Pd_x-Co/C催化甲酸的电氧化性能研究
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摘要
以活性碳(Vulcan XC-72)为载体,用化学还原法制备了不同Pd/Co摩尔比的Pdx-Co/C催化剂。用透射电镜(TEM)、X射线衍射(XRD)及X射线光电子能谱(XPS)对催化剂进行了表征,采用循环伏安法考察了催化剂对甲酸电氧化反应的催化性能。结果表明,Pdx-Co复合催化剂粒子均匀分散在碳载体表面;催化剂中掺入的少量Co元素部分进入Pd晶格,形成了Pd-Co合金;随着Pd/Co摩尔比的增加,Pd颗粒粒径先增大后减小,催化活性也表现出相同的变化趋势;当Pd:Co=8:1时,所得Pd8-Co/C对甲酸氧化的催化活性最高,峰电流密度可达到15.907 mA/cm~2。
Pd_x-Co/C catalysts with different Pd/Co molar ratios were prepared by chemical reduction using activated carbon(Vulcan XC-72) as carrier. The catalysts were characterized by transmission electron microscopy(TEM), X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS). Their catalytic performance for formic acid electrooxidation was investigated by cyclic voltammetry. The results show that the Pdx-Co particles are uniformly dispersed on the surface of the carbon support. A small amount of Co incorporated into the catalyst enters the Pd lattice and formed Pd-Co alloy. With the increase of the Pd/Co molar ratio, Pd particle size first increases and then decreases, and their catalytic activity also shows the same trend. When the Pd:Co is 8:1, the obtained Pd8-Co/C has the highest catalytic activity for formic acid oxidation, and the peak current density reaches to 15.907 mA/cm~2.
Pd_x-Co/C catalysts with different Pd/Co molar ratios were prepared by chemical reduction using activated carbon(Vulcan XC-72) as carrier. The catalysts were characterized by transmission electron microscopy(TEM), X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS). Their catalytic performance for formic acid electrooxidation was investigated by cyclic voltammetry. The results show that the Pdx-Co particles are uniformly dispersed on the surface of the carbon support. A small amount of Co incorporated into the catalyst enters the Pd lattice and formed Pd-Co alloy. With the increase of the Pd/Co molar ratio, Pd particle size first increases and then decreases, and their catalytic activity also shows the same trend. When the Pd:Co is 8:1, the obtained Pd8-Co/C has the highest catalytic activity for formic acid oxidation, and the peak current density reaches to 15.907 mA/cm~2.
引文
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[23]LEE J K,LEE J,HAN J,et al.Influence of Au contents of AuPt anode catalyst on the performance of direct formic acid fuel cell[J].Electrochimica acta,2008,53(9):3474-3478.
[2]洪平,廖世军.直接甲酸燃料电池研究进展[J].现代化工,2009,29(8):15-20.HONG P,LIAO S J.Research progress of direct formic acid fuel cell[J].Modern chemical industry,2009,29(8):15-20.
[3]刘洋.碳载Pd及碳载Pd-Au催化剂对甲酸电催化氧化的研究[D].哈尔滨:哈尔滨师范大学,2010.LIU Y.Studies on the electrocatalytic oxidation of formic acid over carbon supported Pd and carbon supported Pd-Au catalysts[D].Harbin:Harbin Normal University,2010.
[4]涂丹丹.碳载PdSn催化剂对甲酸电催化氧化的研究[D].哈尔滨:哈尔滨师范大学,2011.TU D D.Study on the electrocatalytic oxidation of formic acid over carbon supported PdSn catalyst[d].Harbin:Harbin Normal University,2011.
[5]李红彬.碳载Au基低温燃料电池阳极催化剂电化学性能研究[D].昆明:昆明理工大学,2010.LI H B.Electrochemical performance of carbon supported Au based low temperature fuel cell anode catalyst[D].Kunming:Kunming University of Technology,2010.
[6]孙丽美,石乐乐,张帅帅,等.Pdn-Fe纳米合金作为Mg-H2O2半燃料电池阴极研究[J].无机材料学报,2018,33(1):81-86.SUN L M,SHI L L,ZHANG S S,et al.Cathode performance of Mg-H2O2 semi-fuel cell with Pdn-Fe alloy as cathode[J].Journal of inorganic materials,2018,33(1):81-86.
[7]何乌日嘎木拉,李宏霞,石乐乐,等.SnO2纳米棒负载Pd-Sb催化甲酸电氧化[J].贵金属,2017,38(1):1-5.HE W,LI H X,SHI L L,et al.Electrocatalytic oxidation of formic acid on Pd-Sb doping SnO2 nanorod[J].Precious metals,2017,38(1):1-5.
[8]LU L,LI H,HONG Y,et al.Improvement of electrocatalytic performance of carbon supported Pd anodic catalyst in direct formic acid fuel cell by ethylenediamine-tetramethylene phosphonic acid[J].Journal of power sources,2012,210:154-157.
[9]CHANG J,SUN X,FENG L,et al.Effect of nitrogen-doped acetylene carbon black supported Pd nanocatalyst on formic acid electrooxidation[J].Journal of power sources,2013,239:94-102.
[10]LV Q,CHANG J,XING W,et al.Dispersion-controlled PtCu clusters synthesized with citric acid using galvanic displacement with high electrocatalytic activity toward methanol oxidation[J].RSC advances,2014,62(4):32997.
[11]沈娟章,陈滢,杨改秀,等.直接甲酸燃料电池炭载Pd阳极催化剂的稳定性[J].高等学校化学学报,2011,32(11):2626-2629.SHEN J Z,CHEN Y,YANG G X,et al.Stability of carbon supported Pd/C catalyst in direct formic acid fuel cell[J].Chemical journal of Chinese universities,2011,32(11):2626-2629.
[12]YAN L,YAO S,CHANG J,et al.Pd oxides/hydrous oxides as highly efficient catalyst for formic acid electrooxidation[J].Journal of power sources,2014,250(9):128-133.
[13]季芸,沈莉萍,孙丹丹,等.直接甲酸燃料电池近年来的发展概况[J].电池工业,2013,18(1):86-89.JI Y,SHEN L P,SUN D D,et al.Development of direct formic acid fuel cells in recent years[J].Battery industry,2013,18(1):86-89.
[14]程年才.直接甲酸燃料电池用Pd/C催化剂制备及其性能研究[D].武汉:武汉理工大学,2010.CHENG N C.Preparation and properties of Pd/Ccatalysts for direct formic acid fuel cells[D].Wuhan:Wuhan University of Technology,2010.
[15]王荣跃.直接甲酸燃料电池催化剂的设计、制备与性能研究[D].济南:山东大学,2012.WANG Y R.Design preparation and performance study of direct formic acid fuel cell catalyst[D].Jinan:Shandong University,2012.
[16]LEE J K,JEON H,UHM S,et al.Influence of underpotentially deposited Sb onto Pt anode surface on the performance of direct formic acid fuel cells[J].Electrochimica acta,2008,53(21):6089-6092.
[17]WANG X,TANG Y,GAO Y,et al.Carbon-supported Pd-Ir catalyst as anodic catalyst in direct formic acid fuel cell[J].Journal of power sources,2008,175(2):784-788.
[18]ZHANG L,LU T,BAO J,et al.Preparation method of an ultrafine carbon supported Pd catalyst as an anodic catalyst in a direct formic acid fuel cell[J].Electrochemistry communications,2006,8(10):1625-1627.
[19]ZHANG L,TANG Y,BAO J,et al.A carbon-supported Pd-P catalyst as the anodic catalyst in a direct formic acid fuel cell[J].Journal of power sources,2006,162(1):177-179.
[20]ZHU Y,KHAN Z,MASEL R I.The behavior of palladium catalysts in direct formic acid fuel cells[J].Journal of power sources,2005,139(1):15-20.
[21]GE J,XING W,XUE X,et al.Controllable synthesis of Pd nanocatalysts for direct formic acid fuel cell(DFAFC)application:From Pd hollow nanospheres to Pd nanoparticles[J].The journal of physical chemistry C,2007,111(46):17305-17310.
[22]HA S,LARSEN R,MASEL R I.Performance characterization of Pd/C nanocatalyst for direct formic acid fuel cells[J].Journal of power sources,2005,144(1):28-34.
[23]LEE J K,LEE J,HAN J,et al.Influence of Au contents of AuPt anode catalyst on the performance of direct formic acid fuel cell[J].Electrochimica acta,2008,53(9):3474-3478.