Modulation of Electronic Structure of Single-Atom Catalysts for Sustainable Production of Full-Spectrum Amines from Renewable Biomass

Abstract

Abstract Using renewable biomass to replace fossil resources for producing low-carbon-footprint but high-value chemicals is a sustainable approach to pursue a carbon-neutral society. Herein, a boron nitrogen doped carbon (BNC) confined Pd single atom catalyst (Pd SAs/BNC) is synthesized and used as a robust catalyst toward the reductive amination reaction to produce low-carbon-footprint amines from renewable biomass. Because of the finely tuned electron structure, the as-synthesized single atom catalyst delivers an ultrahigh turn-over frequency value (max. 1368 h− 1) in the reductive amination of aldehydes/ketones and demonstrates a great conversion capacity for various aldehyde/ketone and amine/nitro-compound substrates. Extensive characterizations and density functional theory calculations show that the highly polar metal-N site formed between the central Pd single atom and its neighboring N and B atoms favors hydrogen activation from the donor (reductants) and hydrogen transformation to the receptor (C = O group), resulting in a great selectivity. This system could be further extended to directly produce various aromatic and furonic amines from renewable lignocellulosic biomass, and their greenhouse gas emission potentials are negative compared to those of fossil-fuel resource-based amines. This work offers a highly efficient and sustainable approach to construct C-N bonds for the production of numerous amines from carbon-neutral biomass resources.