Integration of Enzymes and Photosensitizers in a Hierarchical Mesoporous Metal–Organic Framework for Light-Driven CO2 Reduction
Abstract
Protection of enzymes with synthetic materials is a viable strategy to stabilize, and hence to retain, the reactivity of these highly active biomolecules in non-native environments. Active synthetic supports, coupled to encapsulated enzymes, can enable efficient cascade reactions which are necessary for processes like light-driven CO2 reduction, providing a promising pathway for alternative energy generation. Herein, a semi-artificial system—containing an immobilized enzyme, formate dehydrogenase, in a light harvesting scaffold—is reported for the conversion of CO2 to formic acid using white light. The electron-mediator Cp*Rh(2,2'-bipyridyl-5,5'-dicarboxylic acid)Cl was anchored to the nodes of the metal–organic framework NU-1006 to facilitate ultrafast photo-induced electron transfer when irradiated, leading to the reduction of the coenzyme nicotinamide adenine dinucleotide at a rate of about 28 mM·h-1. Most importantly, the immobilized enzyme utilizes the reduced coenzyme to generate formic acid selectively from CO2 at a high turnover frequency of about 865 h-1 in 24 h. The outcome of this research is the demonstration of a feasible pathway for solar-driven carbon fixation.
- Authors:
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[1];
[1];
[1];
[1];
[1];
[2];
[3];
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[1]
- Northwestern Univ., Evanston, IL (United States)
- Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States
- Northwestern Univ., Evanston, IL (United States); Tianjin Univ. (China). Institute for Molecular Design and Synthesis; Univ. of New South Wales, Sydney, NSW (Australia)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1865071
- Grant/Contract Number:
- SC0000989; SC0001059; CHE-1048773; DMR0521267; NSF NNCI-1542205; NSF DMR-1720139
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 142; Journal Issue: 4; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Metal organic frameworks; Peptides and proteins; Photosensitization; Irradiation; Light
Citation Formats
Chen, Yijing, Li, Peng, Zhou, Jiawang, Buru, Cassandra T., Đorđević, Luka, Li, Penghao, Zhang, Xuan, Cetin, M. Mustafa, Stoddart, J. Fraser, Stupp, Samuel I., Wasielewski, Michael R., and Farha, Omar K. Integration of Enzymes and Photosensitizers in a Hierarchical Mesoporous Metal–Organic Framework for Light-Driven CO2 Reduction. United States: N. p., 2020.
Web. doi:10.1021/jacs.9b12828.
Chen, Yijing, Li, Peng, Zhou, Jiawang, Buru, Cassandra T., Đorđević, Luka, Li, Penghao, Zhang, Xuan, Cetin, M. Mustafa, Stoddart, J. Fraser, Stupp, Samuel I., Wasielewski, Michael R., & Farha, Omar K. Integration of Enzymes and Photosensitizers in a Hierarchical Mesoporous Metal–Organic Framework for Light-Driven CO2 Reduction. United States. https://doi.org/10.1021/jacs.9b12828
Chen, Yijing, Li, Peng, Zhou, Jiawang, Buru, Cassandra T., Đorđević, Luka, Li, Penghao, Zhang, Xuan, Cetin, M. Mustafa, Stoddart, J. Fraser, Stupp, Samuel I., Wasielewski, Michael R., and Farha, Omar K. Mon .
"Integration of Enzymes and Photosensitizers in a Hierarchical Mesoporous Metal–Organic Framework for Light-Driven CO2 Reduction". United States. https://doi.org/10.1021/jacs.9b12828. https://www.osti.gov/servlets/purl/1865071.
@article{osti_1865071,
title = {Integration of Enzymes and Photosensitizers in a Hierarchical Mesoporous Metal–Organic Framework for Light-Driven CO2 Reduction},
author = {Chen, Yijing and Li, Peng and Zhou, Jiawang and Buru, Cassandra T. and Đorđević, Luka and Li, Penghao and Zhang, Xuan and Cetin, M. Mustafa and Stoddart, J. Fraser and Stupp, Samuel I. and Wasielewski, Michael R. and Farha, Omar K.},
abstractNote = {Protection of enzymes with synthetic materials is a viable strategy to stabilize, and hence to retain, the reactivity of these highly active biomolecules in non-native environments. Active synthetic supports, coupled to encapsulated enzymes, can enable efficient cascade reactions which are necessary for processes like light-driven CO2 reduction, providing a promising pathway for alternative energy generation. Herein, a semi-artificial system—containing an immobilized enzyme, formate dehydrogenase, in a light harvesting scaffold—is reported for the conversion of CO2 to formic acid using white light. The electron-mediator Cp*Rh(2,2'-bipyridyl-5,5'-dicarboxylic acid)Cl was anchored to the nodes of the metal–organic framework NU-1006 to facilitate ultrafast photo-induced electron transfer when irradiated, leading to the reduction of the coenzyme nicotinamide adenine dinucleotide at a rate of about 28 mM·h-1. Most importantly, the immobilized enzyme utilizes the reduced coenzyme to generate formic acid selectively from CO2 at a high turnover frequency of about 865 h-1 in 24 h. The outcome of this research is the demonstration of a feasible pathway for solar-driven carbon fixation.},
doi = {10.1021/jacs.9b12828},
journal = {Journal of the American Chemical Society},
number = 4,
volume = 142,
place = {United States},
year = {Mon Jan 13 00:00:00 EST 2020},
month = {Mon Jan 13 00:00:00 EST 2020}
}
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