Promoting Surface Reconstruction in Spinel Oxides via Tetrahedral-Octahedral Phase Boundary Construction for Efficient Oxygen Evolution.

Autor: Zou A; College of Materials Science and Engineering, Sichuan University, Chengdu, 610065, China., Wu C; 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 (A*STAR), 1 Pesek Road Jurong Island, Singapore, 627833, Republic of Singapore., Zhang Q; Department of Materials Science and Engineering, National University of Singapore, Singapore, 117575, Republic of Singapore., Tang Y; College of Materials Science and Engineering, Sichuan University, Chengdu, 610065, China., Li J; College of Materials Science and Engineering, Sichuan University, Chengdu, 610065, China., Meng H; College of Materials Science and Engineering, Sichuan University, Chengdu, 610065, China., Wang Z; College of Materials Science and Engineering, Sichuan University, Chengdu, 610065, China., Diao C; Singapore Synchrotron Light Sources (SSLS), National University of Singapore, Singapore, 117603, Republic of Singapore., Yu Z; Institute of High Performance Computing, Agency for Science, Technology and Research, Singapore, 138632, Republic of Singapore., Xue J; Department of Materials Science and Engineering, National University of Singapore, Singapore, 117575, Republic of Singapore., Xi S; Institute of Sustainability for Chemical, Energy and Environment (ISCE2), Agency for Science, Technology and Research (A*STAR), 1 Pesek Road Jurong Island, Singapore, 627833, Republic of Singapore., Wang X; College of Materials Science and Engineering, Sichuan University, Chengdu, 610065, China.; State Key Laboratory of Intelligent Construction and Healthy Operation and Maintenance of Deep Underground Engineering, Sichuan University, Chengdu, 610065, China., Wu J; College of Materials Science and Engineering, Sichuan University, Chengdu, 610065, China.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Oct 14; Vol. 63 (42), pp. e202409912. Date of Electronic Publication: 2024 Sep 12.
DOI: 10.1002/anie.202409912
Abstrakt: Understanding the origin of surface reconstruction is crucial for developing highly efficient lattice oxygen oxidation mechanism (LOM) based spinel oxides. Traditionally, the reconstruction has been achieved through electrochemical procedures, such as cyclic voltammetry (CV), linear sweep voltammetry (LSV). In this work, we found that the surface reconstruction in LOM-based CoFe 0.25 Al 1.75 O 4 catalyst was an irreversible oxygen redox chemical reaction. And a lower oxygen vacancy formation energy (E O-V ) could benefit the combination of the activated lattice oxygen atoms with adsorbed water molecular. Motivated by this finding, a strategy of phase boundary construction from Co tetrahedral to octahedral was employed to decrease E O-V in CoFe 0.25 Al 1.75 O 4 . The results showed that as the Co octahedral occupancy ratio rose to 64 %, a 3.5 nm-thick reconstructed layer formed on the catalyst surface with a 158 mV decrease in overpotential. Further experiments indicated that the coexistence of tetrahedral-octahedral (O-T) phase would result in lattice mismatch, promoting non-bonding oxygen states and lowering E O-V . Then more active lattice oxygen combined with H 2 O molecules to generate hydroxide ions (OH - ), followed by soluble cation leaching, which enhanced the reconstruction process. This work provided new insights into the relationship between the intrinsic structure of pre-catalysts and surface reconstruction in LOM-based spinel electrocatalysts.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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