本文選題：犧牲模板 + 置換反應(yīng)��； 參考：《哈爾濱工業(yè)大學(xué)》2017年博士論文

【摘要】：納米材料制備技術(shù)的發(fā)展已使單一組分均勻地摻入復(fù)合材料成為可能,而且不同組分之間的協(xié)同作用可以賦予納米復(fù)合材料全新的功能�？煽匦蚊才c尺寸貴金屬納米顆粒的制備成為近年來的研究熱點,應(yīng)用涉及光學(xué)、傳感和電化學(xué)等多個領(lǐng)域。高的生產(chǎn)成本、還原反應(yīng)過程中污染物的引入、納米顆粒的團聚等問題的存在使貴金屬納米材料的應(yīng)用和推廣受到限制。本論文提出以中間價態(tài)過渡金屬氧化物(Cu_2O與Mn_3O_4)為犧牲模板制備Ag、Pt納米復(fù)合材料的方法,具有實驗條件溫和、原子經(jīng)濟等優(yōu)點,有利于高性能、高純度貴金屬納米材料的制備。本研究采用中間價態(tài)過渡金屬氧化物Cu_2O和Mn_3O_4作為貴金屬納米顆粒(Ag、Pt)的還原劑和成核位點,分別制備了Ag/Cu_2O納米復(fù)合材料、Pt/Mn_3O_4-rGO三元復(fù)合材料以及Ag/Ag_2S/Ag_3CuS_2三元復(fù)合材料,并且將多元貴金屬納米復(fù)合材料應(yīng)用于表面增強拉曼光譜(SERS)的分子檢測、可見光催化降解甲基橙和催化氧還原反應(yīng)(ORR)等多種領(lǐng)域。Cu_2O和Mn_3O_4為犧牲模板與Ag+或Pt4+反應(yīng),利用它們之間的電位差制備形貌和粒徑可控的貴金屬納米復(fù)合材料和多元復(fù)合材料,特別是在Ag/Cu_2O和Pt/Mn_3O_4-rGO多元復(fù)合材料的制備過程中置換反應(yīng)沒有進行徹底,因此納米復(fù)合材料能夠保持犧牲模板原有的三維形貌。此種方法制備出的Ag基及Pt基納米復(fù)合材料表面清潔,新穎而均一的微觀形貌能夠賦予貴金屬納米顆粒更優(yōu)良的催化和分子檢測性能。通過電沉積方法在氧化銦錫玻璃(ITO)表面制備分支狀Cu_2O晶體,Cu_2O與Ag+離子在不同酸(5-磺基水楊酸、檸檬酸、乳酸、樟腦磺酸)誘導(dǎo)下反應(yīng)生成Ag/Cu_2O復(fù)合材料,發(fā)現(xiàn)只有在5-磺基水楊酸的作用下可以使Ag納米粒子均勻地生長在Cu_2O基體上,原因可能是5-磺基水楊酸根與Ag+離子的絡(luò)合有利于Ag粒子的成核和生長。將Ag/Cu_2O作為SERS基底對亞甲基藍(MB)、羅丹明B(RhB)和生理濃度范圍內(nèi)的尿素分子進行拉曼檢測。結(jié)果表明,Ag/Cu_2O納米顆粒對MB和RhB的檢測限可以達到10-9 mol/L,通過尿素濃度和積分強度的關(guān)系曲線可實現(xiàn)尿素分子的痕量及定量檢測。將分支狀Cu_2O晶體與Na_2S反應(yīng)生成Cu_2O@Cu_7S_4核殼結(jié)構(gòu),用NH3·H_2O腐蝕Cu_2O核后生成Cu_7S_4殼,Cu_7S_4與Ag+離子發(fā)生置換反應(yīng)后生成玫瑰花狀A(yù)g/Ag_2S/Ag_3CuS_2三元納米復(fù)合材料,控制反應(yīng)時間和摻雜酸(檸檬酸、單寧酸、樟腦磺酸、苯甲酸)種類調(diào)節(jié)Ag/Ag_2S/Ag_3CuS_2納米復(fù)合材料的形貌,研究Ag/Ag_2S/Ag_3CuS_2納米復(fù)合材料作為SERS基底的分子檢測以及作為光催化劑和化學(xué)催化的多重性能。結(jié)果表明,Ag/Ag_2S/Ag_3CuS_2納米復(fù)合材料的SERS性能較Ag納米顆粒弱,但優(yōu)于Cu_7S_4。反應(yīng)10 min得到的Ag/Ag_2S/Ag_3CuS_2三元納米復(fù)合材料在可見光條件下催化降解甲基橙(MO)性能較理想,研究發(fā)現(xiàn)反應(yīng)過程中超氧陰離子自由基(·O2-)和空穴(h+)是三元納米復(fù)合材料的催化活性物種。在rGO表面生長均勻的Mn_3O_4納米粒子構(gòu)筑rGO-Mn_3O_4納米復(fù)合材料,然后rGO-Mn_3O_4與H_2Pt Cl6發(fā)生置換反應(yīng)生成Pt/Mn_3O_4-rGO三元復(fù)合材料。通過調(diào)節(jié)H_2Pt Cl6的用量可以改變Pt納米粒子的尺寸、分布和含量,比較了不同Pt含量的Pt/Mn_3O_4-rGO三元復(fù)合材料的ORR活性。當2~3 nm的Pt納米粒子均勻分布在rGO-Mn_3O_4載體上時,Pt的負載量為10.06 wt%,較20%的商業(yè)Pt/C顯示出更好ORR催化活性,表明所制備的Pt/Mn_3O_4-rGO納米復(fù)合材料在低Pt負載量時具有較強的電催化性能。
[Abstract]:The development of nano material preparation technology has made a single component evenly mixed into composite materials as possible, and the synergy between the different components can endow nano composite material. The new controllable morphology and size of noble metal nanoparticles preparation has become a research hotspot in recent years, the application relates to many fields of optical sensing andelectrochemistry. High production costs, introduction of pollutants in the process of reduction reaction, there are problems such as the aggregation of nanoparticles to the popularization and application of nano metal materials Limited. This thesis presents an intermediate valence transition metal oxides (Cu_2O and Mn_3O_4) as sacrificial template preparation method of Pt nano composite Ag the material, with mild experimental conditions, atom economy and other advantages, is conducive to high performance, high purity of noble metal nano material preparation. This study uses intermediate valence transition metal oxides Cu_2O and M N_3O_4 as the noble metal nanoparticles (Ag, Pt) of the reducing agent and the nucleation sites were prepared Ag/Cu_2O nano composite materials, composite materials three yuan three yuan composite material Pt/Mn_3O_4-rGO and Ag/Ag_2S/Ag_3CuS_2, and the application of multielement noble metal nanocomposites by surface enhanced Raman spectroscopy (SERS) molecular detection, visible light photocatalytic the catalytic degradation of methyl orange and oxygen reduction reaction (ORR) and other areas of.Cu_2O and Mn_3O_4 as sacrificial templates with Ag+ or Pt4+ reaction, poor preparation of noble metal nano particle size and morphology controllable composite materials and composite materials with potential between them, especially in the preparation process of replacement reaction in the Ag/Cu_2O and Pt/Mn_3O_4-rGO composite materials the system is not thorough, so nano composite materials can keep the original 3D sacrifice template. The preparation method of the Ag based and Pt based nano composite material Surface cleaning, morphology and uniform novel can detect the performance of noble metal nanoparticles gives better catalysis and molecular. By electrodeposition method on indium tin oxide glass (ITO) surface preparation of branched Cu_2O crystal, Cu_2O and Ag+ ions in different 5- acid (sulfosalicylic acid, citric acid, lactic acid, camphor sulfonic acid) induced reaction of Ag/Cu_2O composite material, found only in the 5- sulfosalicylic acid under the action of the Ag nanoparticles grown on Cu_2O substrate, may be due to complexation of 5- sulfosalicylic acid root and Ag+ ion facilitates the nucleation and growth of Ag particles. The Ag/Cu_2O will be used as SERS substrates for methylene blue (MB), Luo Danming B (RhB) and the physiological concentration range of urea molecules in Raman detection. The results showed that Ag/Cu_2O nanoparticles of MB and RhB of the detection limit can reach 10-9 mol/L, the relation curve of concentration of urea and integral strength Lines can be used to trace and quantitative detection of urea molecules. The branched Cu_2O crystal and Na_2S reaction of Cu_2O@Cu_7S_4 core-shell structure, formation of Cu_7S_4 shell with NH3 H_2O corrosion Cu_2O core, Cu_7S_4 and Ag+ ion replacement reaction generated after rosettelike Ag/Ag_2S/Ag_3CuS_2 three nano composite materials, controlling the reaction time and doping acid (citric acid, tannic acid, camphor sulfonic acid, benzoic acid) were regulating the types of Ag/Ag_2S/Ag_3CuS_2 nanocomposites, Ag/Ag_2S/Ag_3CuS_2 nano composite materials were used as substrates for the detection of molecular SERS as well as the photocatalytic performance of multi agent and chemical catalysis. The results show that the performance of SERS Ag/Ag_2S/Ag_3CuS_2 nanocomposites with Ag nanoparticles is weak, but the reaction is better than that of Cu_7S_4. 10 min Ag/Ag_2S/Ag_3CuS_2 three nanocomposites under visible light catalytic degradation of methyl orange (MO) ideal performance The study found that the reaction process of superoxide anion radical (O2-) and hole (h+) is the catalytic active species and three yuan of nano composites. The growth of Mn_3O_4 nanoparticles with uniform structure of rGO-Mn_3O_4 nano composite materials on the surface of rGO, rGO-Mn_3O_4 and H_2Pt and Cl6 put three yuan composite reaction by adjusting the H_2Pt Cl6 Pt/Mn_3O_4-rGO. The amount of Pt can change the particle size, distribution and content, compared with three yuan of composite materials with different content of Pt Pt/Mn_3O_4-rGO ORR Pt 2~3 nm activity. When the nanoparticles are evenly distributed on the rGO-Mn_3O_4 carrier, Pt loading is 10.06 wt%, compared with 20% commercial Pt/C showed better catalytic activity of ORR, which indicated that Pt/Mn_3O_4-rGO nanocomposites have strong electrocatalytic properties with low Pt loading.

【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TB383.1;O643.36

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