Selective photooxidation of 5-hydroxymethylfurfural in water enabled by highly dispersed gold nanoparticles on graphitic carbon nitride

Abstract

Photocatalytic synthesis of chemicals is highly recognized for its eco-friendliness and mild reaction conditions, yet it faces considerable challenges regarding catalytic efficiency, stability and cost. The selective photooxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran in water is a cost-effective and sustainable route for biomass valorization. The capability of a photocatalyst to capture visible light is paramount for efficiently harnessing solar energy and is the most critical initial step. Therefore, metal nanocatalysts with visible-light response and localized surface plasmon resonance have received widespread attention. In this work, graphitic carbon nitride (g-C₃N₄) with different morphologies was synthesized through high-temperature calcination of various organic precursors. Following that, the photodeposition of Au nanoparticles was used to construct a Schottky junction photocatalyst endowed with the localized surface plasmon resonance effect. The optimal Au/CN(I) catalyst achieved a 26% yield of 2,5-diformylfuran and productivity of 72.7 mg_DFF g_catal.^-1 h^-1 under simulated sunlight in oxygen and water without any additives. This outstanding result outperformed most g-C₃N₄ and metal oxide photocatalysts ever reported in the literature. The interfacial electronic interactions between Au nanoparticles and g-C₃N₄ semiconductors were meticulously elucidated using comprehensive characterizations and computational calculations. The roles of different reactive oxygen species were clarified by a series of controlled experiments. A plausible mechanism explaining the origin of visible-light response and photocatalytic performance was discussed.

Keywords

Photocatalysis / 2,5-diformylfuran / visible light / localized surface plasmon resonance / schottky junction / green synthesis

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