Design, Synthesis, and Characterization of Metal-Organic Frameworks for Enhanced Sorption of Chemical Warfare Agent Simulants

被引:41
作者
Ruffley, Jonathan P. [1 ]
Goodenough, Isabella [3 ]
Luo, Tian-Yi [2 ]
Richard, Melissandre [3 ,4 ]
Borguet, Eric [3 ]
Rosi, Nathaniel L. [1 ,2 ]
Johnson, J. Karl [1 ]
机构
[1] Univ Pittsburgh, Dept Chem & Petr Engn, Pittsburgh, PA 15261 USA
[2] Univ Pittsburgh, Dept Chem, Pittsburgh, PA 15261 USA
[3] Temple Univ, Dept Chem, Philadelphia, PA 19122 USA
[4] Univ Lille, CNRS, UMR 8181, UCCS, Bat C3 Cite Sci, F-59655 Villeneuve Dascq, France
基金
美国国家科学基金会;
关键词
DIMETHYL METHYLPHOSPHONATE; FORCE-FIELD; WATER STABILITY; CARBON-DIOXIDE; BASIS-SETS; ADSORPTION; UIO-66; DESORPTION; DEGRADATION; REMOVAL;
D O I
10.1021/acs.jpcc.9b05574
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Metal-organic frameworks (MOFs) and specifically the UiO family of MOFs have been extensively studied for the adsorption and degradation of chemical warfare agents (CWAs) and their simulants. We present a combined experimental and computational study of the adsorption of dimethyl methylphosphonate (DMMP), a CWA adsorption simulant, in functionalized UiO-67. We have used density functional theory (DFT) to design functionalized MOFs having a range of binding energies for DMMP. We have selected three different functionalized MOFs for experimental synthesis and characterization from a total of eight studied with DFT. These three MOFs were identified as having the weakest, intermediate, and strongest binding energies for DMMP of the set, as predicted by our DFT calculations. We find that the order of predicted binding energies agrees with data from temperature-programmed desorption experiments. Moreover, the values of the binding energies are also in good agreement. This serves as a proof of concept that ab initio calculations can guide experiments in designing MOFs that exhibit a higher affinity for CWAs and their simulants. One surprising outcome of this work is that reactions between DMMP and the three functionalized UiO-67 MOFs were not observed under ultrahigh-vacuum conditions for the exposure of DMMP of up to 9000 L. This lack of reactivity is attributed to the low levels of defects in the materials used.
引用
收藏
页码:19748 / 19758
页数:11
相关论文
共 100 条
[1]  
[Anonymous], ADS DES CHEM WARF AG
[2]  
[Anonymous], J CHEM PHYS
[3]  
[Anonymous], 2017, COMPUTER SIMULATION
[4]  
[Anonymous], CHEM ENG NEWS
[5]  
[Anonymous], COMMUNICATION 0305
[6]   Interaction of dimethyl methylphosphonate with alkanethiolate monolayers studied by temperature-programmed desorption and infrared spectroscopy [J].
Bertilsson, L ;
Engquist, I ;
Liedberg, B .
JOURNAL OF PHYSICAL CHEMISTRY B, 1997, 101 (31) :6021-6027
[7]   A General Strategy for the Synthesis of Functionalised UiO-66 Frameworks: Characterisation, Stability and CO2 Adsorption Properties [J].
Biswas, Shyam ;
Van der Voort, Pascal .
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2013, (12) :2154-2160
[8]   Metal-organic frameworks for the removal of toxic industrial chemicals and chemical warfare agents [J].
Bobbitt, N. Scott ;
Mendonca, Matthew L. ;
Howarth, Ashlee J. ;
Islamoglu, Timur ;
Hupp, Joseph T. ;
Farha, Omar K. ;
Snurr, Randall Q. .
CHEMICAL SOCIETY REVIEWS, 2017, 46 (11) :3357-3385
[9]   CALCULATION OF SMALL MOLECULAR INTERACTIONS BY DIFFERENCES OF SEPARATE TOTAL ENERGIES - SOME PROCEDURES WITH REDUCED ERRORS [J].
BOYS, SF ;
BERNARDI, F .
MOLECULAR PHYSICS, 1970, 19 (04) :553-&
[10]   Alkylaminopyridine-Modified Aluminum Aminoterephthalate Metal-Organic Frameworks As Components of Reactive Self-Detoxifying Materials [J].
Bromberg, Lev ;
Klichko, Yaroslav ;
Chang, Emily P. ;
Speakman, Scott ;
Straut, Christine M. ;
Wilusz, Eugene ;
Hatton, T. Alan .
ACS APPLIED MATERIALS & INTERFACES, 2012, 4 (09) :4595-4602