Promoting CO2 methanation via ligand-stabilized metal oxide clusters as hydrogen-donating motifs

Abstract

Electroreduction uses renewable energy to upgrade carbon dioxide to value-added chemicals and fuels. Renewable methane synthesized using such a route stands to be readily deployed using existing infrastructure for the distribution and utilization of natural gas. Here we design a suite of ligand-stabilized metal oxide clusters and find that these modulate carbon dioxide reduction pathways on a copper catalyst, enabling thereby a record activity for methane electroproduction. Density functional theory calculations show adsorbed hydrogen donation from clusters to copper active sites for the *CO hydrogenation pathway towards *CHO. We promote this effect via control over cluster size and composition and demonstrate the effect on metal oxides including cobalt(II), molybdenum(VI), tungsten(VI), nickel(II) and palladium(II) oxides. We report a carbon dioxide-to-methane faradaic efficiency of 60% at a partial current density to methane of 135 milliampere per square centimetre. We showcase operation over 18 h that retains a faradaic efficiency exceeding 55%.

Au-activated N motifs in non-coherent cupric porphyrin metal organic frameworks for promoting and stabilizing ethylene production

“…On top of that, AuNN introduced into the MOF interior would further increase the concentration of CO trapped inside the MOF tunnels, due to the spatial confinement effect 50,51 . Such increase in CO concentration would not only improve the probability of C-C coupling when the active sites are brought to sufficient proximity, but also boost the CO 2 RR kinetics 52 .…”

Simultaneous Manipulation of Bulk Excitons and Surface Defects for Ultrastable and Highly Selective CO2 Photoreduction

“…In this context, converting superfluous CO 2 into value‐added fuels or chemical feedstock is a possible avenue to achieving energy and environmental sustainability. [ 1–7 ] Among the CO 2 utilization approaches currently available, photosynthesis‐mimicking photocatalytic CO 2 reduction (PCR) is the most promising. Artificial PCR is characterized by ambient CO 2 activation using cheap semiconductors as the catalysts, solar light as the energy source, and water as the co‐reactant.…”

Molecular Stabilization of Sub‐Nanometer Cu Clusters for Selective CO2 Electromethanation

“…[4][5][6] Methane, the major constituent of natural gas, is of interest because it is widely used as cleaner fuels, and the infrastructure for storage, distribution, and utilization is well-established. [7][8][9] Adsorbed CO (*CO) is a key reaction intermediate along the pathway of CO 2 RR to branch to C 1 (e. g., CH 4 ) or C 2 (e. g., C 2 H 4 , C 2 H 5 OH) products. [10,11] Hydrogenation of *CO to *CHO or *COH leads to C 1 while coupling *CO with another *CO to form *OCCO embarking on the C 2 pathway.…”

“…Electrochemical CO 2 reduction reaction (CO 2 RR) using renewable electricity has emerged as an attractive CCU approach to the production of value‐added chemical feedstocks and fuels [4–6] . Methane, the major constituent of natural gas, is of interest because it is widely used as cleaner fuels, and the infrastructure for storage, distribution, and utilization is well‐established [7–9] …”