Just Accepted
Just Accepted Articles have been posted online after technical editing and typesetting for immediate view. The final edited version with page numbers will appear in the Current Issue soon.
Submit a Manuscript
Boosting efficient electrocatalytic CO2 reduction by two-dimensional polyoxometalate@metal-organic framework composites with asymmetric sites
Teng-Fei Yao, Guo-Ping Yang*, Yao-Yu Wang
https://doi.org/10.1016/j.cjsc.2026.100948
Polyoxometalates; Metal-organic frameworks; Asymmetric coordination sites; Electrocatalytic CO2 reduction reaction
ABSTRACT
To address environmental challenges associated with CO2 emissions, the electrocatalytic reduction of CO2 to CO has emerged as a promising strategy. Silver-based catalysts exhibit high selectivity for CO, yet their performance is limited by the high energy barrier of the proton-coupled electron transfer step. Enhancing *H generation is therefore key to lowering this barrier and improving catalytic efficiency. Herein, a rational design integrating polyoxometalates (POMs) with controlled solvent ratios is reported to induce asymmetric active sites, enabling the synthesis of two types of two-dimensional silver-based polyoxometalate@metal−organic framework (POM@MOF) composites (Ag-TPT-SiW12-1 and Ag-TPT-SiW12-2, TPT = 2,4,6-tris(4-pyridyl)-1,3,5-triazine). Ag-TPT-SiW12-2 contains asymmetric bifunctional sites (Ag-N2O1 and Ag-N3) that operate synergistically: Ag-N2O1 activates CO2, while Ag-N3 promotes *H generation, thereby accelerating the formation of the *COOH intermediate and enhancing overall catalytic activity, compared with Ag-TPT-SiW12-1. Ag-TPT-SiW12-2 achieves a CO Faradaic efficiency exceeding 90% over a wide potential range (−0.7 V to −1.2 V vs. RHE), maximum at 94.2% at −1.0 V, which is 120% of that of Ag-TPT-SiW12-1. Theoretical calculations combined with experiments indicate that POMs donate electrons to catalytic centers, while cooperative interaction between the asymmetric bifunctional sites lowers the hydrogenation activation energy barrier. This work presents a new paradigm for designing high-performance electrocatalysts through precise electronic modulation and reaction pathway optimization.
- Address: Fuzhou High & New Technology Industrial Zone, Shangjie, Minhou, Fuzhou, Fujian 350108, China
- Tel: (86)-591-63173769, 63173770
- E-mail: cjsc@fjirsm.ac.cn
CN 35–1112/TQ, ISSN 0254–5861, Online ISSN: 2949-768X Copyright @ 2022 Chinese Journal of Structural Chemistry-www.Chinese Journal of Structural Chemistry.net. All Rights Reserved 闽ICP备2022002645号-1