Photoreactive Carbon Dioxide Capture by a Zirconium-Nanographene Metal-Organic Framework

Xin Zheng; Matthew C. Drummer; Haiying He; Thomas M. Rayder; Jens Niklas; Nicholas P. Weingartz; Igor L. Bolotin; Varun Singh; Boris V. Kramar; Lin X. Chen; Joseph T. Hupp; Oleg G. Poluektov; Omar K. Farha; Peter Zapol; Ksenija D. Glusac

doi:10.1021/acs.jpclett.3c00049

Photoreactive Carbon Dioxide Capture by a Zirconium-Nanographene Metal-Organic Framework

Xin Zheng, Matthew C. Drummer, Haiying He, Thomas M. Rayder, Jens Niklas, Nicholas P. Weingartz, Igor L. Bolotin, Varun Singh, Boris V. Kramar, Lin X. Chen, Joseph T. Hupp, Oleg G. Poluektov, Omar K. Farha, Peter Zapol, Ksenija D. Glusac^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

The mechanism of photochemical CO₂ reduction to formate by PCN-136, a Zr-based metal-organic framework (MOF) that incorporates light-harvesting nanographene ligands, has been investigated using steady-state and time-resolved spectroscopy and density functional theory (DFT) calculations. The catalysis was found to proceed via a “photoreactive capture” mechanism, where Zr-based nodes serve to capture CO₂ in the form of Zr-bicarbonates, while the nanographene ligands have a dual role of absorbing light and storing one-electron equivalents for catalysis. We also find that the process occurs via a “two-for-one” route, where a single photon initiates a cascade of electron/hydrogen atom transfers from the sacrificial donor to the CO₂-bound MOF. The mechanistic findings obtained here illustrate several advantages of MOF-based architectures in molecular photocatalyst engineering and provide insights on ways to achieve high formate selectivity.

Original language	English (US)
Pages (from-to)	4334-4341
Number of pages	8
Journal	Journal of Physical Chemistry Letters
Volume	14
Issue number	18
DOIs	https://doi.org/10.1021/acs.jpclett.3c00049
State	Published - May 11 2023

Funding

This work is supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Science, Division of Chemical Sciences, Geosciences, and Biosciences, through Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We acknowledge the computational resources provided by the Laboratory Computing Resource Center at Argonne National Laboratory and the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The EPR work (O.G.P,. J.N.) was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Contract no. DE-AC-02-06CH11357. J.T.H. gratefully acknowledges support from the U.S. DOE, Office of Science, Basic Energy Sciences (Grant DE-FG02-87ER13808). O.K.F. and T.M.R. acknowledge a grant from Department of Energy (DE-SC0022332). We thank Rosmi Reji for her help with time-resolved spectroscopy experiments. We also thank Dr. Zhijie Chen, Dr. Subhadip Goswami, and Dr. Yang Song for suggestions regarding the pbz-MOF-1 synthesis and XRD characterization. We thank Shirin Saffar Avval and Prof. Brian Chaplin for their help with protocols for formate detection. SEM work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern’s MRSEC program (NSF DMR-1720139).

ASJC Scopus subject areas

General Materials Science
Physical and Theoretical Chemistry

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10.1021/acs.jpclett.3c00049

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Zheng, X., Drummer, M. C., He, H., Rayder, T. M., Niklas, J., Weingartz, N. P., Bolotin, I. L., Singh, V., Kramar, B. V., Chen, L. X., Hupp, J. T., Poluektov, O. G., Farha, O. K., Zapol, P., & Glusac, K. D. (2023). Photoreactive Carbon Dioxide Capture by a Zirconium-Nanographene Metal-Organic Framework. Journal of Physical Chemistry Letters, 14(18), 4334-4341. https://doi.org/10.1021/acs.jpclett.3c00049

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title = "Photoreactive Carbon Dioxide Capture by a Zirconium-Nanographene Metal-Organic Framework",

abstract = "The mechanism of photochemical CO2 reduction to formate by PCN-136, a Zr-based metal-organic framework (MOF) that incorporates light-harvesting nanographene ligands, has been investigated using steady-state and time-resolved spectroscopy and density functional theory (DFT) calculations. The catalysis was found to proceed via a “photoreactive capture” mechanism, where Zr-based nodes serve to capture CO2 in the form of Zr-bicarbonates, while the nanographene ligands have a dual role of absorbing light and storing one-electron equivalents for catalysis. We also find that the process occurs via a “two-for-one” route, where a single photon initiates a cascade of electron/hydrogen atom transfers from the sacrificial donor to the CO2-bound MOF. The mechanistic findings obtained here illustrate several advantages of MOF-based architectures in molecular photocatalyst engineering and provide insights on ways to achieve high formate selectivity.",

author = "Xin Zheng and Drummer, {Matthew C.} and Haiying He and Rayder, {Thomas M.} and Jens Niklas and Weingartz, {Nicholas P.} and Bolotin, {Igor L.} and Varun Singh and Kramar, {Boris V.} and Chen, {Lin X.} and Hupp, {Joseph T.} and Poluektov, {Oleg G.} and Farha, {Omar K.} and Peter Zapol and Glusac, {Ksenija D.}",

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month = may,

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doi = "10.1021/acs.jpclett.3c00049",

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Zheng, X, Drummer, MC, He, H, Rayder, TM, Niklas, J, Weingartz, NP, Bolotin, IL, Singh, V, Kramar, BV, Chen, LX , Hupp, JT, Poluektov, OG, Farha, OK, Zapol, P & Glusac, KD 2023, 'Photoreactive Carbon Dioxide Capture by a Zirconium-Nanographene Metal-Organic Framework', Journal of Physical Chemistry Letters, vol. 14, no. 18, pp. 4334-4341. https://doi.org/10.1021/acs.jpclett.3c00049

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AU - Zheng, Xin

AU - Drummer, Matthew C.

AU - He, Haiying

AU - Rayder, Thomas M.

AU - Niklas, Jens

AU - Weingartz, Nicholas P.

AU - Bolotin, Igor L.

AU - Singh, Varun

AU - Kramar, Boris V.

AU - Chen, Lin X.

AU - Hupp, Joseph T.

AU - Poluektov, Oleg G.

AU - Farha, Omar K.

AU - Zapol, Peter

AU - Glusac, Ksenija D.

PY - 2023/5/11

Y1 - 2023/5/11

N2 - The mechanism of photochemical CO2 reduction to formate by PCN-136, a Zr-based metal-organic framework (MOF) that incorporates light-harvesting nanographene ligands, has been investigated using steady-state and time-resolved spectroscopy and density functional theory (DFT) calculations. The catalysis was found to proceed via a “photoreactive capture” mechanism, where Zr-based nodes serve to capture CO2 in the form of Zr-bicarbonates, while the nanographene ligands have a dual role of absorbing light and storing one-electron equivalents for catalysis. We also find that the process occurs via a “two-for-one” route, where a single photon initiates a cascade of electron/hydrogen atom transfers from the sacrificial donor to the CO2-bound MOF. The mechanistic findings obtained here illustrate several advantages of MOF-based architectures in molecular photocatalyst engineering and provide insights on ways to achieve high formate selectivity.

AB - The mechanism of photochemical CO2 reduction to formate by PCN-136, a Zr-based metal-organic framework (MOF) that incorporates light-harvesting nanographene ligands, has been investigated using steady-state and time-resolved spectroscopy and density functional theory (DFT) calculations. The catalysis was found to proceed via a “photoreactive capture” mechanism, where Zr-based nodes serve to capture CO2 in the form of Zr-bicarbonates, while the nanographene ligands have a dual role of absorbing light and storing one-electron equivalents for catalysis. We also find that the process occurs via a “two-for-one” route, where a single photon initiates a cascade of electron/hydrogen atom transfers from the sacrificial donor to the CO2-bound MOF. The mechanistic findings obtained here illustrate several advantages of MOF-based architectures in molecular photocatalyst engineering and provide insights on ways to achieve high formate selectivity.

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Photoreactive Carbon Dioxide Capture by a Zirconium-Nanographene Metal-Organic Framework

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