Molecular enhancement of heterogeneous CO2 reduction

Abstract

The   electrocatalytic carbon dioxide reduction reaction (CO 2 RR) addresses the need for storage of renewable energy in valuable carbon-based fuels and feedstocks, yet challenges remain in the improvement of electrosynthesis pathways for highly selective hydrocarbon production. To improve catalysis further, it is of increasing interest to lever synergies between heterogeneous and homogeneous approaches. Molecules adjacent to the active site provide additional binding interactions that may tune the stability of intermediates, improving catalytic performance by increasing Faradaic efficiency (product selectivity), as well as decreasing overpotential. We offer a forward-looking perspective on molecularly enhanced heterogeneous catalysis for CO 2 RR. We discuss four categories of molecularly enhanced strategies: molecular-additive-modified heterogeneous catalysts, immobilized organometallic complex catalysts, reticular catalysts and metal-free polymer catalysts. We introduce presentday challenges in molecular strategies and describe a vision for CO 2 RR electrocatalysis towards multi-carbon products. These strategies provide potential avenues to address the challenges of catalyst activity, selectivity and stability in the further development of CO 2 RR.

Strong Electronic Coupling of Graphene Nanoribbons onto Basal Plane of Glassy Carbon Electrode

“…This simple electrochemical treatment provides a promising method towards deposition of molecular species to the carbon electrode and can be useful to the field of molecular enhancement of heterogeneous electrocatalysis. 40 We now seek to answer the following question: does deposited GNR behave like the molecular species in solution or does it undergo the field-induced electrochemistry observed previously [23][24][25] for molecular species that are in strong electronic communication with the electrode? To address this, we compared Pourbaix diagrams for as-deposited GNRs (first CV scan) and monolayer GNRs (second CV scan).…”

Surface Modification for Promoting Durable, Efficient, and Selective Electrocatalysts

“…All the different examples described in the above sections demonstrate the impact of surface modification with organic molecules on several electrocatalytic processes. This molecular approach appears now very promising . The effects or the fundamental reasons for such molecular enhancement of electrocatalysis performance are not yet established.…”

Ultrahigh Photocatalytic CO2 Reduction Efficiency by Single Metallic Atom Oxide on TiO2

“…We also assessed reference samples without CO 2 gas and without H 2 O gas for comparison ( Figure S8), showing that the CO 2 reduction and H 2 O splitting occur on the catalytic sites without any sensitizers or sacri ces. Although little extra surfactants are bene t for Ti 3+ appearance and might be involved in electron-hole separation [41,83], the little residue of that has not much in uence on CO or CH 4 reproductively generation in experiments. To illuminate the mechanism for the remarkably high e ciency of STAO at step sites, the photoelectric properties and kinetic pathway of photocarriers were systematically investigated.…”