Pt基催化劑的制備及在甲醇電化學(xué)氧化中的應(yīng)用研究
發(fā)布時間：2018-12-15 07:41
【摘要】：近年來,直接甲醇燃料電池陽極Pt基催化劑的研究受到了廣泛關(guān)注。Pt催化劑被認(rèn)為是最有效的甲醇燃料電池催化劑,但因其資源稀缺、價格昂貴、且容易吸附中間產(chǎn)物CO而中毒失活,制約了燃料電池的發(fā)展。第二種金屬(如Ru、Rh、Sn、Ni、Co等)的加入,不僅可改變Pt的表面電學(xué)性質(zhì),還可在較低電勢下提供含氧物種,增強其抗CO毒化能力,從而提高催化劑的活性和穩(wěn)定性,此外,還可減少Pt的用量,降低催化劑成本。本論文以混酸(HF與HNO3)刻蝕法制得的高比表面積的刻蝕碳化硅(SiCetched)為基底,以H2PtCl6·2H2O、NiCl2·6H2O、CoCl2·6H2O為前驅(qū)物,通過化學(xué)還原法制備了一系列PtNi/SiCetched、PtCo/SiCetched型雙金屬催化劑,研究了不同PtN、PtCo比例對催化劑在甲醇電氧化中催化性能的影響；此外,以SiCetched和摻銻氧化錫(antimony tin oxide, ATO)混合物為基底,制備了不同ATO加入量的Pt基催化劑,研究了基底中ATO的加入量對催化劑的甲醇催化性能的影響。本論文共分為六章,主要研究內(nèi)容及結(jié)論如下：第一章主要從Pt基催化劑的活性組分和載體兩方面,對直接甲醇燃料電池(DMFC)陽極催化劑的研究進展進行綜述,并介紹了本論文的選題意義、研究內(nèi)容和創(chuàng)新點。第二章對本論文所用到的實驗儀器,藥品以及催化劑的制備、表征方法等進行了詳細(xì)說明。第三章以SiCetched為載體,制備了一系列不同摩爾比的PtNi/SiCetched催化劑,通過UV、XRD、TEM、CV和CA手段對催化劑進行表征。結(jié)果表明,PtNi/SiCetched催化劑在焙燒過程中,Ni會摻雜到Pt的面心立方晶格中,形成PtNi合金,當(dāng)n(Pt):n(Ni)=3時,PtNi/SiCetched催化劑對甲醇電氧化的催化活性最好,電流密度是Pt/SiCetched型催化劑的3倍左右,Ni的加入可以明顯的改善Pt催化劑的催化活性和穩(wěn)定性。第四章以SiCetched為載體,制備了PtCo/SiCetahed催化劑,然后用XRD、 TEM、CV和CA手段對其表征。結(jié)果表明,當(dāng)n(Pt):n(Co)=1時,PtCo/SiCetehed型催化劑對甲醇的催化活性和穩(wěn)定性最好,Pt-Co合金可以削弱Pt-CO鍵的強度,改善催化劑的抗CO中毒能力。第五章以摻雜ATO的SiCetched為復(fù)合載體,制備了不同基底的Pt基催化劑：Pt/SiCetched、Pt/(SiCetched+ATO)和Pt/ATO。通過電化學(xué)方法對其進行了表征,研究了復(fù)合載體中ATO與SiCetched的比例對催化效果的影響。研究結(jié)果表明,與Pt/SiCetetched、 Pt/ATO型催化劑相比,以復(fù)合材料為載體得到的Pt/(SiCetched+ATO)催化劑對甲醇電氧化的催化效果最好,說明ATO的加入有效的提高了催化劑的穩(wěn)定性。第六章對本論文進行了總結(jié),并提出了論文中亟待解決的問題及展望。
[Abstract]:In recent years, the research of direct methanol fuel cell anode Pt catalyst has received extensive attention. Pt catalyst is considered as the most effective methanol fuel cell catalyst, but its resource is scarce and the price is expensive. Moreover, it is easy to adsorb intermediate product CO and become toxic and inactivated, which restricts the development of fuel cell. The addition of the second metal (such as Ru,Rh,Sn,Ni,Co, etc.) can not only change the surface electrical properties of Pt, but also provide oxygen-containing species at lower potential, and enhance its ability to resist CO poisoning, thus improving the activity and stability of the catalyst. In addition, the amount of Pt can be reduced and the cost of catalyst reduced. In this paper, a series of PtNi/SiCetched, was prepared by chemical reduction method using high specific surface area etching silicon carbide (SiCetched) prepared by mixed acid (HF and HNO3) etching method and H2PtCl6 2H 2O NiCl 26 H 2O CoCl 2 6H2O as precursor. The effects of different PtN,PtCo ratios on the catalytic performance of PtCo/SiCetched bimetallic catalysts in methanol electrooxidation were studied. In addition, based on the mixture of SiCetched and antimony doped tin oxide (antimony tin oxide, ATO), different amount of ATO based catalysts were prepared. The effect of the amount of ATO in the substrate on the catalytic performance of methanol was studied. This thesis is divided into six chapters. The main research contents and conclusions are as follows: in chapter 1, the research progress of (DMFC) anode catalyst for direct methanol fuel cell (DMFC) is reviewed from the aspects of active component and support of (DMFC) catalyst. It also introduces the significance, research content and innovation of this paper. In the second chapter, the experimental instruments, preparation and characterization methods of drugs and catalysts are described in detail. In chapter 3, a series of PtNi/SiCetched catalysts with different molar ratios were prepared using SiCetched as the support. The catalysts were characterized by UV,XRD,TEM,CV and CA. The results show that during the calcination of PtNi/SiCetched catalyst, Ni will be doped into the face centered cubic lattice of Pt to form PtNi alloy. When n (Pt): n (Ni) = 3, the catalytic activity of PtNi/SiCetched catalyst for methanol electrooxidation is the best. The current density is about 3 times of that of Pt/SiCetched catalyst. The addition of Ni can obviously improve the catalytic activity and stability of Pt catalyst. In chapter 4, PtCo/SiCetahed catalyst was prepared on SiCetched and characterized by XRD, TEM,CV and CA. The results showed that when n (Pt): n (Co) = 1, the catalytic activity and stability of PtCo/SiCetehed type catalyst for methanol was the best, and Pt-Co alloy could weaken the strength of Pt-CO bond and improve the resistance to CO poisoning of the catalyst. In chapter 5, using SiCetched doped with ATO as composite support, different substrates of Pt based catalysts, Pt/SiCetched,Pt/ (SiCetched ATO) and Pt/ATO., were prepared. The effect of the ratio of ATO to SiCetched on the catalytic performance was studied by electrochemical method. The results showed that compared with the Pt/SiCetetched, Pt/ATO catalyst, the Pt/ (SiCetched ATO) catalyst supported on the composite material had the best catalytic effect on methanol electrooxidation, which indicated that the addition of ATO could effectively improve the stability of the catalyst. The sixth chapter summarizes this paper, and puts forward the problems and prospects to be solved.
【學(xué)位授予單位】：山西大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：O643.36;TM911.4
本文編號：2380273
[Abstract]:In recent years, the research of direct methanol fuel cell anode Pt catalyst has received extensive attention. Pt catalyst is considered as the most effective methanol fuel cell catalyst, but its resource is scarce and the price is expensive. Moreover, it is easy to adsorb intermediate product CO and become toxic and inactivated, which restricts the development of fuel cell. The addition of the second metal (such as Ru,Rh,Sn,Ni,Co, etc.) can not only change the surface electrical properties of Pt, but also provide oxygen-containing species at lower potential, and enhance its ability to resist CO poisoning, thus improving the activity and stability of the catalyst. In addition, the amount of Pt can be reduced and the cost of catalyst reduced. In this paper, a series of PtNi/SiCetched, was prepared by chemical reduction method using high specific surface area etching silicon carbide (SiCetched) prepared by mixed acid (HF and HNO3) etching method and H2PtCl6 2H 2O NiCl 26 H 2O CoCl 2 6H2O as precursor. The effects of different PtN,PtCo ratios on the catalytic performance of PtCo/SiCetched bimetallic catalysts in methanol electrooxidation were studied. In addition, based on the mixture of SiCetched and antimony doped tin oxide (antimony tin oxide, ATO), different amount of ATO based catalysts were prepared. The effect of the amount of ATO in the substrate on the catalytic performance of methanol was studied. This thesis is divided into six chapters. The main research contents and conclusions are as follows: in chapter 1, the research progress of (DMFC) anode catalyst for direct methanol fuel cell (DMFC) is reviewed from the aspects of active component and support of (DMFC) catalyst. It also introduces the significance, research content and innovation of this paper. In the second chapter, the experimental instruments, preparation and characterization methods of drugs and catalysts are described in detail. In chapter 3, a series of PtNi/SiCetched catalysts with different molar ratios were prepared using SiCetched as the support. The catalysts were characterized by UV,XRD,TEM,CV and CA. The results show that during the calcination of PtNi/SiCetched catalyst, Ni will be doped into the face centered cubic lattice of Pt to form PtNi alloy. When n (Pt): n (Ni) = 3, the catalytic activity of PtNi/SiCetched catalyst for methanol electrooxidation is the best. The current density is about 3 times of that of Pt/SiCetched catalyst. The addition of Ni can obviously improve the catalytic activity and stability of Pt catalyst. In chapter 4, PtCo/SiCetahed catalyst was prepared on SiCetched and characterized by XRD, TEM,CV and CA. The results showed that when n (Pt): n (Co) = 1, the catalytic activity and stability of PtCo/SiCetehed type catalyst for methanol was the best, and Pt-Co alloy could weaken the strength of Pt-CO bond and improve the resistance to CO poisoning of the catalyst. In chapter 5, using SiCetched doped with ATO as composite support, different substrates of Pt based catalysts, Pt/SiCetched,Pt/ (SiCetched ATO) and Pt/ATO., were prepared. The effect of the ratio of ATO to SiCetched on the catalytic performance was studied by electrochemical method. The results showed that compared with the Pt/SiCetetched, Pt/ATO catalyst, the Pt/ (SiCetched ATO) catalyst supported on the composite material had the best catalytic effect on methanol electrooxidation, which indicated that the addition of ATO could effectively improve the stability of the catalyst. The sixth chapter summarizes this paper, and puts forward the problems and prospects to be solved.
【學(xué)位授予單位】：山西大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：O643.36;TM911.4
【參考文獻】
相關(guān)期刊論文 前1條
1 ;Carbon nanotubes-Nafion composites as Pt-Ru catalyst support for methanol electro-oxidation in acid media[J];Journal of Natural Gas Chemistry;2009年02期
，本文編號：2380273
本文鏈接：http://sikaile.net/kejilunwen/huagong/2380273.html
最近更新
教材專著
