铂合金纳米立方块催化剂的氧还原反应活性比较

汤永安; 代  琳; 邹受忠

doi:10.13208/j.electrochem.161249

电化学 >

2017 , Vol. 23 >Issue 2: 199 - 206

DOI: https://doi.org/10.13208/j.electrochem.161249

田昭武先生90大寿祝贺专辑（厦门大学孙世刚林昌健教授主编）

铂合金纳米立方块催化剂的氧还原反应活性比较

汤永安 ,
代琳 ,
邹受忠

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1. 美国迈阿密大学化学与生物化学系，牛津，俄亥俄 45056; 2. 美国美利坚大学化学系，华盛顿特区 20016; 3. 美国奥克兰大学化学系，罗切斯特, 密歇根 48039

收稿日期: 2017-01-17

修回日期: 2017-02-15

网络出版日期: 2017-02-16

基金资助

美国国家科学基金项目（CHE 1156425，CHE 1559670）资助.

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Comparison of Oxygen Reduction Reaction Activity of Pt-Alloy Nanocubes

Yongan Tang ,
Lin Dai ,
Shouzhong Zou

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1. Department of Chemistry and Biochemistry, Miami University, Oxford, OH 45056, USA; 2. Department of Chemistry, American University, Washington DC 20016, USA; 3. Department of Chemistry, Oakland University, Rochester, MI 48039, USA

Received date: 2017-01-17

Revised date: 2017-02-15

Online published: 2017-02-16

Supported by

This work was supported by the US National Science Foundation (CHE 1156425，CHE 1559670).

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摘要

氧还原反应是质子交换膜燃料电池和金属-空气电池的重要反应，贵金属铂（Pt）与元素周期表中第一排的非贵过渡金属（M）形成铂合金催化剂（PtM）可以提高氧还原反应活性. 但是，有关活性的提高有多大程度上是来自合金元素的贡献却仍然存在争议. 为了研究合金元素对PtM催化活性的影响，本工作合成了颗粒形状与合金元素含量相似的铂锰（PtMn）, 铂铁（PtFe）, 铂钴（PtCo）和铂镍（PtNi）纳米立方块催化剂，并考察了不同铂合金催化剂在酸性介质中的氧还原反应活性. 选择制备立方块形状纳米颗粒催化剂进行比较，可以将颗粒表面结构对催化活性的影响降到最小. 结果表明，氧还原反应活性与铂d-带中心值曲线呈现火山形关系，其中PtCo纳米立方块催化剂的活性最高. 本文所得到的实验结果与基于d-带理论框架已知表面的密度泛函理论计算结果一致.

关键词： 铂合金纳米立方块; 氧还原反应; 质子交换膜燃料电池; d-带理论

本文引用格式

汤永安 , 代琳 , 邹受忠 . 铂合金纳米立方块催化剂的氧还原反应活性比较[J]. 电化学, 2017 , 23(2) : 199 -206 . DOI: 10.13208/j.electrochem.161249

Abstract

Alloying Pt with the first row non-noble transition metals has been demonstrated to increase the catalytic activity toward oxygen reduction reaction (ORR), which is the cathode reaction of the proton exchange membrane fuel cells (PEMFCs) and metal-air batteries. However, how much the ORR activity improvement comes from the alloying elements remains controversial. In this paper, the nanocubes of PtMn, PtFe, PtCo, and PtNi with the similar size and composition were prepared and their ORR activities were explored, in order to investigate the effects of alloying elements on the catalytic activity. The use of cubic shape particles minimizes the contribution to the activity from particle surface structural difference. The results showed that the ORR activity vs. Pt d-band center plot had a volcano shape and PtCo nanocube is the most active. These observations are in harmony with density functional theory calculations on well-defined surfaces in the framework of the d-band theory.

Key words： Pt-alloy nanocubes; oxygen reduction reaction; proton exchange membrane fuel cells; d-band theory

参考文献

[1] Vielstich W, Lamm A, Gasteiger HA: Handbook of Fuel Cells: Fundamentals. Technology. Applications[J]. Wiley: New York 2003.

[2] Gasteiger HA, Kocha SS, Sompalli B, et al.: Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs[J]. Applied Catalysis B-Environmental 2005, 56:9-35.

[3] Mukerjee S, Srinivasan S: ENHANCED ELECTROCATALYSIS OF OXYGEN REDUCTION ON PLATINUM ALLOYS IN PROTON-EXCHANGE MEMBRANE FUEL-CELLS[J]. Journal of Electroanalytical Chemistry 1993, 357:201-24.

[4] Stamenkovic VR, Mun BS, Arenz M, et al.: Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces[J]. Nature Materials 2007, 6:241-7.

[5] Mukerjee S, Srinivasan S, Soriaga MP, et al.: ROLE OF STRUCTURAL AND ELECTRONIC-PROPERTIES OF PT AND PT ALLOYS ON ELECTROCATALYSIS OF OXYGEN REDUCTION - AN IN-SITU XANES AND EXAFS INVESTIGATION[J]. Journal of the Electrochemical Society 1995, 142:1409-22.

[6] Watanabe M, Tsurumi K, Mizukami T, et al.: ACTIVITY AND STABILITY OF ORDERED AND DISORDERED CO-PT ALLOYS FOR PHOSPHORIC-ACID FUEL-CELLS[J]. Journal of the Electrochemical Society 1994, 141:2659-68.

[7] Koh S, Leisch J, Toney MF, et al.: Structure-activity-stability relationships of Pt-Co alloy electrocatalysts in gas-diffusion electrode layers[J]. Journal of Physical Chemistry C 2007, 111:3744-52.

[8] Stamenkovic V, Schmidt TJ, Ross PN, et al.: Surface segregation effects in electrocatalysis: kinetics of oxygen reduction reaction on polycrystalline Pt3Ni alloy surfaces[J]. Journal of Electroanalytical Chemistry 2003, 554:191-9.

[9] Toda T, Igarashi H, Uchida H, et al.: Enhancement of the electroreduction of oxygen on Pt alloys with Fe, Ni, and Co[J]. Journal of the Electrochemical Society 1999, 146:3750-6.

[10] Paulus UA, Wokaun A, Scherer GG, et al.: Oxygen reduction on carbon-supported Pt-Ni and Pt-Co alloy catalysts[J]. Journal of Physical Chemistry B 2002, 106:4181-91.

[11] Bing YH, Liu HS, Zhang L, et al.: Nanostructured Pt-alloy electrocatalysts for PEM fuel cell oxygen reduction reaction[J]. Chemical Society Reviews 2010, 39:2184-202.

[12] Stamenkovic V, Mun BS, Mayrhofer KJJ, et al.: Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure[J]. Angewandte Chemie-International Edition 2006, 45:2897-901.

[13] Han B, Carlton CE, Suntivich J, et al.: Oxygen Reduction Activity and Stability Trends of Bimetallic Pt0.5M0.5 Nanoparticle in Acid[J]. The Journal of Physical Chemistry C 2015, 119:3971-8.

[14] Zhang J, Yang HZ, Fang JY, et al.: Synthesis and Oxygen Reduction Activity of Shape-Controlled Pt3Ni Nanopolyhedra[J]. Nano Letters 2010, 10:638-44.

[15] Zhang C, Hwang SY, Trout A, et al.: Solid-State Chemistry-Enabled Scalable Production of Octahedral Pt–Ni Alloy Electrocatalyst for Oxygen Reduction Reaction[J]. Journal of the American Chemical Society 2014, 136:7805-8.

[16] Choi S-I, Xie S, Shao M, et al.: Controlling the Size and Composition of Nanosized Pt–Ni Octahedra to Optimize Their Catalytic Activities toward the Oxygen Reduction Reaction[J]. ChemSusChem 2014, 7:1476-83.

[17] Chou S-W, Lai Y-R, Yang YY, et al.: Uniform size and composition tuning of PtNi octahedra for systematic studies of oxygen reduction reactions[J]. Journal of Catalysis 2014, 309:343-50.

[18] Zhang J, Fang JY: A General Strategy for Preparation of Pt 3d-Transition Metal (Co, Fe, Ni) Nanocubes[J]. Journal of the American Chemical Society 2009, 131:18543-7.

[19] Gilroy KD, Ruditskiy A, Peng H-C, et al.: Bimetallic Nanocrystals: Syntheses, Properties, and Applications[J]. Chemical Reviews 2016, 116:10414-72.

[20] Kang YJ, Murray CB: Synthesis and Electrocatalytic Properties of Cubic Mn-Pt Nanocrystals (Nanocubes)[J]. Journal of the American Chemical Society 2010, 132:7568-+.

[21] Maillard F, Eikerling M, Cherstiouk OV, et al.: Size effects on reactivity of Pt nanoparticles in CO monolayer oxidation: The role of surface mobility[J]. Faraday Discussions 2004, 125:357-77.

[22] Yano H, Inukai J, Uchida H, et al.: Particle-size effect of nanoscale platinum catalysts in oxygen reduction reaction: an electrochemical and Pt-195 EC-NMR study[J]. Physical Chemistry Chemical Physics 2006, 8:4932-9.

[23] Mayrhofer KJJ, Blizanac BB, Arenz M, et al.: The impact of geometric and surface electronic properties of Pt-catalysts on the particle size effect in electocatalysis[J]. Journal of Physical Chemistry B 2005, 109:14433-40.

[24] Yang H, Tang Y, Zou S: Electrochemical removal of surfactants from Pt nanocubes[J]. Electrochemistry Communications 2014, 38:134-7.

[25] Aran-Ais RM, Vidal-Iglesias FJ, Solla-Gullon J, et al.: Electrochemical Characterization of Clean Shape-Controlled Pt Nanoparticles Prepared in Presence of Oleylamine/Oleic Acid[J]. Electroanalysis 2015, 27:945-56.

[26] Solla-Gullon J, Vidal-Iglesias FJ, Lopez-Cudero A, et al.: Shape-dependent electrocatalysis: methanol and formic acid electrooxidation on preferentially oriented Pt nanoparticles[J]. Physical Chemistry Chemical Physics 2008, 10:3689-98.

[27] Mayrhofer KJJ, Juhart V, Hartl K, et al.: Adsorbate-Induced Surface Segregation for Core-Shell Nanocatalysts[J]. Angewandte Chemie-International Edition 2009, 48:3529-31.

[28] Li D, Wang C, Strmcnik DS, et al.: Functional links between Pt single crystal morphology and nanoparticles with different size and shape: the oxygen reduction reaction case[J]. Energy & Environmental Science 2014, 7:4061-9.

[29] Kitchin JR, Norskov JK, Barteau MA, et al.: Modification of the surface electronic and chemical properties of Pt(111) by subsurface 3d transition metals[J]. Journal of Chemical Physics 2004, 120:10240-6.

[30] Medford AJ, Vojvodic A, Hummelshøj JS, et al.: From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis[J]. Journal of Catalysis 2015, 328:36-42.

[31] Markovic NM, Schmidt TJ, Stamenkovic V, et al.: Oxygen Reduction Reaction on Pt and Pt Bimetallic Surfaces: A Selective Review[J]. Fuel Cells 2001, 1:105-16.

[32] Viswanathan V, Hansen HA, Rossmeisl J, et al.: Universality in Oxygen Reduction Electrocatalysis on Metal Surfaces[J]. ACS Catalysis 2012, 2:1654-60.

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