本文選題：直接甲醇燃料電池 + 直接甲酸燃料電池　； 參考：《華東師范大學》2017年碩士論文

【摘要】：近年來,燃料電池由于其能量轉(zhuǎn)化率高,環(huán)境穩(wěn)定性好等優(yōu)點受到了人們的廣泛關注。液體燃料電池因其運輸便利,儲存簡單的優(yōu)點也促進了有機小分子作為新的可替代能源的發(fā)展。甲醇與甲酸分子中不含C-C鍵且具有較高的氫碳比,為其在低溫下的完全氧化提供了合理的氧化動力學機理。以上這些優(yōu)點都促進了直接甲醇燃料電池(DMFC)及直接甲酸燃料電池(DFAFC)做為新的便攜式能源轉(zhuǎn)化裝置的發(fā)展。目前,在直接甲醇燃料電池與直接甲酸燃料電池中具有最好電催化性能的催化劑為Pt催化劑。然而Pt為貴金屬存儲有限、成本較高且甲醇與甲酸在Pt表面的氧化過程較為復雜易產(chǎn)生CO_ads造成催化劑中毒,這就限制了直接甲醇燃料電池與直接甲酸燃料電池的商業(yè)化進展。為了改變這一現(xiàn)狀,降低Pt納米顆粒的負載量,降低成本,提高其催化效率,可以選擇比表面積大,可降低催化劑負載量的電極材料來負載Pt催化劑,如高度石墨化的碳材料、導電聚合物材料等。碳材料具有導電性好,比表面積大,穩(wěn)定性好等優(yōu)點被廣泛用作電極材料。除此之外,導電聚合物(CPs)作為新型的有機半導體材料,具有較大的比表面積和較好的穩(wěn)定性近年來也常用來負載和分散燃料電池的催化劑Pt。在眾多的導電聚合物中聚苯胺(PANI)及其衍生物易在電極表面合成,在酸性介質(zhì)中穩(wěn)定,因此常被用來負載燃料電池的催化劑Pt。本論文制備出碳糊電極(CPE)和電池活性炭摻雜碳糊電極(YBCPE)并研究其與聚鄰甲氧基苯胺(POA)相結(jié)合負載Pt納米顆粒對甲醇的電催化氧化的影響。其次還選用不同的碳材料電極分別與聚鄰甲氧基苯胺(POA)和聚鄰氨基苯酚(POAP)相結(jié)合負載Pt納米顆粒電催化氧化甲酸,研究底電極材料,導電聚合物的種類及導電聚合物的制備方法對復合電極電催化氧化甲酸的影響。以下是本論文初步研究的一些內(nèi)容:(1)電池活性炭摻雜碳糊電極的電化學行為及其電催化氧化甲醇的研究用石墨粉,電池活性炭和石蠟油作為原材料制備出碳糊電極(CPE)和摻雜不同含量電池活性炭的(YBCPE)電極。并試圖用電化學交流阻抗技術對制備出的碳糊電極和電池活性炭摻雜碳糊電極的可逆性和電荷轉(zhuǎn)移情況進行定性和定量的研究。同時將制備好的底電極負載金屬Pt得到Pt/YBCPE復合電極并用于甲醇的電催化氧化,用SEM對得到的Pt復合電極形貌進行表征。研究表明YBCPE比CPE具有更小的電荷轉(zhuǎn)移電阻,對催化劑Pt具有更好的分散作用。Pt/YBCPE復合電極電催化氧化甲醇的活性先隨摻雜電池活性炭含量的增加而增加,隨后再減小。其中Pt/YBCPE(14%)對甲醇具有最好的電催化氧化活性。(2)聚鄰甲氧基苯胺修飾電池活性炭摻雜碳糊電極電催化氧化甲醇的研究將已經(jīng)制備好的CPE和YBCPE(14%)用聚鄰甲氧基苯胺膜(POA)進行修飾并用來負載Pt納米顆粒,得到Pt/POA/YBCPE復合電極。將得到的Pt/POA/YBCPE復合電極用于甲醇的電催化氧化,對比Pt/POA/YBCPE復合電極與Pt/YBCPE復合電極電催化氧化甲醇活性的高低。用TEM對復合電極上Pt的分散情況進行表征,對比研究POA膜的存在對催化劑在電極表面分散情況的影響。通過電化學交流阻抗技術研究POA/YBCPE電極與電解質(zhì)溶液界面間的電荷轉(zhuǎn)移情況及Pt/POA/YBCPE電極與電解質(zhì)溶液界面之間的電荷轉(zhuǎn)移情況。除此之外還系統(tǒng)性的研究鄰甲氧基苯胺單體的濃度、聚鄰甲氧基苯胺的膜厚度等因素對復合電極電催化氧化性能的影響。研究結(jié)果表明,POA膜的存在會影響Pt在電極表面的成核情況,有利于Pt納米顆粒的分散,增加復合電極的電化學活性比表面積,使復合電極的電催化氧化活性提高。(3)Pt/CPOA/GC,Pt/CPOA/YBCPE,Pt/POA/GC,Pt/POA/YBCPE 復合電極對甲酸電催化氧化的研究選用YBCPE(14%)與玻碳電極(GC)為底電極分別在YBCPE(14%)及GC電極上用循環(huán)伏安法或恒電位電解法制備聚鄰甲氧基苯胺膜(分別表示為CPOA和POA),得到 CPOA/YBCPE,POA/YBCPE,CPOA/GC 和 POA/GC 電極。并將 Pt電沉積在這些電極上,將得到的復合電極用于甲酸的電催化氧化。比較研究底電極材料及制備方法對復合電極電催化氧化甲酸活性和機理的影響。實驗結(jié)果表明,當用循環(huán)伏安法制備POA膜時,Pt/CPOA/YBCPE比Pt/CPOA/GC對甲酸有更好的電催化氧化活性。當用恒電位電解法制備POA膜時,Pt/POA/GC比Pt/POA/YBCPE對甲酸有更好的電催化氧化活性。在本實驗條件下Pt/POA(40mC)/GC與Pt/POA(40mC)/YBCPE復合電極對甲酸具有較好的電催化氧化活性和穩(wěn)定性。(4)初步探究了聚鄰甲氧基苯胺的電化學制備方法對Pt/聚鄰甲氧基苯胺/碳材料復合電極電催化氧化甲酸活性的影響主要研究了在相同的碳材料電極上用循環(huán)伏安法和恒電位電解法制備相同膜厚度的CPOA和POA膜。研究其負載Pt納米顆粒后對甲酸電催化氧化活性和穩(wěn)定性的影響。用電化學交流阻抗手段研究不同制備方法對CPOA/碳材料電極和POA/碳材料電極的電荷轉(zhuǎn)移情況和表面粗糙度。并用TEM對催化劑的分散情況進行表征。其實驗結(jié)果表明當?shù)纂姌O材料相同時恒電位電解法制備的POA膜比循環(huán)伏安法制備的CPOA膜有更小的電荷轉(zhuǎn)移電阻,表面粗糙度更小,更有利于載鉑后復合電極對甲酸的電催化氧化。(5)聚鄰氨基苯酚修飾碳材料電極載鉑后電催化氧化甲酸行為研究選用GC與YBCPE(14%)為底電極,用循環(huán)伏安法制備聚鄰氨基苯酚膜(CPOAP),得到CPOAP/GC與CPOAP/YBCPE電極,將得到的電極負載Pt納米顆粒用于甲酸的電催化氧化研究。同時對比了聚鄰甲氧基苯胺與聚鄰氨基苯酚膜對甲酸電催化氧化活性的影響,并用TEM對聚鄰甲氧基苯胺膜和聚鄰氨基苯酚膜上Pt納米顆粒的分散情況進行研究。實驗結(jié)果表明,在本實驗的實驗條件下CPOA比CPOAP更易合成,對Pt具有更好的分散作用。所以用CPOA負載Pt納米顆粒比用CPOAP負載Pt納米顆粒對甲酸具有更好的電催化氧化活性。
[Abstract]:In recent years, fuel cells have attracted wide attention because of their high energy conversion and good environmental stability. Because of their convenient transportation and simple storage, liquid fuel cells have also promoted the development of small organic molecules as a new alternative energy source. Methanol and formic acids have no C-C bonds and have high hydrogen carbon ratio. The complete oxidation at low temperature provides a reasonable oxidation kinetic mechanism, which all promote the development of the direct methanol fuel cell (DMFC) and the direct formic fuel cell (DFAFC) as a new portable energy conversion device. At present, it has the best electrocatalysis in the direct methanol fuel cell and the direct formic fuel cell. The performance catalyst is Pt catalyst. However, Pt is limited in the storage of precious metals, the cost is high and the oxidation process of methanol and formic acid on the Pt surface is more complex and easy to produce CO_ads to cause catalyst poisoning. This restricts the commercialization of direct methanol fuel cells and direct formic acid fuel cells. In order to change this situation, reduce Pt nanoscale. The load of grain, reducing cost and improving its catalytic efficiency can be used to load Pt catalyst, such as highly graphitized carbon material and conductive polymer material, which have large surface area and can reduce the load of catalyst, such as highly graphitized carbon material, conductive polymer material and so on. The carbon material has many advantages, such as good conductivity, large surface area, good stability and so on. In addition, the conductive polymer (CPs), as a new organic semiconductor material, has a larger specific surface area and better stability. In recent years, the catalyst Pt. is often used to load and disperse the catalyst of the fuel cell. Polyaniline (PANI) and its derivatives are easily synthesized on the surface of the electrode in many conductive polymers and are stable in acid medium, so they are often used. The carbon paste electrode (CPE) and battery activated carbon doped carbon paste electrode (YBCPE) were prepared in this paper, and the effect of Pt nanoparticles on the electrocatalytic oxidation of methanol was studied. Secondly, the different carbon material electrodes and poly (o methoxy) aniline (POA) were used in Pt.. Electrocatalytic oxidation of formic acid with poly (o-aminophenol) (POAP) loaded Pt nanoparticles was used to study the effects of the base electrode materials, the types of conductive polymers and the preparation methods of conducting polymers on the electrocatalytic oxidation of formic acid by composite electrodes. The following are the internal capacity of the preliminary study in this paper: (1) electrochemical oxidation of activated carbon doped carbon paste electrode The behavior and electrocatalytic oxidation of methanol used graphite powder, battery activated carbon and paraffin oil as raw materials to prepare carbon paste electrode (CPE) and (YBCPE) electrode doped with different content of battery active carbon, and try to use electrochemical impedance technique to prepare the carbon paste electrode and the reversibility and charge of the battery activated carbon doped carbon paste electrode. The transfer situation was studied qualitatively and quantitatively. At the same time, the Pt/YBCPE composite electrode was obtained by the prepared base electrode loaded metal Pt and used for the electrocatalytic oxidation of methanol. The morphology of the Pt composite electrode obtained by SEM was characterized. The study shows that YBCPE has a smaller charge transfer resistivity than CPE and has a better dispersion effect on the catalyst Pt.Pt. The activity of electrocatalytic oxidation of methanol by /YBCPE composite electrode increased first with the increase of the content of activated carbon in the doped cell, and then decreased. Among them, Pt/YBCPE (14%) had the best electrocatalytic oxidation activity to methanol. (2) the study on the electrocatalytic oxidation of methanol by the active carbon doped carbon paste electrode of the polyo methoxy aniline modified battery would have been prepared for a good CPE And YBCPE (14%) was modified with polyo-methoxy aniline membrane (POA) and used to load Pt nanoparticles and get Pt/POA/YBCPE composite electrode. The Pt/POA/YBCPE composite electrode was used for electrocatalytic oxidation of methanol. The activity of methanol oxidation by Pt/POA/YBCPE composite electrode and Pt/YBCPE composite electrode was compared with that of Pt/YBCPE composite electrode. On the composite electrode, TEM was used on the composite electrode. The dispersion of Pt was characterized, and the influence of the presence of POA film on the dispersion of the catalyst on the surface of the electrode was compared. The charge transfer between the interface of the POA/YBCPE electrode and the electrolyte solution and the charge transfer between the Pt/POA/YBCPE electrode and the electrolyte solution interface were investigated by electrochemical impedance spectroscopy. The influence of the concentration of o-methoxy aniline monomer and the film thickness of poly (o-methoxy) aniline on the electrocatalytic oxidation performance of the composite electrode was investigated. The results showed that the existence of POA film would affect the nucleation of Pt on the surface of the electrode, be beneficial to the dispersion of Pt nanoparticles and increase the specific surface area of the electrochemical activity of the composite electrode. The electrocatalytic oxidation activity of the composite electrode is improved. (3) the study on the electrocatalytic oxidation of formic acid by Pt/CPOA/GC, Pt/CPOA/YBCPE, Pt/POA/GC, Pt/POA/YBCPE composite electrodes, YBCPE (14%) and glassy carbon electrode (GC) are used as the base electrodes to prepare polyo methoxy aniline membranes by cyclic voltammetry or constant potential electrolysis on YBCPE (14%) and GC electrodes respectively. As CPOA and POA), CPOA/YBCPE, POA/YBCPE, CPOA/GC and POA/GC electrodes were obtained. And Pt was deposited on these electrodes and the composite electrodes were used for the electrocatalytic oxidation of formic acid. The effects of the substrate and preparation methods on the activity and mechanism of the electrocatalytic oxidation of formic acid at the composite electrode were compared. When the POA film is prepared by the volt ampere method, Pt/CPOA/YBCPE has better electrocatalytic oxidation activity to formic acid than Pt/CPOA/GC. When the POA film is prepared by constant potential electrolysis, Pt/POA/GC has better electrocatalytic oxidation activity to formic acid than Pt/POA/YBCPE. The Pt/POA (40mC) /GC and Pt/POA (40mC) /YBCPE composite electrodes have better electricity for formic acid under this experimental condition. Catalytic oxidation activity and stability. (4) the effect of electrochemical preparation of poly (o methoxy) aniline on the activity of electrocatalytic oxidation of formic acid by Pt/ polymethoxy aniline / carbon composite electrode was mainly studied. The CPOA and POA of the same film thickness were prepared by cyclic voltammetry and constant potential electrolysis on the same carbon electrode. The effects of the Pt nanoparticles on the activity and stability of the electrocatalytic oxidation of formic acid were investigated. The charge transfer and surface roughness of the CPOA/ carbon material electrode and the POA/ carbon electrode were investigated by electrochemical impedance spectroscopy. The dispersion of the catalysts was characterized by TEM. The experimental results showed that the dispersion of the catalysts was characterized by the electrochemical impedance method. The POA films prepared by constant potential electrolysis at the same bottom electrode materials have smaller charge transfer resistance than the CPOA films prepared by cyclic voltammetry, with smaller surface roughness and more favorable for electrocatalytic oxidation of formic acid by composite electrodes after platinum loading. (5) study on the behavior of electrocatalytic oxidation of formic acid after electropolar platinum modification of polyo aminophenol modified carbon materials by G C and YBCPE (14%) were used as the base electrode to prepare polyo-aminophenol membrane (CPOAP) by cyclic voltammetry. The CPOAP/GC and CPOAP/YBCPE electrodes were obtained. The electrocatalytic oxidation of the electrode loaded Pt nanoparticles was used to study the electrocatalytic oxidation of formic acid. The effect of polyo-methoxy aniline and polyo-aminophenol film on the activity of Formic acid electrooxidation was compared, and TEM was compared with TEM. The dispersion of Pt nanoparticles on polyo-methoxy aniline film and polyo-aminophenol film is studied. The experimental results show that under the experimental conditions, CPOA is more easily synthesized than CPOAP, and has a better dispersion effect on Pt. So CPOA loaded Pt nanoparticles have better electrical activity to formic acid than CPOAP negative Pt nanoparticles. Oxidative activity.
【學位授予單位】：華東師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36;TM911.4
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本文編號：1991315