@article{Li2025, 
author = {Can Li and Yan Zhang and Lei Shu and Yun-Lei Teng and Yan-Rong Wang and Bao-Xia Dong},
title = {Boosting electrochemical reduction of CO2 to CO via fixation Keggin-type polyoxoanions XW11Co (X = Si, P, Co) into ZIF-8 cavities: Pivotal role of central atoms in catalytic performance},
year = {2025},
journal = {Polyoxometalates},
volume = {4},
number = {3},
pages = {9140097},
keywords = {polyoxometalate, ZIF-8, synthetic encapsulation, electrochemical reduction of carbon dioxide, Keggin},
url = {https://www.sciopen.com/article/10.26599/POM.2025.9140097},
doi = {10.26599/POM.2025.9140097},
abstract = {A series of polyoxometalate (POM)-based metal–organic framework composites, XW11Co@ZIF-8 (X = Si, P, Co), were prepared by encapsulating single cobalt-substituted Keggin XW11Co polyoxoanions into the cavities of ZIF-8 at ambient temperature using a synthetic encapsulation strategy. This study investigated the impact of the central atoms in POMs on the electrochemical reduction of carbon dioxide (eCO2RR). The results of the electrochemical test illustrated a significant enhancement in the current densities and eCO2RR performance of the composites compared with pristine ZIF-8. Specifically, CoW11Co@ZIF-8 exhibited 72.4% CO selectivity at a potential of −1.10 V vs. reversible hydrogen electrode (RHE), which was 1.5 times higher than that of ZIF-8 under the same potential. SiW11Co@ZIF-8 and PW11Co@ZIF-8 also exhibited improved electrocatalytic performance, though less pronounced, with faradaic efficiency for CO production (FECO) values of 63.6% and 57.0%, respectively. The central atom in XW11Co significantly affects the catalytic performance of the composites. The [CoIIIW11O39CoII(H2O)]7– species carries more negative charges, enabling the provision of additional electrons to the active sites. Consequently, CoW11Co@ZIF-8 exhibited the highest negative charge and charge transfer efficiency, the largest electrochemically active surface area, and the highest eCO2RR activity.}
}