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Desulfurization Efficiency Preserved in a Heterometallic MOF: Synthesis and Thermodynamically Controlled Phase Transition.

ABSTRACT: Efficient removal of heterocyclic organosulfur compounds from fuels can relieve increasingly serious environmental problems (e.g., gas exhaust contaminants triggering the formation of acid rain that can damage fragile ecological systems). Toward this end, novel metal-organic frameworks (MOFs)-based sorbent materials are designed and synthesized with distinct hard and soft metal building units, specifically {[Yb₆Cu₁₂(OH)₄(PyC)₁₂(H₂O)₃₆]·(NO₃)₁₄·xS} _n (QUST-81) and {[Yb₄O(H₂O)₄Cu₈(OH)_8/3(PyC)₈(HCOO)₄]·(NO₃)_10/3·xS} _n (QUST-82), where H₂PyC = 4-Pyrazolecarboxylic acid. Exploiting the hard/soft duality, it is shown that the more stable QUST-82 can preserve desulfurization efficiency in the presence of competing nitrogen-containing contaminate. In addition, thermodynamically controlled single-crystal-to-single-crystal (SC-SC) phase transition is uncovered from QUST-81 to QUST-82, and in turn, mechanistic features are probed via X-ray diffraction, inductively coupled plasma atomic emission spectroscopy, and ab initio molecular dynamics simulations.

SUBMITTER: Han Y

PROVIDER: S-EPMC6446612 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

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Desulfurization Efficiency Preserved in a Heterometallic MOF: Synthesis and Thermodynamically Controlled Phase Transition.

Han Yi Y Sinnwell Michael A MA Teat Simon J SJ Sushko Maria L ML Bowden Mark E ME Miller Quin R S QRS Schaef Herbert T HT Liu Lili L Nie Zimin Z Liu Jun J Thallapally Praveen K PK

Advanced science (Weinheim, Baden-Wurttemberg, Germany) 20190208 7

Efficient removal of heterocyclic organosulfur compounds from fuels can relieve increasingly serious environmental problems (e.g., gas exhaust contaminants triggering the formation of acid rain that can damage fragile ecological systems). Toward this end, novel metal-organic frameworks (MOFs)-based sorbent materials are designed and synthesized with distinct hard and soft metal building units, specifically {[Yb6Cu12(OH)4(PyC)12(H2O)36</ ...[more]

PMID: 30989028

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Project description:Elucidating the microstructure of supramolecular copolymers remains challenging, despite the progress in the field of supramolecular polymers. In this work, we present a detailed approach to investigate supramolecular copolymerizations under thermodynamic control. Our approach provides insight into the interactions of different types of monomers and hereby allows elucidating the microstructure of copolymers. We select two monomers that undergo cooperative supramolecular polymerization by way of threefold intermolecular hydrogen bonding in a helical manner, namely, benzene-1,3,5-tricarboxamide (BTA) and benzene-1,3,5-tris(carbothioamide) (thioBTA). Two enantiomeric forms and an achiral analogue of BTA and thioBTA are synthesized and their homo- and copolymerizations are studied using light scattering techniques, infrared, ultraviolet, and circular dichroism spectroscopy. After quantifying the thermodynamic parameters describing the homopolymerizations, we outline a method to follow the self-assembly of thioBTA derivatives in the copolymerization with BTA, which involves monitoring a characteristic spectroscopic signature as a function of temperature and relative concentration. Using modified types of sergeants-and-soldiers and majority-rules experiments, we obtain insights into the degree of aggregation and the net helicity. In addition, we apply a theoretical model of supramolecular copolymerization to substantiate the experimental results. We find that the model describes the two-component system well and allows deriving the hetero-interaction energies. The interactions between the same kinds of monomers (BTA-BTA and thioBTA-thioBTA) are slightly more favorable than those between different monomers (BTA-thioBTA), corresponding to a nearly random copolymerization. Finally, to study the interactions of the monomers at the molecular level, we perform density functional theory-based computations. The results corroborate that the two-component system exhibits a random distribution of the two monomer units along the copolymer chain.

Dataset Information

Desulfurization Efficiency Preserved in a Heterometallic MOF: Synthesis and Thermodynamically Controlled Phase Transition.

Publications

Desulfurization Efficiency Preserved in a Heterometallic MOF: Synthesis and Thermodynamically Controlled Phase Transition.

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