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Synthesis and Self-assembly of Polymer-Grafted Metal-Organic Frameworks
Synthesis and Self-assembly of Polymer-Grafted Metal-Organic Frameworks
Synthesis and Self-assembly of Polymer-Grafted Metal-Organic Frameworks

상세정보

자료유형  
 학위논문 서양
최종처리일시  
20250211150916
ISBN  
9798384082705
DDC  
540
저자명  
Barcus, Kyle.
서명/저자  
Synthesis and Self-assembly of Polymer-Grafted Metal-Organic Frameworks
발행사항  
[Sl] : University of California, San Diego, 2024
발행사항  
Ann Arbor : ProQuest Dissertations & Theses, 2024
형태사항  
181 p
주기사항  
Source: Dissertations Abstracts International, Volume: 86-03, Section: B.
주기사항  
Advisor: Cohen, Seth M.
학위논문주기  
Thesis (Ph.D.)--University of California, San Diego, 2024.
초록/해제  
요약Metal-organic frameworks (MOFs) are crystalline, porous materials with unique properties valued for applications in chemical storage, separation, and catalysis. While MOFs have shown great potential for these applications, a major shortcoming of these materials is their inherently crystalline nature, which limits their processability into the form factors required for these applications. To overcome this issue, MOFs have been combined with polymers in order to form composites that incorporate the flexibility and processability of polymers while retaining the properties of the MOF material. However, incompatibilities between the MOF surface and the polymer matrix can result in defects and mechanical failure. Lowering the MOF loading to circumvent this greatly diminishes or negates the contribution of the MOF to the material properties. Therefore, a method is needed to formulate composites that allows for high MOF loading while retaining the desirable properties of the polymer. To develop a solution to this issue, Chapter 2 describes the preparation of polymer-coated MOFs using surface-initiated controlled radical polymerization (SI-CRP) from coordinating initiators. This method allows for the preparation of single nanoparticle composites, with the polymer directly attached to the MOF surface. The resulting particles were then self-assembled into monolayers at the air-water interface that were found to be freestanding when removed from the water surface. This method was found to be generalizable to several other MOFs, providing a platform for polymer-MOF composites with intrinsically high loadings of MOF particles.Chapter 3 systematically studies the different factors of polymer-grafted MOFs on both the particle self-assembly and the physical properties of the resulting monolayers. The effect of particle size, polymer length, and polymer composition were systematically varied. Monolayers of exceptional flexibility and toughness were found using poly(methyl acrylate). Additionally, the self-assembly of particles into ordered structures was studied both experimentally and computationally to be a result of particle size, polymer grafting density, and polymer hydrophobicity.Chapter 4 analyzes the coordination of different ligands to the surface of MOFs. Using a fluorescent dye containing a coordinating ligand, the amount of ligand present on the MOF surface can be determined using UV-visible spectroscopy. Furthermore, the stability of this coordination can be easily measured by analyzing the amount of dye that disassociates from the surface under various conditions. This feature was used as a diagnostic to determine the binding strength of several classes of ligands to different MOFs and provides a simple platform for the analysis of MOF surface coordination.
일반주제명  
Chemistry
일반주제명  
Materials science
일반주제명  
Polymer chemistry
일반주제명  
Analytical chemistry
일반주제명  
Nanoscience
키워드  
Metal-organic framework
키워드  
Polymers
키워드  
Self-assembly
키워드  
Composites
키워드  
Hydrophobicity
기타저자  
University of California, San Diego Chemistry and Biochemistry
기본자료저록  
Dissertations Abstracts International. 86-03B.
전자적 위치 및 접속  
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MARC

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■1001  ▼aBarcus,  Kyle.
■24510▼aSynthesis  and  Self-assembly  of  Polymer-Grafted  Metal-Organic  Frameworks
■260    ▼a[Sl]▼bUniversity  of  California,  San  Diego▼c2024
■260  1▼aAnn  Arbor▼bProQuest  Dissertations  &  Theses▼c2024
■300    ▼a181  p
■500    ▼aSource:  Dissertations  Abstracts  International,  Volume:  86-03,  Section:  B.
■500    ▼aAdvisor:  Cohen,  Seth  M.
■5021  ▼aThesis  (Ph.D.)--University  of  California,  San  Diego,  2024.
■520    ▼aMetal-organic  frameworks  (MOFs)  are  crystalline,  porous  materials  with  unique  properties  valued  for  applications  in  chemical  storage,  separation,  and  catalysis.  While  MOFs  have  shown  great  potential  for  these  applications,  a  major  shortcoming  of  these  materials  is  their  inherently  crystalline  nature,  which  limits  their  processability  into  the  form  factors  required  for  these  applications.  To  overcome  this  issue,  MOFs  have  been  combined  with  polymers  in  order  to  form  composites  that  incorporate  the  flexibility  and  processability  of polymers  while  retaining  the  properties  of  the  MOF  material.  However,  incompatibilities  between  the  MOF  surface  and  the  polymer  matrix  can  result  in  defects  and  mechanical  failure.  Lowering  the  MOF  loading  to  circumvent  this  greatly  diminishes  or  negates  the  contribution  of  the  MOF  to  the  material  properties.  Therefore,  a  method  is  needed  to  formulate  composites  that  allows  for  high  MOF  loading  while  retaining  the  desirable  properties  of  the  polymer. To  develop  a  solution  to  this  issue,  Chapter  2  describes  the  preparation  of  polymer-coated  MOFs  using  surface-initiated  controlled  radical  polymerization  (SI-CRP)  from  coordinating  initiators.  This  method  allows  for  the  preparation  of  single  nanoparticle  composites,  with  the  polymer  directly  attached  to  the  MOF  surface.  The  resulting  particles  were  then  self-assembled  into  monolayers  at  the  air-water  interface  that  were  found  to  be  freestanding  when  removed  from  the  water  surface.  This  method  was  found  to  be  generalizable  to  several  other  MOFs,  providing  a  platform  for  polymer-MOF  composites  with  intrinsically  high  loadings  of  MOF  particles.Chapter  3  systematically  studies  the  different  factors  of  polymer-grafted  MOFs  on  both  the  particle  self-assembly  and  the  physical  properties  of  the  resulting  monolayers.  The  effect  of  particle  size,  polymer  length,  and  polymer  composition  were  systematically  varied.  Monolayers  of  exceptional  flexibility  and  toughness  were  found  using  poly(methyl  acrylate).  Additionally,  the  self-assembly  of  particles  into  ordered  structures  was  studied  both  experimentally  and  computationally  to  be  a  result  of  particle  size,  polymer  grafting  density,  and  polymer  hydrophobicity.Chapter  4  analyzes  the  coordination  of  different  ligands  to  the  surface  of  MOFs.  Using  a  fluorescent  dye  containing  a  coordinating  ligand,  the  amount  of  ligand  present  on  the  MOF  surface  can  be  determined  using  UV-visible  spectroscopy.  Furthermore,  the  stability  of  this coordination  can  be  easily  measured  by  analyzing  the  amount  of  dye  that  disassociates  from  the  surface  under  various  conditions.  This  feature  was  used  as  a  diagnostic  to  determine  the  binding  strength  of  several  classes  of  ligands  to  different  MOFs  and  provides  a  simple  platform  for  the  analysis  of  MOF  surface  coordination.
■590    ▼aSchool  code:  0033.
■650  4▼aChemistry
■650  4▼aMaterials  science
■650  4▼aPolymer  chemistry
■650  4▼aAnalytical  chemistry
■650  4▼aNanoscience
■653    ▼aMetal-organic  framework
■653    ▼aPolymers
■653    ▼aSelf-assembly
■653    ▼aComposites  
■653    ▼aHydrophobicity
■690    ▼a0485
■690    ▼a0565
■690    ▼a0486
■690    ▼a0794
■690    ▼a0495
■71020▼aUniversity  of  California,  San  Diego▼bChemistry  and  Biochemistry.
■7730  ▼tDissertations  Abstracts  International▼g86-03B.
■790    ▼a0033
■791    ▼aPh.D.
■792    ▼a2024
■793    ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17160137▼nKERIS▼z이  자료의  원문은  한국교육학술정보원에서  제공합니다.

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