<p>The selective conversion of glycerol, an abundant biomass-derived platform chemical, into longer carbon chain, high-value compounds is appealing but highly challenging. Conventional oxidation processes are prone to C–C bond cleavage, resulting in the inefficient utilization of the glycerol three-carbon backbone. Here we report a spatially decoupled photoelectrocatalytic–biocatalytic relay system that is able to efficiently upgrade glycerol to sorbose, an important six-carbon sugar used in the food, pharmaceutical and cosmetic industries. This system uses a WO<sub>3</sub>–Bi photoanode to selectively oxidize glycerol into two distinct three-carbon products: glyceraldehyde and dihydroxyacetone. Subsequently, these two three-carbon products are coupled via an aldol addition reaction, driven by a mutant fructose-6-phosphate aldolase catalyst. Continuous tandem operation enables the highly selective conversion of glycerol into a single six-carbon product, sorbose. Furthermore, coupling the WO<sub>3</sub>–Bi photoanode with an Si photocathode followed by enzyme catalysis relay achieves a sorbose yield of 31.66 mmol g<sub>enzyme</sub><sup>−1</sup> h<sup>−1</sup> under solar light irradiation without the need of external energy input. This work presents a sustainable platform for upgrading biomass-derived glycerol into valuable six-carbon chemicals under mild conditions, providing a green and efficient route for biomass valorization.</p>

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Upgrading glycerol to sorbose via a tandem photoelectrocatalysis–enzyme catalysis relay

  • Caiyi Liu,
  • Guangyu Liu,
  • Zehua Liu,
  • Shipeng Zhu,
  • Kanghong Wang,
  • Jianghong Liu,
  • Shenghe Si,
  • Zhongpeng Zhu,
  • Dong Liu,
  • Chao Gao,
  • Bin Liu,
  • Yujie Xiong

摘要

The selective conversion of glycerol, an abundant biomass-derived platform chemical, into longer carbon chain, high-value compounds is appealing but highly challenging. Conventional oxidation processes are prone to C–C bond cleavage, resulting in the inefficient utilization of the glycerol three-carbon backbone. Here we report a spatially decoupled photoelectrocatalytic–biocatalytic relay system that is able to efficiently upgrade glycerol to sorbose, an important six-carbon sugar used in the food, pharmaceutical and cosmetic industries. This system uses a WO3–Bi photoanode to selectively oxidize glycerol into two distinct three-carbon products: glyceraldehyde and dihydroxyacetone. Subsequently, these two three-carbon products are coupled via an aldol addition reaction, driven by a mutant fructose-6-phosphate aldolase catalyst. Continuous tandem operation enables the highly selective conversion of glycerol into a single six-carbon product, sorbose. Furthermore, coupling the WO3–Bi photoanode with an Si photocathode followed by enzyme catalysis relay achieves a sorbose yield of 31.66 mmol genzyme−1 h−1 under solar light irradiation without the need of external energy input. This work presents a sustainable platform for upgrading biomass-derived glycerol into valuable six-carbon chemicals under mild conditions, providing a green and efficient route for biomass valorization.