物理化学学报 >> 2026, Vol. 42 >> Issue (3): 100165.doi: 10.1016/j.actphy.2025.100165

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[Cp*Rh(bpy)H2O]2+自组装CdIn2S4花状微球的高效光催化NADH再生与酶促CO2还原

高春慧1,2, 李璐嵘2, 彭官威2, 沈锦妮2, 戴文新1,2,3, 张子重1,2,*()   

  1. 1 福州大学, 化工学院, 福建 福州 350116
    2 福州大学, 化学学院, 核生化防护化学全国重点实验室, 福建 福州 350116
    3 清源创新实验室, 福建 泉州 362801
  • 收稿日期:2025-07-15 修回日期:2025-08-14 录用日期:2025-08-17 发布日期:2026-01-05
  • 通讯作者: Email: z.zhang@fzu.edu.cn (张子重)

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

Chunhui Gao1,2, Lurong Li2, Guanwei Peng2, Jinni Shen2, Wenxin Dai1,2,3, Zizhong Zhang1,2,*()   

  1. 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
  • Received:2025-07-15 Revised:2025-08-14 Accepted:2025-08-17 Published:2026-01-05
  • Contact: Email: z.zhang@fzu.edu.cn (Zizhong Zhang)

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摘要：

将光催化辅因子再生与酶催化偶联有助于实现可持续的CO2增值利用，但该技术仍面临氢源有限、均相介体及光生空穴诱导酶失活等挑战。本研究表明，L-抗坏血酸(L-AA)的低氧化电位可增强质子供给并促进[Cp*Rh(bpy)H]+中间体形成。仅需0.26 mg (≈ 0.12 mmol L−1) [Cp*Rh(bpy)Cl]Cl即可实现高效/选择性还原型烟酰胺腺嘌呤二核苷酸(NADH)再生，其效率是典型牺牲剂三乙醇胺(TEOA)的两倍以上。本研究开发了一种将[Cp*Rh(bpy)H2O]2+静电自组装在CdIn2S4微球光催化剂上的新策略。这种创新集成方式通过空间分区将游离介体和光生空穴与酶隔离，有效抑制了酶失活。最优集成光催化体系在420 nm光照40 min内实现90%的NADH再生效率，优于已报道的同类体系。与甲酸脱氢酶(FDH)偶联时，该集成体系甲酸生成速率达443.5 μmol g−1 h−1 (明暗循环)和202.7 μmol g−1 h−1 (持续光照)，分别是含游离介体体系的1.2倍和3.2倍。本研究为光驱动辅酶再生及酶催化CO2合成高附加值化学品提供了高效可持续的新策略。

关键词: 光-酶偶联催化, CdIn2S4微球, CO2转化, 电子介体集成, NADH再生

Abstract:

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.

Key words: Photoenzyme-coupled catalysis, CdIn2S4 microspheres, CO2 conversion, Electronic mediator integration, NADH regeneration