本文關鍵詞： 金屬有機框架結構模板 多孔材料 二硫化鉬 光催化產(chǎn)氫　出處：《鄭州大學》2017年碩士論文　論文類型：學位論文

【摘要】：自1972年Fujishima和Honda等人首次報道Pt-TiO_2電極上的水光解現(xiàn)象以來,半導體作為水分解催化劑的應用受到廣泛關注,此類研究中催化劑的合成尤為重要。金屬有機框架(MOFs)材料可以作為模板合成形貌可控、孔洞均勻、比表面積大的結構,在催化材料的制備方面逐漸展現(xiàn)出諸多優(yōu)勢。近年來,二硫化鉬因具有超高的催化活性和低廉的造價而頗具競爭力,與其他材料的復合迅速成為研究熱點。為了解決二硫化鉬基材料尺寸太大和活性位點不夠的問題,本文選擇兩個經(jīng)典的MOFs結構為模板合成得到基于二硫化鉬的復合材料,并將其應用于光、電催化分解水產(chǎn)氫的研究,證明MOFs作為模板能夠實現(xiàn)二硫化鉬基復合催化材料的可控合成,為此類材料的實際成產(chǎn)提供理論依據(jù)和研究基礎。具體工作內容如下:(1)利用NH_2-MIL-125(Ti)為前驅體,與硫脲、鉬酸鈉在高溫下制備出水熱法得到花狀的多孔MoS_2@TiO_2三維復合光催化劑,接著全面分析其結晶類型、微觀結構、組成元素及價態(tài),并對其光學性質和電學性質進行研究。在與光敏劑熒光素(Fl)和犧牲劑三乙醇胺(TEOA)共同構筑成三組分光催化體系后,考察了該催化體系的光催化產(chǎn)氫性能。此外,文章對影響體系產(chǎn)氫活性的因素進行篩選,證明在熒光素為光敏劑,10 vol%TEOA,丙酮與水1:3,p H=11,14.6 wt%Mo S2的條件下,該催化劑的產(chǎn)氫速率極高,可達10046μmol h~(-1)g~(-1)。同時,文章對產(chǎn)氫體系的穩(wěn)定性和電子傳輸過程進行較為深入的探究:循環(huán)產(chǎn)氫實驗表明,該復合光催化劑具有良好的產(chǎn)氫穩(wěn)定性,經(jīng)歷三次共33小時的循環(huán)后,體系的產(chǎn)氫效率并無明顯變化;一系列穩(wěn)態(tài)熒光和熒光壽命測試證明,在經(jīng)過可見光激發(fā)后,光敏劑通過還原猝滅將電子傳遞給催化劑,進行催化產(chǎn)氫反應。(2)利用金屬(Ni,Zn,Cu)摻雜的ZIF-67(Co)前驅體與硫脲、鉬酸鈉合成并篩選得到孔洞結構豐富的三維Cu_(0.9)Co_(2.1)S_4@MoS_2復合光催化劑,并對其進行一系列表征。該催化劑可以在純水相中進行穩(wěn)定催化,避免了使用有機溶劑帶來的二次污染。經(jīng)過對產(chǎn)氫條件的篩選,證明摻雜金屬銅(比例為Cu:Co=3:7)且二硫化鉬負載量為25.8 wt%的復合光催化劑,在TEOA含量為5.3vol%、p H=13的純水體系中,催化效果最佳,產(chǎn)氫量可以達到19058μmol h~(-1)g~(-1)。此外本論文中不僅對電子的傳輸渠道進行證明,也利用光電流響應實驗和電化學阻抗實驗對文中合成催化劑的成功復合進行說明驗證。
[Abstract]:Since the reported water photolysis phenomenon of Pt-TiO_2 on the electrode for the first time since 1972 Fujishima and Honda et al., application of semiconductor as water decomposition catalyst has attracted wide attention, synthesis catalyst in such studies is particularly important. Metal organic frameworks (MOFs) materials can be used as a template forming pore morphology controllable, uniform, large surface area structure in catalysis material preparation has gradually showed many advantages. In recent years, because of its ultra high catalytic activity of molybdenum disulfide and low cost and competitive, and other composite materials rapidly become a research hotspot. In order to solve the problem of too large and active sites of the problem of insufficient MoS2 based material size, this paper synthesized MoS2 Composite template based on the MOFs structure of the two classic, and applied to the study of catalytic decomposition of hydrogen light, electricity, proof of MOFs as a template to The controllable synthesis of MoS2 based composite materials, such as material of actual production and provide a theoretical basis and research basis. The specific works are as follows: (1) using NH_2-MIL-125 (Ti) as precursor, and thiourea, sodium molybdate prepared at high temperature water thermal method to obtain three-dimensional composite photocatalyst porous flower like MoS_2@TiO_2 then, a comprehensive analysis of the crystallization type, microstructure, composition and valence, and Study on its optical and electrical properties. With the photosensitizer fluorescein (Fl) and sacrifice triethanolamine (TEOA) to establish the three components of the photocatalytic system, the catalytic system of photocatalytic hydrogen production performance were investigated. In addition, the factors that affect the system of hydrogen production activity screening, demonstrated in fluorescein as photosensitizer, 10 vol%TEOA acetone and water 1:3, S2 P H=11,14.6 wt%Mo under the condition of high hydrogen production rate of the catalyst can be. Up to 10046 mol h~ (-1) g~ (-1). At the same time, the stability and the electron transfer process of hydrogen production system in a more in-depth inquiry: circulating hydrogen production experiments showed that the composite photocatalyst has good stability of hydrogen production, a total of 33 hours after three cycles, no hydrogen production efficiency system the obvious change; a series of fluorescence and fluorescence lifetime test proved that after the visible light excitation, the photosensitizer electron transfer quenching catalyst reduction, hydrogen production using a catalytic reaction. (2) the use of metal (Ni, Zn, Cu) doped ZIF-67 (Co) precursor and thiourea, sodium molybdate and synthesis screened Cu_ three-dimensional structure rich hole (0.9) Co_ (2.1) S_4@MoS_2 composite photocatalyst, and a series of characterization of the catalyst. The catalytic stability can be carried out in water phase, avoid pollution two bring. After the use of organic solvents on hydrogen production conditions of the screen That election, doping copper (Cu:Co=3:7 ratio) and the load of MoS2 Composite Photocatalyst wt% 25.8, the content of TEOA is 5.3vol%, P, H=13 in water system, the best catalytic effect, hydrogen yield can reach 19058 mol h~ (-1) g~ (-1). In addition, this thesis not only for transmission the electronic channels that use the photocurrent response and electrochemical impedance experiments on the synthesis of the composite catalyst is described successfully verified.

【學位授予單位】：鄭州大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36;TQ116.2

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