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.
Original language | English (US) |
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Pages (from-to) | 1768-1773 |
Number of pages | 6 |
Journal | Journal of the American Chemical Society |
Volume | 142 |
Issue number | 4 |
DOIs | |
State | Published - Jan 29 2020 |
Funding
This research was primarily supported as part of the Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE-SC0001059 (Y.C., O.K.F., J.Z., M.R.W.) MOF syntheses and characterization, enzyme encapsulation, photophysics, and catalysis). Research in the Stupp laboratory (photocatalysis) was supported by the Center for Bio-Inspired Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE-SC0000989. This research made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois through the IIN. This research made use of the IMSERC at Northwestern University, which receives support from the NSF (CHE-1048773 and DMR0521267); the SHyNE Resource (NSF NNCI-1542205); the State of Illinois; and the IIN. J.F.S. and P.L. acknowledge the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU) for supporting the synthesis of the organic ligand. We thank Dr. Islamoglu for providing some organic precursors.
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry