The discovery of systems that preferentially promote selective and efficient CO2 reduction to single products while suppressing competitive H2-evolution is critically important for the realization of electrochemical CO2 conversion. In biological systems, fast catalytic activity and high product selectivity are achieved by carefully controlling the primary, secondary, and outer coordination spheres of the enzyme’s active site. We have studied the influence of primary, secondary, and outer-coordination sphere effects on the electrocatalytic CO2 reduction activity and product selectivity by polymer-encapsulated macrocyclic metal complexes. In particular, through specific modifications of the catalyst-polymer system, we have studied the dependence of a metal phthalocyanine’s CO2-reduction performance on 1) the axial coordination of polymer moieties to the metal site, 2) the secondary coordination sphere stabilization of reactive intermediates, and 3) the outer-coordination sphere delivery of H+ to the metal active sites.

Promoting selective electrocatalytic carbon dioxide reduction through modification of a metal's secondary and outer coordination spheres

253rd National Meeting (2017)

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