铂催化氧还原反应过程中磷酸的影响及抑制磷酸吸附策略

doi:10.1016/S1872-2067(16)62472-5

催化学报 ›› 2016, Vol. 37 ›› Issue (7): 1134-1141.DOI: 10.1016/S1872-2067(16)62472-5

铂催化氧还原反应过程中磷酸的影响及抑制磷酸吸附策略

李玉萍^a,b, 姜鲁华^a, 王素力^a, 孙公权^a

a. 中国科学院大连化学物理研究所, 洁净能源国家实验室(筹), 辽宁大连 116023;
b. 中国科学院大学, 北京 100049

收稿日期:2016-04-23 修回日期:2016-05-23 出版日期:2016-06-17 发布日期:2016-06-17
通讯作者: Luhua Jiang, Gongquan Sun
基金资助:
中国科学院战略先导专项(XDA09030104);国家重点基础研究发展计划(973计划,2012CB215500);中国科学院重点项目(KGZD-EW-T08).

Influence of phosphoric anions on oxygen reduction reaction activity of platinum, and strategies to inhibit phosphoric anion adsorption

Yuping Li^a,b, Luhua Jiang^a, Suli Wang^a, Gongquan Sun^a

a. Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2016-04-23 Revised:2016-05-23 Online:2016-06-17 Published:2016-06-17
Contact: Luhua Jiang, Gongquan Sun
Supported by:
This work is supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA09030104), the National Basic Research Program of China (973 Program, 2012CB215500), and the Key Program of the Chinese Academy of Sciences (KGZD-EW-T08).

摘要/Abstract

摘要：

与低温(<100℃)质子交换膜燃料电池相比,磷酸掺杂PBI膜燃料电池可工作于100-200℃,工作温度的提高有利于提高电极反应动力学速率、增加Pt催化剂对CO等毒物的耐受性,以及简化电池水管理等.然而,磷酸在Pt催化剂表面吸附较强,这将造成Pt一定程度的毒化.基于"第三体效应",即在Pt表面预吸附某些小分子,可在一定程度上抑制磷酸吸附,然而预吸附分子同时也将占据Pt表面部分活性位点,因而Pt的催化性能最终由两个因素决定:磷酸抑制程度和预吸附分子在Pt表面的覆盖度.本文系统考察了Pt表面预吸附分子覆盖度和预吸附分子链长对其催化氧还原反应(ORR)活性的影响.首先,通过控制预吸附了胺类分子的Pt电极的电位,得到表面具有不同覆盖度的Pt电极,考察了0.1mol/LH₃PO₄电解液中Pt电极对ORR的催化活性随预吸附分子覆盖度的变化规律;为分离磷酸吸附和修饰分子吸附本身对Pt催化活性的影响,对比了0.1mol/LHClO₄电解液中Pt电极对ORR的催化活性随预吸附分子覆盖度的变化规律.进一步对比研究了不同链长胺分子-正丁胺(BA)、正辛胺(OA)及十二胺(DA)等作为修饰分子对Pt/C催化剂电催化ORR活性的影响.结果表明,随修饰分子在Pt表面覆盖度提高,在0.1mol/LHClO₄溶液中,由于预吸附分子占据Pt部分活性位,修饰后光滑Pt电极表面的本征活性单调下降;而在0.1mol/LH₃PO₄中,修饰后光滑Pt电极表面的ORR活性呈现先升高后降低的趋势,当预吸附分子覆盖度约为20%时,其ORR活性最高,为未修饰的光滑Pt电极表面的1.67倍.这表明预吸附分子有效抑制了磷酸的吸附,且当预吸附分子覆盖度约为20%时,预吸附分子对Pt表面的占据与其抑制磷酸吸附的作用达到最佳平衡点.然而,当修饰分子BA,OA和DA在Pt表面覆盖度分别为38.6%,26.1%和26.1%时,Pt/C在0.1mol/LH₃PO₄中的ORR催化活性接近,分别为未经修饰Pt/C电催化剂的1.7,1.8和2.0倍,这表明预吸附分子链长对ORR催化活性影响较小,表面预吸附分子抑制磷酸吸附的策略对Pt/C催化剂也同样适用.同时,Pt/C电极经BA,OA和DA修饰后,其在0.1mol/LHClO₄中的比表面活性分别为未经修饰Pt/C电催化剂的1.0,1.1和1.3倍,与修饰后光滑Pt电极表面本征ORR活性变化规律不一致.然而,与Pt在HClO₄电解质中的ORR活性相比,ORR的半波电位仍有大约123mV的差距,今后还需继续从催化剂的角度,如调控Pt表面的吸附特性,或从创新电解质的角度,如有机磷酸电解质等出发解决磷酸毒化的问题.

关键词: 铂, 磷酸毒化, 氧还原反应, 修饰电极, 磷酸掺杂PBI膜燃料电池

Abstract:

Nafion-membrane-based proton exchange fuel cells (PEMFCs) typically operate at below 100 ℃. However, H₃PO₄-doped polybenzimidazole (PBI)-based PEMFCs can operate at 100-200 ℃. This is advantageous because of accelerated reaction rates and enhanced tolerance to poisons such as CO and SO₂, which can arise from reformed gas or the atmosphere. However, the strong adsorption of phosphoric anions on the Pt surface dramatically decreases the electrocatalytic activity. This study exploits the "third-body effect", in which a small amount of organic molecules are pre-adsorbed on the Pt surface to inhibit the adsorption of phosphoric anions. Pre-adsorbate species inhibit the adsorption of phosphoric anions, but can also partially occlude active sites. Thus, the optimum pre-adsorbate coverage is studied by correlating the oxygen reduction reaction (ORR) activity of Pt with pre-adsorbate coverage on the Pt surface. The influence of the pre-adsorbate molecule length is investigated using the organic amines, butylamine, octylamine, and dodecylamine, in both 0.1 mol/L HClO₄ and 0.1 mol/L H₃PO₄. Such amines readily bond to the Pt surface. In aqueous HClO₄ electrolyte, the ORR activity of Pt decreases monotonically with increasing pre-adsorbate coverage. In aqueous H₃PO₄ electrolyte, the ORR activity of Pt initially increases and then decreases with increasing pre-adsorbate coverage. The maximum ORR activity in H₃PO₄ occurs at a pre-adsorbate coverage of around 20%. The effect of molecular length of the pre-adsorbate is negligible, but its coverage strongly affects the degree to which phosphoric anion adsorption is inhibited. Butylamine adsorbs to Pt at partial active sites, which decreases the electrochemically active surface area. Adsorbed butylamine may also modify the electronic structure of the Pt surface. The ORR activity in the phosphoric acid electrolyte remains relatively low, even when using the pre-adsorbate modified Pt/C catalysts. Further development of the catalyst and electrolyte is required before the commercialization of H₃PO₄-PBI-based PEMFCs can be realized.

Key words: Platinum, Phosphoric anion poisoning, Oxygen reduction reaction, Modified electrode, H₃PO₄-PBI based fuel cells

李玉萍, 姜鲁华, 王素力, 孙公权. 铂催化氧还原反应过程中磷酸的影响及抑制磷酸吸附策略[J]. 催化学报, 2016, 37(7): 1134-1141.

Yuping Li, Luhua Jiang, Suli Wang, Gongquan Sun. Influence of phosphoric anions on oxygen reduction reaction activity of platinum, and strategies to inhibit phosphoric anion adsorption[J]. Chinese Journal of Catalysis, 2016, 37(7): 1134-1141.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(16)62472-5

https://www.cjcatal.com/CN/Y2016/V37/I7/1134

参考文献

[1] Q. F. Li, R. H. He, J. O. Jensen, N. J. Bjerrum, Chem. Mater., 2003, 15, 4896-4915.
[2] Y. L. Ma, J. S. Wainright, M. H. Litt, R. F. Savinell, J. Electrochem. Soc., 2004, 151, A8-A16.
[3] M. Schuster, T. Rager, A. Noda, K. D. Kreuer, J. Maier, Fuel Cells, 2005, 5, 355-365.
[4] S. J. Paddison, K. D. Kreuer, J. Maier, Phys. Chem. Chem. Phys., 2006, 8, 4530-4542.
[5] H. Steininger, M. Schuster, K. D. Kreuer, A. Kaltbeitzel, B. Bingol, W. H. Meyer, S. Schauff, G. Brunklaus, J. Maier, H. W. Spiess, Phys. Chem. Chem. Phys., 2007, 9, 1764-1773.
[6] J. S. Yang, R. H. He, Q. T. Che, X. L. Gao, L. L. Shi, Polym. Int., 2010, 59, 1695-1700.
[7] P. Zelenay, B. R. Scharifker, J. O'M. Bockris, D. Gervasio, J. Electrochem. Soc., 1986, 133, 2262-2267.
[8] Q. G. He, X. F. Yang, W. Chen, S. Mukerjee, B. Koel, S. W. Chen, Phys. Chem. Chem. Phys., 2010, 12, 12544-12555.
[9] Y. H. Chung, D. Y. Chung, N. Jung, Y. E. Sung, J. Phys. Chem. Lett., 2013, 4, 1304-1309.
[10] K. S. Lee, S. J. Yoo, D. Ahn, S. K. Kim, S. J. Hwang, Y. E. Sung, H. J. Kim, E. Cho, D. Henkensmeier, T. H. Lim, J. H. Jang, Electrochim. Acta, 2011, 56, 8802-8810.
[11] Y. H. Chung, S. J. Kim, D. Y. Chung, M. J. Lee, J. H. Jang, Y. E. Sung, Phys. Chem. Chem. Phys., 2014, 16, 13726-13732.
[12] Q. G. He, B. Shyam, M. Nishijima, D. Ramaker, S. Mukerjee, J. Phys. Chem. C, 2013, 117, 4877-4887.
[13] S. Kaserer, K. M. Caldwell, D. E. Ramaker, C. Roth, J. Phys. Chem. C, 2013, 117, 6210-6217.
[14] J. E. Lim, U. J. Lee, S. H. Ahn, E. Cho, H. J. Kim, J. H. Jang, H. Son, S. K. Kim, Appl. Catal. B, 2015, 165, 495-502.
[15] D. Strmcnik, M. Escudero-Escribano, K. Kodama, V. R. Stamenkovic, A. Cuesta, N. M. Markovi?, Nat. Chem., 2010, 2, 880-885.
[16] H. Angerstein-Kozlowska, B. MacDougall , B. E. Conway, J. Electrochem. Soc., 1973, 120, 756-766.
[17] E. G. Ciapina, P. P. Lopes, R. Subbaraman, E. A. Ticianelli, V. Stamenkovic, D. Strmcnik, N. M. Markovic, Electrochem. Commun., 2015, 60, 30-33.
[18] L. Qiu, F. Liu, L. Zhao, W. S. Yang, J. N. Yao, Langmuir, 2006, 22, 4480-4482.
[19] Z. Y. Zhou, X. W. Kang, Y. Song, S. W. Chen, J. Phys. Chem. C, 2012, 116, 10592-10598.
[20] Z. Y. Zhou, X. W. Kang, Y. Song, S. W. Chen, Chem. Commun., 2012, 48, 3391-3393.
[21] J. E. Newton, J. A. Preece, N. V. Rees, S. L. Horswell, Phys. Chem. Chem. Phys., 2014, 16, 11435-11446.
[22] K. Miyabayashi, H. Nishihara, M. Miyake, Langmuir, 2014, 30, 2936-2942.
[23] Y. H. Chung, S. J. Kim, D. Y. Chung, H. Y. Park, Y. E. Sung, S. J. Yoo, J. H. Jang, Chem. Commun., 2015, 51, 2968-2971.
[24] J. Liu, L. H. Jiang, Q. W. Tang, E. D. Wang, L. T. Qi, S. L. Wang, G. Q. Sun, Appl. Catal. B, 2014, 148-149, 212-220.
[25] U. A. Paulus, T. J. Schmidt, H. A. Gasteiger, R. J. Behm, J. Electroanal. Chem., 2001, 495, 134-145.
[26] Y. Garsany, O. A. Baturina, K. E. Swider-Lyons, S. S. Kocha, Anal. Chem., 2010, 82, 6321-6328.
[27] F. Silva, A. Martins, Electrochim. Acta, 1998, 44, 919-929.
[28] M. D. Maciá, J. M. Campiña, E. Herrero, J. M. Feliu, J. Electroanal. Chem., 2004, 564, 141-150.
[29] M. Razaq, A. Razaq, E. Yeager, D. D. DesMarteau, S. Singh, J. Electrochem. Soc., 1989, 136, 385-390.
[30] E. Heider, N. Ignatiev, L. Jörissen, A. Wenda, R. Zeis, Electrochem. Commun., 2014, 48, 24-27.
[31] E. Heider, Z. Jusys, R. J. Behm, L. Jörissen, R. Zeis, J. Phys. Chem. C, 2015, 119, 18859-188.

铂催化氧还原反应过程中磷酸的影响及抑制磷酸吸附策略

Influence of phosphoric anions on oxygen reduction reaction activity of platinum, and strategies to inhibit phosphoric anion adsorption

PDF

可视化

被引次数

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	赵磊, 张震, 朱昭昭, 李平波, 蒋金霞, 杨婷婷, 熊佩, 安旭光, 牛晓滨, 齐学强, 陈俊松, 吴睿. 缺陷氮掺杂碳耦合Co-N₅单原子位点用于高效锌-空气电池[J]. 催化学报, 2023, 51(8): 216-224.
[2]	贡立圆, 王颖, 刘杰, 王显, 李阳, 侯帅, 武志坚, 金钊, 刘长鹏, 邢巍, 葛君杰. 重塑位于火山曲线右支的弱吸附金属单原子位点的配位环境及电子结构[J]. 催化学报, 2023, 50(7): 352-360.
[3]	张光颖, 刘旭, 张欣欣, 梁志坚, 邢耕宇, 蔡斌, 沈迪, 王蕾, 付宏刚. P修饰提高Fe-N-C的氧反应活性用于高稳定的锌-空气电池[J]. 催化学报, 2023, 49(6): 141-151.
[4]	姜润, 乔泽龙, 许昊翔, 曹达鹏. 用于氧还原反应的Fe-N-C单原子催化剂的缺陷工程[J]. 催化学报, 2023, 48(5): 224-234.
[5]	张文静, 李静, 魏子栋. 碳基氧还原电催化剂: 机理研究和多孔结构[J]. 催化学报, 2023, 48(5): 15-31.
[6]	张锋伟, 郭河芳, 刘萌萌, 赵阳, 洪峰, 李静静, 董正平, 乔波涛. 表面应力介导的碳基Pt纳米催化剂用于硝基芳烃的高选择性加氢[J]. 催化学报, 2023, 48(5): 195-204.
[7]	詹麒尼, 帅婷玉, 徐慧民, 黄陈金, 张志杰, 李高仁. 单原子催化剂的合成及其在电化学能量转换中的应用[J]. 催化学报, 2023, 47(4): 32-66.
[8]	唐甜蜜, 王寅, 韩憬怡, 张巧巧, 白雪, 牛效迪, 王振旅, 管景奇. 用于氧还原反应的双原子钴-铁催化剂[J]. 催化学报, 2023, 46(3): 48-55.
[9]	吴则星, 高玉肖, 王子璇, 肖卫平, 王新萍, 李彬, 李镇江, 刘晓斌, 马天翼, 王磊. 表面富集的超小铂纳米颗粒耦合缺陷磷化钴用于高效的电催化水分解和柔性锌空气电池[J]. 催化学报, 2023, 46(3): 36-47.
[10]	刘轩, 梁嘉顺, 李箐. 燃料电池金属间Pt-M合金氧还原催化剂的设计原理及合成方法[J]. 催化学报, 2023, 45(2): 17-26.
[11]	李昱杰, 刘媛媛, 王泽岩, 王朋, 郑昭科, 程合锋, 戴瑛, 黄柏标. 沉积于含硼金属有机框架的Pt(II)通过抑制分解来增强光催化H₂O₂的产生[J]. 催化学报, 2023, 45(2): 132-140.
[12]	樊哲琛, 万浩, 余浩, 葛君杰. 用于氧还原电催化的Fe-M-N-C基双原子催化剂的研究进展[J]. 催化学报, 2023, 54(11): 56-87.
[13]	夏苏为, 周其兴, 孙若栩, 陈立章, 张明义, 庞欢, 徐林, 杨军, 唐亚文. 在N掺杂碳纳米管/纳米线耦合超结构中原位固载CoNi纳米颗粒制备莫特-肖特基催化剂并用于高效电催化氧还原反应[J]. 催化学报, 2023, 54(11): 278-289.
[14]	程瑶佳, 宋昊强, 于镜坤, 常江伟, Geoffrey I. N. Waterhouse, 唐智勇, 杨柏, 卢思宇. 碳点衍生的碳纳米花负载钴单原子和纳米颗粒用于高效的氧还原反应[J]. 催化学报, 2022, 43(9): 2443-2452.
[15]	白雪, 管景奇. 过渡金属碳氮化物在电催化领域的应用: 改性和杂化[J]. 催化学报, 2022, 43(8): 2057-2090.