Selective C3–C4 Cleavage via Glucose Photoreforming under the Effect of Nucleophilic Dimethyl Sulfoxide

Abstract

Biomass photorefinery is an ideal concept to help alleviate the current energy crisis and move toward carbon neutrality. Nevertheless, limited by the complex structure and multiple functional groups of biomass and its derivatives, current biomass photorefinery still suffers from inefficient substrate conversion and product selectivity. In this work, we rationally design polymeric carbon nitride (CN) by supramolecular self-assembly coupled with an organic copolymerization process method to convert glucose, a widely used model biomass molecule, into glycerol which is a value-added photorefinery product. This molecularly engineered photocatalyst improves the charge separation efficiency and significantly enhances visible light absorption. Importantly, ∼95% glucose conversion is achieved by the photogenerated reactive species of •O2 –, h+, and •OH under mild conditions with selective C3–C4 cleavage via a retro-aldol reaction pathway. The presence of O2 could provide favorable reactive oxygen species during the photoreforming process, and glycerol is the main product with >50% selectivity under the effect of nucleophilic dimethyl sulfoxide (DMSO), which realizes the hydrogenation reaction of 1,3-dihydroxyacetone (DHA) and glyceraldehyde. Our density functional theory (DFT) analysis reveals that DHA is the more favored intermediate compared to glyceraldehyde. This work demonstrates an example of using engineered photocatalysts and reaction systems for selective biomass valorization into biofuels/chemicals via a mild photocatalytic process.

Air-promoted light-driven hydrogen production from bioethanol over core/shell CrOx@GaN nanoarchitecture

“…As of today, there is fast growing number of researches that focus on exploring rational photocatalytic architectures for biomass derivatives reforming to H 2 based on the most studied semiconductors of metal oxides (e.g., TiO 2 , Co 3 O 4 ) 7,8 , metal sul des (e.g., CdS, Cu 2 S) 9,10 , C 3 N 4 11 , and so on. Moreover, a variety of approaches e.g., band structure engineering 12 , heterojunction 13 , defect engineering 14 , and co-catalysts decorations 15 have been explored for advancing the photocatalysts existed.…”

Solar-Driven Cellulose Photorefining into Arabinose over Oxygen-Doped Carbon Nitride

“…3,4 In the past few years, we and others have already demonstrated the feasibility of selective converting biomass-derived soluble components into a series of value-added biochemicals by rational photocatalyst design and reaction condition regulation. 5−8 For example, we can convert glucose, the basic chemical building block of cellulose, into arabinose, 8 glycerol, 9 lactic acid, 10 fructose, 11 and gluconic acid, 12 respectively, by adjusting photocatalyst band gap energy, morphology, and surface chemistry, as well as regulating reaction pH, atmosphere, and solvent media. However, directly and selectively converting cellulose into high-value bioproducts via photocatalysis has been challenging.…”

In Situ Photo-Fenton-Like Tandem Reaction for Selective Gluconic Acid Production from Glucose Photo-Oxidation

“…Polymeric carbon nitride (CN) has been considered to be an ideal and eco-friendly photocatalyst along with surpassing visible light response and promising band positions. , More importantly, CN has been demonstrated to have highly selective H 2 O 2 production via the 2e – oxygen reduction reaction (2e-ORR). , However, the bulk CN derived from ordinary thermal polymerization usually suffers from low efficiency owing to severe recombination of electron–hole pairs . Band gap engineering is a capable approach to improve the 2e-ORR process of CN-based photocatalysts to form H 2 O 2 . − Additionally, alkalinization with cyano groups has been proven to effectively decompose H 2 O 2 into • OH via photo-Fenton process .…”

“…Polymeric carbon nitride (CN) has been considered to be an ideal and eco-friendly photocatalyst along with surpassing visible light response and promising band positions. 27,28 More importantly, CN has been demonstrated to have highly selective H 2 O 2 production via the 2e − oxygen reduction reaction (2e-ORR). 29,30 However, the bulk CN derived from ordinary thermal polymerization usually suffers from low efficiency owing to severe recombination of electron−hole pairs.…”