臺灣博碩士論文加值系統

本實驗利用Graphene@ZnS和polyaniline/ZnS (P-ZnS) 奈米粒子光觸媒作為產氫的媒介，在第一部份，硫化鋅為核，用醋酸鋅和硫脲作為前驅物並以水熱法製備， 再以聚苯胺包覆在硫化鋅外層成為新的光觸媒，並以冷場發掃描式電子顯微鏡、X射線繞射分析儀、高解析電子顯微鏡、能量散佈光譜儀、化學分析電子能譜儀、反射式可見光光譜儀、產氫測試。以光觸媒分解犧牲劑產生氫氣，P-ZnS光觸媒能達到 6430 μmol h-1 g-1的產率。回收的光觸媒仍保有好的活性，回收觸媒三次後還是可以維持不錯的產氫效率。
第二部分中，硫化鋅為殼、石墨烯為核來製備光觸媒，石墨烯/摻雜鎳的硫化鋅光觸媒也以水熱法製備，摻雜後幫助電子電洞對的分離來加強光觸媒活性，從能量散佈光譜儀可在光觸媒中發現微量鎳的成分，鎳的摻雜有助於光誘發電子/電洞對的分離，表面積的增加有助於光觸媒與犧牲劑的接觸面積，未摻雜的石墨烯/硫化鋅光觸媒有5967 μmol h-1 g-1的產率，摻雜後的石墨烯/硫化鋅光觸媒摻雜鎳後產率可到達8683 μmol h－1g－1. 我們研究硫化鋅摻雜石墨烯後的表面化學、結晶性、光學性質、表面型態和光觸媒產氫的性質，以鎳摻雜硫化鋅修飾在石墨烯表面有助於使光觸媒形成好的分散性、增加表面積、好的吸收度和強化光電子/電洞對分離效果來增加光觸媒活性。
關鍵字: 光觸媒, 產氫, 硫化鋅, 聚苯胺, 石墨烯, 核殼結構, 鎳摻雜

Graphene@ZnS and polyaniline/ZnS (P-ZnS) nanoparticle were use as hydrogen production photocatalysts. In first part, ZnS nanoparticles were prepared as the core material by a solvothermal process with zinc acetate and thiourea as precursors. ZnS nanoparticles were encapsulated by polyaniline to make the composite photocatalysts. Properties of the photocatalysts were characterized by field-emission scanning electron microscope (FESEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), ultraviolet-visible diffuse reflectance spectroscopy (DRS), photoinduced current, and photocatalytic hydrogen evolution test. The photocatalytic activity of the catalysts was evaluated by splitting Na2S/Na2SO3 solution into H2. The optimized photocatalytic hydrogen production rates of P-ZnS nanoparticles reach 6430 μmol h-1 g-1, respectively. All the photocatalysts can be recycled. Recycled photocatalysts exhibit good hydrogen generation performance after being recycled for three times.
In second part, ZnS which mentioned above is use as the shell which fabricate on graphene nanosheet. Ni-doped graphene@ZnS photocatalysts for photocatalytic hydrogen production was also prepared by a solvothermal method. Doped Ni helps the separation of
the photon induced electron and hole pairs, hence enhances the photocatalytic activity. Energy- dispersive X-ray spectroscopy (EDX) analysis indicated that a small amount of Ni is loaded on the ZnS. Because of increased surface area of ZnS layer, enhanced separation of the photoinduced carriers by Ni-doping, and effective contact among sacrificial aqueous solution and the ZnS shell, The optimized photocatalytic hydrogen production rates of graphene@ZnS nanoparticles reach 5967 μmol h-1 g-1. And the graphene@Ni-doped ZnS nanocomposites are highly active photocatalysts for hydrogen evolution and the highest photocatalytic activity reaches 8683 μmol h－1g－1. Effects of introducing graphene, doping, and decorated ZnS on the surface chemistry, crystalline property, optical property, surface morphology, and photocatalytic hydrogen production performance were studied. Ni-doping and decorated ZnS on graphene improved the photocatalytic H2 production activity because of improved dispersing property, increased surface area, increased absorption, and enhanced transfer of photogenerated electrons.
Keywords: Photocatalysts, H2 Production, ZnS, PANI, Graphene, Core-shell, ZnS, graphene, Ni2+-doping

Content
摘要 II
ABSTRACT IV
CONTENT VII
FIGURE CONTENT IX
TABLE CONTENT XII

PART I GENERAL INTRODUCTION 1
CHAPTER 1 BACKGROUND AND MOTIVATION 1
1.1 Energy Shortage and Related Environment Concern 1
1.2 Hydrogen production 3
1.3 Water Spliting 5
CHAPTER 2 INTRODUCTION OF PHOTOCATALYST 6
2.1 Application of Photocatalyst 6
2.2 Conducting polymer 10
2.3 Graphene 17
2.4 Recycling of Photocatalysts 21
MOTIVATION 23
PART II METHODS 24
CHAPTER 3 EXPERIMENTAL METHODS AND PROCEDURES 24
3.1 Materials 24
3.2 Instrument 25
3.3 PREPARATION OF DOPED ZNS DECORATED GRAPHENE PHOTOCATALYSTS 26
3.4 PREPARATION OF P-ZNS COMPOSITE PHOTOCATALYST 27
3.5 Photocatalytic hydrogen production 28
3.6 Preparation of samples for photoelectrochemical test 28
3.7 Characterization 29
3.8 Nomenclature 30
3.8.1 Graphene@ZnS 30
3.8.2 ZnS@PANI 30
PART III RESULTS AND DISCUSSION 31
CHAPTER 4 POLYANILINE ENCAPSULATED ZNS AS PHOTOCATALYSTS FOR H2 PRODUCTION. 31
4.1. SURFACE MORPHOLOGY 31
4.2. Crystalline properties 35
4.3. Chemical property 37
4.4. Optical properties (DRS) 40
4.6. Dispersing stability 44
4.7. The reusability of photocatalyst 46
CHAPTER 5 ZNS DECORATED GRAPHENE AS PHOTOCATALYSTS 49
5.1. Surface morphology and dispersing property 49
5.2. Surface chemistry and crystal structure 54
5.3. Optical property 58
5.4. BET Surface Area 59
5.5. Photocatalytic H2 production activity and stability 62
5.6. Photoelectrochemical (PEC) property 67
CONCLUSION 70
REFERENCE 72

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