Exploring the role of sandwich-type polyoxometalates in {K10(PW9O34)2M4(H2O)2}@PCN-222 (M = Mn, Ni, Zn) for electroreduction of CO2 to CO

Abstract

To overcome the drawbacks of high solubility and instability of polyoxometalates (POMs) in aqueous solution and to expand their application in the electrocatalytic reduction of CO₂ (ECR), we assemble sandwich-type POMs, K₁₀[(PW₉O₃₄)₂M₄(H₂O)₂] (M = Mn, Ni, Zn, shortened as P₂W₁₈M₄), into the hexagonal channel of a porphyrin-based metal–organic framework (MOF) PCN-222 to form P₂W₁₈M₄@PCN-222 composites. Their ECR behavior displays polyoxoanion-dependent activity. P₂W₁₈Mn₄@PCN-222 demonstrates a faradaic efficiency of 72.6% for the CO product (FE_CO), more than four times that of PCN-222 (FE_CO = 18.1%), and exhibits exceptional electrochemical stability over 36 h. P₂W₁₈Ni₄@PCN-222 and P₂W₁₈Zn₄@PCN-222 slightly increase (26.9%) and decrease (3.2%) in FE_CO, respectively. We combine the results with density functional theory (DFT) calculations to help understand the intrinsic reasons which reveals that the rate-determining step (RDS) reaction energy of P₂W₁₈Mn₄@PCN-222 and P₂W₁₈Ni₄@PCN-222 is significantly reduced compared to that of PCN-222. It is different in P₂W₁₈Zn₄@PCN-222. Frontier molecular orbitals electron distribution results hint at directional electron transfer from P₂W₁₈Mn₄/P₂W₁₈Ni₄ to the porphyrin ring active center in PCN-222, promoting the electro-reduction of CO₂ activity. By contrast, P₂W₁₈Zn₄ may accumulate electrons from PCN-222, thus facilitating the hydrogen evolution reaction (HER). This work reveals the critical role of sandwich-type POMs in manipulating the electron transfer pathway during the electrocatalytic process. Our findings would broaden the scope of POM applications in electrochemical carbon dioxide reduction.