本文選題：直接乙醇燃料電池 + 陽極催化劑　； 參考：《福州大學(xué)》2014年博士論文

【摘要】：直接乙醇燃料電池(DEFC)是一種非常有前景的燃料電池技術(shù),有望應(yīng)用于移動電子設(shè)備、電動汽車和發(fā)電站等。目前阻礙DEFC應(yīng)用發(fā)展的主要原因是陽極催化劑的催化反應(yīng)活性低并且價格高昂。本文主要尋找DEFC陽極催化劑的新材料和新制備方法,利用物理表征所制備的不同催化劑材料具有的合金化程度、平均粒徑、形貌、結(jié)構(gòu)和成分組成等物理特性,并研究催化劑的物理特性與對電化學(xué)性能之間的構(gòu)效關(guān)系,得到以下主要結(jié)果：以MnOx-CNTs復(fù)合材料作為載體,采用微波乙二醇還原制備Pt/MnOx-CNTs催化劑。研究表明：Pt納米顆粒均勻地分散在載體上,其平均粒徑2.2nm。催化劑中Mn元素以多種價態(tài)形式存在,有利于溶液中H+離子的傳遞；MnOx-CNTs復(fù)合載體中MnOx與CNTs最優(yōu)的質(zhì)量含量比為1：1,Pt/MnOx-CNTs (1:1)催化劑在酸性介質(zhì)中對乙醇電催化氧化的峰電流密度為1141.4 mA mg-1 Pt,是Pt催化劑(626.4 mA mg-1 Pt)的1.8倍,MnOx在乙醇陽極氧化過程中即可以促進(jìn)脫氫反應(yīng),又能夠增加含氧物種,明顯促進(jìn)了除去催化劑表面中毒中間產(chǎn)物能力。選擇低成本Pd作為基體,通過微波乙二醇法還原制備PdM/C (M=Te, Sb)二元催化劑,研究表明：PdTex/C和PdSbx/C催化劑中存在合金相；加入Te和Sb均能增加催化劑表面含氧物種,提高催化劑對毒性中間產(chǎn)物的氧化除去,促進(jìn)乙醇吸附和進(jìn)一步氧化。乙醇電催化氧化峰電流密度在PdTe1.5/C和PdSb0.15/C催化劑上分別為190.3 mA cm-2和117.5 mA cm-2,是Pd/C催化劑的2.8倍和1.7倍。在室溫條件下,采用自組裝法合成了PdBi/C和Cu@PdCu/C催化劑,研究表明：(1)Bi3+離子容易在Pd粒子上發(fā)生不可逆吸附可便捷高效地合成PdBi/C催化劑。Pd吸附Bi后,催化劑粒徑相比于吸附前的Pd粒子增大,沉積的Bi物種多以氧化態(tài)形式存在,并與Pd之間存在強(qiáng)電子相互作用,并促進(jìn)Pd對溶液中OH"吸附,提高催化劑氧化毒性中間產(chǎn)物的能力,乙醇陽極氧化峰電流密度在PdBi/C (20:1)催化劑上為180.5 mA cm-2,是Pd/C的2.4倍；(2)通過Pd2+離子和Cu粒子的靜電取代合成Cu@PdCu/C催化劑,該催化劑具有Cu內(nèi)核和PdCu合金外殼層結(jié)構(gòu),外殼層厚度約為0.5nnm；核殼結(jié)構(gòu)提高了Pd的利用率,且外殼層PdCu合金能夠提高催化劑表面含氧物種生成,促進(jìn)表面毒性物種的氧化去除,從而提高催化劑對乙醇的電催化氧化活性,Cu@PdCu/C催化劑對乙醇電氧化的活性為166.0 mA cm-2,是Pd/C(硼氫化鈉還原)的2.8倍。
[Abstract]:Direct ethanol fuel cell (DEFC) is a promising fuel cell technology, which is expected to be used in mobile electronics, electric vehicles and power plants. At present, the main obstacle to the development of DEFC application is the low catalytic activity and high price of the anode catalyst. In this paper, a new material and a new preparation method for DEFC anode catalyst are sought. The physical properties of the different catalyst materials are characterized by physical properties, such as alloying degree, average particle size, morphology, structure and composition. The structure-activity relationship between the physical properties and electrochemical properties of the catalyst was studied. The main results were as follows: the Pt/MnOx-CNTs catalyst was prepared by microwave ethylene glycol reduction with MnOx-CNTs composite as the carrier. The results show that the particles are uniformly dispersed on the support, and the average particle size is 2.2 nm. Mn exists in various valence states in the catalyst. The optimum mass ratio of MnOx to CNTs is 1: 1 Pt- Mn-Ox-CNTs 1: 1) the peak current density of ethanol electrocatalytic oxidation in acidic medium is 1141.4 Ma mg-1 PT, which is Pt catalyst 626.4 Ma mg-1. 1.8-fold MNO _ x can promote the dehydrogenation reaction in the process of ethanol anodic oxidation. It can also increase the oxygen species and obviously promote the ability to remove the intermediate products from the surface poisoning of the catalyst. Using low cost PD as the matrix, the binary catalyst of PdM/C / MMT Te- (SB) was prepared by microwave ethylene glycol reduction. The results showed that there were alloy phases in the catalyst of w / PdTexr / C and PdSbx/C, and the addition of Te and SB could increase the oxygen-containing species on the surface of the catalyst. The oxidation removal of toxic intermediate products by catalyst was improved, and ethanol adsorption and further oxidation were promoted. The peak current density on PdTe1.5/C and PdSb0.15/C is 190.3 Ma cm-2 and 117.5 Ma cm-2 respectively, which is 2.8-fold and 1.7-fold higher than that of Pd/C catalyst. At room temperature, PdBi/C and Cu@PdCu/C catalysts were synthesized by self-assembly method. The results show that the irreversible adsorption of PdBi/C catalyst. PD can easily and efficiently adsorb Bi on PD particles. The particle size of the catalyst is larger than that of the PD particles before adsorption. The deposited Bi species exist in the form of oxidation, and there is a strong electron interaction with PD, which also promotes the adsorption of OH "in solution by PD." The peak current density of ethanol anodic oxidation was 180.5 Ma cm-2 on PdBi/C 20: 1 catalyst, which was 2.4-fold of that of Pd/C. Cu@PdCu/C catalyst was synthesized by electrostatic substitution of Pd2 ion and Cu particle. The catalyst has Cu core and PdCu alloy shell structure, the shell thickness is about 0.5 nm, the core-shell structure increases PD utilization rate, and the shell layer PdCu alloy can improve the formation of oxygen species on the surface of the catalyst and promote the oxidation removal of surface toxic species. Thus, the electrocatalytic oxidation activity of the catalyst for ethanol was improved by 166.0 Ma cm-2, which was 2.8 times higher than that of PD / C (reduction of sodium borohydride).
【學(xué)位授予單位】：福州大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：O643.36;TM911.4

【相似文獻(xiàn)】

相關(guān)期刊論文 前10條

1 王樹博;王要武;謝曉峰;汪浩;嚴(yán)輝;;直接甲醇燃料電池陽極催化劑的制備[J];化工進(jìn)展;2006年06期

2 李金峰;宋煥巧;邱新平;;直接甲醇燃料電池陽極催化劑的研究進(jìn)展[J];電源技術(shù);2007年02期

3 稅安澤;夏海斌;劉平安;曾令可;王慧;程小蘇;;直接甲醇燃料電池陽極催化劑的研究進(jìn)展[J];材料導(dǎo)報;2007年S3期

4 鞠劍峰;吳東輝;;直接甲醇燃料電池陽極催化劑的研究進(jìn)展[J];化工進(jìn)展;2009年04期

5 楊民力;;直接甲醇燃料電池鉑基陽極催化劑碳載體發(fā)展[J];材料導(dǎo)報;2010年07期

6 周衛(wèi)江,周振華,李文震,孫公權(quán),辛勤;直接甲醇燃料電池陽極催化劑研究進(jìn)展[J];化學(xué)通報;2003年04期

7 羅遠(yuǎn)來;梁振興;廖世軍;;直接甲醇燃料電池陽極催化劑研究進(jìn)展[J];催化學(xué)報;2010年02期

8 楊民力;;直接甲醇燃料電池鉑基陽極催化劑的非碳載體[J];稀有金屬;2010年03期

9 張敏;唐艷茹;丁鵬;趙侖;;直接甲醇燃料電池陽極催化劑進(jìn)展中粒徑和載體的作用[J];長春師范學(xué)院學(xué)報;2013年10期

10 高文君;鄭穎平;查燕;孫岳明;;甲烷為燃料的固體氧化物燃料電池陽極催化劑研究進(jìn)展[J];江蘇化工;2008年04期

相關(guān)會議論文 前10條

1 張日清;周震濤;;直接甲醇燃料電池三元陽極催化劑的研制[A];電動車及新型電池學(xué)術(shù)交流會論文集[C];2003年

2 呂清葉;楊波;莊林;陸君濤;;納米Pt-Ru催化劑構(gòu)效關(guān)系的模式識別[A];第十三次全國電化學(xué)會議論文摘要集（上集）[C];2005年

3 邢巍;陸天虹;;直接醇燃料電池陽極催化劑研究[A];中國化學(xué)會第二十五屆學(xué)術(shù)年會論文摘要集（上冊）[C];2006年

4 劉軍民;蔡育芬;廖世軍;;直接甲醇燃料電池陽極催化劑PtMoSi／C的制備和表征[A];第十三次全國電化學(xué)會議論文摘要集（上集）[C];2005年

5 王耀輝;高山;李良瓊;姜春萍;陳金偉;王瑞林;;直接甲醇燃料電池陽極催化劑的PtRu/C的制備及表征[A];2008 International Hydrogen Forum Programme and Abstract[C];2008年

6 王耀輝;高山;李良瓊;姜春萍;陳金偉;王瑞林;;直接甲醇燃料電池陽極催化劑的PtRu/C的制備及表征[A];中國化學(xué)會第26屆學(xué)術(shù)年會新能源與能源化學(xué)分會場論文集[C];2008年

7 陸天虹;;直接甲酸燃料電池Pd陽極催化劑電催化性能不穩(wěn)定的原因[A];第30屆全國化學(xué)與物理電源學(xué)術(shù)年會論文集[C];2013年

8 鄭燕貞;王翠芳;郭永榔;;直接乙醇燃料電池PtSn／C陽極催化劑的制備和表征[A];第二十七屆全國化學(xué)與物理電源學(xué)術(shù)年會論文集[C];2006年

9 陳煜;唐亞文;劉長鵬;邢巍;陸天虹;;碳載高合金化Pt-Ru催化劑的制備及性能[A];第十三次全國電化學(xué)會議論文摘要集（上集）[C];2005年

10 毛示e，

本文編號：1908473