Hierarchical ZIF-8 Materials via Acid Gas-Induced Defect Sites: Synthesis, Characterization, and Functional Properties

Ganesan, Arvind; Leisen, Johannes; Thyagarajan, Raghuram; Sholl, David S.; Nair, Sankar

doi:10.1021/acsami.3c08344

Title: Hierarchical ZIF-8 Materials via Acid Gas-Induced Defect Sites: Synthesis, Characterization, and Functional Properties

Journal Article · 18 August 2023 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.3c08344 · OSTI ID:1995854

^[1]; Leisen, Johannes ^[1];

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Georgia Institute of Technology, Atlanta, GA (United States)
Georgia Institute of Technology, Atlanta, GA (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Microporous metal-organic frameworks (MOFs) have been widely studied for molecular separation and catalysis. The uniform micropores of MOFs (<2 nm) can introduce diffusion limitations and render the interiors of the crystal inaccessible to target molecules. The introduction of hierarchical porosity (interconnected micro and mesopores) can enhance intra-crystalline diffusion while maintaining the separation/catalytic selectivity. Conventional hierarchical MOF synthesis involves complex strategies such as elongated linkers, soft templating, and sacrificial templates. Here, we demonstrate a more general approach using our controlled acid gas-enabled degradation and reconstruction (Solvent-Assisted Crystal Redemption) strategy. Selective linker labilization of ZIF-8 is shown to generate a hierarchical pore structure with mesoporous cages (~50 nm) while maintaining microporosity. Detailed structural and spectroscopic characterization of the controlled degradation, linker insertion, and subsequent linker thermolysis is presented to show the clustering of acid gas-induced defects and the generation of mesopores. These findings indicate the generality of controlled degradation and reconstruction as a means for linker insertion in a wider variety of MOFs and creating hierarchical porosity. Enhanced molecular diffusion and catalytic activity in the hierarchical ZIF-8 are demonstrated by the adsorption kinetics of 1-butanol and a Knoevenagel condensation reaction.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725; SC0012577

OSTI ID:: 1995854

Alternate ID(s):: OSTI ID: 2229230

Journal Information:: ACS Applied Materials and Interfaces, Vol. 15, Issue 34; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
MOFs
acid gas
defects
hierarchical
Knoevenagel

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