Abstract: The development of chemistry to convert CO2 into high-volume commodities could usher in a new era in the chemical industry in which CO2 is a resource. This talk will describe our recent efforts in electrochemical and chemical CO2 conversion catalysis, with an emphasis on the use of defects to engender reactivity.
For CO2 and CO electroreduction catalysis, we have pioneered the use of grain boundaries to create metastable active surfaces and recently elucidated a structural model to explain grain boundary effects. I will discuss the prospects for exploiting grain boundary effects in electrosynthesis and the design of prototype reactors that provide high synthesis rates and concentrated product streams.
In the second part of my talk, I will describe a new strategy for catalyzing the insertion of CO2 into hydrocarbon C–H bonds to form carboxylic acids and their derivatives. CO2 insertion has never previously been performed in a catalytic process. We have found systems in which nanomaterials containing structurally disordered carbonate salts can deprotonate un-activated C–H bonds, generating carbon-centered nucleophiles that undergo C–C bond-formation with CO2 to form carboxylates (C–CO2 –). This chemistry can be coupled with CO2 -promoted volatilization reactions, which convert the carboxylates into isolable carboxylic acids or esters and re-generate carbonate. The net result is a carbonate-catalyzed CO2 insertion reaction.
I will discuss the fundamental nanoscience challenges for improving the rate and scope of this catalysis to unlock CO2 -based routes to numerous commodity chemicals.