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Fundamental Inorganic Chemistry for Renewable Energy Resources: Highlights in Tellurium, Zirconium, Hafnium, and Neptunium Coordination Chemistry
Fundamental Inorganic Chemistry for Renewable Energy Resources: Highlights in Tellurium, Z...
Fundamental Inorganic Chemistry for Renewable Energy Resources: Highlights in Tellurium, Zirconium, Hafnium, and Neptunium Coordination Chemistry

Detailed Information

자료유형  
 학위논문 서양
최종처리일시  
20250211152752
ISBN  
9798342123211
DDC  
600
저자명  
Uible, Madeleine Claire.
서명/저자  
Fundamental Inorganic Chemistry for Renewable Energy Resources: Highlights in Tellurium, Zirconium, Hafnium, and Neptunium Coordination Chemistry
발행사항  
[Sl] : Purdue University, 2024
발행사항  
Ann Arbor : ProQuest Dissertations & Theses, 2024
형태사항  
271 p
주기사항  
Source: Dissertations Abstracts International, Volume: 86-04, Section: B.
주기사항  
Advisor: Bart, Suzanne Doucette;Andrews, Justin;Agarwal, Rakesh;Tian, Shiliang.
학위논문주기  
Thesis (Ph.D.)--Purdue University, 2024.
초록/해제  
요약The separation of tellurium from cadmium telluride is examined using a unique combination of mild, anhydrous chlorination and complexation of the subsequent tellurium tetrachloride with 3,5-di-tert-butylcatechol. The resulting tellurium complex, Te(dtbc)2, is isolated in moderate yield and features a 103 to 104reduction in cadmium content, as provided by XRF and ICP-MS analysis. Similar results were obtained from zinc telluride. A significant separation between Te, Se, and S was observed after treating a complex mixture of metal chalcogenides with this protocol. These three tunable steps can be applied for future applications of CdTe photovoltaic waste.We report the synthesis and characterization of the first series of tellurium and selenium complexes featuring an η5 -cyclopentadienyl ligand. Reaction ofPh3TeX(X = Cl, S2CNEt2) with Mcpr (M = Li, K; R = H, Me4, Me5) results in high yields of [Cp][TePh3] (1), [Cpme4][TePh3] (2), and [Cp*][TePh3](3), respectively. Similarly, reaction of Ph3SeCl with LiCp and KCp* furnishes [Cp][SePh3] (4) and [Cp*][SePh3] (5). Each was characterized by X-ray crystallography, revealing similar η5 -coordination with little distortion from an idealized half-sandwich geometry, presumably from the remaining lone pair on tellurium and selenium. The Te-centroid distances are relatively long (1: 2.770(3), 2: 2.746(1), and 3: 2.733(1) A), suggesting a mostly ionic interaction. Se-centroid distances (4: 2.748(3), 5: 2.707(2), 2.730(2) A) were found to be surprisingly similar despite its smaller atomic radius. Compounds 2, 3, and 5 display rapid decomposition at room temperature, extruding a phenylated cyclopentadiene and the and the respective diphenylchalcogenide. The nature of bonding within these complexes was investigated through DFT methods and found to be primarily ionic in nature.Synthesis of homoleptic zirconium and hafnium dithiocarbamate via carbon disulfide insertion into zirconium and hafnium amides were investigated for their utility as soluble molecular precursors for chalcogenide perovskites and binary metal sulfides. TreatingM(NEtR)4 (M= Zr, Hf and R= Me, Et) with CS2 resulted in quantitative yields of homoleptic Group IV dithiocarbamates.Zr( 2 -S2CNMeEt) (1), Zr( 2 -S2CNEt2)4 (2), and Hf( 2 -S2CNEt2)4 (4), a rare example of a crystal of a homoleptic hafnium CS2 inserted amide species, were characterized. A computational analysis confirmed assignments for IR spectroscopy. To exemplify the utility of the 11 Group IV dithiocarbamates, a solution-phase nanoparticle synthesis was performed to obtain ZrS3 via the thermal decomposition ofZr(S2CNMeEt)4.Chalcogenide perovskites have garnered interest for applications in semiconductor devices due to their excellent predicted optoelectronic properties and stability. However, high synthesis temperatures have historically made these materials incompatible with the creation of photovoltaic devices. Here, we demonstrate the solution processed synthesis of luminescent BaZrS3 and BaHfS3 chalcogenide perovskite films using single-phase molecular precursors at sulfurization temperatures of 575 °C and sulfurization times as short as one hour. These molecular precursor inks were synthesized using known carbon disulfide insertion chemistry to create Group 4 metal dithiocarbamates, and this chemistry was extended to create species, such as barium dithiocarboxylates, that have never been reported before. These findings, with added future research, have the potential to yield fully solution processed thin films of chalcogenide perovskites for various optoelectronic applications.Np(IV) Lewis base adducts were prepared by ligand substitution of NpCl4(DME)2. Using acetonitrile and pyridine, NpCl4(MeCN)4 (1) and NpCl4(pyr)4(2), were isolated, respectively. All species were fully characterized using spectroscopic and structural analyses.
일반주제명  
Metals
일반주제명  
Mass spectrometry
일반주제명  
Cadmium telluride
일반주제명  
Hydrocarbons
일반주제명  
Oxidation
일반주제명  
Single crystals
일반주제명  
Carbon
일반주제명  
Zirconium
일반주제명  
Zinc telluride
일반주제명  
Decomposition
일반주제명  
Sulfur
일반주제명  
Selenium
일반주제명  
Scientific imaging
일반주제명  
Quantum dots
일반주제명  
Physical properties
일반주제명  
Thin films
일반주제명  
Geometry
일반주제명  
Crystallography
일반주제명  
Analytical chemistry
일반주제명  
Condensed matter physics
일반주제명  
Materials science
일반주제명  
Quantum physics
기타저자  
Purdue University.
기본자료저록  
Dissertations Abstracts International. 86-04B.
전자적 위치 및 접속  
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■1001  ▼aUible,  Madeleine  Claire.
■24510▼aFundamental  Inorganic  Chemistry  for  Renewable  Energy  Resources:  Highlights  in  Tellurium,  Zirconium,  Hafnium,  and  Neptunium  Coordination  Chemistry
■260    ▼a[Sl]▼bPurdue  University▼c2024
■260  1▼aAnn  Arbor▼bProQuest  Dissertations  &  Theses▼c2024
■300    ▼a271  p
■500    ▼aSource:  Dissertations  Abstracts  International,  Volume:  86-04,  Section:  B.
■500    ▼aAdvisor:  Bart,  Suzanne  Doucette;Andrews,  Justin;Agarwal,  Rakesh;Tian,  Shiliang.
■5021  ▼aThesis  (Ph.D.)--Purdue  University,  2024.
■520    ▼aThe  separation  of  tellurium  from  cadmium  telluride  is  examined  using  a  unique  combination  of  mild,  anhydrous  chlorination  and  complexation  of  the  subsequent  tellurium  tetrachloride  with  3,5-di-tert-butylcatechol.  The  resulting  tellurium  complex,  Te(dtbc)2,  is  isolated  in  moderate  yield  and  features  a  103  to  104reduction  in  cadmium  content,  as  provided  by  XRF  and  ICP-MS  analysis.  Similar  results  were  obtained  from  zinc  telluride.  A  significant  separation  between  Te,  Se,  and  S  was  observed  after  treating  a  complex  mixture  of  metal  chalcogenides  with  this  protocol.  These  three  tunable  steps  can  be  applied  for  future  applications  of  CdTe  photovoltaic  waste.We  report  the  synthesis  and  characterization  of  the  first  series  of  tellurium  and  selenium  complexes  featuring  an  η5  -cyclopentadienyl  ligand.  Reaction  ofPh3TeX(X  =  Cl,  S2CNEt2)  with  Mcpr  (M  =  Li,  K;  R  =  H,  Me4,  Me5)  results  in  high  yields  of  [Cp][TePh3]  (1),  [Cpme4][TePh3]  (2),  and  [Cp*][TePh3](3),  respectively.  Similarly,  reaction  of  Ph3SeCl  with  LiCp  and  KCp*  furnishes  [Cp][SePh3]  (4)  and  [Cp*][SePh3]  (5).  Each  was  characterized  by  X-ray  crystallography,  revealing  similar  η5  -coordination  with  little  distortion  from  an  idealized  half-sandwich  geometry,  presumably  from  the  remaining  lone  pair  on  tellurium  and  selenium.  The  Te-centroid  distances  are  relatively  long  (1:  2.770(3),  2:  2.746(1),  and  3:  2.733(1)  A),  suggesting  a  mostly  ionic  interaction.  Se-centroid  distances  (4:  2.748(3),  5:  2.707(2),  2.730(2)  A)  were  found  to  be  surprisingly  similar  despite  its  smaller  atomic  radius.  Compounds  2,  3,  and  5  display  rapid  decomposition  at  room  temperature,  extruding  a  phenylated  cyclopentadiene  and  the  and  the  respective  diphenylchalcogenide.  The  nature  of  bonding  within  these  complexes  was  investigated  through  DFT  methods  and  found  to  be  primarily  ionic  in  nature.Synthesis  of  homoleptic  zirconium  and  hafnium  dithiocarbamate  via  carbon  disulfide  insertion  into  zirconium  and  hafnium  amides  were  investigated  for  their  utility  as  soluble  molecular  precursors  for  chalcogenide  perovskites  and  binary  metal  sulfides.  TreatingM(NEtR)4  (M=  Zr,  Hf  and  R=  Me,  Et)  with  CS2  resulted  in  quantitative  yields  of  homoleptic  Group  IV  dithiocarbamates.Zr(  2  -S2CNMeEt)  (1),  Zr(  2  -S2CNEt2)4  (2),  and  Hf(  2  -S2CNEt2)4  (4),  a  rare  example  of  a  crystal  of  a  homoleptic  hafnium  CS2  inserted  amide  species,  were  characterized.  A  computational  analysis  confirmed  assignments  for  IR  spectroscopy.  To  exemplify  the  utility  of  the  11  Group  IV  dithiocarbamates,  a  solution-phase  nanoparticle  synthesis  was  performed  to  obtain  ZrS3  via  the  thermal  decomposition  ofZr(S2CNMeEt)4.Chalcogenide  perovskites  have  garnered  interest  for  applications  in  semiconductor  devices  due  to  their  excellent  predicted  optoelectronic  properties  and  stability.  However,  high  synthesis  temperatures  have  historically  made  these  materials  incompatible  with  the  creation  of  photovoltaic  devices.  Here,  we  demonstrate  the  solution  processed  synthesis  of  luminescent  BaZrS3  and  BaHfS3  chalcogenide  perovskite  films  using  single-phase  molecular  precursors  at  sulfurization  temperatures  of  575 °C  and  sulfurization  times  as  short  as  one  hour.  These  molecular  precursor  inks  were  synthesized  using  known  carbon  disulfide  insertion  chemistry  to  create  Group  4  metal  dithiocarbamates,  and  this  chemistry  was  extended  to  create  species,  such  as  barium  dithiocarboxylates,  that  have  never  been  reported  before.  These  findings,  with  added  future  research,  have  the  potential  to  yield  fully  solution  processed  thin  films  of  chalcogenide  perovskites  for  various  optoelectronic  applications.Np(IV)  Lewis  base  adducts  were  prepared  by  ligand  substitution  of  NpCl4(DME)2.  Using  acetonitrile  and  pyridine,  NpCl4(MeCN)4  (1)  and  NpCl4(pyr)4(2),  were  isolated,  respectively.  All  species  were  fully  characterized  using  spectroscopic  and  structural  analyses.
■590    ▼aSchool  code:  0183.
■650  4▼aMetals
■650  4▼aMass  spectrometry
■650  4▼aCadmium  telluride
■650  4▼aHydrocarbons
■650  4▼aOxidation
■650  4▼aSingle  crystals
■650  4▼aCarbon
■650  4▼aZirconium
■650  4▼aZinc  telluride
■650  4▼aDecomposition
■650  4▼aSulfur
■650  4▼aSelenium
■650  4▼aScientific  imaging
■650  4▼aQuantum  dots
■650  4▼aPhysical  properties
■650  4▼aThin  films
■650  4▼aGeometry
■650  4▼aCrystallography
■650  4▼aAnalytical  chemistry
■650  4▼aCondensed  matter  physics
■650  4▼aMaterials  science
■650  4▼aQuantum  physics
■690    ▼a0486
■690    ▼a0611
■690    ▼a0794
■690    ▼a0599
■71020▼aPurdue  University.
■7730  ▼tDissertations  Abstracts  International▼g86-04B.
■790    ▼a0183
■791    ▼aPh.D.
■792    ▼a2024
■793    ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17163779▼nKERIS▼z이  자료의  원문은  한국교육학술정보원에서  제공합니다.

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