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

Han, Yi; Sinnwell, Michael A.; Teat, Simon J.; Sushko, Maria L.; Bowden, Mark E.; Miller, Quin R. S.; Schaef, Herbert T.; Liu, Lili; Nie, Zimin; Liu, Jun; Thallapally, Praveen K.

doi:10.1002/advs.201802056

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

Journal Article · Fri Feb 08 00:00:00 EST 2019 · Advanced Science

DOI:https://doi.org/10.1002/advs.201802056· OSTI ID:1493944

Han, Yi ^[1]; Sinnwell, Michael A. ^[2]; Teat, Simon J. ^[3]; Sushko, Maria L. ^[2]; Bowden, Mark E. ^[2]; Miller, Quin R. S. ^[2]; Schaef, Herbert T. ^[2]; Liu, Lili ^[2]; Nie, Zimin ^[2]; Liu, Jun ^[2];

^[2]

Key Laboratory of Eco‐Chemical EngineeringCollege of Chemistry and Molecular EngineeringQingdao University of Science and Technology Qingdao 266042 P. R. China, Pacific Northwest National Laboratory Richland WA 99352 USA
Pacific Northwest National Laboratory Richland WA 99352 USA
Advanced Light SourceLawrence Berkeley National Laboratory Berkeley CA 94720 USA

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.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Qingdao Univ. of Science and Technology (China)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); Natural Science Foundation of Shandong Province (China)

Grant/Contract Number:: AC05-76RL01830; AC02-05CH11231; 21601102; ZR2016BQ34; 20170035

OSTI ID:: 1493944

Alternate ID(s):: OSTI ID: 1493945; OSTI ID: 1524154; OSTI ID: 1579334

Report Number(s):: PNNL-SA-136448; 1802056

Journal Information:: Advanced Science, Journal Name: Advanced Science Vol. 6 Journal Issue: 7; ISSN 2198-3844

Publisher:: WileyCopyright Statement

Country of Publication:: Germany

Language:: English

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Cited by: 13 works

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42 ENGINEERING
desulfurization
metal-organic frameworks
phase transitions
preserved adsorption
purification

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

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