Photocatalytic degradable polymer precursor production and C–C bond synthesis with CO2 over sulfur vacancies enriched ZnIn2S4 nanosheets

Abstract

It is of significant importance, promise and challenge to combine the waste carbon resource CO2 transformation and the renewable biomass utilization in highly value-added chemical intermediates preparation. In this work, degradable polymer precursor 2,5-furandicarboxylic acid (FDCA) could be easily produced through efficient furfural in situ oxidation, furan ring sp2 C–H activation as well as CO2 reduction over photocatalyst ZnIn2S4 in green solvent H2O. It is worth mentioning that furan ring sp2 C–H activation could be achieved under rather mild conditions, and no sacrificial agent was needed during the photocatalytic carboxylation process to produce FDCA. Different aromatic hydrocarbons and olefins could also be converted to carboxylation products with excellent yield under 1 atm CO2. On the other side, the ZnIn2S4 nanosheets, which had reduced thickness along with improved photogenerated charge transfer efficiency, obviously improved the photocatalytic carboxylation efficiency. When S vacancies were introduced into ZnIn2S4 nanosheets, the photocatalytic carboxylation efficiency improvement was ascribed to the photogenerated electrons enrichment and substrates capture ability enhancement.