本文選題：仿生制氫　切入點(diǎn)：光陽極　出處：《北京工業(yè)大學(xué)》2015年碩士論文

【摘要】：人工仿生制氫技術(shù)以取之不盡用之不竭的太陽能制取清潔高效的氫氣,對(duì)緩解能源危機(jī)、改善人類生存環(huán)境和實(shí)現(xiàn)可持續(xù)發(fā)展有重要意義。開發(fā)具有更高光生載流子分離效率和光氫轉(zhuǎn)換效率的鈦基膜光陽極是人工仿生制氫技術(shù)研究的重點(diǎn)之一。本論文研究利用飛秒激光沉積法制備了TiO2納米粒子膜,利用陽極氧化法制備了TiO2納米管光子晶體膜和TiO2納米棒陣列膜,并對(duì)所制得的TiO2納米管光子晶體膜和TiO2納米棒陣列膜進(jìn)行了EosinY染料敏化,進(jìn)而利用SEM、AFM、XPS、XRD、UV-Vis DRS等物理化學(xué)手段和光電流密度時(shí)間曲線、光電壓時(shí)間曲線和Mott-Schottky曲線等電化學(xué)手段對(duì)所制光電極的表面形貌、元素組成、晶型、光響應(yīng)性能和光電化學(xué)性能進(jìn)行了綜合分析。用飛秒激光沉積法制備出TiO2納米粒子膜,在較高靶室氧壓(1mbar)下沉積得到的TiO2納米粒子的平均直徑為240nm,且具有相對(duì)較大粒子間的空隙率,而在較低氧壓(0.1mbar)下制得的樣品平均粒徑為100nm,其粒子分布密度較大且粒徑分布較窄。隨著沉積時(shí)間的增長,更多的TiO2納米粒子聚集到Ti基底上,這在光電制氫過程中能夠產(chǎn)生更多光活性位。當(dāng)靶室氧壓為1mbar和沉積時(shí)間為3h,所制得的TiO2納米粒子膜經(jīng)500°C在空氣中熱處理后為純金紅石晶相,比在靶室真空條件下制得的混晶相樣品的光化學(xué)電性能好。用兩步陽極氧化法制備出TiO2納米管光子晶體膜,其在管長2μm的納米管陣列表面具有周期性蜂窩環(huán)狀結(jié)構(gòu),環(huán)邊長約為150nm,環(huán)壁厚約為40nm,所制TiO2納米管光子晶體膜在400~800nm區(qū)域出現(xiàn)光子晶體所特有的多次振蕩吸收峰,經(jīng)過水溶和醇溶EosinY 12小時(shí)的染料敏化后,樣品出現(xiàn)染料特征吸收峰。經(jīng)染料敏化得Ti O2納米管光子晶體電極的光電性能有很大提高,且醇溶EosinY染料敏化后的光子晶體光電性能提高幅度大于水溶EosinY,具有最高光電化學(xué)性能的樣品的染料敏化時(shí)間為8小時(shí)。用陽極氧化法通過控制升壓速率制備出TiO2納米棒陣列膜,納米棒直徑約為20-30nm,納米棒長度50-150nm。對(duì)其進(jìn)行12小時(shí)的醇溶EosinY染料敏化,敏化后的TiO2納米棒陣列膜在450-800nm處的吸光性有明顯提高,且光電化學(xué)性能有所提高�；谏鲜鲅芯繉�(duì)不同方法制備的鈦基膜電極的表面參數(shù)對(duì)光電流密度、光電壓以及染料敏化過程的影響進(jìn)行了綜合分析。在所制TiO2納米粒子膜、TiO2納米管光子晶體膜和Ti O2納米棒陣列膜中,膜厚對(duì)光電流影響最大,而對(duì)光電壓影響較小,其中管長為2μm的TiO2納米管光子晶體膜具有最大光電流密度。TiO2納米粒子膜由粒徑為100~240nm團(tuán)簇粒子構(gòu)成,具有最大的光電壓。相對(duì)于納米棒陣列膜,納米管光子晶體膜的表面蜂窩環(huán)狀結(jié)構(gòu)更有利于染料的吸附和鍵聯(lián)。
[Abstract]:Artificial bionic hydrogen production technology to inexhaustible solar energy to produce clean and efficient hydrogen, to alleviate the energy crisis, It is of great significance to improve human living environment and realize sustainable development. The development of titanium substrate photocathode with higher photovoltaic carrier separation efficiency and photohydrogen conversion efficiency is one of the emphases of artificial bionic hydrogen production technology. In this paper, TiO2 nanocrystalline films were prepared by femtosecond laser deposition. TiO2 nanotube photonic crystal film and TiO2 nanorod array film were prepared by anodic oxidation method. The TiO2 nanotube photonic crystal film and TiO2 nanorod array film were sensitized by EosinY dye. Then the surface morphology, elemental composition and crystal form of the photoelectrode were investigated by means of physical and chemical means, such as SEMMA-AFMS-XRDX DRS, photocurrent density time curve, photovoltage time curve and Mott-Schottky curve, etc. The photoresponse and photochemical properties of TiO2 nanoparticle films were synthesized by femtosecond laser deposition. The average diameter of the TiO2 nanoparticles deposited at a high oxygen pressure of 1 mb is 240 nm, and the porosity of the particles is relatively large. The average particle size of the sample was 100 nm under the condition of low oxygen pressure (0.1mb), and the particle density was higher and the particle size distribution was narrower. With the increase of deposition time, more TiO2 nanoparticles gathered on Ti substrate. When the oxygen pressure in the target chamber is 1mbar and the deposition time is 3 h, the prepared TiO2 nanoparticles film is pure rutile crystal phase after heat treatment in air at 500 擄C. The photonic crystal films of TiO2 nanotubes were prepared by two-step anodization method, and they had periodic honeycomb ring structure on the surface of nanotube arrays with 2 渭 m in length. The length of the ring side is about 150 nm, and the thickness of the ring wall is about 40 nm. The photonic crystal film of TiO2 nanotubes has several oscillatory absorption peaks unique to photonic crystals in the region of 400~800nm, and is sensitized by water solution and 12 hours of EosinY solution. The photovoltaic properties of TIO _ 2 nanotube photonic crystal electrode were greatly improved by dye sensitization. The photosensitized photonic crystal of alcohol-soluble EosinY dye is more effective than the water-soluble Eosin Y. the dye sensitization time of the sample with the highest photoelectrochemical property is 8 hours. The TiO2 nanorod array film was prepared by anodic oxidation method by controlling the voltage rise rate. The diameter of nanorods was about 20-30 nm, and the length of nanorods was 50-150 nm. The sensitized TiO2 nanorod arrays were sensitized with alcohol-soluble EosinY dyes for 12 hours. The absorptivity of TiO2 nanorod array films at 450-800nm was improved obviously. Based on the above research, the surface parameters of titanium substrate electrode prepared by different methods were compared with the optical current density. The effects of photovoltage and dye sensitization were comprehensively analyzed. In the photonic crystal films of TiO2 nanotubes and TIO 2 nanorods array films, the thickness of the films had the greatest effect on photocurrent, but little effect on the photovoltage. The TiO2 nanotube photonic crystal film with 2 渭 m tube length has the maximum photocurrent density. The TiO2 nanoparticles film is composed of 100~240nm cluster particles with the largest photovoltage. The honeycomb ring structure of nanotube photonic crystal film is more favorable for dye adsorption and bonding.
【學(xué)位授予單位】：北京工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TQ116.2
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本文編號(hào)：1678894