高活性和高稳定性的核壳结构PtPx@Pt/C催化氧还原

doi:10.1016/S1872-2067(21)63901-3

催化学报 ›› 2021, Vol. 42 ›› Issue (12): 2173-2180.DOI: 10.1016/S1872-2067(21)63901-3

高活性和高稳定性的核壳结构PtP_x@Pt/C催化氧还原

李伟泽^a, 卢帮安^a, 干林^b, 田娜^a^,^#(), 张朋阳^a, 颜伟^a, 陈玮鑫^a, 陈友虎^a, 周志有^a, 孙世刚^a^,^*()

^a厦门大学化学化工学院, 化学能源协同中心, 固体表面物理化学国家重点实验室, 福建厦门361005
^b清华大学深圳国际研究生院材料研究院, 广东深圳518055

收稿日期:2021-02-05 接受日期:2021-02-05 出版日期:2021-12-18 发布日期:2021-09-10
通讯作者: 田娜,孙世刚
基金资助:
国家重点研发项目(2020YFB1505804);国家自然科学基金(92045302);国家自然科学基金(21573183);深圳市基础研究计划(JCYJ20170817161445322)

High activity and durability of carbon-supported core-shell PtP_x@Pt/C catalyst for oxygen reduction reaction

Wei-Ze Li^a, Bang-An Lu^a, Lin Gan^b, Na Tian^a^,^#(), Peng-Yang Zhang^a, Wei Yan^a, Wei-Xin Chen^a, You-Hu Chen^a, Zhi-You Zhou^a, Shi-Gang Sun^a^,^*()

^aState Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China
^bInstitute of Materials Research, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, Guangdong, China

Received:2021-02-05 Accepted:2021-02-05 Online:2021-12-18 Published:2021-09-10
Contact: Na Tian,Shi-Gang Sun
About author:# E-mail: tnsd@xmu.edu.cn
* E-mail: sgsun@xmu.edu.cn;
Supported by:
National Key Research and Development Program of China(2020YFB1505804);National Natural Science Foundation of China(92045302);National Natural Science Foundation of China(21573183);Basic Research Program of Shenzhen(JCYJ20170817161445322)

摘要/Abstract

摘要：

在质子交换膜燃料电池中, 金属铂是最高效的阴极氧还原催化剂之一, 但是铂昂贵的价格严重阻碍了其在燃料电池领域中的大规模商业化应用. 通过铂与3d过渡金属(Fe、Co和Ni)合金化可以有效提高催化剂的氧还原活性, 然而在实际的高腐蚀性、高电压和高温的燃料电池运行环境中, 铂合金纳米粒子易发生溶解、迁移和团聚, 从而导致催化剂耐久性差. 同时过渡金属离子的溶出会影响质子交换膜的质子传导, 并且一些过渡金属离子会催化芬顿反应, 产生高腐蚀性•OH自由基, 加快Nafion和催化剂的劣化.

与过渡金属掺杂相比, 非金属掺杂具有明显优势: 一方面, 非金属溶出产生的阴离子不会取代Nafion中的质子, 也不会催化芬顿反应; 另一方面, 与3d过渡金属相比, 非金属具有更高的电负性, 其掺杂很容易调节Pt的电子结构. 因此, 本文通过非金属磷掺杂合成具有优异稳定性的核壳结构PtP_x@Pt/C氧还原催化剂. 通过热处理磷化商业碳载铂形成磷化铂(PtP₂), 经由酸洗处理产生富铂壳层, 即PtP_x@Pt/C. X射线粉末多晶衍射结果证明了PtP₂相的存在, 并且进一步通过电子能量损失谱对纳米粒子进行微区面扫描分析以及X射线光电子能谱分析证实了富铂壳层的存在, 壳层厚度约1 nm. 得益于核壳结构及磷掺杂引起的电子结构效应, PtP_1.4@Pt/C催化剂在0.90 V (RHE)时的面积活性(0.62 mA cm^-2)与质量活性(0.31 mA μg_Pt^-1)分别是商业Pt/C的2.8倍和2.1倍. 更重要的是, 在加速耐久性测试中, PtP_1.4@Pt/C催化剂在30000圈电位循环后质量活性仅衰减6%, 在90000圈电位循环后仅衰减25%; 而商业Pt/C催化剂在30000圈电位循环后就衰减46%. PtP_1.4@Pt/C催化剂高活性与高稳定性主要归功于核壳结构、磷掺杂引起的电子结构效应以及磷掺杂增加了碳载体对催化剂粒子的锚定作用进而阻止了其迁移团聚. 综上所述, 本文为设计同时具有优异活性与稳定性非金属掺杂Pt基氧还原催化剂提供新的思路.

关键词: 氧还原反应, 非金属掺杂, 磷化处理, 核壳结构, 耐久性

Abstract:

Alloying Pt with transition metals can significantly improve the catalytic properties for the oxygen reduction reaction (ORR). However, the application of Pt-transition metal alloys in fuel cells is largely limited by poor long-term durability because transition metals can easily leach. In this study, we developed a nonmetallic doping approach and prepared a P-doped Pt catalyst with excellent durability for the ORR. Carbon-supported core-shell nanoparticles with a P-doped Pt core and Pt shell (denoted as PtP_x@Pt/C) were synthesized via heat-treatment phosphorization of commercial Pt/C, followed by acid etching. Compositional analysis using electron energy loss spectroscopy and X-ray photoelectron spectroscopy clearly demonstrated that Pt was enriched in the near-surface region (approximately 1 nm) of the carbon-supported core-shell nanoparticles. Owning to P doping, the ORR specific activity and mass activity of the PtP_1.4@Pt/C catalyst were as high as 0.62 mA cm^-2 and 0.31 mA μg_Pt^-1, respectively, at 0.90 V, and they were enhanced by 2.8 and 2.1 times, respectively, in comparison with the Pt/C catalyst. More importantly, PtP_1.4@Pt/C exhibited superior stability with negligible mass activity loss (6% after 30000 potential cycles and 25% after 90000 potential cycles), while Pt/C lost 46% mass activity after 30000 potential cycles. The high ORR activity and durability were mainly attributed to the core-shell nanostructure, the electronic structure effect, and the resistance of Pt nanoparticles against aggregation, which originated from the enhanced ability of the PtP_1.4@Pt to anchor to the carbon support. This study provides a new approach for constructing nonmetal-doped Pt-based catalysts with excellent activity and durability for the ORR.

Key words: Oxygen reduction reaction, Nonmetallic doping, Phosphorization, Core-shell nanostructure, Durability

李伟泽, 卢帮安, 干林, 田娜, 张朋阳, 颜伟, 陈玮鑫, 陈友虎, 周志有, 孙世刚. 高活性和高稳定性的核壳结构PtP_x@Pt/C催化氧还原[J]. 催化学报, 2021, 42(12): 2173-2180.

Wei-Ze Li, Bang-An Lu, Lin Gan, Na Tian, Peng-Yang Zhang, Wei Yan, Wei-Xin Chen, You-Hu Chen, Zhi-You Zhou, Shi-Gang Sun. High activity and durability of carbon-supported core-shell PtP_x@Pt/C catalyst for oxygen reduction reaction[J]. Chinese Journal of Catalysis, 2021, 42(12): 2173-2180.

×
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(21)63901-3

https://www.cjcatal.com/CN/Y2021/V42/I12/2173

图/表 6

Fig. 1. TEM image (a) and particle size histogram (b) of PtP1.4@Pt/C after acid etching treatment; (c) HRTEM image of PtP1.4@Pt/C (The inset shows the FFT pattern of the image); (d) XRD patterns of PtP1.4@Pt/C and commercial Pt/C.

Fig. 2. Structural and compositional characterization of PtP1.4@Pt/C. (a) HAADF-STEM image; (b)-(e) EELS mapping images; (f) Atomic models of PtP1.4@Pt; (g) EELS line-scanning profiles extracted from the boxed area in (e), showing that the Pt shell is ~1 nm thick.

Fig. 3. XPS of Pt 4f of PtP1.4@Pt/C and commercial Pt/C catalysts (a), and P 2p of PtP1.4@Pt/C (b).

Fig. 4. (a) ORR polarization curves of PtPx@Pt/C (x = 1.4, 0.5, and 0.06) and commercial Pt/C catalysts in an O2-saturated 0.1 M HClO4 solution, recorded at 10 mV s-1 at 30 °C; (b) CV curves in an Ar-saturated 0.1 M HClO4 solution at 50 mV s-1; (c) SA (solid bars) and MA (dashed bars) of the electrocatalysts for ORR at 0.90 V; (d) H2O2 yield (%H2O2) and electron transfer number (n) of ORR on Pt@PtP1.4/C.

Fig. 5. ORR polarization curves of PtP1.4@Pt/C (a) and Pt/C (b) before and after ADTs of potential cycling between 0.60 and 1.0 V; (c) ORR MAs at 0.90 V of the electrocatalysts before and after ADTs; (d) Loss of MAs for PtP1.4@Pt/C catalyst compared with reference results shown in Table S3.

Fig. 6. (a) Loss of ECSA for PtP1.4@Pt/C and commercial Pt/C after ADTs; TEM images of PtP1.4@Pt/C after ADTs of 30000 (b) and 90000 (c) potential cycles, and Pt/C after ADTs of 30000 potential cycles (d).

参考文献

[1]	Y. Bing, H. Liu, L. Zhang, D. Ghosh, J. Zhang, Chem. Soc. Rev., 2010, 39, 2184-2202.
[2]	B. A. Lu, N. Tian, S. G. Sun, Curr. Opin. Electrochem., 2017, 4, 76-82.
[3]	R. Borup, J. Meyers, B. Pivovar, Y. S. Kim, R. Mukundan, N. Garland, D. Myers, M. Wilson, F. Garzon, D. Wood, P. Zelenay, K. More, K. Stroh, T. Zawodzinski, J. Boncella, J. E McGrath, M. Inaba, K. Miyatake, M. Hori, K. Ota, Z. Ogumi, S. Miyata, A. Nishikata, Z. Siroma, Y. Uchimoto, K. Yasuda, K. i. Kimijima, N. Iwashita, Chem. Rev., 2007, 107, 3904-3951.
[4]	Y. J. Wang, N. N. Zhao, B. Z. Fang, H. Li, X. T. T Bi, H. J. Wang, Chem. Rev., 2015, 115, 3433-3467.
[5]	X. Tian, X. Zhao, Y. Q. Su, L. Wang, H. Wang, D. Dang, B. Chi, H. Liu, E. J. M Hensen, X. W. D. Lou, B.Y. Xia, Science, 2019, 366, 850-856.
[6]	S. Wang, L. Xiong, J. Bi, X. Zhang, G. Yang, S. Yang, ACS Appl. Mater. Interfaces, 2018, 10, 27009-27018.
[7]	B. A. Lu, T. Sheng, N. Tian, Z. C. Zhang, C. Xiao, Z. M. Cao, H. B. Ma, Z. Y. Zhou, S. G. Sun, Nano Energy, 2017, 33, 65-71.
[8]	J. Kim, Y. Lee, S.h. Sun, J. Am. Chem. Soc., 2010, 132, 4996-4997.
[9]	V. Mazumder, M. Chi, K. L. More, S. Sun, J. Am. Chem. Soc., 2010, 132, 7848-7849.
[10]	L. Z. Bu, N. Zhang, S. J. Guo, X. Zhang, J. Li, J. L. Yao, T. Wu, G. Lu, J. Y. Ma, D. Su, X. Q. Huang, Science, 2016, 354, 1410-1414.
[11]	K. Jiang, D. Zhao, S. Guo, X. Zhang, X. Zhu, J. Guo, G. Lu, X. Huang, Sci. Adv., 2017, 3, 1601705.
[12]	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.
[13]	V. R. Stamenkovic, B. Fowler, B. S. Mun, G. Wang, P. N. Ross, C. A. Lucas, N. M. Marković, Science, 2007, 315, 493-497.
[14]	S. Li, Z. Q. Tian, Y. Liu, Z. Jang, S. W. Hasan, X. Chen, P. Tsiakaras, P. K. Shen, Chin. J. Catal., 2021, 42, 648-657.
[15]	J. A. Gilbert, N. N. Kariuki, R. Subbaraman, A. J. Kropf, M. C. Smith, E. F. Holby, D. Morgan, D. J. Myers, J. Am. Chem. Soc., 2012, 134, 14823-14833.
[16]	J. Huang, C. Ding, Y. Yang, G. Liu, W. B. Cai, Chin. J. Catal., 2019, 40, 1895-1903.
[17]	Y. Shao, G. Yin, Y. Gao, P. Shi, J. Electrochem. Soc., 2006, 153, A1093-A1097.
[18]	J. Li, Z. Xi, Y. T. Pan, J. S. Spendelow, P. N. Duchesne, D. Su, Q. Li, C. Yu, Z. Yin, B. Shen, Y. S. Kim, P. Zhang, S. Sun, J. Am. Chem. Soc., 2018, 140, 2926-2932.
[19]	J. Liang, Z. Miao, F. Ma, R. Pan, X. Chen, T. Wang, H. Xie, Q. Li, Chin. J. Catal., 2018, 39, 583-589.
[20]	Y. H. Wen, R. Huang, C. Li, Z. Z. Zhu, S. G. Sun, J. Mater. Chem., 2012, 22, 7380-7386.
[21]	Q. Xu, W. Chen, Y. Yan, Z. Wu, Y. Jiang, J. Li, T. Bian, H. Zhang, J. Wu, D. Yang, Sci. Bull., 2018, 63, 494-501.
[22]	V. Beermann, M. Gocyla, E. Willinger, S. Rudi, M. Heggen, R. E Dunin Borkowski, M. G. Willinger, P. Strasser, Nano Lett., 2016, 16, 1719-1725.
[23]	K. Okaya, H. Yano, K. Kakinuma, M. Watanabe, H. Uchida, ACS Appl. Mater. Interfaces, 2012, 4, 6982-6991.
[24]	L. Dubau, J. Nelayah, T. Asset, R. Chattot, F. Maillard, ACS Catal., 2017, 7, 3072-3081.
[25]	T. Okada, Y. Ayato, M. Yuasa, I. Sekine, J. Phys. Chem. B, 1999, 103, 3315-3322.
[26]	K. Barbusiński, Ecolog. Chem. Eng. S, 2009, 16, 347-358.
[27]	M. Wang, X. Qin, K. Jiang, Y. Dong, M. Shao, W. B. Cai, J. Phys. Chem. C, 2017, 121, 3416-3423.
[28]	J. Li, J. Chen, Q. Wang, W. B. Cai, S. Chen, Chem. Mater., 2017, 29, 10060-10067.
[29]	A. R. J Kucernak, K. F. Fahy, V. N. N. Sundaram, Catal. Today, 2016, 262, 48-56.
[30]	Y. Xiong, Y. Ma, L. Zou, S. Han, H. Chen, S. Wang, M. Gu, Y. Shen, L. Zhang, Z. Xia, J. Li, H. Yang, J. Catal., 2020, 382, 247-255.
[31]	L. Zhang, M. Wei, S. Wang, Z. Li, L.X. Ding, H. Wang, Chem. Sci., 2015, 6, 3211-3216.
[32]	L. Feng, H. Xue, ChemElectroChem, 2017, 4, 20-34.
[33]	M. V. Gerasimov, Y. N. Simirskii, Metallurgist, 2008, 52, 477-481.
[34]	A. R. J Kucernak, V. N. Naranammalpuram Sundaram, J. Mater. Chem. A, 2014, 2, 17435-17445.
[35]	Y. R. Luo, Comprehensive Handbook of Chemical Bond Energies, CRC Press, 2007, 965.
[36]	B. A. Lu, L. F. Shen, J. Liu, Q. H. Zhang, L. Y. Wan, D. J. Morris, R. X. Wang, Z. Y. Zhou, G. Li, T. Sheng, L. Gu, P. Zhang, N. Tian, S. G. Sun, ACS Catal., 2020, 11, 355-363.
[37]	S. Suzuki, Y. Ohbu, T. Mizukami, Y. Takamori, M. Morishima, H. Daimon, M. Hiratani, J. Electrochem. Soc., 2009, 156, B27-B31.
[38]	M. Jiang, L. Ma, M. Gan, L. Hu, H. He, F. Xie, H. Zhang, Electrochim. Acta, 2019, 293, 30-39.
[39]	R. Guo, W. Bi, K. Zhang, Y. Liu, C. Wang, Y. Zheng, M. Jin, Chem. Mater., 2019, 31, 8205-8211.
[40]	W. Tian, Y. W. Wang, W. W. Fu, J. F. Su, H. Zhang, Y. Wang, J. Mater. Chem. A, 2020, 8, 20463-20473.
[41]	K. D. Jensen, J. Tymoczko, J. Rossmeisl, A. S. Bandarenka, I. Chorkendorff, M. Escudero Escribano, I. E. L. Stephens, Angew. Chem. Int. Ed., 2018, 57, 2800-2805.
[42]	D. Y. Chung, S. W. Jun, G. Yoon, S. G. Kwon, D. Y. Shin, P. Seo, J. M. Yoo, H. Shin, Y. H. Chung, H. Kim, B. S. Mun, K. S. Lee, N. S. Lee, S. J. Yoo, D. H. Lim, K. Kang, Y. E. Sung, T. Hyeon, J. Am. Chem. Soc., 2015, 137, 15478-15485.
[43]	H. Li, P. Wen, D. S. Itanze, Z. D. Hood, S. Adhikari, C. Lu, X. Ma, C. Dun, L. Jiang, D. L. Carroll, Y. Qiu, S. M. Geyer, Nat. Commun., 2020, 11, 3928.

高活性和高稳定性的核壳结构PtP_x@Pt/C催化氧还原

High activity and durability of carbon-supported core-shell PtP_x@Pt/C catalyst for oxygen reduction reaction

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 6

参考文献

相关文章 15

编辑推荐

Metrics

[1]	孙丽娟, 于晓慧, 唐丽永, 王伟康, 刘芹芹. 构建K₃PW₁₂O₄₀/CdS核壳S型异质结实现同步太阳能光催化分解水和选择性苯甲醇氧化反应[J]. 催化学报, 2023, 52(9): 164-175.
[2]	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.
[3]	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.
[4]	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.
[5]	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.
[6]	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.
[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]	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.
[12]	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.
[13]	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.
[14]	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.
[15]	邱春禹, 万里洋, 王宇成, Muhammad Rauf, 洪宇浩, 袁家寅, 周志有, 孙世刚. 工况表征方法揭示燃料电池催化层中过氧化氢浓度[J]. 催化学报, 2022, 43(7): 1918-1926.

高活性和高稳定性的核壳结构PtPx@Pt/C催化氧还原

High activity and durability of carbon-supported core-shell PtPx@Pt/C catalyst for oxygen reduction reaction

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 6

参考文献

相关文章 15

编辑推荐

Metrics

高活性和高稳定性的核壳结构PtP_x@Pt/C催化氧还原

High activity and durability of carbon-supported core-shell PtP_x@Pt/C catalyst for oxygen reduction reaction