Amyloid-Like Protein-Modified Carbon Nitride as a Bioinspired Material for Enhanced Photocatalytic CO2 Reduction.

Abstract

Modification of g-C3N4 with metal-free biomaterials through an environmentally friendly, low-energy, facile, and rapid single-step method is desired for the preparation of photocatalysts with efficient activity and high selectivity of CO2 reduction but remains a great challenge. Herein, we develop a phase-transitioned protein modification strategy for photocatalysts through superfast amyloid-like protein assembly on surfaces using a one-step sequential coating method. Metal-free carbon nitride/protein heterojunction composite photocatalysts (the phase-transitioned lysozyme (PTL), phase-transitioned bovine serum albumin (PTB), and phase-transitioned ovalbumin (PTO)-coated carbon nitride@SiO2 (CN@SiO2) and bioinspired carbon nitride hollow nanospheres (CN-HS) obtained by etching of CN@SiO2) are prepared using lysozyme, bovine serum albumin, and ovalbumin. The insulator-semiconductor heterojunctions formed at the protein-carbon nitride interface promote the migration and separation of photogenerated charges. The exposed hydrophobic alkyl and aryl groups of the surface-modified protein enable the formation of a CO2-aqueous solution-photocatalyst three-phase interface on the catalyst surface and the exposed -NH2 groups provide sites for CO2 adsorption, which effectively increases CO2 mass transfer and its adsorption as well as hydrophobicity, promoting CO2 reduction and inhibiting hydrogen production. Therefore, protein modification effectively improves the CO2 reduction activity and CO selectivity. For instance, compared to CN-HS, the CO yield of the PTL-modified CN-HS (1346.5 μmol g-1) increased by 24.5 times and the CO selectivity reached 90.5%. These findings represent a critical advancement in the surface modification of carbon nitride for CO2 reduction and the design of bioinspired materials for various applications.