Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, 210023, Nanjing, Jiangsu, China.
Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, 210023, Nanjing, Jiangsu, China.
Nat Commun. 2022 Jun 2;13(1):3063. doi: 10.1038/s41467-022-30766-x.
Single-atom catalysts represent a unique catalytic system with high atomic utilization and tunable reaction pathway. Despite current successes in their optimization and tailoring through structural and synthetic innovations, there is a lack of dynamic modulation approach for the single-atom catalysis. Inspired by the electrostatic interaction within specific natural enzymes, here we show the performance of model single-atom catalysts anchored on two-dimensional atomic crystals can be systematically and efficiently tuned by oriented external electric fields. Superior electrocatalytic performance have been achieved in single-atom catalysts under electrostatic modulations. Theoretical investigations suggest a universal "onsite electrostatic polarization" mechanism, in which electrostatic fields significantly polarize charge distributions at the single-atom sites and alter the kinetics of the rate determining steps, leading to boosted reaction performances. Such field-induced on-site polarization offers a unique strategy for simulating the catalytic processes in natural enzyme systems with quantitative, precise and dynamic external electric fields.
单原子催化剂代表了一种独特的催化体系，具有高原子利用率和可调反应途径。尽管通过结构和合成创新在其优化和定制方面取得了当前的成功，但对于单原子催化仍然缺乏动态调节方法。受特定天然酶中静电相互作用的启发，我们展示了锚定在二维原子晶体上的模型单原子催化剂的性能可以通过定向外部电场进行系统且有效地调节。在静电调节下，单原子催化剂表现出优异的电催化性能。理论研究表明存在一种通用的“局域静电极化”机制，其中静电场显著地极化单原子位上的电荷分布并改变速率决定步骤的动力学，从而提高反应性能。这种场诱导的局域极化为使用定量、精确和动态的外部电场模拟天然酶系统中的催化过程提供了一种独特的策略。
