨的高法拉第效率 (FE) 是关闭循环的关键.
研究的目的:
- 研究过渡金属催化剂用于电催化酸盐转化为氨.
- 了解 HER 和 NO3RR 在各种过渡金属上的动力相互作用.
- 阐明控制中性介质中的选择性的因素.
主要方法:
- 过渡金属催化剂 (Ti,Fe,Co,Ni,Ni0.68Cu0.32,Cu,Ag) 的选
- 电化学测量以确定的法拉第效率 (FE).
- 开发一个微动力学模型来分析反应动力学和竞争性吸附.
- 密度函数理论 (DFT) 计算用于探测催化机制.
主要成果:
- FE的含量有很大的差异,从3.6% (Ag) 到93.7% (Co).
- 微动力学模型显示,和原子之间的竞争吸附 (H*) 是电压依赖率的关键.
- 由于电子竞争,高的HER活性与NO3RR FE的降低相关.
- 具有异常高的选择性,这是由于强烈的化物结合和氧化解离促进.
结论:
- 用于有效的电催化降解的催化剂设计需要仔细调整电子特性和表面相互作用.
- 基于的催化剂在选择性氨生产方面表现出卓越的性能.
- 了解竞争性吸附机制对于推进可再生氨合成至关重要.
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