College of Materials Science and Engineering, Sichuan University, Chengdu, 610065, China.
Institute of Sustainability for Chemical, Energy and Environment (ISCE2), Agency for Science, Technology and Research, Singapore, 627833, Singapore.
Angew Chem Int Ed Engl. 2023 May 15;62(21):e202218599. doi: 10.1002/anie.202218599. Epub 2023 Apr 17.
A fundamental understanding of surface reconstruction process is pivotal to developing highly efficient lattice oxygen oxidation mechanism (LOM) based electrocatalysts. Traditionally, the surface reconstruction in LOM based metal oxides is believed as an irreversible oxygen redox behavior, due to the much slower rate of OH refilling than that of oxygen vacancy formation. Here, we found that the surface reconstruction in LOM based metal oxides is a spontaneous chemical reaction process, instead of an electrochemical reaction process. During the chemical process, the lattice oxygen atoms were attacked by adsorbed water molecules, leading to the formation of hydroxide ions (OH ). Subsequently, the metal-site soluble atoms leached from the oxygen-deficient surface. This work also suggests that the enhancement of surface hydrophilicity could accelerate the surface reconstruction process. Hence, such a finding could add a new layer for the understanding of surface reconstruction mechanism.
深入理解表面重构过程对于开发高效的晶格氧氧化机制(LOM)基电催化剂至关重要。传统上,由于 OH 再填充速率比氧空位形成速率慢得多,因此人们认为 LOM 基金属氧化物中的表面重构是一种不可逆的氧氧化还原行为。在这里,我们发现 LOM 基金属氧化物中的表面重构是一个自发的化学反应过程,而不是一个电化学反应过程。在化学过程中,晶格氧原子受到吸附水分子的攻击,导致形成氢氧根离子(OH-)。随后,金属位可溶性原子从缺氧表面浸出。这项工作还表明,提高表面亲水性可以加速表面重构过程。因此,这一发现为理解表面重构机制增添了新的认识。