Molecular Transition Metal Oxide Electrocatalysts for the Reversible Carbon Dioxide–Carbon Monoxide Transformation

Abstract

Carbon monoxide dehydrogenase (CODH) enzymes are active for the reversible CO oxidation-CO 2 reduction reaction and are of interest in the context of CO 2 abatement and carbon-neutral solar fuels.B ioinspired by the active-site composition of the CODHs,polyoxometalates triply substituted with first-rowt ransition metals were modularly synthesized.T he polyanions,i ns hort, {SiM 3 W 9 }a nd {SiM' 2 M''W 9 }, M, M',M '' = Cu II ,N i II ,F e III are shown to be electrocatalysts for reversible CO oxidation-CO 2 reduction. A catalytic Tafel plot showed that {SiCu 3 W 9 }w as the most reactive for CO 2 reduction, and electrolysis reactions yielded significant amounts of CO with 98 %f aradaic efficiency.I n contrast, Fe-Ni compounds such as {SiFeNi 2 W 9 }p referably catalyzedt he oxidation of CO to CO 2 similar to what is observed for the [NiFe]-CODH enzyme.C ompositional control of the heterometal complexes,now and in the future,leads to control of reactivity and selectivity for CO 2 electrocatalytic reduction.

Lithium-CO2 batteries and beyond

“…However, there are other materials that can be explored for efficient catalyst including single metal-based compounds (Fe, Co, Ni, Ti, Zn and Cu), and mixed metal compounds (FeCoW, NiCoOx, CoFeOx, LaMnO 3 ; C. Liu et al, 2012;Sun Y. et al, 2021). Furthermore, potential transition metal based catalysts can be reviewed in literature (Franco et al, 2020;Azaiza-Dabbah et al, 2022;Lv et al, 2022).…”

Developing Insoluble Polyoxometalate Clusters to Bridge Homogeneous and Heterogeneous Water Oxidation Photocatalysis

“…Having these attractive attributes, POMs have received considerable attention in academic research and also been successfully applied in industrial catalysis [15–17] . In particular, as an alternative to metal oxides, a substantial number of POMs have been produced for H 2 evolution, O 2 evolution, CO 2 reduction reactions and more with the aim to reduce and resolve the global challenges of the energy crisis and climate change [18–41] . POMs are usually used as homogeneous catalysts due to their good solubility in water.…”

Two bimetal-doped (Fe/Co, Mn) polyoxometalate-based hybrid compounds for visible-light-driven CO2 reduction

“…thus, they can combine with lacunary POMs to form diverse transition-metal-substituted polyoxometalates (TMSPs). 23–26 TMSPs can be classified into single transition-metal-substituted (single TMSPs) and mixed transition-metal-substituted polyoxometalates (mixed TMSPs), depending on the type of transition metals introduced. 27…”

“…thus, they can combine with lacunary POMs to form diverse transition-metal-substituted polyoxometalates (TMSPs). [23][24][25][26] TMSPs can be classified into single transitionmetal-substituted (single TMSPs) and mixed transition-metalsubstituted polyoxometalates (mixed TMSPs), depending on the type of transition metals introduced. 27 Over the years, a large number of single TMSPs have been reported; as a matter of fact, iron-substituted polyoxometalates (FeSPs) generally have an advantage in terms of magnetism, whereas cobalt-substituted polyoxometalates (CoSPs) have been widely studied in the field of photocatalysis.…”