RESUMEN
Maleic anhydride (MA) is an important polyester monomer that can be produced from oxidizing renewable furfural derived from biomass. However, MA generation from furfural requires harsh reaction conditions, and suffers from low efficiency and solvent corrosion. Herein, we design a Nb2 O5 photocatalyst loaded of highly dispersed CuOx (CuOx /Nb2 O5 ), which selectively catalyzes furfural oxidation to MA and the precursor (5-hydroxy-2(5H)-furanone, HF). Due to CuOx loading and forming a complex of ligand to metal charge transfer (LMCT) between the Nb2 O5 surface and adsorbed furfural, the CuOx /Nb2 O5 absorbs visible light to activate furfural though Nb2 O5 has a large band-gap energy (3.2â eV). Singlet oxygen (1 O2 ) is the key active species for C-C bond cleavage and CO generation. MA and HF is produced with a combined yield of 59 % under optimized conditions. This work provides a mild way to provide renewable maleic anhydride via oxidative C-C bond cleavage.
RESUMEN
Photocatalytic 2-iodoethanol (IEO) coupling provides 1,4-butanediol (BDO) of particular interest to produce degradable polyesters. However, the reduction potential of IEO is too negative (-1.9 vs NHE) to be satisfied by most of the semiconductors, and the kinetics of transferring one electron for IEO coupling is slow. Here we design a catalytic Ni complex, which works synergistically with TiO2 , realizing reductive coupling of IEO powered by photo-energy. Coordinating by terpyridine stabilizes Ni2+ from being photo-deposited to TiO2 , thereby retaining the steric configuration beneficial for IEO coupling. The Ni complex can rapidly extract electrons from TiO2 , generating a low-valent Ni capable of reducing IEO. The photocatalytic IEO coupling thus provides BDO in 72 % selectivity. By a stepwise procedure, BDO is obtained with 70 % selectivity from ethylene glycol. This work put forward a strategy for the photocatalytic reduction of molecules requiring strong negative potential.