Engineering of Local Coordination Microenvironment in Single-Atom Catalysts Enabling Sustainable Conversion of Biomass into a Broad Range of Amines.

Abstract

Utilizing renewable biomass as a substitute for fossil resources to produce high-value chemicals with a low carbon footprint is an effective strategy for achieving a carbon-neutral society. Production of chemicals via single-atom catalysis is an attractive proposition due to its remarkable selectivity and high atomic efficiency. In this work, a supramolecular-controlled pyrolysis strategy is employed to fabricate a palladium single-atom (Pd1 /BNC) catalyst with B-doped Pd-Nx atomic configuration. Owing to the meticulously tailored local coordination microenvironment, the as-synthesized Pd1 /BNC catalyst exhibits remarkable conversion capability for a wide range of biomass-derived aldehydes/ketones. Thorough characterizations and density functional theory calculations reveal that the highly polar metal-N-B site, formed between the central Pd single atom and its adjacent N and B atoms, promotes hydrogen activation from the donor (reductants) and hydrogen transfer to the acceptor (C═O group), consequently leading to exceptional selectivity. This system can be further extended to directly synthesize various aromatic and furonic amines from renewable lignocellulosic biomass, with their greenhouse gas emission potentials being negative in comparison to those of fossil-fuel resource-based amines. This research presents a highly effective and sustainable methodology for constructing C─N bonds, enabling the production of a diverse array of amines from carbon-neutral biomass resources.