Dialing in Catalytic Sites on Metal Organic Framework Nodes: MIL-53(Al) and MIL-68(Al) Probed with Methanol Dehydration Catalysis

Wang, Zhengyan; Babucci, Melike; Zhang, Yafeng; Wen, Yujie; Peng, Luming; Yang, Bing; Gates, Bruce C.; Yang, Dong

doi:10.1021/acsami.0c16559

Title: Dialing in Catalytic Sites on Metal Organic Framework Nodes: MIL-53(Al) and MIL-68(Al) Probed with Methanol Dehydration Catalysis

Journal Article · Thu Nov 12 00:00:00 EST 2020 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.0c16559· OSTI ID:1771298

Wang, Zhengyan ^[1];

^[2]; Zhang, Yafeng ^[3]; Wen, Yujie ^[4];

^[4];

^[3];

^[2];

^[1]

Nanjing Tech Univ., Jiangsu (China)
Univ. of California at Davis, CA (United States)
Chinese Academy of Sciences, Liaoning (China)
Nanjing Univ., Jiangsu (China)

Many metal organic frameworks (MOFs) incorporate metal oxide clusters as nodes. Node sites where linkers are missing can be catalytic sites. We now show how to dial in the number and occupancy of such sites in MIL-53 and MIL-68, which incorporate aluminum-oxide-like nodes. Here, the methods involve modulators used in synthesis and postsynthesis reactions to control the modulator-derived groups on these sites. We illustrate the methods using formic acid as a modulator, giving formate ligands on the sites, and these can be removed to leave μ₂-OH groups and open Lewis acid sites. Methanol dehydration was used as a catalytic reaction to probe these sites, with infrared spectra giving evidence of methoxide ligands as reaction intermediates. Control of node surface chemistry opens the door for placement of a variety of ligands on a wide range of metal oxide cluster nodes for dialing in reactivity and catalytic properties of a potentially immense class of structurally well-defined materials.

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Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States)

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

Grant/Contract Number:: SC0012702

OSTI ID:: 1771298

Journal Information:: ACS Applied Materials and Interfaces, Vol. 12, Issue 47; 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
metal−organic frameworks
MIL-53(Al)
MIL-68(Al)
defects
methanol dehydration catalysis
organic acids
ligands
metal organic frameworks
phase transitions

Title: Dialing in Catalytic Sites on Metal Organic Framework Nodes: MIL-53(Al) and MIL-68(Al) Probed with Methanol Dehydration Catalysis

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