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Cyanometallate Coordination Polymer Nanostructures and Thin Films

Permanent Link: http://ufdc.ufl.edu/UFE0041117/00001

Material Information

Title: Cyanometallate Coordination Polymer Nanostructures and Thin Films Synthesis and Applications
Physical Description: 1 online resource (144 p.)
Language: english
Creator: Rummel, Ian
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2009

Subjects

Subjects / Keywords: blue, cells, dioxide, dye, langmuir, monolayers, prussian, sensitized, solar, titanium
Chemistry -- Dissertations, Academic -- UF
Genre: Chemistry thesis, Ph.D.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: Prussian blue analogs (PBAs) are cyanometallate coordination polymers whose electronic properties can be modified by varying the material s constituent metals. This research investigated how the structural and electronic properties of PBA nanostructures such as monolayers, thin films, and nanoparticles can be exploited in applications related to charge storage, solid-state electrolytics, and supramolecular assembly of materials. It was demonstrated herein that two-dimensional monolayers of PBA with specific geometries can be synthesized at the air/water interface by employing blocking ligands when reacting an amphiphilic monolayer with aqueous subphase components. Charge balance was found to be a key consideration in such systems. The feasibility of creating two-dimensional networks of PBA at the air/water interface by employing more complex oligomeric cyanometallate subphase species was also investigated. It was hoped that such networks would demonstrate ferromagnetism due to coupling between the cyanometallate oligomers and the amphiphilic monolayer component. Although evidence of cyanometallate network formation was present, no evidence of magnetic interactions was observed. The charge-storage capabilities of PB were investigated by creating nanoparticles of PB coated in TiO2. It was demonstrated that photo-excited electrons from the TiO2 transferred into the PB upon irradiation with near-UV light, that the electrons could be removed by oxidizing the PB, and that the material could by cycled multiple times. Finally, thin films of PBA were deposited onto dyed TiO2 substrates to investigate the feasibility of using PBAs as solid-state electrolytes in DSSCs. The efficiency of the resulting cells was found to be extremely low, likely due to poor contact between the highly-porous TiO2 film and the PBA.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by Ian Rummel.
Thesis: Thesis (Ph.D.)--University of Florida, 2009.
Local: Adviser: Talham, Daniel R.
Electronic Access: RESTRICTED TO UF STUDENTS, STAFF, FACULTY, AND ON-CAMPUS USE UNTIL 2010-06-30

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2009
System ID: UFE0041117:00001

Permanent Link: http://ufdc.ufl.edu/UFE0041117/00001

Material Information

Title: Cyanometallate Coordination Polymer Nanostructures and Thin Films Synthesis and Applications
Physical Description: 1 online resource (144 p.)
Language: english
Creator: Rummel, Ian
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2009

Subjects

Subjects / Keywords: blue, cells, dioxide, dye, langmuir, monolayers, prussian, sensitized, solar, titanium
Chemistry -- Dissertations, Academic -- UF
Genre: Chemistry thesis, Ph.D.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: Prussian blue analogs (PBAs) are cyanometallate coordination polymers whose electronic properties can be modified by varying the material s constituent metals. This research investigated how the structural and electronic properties of PBA nanostructures such as monolayers, thin films, and nanoparticles can be exploited in applications related to charge storage, solid-state electrolytics, and supramolecular assembly of materials. It was demonstrated herein that two-dimensional monolayers of PBA with specific geometries can be synthesized at the air/water interface by employing blocking ligands when reacting an amphiphilic monolayer with aqueous subphase components. Charge balance was found to be a key consideration in such systems. The feasibility of creating two-dimensional networks of PBA at the air/water interface by employing more complex oligomeric cyanometallate subphase species was also investigated. It was hoped that such networks would demonstrate ferromagnetism due to coupling between the cyanometallate oligomers and the amphiphilic monolayer component. Although evidence of cyanometallate network formation was present, no evidence of magnetic interactions was observed. The charge-storage capabilities of PB were investigated by creating nanoparticles of PB coated in TiO2. It was demonstrated that photo-excited electrons from the TiO2 transferred into the PB upon irradiation with near-UV light, that the electrons could be removed by oxidizing the PB, and that the material could by cycled multiple times. Finally, thin films of PBA were deposited onto dyed TiO2 substrates to investigate the feasibility of using PBAs as solid-state electrolytes in DSSCs. The efficiency of the resulting cells was found to be extremely low, likely due to poor contact between the highly-porous TiO2 film and the PBA.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by Ian Rummel.
Thesis: Thesis (Ph.D.)--University of Florida, 2009.
Local: Adviser: Talham, Daniel R.
Electronic Access: RESTRICTED TO UF STUDENTS, STAFF, FACULTY, AND ON-CAMPUS USE UNTIL 2010-06-30

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2009
System ID: UFE0041117:00001


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PAGE 5

N

PAGE 8

1 4

PAGE 9

1 2 2 2 2 2 2 2 2 2

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2 1 1 1 1 1 1 1 4 1 4 1 4 1 4 1 1

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1 trans

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Supramolecular Chemistry

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Supramolecular Assembly with Langmuir Monolayers

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mw w m

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Use of Langmuir Monolayers as a StructureDirecting Element

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Characterization of Langmuir Monolayers with Underlying Cyanometallate Coordination Networks Brewster Angle Microscopy

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Attenuated total reflectance infrared spectroscopy

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Scope of the Thesis

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A B C

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Introduction

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1 2 1 3) 4 4 2

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Experimental Synthesis Pentacyanoferrate amphiphile synthesis 1 N -m ethyl -4-(didodecylam ino)pyridinium iodide N N 4-(Didodecylamino)pyridine N N

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Bis(tetramethylammonium)pentacyano(4 (didodecylamino) pyridine) ferrate(III)

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Ru(II/III)tetracarboxylate chloride 1 ,4,8,11 -tetraazacyclotetradecane nickel (II) perchlorate

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1-octadecyl -1,3,6,10,13pentaazacyclotetradecane nickel (II) chloride Materials Instrumentation

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Langmuir Monolayer Pr eparation 1 2 1 3 4 2

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2 Results Synthesis Bis(tetramethylammonium)pentacyano(4 (didodecylamino) pyridine) ferrate(III) 1 Ru(II/III)tetracarboxylate chloride 4 1,4,8,11 -tetraazacyclotetradecane nickel (II) perchlorate

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1-octadecyl -1,3,6,10,13pentaazacyclotetradecane nickel (II) chloride Macrocyclic NiII Amphiphile with K4Fe(CN)6 Subphase Surface pressure vs. mean molecular area isotherms 2 BAM 2 2

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ATR FT -IR 2 XPS 2 AFM Creep observations

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Pentacyanoferrate Amphiphile with Macrocyclic Tetraaza Ni (II) Subphase Surface pressure vs. mean molecular area isotherms 1

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BAM XPS 1 Pentacya noferrate Amphiphile with Ru (II/III) Tetracarboxylate Subphase Surface pressure vs. mean molecular area isotherms

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BAM 1 4 1 ATR FT -IR 1 XPS 4

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Discussion Macrocyclic NiII Amphiphile with K4Fe(CN)6 Subphase 1

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Pentacyanoferrate Amphiphile with Macrocyclic Tetraaza Ni (II) Subphase 1

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Pentacyano ferrate Amphiphile with Ru (II/III) Tetracarboxylate Subphase General Discussion 2 1

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Conclusions and Future Work

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1 3

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1 4

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2

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2 RuCl3+ 4 CH3COOH O2C4H6O3 + 4HCl H2O H2O + 2H2O H2O NaBH4 2ClO4 2ClO4 2ClO4

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1 5 5 15 25 35 45 0 50 100 150 200 Surface Pressure (mN/m) Mean Molecular Area ( 2 ) Ferrocyanide Subphase NaCl Subphase 2 2

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Absorbance cm 1 2 Abosrbance cm 1 2

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Absorbance cm 1 2 2 Binding Energy (eV) N(E)

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Binding Energy (eV) N(E) 2 Binding Energy (eV) N(E) 2 2

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Mean Molecular Area ( 2 ) Time (minutes) 2

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Surface Pressure (mN/m) Mean Molecular Area ( 2 ) 1

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1 Binding Energy (eV) N(E) 1

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1 1

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10 0 10 20 30 40 50 60 70 0 50 100 150 200 250 300 Surface Pressure (mN/m) Mean Molecular Area ( 2 ) 1 hour 3 hours 16 hours 1

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Absorbance cm 1 1 4 Absorbance cm 1 1 4 Absorbance cm 1 1 4

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cm 1 Absorbance 1 4 1 1

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1

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Introduction Trans M

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eg t2g Experimental Synthesis t rans Monolayer Preparation Results Surface P ressure vs. M ean M olecular A rea I sotherms

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BAM ATR FT -IR XPS

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SQUID M agnetometry M H T M H T M H g T Discussion

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Conclusions t rans M

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trans Surface Pressure (mN/m) Mean Molecular Area ( 2 )

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01234567 0 1 2 3 4 5 Mp (104 emuG/mol) Mtotal Md 1Ni:2Cr (phenom. expect.) TR = 0.2 T = 2 K 0 50100150200250300 0.0 0.2 0.4 0.6 0.8 1.0 1.2 p (emu/mol)T (K) zfc d(2K) Curie law fit H = 100 G

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01234567 0 1 2 3 4 5 6 7 Mp (104 emuG/mol)H (T) Mtotal Md 1 Ni:4Fe, g(Fe) = 3.2 (phenom. expect.) T = 2 K0 50100150200250300 1 2 3 4 5 6 p (emu/mol)T (K) zfc d Curie law fit T = 2 K

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Introduction A A

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Experimental Synthesis Prussian blue nanoparticles NiIICrIII PBA nanoparticles

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TiO2-Coated Prussian Blue Particles Thallium Staining for TEM Analysis Photo -oxidative Experiments

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Visible Light -Induced Charge Transfer Evaluation Materials Instrumentation

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Results Prussian Blue/TiO2 Nanocomposite Synthesis NiCr PBA/TiO2 Nanocomposite Synthesis UV Photo -Induced Charge Transfer Evaluation

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Photocatalysis Visible Light Sensitization with Rhodamine B.

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Discussion

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Conclusions and Future Work

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Prussian blue Silver Prussian blue composite TiO2 Rhodamine B

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+ 20 nm 10 nm 200 nm

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Absorbance Wavelength (nm) Prussian Blue/TiO2Nanoparticles Prussian Blue Nanoparticles

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time (min) Abs at 750 nm nm

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0.0192 +/ -0.0043 0.0167 +/ -0.0020 0.0011 +/ -0.0001

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0.00524 +/ -0.00035 0.00148 +/ -0.00036 0.000157 +/ -0.0003 wavelength (nm)Abs

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Introduction Dye -Sensitized Solar Cells

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DSSC Electrolytes

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Prussian Blue Analogs as Solid DSSC Electrolyt es

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1 1 1

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Experimental Dye Synthesis

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Dyed TiO2 Electrode Fabrication

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PBA electrolyte deposition

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Back electrode deposition Efficiency measu rements o iP P E Results (4,4 -dcbpy)2(CN)2Ru(II) Dye Synthesis

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Finished Cell PBA Depos ition

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CoFe PBA Penetration into TiO2 Film Cell Efficiency Under Simulated Sunlight

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Discussion

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Conclusions and Future Work

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Voltage (V) Current (A) voltage (V)

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0 0.1 0.2 0.3 0.4 750 1250 1750 2250 2750 Absorbance Wavenumber 0 0.5 1 1.5 2 2.5 3 600 1100 1600 2100 2600 3100 3600 Absorbance Wavenumber

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0 0.2 0.4 0.6 0.8 600 1100 1600 2100 2600 3100 3600 Absorbance Wavenumber 0 0.2 0.4 0.6 0.8 1 1.2 800 1300 1800 2300 2800 3300 3800 Absorbance Wavenumber

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0.06 0.08 0.1 0.12 0.14 600 1100 1600 2100 2600 3100 3600 Absorbance Wavenumber 0.1 0.2 0.3 0.4 600 1100 1600 2100 2600 3100 3600 Absorbance Wavenumber

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0.1 0.1 0.3 0.5 0.7 0.9 500 1000 1500 2000 2500 3000 3500 Absorbance Wavenumber

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