Seeding Atomic Silver into Internal Lattice Sites of Transition Metal Oxide for Advanced Electrocatalysis

• Published in: Advanced materials (Weinheim) Vol. 36; no. 28; pp. e2312566 - n/a
• Main Authors: Song, Wenjun, He, Kun, Li, Chenghang, Yin, Ruonan, Guo, Yaqing, Nie, Anmin, Li, Yanshuai, Yang, Keqin, Zhou, Mengting, Lin, Xiaoruizhuo, Wang, Zheng‐Jun, Ren, Qingqing, Zhu, Shaojun, Xu, Ting, Liu, Suya, Jin, Huile, Lv, Jing‐Jing, Wang, Shun, Yuan, Yifei
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01.07.2024
• Subjects: atomic catalyst; Atomic structure; Catalysts; Chemical reduction; Configuration management; Crystal lattices; dual‐form silver; Electrocatalysts; electrochemical CO2 reduction; internal lattice; Lattice design; Lattice sites; Manganese dioxide; Nanoparticles; Silver; Strings; Substrates; Transition metal oxides; Tunnels; tunnel‐structured MnO2; Tunnel‐structured MnO2; Electrochemical CO2 reduction; Atomic catalyst; Dual‐form silver; Internal lattice
• ISSN: 0935-9648; 1521-4095; 1521-4095
• DOI: 10.1002/adma.202312566

Transition metal oxides (TMOs) are widely studied for loading of various catalysts due to their low cost and high structure flexibility. However, the prevailing close‐packed nature of most TMOs crystals has restricted the available loading sites to surface only, while their internal bulk lattice remains unactuated due to the inaccessible narrow space that blocks out most key reactants and/or particulate catalysts. Herein, using tunnel‐structured MnO2, this study demonstrates how TMO's internal lattice space can be activated as extra loading sites for atomic Ag in addition to the conventional surface‐only loading, via which a dual‐form Ag catalyst within MnO2 skeleton is established. In this design, not only faceted Ag nanoparticles are confined onto MnO2 surface by coherent lattice‐sharing, Ag atomic strings are also seeded deep into the sub‐nanoscale MnO2 tunnel lattice, enriching the catalytically active sites. Tested for electrochemical CO2 reduction reaction (eCO2RR), such dual‐form catalyst exhibits a high Faradaic efficiency (94%), yield (67.3 mol g−1 h−1) and durability (≈48 h) for CO production, exceeding commercial Ag nanoparticles and most Ag‐based electrocatalysts. Theoretical calculations further reveal the concurrent effect of such dual‐form catalyst featuring facet‐dependent eCO2RR for Ag nanoparticles and lattice‐confined eCO2RR for Ag atomic strings, inspiring the future design of catalyst–substrate configuration. This work demonstrates how the internal lattice sites of transition metal oxide, more specifically, MnO2, can be utilized for efficient electrochemical CO2 reduction reaction (eCO2RR) by accommodating atomic Ag catalysts within its sub‐nanoscale tunnel space. A dual‐form Ag catalyst featuring faceted Ag nanoparticles on MnO2 surface and atomic Ag strings within MnO2 tunnels is thus designed with high eCO2RR performance.