铂纳米晶的电子结构调控用于高效乙醇电化学氧化

引用本文: 张生, 刘海, 张娜, 夏荣, 况思宇, 尹鸽平, 马新宾. 铂纳米晶的电子结构调控用于高效乙醇电化学氧化[J]. 催化学报, 2019, 40(12): 1904-1911. doi: S1872-2067(19)63442-X shu

Citation: Sheng Zhang, Hai Liu, Na Zhang, Rong Xia, Siyu Kuang, Geping Yin, Xinbin Ma. Tuning the electronic structure of platinum nanocrystals towards high efficient ethanol oxidation[J]. Chinese Journal of Catalysis, 2019, 40(12): 1904-1911. doi: S1872-2067(19)63442-X shu

铂纳米晶的电子结构调控用于高效乙醇电化学氧化

张生 ^a, ,
刘海 ^a, ,
张娜 ^c, ,
夏荣 ^a, ,
况思宇 ^a, ,
尹鸽平 ^b, ,
马新宾 ^a,

a 天津大学化工学院, 绿色合成与转化教育部重点实验室, 天津化学化工协同创新中心, 天津 300072;
b 哈尔滨工业大学化工与化学学院, 城市水资源与环境国家重点实验室, 黑龙江哈尔滨 150001;
c 北京航天动力研究所, 北京 100076
基金项目:
天津市重点研发项目（18ZXJMTG00180）；国家自然科学基金（21433003）.

摘要: 直接乙醇燃料电池是一种高效、绿色的低温燃料电池，但其发展受到阳极电催化氧化乙醇缓慢动力学的限制.目前，Pt基材料是最适合用于乙醇氧化反应（EOR）的电催化剂.然而其活性中心容易被反应过程中生成的中间体CO吸附而中毒，在很大程度上降低了催化剂的活性和稳定性.减轻Pt中毒的一种有效方法是引入第二种金属（如Sn，Ru，Rh等）以形成双金属催化剂.其中，Pt-Sn双金属催化剂由于其优异的乙醇氧化性能而得到了广泛研究.根据相关报道，与Pt相邻的Sn原子有利于H₂O在其表面吸附解离并形成OH_ads活性物种，从而促进Pt表面反应中间体CO的氧化并重新释放出活性位.在金属氧化物中，氧化锡（SnO_x）由于其在酸性电解质中较高的稳定性而被广泛用作DAFC中的助催化剂.目前，大多数研究认为，引入第二金属后催化活性的增强源于几何效应，而其中电子效应的影响却不明确.因此，深入了解Pt和SnO_x之间的电子效应对于提高乙醇的电催化性能具有重要意义.
本文首先通过乙二醇法合成了Pt/SnO_x/石墨烯纳米复合材料，通过X-射线衍射（XRD）和透射电子显微镜（TEM）对催化剂的结构和形貌进行了表征.结果表明，Pt/SnO_x异质结构均匀分散在石墨烯载体上.XPS表明，催化剂中的Pt主要以Pt⁰形式存在，其被认为是乙醇氧化的主要活性位点.同时，Pt/SnO_x/石墨烯中Pt 4f的结合能相对于Pt/C催化剂负向移动了0.37eV，这主要是由于存在从石墨烯和SnO_x到Pt的电子转移，证明了载体和金属氧化物对Pt活性中心的电子改性.
电化学循环伏安（CV）曲线中，正扫的氧化峰反映了电催化剂对乙醇的氧化能力.Pt/SnO_x/石墨烯和Pt/石墨烯的峰电流密度分别是商业Pt/XC-72催化剂的2.82和1.82倍，表明Pt/SnO_x/石墨烯具有更加优异的乙醇电催化氧化活性.此外，Pt/SnO_x/石墨烯的正向氧化峰电位比Pt/石墨烯和Pt/XC-72低约30至40mV，表明SnO_x和石墨烯的引入降低了乙醇氧化的起始电位.
CO氧化实验中，Pt/SnO_x/石墨烯对应乙醇氧化的起始电位和峰电位都有所下降，表明CO在Pt/SnO_x/石墨烯上更容易被氧化.Pt/SnO_x/石墨烯催化剂的CO氧化增强效应可以解释为SnO_x和石墨烯的供电子效应降低了Pt对CO中π反键轨道的电子给予能力，从而削弱了CO在Pt上的吸附.此外，在Pt/SnO_x异质结构中，SnO_x的电子给予效应可促进H₂O的解离，在Pt上产生更多的OH_ads并加速相邻Pt活性位点上CO_ads的氧化.Pt/SnO_x/石墨烯也显示出良好的稳定性，这主要是由于石墨烯和SnO_x的电子给予效应使得Pt表面的电子亲和力减弱，从而产生更多的氧化物质（如水分解中的OH_ads），加速了中毒中间体的氧化和去除效率.
与常规的铂纳米催化剂相比，该催化剂表现出较高的活性和稳定性，是非常有潜力的乙醇电氧化催化剂.

关键词:

English

Tuning the electronic structure of platinum nanocrystals towards high efficient ethanol oxidation

a Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Centre of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China;
b State Key Laboratory of Urban Water Resource and Environment, School of Chemical Engineering & Technology, Harbin Institute of Technology, Harbin 150001, Heilongjiang, China;
c Beijing Aerospace Propulsion Institute, Beijing 100076, China
Received Date: 29 April 2019
Revised Date: 28 June 2019
Fund Project:
The authors are grateful to the financial support from the Key Research and Development Project of Tianjin (18ZXJMTG00180), and the National Nature Science Foundation of China (21433003).

Abstract: Direct ethanol fuel cell is a promising low temperature fuel cell, but its development is hindered by sluggish kinetics of anode catalysts for ethanol oxidation. Here a high efficient platinum/tin oxide/Graphene nanocomposite is synthesized through a facile and environmentally benign method. The structure and morphology are carefully characterized by X-ray diffraction and Transmission electron microscopy, showing a clear platinum/tin oxide heterostructure uniformly dispersed on graphene support. This catalyst demonstrates the highest activity among the reported catalysts and much higher durability towards ethanol oxidation compared to conventional platinum nanocatalysts. The ultrahigh activity originates from promoted removal of poisoning carbon monoxide immediate species on platinum due to a strong electronic donating effect from both tin oxide and graphene, which is fully supported by carbon monoxide stripping and X-ray photoelectron spectroscopy analysis. Our platinum/tin oxide/Graphene appears to be a promising candidate for ethanol oxidation electrocatalysts.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

铂纳米晶的电子结构调控用于高效乙醇电化学氧化

English

Tuning the electronic structure of platinum nanocrystals towards high efficient ethanol oxidation

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

铂纳米晶的电子结构调控用于高效乙醇电化学氧化

English

Tuning the electronic structure of platinum nanocrystals towards high efficient ethanol oxidation

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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