Crystal Facet Engineering of Copper-Based Metal−Organic Frameworks with Inorganic Modulators

Wang, Zhanke and Ge, Lei ORCID: https://orcid.org/0000-0003-2989-0329 and Feng, Desheng and Jiang, Zongrui and Wang, Hao and Li, Mengran and Lin, Rijia and Zhu, Zhonghua (2021) Crystal Facet Engineering of Copper-Based Metal−Organic Frameworks with Inorganic Modulators. Crystal Growth & Design, 21 (2):122031. pp. 926-934. ISSN 1528-7483


Abstract

Manipulating the exposed facets of metal–organic frameworks (MOFs) is of importance toward understanding their facet-dependent property in a variety of applications. Herein, we apply a novel inorganic competitive coordination strategy to control the growth orientation of copper-based MOFs (HKUST-1, MOF-14, and Cu-MOF-74) without sacrificing the pore accessibility and crystallinity. Through monitoring the reactant composition, we find that the competitive coordination induced by the added aluminium nitrate mainly affects the crystal growth stage rather than the nucleation stage. The kinetic study further reveals that Al3+ competes with Cu2+ to coordinate with ligands, restraining the growth rate of certain facets and resulting in the orientated growth of copper-based MOFs. Compared to the reduced pore accessibility of HKUST-1 crystals modulated by the organic modulation method, Al3+-modulated HKUST-1 displays a much larger surface area (>2200 m2/g) and more accessible Cu active sites. Hydroxylation of toluene was utilized as a model reaction to investigate the facet-catalytic activity for as-synthesized HKUST-1. The selectivity of the preferred product cresol increases with the morphology transformation of HKUST-1 from octahedron to cube.


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Item Type: Article (Commonwealth Reporting Category C)
Refereed: Yes
Item Status: Live Archive
Faculty/School / Institute/Centre: Current - Institute for Advanced Engineering and Space Sciences - Centre for Future Materials (1 Jan 2017 -)
Faculty/School / Institute/Centre: Current - Institute for Advanced Engineering and Space Sciences - Centre for Future Materials (1 Jan 2017 -)
Date Deposited: 15 Mar 2021 01:05
Last Modified: 15 Mar 2021 01:05
Uncontrolled Keywords: Catalytic kinetics; Lewis acid site; Metal-organic framework; Morphology control; NH3-SCR
Fields of Research (2008): 03 Chemical Sciences > 0303 Macromolecular and Materials Chemistry > 030301 Chemical Characterisation of Materials
03 Chemical Sciences > 0303 Macromolecular and Materials Chemistry > 030306 Synthesis of Materials
09 Engineering > 0904 Chemical Engineering > 090402 Catalytic Process Engineering
Fields of Research (2020): 34 CHEMICAL SCIENCES > 3403 Macromolecular and materials chemistry > 340301 Inorganic materials (incl. nanomaterials)
40 ENGINEERING > 4004 Chemical engineering > 400408 Reaction engineering (excl. nuclear reactions)
Identification Number or DOI: https://doi.org/10.1016/j.jssc.2021.122031
URI: http://eprints.usq.edu.au/id/eprint/41559

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