Alkylamine-Grafted Organic Semiconductors with Plasma-Induced Defects as Electron Promoters of CO-Resistant Pd-Based Nanoparticles for Efficient Light-Driven On-Demand H2 Generation

Tailoring the adsorption characteristics of catalytic substrates and the electronic behavior of catalytically active species in heterogeneous catalysts is beneficial for regulating their catalytic performance. Herein, we report a highly efficient room-temperature photocatalytic formic acid (HCOOH) dehydrogenation system, where plasma-induced carbon nitrides (CNs) grafted by aminosilanes are used as electron promoters of catalytically active AuPdM (M = Ni and Co) nanoparticles (NPs). The various characterizations verify that the plasma-induced CNs have rich nitrogen defects and the efficient separation of photogenerated charge carriers. The visible-light-driven synergism of alkylamine and defective CNs with tunable band structures in the catalysts accounts for their enhanced HCOOH adsorption and the enriched electron density of metal NPs. This indicates that the catalysts have 100% H-2 selectivity and higher activities under visible light irradiation than in the dark. The optimal CO-resistant AuPdNi catalyst possesses 66.9% of apparent quantum yield at 420 nm and exhibits the record room-temperature H-2 generation activity with the total turnover frequencies of 1075 and 1278 h(-1) in the absence and presence of scavenger of photogenerated holes, respectively.

Automated summary

The study presented a highly efficient room-temperature photocatalytic formic acid dehydrogenation system using plasma-induced carbon nitrides grafted with aminosilanes as electron promoters for AuPdM nanoparticles. The synergistic effect of alkylamine and defective CNs with tunable band structures in the catalysts enhanced HCOOH adsorption and increased electron density of metal NPs. The optimal CO-resistant AuPdNi catalyst showed significant room-temperature hydrogen generation activity with high apparent quantum yield and turnover frequencies.