碳纳米管负载四硝基金属酞菁-MnO_2双催化剂催化氧还原性能
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摘要
过渡金属酞菁具有很高的氧还原催化活性,MnO_2对氧还原反应有催化作用,但是将过渡金属酞菁和MnO_2作为氧还原反应的双催化剂的研究较少。本文采用苯酐-尿素法合成了碳纳米管(CNT)负载四硝基金属酞菁(TNMPc)组装体,联合γ-MnO_2作为氧还原反应的双催化剂。借助循环伏安法对双催化剂的配比进行优化,得到二者的最佳比例。研究了四硝基金属酞菁的中心金属离子对最佳比例双催化剂催化性能的影响和双催化剂的抗甲醇性能,结果表明,双催化剂对氧还原反应的催化能力主要受到金属离子本性的影响,双催化剂对氧还原反应的催化效率顺序为CNT/TNFePc-MnO_2> CNT/TNCoPc-MnO_2> CNT/TNNiPc-MnO_2> CNT/TNCuPc-MnO_2; 4种双催化剂均具有较好的抗甲醇中毒性能。
The transition metal phthalocyanine has a high catalytic activity for oxygen reduction. MnO_2 can catalyze the oxygen reduction reaction. However,the use of transition metal phthalocyanine and MnO_2 as dual catalysts for oxygen reduction is quite few. Four types of carbon nanotubes supported tetra-nitro-metal phthalocyanines assemblies (CNT/TNMPc) were synthesized by phthalic anhydride-urea method. Dual catalyst CNT/TNMPc-MnO_2 was prepared via adding γ-MnO_2 into CNT/TNMPc. The optimal ratio of CNT/TNMPc to MnO_2 was obtained by means of cyclic voltammetry. Effects of central metal ions of CNT/TNMPc on the catalytic performance for oxygen reduction reactivity were investigated. The results show that the catalytic efficiency order of the dual catalyst for oxygen reduction reactivity is CNT/TNFePc-MnO_2> CNT/TNCoPcMnO_2> CNT/TNNi Pc-MnO_2> CNT/TNCuPc-MnO_2. All of those suggest that the catalytic activity of dual catalysts for oxygen reduction reaction is mainly affected by the nature of metal ions. In addition,the anti methanol performance of dual catalyst was tested in 0. 1 mol/L KOH + 0. 5 mol/L CH_3OH electrolyte solution.The results indicate that methanol-tolerant abilities of the CNT/TNMPc-MnO_2 are excellent.
The transition metal phthalocyanine has a high catalytic activity for oxygen reduction. MnO_2 can catalyze the oxygen reduction reaction. However,the use of transition metal phthalocyanine and MnO_2 as dual catalysts for oxygen reduction is quite few. Four types of carbon nanotubes supported tetra-nitro-metal phthalocyanines assemblies (CNT/TNMPc) were synthesized by phthalic anhydride-urea method. Dual catalyst CNT/TNMPc-MnO_2 was prepared via adding γ-MnO_2 into CNT/TNMPc. The optimal ratio of CNT/TNMPc to MnO_2 was obtained by means of cyclic voltammetry. Effects of central metal ions of CNT/TNMPc on the catalytic performance for oxygen reduction reactivity were investigated. The results show that the catalytic efficiency order of the dual catalyst for oxygen reduction reactivity is CNT/TNFePc-MnO_2> CNT/TNCoPcMnO_2> CNT/TNNi Pc-MnO_2> CNT/TNCuPc-MnO_2. All of those suggest that the catalytic activity of dual catalysts for oxygen reduction reaction is mainly affected by the nature of metal ions. In addition,the anti methanol performance of dual catalyst was tested in 0. 1 mol/L KOH + 0. 5 mol/L CH_3OH electrolyte solution.The results indicate that methanol-tolerant abilities of the CNT/TNMPc-MnO_2 are excellent.
引文
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[17]Zhang D,Chi D,Okajima T,et al.Catalytic Activity of Dual Catalysts System Based on Nano-manganese Oxide and Cobalt Octacyanophthalocyanine Toward Four-Electron Reduction of Oxygen in Alkaline Media[J].Electrochim Acta,2007,52(17):5400-5406.
[18]Li F,Chen W,Zhang S S.Development of DNA Electrochemical Biosensor Based on Covalent Immobilization of Probe DNAby Direct Coupling of Sol-Gel and Self-assembly Technologies[J].Biosens Bioelectron,2008,24(4):787-792.
[19]Choi S,Choi R,Han S W,et al.Synthesis and Characterization of Pt9Co Nanocubes with High Activity for Oxygen Reduction[J].Chem Commun,2010,46(27):4950-4952.
[20]Wu G,Zelenay P.Nanostructured Nonprecious Metal Catalysts for Oxygen Reduction Reaction[J].Acc Chem Res,2013,46(8):1878-1889.
[21]Tammeveski K,Kontturi K,Nichols R J,et al.Surface Redox Catalysis for O2Reduction on Quinone-Modified Glassy Carbon Electrodes[J].J Electroanal Chem,2001,515(1/2):101-112.
[22]Wiesener K,Ohms D,Neumann V,et al.N4 Macrocycles as Electrocatalysts for the Cathodic Reduction of Oxygen[J].Mater Chem Phys,1989,22(7/8):457-475.
[23]ZHANG Huan.Preparation of Nanoporous Nobel Metals and Their Catalytic Performance Towards Oxygen Reduction Reaction[D].Ji'nan:University of Ji'nan,2013:21-22(in Chinese).张焕.纳米多孔贵金属合金的制备及其氧还原性能研究[D].济南:济南大学,2013.
[2]TONG Yexiang,LIU Peng,SHEN Peikang,et al.Prospects for Polymer Electrolyte Membrane Fuel Cell and Direct Methanol Fuel Cell[J].Battery,2002,32(3):178-180(in Chinese).童叶翔,刘鹏,沈培康,等.质子交换膜和直接甲醇燃料电池进展[J].电池,2002,32(3):178-180.
[3]LIU Changpeng,YANG Hui,XING Wei,et al.Electrocatalytic Performance of Pt-TiO2/C Complex Catalysts for Oxidation of Methanol[J].Chem J Chinese Univ,2002,23(7):1367-1370(in Chinese).刘长鹏,杨辉,邢巍,等.碳载Pt-TiO2复合催化剂对甲醇氧化的电催化性能[J].高等学校化学学报,2002,23(7):1367-1370.
[4]ZHAO Weili,ZHOU Debi,SUN Xinyang,et al.One-Step Preparation of Carbon Supported Co-Phthalocyanine and Its Electrochemical Reduction of Oxygen in Base Medium[J].Chinese J Appl Chem,2010,27(2):183-190(in Chinese).赵伟利,周德璧,孙新阳,等.碳载钴酞菁催化剂的一步法制备及其在碱性条件下对氧的电催化还原[J].应用化学,2010,27(2):183-190.
[5]LI Xuguang,HAN Fei,XING Wei,et al.Influence of Methanol on the Kinetics of Oxygen Reduction on Pt/C and Co Pc Tc/C[J].Acta Phys-Chim Sin,2003,19(4):380-384(in Chinese).李旭光,韩飞,邢巍,等.甲醇对炭载铂和四羧基酞菁钴催化氧还原动力学的影响[J].物理化学学报,2003,19(4):380-384.
[6]Kruusenberg I,Matisen L,Tammeveski K.Oxygen Electroreduction on Multi-Walled Carbon Nanotube Supported Metal Phthalocyanines and Porphyrins in Acid Media[J].Int J Electrochem Sci,2013,8(1):1057-1066.
[7]Xu Z W,Li H J,Cao G X,et al.Electrochemical Performance of Carbon Nanotube-Supported Cobalt Phthalocyanine and Its Nitrogen-Rich Derivatives for Oxygen Reduction[J].J Mol Catal A:Chem,2011,335(1/2):89-96.
[8]Zhang L X,Liu C S,Zhuang L,et al.Manganese Dioxide as an Alternative Cathodic Catalyst to Platinum in Microbial Fuel Cells[J].Biosens Bioelectron,2009,24(9):2825-2829.
[9]ZHU Jianguo,ZHU Xiaohong,JIAO Rui,et al.The Synthesis of Phthalocyanin Complex of Cobalt and Its Determination[J].J Southwest Univ Natl(Nat Sci Ed),2006,32(2):238-240(in Chinese).朱建国,朱晓红,焦锐,等.金属酞菁钴的合成及其表征[J].西南民族大学学报,2006,32(2):238-240.
[10]Shaabani A,Maleki-Moghaddam R,Maleki A,et al.Microwave Assisted Synthesis of Metal-Free Phthalocyanine and Metalophthalocyanines[J].Dyes Pigm,2007,74(74):279-282.
[11]CONG Fangdi,NING Bo,DU Xiguang,et al.Spectroanalysis of Teraamino-Phthalocyanines M(Ⅱ)[J].J Mol Sci,2004,20(1):27-32(in Chinese).丛方地,宁波,杜锡光,等.四氨基取代金属酞菁的光谱分析[J].分子科学学报,2004,20(1):27-32.
[12]CHEN Wei,DUAN Wubiao,HE Chunying,et al.Synthesis and Characterization of Two Monoamino Substituted Asymmetrical Phthalocyanine Zinc(Ⅱ)[J].J Nat Sci Heilongjiang Univ,2006,23(6):671-680(in Chinese).陈伟,段武彪,贺春英,等.两种单氨基取代不对称酞菁锌的合成与表征[J].黑龙江大学自然科学学报,2006,23(6):671-680.
[13]Cortina H,Senent M L,Smeyers Y G.Ab Initio Comparative Study of the Structure and Properties of H2-Porphin and H2-Phthalocyanine.The Electronic Absorption Spectra[J].J Phys Chem A,2003,107(42):8968-8974.
[14]XU Zhanwei.Preparation and Properties of One and Two Dimensional Carbon Nanostructured Electrocatalytic Material[D].Northwestern Polytechnical University,2011:29-30(in Chinese).许占位.一二维碳纳米基电催化材料的制备及性能研究[D].西北工业大学,2011.
[15]Zhang M Y,Shao C L,Guo Z C,et al.Highly Efficient Decomposition of Organic Dye by Aqueous-Solid Phase Transfer and in situ Photocatalysis Using Hierarchical Copper Phthalocyanine Hollow Spheres[J].ACS Appl Mater Interfaces,2011,3(7):2573-2578.
[16]ZHANG Jianqing.Electrochemical Measurement Technology[M].Beijing:Chemical Industry Press,2010(in Chinese).张鉴清.电化学测试技术[M].北京:化学工业出版社,2010.
[17]Zhang D,Chi D,Okajima T,et al.Catalytic Activity of Dual Catalysts System Based on Nano-manganese Oxide and Cobalt Octacyanophthalocyanine Toward Four-Electron Reduction of Oxygen in Alkaline Media[J].Electrochim Acta,2007,52(17):5400-5406.
[18]Li F,Chen W,Zhang S S.Development of DNA Electrochemical Biosensor Based on Covalent Immobilization of Probe DNAby Direct Coupling of Sol-Gel and Self-assembly Technologies[J].Biosens Bioelectron,2008,24(4):787-792.
[19]Choi S,Choi R,Han S W,et al.Synthesis and Characterization of Pt9Co Nanocubes with High Activity for Oxygen Reduction[J].Chem Commun,2010,46(27):4950-4952.
[20]Wu G,Zelenay P.Nanostructured Nonprecious Metal Catalysts for Oxygen Reduction Reaction[J].Acc Chem Res,2013,46(8):1878-1889.
[21]Tammeveski K,Kontturi K,Nichols R J,et al.Surface Redox Catalysis for O2Reduction on Quinone-Modified Glassy Carbon Electrodes[J].J Electroanal Chem,2001,515(1/2):101-112.
[22]Wiesener K,Ohms D,Neumann V,et al.N4 Macrocycles as Electrocatalysts for the Cathodic Reduction of Oxygen[J].Mater Chem Phys,1989,22(7/8):457-475.
[23]ZHANG Huan.Preparation of Nanoporous Nobel Metals and Their Catalytic Performance Towards Oxygen Reduction Reaction[D].Ji'nan:University of Ji'nan,2013:21-22(in Chinese).张焕.纳米多孔贵金属合金的制备及其氧还原性能研究[D].济南:济南大学,2013.