不同表面修饰石墨烯载Pd催化剂对甲酸氧化的电催化性能

doi:10.3724/SP.J.1095.2013.30023

摘要/Abstract

摘要： 采用对氨基苯磺酸对氧化石墨烯（GO）进行表面功能化，进而负载贵金属Pd，解决了Pd团聚和不易在载体表面负载的问题，从而提高了Pd基催化剂对于甲酸的催化能力。实验研究了相同实验条件下，Pd在氧化石墨烯、还原石墨烯（RGO）和磺化处理的石墨烯（SGO）表面的分散和负载量以及得到的复合催化剂的催化性能。实验结果表明，SGO更容易负载贵金属，得到的催化剂对O2气的电催化还原能力优于Pd/GO和Pd/RGO，此外Pd/SGO催化剂对CO的耐受力也明显提升，这可能是苯环上的π-π键和—SO3H的范德华力协同作用更有利于Pd的固定与分散。对Pd/SGO催化氧还原的机理也进行了分析，该氧还原为2电子反应过程。

关键词: 直接甲酸燃料电池, 氧化石墨烯, 官能团化

Abstract: In this work, the surface of GO was functionalized by different method and used to load noble metal Pd. It is found that the surface modification of GO can effectively enhance the loading amount of Pd and reduce the Pd agglomeration on the support surface, and thereby improve the catalytic activity of Pd-based catalyst for oxidation of formic acid. The activity of Pd-based electrocatalyst toward the oxygen reduction-reaction(ORR) was examined using cyclic voltammetry through roating-disk electrode measurements in 0.5 mol/L H2SO4 electrolyte. Under the same experimental conditions, the loading amount and the catalytic performance of Pd on graphene oxide(GO), reduced graphene oxide(RGO) and sulfonated graphene(SGO) were studied. The results show that SGO is easier to load Pd and the obtained composite catalyst for CO tolerance is also improved significantly, which may be due to the synergetic effect from the π-π bonding of graphene and the van der Waals interactions of the —SO3H functionality, enhancing the loading and dispersion of Pd on the supporting materials effectively.

Key words: direct formic acid fuel cell, graphene oxide, functionalized

中图分类号:

O646

卫华, 鲁振江, 包淑娟, 季辰辰, 蔡长君, 杨帆. 不同表面修饰石墨烯载Pd催化剂对甲酸氧化的电催化性能[J]. 应用化学, DOI: 10.3724/SP.J.1095.2013.30023.

WEI Hua, LU Zhenjiang, BAO Shujuan*, JI Chenchen, CAI Changjun, YANG Fan. Functionalized Graphene Supported Pd Catalyst for Catalytic Oxidation of Formic Acid[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2013.30023.

参考文献

[1] Grasemann M，Laurenczy G. Formic Acid as a Hydrogen Source-Recent Developments and Future Trends[J]. Energy Environ Sci,2012,5(8):8171.

[2] Lee Y W,Han S B,Ko A R,et al. Glycerol-mediated Synthesis of Pd Nanostructures with Dominant {111} Facets for Enhanced Electrocatalytic Activity[J]. Catal Commun,2011,15(1):137-140.

[3] Zhu Y,Khan Z,Masel R I. The Behavior of Palladium Catalysts in Direct Formic Acid Fuel Cells[J]. J Power Sources,2005,139(1/2):15-20.

[4] Waszczuk P,Barnard T M,Rice C,et al. A Nanoparticle Catalyst with Superior Activity for Electrooxidation of Formic Acid[J]. Electrochem Commun,2002,4:599-603.

[5] Ricea C,Ha S,Masela R I,et al. Direct Formic Acid Fuel Cells[J]. J Power Sources,2002,111:83-89.

[6] Tu D D,Wu B,Wang B,et al. A Highly Sctive Carbon-supported PdSn Catalyst for Formic Acid Electrooxidation[J]. Appl Catal B,2011,103(1/2):163-168.

[7] Jung W S,Han J,Yoon S P,et al. Performance Degradation of Direct Formic Acid Fuel Cell Incorporating a Pd Anode Catalyst[J]. J Power Sources,2011,196(10):4573-4578.

[8] Zhou Y,Liu J,Ye J L,et al. Poisoning and Regeneration of Pd Catalyst in Direct Formic Acid Fuel Cell[J]. Electrochim Acta,2010,55(17):5024-5027.

[9] Ma J,Ji Y G,Sun H J,et al. Synthesis of Carbon Supported Palladium Nanoparticles Catalyst Using a Facile Homogeneous Precipitation-reduction Reaction Method for Formic Acid Electrooxidation[J]. Appl Surf Sci,2011,257(24):10483-10488.

[10] Meng H,Xie F Y,Chen J,et al. Electrodeposited Palladium Nanostructure as Novel Anode for Direct Formic Acid Fuel Cell[J]. J Mater Chem,2011,21(30):11352.

[11] Aravind S S J,Ramaprabhu S. Pt Nanoparticle-Dispersed Graphene-Wrapped MWNT Composites as Oxygen Reduction Reaction Electrocatalyst in Proton Exchange Membrane Fuel Cell[J]. ACS Appl Mater Interfaces,2012,4(8):3805-3810.

[12] Nesselberger M,Ashton S,Meier J,et al. The Particle Size Effect on the Oxygen Reduction Reaction Activity of Pt Catalysts:Influence of Electrolyte and Relation to Single Crystal Models[J]. J Am Chem Soc,2011,133(43):17428-17433.

[13] Ogi T,Honda R,Tamaoki K,et al. Direct Room-temperature Synthesis of a Highly Dispersed Pd Nanoparticle Catalyst and Its Electrical Properties in a Fuel Cell[J]. Powder Technol,2011,205(1/3):143-148.

[14] Antolini E. Graphene as a New Carbon Support for Low-temperature Fuel Cell Catalysts[J]. Appl Catal B,2012,123/124:52-68.

[15] Huang C C,Li C,Shi G Q. Graphene Based Catalysts[J]. Energy Environ Sci,2012,5(10):8848.

[16] Huang H J,Wang X. Pd Nanoparticles Supported on Low-defect Graphene Sheets:for Use as High-performance Electrocatalysts for Formic Acid and Methanol Oxidation[J]. J Mater Chem,2012,22(42):22533.

[17] Huang X,Qi X Y,Boey F,et al. Graphene-based Composites[J]. Chem Soc Rev,2012,41(2):666.

[18] Kuila T,Bose S,Mishra A K,et al. Chemical Functionalization of Graphene and Its Applications[J]. Prog Mater Sci,2012,57(7):1061-1105.

[19] Kim J,Cote L J,Huang J X. Two Dimensional Soft Material:New Faces of Graphene Oxide[J]. Acc Chem Res,2012,45:1356-1364.

[20] Cui X,Zhang C Z,Hao R,et al. Liquid-phase Exfoliation, Functionalization and Applications of Graphene[J]. Nanoscale,2011,3(5):2118.

[21] Li H Y,Zhang X Y,Pang H L,et al. PMo12-Functionalized Graphene Nanosheet-supported PtRu Nanocatalysts for Methanol Electro-oxidation[J]. J Solid State Electrochem,2010,14(12):2267-2274.

[22] Hummers W S,Offeman R B. Preparation of Graphitic Oxide[J]. J Amer Chem Soc,1958,80:1339.

[23] Shin H J,Kim K K,Benayad A,et al. Efficient Reduction of Graphite Oxide by Sodium Borohydride and Its Effect on Electrical Conductance[J]. Adv Funct Mater,2009,19(12):1987-1992.

[24] Marcano D C,Kosynkin D V,Berlin J M,et al. Improved Synthesis of Graphene Oxide[J]. ACS Nano,2010,4:4806-4814.

[25] Xu Y X,Bai H,Lu G W,et al. Flexible Graphene Films via the Filtration of Water-Soluble Noncovalent Functionalized Graphene Sheets[J]. J Am Chem Soc,2008,130:5856-5857.

[26] Liu F J,Sun J,Zhu L F,et al. Sulfated Graphene as an Eefficient Solid Catalyst for Acid-catalyzed Liquid Reactions[J]. J Mater Chem,2012,22(12):5495.

[27] Pascual J J S,Cigarroa S C,Feria O S. Kinetics of Oxygen Reduction Reaction on Nanosized Pd Electrocatalyst in Acid Media[J]. J Power Sources,2007,172(1):229-234.