Influence of Metal Identity on Light-Induced Switchable Adsorption in Azobenzene-Based Metal-Organic Frameworks

Hannah F. Drake; Zhifeng Xiao; Gregory S. Day; Shaik Waseem Vali; Luke L. Daemen; Yongqiang Cheng; Peiyu Cai; Jason E. Kuszynski; Hengyu Lin; Hong Cai Zhou; Matthew R. Ryder

doi:10.1021/acsami.1c18266

Influence of Metal Identity on Light-Induced Switchable Adsorption in Azobenzene-Based Metal-Organic Frameworks

Hannah F. Drake, Zhifeng Xiao, Gregory S. Day, Shaik Waseem Vali, Luke L. Daemen, Yongqiang Cheng, Peiyu Cai, Jason E. Kuszynski, Hengyu Lin, Hong Cai Zhou, Matthew R. Ryder

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

15 Scopus citations

Abstract

Energy-efficient capture and release of small gas molecules, particularly carbon dioxide (CO₂) and methane (CH₄), are of significant interest in academia and industry. Porous materials such as metal-organic frameworks (MOFs) have been extensively studied, as their ultrahigh porosities and tunability enable significant amounts of gas to be adsorbed while also allowing specific applications to be targeted. However, because of the microporous nature of MOFs, the gas adsorption performance is dominated by high uptake capacity at low pressures, limiting their application. Hence, methods involving stimuli-responsive materials, particularly light-induced switchable adsorption (LISA), offer a unique alternative to thermal methods. Here, we report the mechanism of a well-known LISA system, the azobenzene-based material PCN-250, for CO₂ and CH₄ adsorption. There is a noticeable difference in the LISA effect dependent on the metal cluster involved, with the most significant being PCN-250-Al, where the adsorption can change by 83.1% CH₄ and 56.1% CO₂ at 298 K and 1 bar and inducing volumetric storage changes of 36.2 and 33.9 cm³/cm³ at 298 K between 5 and 85 bar (CH₄) and 2 and 9 bar (CO₂), respectively. Using UV light in both single-crystal X-ray diffraction and gas adsorption testing, we show that upon photoirradiation, the framework undergoes a “localized heating” phenomenon comparable to an increase of 130 K for PCN-250-Fe and improves the working capacity. This process functions because of the constrained nature of the ligand, preventing the typical trans-to-cis isomerization observed in free azobenzene. In addition, we observed that the degree of localized heating is highly dependent on the metal cluster involved, with the series of isostructural PCN-250 systems showing variable performance based upon the degree of interaction between the ligand and the metal center.

Original language	English
Pages (from-to)	11192-11199
Number of pages	8
Journal	ACS Applied Materials and Interfaces
Volume	14
Issue number	9
DOIs	https://doi.org/10.1021/acsami.1c18266
State	Published - Mar 9 2022

Funding

H.F.D., G.S.D., and M.R.R. acknowledge the U.S. Department of Energy (DOE) Office of Science Graduate Student Research (SCGSR) program for funding. The SCGSR program is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE under contract number DE-SC0014664. M.R.R. also acknowledges the DOE Office of Science (Basic Energy Sciences) and DOE Office of Fossil Energy and Carbon Management for research funding and the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility operated under Contract No. DE-AC02-05CH11231 for access to supercomputing resources. H.-C.Z. acknowledges the Robert A. Welch Foundation for a Welch Endowed Chair (A-0030), the financial support of the Qatar National Research Fund award NPRP9-377-1-080, and the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the DOE Office of Science (Basic Energy Sciences) under Contract Number DE-SC0001015. In addition, the authors acknowledge the Texas A&M X-ray Diffraction Laboratory and the NMR User Facility and Dr. Paul A. Lindahl for his contributions to the Mössbauer studies (National Institute of Health R35 GM127021). H.F.D. acknowledges the FYP Chemistry Program at Texas A&M University and Dr. Edward Lee for access to equipment. This research used resources at the Spallation Neutron Source (SNS), a DOE Office of Science User Facility operated by Oak Ridge National Laboratory, and the Advanced Light Source (ALS), a DOE Office of Science User Facility operated under contract no. DE-AC02-05CH11231 by Lawrence Berkley National Laboratory. ALS beamline 12.2.1 and Dr. Simon J. Teat are gratefully acknowledged. H.F.D., G.S.D., and M.R.R. acknowledge the U.S. Department of Energy (DOE) Office of Science Graduate Student Research (SCGSR) program for funding. The SCGSR program is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE under contract number DE-SC0014664. M.R.R. also acknowledges the DOE Office of Science (Basic Energy Sciences) and DOE Office of Fossil Energy and Carbon Management for research funding and the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility operated under Contract No. DE-AC02-05CH11231 for access to supercomputing resources. H.-C.Z. acknowledges the Robert A. Welch Foundation for a Welch Endowed Chair (A-0030), the financial support of the Qatar National Research Fund award NPRP9-377-1-080, and the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the DOE Office of Science (Basic Energy Sciences) under Contract Number DE-SC0001015. In addition, the authors acknowledge the Texas A&M X-ray Diffraction Laboratory and the NMR User Facility and Dr. Paul A. Lindahl for his contributions to the Mo?ssbauer studies (National Institute of Health R35 GM127021). H.F.D. acknowledges the FYP Chemistry Program at Texas A&M University and Dr. Edward Lee for access to equipment. This research used resources at the Spallation Neutron Source (SNS), a DOE Office of Science User Facility operated by Oak Ridge National Laboratory, and the Advanced Light Source (ALS), a DOE Office of Science User Facility operated under contract no. DE-AC02-05CH11231 by Lawrence Berkley National Laboratory. ALS beamline 12.2.1 and Dr. Simon J. Teat are gratefully acknowledged.

Funders	Funder number
DOE Office of Fossil Energy and Carbon Management
Office of Science Graduate Student Research
SCGSR
National Institutes of Health	R35 GM127021
U.S. Department of Energy
Welch Foundation	A-0030
Office of Science
Basic Energy Sciences
Oak Ridge National Laboratory
Oak Ridge Institute for Science and Education	DE-SC0014664
Lawrence Berkeley National Laboratory
Texas A and M University
Qatar National Research Fund	NPRP9-377-1-080, DE-SC0001015
National Energy Research Scientific Computing Center	DE-AC02-05CH11231

Keywords

coordination chemistry
energy storage
gas storage
light-induced switchable adsorption
metal−organic frameworks
photoresponsive materials

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10.1021/acsami.1c18266

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@article{8117d3eb81374ffa8121d08eaab993fe,

title = "Influence of Metal Identity on Light-Induced Switchable Adsorption in Azobenzene-Based Metal-Organic Frameworks",

abstract = "Energy-efficient capture and release of small gas molecules, particularly carbon dioxide (CO2) and methane (CH4), are of significant interest in academia and industry. Porous materials such as metal-organic frameworks (MOFs) have been extensively studied, as their ultrahigh porosities and tunability enable significant amounts of gas to be adsorbed while also allowing specific applications to be targeted. However, because of the microporous nature of MOFs, the gas adsorption performance is dominated by high uptake capacity at low pressures, limiting their application. Hence, methods involving stimuli-responsive materials, particularly light-induced switchable adsorption (LISA), offer a unique alternative to thermal methods. Here, we report the mechanism of a well-known LISA system, the azobenzene-based material PCN-250, for CO2 and CH4 adsorption. There is a noticeable difference in the LISA effect dependent on the metal cluster involved, with the most significant being PCN-250-Al, where the adsorption can change by 83.1% CH4 and 56.1% CO2 at 298 K and 1 bar and inducing volumetric storage changes of 36.2 and 33.9 cm3/cm3 at 298 K between 5 and 85 bar (CH4) and 2 and 9 bar (CO2), respectively. Using UV light in both single-crystal X-ray diffraction and gas adsorption testing, we show that upon photoirradiation, the framework undergoes a “localized heating” phenomenon comparable to an increase of 130 K for PCN-250-Fe and improves the working capacity. This process functions because of the constrained nature of the ligand, preventing the typical trans-to-cis isomerization observed in free azobenzene. In addition, we observed that the degree of localized heating is highly dependent on the metal cluster involved, with the series of isostructural PCN-250 systems showing variable performance based upon the degree of interaction between the ligand and the metal center.",

keywords = "coordination chemistry, energy storage, gas storage, light-induced switchable adsorption, metal−organic frameworks, photoresponsive materials",

author = "Drake, {Hannah F.} and Zhifeng Xiao and Day, {Gregory S.} and Vali, {Shaik Waseem} and Daemen, {Luke L.} and Yongqiang Cheng and Peiyu Cai and Kuszynski, {Jason E.} and Hengyu Lin and Zhou, {Hong Cai} and Ryder, {Matthew R.}",

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doi = "10.1021/acsami.1c18266",

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T1 - Influence of Metal Identity on Light-Induced Switchable Adsorption in Azobenzene-Based Metal-Organic Frameworks

AU - Drake, Hannah F.

AU - Xiao, Zhifeng

AU - Day, Gregory S.

AU - Vali, Shaik Waseem

AU - Daemen, Luke L.

AU - Cheng, Yongqiang

AU - Cai, Peiyu

AU - Kuszynski, Jason E.

AU - Lin, Hengyu

AU - Zhou, Hong Cai

AU - Ryder, Matthew R.

PY - 2022/3/9

Y1 - 2022/3/9

N2 - Energy-efficient capture and release of small gas molecules, particularly carbon dioxide (CO2) and methane (CH4), are of significant interest in academia and industry. Porous materials such as metal-organic frameworks (MOFs) have been extensively studied, as their ultrahigh porosities and tunability enable significant amounts of gas to be adsorbed while also allowing specific applications to be targeted. However, because of the microporous nature of MOFs, the gas adsorption performance is dominated by high uptake capacity at low pressures, limiting their application. Hence, methods involving stimuli-responsive materials, particularly light-induced switchable adsorption (LISA), offer a unique alternative to thermal methods. Here, we report the mechanism of a well-known LISA system, the azobenzene-based material PCN-250, for CO2 and CH4 adsorption. There is a noticeable difference in the LISA effect dependent on the metal cluster involved, with the most significant being PCN-250-Al, where the adsorption can change by 83.1% CH4 and 56.1% CO2 at 298 K and 1 bar and inducing volumetric storage changes of 36.2 and 33.9 cm3/cm3 at 298 K between 5 and 85 bar (CH4) and 2 and 9 bar (CO2), respectively. Using UV light in both single-crystal X-ray diffraction and gas adsorption testing, we show that upon photoirradiation, the framework undergoes a “localized heating” phenomenon comparable to an increase of 130 K for PCN-250-Fe and improves the working capacity. This process functions because of the constrained nature of the ligand, preventing the typical trans-to-cis isomerization observed in free azobenzene. In addition, we observed that the degree of localized heating is highly dependent on the metal cluster involved, with the series of isostructural PCN-250 systems showing variable performance based upon the degree of interaction between the ligand and the metal center.

AB - Energy-efficient capture and release of small gas molecules, particularly carbon dioxide (CO2) and methane (CH4), are of significant interest in academia and industry. Porous materials such as metal-organic frameworks (MOFs) have been extensively studied, as their ultrahigh porosities and tunability enable significant amounts of gas to be adsorbed while also allowing specific applications to be targeted. However, because of the microporous nature of MOFs, the gas adsorption performance is dominated by high uptake capacity at low pressures, limiting their application. Hence, methods involving stimuli-responsive materials, particularly light-induced switchable adsorption (LISA), offer a unique alternative to thermal methods. Here, we report the mechanism of a well-known LISA system, the azobenzene-based material PCN-250, for CO2 and CH4 adsorption. There is a noticeable difference in the LISA effect dependent on the metal cluster involved, with the most significant being PCN-250-Al, where the adsorption can change by 83.1% CH4 and 56.1% CO2 at 298 K and 1 bar and inducing volumetric storage changes of 36.2 and 33.9 cm3/cm3 at 298 K between 5 and 85 bar (CH4) and 2 and 9 bar (CO2), respectively. Using UV light in both single-crystal X-ray diffraction and gas adsorption testing, we show that upon photoirradiation, the framework undergoes a “localized heating” phenomenon comparable to an increase of 130 K for PCN-250-Fe and improves the working capacity. This process functions because of the constrained nature of the ligand, preventing the typical trans-to-cis isomerization observed in free azobenzene. In addition, we observed that the degree of localized heating is highly dependent on the metal cluster involved, with the series of isostructural PCN-250 systems showing variable performance based upon the degree of interaction between the ligand and the metal center.

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KW - energy storage

KW - gas storage

KW - light-induced switchable adsorption

KW - metal−organic frameworks

KW - photoresponsive materials

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Influence of Metal Identity on Light-Induced Switchable Adsorption in Azobenzene-Based Metal-Organic Frameworks

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Keywords

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