分级骨架和多层的Pt-Ni纳米晶体用于高效氧还原和甲醇氧化反应

doi:10.1016/S1872-2067(20)63680-4

催化学报 ›› 2021, Vol. 42 ›› Issue (4): 648-657.DOI: 10.1016/S1872-2067(20)63680-4

分级骨架和多层的Pt-Ni纳米晶体用于高效氧还原和甲醇氧化反应

李石波^a^,^b, 田植群^a^,^b, 刘洋^a^,^b, 蒋政^a, 哈森^a, 陈兴发^a, 帕纳斯^c^,^d^,^e^,^*(), 沈培康^a^,^b^,^#()

^a广西大学化学化工学院, 广西电化学能源材料重点实验室, 广西大学可持续能源材料中心, 广西南宁530004, 中国
^b广西大学有色金属与材料新加工技术重点实验室, 南宁530004, 中国
^c高温电化学研究所, 叶卡捷琳堡620990, 俄罗斯
^d乌拉尔联邦大学, 叶卡捷琳堡620002, 俄罗斯
^e塞萨莉大学机械工程系, 能源转换实验室, 希腊38834

收稿日期:2020-05-11 接受日期:2020-06-20 出版日期:2021-04-18 发布日期:2021-01-22
通讯作者: 帕纳斯,沈培康
基金资助:
国家重点研究开发计划(2017YFB0103001);国家自然科学基金与福建省自然科学基金(U1705252);广西科技项目(AA17204083);广西科技项目(AB16380030);广西研究生教育创新项目(YCBZ2019012)

Hierarchically skeletal multi-layered Pt-Ni nanocrystals for highly efficient oxygen reduction and methanol oxidation reactions

Shibo Li^a^,^b, Zhi Qun Tian^a^,^b, Yang Liu^a^,^b, Zheng Jang^a, Syed Waqar Hasan^a, Xingfa Chen^a, Panagiotis Tsiakaras^c^,^d^,^e^,^*(), Pei Kang Shen^a^,^b^,^#()

^aCollaborative Innovation Center of Sustainable Energy Materials, Guangxi Key Laboratory of Electrochemical Energy Materials, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China
^bKey Laboratory of New Processing Technology for Non-ferrous Metal and Materials, Ministry of Education, Guangxi University, Nanning 530004, Guangxi, China
^cInstitute of High Temperature Electrochemistry, RAS, Yekaterinburg 620990, Russia
^dUral Federal University, 19 Mira Str., Yekaterinburg 620002, Russia
^eLaboratory of Alternative Energy Conversion Systems, Department of Mechanical Engineering, University of Thessaly, Pedion Areos 38834, Greece

Received:2020-05-11 Accepted:2020-06-20 Online:2021-04-18 Published:2021-01-22
Contact: Panagiotis Tsiakaras,Pei Kang Shen
About author:^#E-mail: pkshen@gxu.edu.cn
^*E-mail: tsiak@mie.uth.gr;
Supported by:
National Key Research and Development Plan(2017YFB0103001);link project of the National Natural Science Foundation of China and Fujian Province(U1705252);Guangxi Science and Technology Projects(AA17204083);Guangxi Science and Technology Projects(AB16380030);innovation project of Guangxi Graduate Education(YCBZ2019012)

摘要/Abstract

摘要：

燃料电池是电动汽车和电子设备最有前途的清洁能源之一. Pt催化剂在氧还原反应(ORR)和甲醇氧化反应(MOR)中的电催化性能对电池系统的能源效率和电池的价格起着至关重要的作用, 因此设计高效的电催化剂以最大限度地提高铂的利用率, 从而增强电催化效果、降低成本, 已经成为燃料电池发展的一个重要方向. 早期的研究表明, 铂基催化剂可以有效地提高电催化性能, 并且它们的组成和形貌被认为是影响催化剂活性的两个关键因素. 至今, 已合成出各种各样的Pt基催化剂, 如Pt-Pb/Pt核壳纳米盘、Pt₃Co凹面立方体、Pt-Cu-Rh纳米笼、Pt-Pd纳米枝晶等, 其中纳米枝晶结构的催化剂表现出很好的氧还原性能, 其高效的催化活性被认为是暴露出的较高的比表面积促进了电子转移以及拥有较多的Pt活性位点. 本文采用简单的溶剂热法合成了具有大比表面积的Pt-Ni分层骨架结构(Pt-Ni HSNs)催化剂, 为了验证反应物所起的作用, 通过收集不同反应时间下的产物和控制单一变量, 我们发现在合成配方中加入H₂SO₄是此类Pt-Ni纳米晶体成功生长的关键触发因素. 在H₂SO₄的诱导下, Pt和Ni原子倾向于沉积在(111)面, 促使Pt-Ni合金沿晶面方向生长为八面体结构, 在此过程中发生了粒子自组装成长以及相分离过程, 最后我们用酸蚀法制造了Pt-Ni HSNs, 并通过TEM, XRD和XPS表征其微观结构及组成, 证实了Pt-Ni HSNs已经形成合金结构.
在酸性条件下, Pt-Ni HSNs在ORR反应中展示出比商业Pt/C更好的活性. 在0.9 V时的质量活性为1.25 A mg_pt^-1, 是商业Pt/C质量活性的8.9倍, 并且在10000圈的耐久性测试中, Pt-Ni HSNs的质量活性仅仅损失了21.6%, 远低于Pt/C损失的活性比例. Tafel曲线和旋转环盘测试结果表明, Pt-Ni HSNs在ORR反应中发生的是4电子过程, 证实了它的高活性. 另外, 在酸性溶液中, Pt-Ni HSNs表现出了比商业Pt/C更好的MOR催化活性, 且抗CO中毒能力更强. 这可归因于两点: (1) Pt-Ni HSNs是由多个小颗粒组装而成, 大大提高了与电解液的接触面积; (2)它独特的骨架结构减少了颗粒间团聚的可能性, 有利于质子的转移. 本文为设计先进的铂基电催化剂提供了一种新的自组装方法.

关键词: Pt-Ni分层骨架结构, 自组装, 溶剂热法, 氧还原, 甲醇氧化, 燃料电池, 活性

Abstract:

Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) in fuel cells. Maximizing the utilization of Pt based materials by modulating their morphologies to expose more active sites is a fundamental objective for the practical application of fuel cells. Herein, we report a new class of hierarchically skeletal Pt-Ni nanocrystals (HSNs) with a multi-layered structure, prepared by an inorganic acid-induced solvothermal method. The addition of H₂SO₄ to the synthetic protocol provides a critical trigger for the successful growth of Pt-Ni nanocrystals with the desired structure. The Pt-Ni HSNs synthesized by this method exhibit enhanced mass activity of 1.25 A mg_pt^-1 at 0.9 V (versus the reversible hydrogen electrode) towards ORR in 0.1-M HClO₄, which is superior to that of Pt-Ni multi-branched nanocrystals obtained by the same method in the absence of inorganic acid; it is additionally 8.9-fold higher than that of the commercial Pt/C catalyst. Meanwhile, it displays enhanced stability, with only 21.6% mass activity loss after 10,000 cycles (0.6-1.0 V) for ORR. Furthermore, the Pt-Ni HSNs show enhanced activity and anti-toxic ability in CO for MOR. The superb activity of the Pt-Ni HSNs for ORR and MOR is fully attributed to an extensively exposed electrochemical surface area and high intrinsic activity, induced by strain effects, provided by the unique hierarchically skeletal alloy structure. The novel open and hierarchical structure of Pt-Ni alloy provides a promising approach for significant improvements of the activity of Pt based alloy electrocatalysts.

Key words: Hierarchically skeletal Pt-Ni nanocrystals, Self-assembly, Solvent thermal method, Oxygen reduction reaction, Methanol oxidation reaction, Fuel cells, Activity

李石波, 田植群, 刘洋, 蒋政, 哈森, 陈兴发, 帕纳斯, 沈培康. 分级骨架和多层的Pt-Ni纳米晶体用于高效氧还原和甲醇氧化反应[J]. 催化学报, 2021, 42(4): 648-657.

Shibo Li, Zhi Qun Tian, Yang Liu, Zheng Jang, Syed Waqar Hasan, Xingfa Chen, Panagiotis Tsiakaras, Pei Kang Shen. Hierarchically skeletal multi-layered Pt-Ni nanocrystals for highly efficient oxygen reduction and methanol oxidation reactions[J]. Chinese Journal of Catalysis, 2021, 42(4): 648-657.

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图/表 8

Fig. 1. Pt-Ni bimetallic nanocomposites synthesized with the inclusion of H2SO4 in the first step: (a) SEM image, (b) low-resolution TEM images and line profile analysis, (c,d) high-magnification TEM image and (e) HAADF-STEM image with elemental mapping of a single particle. Hierarchically skeletal Pt-Ni nanocrystals (HSNs) after acid-leaching treatment: (f,g) STEM image, (h,i) high-resolution TEM images and (g) the HAADF-STEM image with EDS mapping images of a single Pt-Ni HSN.

Fig. 2. Multi-branched Pt-Ni catalyst synthesized without H2SO4: (a,b) the HAADF-STEM image of the (MBs) and (c) EDS mapping images. (d) Bright-field TEM image of an individual Pt-Ni MB; (e) the corresponding local HR-TEM image. The inset shows the corresponding FFT pattern. (f) The EDS spectra and atomic compositions of Pt-Ni MBs.

Fig. 3. HAADF-STEM images of Pt-Ni HSNs obtained at 5 (a), 8 (b), 12 (c), 16 (d), and 20 (e) h and after the chemical etching process (f). The insets depict high magnification images of the corresponding individual Pt-Ni nanostructure.

Scheme 1. The growth mechanism of Pt-Ni HSNs.

Fig. 4. (a) XRD patterns of Pt-Ni HSNs, Pt-Ni MBs, and commercial Pt/C; The corresponding XPS spectra of Pt 4f (b) and Ni 2p (c).

Fig. 5. Electrochemical properties of the Pt-Ni HSNs/C catalyst, Pt-Ni MBs and commercial Pt/C catalyst toward ORR. (a) CV curves in N2-saturated electrolyte at 50 mV s-1; (b) LSV recorded at 10 mV s-1 and 1600 rpm; (c) Mass activity comparison at 0.9 V versus RHE; (d) Normalized mass activity; (e) ORR polarization curves of the Pt-Ni HSNs and the TKK-Pt/C before and after scanning 10,000 cycles in 0.1 M HClO4 aqueous solution; (f) Performance comparison with Pt/C.

Fig. 6. (a) Tafel plots for the Pt-Ni HSNs/C catalyst, Pt-Ni MBs and commercial Pt/C catalyst; (b) the curve for the RRDE test; (c) the curve of electron transfer number of the Pt-Ni HSNs/C catalyst.

Fig. 7. Electrochemical performances of the as-prepared Pt-Ni HSNs, Pt-Ni MBs and commercial Pt/C catalysts toward MOR. (a) CV curves in 0.5-M H2SO4 + 1.0-M CH3OH aqueous solution; (b) Mass activity of the three catalysts at the peak potential; (c) CO stripping voltammograms of the three catalysts in 0.5 M H2SO4.

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分级骨架和多层的Pt-Ni纳米晶体用于高效氧还原和甲醇氧化反应

Hierarchically skeletal multi-layered Pt-Ni nanocrystals for highly efficient oxygen reduction and methanol oxidation reactions

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