Heat-fueled enzymatic cascade for selective oxyfunctionalization of hydrocarbons.

Heat is a fundamental feedstock, where more than 80% of global energy comes from fossil-based heating process. However, it is mostly wasted due to a lack of proper techniques of utilizing the low-quality waste heat (<100 °C). Here we report thermoelectrobiocatalytic chemical conversion systems for heat-fueled, enzyme-catalyzed oxyfunctionalization reactions. Thermoelectric bismuth telluride (Bi 2 Te 3 ) directly converts low-temperature waste heat into chemical energy in the form of H 2 O 2 near room temperature. The streamlined reaction scheme (e.g., water, heat, enzyme, and thermoelectric material) promotes enantio- and chemo-selective hydroxylation and epoxidation of representative substrates (e.g., ethylbenzene, propylbenzene, tetralin, cyclohexane, cis-β-methylstyrene), achieving a maximum total turnover number of rAaeUPO (TTN rAaeUPO ) over 32000. Direct conversion of vehicle exhaust heat into the enantiopure enzymatic product with a rate of 231.4 μM h -1 during urban driving envisions the practical feasibility of thermoelectrobiocatalysis.