本文選題：二氧化鈦　切入點(diǎn)：氫　出處：《北京科技大學(xué)》2015年博士論文　論文類型：學(xué)位論文

【摘要】：氫在氧化物材料中的研究工作目前還很少,一般認(rèn)為氫很少與氧化物材料發(fā)生反應(yīng)。傳統(tǒng)上,氫對(duì)材料作用的研究起始于冶煉、酸洗、電鍍和焊接等過(guò)程中引起的金屬材料的氫致塑性損傷(氫脆)以及氫致裂紋及斷裂等危害,從而開(kāi)啟了人們對(duì)氫在金屬材料中的影響研究。而近期的研究表明,氫對(duì)一些半導(dǎo)體氧化物材料的電學(xué)、磁學(xué)、光學(xué)等性能都能起到非常顯著的影響。尤其針對(duì)二氧化鈦材料的研究,有越來(lái)越多的研究表明氫對(duì)二氧化鈦的光催化性能、電學(xué)性能等均有顯著的影響。本論文以金紅石型二氧化鈦材料為研究對(duì)象,對(duì)氫在二氧化鈦材料中的行為規(guī)律進(jìn)行研究。研究?jī)?nèi)容主要分為四個(gè)部分：氫的侵入、存在、擴(kuò)散和改性。結(jié)合實(shí)驗(yàn)和第一性原理計(jì)算,得出以下幾個(gè)結(jié)論： 1.研究了兩種不同的氫處理方式(高溫氣相氫處理和電化學(xué)氫處理)下二氧化鈦材料中的氫原子存在形式。通過(guò)實(shí)驗(yàn),尤其是通過(guò)第一性原理計(jì)算從實(shí)驗(yàn)和理論兩個(gè)方面研究了氫在二氧化鈦中的具體形式。在高溫氣相氫處理中,氫原子傾向于處在氧空位的位置；在電化學(xué)氫處理中,氫原子傾向于處于氧原子的八面體間隙位置中。處于氧空位上的氫原子在晶體中是得電子的,并呈電負(fù)性；而處于間隙位置的氫原子是失電子的,呈現(xiàn)電正性,并與最近的氧原子形成OH鍵。同時(shí),對(duì)比二氧化鈦的結(jié)構(gòu)變化,發(fā)現(xiàn)氧空位對(duì)二氧化鈦晶格參數(shù)的影響最大,其次是間隙氫原子,影響最小的是氧空位上的氫原子。 2.通過(guò)對(duì)不同溫度和在不同退火時(shí)間的氫處理的二氧化鈦樣品,以及在不同溫度下的氘氣的滲透率來(lái)對(duì)氫在二氧化鈦中的擴(kuò)散行為進(jìn)行研究。研究發(fā)現(xiàn)隨著氫處理時(shí)間的增加,二氧化鈦樣品中的氫含量也隨著增加。當(dāng)經(jīng)過(guò)50小時(shí)的氫處理樣品中的氫原子達(dá)到飽和后,氫含量趨于穩(wěn)定。氫處理溫度在200到1000攝氏度的溫度范圍內(nèi),溫度越高,二氧化鈦中的氫含量也越大。同時(shí),氫在二氧化鈦陶瓷和單晶材料中的擴(kuò)散也存在差異,在溫度較低時(shí),二氧化鈦陶瓷中的氫含量較高。而在溫度較高時(shí),二氧化鈦單晶中的氫含量較高。通過(guò)氫在二氧化鈦薄膜中的滲透速率還計(jì)算出了氫在二氧化鈦薄膜材料的滲透能。 3.二氧化鈦的氫致改性研究主要從三個(gè)方面：電學(xué)、光學(xué)和親疏水性。對(duì)電學(xué)性能的研究,發(fā)現(xiàn)通過(guò)氫處理能夠讓二氧化鈦的電導(dǎo)增加,使材料從半導(dǎo)體向?qū)w轉(zhuǎn)變；對(duì)光學(xué)性能的研究,發(fā)現(xiàn)氫處理能夠調(diào)控二氧化鈦的能帶結(jié)構(gòu),使材料的帶隙減小并對(duì)可見(jiàn)光波段的吸收增強(qiáng)；對(duì)親疏水性的研究,發(fā)現(xiàn)氫處理能增強(qiáng)二氧化鈦表面的疏水性。 通過(guò)以上對(duì)氫在二氧化鈦材料的行為研究,能夠進(jìn)一步擴(kuò)展二氧化鈦材料在環(huán)境保護(hù)、新能源等領(lǐng)域的開(kāi)發(fā)和應(yīng)用。同時(shí)也為氫在其他氧化物材料中的行為規(guī)律的研究提供實(shí)驗(yàn)和理論參考,為其它氧化物材料的開(kāi)發(fā)應(yīng)用提供幫助。
[Abstract]:Research work on hydrogen in oxide materials is still rare, and it is generally believed that hydrogen rarely reacts with oxide materials. Traditionally, the study of hydrogen's effect on materials began with smelting, pickling and pickling. Hydrogen induced plastic damage (hydrogen embrittlement) and hydrogen induced cracks and fractures in metal materials caused by electroplating and welding have opened up the study of the influence of hydrogen on metal materials. Hydrogen has a significant effect on the electrical, magnetic and optical properties of some semiconductor oxide materials. In this thesis, the behavior of hydrogen in titanium dioxide materials is studied. The research contents are divided into four parts: the invasion of hydrogen, the existence of hydrogen, the existence of hydrogen, and so on. Diffusion and modification. Combined with experiments and first-principles calculations, the following conclusions are drawn:. 1. The existence forms of hydrogen atoms in titanium dioxide materials under two different hydrogen treatment methods (high temperature gas phase hydrogen treatment and electrochemical hydrogen treatment) have been studied. In particular, the specific forms of hydrogen in titanium dioxide have been studied from both experimental and theoretical aspects through first-principle calculations. In high temperature gas phase hydrogen treatment, hydrogen atoms tend to be in the position of oxygen vacancy, and in electrochemical hydrogen treatment, Hydrogen atoms tend to be in the octahedron gap of oxygen atoms. Hydrogen atoms in oxygen vacancies are electronegativity in crystals, while hydrogen atoms in the gap position are electron-lost and electronpositive. At the same time, compared with the structural changes of titanium dioxide, it is found that the oxygen vacancy has the greatest influence on the lattice parameters of titanium dioxide, followed by the interstitial hydrogen atom, and the hydrogen atom on the oxygen vacancy is the least. 2. The diffusion behavior of hydrogen in titanium dioxide was studied by the permeability of hydrogen treated at different temperature and annealing time, and deuterium gas at different temperature. It is found that the diffusion behavior of hydrogen in titanium dioxide increases with the increase of hydrogen treatment time. The hydrogen content in the titanium dioxide sample also increases. When the hydrogen atom in the sample reaches saturation after 50 hours of hydrogen treatment, the hydrogen content tends to stabilize. The higher the temperature, the higher the hydrogen treatment temperature is in the range of 200 to 1000 degrees Celsius. At the same time, the diffusion of hydrogen in titanium dioxide ceramics and single crystal materials is also different. At lower temperature, the hydrogen content in titanium dioxide ceramics is higher, but at higher temperature, the content of hydrogen in titanium dioxide ceramics is higher than that in titanium dioxide ceramics. The hydrogen content in titanium dioxide single crystal is high and the permeation energy of hydrogen in titanium dioxide thin film is calculated by the permeation rate of hydrogen in titanium dioxide film. 3. The research of hydrogen induced modification of titanium dioxide is mainly from three aspects: electricity, optics and hydrophobicity. It is found that the conductivity of titanium dioxide can be increased by hydrogen treatment, and the material can be changed from semiconductor to conductor; It is found that hydrogen treatment can regulate the energy band structure of titanium dioxide, decrease the band gap and enhance the absorption of visible light wave band, and the hydrophobicity can enhance the hydrophobicity of titanium dioxide surface. Through the above research on the behavior of hydrogen in titanium dioxide materials, it is possible to further expand the environmental protection of titanium dioxide materials. The development and application of new energy and other fields also provide experimental and theoretical reference for the study of the behavior of hydrogen in other oxide materials, and provide help for the development and application of other oxide materials.
【學(xué)位授予單位】：北京科技大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：TQ134.11

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