2024/06/11 by Yan Zhang, Can Li, Lei Shu +4
Chemistry · Materials Science · #Catalysis #Chemistry #Covalent Organic Framework Applications #Electrochemistry #Electrode #Electron #Electron transfer #Metal #Metal-Organic Frameworks: Synthesis and Applications #Nanotechnology #Organic chemistry #Photochemistry #Physical chemistry #Polyoxometalates: Synthesis and Applications #Quantum mechanics #Transition metal
paper · doi:10.1021/acs.inorgchem.4c00840
openalex publication_date 2024/06/11 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/27
In order to take advantage of the distinct reversible multielectron transfer properties of polyoxometalates (POMs) and increase the electron density at the active sites during the electrochemical reduction of CO 2 (CO 2 RR), a range of transition metal-doped polyoxometalates (TMSPOMs) was entrapped within the porphyrin-based framework of PCN-224 via an encapsulation method, known as TMSPOMs@PCN-224 (TMSPOMs = [XW 11 O 39 M II (H 2 O)] n–, [XW 11 O 40 V IV ] n–, M = Co II, Mn II; X = Si, n = 6; X = P, n = 5). The central elements (Si, P) and the incorporated transition metals (V IV, Co II, and Mn II ) both play a role in adjusting the electronic structure and electron transfer during the CO 2 RR process. Remarkably, the composite material with cobalt substitution displayed significantly improved performance. Through fine-tuning the POM loading, the electrocatalytic activity was optimized, leading to an impressive Faradaic efficiency for CO production (FE CO ) of 89.9% for SiW 11 Co@PCN-224, a significant improvement compared to the 12.1% FE CO of PCN-224. Furthermore, the electrochemical stability of this catalyst was demonstrated over 20 h. Comparative analyses involving six composite materials indicated a relationship between the negative charge of the polyanions and their ability to facilitate effective electron transfer, ultimately enhancing the catalyst’s performance. Meanwhile, these findings were supported by density functional theory (DFT) calculations.