二氧化鈦光陽極體系優(yōu)化及太陽能光電化學(xué)分解水制氫應(yīng)用
發(fā)布時(shí)間：2018-10-18 15:45
【摘要】：隨著人們對(duì)太陽能-氫能這一轉(zhuǎn)化過程關(guān)注的日益增加,光電化學(xué)(PEC)分解水制氫技術(shù)逐步在解決能源危機(jī)以及能源消耗方面取得了巨大進(jìn)展。研究并拓展高效穩(wěn)定光電極,使其具有可見光響應(yīng)能力進(jìn)而提高對(duì)太陽能利用率,這是優(yōu)化PEC分解水制氫體系的先決條件。作為一類優(yōu)異的光電極候選材料,二氧化鈦(TiO_2)具有諸多優(yōu)點(diǎn),例如高光催化活性,持久穩(wěn)定性,低成本和易合成等。同時(shí),TiO_2也存在一些顯著缺點(diǎn),主要因?yàn)槠鋬H能對(duì)紫外光響應(yīng)(僅占太陽光的5%)并且光生電子-空穴對(duì)極易復(fù)合,所以單一TiO_2光電極的這些缺點(diǎn)已成為限制其工業(yè)應(yīng)用的關(guān)鍵問題。目前已有多種方法被開發(fā)并用于提高TiO_2光電極的整體PEC效率,其中如何抑制PEC水分解制氫過程中的光生電子-空穴對(duì)復(fù)合是解決如上問題的主要思路。目前具體改進(jìn)措施包括貴金屬負(fù)載,缺陷引入,高分子材料復(fù)合和元素?fù)诫s等�；谝陨涎芯勘尘�,本論文提出了如下三種TiO_2光電極優(yōu)化方案并實(shí)現(xiàn)了高性能PEC新體系的構(gòu)建:(1)首先我們通過多種合成方法制備了Au@CdS/RGO/TiO_2光電極,并通過SEM、TEM、Raman和XPS等表征證明了該獨(dú)特異質(zhì)結(jié)光電極已被成功制備。本工作首次將Au@CdS核-殼納米粒子引入TiO_2光電極,以此賦予了TiO_2以可見光響應(yīng)能力和等離體性能。此外,處于TiO_2和Au@CdS核-殼納米顆粒中間的氧化還原石墨烯(RGO)薄膜在提高光生電荷傳輸速率方面發(fā)揮了重要作用。(2)通過原位光電還原法,我們?cè)贐iOCl納米片表面成功修飾了等離子體Bi納米顆粒(Bi/BiOCl),且將Bi/BiOCl作為光電陰極應(yīng)用于TiO_2 Bi/BiOCl PEC太陽能水分解體系。同時(shí),我們探討了PEC性能與Bi/BiOCl復(fù)合比例之間的關(guān)系,并通過密度泛函理論證明了電荷是由Bi簇轉(zhuǎn)移至BiOCl(001)面。根據(jù)IV曲線和電荷注入效率數(shù)據(jù),我們進(jìn)一步優(yōu)化了Bi/BiOCl光電陰極。該體系中優(yōu)異的PEC分解水效果主要?dú)w因于Bi納米顆粒的電荷轉(zhuǎn)移增強(qiáng)和表面等離子體共振(SPR)效應(yīng)雙重作用。(3)為了提高太陽光的利用和光電極的穩(wěn)定性,我們使用有機(jī)聚合物多巴胺進(jìn)一步敏化TiO_2光電極。在該體系中,我們將Bi-AgIn5S8負(fù)載于TiO_2光電極表面以實(shí)現(xiàn)其可見響應(yīng)能力。在此基礎(chǔ)上,進(jìn)一步通過水熱法制備了TiO_2/Bi-AgIn5S8/PDA異質(zhì)結(jié)光電極。最后討論了TiO_2/Bi-AgIn5S8/PDA異質(zhì)結(jié)光電極的PEC分解水的機(jī)理,并分析了影響其PEC轉(zhuǎn)換效率的因素。
[Abstract]:With the increasing attention to the conversion process of solar energy and hydrogen energy, photochemical (PEC) has gradually made great progress in resolving the energy crisis and energy consumption. It is a prerequisite to optimize the hydrogen production system of PEC decomposition water by studying and extending the high efficient and stable photoelectrode, which has the ability to respond to visible light and improve the utilization ratio of solar energy. As a kind of excellent optoelectronic candidate material, titanium dioxide (TiO_2) has many advantages, such as high photocatalytic activity, durable stability, low cost and easy synthesis. At the same time, TiO_2 also has some obvious disadvantages, mainly because it can only respond to ultraviolet light (only 5% of solar light) and photogenerated electron-hole pair is easy to recombine. So these disadvantages of single TiO_2 photoelectrode have become the key problem of limiting its industrial application. At present, many methods have been developed to improve the overall PEC efficiency of the TiO_2 photoelectrode, among which how to suppress the photogenerated electron-hole pair recombination in the process of the hydrogen production by the water decomposition of PEC is the main way to solve the above problem. At present, the specific improvement measures include noble metal loading, defect introduction, polymer composite and element doping. Based on the above research background, this paper proposes three kinds of TiO_2 optoelectronic pole optimization schemes and realizes the construction of a new high performance PEC system. (1) first, we have prepared the Au@CdS/RGO/TiO_2 photoelectrode by a variety of synthesis methods. The unique heterojunction photoelectrode has been successfully fabricated by SEM,TEM,Raman and XPS characterization. In this work, Au@CdS core-shell nanoparticles were introduced into the TiO_2 photoelectrode for the first time, thus giving TiO_2 the ability of visible light response and in vitro performance. In addition, redox graphene (RGO) films in the middle of TiO_2 and Au@CdS core-shell nanoparticles play an important role in increasing photocharge transfer rate. (2) in situ photoreduction, Plasma Bi nanoparticles (Bi/BiOCl) were successfully modified on the surface of BiOCl nanoparticles and Bi/BiOCl was used as photocathode in the TiO_2 Bi/BiOCl PEC solar water decomposition system. At the same time, we discuss the relationship between PEC performance and Bi/BiOCl composition ratio, and prove that the charge is transferred from Bi cluster to BiOCl (001) surface by density functional theory. Based on the IV curve and charge injection efficiency data, we further optimize the Bi/BiOCl photocathode. The excellent water decomposition effect of PEC in this system is mainly attributed to the double effects of the charge transfer enhancement of Bi nanoparticles and the (SPR) effect of surface plasmon resonance. (3) in order to improve the utilization of solar light and the stability of photoelectrode, We use organic polymer dopamine to further sensitize the TiO_2 photoelectrode. In this system, Bi-AgIn5S8 is loaded on the surface of TiO_2 photoelectrode to realize its visible response ability. On this basis, TiO_2/Bi-AgIn5S8/PDA heterojunction photoelectrodes were prepared by hydrothermal method. Finally, the mechanism of the PEC decomposition of the TiO_2/Bi-AgIn5S8/PDA heterojunction photoelectrode is discussed, and the factors affecting the PEC conversion efficiency are analyzed.
【學(xué)位授予單位】：江蘇大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ116.2;O646.5
本文編號(hào)：2279596
[Abstract]:With the increasing attention to the conversion process of solar energy and hydrogen energy, photochemical (PEC) has gradually made great progress in resolving the energy crisis and energy consumption. It is a prerequisite to optimize the hydrogen production system of PEC decomposition water by studying and extending the high efficient and stable photoelectrode, which has the ability to respond to visible light and improve the utilization ratio of solar energy. As a kind of excellent optoelectronic candidate material, titanium dioxide (TiO_2) has many advantages, such as high photocatalytic activity, durable stability, low cost and easy synthesis. At the same time, TiO_2 also has some obvious disadvantages, mainly because it can only respond to ultraviolet light (only 5% of solar light) and photogenerated electron-hole pair is easy to recombine. So these disadvantages of single TiO_2 photoelectrode have become the key problem of limiting its industrial application. At present, many methods have been developed to improve the overall PEC efficiency of the TiO_2 photoelectrode, among which how to suppress the photogenerated electron-hole pair recombination in the process of the hydrogen production by the water decomposition of PEC is the main way to solve the above problem. At present, the specific improvement measures include noble metal loading, defect introduction, polymer composite and element doping. Based on the above research background, this paper proposes three kinds of TiO_2 optoelectronic pole optimization schemes and realizes the construction of a new high performance PEC system. (1) first, we have prepared the Au@CdS/RGO/TiO_2 photoelectrode by a variety of synthesis methods. The unique heterojunction photoelectrode has been successfully fabricated by SEM,TEM,Raman and XPS characterization. In this work, Au@CdS core-shell nanoparticles were introduced into the TiO_2 photoelectrode for the first time, thus giving TiO_2 the ability of visible light response and in vitro performance. In addition, redox graphene (RGO) films in the middle of TiO_2 and Au@CdS core-shell nanoparticles play an important role in increasing photocharge transfer rate. (2) in situ photoreduction, Plasma Bi nanoparticles (Bi/BiOCl) were successfully modified on the surface of BiOCl nanoparticles and Bi/BiOCl was used as photocathode in the TiO_2 Bi/BiOCl PEC solar water decomposition system. At the same time, we discuss the relationship between PEC performance and Bi/BiOCl composition ratio, and prove that the charge is transferred from Bi cluster to BiOCl (001) surface by density functional theory. Based on the IV curve and charge injection efficiency data, we further optimize the Bi/BiOCl photocathode. The excellent water decomposition effect of PEC in this system is mainly attributed to the double effects of the charge transfer enhancement of Bi nanoparticles and the (SPR) effect of surface plasmon resonance. (3) in order to improve the utilization of solar light and the stability of photoelectrode, We use organic polymer dopamine to further sensitize the TiO_2 photoelectrode. In this system, Bi-AgIn5S8 is loaded on the surface of TiO_2 photoelectrode to realize its visible response ability. On this basis, TiO_2/Bi-AgIn5S8/PDA heterojunction photoelectrodes were prepared by hydrothermal method. Finally, the mechanism of the PEC decomposition of the TiO_2/Bi-AgIn5S8/PDA heterojunction photoelectrode is discussed, and the factors affecting the PEC conversion efficiency are analyzed.
【學(xué)位授予單位】：江蘇大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ116.2;O646.5
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