Electroenzymatic Reduction of Furfural to Furfuryl Alcohol by an Electron Mediator and Enzyme Orderly Assembled Biocathode.

The electroenzymatic valorization of biomass derivatives into valuable biochemicals has a promising outlook. However, bottlenecks including poor electron transfer between the electrode surface and oxidoreductase, inefficient regeneration of cofactors, and high cost of enzymes and electron mediators hindered the realistic applications of the technique. Herein, to address the above technical barriers, a novel bio-electrocatalytic system that integrates the electrochemical NADH regeneration and enzymatic reaction was constructed, using an orderly assembled composite bioelectrode consisting of an outer immobilized enzyme layer and a sandwiched redox mediator rhodium complex layer. The as-prepared composite bioelectrode was further applied for the highly selective hydrogenation of furfural into furfural alcohol. Results indicated that the enzyme activity was significantly improved, while the furfural valorization was promoted by effective interfacial electron transition and co-factor regeneration on the composite bioelectrode. Considerable high furfural conversion (96.4%) can be achieved accompanied by a furfural alcohol selectivity of 90.0% at -1.2 V (vs Ag/AgCl). The novel composite bioelectrode also showed good stability and reusability. Up to 85.1% of the original furfural alcohol selectivity can be preserved after 10 times of recycling. This work presents a promising green alternative for the valorization of furfural, which also shows great potential extending to the valorization of other biomass compounds.

Artificial Photoenzymatic Reduction of Carbon Dioxide to Methanol by Using Electron Mediator and Co-factorAssembled ZnIn2 S4 Nanoflowers.

Increased absorption of visible light, low electron-hole recombination, and fast electron transfer are the major objectives for highly effective photocatalysts in biocatalytic artificial photosynthetic systems. In this study, a polydopamine (PDA) layer containing electron mediator, [M], and NAD+ cofactor was assembled on the outer surface of ZnIn2 S4 nanoflower, and the as-prepared nanoparticle, ZnIn2 S4 /PDA@poly/[M]/NAD+ , was used for photoenzymatic methanol production from CO2 . Because of effective capturing of visible light, reduced distance of electron transfer, and elimination of electron-holes recombination, a high NADH regeneration of 80.7±1.43 % could be obtained using the novel ZnIn2 S4 /PDA@poly/[M]/NAD+ . In the artificial photosynthesis system, a maximum methanol production of 116.7±11.8 µm was obtained. The enzymes and nanoparticles in the hybrid bio-photocatalysis system could be easily recovered using the ultrafiltration membrane at the bottom of the photoreactor. This is due to the successful immobilization of the small blocks including the electron mediator and cofactor on the surface of the photocatalyst. The ZnIn2 S4 /PDA@poly/[M]/NAD+ photocatalyst exhibited good stability and recyclability for methanol production. The novel concept presented in this study shows great promise for other sustainable chemical productions through artificial photoenzymatic catalysis.