负载铂的缺陷活性炭作为一种在碱性条件下具有优异氧还原反应性能的催化剂

doi:10.1016/S1872-2067(17)62765-7

摘要/Abstract

摘要：

燃料电池因其高的能量转化效率和无污染的特点而被认为是目前最有发展前景的高效清洁发电技术，然而燃料电池迟缓的阴极氧还原反应（ORR）极大地降低了其整体性能. 目前，铂碳（Pt/C）仍然是催化ORR最有效的催化剂. 但是，由于Pt的价格很高以及其稳定性差等缺点极大地限制了燃料电池的大规模化应用，因此设计与开发廉价高效稳定的ORR电催化剂对实现燃料电池的大规模商业化应用具有重要的意义. 在过去的几十年中，研究发现Pt和其他的非贵金属形成合金，如Pt-Fe，Pt-Ni和Pt-Co等不仅可以降低Pt的用量，而且也可以使所得催化剂具有较高的ORR活性. 此外，研究发现核-壳结构也可以提高铂基ORR催化剂的活性与稳定性. 但是，这些催化剂的制备一般会使用毒性和危险性较高的有机化学试剂并且其制备过程繁杂，因此并不适用于大规模的实际生产. 从这个角度来说，开发一种简易的方法来制备高效廉价的ORR催化剂显得尤为重要.
之前的研究表明，Pt的载体对提高所得ORR催化剂来说非常关键. 可以发现大部分载体都是经过改进的碳材料，如微孔/介孔材料，杂原子掺杂的石墨烯以及缺陷碳等. 尤其是我们课题组最近提出的一种缺陷催化机理表明，在碳材料中特定类型的缺陷（如缺陷活性炭（D-AC）和缺陷石墨烯等）可以使纯的碳材料具有很高的电催化活性. 尽管D-AC的ORR催化活性在不含金属的催化剂中位居前列，但是其催化性能仍然比商业化的Pt/C差. 鉴于此，如果我们可以通过使用具有较高ORR催化活性的D-AC作为Pt的载体而降低Pt的用量，但并不牺牲其催化活性，这将是一个很具有前景的方法来解决昂贵ORR催化剂的问题，进而有可能实现燃料电池的大规模化生产.
在本研究中，我们通过一种简易的液相浸渍法以D-AC作为Pt的载体而制备了一种高效的ORR催化剂. 具体来说，我们通过调节合成过程中的还原温度实现了控制所得催化剂中Pt颗粒尺寸的目的，同时我们也对催化剂中的Pt含量对其催化性能的影响进行了探讨. 研究表明，所得催化剂中Pt的颗粒尺寸以及其结晶性都可能影响其ORR催化活性. 更为重要的是，所得样品D-AC@5.0%Pt中含有约5 wt% 的Pt，然而其在碱性条件下的ORR催化活性已经超过了商业化的含有20 wt% Pt的Pt/C，例如其起始电位和半波电位都优于商业化的Pt/C，并且其稳定性也比商业化的Pt/C好. 除此之外，D-AC@5.0%Pt在催化ORR的过程中表现出了一种一步四电子的反应路径，而且中间产物过氧化氢的产率很低. 所得催化剂D-AC@5.0%Pt优异的ORR反应活性表明D-AC中的特殊缺陷以及负载的Pt纳米颗粒都对提高其催化活性具有很大的贡献，同时也说明选择合适的载体对提高电催化剂的活性至关重要. 实验结果还表明，D-AC@5.0%Pt在酸性条件下的ORR催化活性也有一定的提高，虽然比商业化的Pt/C要差一些. 更进一步减小Pt的颗粒尺寸到亚纳米甚至原子级别可能会明显地提高其在酸性电解液中的ORR催化活性.

关键词: 活性炭, 缺陷, 铂, 氧还原反应, 燃料电池

Abstract:

The exploration of highly active and durable cathodic oxygen reduction reaction (ORR) catalysts with economical production cost is still the bottleneck to realize the large-scale commercialization of fuel cells and metal-air batteries. Given that carbon support is crucial to the electrocatalysts, and Pt is the best-known ORR catalyst so far, in this work, we employed a simple impregnation method for synthesizing a kind of defective activated carbon (D-AC) supported low Pt content electrocatalysts for the ORR. The reduction conditions of the Pt-containing precursor were firstly optimized, and the influence of the Pt loading amount on the ORR was investigated as well. The results show that the obtained D-AC@5.0%Pt sample (contains 5 wt% Pt) has surpassed the commercial Pt/C with 20 wt% Pt for the ORR in an alkaline solution. In the meantime, it is more stable than the commercial Pt/C. The outstanding ORR performance of the D-AC@5.0%Pt confirms that both the unique defects in the D-AC and the introduced Pt particles are indispensable to the ORR. Particularly, the ORR activity of the synthesized catalysts is superior to most of the reported counterparts, but with much easier preparation methods and lower production cost, making them more advantageous in practical fuel cell applications.

Key words: Activated carbon, Defect, Platinum, Oxygen reduction reaction, Fuel cell

严学成, 贾毅, 张龙舟, 姚向东. 负载铂的缺陷活性炭作为一种在碱性条件下具有优异氧还原反应性能的催化剂[J]. 催化学报, 2017, 38(6): 1011-1020.

Xuecheng Yan, Yi Jia, Longzhou Zhang, Xiangdong Yao. Platinum stabilized by defective activated carbon with excellent oxygen reduction performance in alkaline media[J]. Chinese Journal of Catalysis, 2017, 38(6): 1011-1020.

×
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(17)62765-7

https://www.cjcatal.com/CN/Y2017/V38/I6/1011

参考文献

[1] J. Snyder, T. Fujita, M. W. Chen, J. Erlebacher, Nat. Mater., 2010, 9, 904-907.
[2] B. C. H. Steele, A. Heinzel, Nature, 2001, 414, 345-352.
[3] V. R. Stamenkovic, B. Fowler, B. S. Mun, G. F. Wang, P. N. Ross, C. A. Lucas, N. M. Markovi?, Science, 2007, 315, 493-497.
[4] C. Chen, Y. J. Kang, Z. Y. Huo, Z. W. Zhu, W. Y. Huang, H. L. Xin, J. D. Snyder, D. G. Li, J. A. Herron, M. Mavrikakis, M. F. Chi, K. L. More, Y. D. Li, N. M. Markovic, G. A. Somorjai, P. D. Yang, V. R. Stamenkovic, Science, 2014, 343, 1339-1343.
[5] H. A. Gasteiger, S. S. Kocha, B. Sompalli, F. T. Wagner, Appl. Catal. B, 2005, 56, 9-35.
[6] A. Morozan, B. Jousselme, S. Palacin, Energy Environ. Sci., 2011, 4, 1238-1254.
[7] J. Kim, Y. Lee, S. H. Sun, J. Am. Chem. Soc., 2010, 132, 4996-4997.
[8] H. Yano, M. Kataoka, H. Yamashita, H. Uchida, M. Watanabe, Langmuir, 2007, 23, 6438-6445.
[9] C. Venkateswara Rao, B. Viswanathan, J. Phys. Chem. C, 2009, 113, 18907-18913.
[10] F. H. B. Lima, J. R. C. Salgado, E. R. Gonzalez, E. A. Ticianelli, J. Electrochem. Soc., 2007, 154, A369-A375.
[11] X. Q. Huang, Z. P. Zhao, L. Cao, Y. Chen, E. B. Zhu, Z. Y. Lin, M. F. Li, A. M. Yan, A. Zettl, Y. M. Wang, X. F. Duan, T. Mueller, Y. Huang, Science, 2015, 348, 1230-1234.
[12] S. J. Jiang, Y. W. Ma, G. Q. Jian, H. S. Tao, X. Z. Wang, Y. N. Fan, Y. N. Lu, Z. Hu, Y. Chen, Adv. Mater., 2009, 21, 4953-4956.
[13] M. V. Lebedeva, V. Pierron-Bohnes, C. Goyhenex, V. Papaefthimiou, S. Zafeiratos, R. R. Nazmutdinov, V. Da Costa, M. Acosta, L. Zosiak, R. Kozubski, D. Muller, E. R. Savinova, Electrochim. Acta, 2013, 108, 605-616.
[14] K. W. Nam, J. Song, K. H. Oh, M. J. Choo, H. Park, J. K. Park, J. W. Choi, Carbon, 2012, 50, 3739-3747.
[15] D. L. Wang, H. L. Xin, R. Hovden, H. S. Wang, Y. C. Yu, D. A. Muller, F. J. DiSalvo, H. D. Abruña, Nat. Mater., 2013, 12, 81-87.
[16] P. Mani, R. Srivastava, P. Strasser, J. Phys. Chem. C, 2008, 112, 2770-2778.
[17] H. C. Tsai, Y. C. Hsieh, T. H. Yu, Y. J. Lee, Y. H. Wu, B. V. Merinov, P. W. Wu, S. Y. Chen, R. R. Adzic, W. A. Goddard III, ACS Catal., 2015, 5, 1568-1580.
[18] C. Koenigsmann, A. C. Santulli, K. P. Gong, M. B. Vukmirovic, W. P. Zhou, E. Sutter, S. S. Wong, R. R. Adzic, J. Am. Chem. Soc., 2011, 133, 9783-9795.
[19] H. Wang, H. H. Da, S. Ji, S. J. Liao, R. F. Wang, J. Electrochem. Soc., 2013, 160, H266-H270.
[20] S. Limpattayanate, M. Hunsom, J. Solid State Electrochem., 2013, 17, 1221-1231.
[21] X. C. Yan, Y. Jia, J. Chen, Z. H. Zhu, X. D. Yao, Adv. Mater., 2016, 28, 8771-8778.
[22] H. J. Liu, Y. L. Cao, F. Wang, Y. Q. Huang, ACS Appl. Mater. Interfaces, 2014, 6, 819-825.
[23] Z. X. Yan, M. M. Zhang, J. M. Xie, H. E. Wang, W. Wei, J. Power Sources, 2013, 243, 48-53.
[24] M. H. Seo, S. M. Choi, E. J. Lim, I. H. Kwon, J. K. Seo, S. H. Noh, W. B. Kim, B. Han, ChemSusChem, 2014, 7, 2609-2620.
[25] J. E. Park, Y. J. Jang, Y. J. Kim, M. S. Song, S. Yoon, D. H. Kim, S. J. Kim, Phys. Chem. Chem. Phys., 2014, 16, 103-109.
[26] X. C. Yan, Y. Jia, T. Odedairo, X. J. Zhao, Z. Jin, Z. H. Zhu, X. D. Yao, Chem. Commun., 2016, 52, 8156-8159.
[27] H. Y. Zhao, C. H. Sun, Z. Jin, D. W. Wang, X. C. Yan, Z. G. Chen, G. S. Zhu, X. D. Yao, J. Mater. Chem. A, 2015, 3, 11736-11739.
[28] X. J. Zhao, X. Q. Zou, X. C. Yan, C. L. Brown, Z. G. Chen, G. S. Zhu, X. D. Yao, Inorg. Chem. Front., 2016, 3, 417-421.
[29] Y. Jia, L. Z. Zhang, A. J. Du, G. P. Gao, J. Chen, X. C. Yan, C. L. Brown, X. D. Yao, Adv. Mater., 2016, 28, 9532-9538.
[30] U. A. Paulus, T. J. Schmidt, H. A. Gasteiger, R. J. Behm, J. Electroanal. Chem., 2001, 495, 134-145.
[31] Y. Y. Liang, Y. G. Li, H. L. Wang, J. G. Zhou, J. Wang, T. Regier, H. J. Dai, Nat. Mater., 2011, 10, 780-786.
[32] D. Radivojevi?, K. Seshan, L. Lefferts, Appl. Catal. A, 2006, 301, 51-58.
[33] S. Kaneko, M. Izuka, A. Takahashi, M. Ohshima, H. Kurokawa, H. Miura, Appl. Catal. A, 2012, 427-428, 85-91.
[34] F. Fina, H. Menard, J. T. S. Irvine, Phys. Chem. Chem. Phys., 2015, 17, 13929-13936.
[35] M. R. Othman, N. N. N. Mustafa, A. L. Ahmad, Microporous Mesoporous Mater., 2006, 91, 268-275.
[36] J. N. Zheng, J. J. Lü, S. S. Li, M. W. Xue, A. J. Wang, J. J. Feng, J. Mater. Chem. A, 2014, 2, 3445-3451.
[37] J. F. Xu, X. Y. Liu, Y. Chen, Y. M. Zhou, T. H. Lu, Y. W. Tang, J. Mater. Chem., 2012, 22, 23659-23667.
[38] G. T. Fu, L. F. Ding, Y. Chen, J. Lin, Y. W. Tang, T. H. Lu, CrystEngComm, 2014, 16, 1606-1610.
[39] Z. Y. Liu, G. X. Zhang, Z. Y. Lu, X. Y. Jin, Z. Chang, X. M. Sun, Nano Res., 2013, 6, 293-301.
[40] X. Yang, L. F. Gan, C. Z. Zhu, B. H. Lou, L. Han, J. Wang, E. K. Wang, Chem. Commun., 2014, 50, 234-236.
[41] F. P. Pan, Q. P. Zhao, J. Wang, J. Y. Zhang, ChemElectroChem, 2015, 2, 2032-2040.
[42] M. De Koninck, B. Marsan, Electrochim. Acta, 2008, 53, 7012-7021.
[43] Y. Y. Liang, H. L. Wang, J. G. Zhou, Y. G. Li, J. Wang, T. Regier, H. J. Dai, J. Am. Chem. Soc., 2012, 134, 3517-3523.
[44] T. Odedairo, X. C. Yan, J. Ma, Y. L. Jiao, X. D. Yao, A. J. Du, Z. H. Zhu, ACS Appl. Mater. Interfaces, 2015, 7, 21373-21380.
[45] F. Hasche, M. Oezaslan, P. Strasser, Phys. Chem. Chem. Phys., 2010, 12, 15251-15258.
[46] H. Yano, T. Akiyama, P. Bele, H. Uchida, M. Watanabe, Phys. Chem. Chem. Phys., 2010, 12, 3806-3814.
[47] T. J. Kim, G. Kwon, Y. T. Kim, Chem. Commun., 2014, 50, 596-598.
[48] B. Y. S. Lin, D. W. Kirk, S. J. Thorpe, J. Power Sources, 2006, 161, 474-483.
[49] D. S. Su, G. Q. Sun, Angew. Chem. Int. Ed., 2011, 50, 11570-11572.
[50] C. H. Choi, M. W. Chung, H. C. Kwon, S. H. Park, S. I. Woo, J. Mater. Chem. A, 2013, 1, 3694-3699.
[51] K. Mamtani, U. S. Ozkan, Catal. Lett., 2015, 145, 436-450.
[52] J. B. Wu, H. Yang, Acc. Chem. Res., 2013, 46, 1848-1857.