本論文採用水熱反應合成釤、銅基金屬有機骨架化合物，並探討釤基金屬有機骨架(Sm-MOF)的介電性質與銅基金屬有機骨架材料(Cu-MOF)的導電與熱電性質。化合物 [Sm2(bhc)(H2O)6]n (1) 是藉由硝酸釤samarium(III) nitrate 與有機配子benzenehexacarboxylic acid（bhc）以水、乙醇的混合液作為溶劑，並使用水熱法反應合成三維結構之金屬有機骨架。單晶X繞射檢測顯示化合物1的空間群為Pnmn並且是以（4, 8）連接而成三維結晶。經由不同溫度下對介電性質量測顯示化合物1屬於高介電材料，在5 kHz的頻率與310 K的溫度下化合物1具有高介電常數（κ = 45.1），相當於大部分常見的無機金屬氧化物 (如Sm2O3、Ta2O5、HfO2、ZrO2) 之介電數值。此外，將配位的水分子在化合物1中除去後，化合物1在5 kHz頻率與310 K的溫度下仍具有高介電常數（κ = 38.1），化合物1具有低電導率，在頻率為5 kHz約為2.15 × 10–7 S/cm，並同時具有低漏電流(Ileakage = 8.13 × 10–12 Amm–2)。此釤基金屬有機骨架的介電性質研究成果，有希望提供開發高介電材料更為有效的研究方向。
目前在能量儲存和發電的各項能源研究領域中，設計高導電的金屬有機骨架（MOF）為一項具潛在應用價值而受到極大關注的主題。本研究藉由設計銅硫(–Cu–S–)n二維平面於MOF結構內的策略，實現高導電MOF的特性。在水熱反應的條件下，有機物6,6’-dithiodinicotinic acid因原位裂解S–S鍵形成6-mercaptonicotinic acid (1,6-Hmna)與6-mercaptonicotinate (6-mn)，並與硝酸銅反應合成化合物{[Cu2(6-Hmna)(6-mn)]·NH4}n (2)。經由單晶X射線繞射分析，化合物2結晶的空間群為Pna21，並由(–Cu–S–)n 組成二維平面結構。此外，化合物2單晶具有低活化能（6 meV），小帶隙（1.34 eV）與高電導率（10.96 S cm−1）的特性。這種材料適用於電池、熱電、超級電容器與相關領域，為生產高導電MOF提供理想的方向，因此在未來極具應用潛力。
化合物2在本研究中同時被研究於熱電性質之應用，為了進一步提高化合物2之導電性質，化合物2在400 °C與500 °C下被熱裂解藉以獲得Cu2S奈米片狀結構與石墨之複合物。熱裂解之粉末經由冷壓而形成錠片，在溫度45 °C下測量400 °C與500 °C下被熱裂解之化合物2在之熱電特性，其中電導率由0.5 S/m提升至4260 S/m (400 °C)與861 S/m (500 °C)，Seebeck係數也從25 μV/K提升至56.6 μV/K (400 °C) 與144.7 μV/K (500 °C)，導熱率由0.15 W/mK增加至0.58 W/mK (400 °C) 與0.44 W/mK (500 °C)，其熱電優值1.3 × 10−2 (400 °C) 與7.3 × 10−3 (500 °C)遠高於熱裂解前之化合物2 (ZT = 1.2 × 10−6)，超過1000倍的提升。
本論文研究首先以水熱法合成Sm-MOF與Cu-MOF化合物，並經由介電性質對不同溫度與不同頻率的測量證實，Sm-MOF的高介電性質足以成為其它高介電材料之替代物質。此外，Cu-MOF藉著熱裂解的方式有效提高其導電性質，而獲得遠高於Cu-MOF之熱電特性。

Designing highly conducting metal–organic frameworks (MOFs) is currently a subject of great interest for their potential applications in diverse areas encompassing energy storage and generation. In this thesis, samarium and copper based metal–organic frameworks (MOFs) compound were synthesized by hydrothermal reactions. Samarium based metal–organic frameworks have been investigated for their high-κ dielectric properties and copper based metal–organic frameworks were studied for their electrical conductivity as well as their thermoelectric properties. Compound [Sm2(bhc)(H2O)6]n (1) is a three dimensional samarium based metal–organic framework that was synthesized by reacting Sm(NO3)3·6H2O with benzenehexacarboxylic acid (bhc) in a mixture of H2O–EtOH under hydrothermal conditions. A single crystal X-ray analysis of compound 1 showed that it crystallizes in a Pnmn space group and adopted a 3D structure with (4,8) connected nets. Temperature dependent dielectric measurements showed that compound 1 behaves as a high dielectric material with a high dielectric constant (κ = 45.1) at 5 kHz and 310 K, which is comparable to the values for some of the most commonly available dielectric inorganic metal oxides such as Sm2O3, Ta2O5, HfO2, and ZrO2. After the removal of the coordinated polar water molecule from compound 1, it showed a high dielectric constant (κ = 38.1) at 5 kHz and 310 K. In addition, electrical measurements of 1 revealed an electrical conductivity of approximately 2.15 × 10–7 S/cm at a frequency of 5 kHz with a low leakage current (Ileakage = 8.13 × 10–12 Amm–2). Dielectric investigations of the Sm-based MOFs provide an effective path for the development of high dielectric materials in the future.
A strategic design in which a metal–sulfur plane is integrated within a MOF to achieve high electrical conductivity, is successfully demonstrated. Compound {[Cu2(6-Hmna)(6-mn)]·NH4}n (2, 6-Hmna = 6-mercaptonicotinic acid, 6-mn = 6-mercaptonicotinate), consisting of a two dimensional (–Cu–S–)n plane, was synthesized from the reaction of Cu(NO3)2, and 6,6-dithiodinicotinic acid via the in situ cleavage of an S–S bond under hydrothermal conditions. A single-crystal X-ray diffraction analysis of 2 revealed that it crystallizes in the orthorhombic space group Pna21. A single crystal of the MOF was found to have a low activation energy (6 meV), a small bandgap (1.34 eV) and the highest electrical conductivity (10.96 S cm−1) among MOFs for single crystal measurements. This approach provides an ideal roadmap for producing highly conductive MOFs with great potential for applications in batteries, thermoelectric, supercapacitors and related areas.
Compound 2 was also investigated for use in thermoelectric applications. To further improve the electrical conductivity of compound 2, it was pyrolyzed at 400 °C and 500 °C to obtain composites containing Cu2S nanosheets and graphitic carbon. The electrical conductivity of the cold pressed pellet was improved from 0.5 S/m to 4260 S/m at 45 °C in the case of the pyrolysed Cu-MOF at 400 °C and 861 S/m for 500 °C pyrolysed Cu-MOF. The Seebeck coefficient for the pyrolyzed Cu-MOF cold pressed pellet at 400 °C was also improved from 25 μV/K to 56.6 μV/K and 144.7 μV/K for 500 °C pyrolysed Cu-MOF at 45 °C. The thermal conductivity of the pristine Cu-MOF cold pressed pellet was 0.15 W/mK at 45 °C. After pyrolysis at 400 °C the thermal conductivity of the Cu-MOF cold pressed pellet was found to be increased by 0.58 W/mK and for 500 °C pyrolysed Cu-MOF was 0.44 W/mK at 45 °C. The ZT value of the pyrolyzed Cu- MOF cold pressed pellet at 400 °C was 7.3 × 10−3 and for pyrolysed Cu-MOF at 500 °C was 1.3 × 10−2, which was improved more than ~1000 times from pristine Cu-MOF cold pressed pellet (ZT = 1.2 × 10−6).
This thesis describes the synthesis of alternate materials with high-κ dielectric values and a systematic approach for improving the electrical conductivity of metal–organic frameworks and for their use in thermoelectric energy generation applications.

Table of Contents

Acknowledgement...................................................i
Abstract(Chinese)................................................ii
Abstract (English)..............................................iii
Table of Content.................................................vi
List of Figures..................................................ix
List of Tables..................................................xiv
Chapter 1 Introduction............................................1
1.1 Background....................................................1
1.2 Introduction of dielectric material...........................6
1.3 Polarization Mechanisms in Dielectrics........................8
1.3.1 Interface or space charge polarization......................9
1.3.2 Dipole or orientation polarization..........................9
1.3.3 Ionic Polarization..........................................9
1.3.4 Electronic or Atomic Polarization...........................9
1.4 Frequency dependence dielectric constant or complex permittivity .................................................................10
1.5 Application of dielectric materials..........................11
1.6 High-κ materials.............................................12
1.7 Need for High-κ dielectrics..................................12
1.8 Metal–Organic Frameworks as High-κ dielectrics...............13
1.9 Conductive metal–organic frameworks..........................15
1.9.1 The “Through-Bond” Approach to Charge Transport............16
1.9.2 The “Through-Space” Approach to Charge Transport...........23
1.9.3 2D π‐Conjugated MOFs.......................................26
1.10 Thermoelectric materials....................................31
1.11 Thermoelectric metal–organic frameworks.....................35
1.12 Research Motivation.........................................41
Chapter 2 Experimental Section...................................43
2.1 Introduction.................................................43
2.2 Synthesis....................................................43
2.2.1 Crystallization............................................44
2.2.2 Water bath reaction........................................44
2.2.3 Solvothermal reaction......................................44
2.3 Characterization.............................................45
2.3.1 Single crystal X-ray diffraction...........................45
2.3.2 Powder X-ray diffraction...................................47
2.3.3 Fourier transform infrared spectroscopy....................48
2.3.4 Thermogravimetric analysis.................................49
2.3.5 Elemental analysis.........................................50
2.3.6 Solid-state cyclic voltammetry.............................50
2.3.7 Ultraviolet diffuse reflectance spectroscopy...............51
2.3.8 Brunauer-Emmett-Teller (BET) analyzer......................52
2.3.9 Electrical resistivity and Seebeck coefficient measurement .................................................................57
2.4 Chemical Lists...............................................59
Chapter 3 High-κ Samarium-Based Metal–Organic Framework for Gate Dielectric Applications
.................................................................60
3.1 Introduction.................................................60
3.2 Experimental section.........................................61
3.2.1 Materials and methods......................................61
3.2.2 Synthesis of [Sm2(bhc)(H2O)6]n (1).........................63
3.3 Results and Discussion.......................................64
3.3.1 Crystal structure..........................................64
3.3.2 Powder X-ray Diffraction and Thermogravimetric Analysis....67
3.3.3 Dielectric investigation...................................68
3.3.4 Electrical Conductivity Measurements.......................70
3.3.5 Impedance behavior.........................................71
3.3.6 Leakage Current Measurement................................73
3.4 Conclusion...................................................73
Chapter 4 Integration of a (–Cu–S–)n plane in a metal–organic framework affords high electrical conductivity...................75
4.1 Introduction.................................................75
4.2 Methods......................................................77
4.2.1 Electrical measurement and fabrication of single crystal...77
4.2.2 Electrochemical measurements...............................77
4.2.3 X-ray photoelectron spectroscopy measurements..............78
4.2.4 Details of DFT simulations.................................78
4.2.5 PXRD characterization......................................78
4.3 Result and Discussion........................................79
4.3.1 Synthesis of {[Cu2(6-Hmna)(6-mn)]·NH4}n....................79
4.3.2 Crystal structure..........................................82
4.3.3 Electrical conductivity measurement........................86
4.3.4 Bandgap investigations.....................................90
4.3.5 Electrochemical measurements...............................91
4.3.6 Theoretical DFT study of Cu-MOF............................92
4.4 Conclusion...................................................97
Chapter 5 MOF Driven Graphitic Carbon and Cu2S Nanosheets for Thermoelectric Energy Conversion.................................99
5.1 Introduction.................................................99
5.2 Experimental................................................100
5.3 Result and Discussion.......................................101
5.3.1 Thermoelectric properties of Cu-MOF.......................105
5.4 Conclusion..................................................108
Chapter 6 Summary and Conclusion...............................110
References......................................................112
Appendices......................................................129

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