{"title":"Integration of Multiple Enzymes Within Hydrogen-Bonded Organic Frameworks for Efficient Cascade Photocatalytic CO<sub>2</sub>-to-Methanol Conversion in Water.","authors":"Jiakang Tang, Yifei Lei, Qingxuan Tang, Shixing Lei, Qiao-Yan Qi, Zhan-Ting Li, Jia Tian","doi":"10.1002/anie.202516599","DOIUrl":null,"url":null,"abstract":"<p><p>The integration of photocatalysts and enzymes within confined environments offers a promising approach to developing artificial photosynthetic systems for sustainable CO<sub>2</sub> conversion. However, the efficient coupling of photocatalysts with multiple enzymes to enable photo-enzymatic cascade catalysis remains a significant challenge. Herein, we report the construction of hydrogen-bonded organic frameworks (HOFs) that integrate Ru-based photocatalysts with three-enzyme cascades of formate dehydrogenase (FDH), formaldehyde dehydrogenase (FaldDH), and alcohol dehydrogenase (ADH) via in situ co-assembly in water. The RuHOF exhibits exceptional nicotinamide adenine dinucleotide (NADH) photo-regeneration activity (4.5 mM h<sup>-1</sup>), while the FDH@RuHOF hybrid converts CO<sub>2</sub> to formic acid with a turnover frequency (TOF) of 681 h<sup>-1</sup> (238 µM h<sup>-1</sup>) over 24 h. By engineering FDH/FaldDH/ADH@RuHOF ternary systems, we achieve sustained CO<sub>2</sub>-to-methanol conversion through photo-enzymatic cascade catalysis, delivering 2.2 mM methanol production with an apparent quantum efficiency (AQY) of 5.5% (92 µM h<sup>-1</sup>) over 24 h with 85% activity retention after five catalytic cycles. This work opens a promising avenue for the development of efficient multi-enzyme cascade artificial photosynthetic systems toward steady and recyclable CO<sub>2</sub> valorization.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202516599"},"PeriodicalIF":16.9000,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie (International ed. in English)","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1002/anie.202516599","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
Abstract
The integration of photocatalysts and enzymes within confined environments offers a promising approach to developing artificial photosynthetic systems for sustainable CO2 conversion. However, the efficient coupling of photocatalysts with multiple enzymes to enable photo-enzymatic cascade catalysis remains a significant challenge. Herein, we report the construction of hydrogen-bonded organic frameworks (HOFs) that integrate Ru-based photocatalysts with three-enzyme cascades of formate dehydrogenase (FDH), formaldehyde dehydrogenase (FaldDH), and alcohol dehydrogenase (ADH) via in situ co-assembly in water. The RuHOF exhibits exceptional nicotinamide adenine dinucleotide (NADH) photo-regeneration activity (4.5 mM h-1), while the FDH@RuHOF hybrid converts CO2 to formic acid with a turnover frequency (TOF) of 681 h-1 (238 µM h-1) over 24 h. By engineering FDH/FaldDH/ADH@RuHOF ternary systems, we achieve sustained CO2-to-methanol conversion through photo-enzymatic cascade catalysis, delivering 2.2 mM methanol production with an apparent quantum efficiency (AQY) of 5.5% (92 µM h-1) over 24 h with 85% activity retention after five catalytic cycles. This work opens a promising avenue for the development of efficient multi-enzyme cascade artificial photosynthetic systems toward steady and recyclable CO2 valorization.
光催化剂和酶在密闭环境中的整合为开发可持续二氧化碳转化的人工光合系统提供了一条有前途的途径。然而,光催化剂与多种酶的有效偶联以实现光酶级联催化仍然是一个重大挑战。在此,我们报道了氢键有机框架(HOFs)的构建,该框架将钌基光催化剂与甲酸脱氢酶(FDH)、甲醛脱氢酶(FaldDH)和醇脱氢酶(ADH)三酶级联结合在一起,通过水中原位共组装。RuHOF表现出优异的烟酰胺腺嘌呤二核苷酸(NADH)光再生活性(4.5 mM h-1),而FDH@RuHOF复合物在24小时内以681 h-1 (238 μ M h-1)的转换频率(TOF)将CO2转化为甲酸。通过设计FDH/FaldDH/ADH@RuHOF三元体系,我们通过光酶级联催化实现了CO2到甲醇的持续转化。在5次催化循环后,在24小时内以5.5% (92 μ M h-1)的表观量子效率(AQY)生产2.2 mM甲醇,活性保持率为85%。这项工作为开发高效的多酶级联人工光合系统以稳定和可回收的CO2增值开辟了一条有希望的途径。