Synthesis and Characterization of Quaternary Metal Chalcogenide Aerogels for Gas Separation and Volatile Hydrocarbon Adsorption

Handle URI:
http://hdl.handle.net/10754/626176
Title:
Synthesis and Characterization of Quaternary Metal Chalcogenide Aerogels for Gas Separation and Volatile Hydrocarbon Adsorption
Authors:
Edhaim, Fatimah A. ( 0000-0001-9995-5517 )
Abstract:
In this dissertation, the metathesis route of metal chalcogenide aerogel synthesis was expanded by conducting systematic studies between polysulfide building blocks and the 1st-row transition metal linkers. Resulting materials were screened as sorbents for selective gas separation and volatile organic compounds adsorption. They showed preferential adsorption of polarizable gases (CO2) and organic compounds (toluene). Ion exchange and heavy metal remediation properties have also been demonstrated. The effect of the presence of different counter-ion within chalcogel frameworks on the adsorption capacity of the chalcogels was studied on AFe3Zn3S17 (A= K, Na, and Rb) chalcogels. The highest adsorption capacity toward hydrocarbons and gases was observed on Rb based chalcogels. Adopting a new building block [BiTe3]3- with the 1st-row transition metal ions results in the formation of three high BET surface area chalcogels, KCrBiTe3, KZnBiTe3, and KFeBiTe3. The resulting chalcogels showed preferential adsorption of toluene vapor, and remarkable selectivity of CO2, indicating the potential future use of chalcogels in adsorption-based gas or hydrocarbon separation processes. The synthesis and characterization of the rare earth chalcogels NaYSnS4, NaGdSnS4, and NaTbSnS4 are also reported. Rare earth metal ions react with the thiostannate clusters in formamide solution forming extended polymeric networks by gelation. Obtained chalcogels have high BET surface areas, and showed notable adsorption capacity toward CO2 and toluene vapor. These chalcogels have also been engaged in the absorption of different organic molecules. The results reveal the ability of the chalcogels to distinguish among organic molecules on their electronic structures; hence, they could be used as sensors. Furthermore, the synthesis of metal chalcogenide aerogels Co0.5Sb0.33MoS4 and Co0.5Y0.33MoS4 by the sol-gel method is reported. In this system, the building blocks [MoS4]2- chelated with Co2+ and (Sb3+) or (Y3+) salts in nonaqueous solvents forming amorphous networks with gel properties. The chalcogels obtained after supercritical drying have high BET surface areas. These chalcogels showed higher adsorption capacity of toluene vapor over cyclohexane vapor and high selectivity of CO2 over CH4 or H2. The uptake capacity and selectivity of toluene and CO2 adsorption of Co0.5Sb0.33MoS4 were significantly enhanced by the post-synthetic modifications of various metal species like Ni2+, Li+, and Mg2+.
Advisors:
Rothenberger, Alexander
Committee Member:
Takanabe, Kazuhiro ( 0000-0001-5374-9451 ) ; Nunes, Suzana Pereira ( 0000-0002-3669-138X ) ; Khushaim, Muna
KAUST Department:
Physical Sciences and Engineering (PSE) Division
Program:
Chemical Sciences
Issue Date:
Nov-2017
Type:
Dissertation
Appears in Collections:
Dissertations

Full metadata record

DC FieldValue Language
dc.contributor.advisorRothenberger, Alexanderen
dc.contributor.authorEdhaim, Fatimah A.en
dc.date.accessioned2017-11-20T12:23:35Z-
dc.date.available2017-11-20T12:23:35Z-
dc.date.issued2017-11-
dc.identifier.urihttp://hdl.handle.net/10754/626176-
dc.description.abstractIn this dissertation, the metathesis route of metal chalcogenide aerogel synthesis was expanded by conducting systematic studies between polysulfide building blocks and the 1st-row transition metal linkers. Resulting materials were screened as sorbents for selective gas separation and volatile organic compounds adsorption. They showed preferential adsorption of polarizable gases (CO2) and organic compounds (toluene). Ion exchange and heavy metal remediation properties have also been demonstrated. The effect of the presence of different counter-ion within chalcogel frameworks on the adsorption capacity of the chalcogels was studied on AFe3Zn3S17 (A= K, Na, and Rb) chalcogels. The highest adsorption capacity toward hydrocarbons and gases was observed on Rb based chalcogels. Adopting a new building block [BiTe3]3- with the 1st-row transition metal ions results in the formation of three high BET surface area chalcogels, KCrBiTe3, KZnBiTe3, and KFeBiTe3. The resulting chalcogels showed preferential adsorption of toluene vapor, and remarkable selectivity of CO2, indicating the potential future use of chalcogels in adsorption-based gas or hydrocarbon separation processes. The synthesis and characterization of the rare earth chalcogels NaYSnS4, NaGdSnS4, and NaTbSnS4 are also reported. Rare earth metal ions react with the thiostannate clusters in formamide solution forming extended polymeric networks by gelation. Obtained chalcogels have high BET surface areas, and showed notable adsorption capacity toward CO2 and toluene vapor. These chalcogels have also been engaged in the absorption of different organic molecules. The results reveal the ability of the chalcogels to distinguish among organic molecules on their electronic structures; hence, they could be used as sensors. Furthermore, the synthesis of metal chalcogenide aerogels Co0.5Sb0.33MoS4 and Co0.5Y0.33MoS4 by the sol-gel method is reported. In this system, the building blocks [MoS4]2- chelated with Co2+ and (Sb3+) or (Y3+) salts in nonaqueous solvents forming amorphous networks with gel properties. The chalcogels obtained after supercritical drying have high BET surface areas. These chalcogels showed higher adsorption capacity of toluene vapor over cyclohexane vapor and high selectivity of CO2 over CH4 or H2. The uptake capacity and selectivity of toluene and CO2 adsorption of Co0.5Sb0.33MoS4 were significantly enhanced by the post-synthetic modifications of various metal species like Ni2+, Li+, and Mg2+.en
dc.language.isoenen
dc.subjectAbsorptionen
dc.subjectChalcogelsen
dc.subjectGasen
dc.subjectHydrocarbonen
dc.subjectSeparationen
dc.titleSynthesis and Characterization of Quaternary Metal Chalcogenide Aerogels for Gas Separation and Volatile Hydrocarbon Adsorptionen
dc.typeDissertationen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
thesis.degree.grantorKing Abdullah University of Science and Technologyen
dc.contributor.committeememberTakanabe, Kazuhiroen
dc.contributor.committeememberNunes, Suzana Pereiraen
dc.contributor.committeememberKhushaim, Munaen
thesis.degree.disciplineChemical Sciencesen
thesis.degree.nameDoctor of Philosophyen
dc.person.id118483en
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