进化反应和氧减少反应是否真的需要在O2耐受CO2电还原中被抑制,由DAE-BPy-CoPor和Co-TAPP催化?
Pengfei Yuan1, Chong Li2, Jianan Zhang3
1Shandong Laboratory of Yantai Advanced Materials and Green Manufacturing, Yantai, Shandong 265503, China.
The journal of physical chemistry letters
|November 27, 2024
概括
这项研究研究了演变 (HER) 和氧减少 (ORR) 反应如何使用两个模型催化剂影响二氧化碳电还原 (CO2RR). HER通过毒害活性部位影响CO2RR,而ORR的影响有所不同,有时会抑制CO2RR.
科学领域:
- 电化学 电化学 电化学
- 催化剂是一种催化剂.
- 计算化学的计算化学
背景情况:
- 研究耐氧CO2电还原反应 (CO2RR) 对可持续化学至关重要.
- 了解像演化 (HER) 和氧减少 (ORR) 这样的竞争反应对于优化CO2RR催化剂至关重要.
- DAE-BPy-CoPor和Co-TAPP是研究O2耐受性CO2RR的模型催化剂.
研究的目的:
- 用DAE-BPy-CoPor和Co-TAPP催化剂研究HER和ORR对CO2RR的影响.
- 阐明 HER 和 ORR 影响 CO2RR 的周转频率 (TOF) 的机制.
- 将HER和ORR干扰或在CO2RR期间被容忍的条件分类.
主要方法:
- 使用了大规范密度函数理论 (GC-DFT) 和微动力学 (MK) 模拟.
- 在CO2和O2的共同养条件下分析了催化剂的行为.
- 计算了HER和CO2RR的气形成能量和限制潜力.
主要成果:
- HER 影响 CO2RR TOF 基于 *H 形成能量和限制潜力; 负 *H 形成能量可以毒害活性位点.
- ORR对CO2RR的影响分为三种类型:没有效果,由于中间体 (*OH) 的活性位点中毒而抑制,或者当活性位点仍然可用时没有效果.
- 在O2联合养下,DAE-BPy-CoPor和Co-TAPP都表现出CO2RR活性在特定的电位范围 (-0.60到-1.10V) 内.
结论:
- HER,ORR和CO2RR之间的相互作用是复杂的,取决于反应条件和催化剂特性.
- 预测模型 (GC-DFT和MK) 有效地了解这些催化相互作用.
- 了解这些相互竞争的反应是设计高效的催化剂的关键,用于耐氧CO2电还原.
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