Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, Institute of Energy, Hefei Comprehensive National Science Center, CAS Center for Excellence in Nanoscience, Department of Chemistry, Institute of Biomimetic Materials & Chemistry, Anhui Engineering Laboratory of Biomimetic Materials, University of Science and Technology of China, Hefei 230026, China.
Department of Chemical Physics & Hefei National Laboratory for Physical Sciences at Microscales, iChEM, University of Science and Technology of China, Hefei 230026, China.
J Am Chem Soc. 2021 Aug 18;143(32):12600-12608. doi: 10.1021/jacs.1c04653. Epub 2021 Jul 21.
The kinetics of electrode reactions including mass transfer and surface reaction is essential in electrocatalysis, as it strongly determines the apparent reaction rates, especially on nanostructured electrocatalysts. However, important challenges still remain in optimizing the kinetics of given catalysts with suitable constituents, morphology, and crystalline design to maximize the electrocatalytic performances. We propose a comprehensive kinetic model coupling mass transfer and surface reaction on the nanocatalyst-modified electrode surface to explore and shed light on the kinetic optimization in electrocatalysis. Moreover, a theory-guided microchemical engineering (MCE) strategy has been demonstrated to rationally redesign the catalysts with optimized kinetics. Experimental measurements for methanol oxidation reaction in a 3D ordered channel with tunable channel sizes confirm the calculation prediction. Under the optimized channel size, mass transfer and surface reaction in the channeled microreactor are both well regulated. This MCE strategy will bring about a significant leap forward in structured catalyst design and kinetic modulation.
电极反应动力学包括传质和表面反应，在电催化中至关重要，因为它强烈决定了表观反应速率，特别是在纳米结构电催化剂上。然而，在优化具有合适成分、形态和晶体设计的给定催化剂的动力学以最大限度地提高电催化性能方面，仍然存在重要挑战。我们提出了一个综合的动力学模型，将传质和表面反应耦合在纳米催化剂修饰的电极表面上，以探索和阐明电催化中的动力学优化。此外，已经证明了一种理论指导的微化学工程 (MCE) 策略可以合理地重新设计具有优化动力学的催化剂。在具有可调通道尺寸的 3D 有序通道中进行甲醇氧化反应的实验测量证实了计算预测。在优化的通道尺寸下，通道微反应器中的传质和表面反应都得到了很好的调节。这种 MCE 策略将在结构化催化剂设计和动力学调节方面带来重大飞跃。
