We describe recent results from our group showing that different semiconducting and intermetallic nanocrystals show high activity and selectivity for the catalytic reduction of nitrate and nitroarenes. Specific results include one of the first reports of a noble-metal free catalyst made of Earth abundant and biocompatible elements capable of selectively hydrogenating nitrate ions to ammonia. Modification of semiconductors with this same catalyst enables the photocatalytic reduction of nitrate, albeit with limited activity. Also presented is the catalytic reduction of nitroarenes via either direct or coupling routes to anilines or azoxy- and azo-benzenes, respectively. Intermetallic and semiconducting catalysts containing an fcc sublattice are selective for the direct reduction pathway, whereas those with other structure types are selective for the coupling pathway. These results are augmented by molecular dynamics simulations using machine learned potentials. Future reductions of oxyanions and reductive polymerizations of dinitroarenes may be possible based on the chemistry presented here.

Catalytic reductions with colloidal semiconductor and intermetallic nanocrystals

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ACS Fall 2022

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