Structural and Adsorption Properties of ZIF-8-7 Hybrid Materials Synthesized by Acid Gas-Assisted and De Novo Routes

Arvind Ganesan; Peter C. Metz; Raghuram Thyagarajan; Yuchen Chang; Stephen C. Purdy; Krishna C. Jayachandrababu; Katharine Page; David S. Sholl; Sankar Nair

doi:10.1021/acs.jpcc.3c06334

Structural and Adsorption Properties of ZIF-8-7 Hybrid Materials Synthesized by Acid Gas-Assisted and De Novo Routes

Arvind Ganesan, Peter C. Metz, Raghuram Thyagarajan, Yuchen Chang, Stephen C. Purdy, Krishna C. Jayachandrababu, Katharine Page, David S. Sholl, Sankar Nair

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Abstract

The tuning of micropore environments in zeolitic imidazolate frameworks (ZIFs) by mixed-linker synthesis has the potential for enabling new molecular separation properties. However, de novo synthesis of mixed-linker (hybrid) ZIFs is often challenging due to the disparate chemical properties of the different linkers. Here, we elucidate the structure and properties of an unconventional ZIF-8-7 hybrid material synthesized via a controlled-acid-gas-assisted degradation and reconstruction (solvent-assisted crystal redemption, SACRed) strategy. Selective insertion of benzimidazole (ZIF-7 linker) into ZIF-8 using SACRed is used as a facile method to generate a ZIF-8-7 hybrid material that is otherwise difficult to synthesize by de novo methods. Detailed crystal structure and textural characterizations clarify the significant differences in the microstructure of the SACRed-derived ZIF-8-7 hybrid material relative to a de novo synthesized hybrid of the same overall linker composition as well as the parent ZIF-8 material. Unary and binary adsorption measurements reveal the tunability of adsorption characteristics as well as the prevalence of nonideal cooperative mixture adsorption effects that lead to large deviations from predictions made with ideal adsorbed solution theory.

Original language	English
Pages (from-to)	23956-23965
Number of pages	10
Journal	Journal of Physical Chemistry C
Volume	127
Issue number	49
DOIs	https://doi.org/10.1021/acs.jpcc.3c06334
State	Published - Dec 14 2023

Funding

Notice of Copyright: This manuscript has been coauthored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The publisher acknowledges the US government license to provide public access under the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). Acknowledgments This work was supported as part of the Center for Understanding and Controlling Accelerated and Gradual Evolution of Materials for Energy (UNCAGE-ME), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award #DE-SC0012577.

Funders	Funder number
U.S. Department of Energy
Office of Science
Basic Energy Sciences	-SC0012577
UT-Battelle	DE-AC05-00OR22725

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title = "Structural and Adsorption Properties of ZIF-8-7 Hybrid Materials Synthesized by Acid Gas-Assisted and De Novo Routes",

abstract = "The tuning of micropore environments in zeolitic imidazolate frameworks (ZIFs) by mixed-linker synthesis has the potential for enabling new molecular separation properties. However, de novo synthesis of mixed-linker (hybrid) ZIFs is often challenging due to the disparate chemical properties of the different linkers. Here, we elucidate the structure and properties of an unconventional ZIF-8-7 hybrid material synthesized via a controlled-acid-gas-assisted degradation and reconstruction (solvent-assisted crystal redemption, SACRed) strategy. Selective insertion of benzimidazole (ZIF-7 linker) into ZIF-8 using SACRed is used as a facile method to generate a ZIF-8-7 hybrid material that is otherwise difficult to synthesize by de novo methods. Detailed crystal structure and textural characterizations clarify the significant differences in the microstructure of the SACRed-derived ZIF-8-7 hybrid material relative to a de novo synthesized hybrid of the same overall linker composition as well as the parent ZIF-8 material. Unary and binary adsorption measurements reveal the tunability of adsorption characteristics as well as the prevalence of nonideal cooperative mixture adsorption effects that lead to large deviations from predictions made with ideal adsorbed solution theory.",

author = "Arvind Ganesan and Metz, {Peter C.} and Raghuram Thyagarajan and Yuchen Chang and Purdy, {Stephen C.} and Jayachandrababu, {Krishna C.} and Katharine Page and Sholl, {David S.} and Sankar Nair",

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doi = "10.1021/acs.jpcc.3c06334",

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AU - Metz, Peter C.

AU - Thyagarajan, Raghuram

AU - Chang, Yuchen

AU - Purdy, Stephen C.

AU - Jayachandrababu, Krishna C.

AU - Page, Katharine

AU - Sholl, David S.

AU - Nair, Sankar

PY - 2023/12/14

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N2 - The tuning of micropore environments in zeolitic imidazolate frameworks (ZIFs) by mixed-linker synthesis has the potential for enabling new molecular separation properties. However, de novo synthesis of mixed-linker (hybrid) ZIFs is often challenging due to the disparate chemical properties of the different linkers. Here, we elucidate the structure and properties of an unconventional ZIF-8-7 hybrid material synthesized via a controlled-acid-gas-assisted degradation and reconstruction (solvent-assisted crystal redemption, SACRed) strategy. Selective insertion of benzimidazole (ZIF-7 linker) into ZIF-8 using SACRed is used as a facile method to generate a ZIF-8-7 hybrid material that is otherwise difficult to synthesize by de novo methods. Detailed crystal structure and textural characterizations clarify the significant differences in the microstructure of the SACRed-derived ZIF-8-7 hybrid material relative to a de novo synthesized hybrid of the same overall linker composition as well as the parent ZIF-8 material. Unary and binary adsorption measurements reveal the tunability of adsorption characteristics as well as the prevalence of nonideal cooperative mixture adsorption effects that lead to large deviations from predictions made with ideal adsorbed solution theory.

AB - The tuning of micropore environments in zeolitic imidazolate frameworks (ZIFs) by mixed-linker synthesis has the potential for enabling new molecular separation properties. However, de novo synthesis of mixed-linker (hybrid) ZIFs is often challenging due to the disparate chemical properties of the different linkers. Here, we elucidate the structure and properties of an unconventional ZIF-8-7 hybrid material synthesized via a controlled-acid-gas-assisted degradation and reconstruction (solvent-assisted crystal redemption, SACRed) strategy. Selective insertion of benzimidazole (ZIF-7 linker) into ZIF-8 using SACRed is used as a facile method to generate a ZIF-8-7 hybrid material that is otherwise difficult to synthesize by de novo methods. Detailed crystal structure and textural characterizations clarify the significant differences in the microstructure of the SACRed-derived ZIF-8-7 hybrid material relative to a de novo synthesized hybrid of the same overall linker composition as well as the parent ZIF-8 material. Unary and binary adsorption measurements reveal the tunability of adsorption characteristics as well as the prevalence of nonideal cooperative mixture adsorption effects that lead to large deviations from predictions made with ideal adsorbed solution theory.

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Structural and Adsorption Properties of ZIF-8-7 Hybrid Materials Synthesized by Acid Gas-Assisted and De Novo Routes

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