Data collection underpinning the paper "Carbon dioxide reduction with post-transition metal-substituted Keggin-type polyoxometalate"

We report the direct conversion of CO2 to CO by a molecular metal oxide catalyst with over 70% Faradaic efficiency under anhydrous conditions. Electrocatalytic reduction of CO2 using the polyoxometalate (POM) catalyst (TBA)4[BiPW11O39] gave CO as the only product via a C2O42- intermediate. Catalytically active species, intermediates, and products were monitored by UV-visible and FTIR spectroelectrochemistry and by multinuclear NMR, which revealed a switch in the mechanism when protons were present. This study provides fresh mechanistic insight for polyoxometalate-based CO2 reduction electrocatalysts, wherein the Lewis acidic Bi3+ acts as a coordination site and the Lewis basic POM anion as an electron-rich support for the direct conversion of CO2 to CO. Thorough understanding of the catalytic process is essential for the development of affordable and stable catalysts which utilise POMs, and this study highlights how substituted POMs can be exploited further for catalytic applications.

It includes data from mass spectrometry, cyclic voltammetry, spectroelectrochemistry (uv-visible spectrometry and fourier transform infrared spectroscopy), x-ray photoelectron spectroscopy, nuclear magnetic resonance spectroscopy.