Photocatalytic Oxidation of 5-Hydroxymethylfurfural Over Interfacial-Enhanced Ag/TiO2 Under Visible Light Irradiation.

Photocatalytic conversion of biomass-derived 5-hydroxyfurfural (HMF) to value-added 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) is an environmentally friendly process. Here, Ag nanoparticle (NP) supported on TiO2 (Ag/TiO2 ) materials with different interfacial structures were fabricated via incipient wetness impregnation. In the photocatalytic oxidation of 5-HMF to HMFCA, low-temperature reduction (473 K) on Ag/TiO2 could improve the photoinduced charge separation efficiency and promote the reaction due to the "enhanced" localized surface plasmon resonance (LSPR) effects achieved through strong metal-support interaction (SMSI). In particular, 2.5 % Ag/TiO2 -LTR exhibited superior performance with an HMFCA selectivity of up to 96.7 % under visible-light illumination. In contrast, the photocatalytic efficiency was greatly reduced when the reduction temperature increased to 773 K because of the encapsulation of Ag NPs by a thicker TiOx overlay, which significantly weakened visible-light harvesting. Overall, these findings offer an efficient methodology for designing interfacial enhanced plasmonic photocatalysts for the valorization of biomass.

Aerobic Oxidation of 5-Hydroxymethylfurfural over Ag Nanoparticle Catalysts Stabilized by Polyvinylpyrrolidone with Different Molecular Weights.

The metal-support interaction (MSI) has a remarkable effect on the catalytic properties, but how to precisely modulate its degree remains a huge challenge. Herein, polyvinylpyrrolidone (PVP) with three different molecular weights (MWs) (24, 58, and 130 kDa) was used as a capping agent to fabricate Ag nanoparticles (NPs) supported on ZrO2. The physiochemical properties of the catalysts were characterized by X-ray diffraction (XRD), Transmission Electron Microscope (TEM), X-ray Photoelectron Spectroscopy (XPS), and Fourier transform infrared (FT-IR) techniques. The impacts of MSI on the catalytic activity and reaction kinetics for aerobic oxidation of 5-hydroxymethylfurfural (HMF) were investigated. The results showed that the introduction of PVP with various MWs could efficiently tailor the interfacial interactions and charge transfers (CT) among PVP, the support, and Ag NPs, thereby affecting the oxidation activity of HMF. The turnover number (TON) for HMF oxidation decreases in the order of unsupported colloidal Ag clusters > Ag/ZrO2 (58,000) > Ag/ZrO2 (130,000) > Ag/ZrO2 (24,000) > Ag/ZrO2. The reason for this large difference in the catalytic activity for HMF oxidation is that various MWs of PVP result in a change of MSI, thereby facilitating CT from PVP to Ag metal sites. This study offers a new strategy for modulating MSI by varying the MW of capping agents, thereby tuning the catalytic properties in the oxidation of HMF.