Citation: Chunhui Gao, Lurong Li, Guanwei Peng, Jinni Shen, Wenxin Dai, Zizhong Zhang. Efficient photocatalytic NADH regeneration and enzymatic CO₂ reduction over[Cp*Rh(bpy)H₂O]²⁺ self-assembled CdIn₂S₄ flowerlike microspheres[J]. Acta Physico-Chimica Sinica, ;2026, 42(3): 100165. doi: 10.1016/j.actphy.2025.100165 shu

Efficient photocatalytic NADH regeneration and enzymatic CO₂ reduction over[Cp*Rh(bpy)H₂O]²⁺ self-assembled CdIn₂S₄ flowerlike microspheres

Chunhui Gao ^1,2 ,
Lurong Li ² ,
Guanwei Peng ² ,
Jinni Shen ² ,
Wenxin Dai ^1,2,3 ,
Zizhong Zhang ^1,2,,

1.
College of Chemical Engineering, Fuzhou University, Fuzhou 350116, Fujian Province, China;
2.
State Key Laboratory of Chemistry for NBC Hazards Protection, College of Chemistry, Fuzhou University, Fuzhou 350116, Fujian Province, China;
3.
Qingyuan Innovation Laboratory, Quanzhou 362801, Fujian Province, China

Corresponding author: Zizhong Zhang, z.zhang@fzu.edu.cn
Received Date: 15 July 2025
Revised Date: 14 August 2025
Accepted Date: 17 August 2025

Integrating photocatalytic cofactor regeneration with enzymatic cascades enables sustainable CO₂ valorization but faces challenges like limited hydrogen sources and homogeneous mediator and photogenerated holes-induced enzyme deactivation. This study demonstrates that the low oxidation potential of L-ascorbic acid (L-AA) can enhance proton supply and promote the formation of[Cp*Rh(bpy)H]⁺ intermediates. Only 0.26 mg (≈ 0.12 mmol L^-1)[Cp*Rh(bpy)Cl]Cl can achieve efficient/selective reduced nicotinamide adenine dinucleotide (NADH) regeneration, which is more than twice as effective as the typical sacrificial agent triethanolamine (TEOA). A novel strategy was developed via electrostatic self-assembly of [Cp*Rh(bpy)H₂O]²⁺ onto CdIn₂S₄ microsphere photocatalysts. This innovative integration physically separated free mediators and photogenerated holes from enzymes, effectively suppressing enzyme deactivation through spatial compartmentalization. The optimal integrated photocatalytic system achieved 90% NADH regeneration efficiency within 40 min of 420 nm light irradiation, outperforming previously reported systems. When coupled with formate dehydrogenase (FDH), the integrated system achieved formic acid generation rates of 443.5 μmol g^-1 h^-1 (one light-dark cycle) and 202.7 μmol g^-1 h^-1 (continuous light), representing 1.2- and 3.2-fold improvements over free mediator systems, respectively. This study provides an efficient and sustainable new strategy for light driven coenzyme regeneration and enzyme catalyzed CO₂ synthesis of high value-added chemicals.
- Photoenzyme-coupled catalysis,
- CdIn₂S₄ microspheres,
- CO₂ conversion,
- Electronic mediator integration,
- NADH regeneration
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Efficient photocatalytic NADH regeneration and enzymatic CO2 reduction over[Cp*Rh(bpy)H2O]2+ self-assembled CdIn2S4 flowerlike microspheres

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通讯作者: 陈斌, bchen63@163.com

Efficient photocatalytic NADH regeneration and enzymatic CO₂ reduction over[Cp*Rh(bpy)H₂O]²⁺ self-assembled CdIn₂S₄ flowerlike microspheres