臺灣博碩士論文加值系統

由於鋰化合物有廣泛的應用(例如:充電電池、核融合以及飛機機殼之合金)導致近幾年鋰的使用量大幅增加，鋰金屬約三分之一分佈於陸地上，其餘則在海水中(0.17 mg/L)，由於需求甚大，陸地上資源漸逐漸不足，目前從海水中回收鋰的技術中需耗時數月，因此本研究為開發新的海水回收鋰之技術。
由於鋰(Li+)與氫離子(H+)具相似的離子密度，鋰鈦氧化物離子篩對Li+有相對較高的選擇性，利用固體反應(SS)與水熱法(HT)合成Li2TiO3與LiTi2O4鋰鈦氧化物，以鋰鈦氧化物離子篩(H2TiO3與H0.23Li0.77Ti2O4)回收Li+，此外，由於鋰鈦氧化物離子篩具光催化特性，而且在與氫離子交換後其吸收波長具紅移之現象(波長增加、頻率降低)，因此本研究為了解在回收Li+的同時，也探討光催化降解海水中污染物以及產生氫氣之可能性。
掃描式顯微鏡(SEM)分析發現以固體反應合成Li2TiO3與LiTi2O4之粒徑分布分別為0.2~0.4 μm與3~5 μm；而經過水熱合成法合成之Li2TiO3可得到更小的粒徑(0.1~0.3 μm)。經由NMR、XRD及同步輻射EXAFS的分析結果得知，在鋰金屬回收循環過程中並不會改變其化學結構與外觀，水熱法合成之離子篩具有較好的Li+回收率(22~28 mg Li+/g H2TiO3);以固體合成法合成的離子(Li2TiO3與LiTi2O4)回收率分別為20~25 與2~10%，在氫離子交換過程中，離子篩的鈦溶出量是幾乎可以忽略(〈0.1%)，且在經過三次循環，H2TiO3 的回收收效率仍能維持在82%。
亞甲基藍光降解實驗顯示Li2TiO3 (HT)在經過24小時的UV光照射，具92%的去除效果，而且水熱法的去除效果(4-21%)比固體合成法的效果(7~51%)更高，然而，離子篩在海水中的降解效率比在水中低，可能的原因為平均粒徑的增加，導致比表面積大幅下降。此外，利用水熱合成法合成之Li2TiO3具有較好的氫氣產率，鋰鈦氧化物離子篩具選擇性Li+回收能力，也具光催化產氫及光催化降解污染物之多重功能。

Lithium compounds have many applications (i.e., rechargeable batteries, nuclear fusion, and alloy of aircraft), leading to a highly increase of demand, however, the source of lithium is limited in the earth crusts. In spite of the low Li+ concentration in the seawater (0.17 mg/L), the potential resource can be as high as 2.5×〖10〗^14 kg. Therefore, developing an effective method for recovery of lithium from seawater is of increasing importance.
Protonated titanate ion-sieves (H2TiO3) was used to capture Li+ from seawater due to a similar ion density between lithium ions (Li+) and protons (H+). The hydrothermal (HT) and solid-state reaction (SS) methods were used to prepare Li2TiO3 and LiTi2O4. By UV/Vis spectroscopy, the lithium titanates have the aborption zones at 200-410 nm, and a red-shift for protonated titanates was observed. The main objective of this study was, therefore, to investigate the feasibility for the recovery of lithium from seawater using the protonated lithium titanate ion-sieves (H2TiO3 and H0.23Li0.77Ti2O4). In addition, it is also of interest to study whether the lithium titanates have a capability for photocatalytic splitting of H2O in seawater for H2 fuels as well as photocatalytic degradation of organic pollutants during the lithium recovery.
It is worth noting that the particle sizes of the LiTi2O4 (SS) and H0.23Li0.77Ti2O4 (SS) ion-sieves are in the range of 3-5 μm while the Li2TiO3 (SS) and H2TiO3 (SS) are much smaller (0.2-0.4 μm) which were determined by SEM. The Li2TiO3 (HT) and H2TiO3 (HT) ion-sieves have the average particle sizes of 0.1-0.3 μm. Since the surface exchange may play the primary role in the capture of Li+ from seawater, the larger ion-sieves turn out to possess a relatively low capability. Note that chemical structure of the lithium titanates was not perturbed during the consecutive exchanges of H+ and Li+, observed by XRD, Li7-nmr, and EXAFS. The Li2TiO3/H2TiO3 ion-sieve has negligible titanium dissolution during exchanges. After 3 cycles, the Li2TiO3/H2TiO3 (SS and HT) ion-sieve can sustain 82% of its best performance, while the LiTi2O4/H0.23Li0.77Ti2O4 (SS) one possesses 50-75%.
After a 24-h UV-Vis light irradiation, the unconverted MB (1-XMB) for the Li2TiO3 is 8% (or 92% conversion) approximately. The Li2TiO3 prepared by the hydrothermal method have better photcatalysis performances with the unconverted MB in the range of 4-21%, while the lithium titianate prepared by the SS method has the performance in the range of 7-51%. However, in seawater, relatively low conversions are found, which may be associated the fact that the mean diameter and polydispersity index of the lithium/protonated titanates in water are greater than those in seawater.
The lithium titanate ion-sieve catalysts that can also performance photocatalytic splitting of H2O to H2 during the lithium recovery processes has been preliminarily studied, suggesting that it is chemically feasible. It is worth to note that the regenerated Li2TiO3 prepared by the hydrothermal method has better yields of H2. Thus, in the cycles of the Li+ capture and regeneration, the lithium titanate ion-sieves can sustain desirable yields of H2 from photocatalytic splitting of H2O. Proceeding in this fashion, energy required for the lithium recovery processes may be self-supported. In addition, the concept developed in this work may be applied in the photocatalytic degradation of organic pollutants in waste or contaminated underground water. Selected metal ions therein may be captured by ion exchanges with the size-comparable ion-sieves.

摘要 I
ABSTRACT III
誌謝 VI
CONTENT VII
LIST OF FIGURES X
LIST OF TABLES XVII
CHAPTER 1 INTRODUCTION 1
CHAPTER 2 LITERATUE STUDIES 3
2.1 Recovery of Lithium 3
2.2 Manganese oxide ion sieve spinel 5
2.2.1 Synthesis of Tunnel and Layered Manganese Oxides 7
2.2.2 Solid-State Reactions 10
2.2.3 Extraction/insertion Reactions 10
2.2.4 Ion-sieves 13
2.2.5 Applications as Adsorbents 15
2.3 Ion-sieve Lithium Titanate 18
2.4 Photocatalysis 20
2.4.1 Characteristics of Photocatalysts 20
2.4.2 Photocatalytic Activity of Alkali Titanates 24
2.4.3 Photocatalytic Degradation of Pollutants 27
2.4.4 Photocatalytic Splitting of Water 28
CHAPTER 3 EXPERIMENTAL METHODS 30
3.1 Experimental Procedures 30
3.2 Preparations of Ion-sieves 32
3.3 Recovery of Lithium 33
3.4 Photocatalytic Splitting of Water and Degradation of Methylene Blue 35
3.5 Characterization of Ion-Sieves 37
3.5.1 X-ray Diffraction Spectroscopy 37
3.5.2 Field-emission Scanning Electron Microscopy 37
3.5.3 Fourier Transform Infrared Spectroscopy 37
3.5.4 Thermogravimetric Analysis 37
3.5.5 Solid-State Nuclear Magnetic Resonance Spectroscopy 38
3.5.6 Diffuse Reflectance Ultraviolet-Visible Spectroscopy 38
3.5.7 X-ray Absorption Spectroscopy 38
3.5.8 Brunauer-Emmett-Teller Spectroscopy 40
3.5.9 Inductively Coupled Plasma-mass Spectrometer 40
3.5.10 Dynamic Light Scattering 40
CHAPTER 4 RESULTS AND DISCUSSION 41
4.1 Recovery of Lithium from Seawater Using Lithium Titanium Oxide Ion-sieves Prepared by Solid-state Reaction Method 41
4.2 Recovery of Lithium from Seawater Using Lithium Titanium Oxide Ion-sieves Prepared by the Hydrothermal Method 65
4.3 Photocatalytic Degradation of Methylene Blue with ion-sieves 80
4.4 An Exploratory Research: Photocatalytic Generation of H2 from Seawater during the Lithium Recovery Processes Using the Titanate Ion-sieves 100
CHAPTER 5 CONSLUSIONS 107
REFERENCE 109
APPENDIX 122

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