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Metal-Based Clusters Encapsulated in Metal-Organic Framework for Catalysis and Chemical Separations
Metal-Based Clusters Encapsulated in Metal-Organic Framework for Catalysis and Chemical Se...
Metal-Based Clusters Encapsulated in Metal-Organic Framework for Catalysis and Chemical Separations

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자료유형  
 학위논문 서양
최종처리일시  
20260202104659
ISBN  
9798291583661
DDC  
540
저자명  
Sui, Jingyi.
서명/저자  
Metal-Based Clusters Encapsulated in Metal-Organic Framework for Catalysis and Chemical Separations
발행사항  
[Sl] : Northwestern University, 2025
발행사항  
Ann Arbor : ProQuest Dissertations & Theses, 2025
형태사항  
106 p
주기사항  
Source: Dissertations Abstracts International, Volume: 87-02, Section: B.
주기사항  
Advisor: Hupp, Joseph.
학위논문주기  
Thesis (Ph.D.)--Northwestern University, 2025.
초록/해제  
요약Metal-organic frameworks (MOFs) are a class of highly porous and crystalline materials, composed of inorganic nodes connected and multitopic organic linkers. Their high tunability, and large internal surface areas make them promising candidates for a wide range of applications in catalysis, chemical separation, and so on. One powerful strategy to enhance the functionalities of MOFs is post-synthetic metalation, which incorporates metal ions or clusters into the framework without compromising the overall structure. This dissertation explores two strategies to incorporate metal species into MOFs, using the resulting composite as precursors for synthesis ultra-small metal phosphide or sulfide that are otherwise difficult to prepare. In the first approach, we leveraged the labile -OH/H2O on the nodes of Zr-MOFs, depositing nickel oxide clusters that were subsequently converted into nickel phosphide. Results showed that the resulting materials retained crystallinity while having highly dispersed nickel phosphide. Even though the nickel species existed as a mixture of nickel oxide and phosphide, the phosphide component remained active for photocatalytic hydrogen evolution in the presence of photosensitizers and sacrificial electron donors. In the second approach, we functionalized a Zr-MOF with a well-defined metal oxide cluster, polyoxometalate (POM). By judiciously selecting MOFs and POMs, POMs can be immobilized inside the framework via impregnation. The resulting composite had the POMs effectively sculpting the pore volume of the parent MOF. The pore-sculpted POM MOF exhibited enhanced Xe/Kr separation performance, with significant increased Xe and Kr uptake capacities and improved Xe selectivity compared to the parent MOF. Subsequent sulfidation converted the encapsulated POM into a fully sulfided analogue, polythiometalate (PTM). The PTM MOF composite demonstrated rapid and selective Ag+ capture.
일반주제명  
Chemistry
일반주제명  
Inorganic chemistry
일반주제명  
Organic chemistry
키워드  
Metal-organic frameworks
키워드  
Sulfidation
키워드  
Polythiometalate
기타저자  
Northwestern University Chemistry
기본자료저록  
Dissertations Abstracts International. 87-02B.
전자적 위치 및 접속  
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MARC

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■020    ▼a9798291583661
■035    ▼a(MiAaPQ)AAI32116054
■040    ▼aMiAaPQ▼cMiAaPQ
■0820  ▼a540
■1001  ▼aSui,  Jingyi.
■24510▼aMetal-Based  Clusters  Encapsulated  in  Metal-Organic  Framework  for  Catalysis  and  Chemical  Separations
■260    ▼a[Sl]▼bNorthwestern  University▼c2025
■260  1▼aAnn  Arbor▼bProQuest  Dissertations  &  Theses▼c2025
■300    ▼a106  p
■500    ▼aSource:  Dissertations  Abstracts  International,  Volume:  87-02,  Section:  B.
■500    ▼aAdvisor:  Hupp,  Joseph.
■5021  ▼aThesis  (Ph.D.)--Northwestern  University,  2025.
■520    ▼aMetal-organic  frameworks  (MOFs)  are  a  class  of  highly  porous  and  crystalline  materials,  composed  of  inorganic  nodes  connected  and  multitopic  organic  linkers.  Their  high  tunability,  and  large  internal  surface  areas  make  them  promising  candidates  for  a  wide  range  of  applications  in  catalysis,  chemical  separation,  and  so  on.  One  powerful  strategy  to  enhance  the  functionalities  of  MOFs  is  post-synthetic  metalation,  which  incorporates  metal  ions  or  clusters  into  the  framework  without  compromising  the  overall  structure.  This  dissertation  explores  two  strategies  to  incorporate  metal  species  into  MOFs,  using  the  resulting  composite  as  precursors  for  synthesis  ultra-small  metal  phosphide  or  sulfide  that  are  otherwise  difficult  to  prepare.  In  the  first  approach,  we  leveraged  the  labile  -OH/H2O  on  the  nodes  of  Zr-MOFs,  depositing  nickel  oxide  clusters  that  were  subsequently  converted  into  nickel  phosphide.  Results  showed  that  the  resulting  materials  retained  crystallinity  while  having  highly  dispersed  nickel  phosphide.  Even  though  the  nickel  species  existed  as  a  mixture  of  nickel  oxide  and  phosphide,  the  phosphide  component  remained  active  for  photocatalytic  hydrogen  evolution  in  the  presence  of  photosensitizers  and  sacrificial  electron  donors.  In  the  second  approach,  we  functionalized  a  Zr-MOF  with  a  well-defined  metal  oxide  cluster,  polyoxometalate  (POM).  By  judiciously  selecting  MOFs  and  POMs,  POMs  can  be  immobilized  inside  the  framework  via  impregnation.  The  resulting  composite  had  the  POMs  effectively  sculpting  the  pore  volume  of  the  parent  MOF.  The  pore-sculpted  POM  MOF  exhibited  enhanced  Xe/Kr  separation  performance,  with  significant  increased  Xe  and  Kr  uptake  capacities  and  improved  Xe  selectivity  compared  to  the  parent  MOF.  Subsequent  sulfidation  converted  the  encapsulated  POM  into  a  fully  sulfided  analogue,  polythiometalate  (PTM).  The  PTM  MOF  composite  demonstrated  rapid  and  selective  Ag+  capture.
■590    ▼aSchool  code:  0163.
■650  4▼aChemistry
■650  4▼aInorganic  chemistry
■650  4▼aOrganic  chemistry
■653    ▼aMetal-organic  frameworks
■653    ▼aSulfidation
■653    ▼aPolythiometalate
■690    ▼a0485
■690    ▼a0488
■690    ▼a0490
■71020▼aNorthwestern  University▼bChemistry.
■7730  ▼tDissertations  Abstracts  International▼g87-02B.
■790    ▼a0163
■791    ▼aPh.D.
■792    ▼a2025
■793    ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17358419▼nKERIS▼z이  자료의  원문은  한국교육학술정보원에서  제공합니다.

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