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Title: 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 {[Yb 6Cu 12(OH) 4(PyC) 12(H 2O) 36]·(NO 3) 14·xS} n (QUST-81) and {[Yb 4O(H 2O) 4Cu 8(OH) 8/3(PyC) 8(HCOO) 4]·(NO 3) 10/3·xS} n (QUST-82), where H 2PyC = 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.

Authors:
 [1];  [2];  [3];  [2];  [2];  [2];  [2];  [2];  [2];  [2]; ORCiD logo [2]
  1. Qingdao Univ. of Science and Technology (China). College of Chemistry and Molecular Engineering. Key Lab. of Eco-Chemical Engineering; Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Qingdao Univ. of Science and Technology (China)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Natural Science Foundation of China (NNSFC); Natural Science Foundation of Shandong Province (China)
OSTI Identifier:
1493944
Alternate Identifier(s):
OSTI ID: 1493945; OSTI ID: 1524154
Report Number(s):
PNNL-SA-136448
Journal ID: ISSN 2198-3844
Grant/Contract Number:  
AC05-76RL01830; AC02-05CH11231; 21601102; ZR2016BQ34; 20170035
Resource Type:
Journal Article: Published Article
Journal Name:
Advanced Science
Additional Journal Information:
Journal Volume: 6; Journal Issue: 7; Journal ID: ISSN 2198-3844
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
desulfurization; metal-organic frameworks; phase transitions; preserved adsorption; purification

Citation Formats

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, and Thallapally, Praveen K. Desulfurization Efficiency Preserved in a Heterometallic MOF: Synthesis and Thermodynamically Controlled Phase Transition. United States: N. p., 2019. Web. doi:10.1002/advs.201802056.
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. Desulfurization Efficiency Preserved in a Heterometallic MOF: Synthesis and Thermodynamically Controlled Phase Transition. United States. doi:10.1002/advs.201802056.
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, and Thallapally, Praveen K. Fri . "Desulfurization Efficiency Preserved in a Heterometallic MOF: Synthesis and Thermodynamically Controlled Phase Transition". United States. doi:10.1002/advs.201802056.
@article{osti_1493944,
title = {Desulfurization Efficiency Preserved in a Heterometallic MOF: Synthesis and Thermodynamically Controlled Phase Transition},
author = {Han, Yi and Sinnwell, Michael A. and Teat, Simon J. and Sushko, Maria L. and Bowden, Mark E. and Miller, Quin R. S. and Schaef, Herbert T. and Liu, Lili and Nie, Zimin and Liu, Jun and Thallapally, Praveen K.},
abstractNote = {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.},
doi = {10.1002/advs.201802056},
journal = {Advanced Science},
issn = {2198-3844},
number = 7,
volume = 6,
place = {United States},
year = {2019},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/advs.201802056

Citation Metrics:
Cited by: 1 work
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Figures / Tables:

Figure 1 Figure 1: X-ray crystal structure of QUST-81, showing a) distinct heterometallic SBUs, b) cages, and c) 3D framework with pcu topology. Crystal structure of QUST-82, highlighting structural differences and similarities between QUST-81 and QUST-82 in the d) cage-metalloligand, e) SBUs, f) cages, and g) pcu topology. Atom colors: Yb =more » green; Cu = light blue; O = red; C = black; N = dark blue. Parts of coordinated water molecules are omitted for clarity.« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.