铂—钌电催化剂中助剂钌的形态及稳定性研究
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摘要
PtRu催化剂是迄今为止最有效的直接甲醇燃料电池(DMFC)的阳极催化剂,目前对于何种氧化态的钌在实际电催化过程中起有效的助催化作用尚未澄清。系统考察助剂钌的化学状态与其助催化性能的关系对于提高Pt基催化剂的催化活性以及改善DMFC的性能无疑具有重要意义。本工作制备了一系列只含水合氧化钉(RuOxHy)物种的Pt-(RuOxHy)m/MWCNTs催化剂(m为Ru／Pt原子比),系统研究了催化剂组成(Ru／Pt原子比),预处理电势等因素对于水合氧化钌助催化性能的影响,并对有效稳定阳极催化剂中水合氧化钉物种的多种途径深入探索研究,取得了以下主要结果：
1)采用分步负载法制备了Pt-(RuOxHy)m/MWCNTs系列电催化剂,使用X射线衍射,X射线光电子能谱,透射电子显微镜,程序升温还原和热重分析等手段对催化剂的结构和组成进行了系统表征。结果显示,所合成样品中的钉物种均以RuOxHy状态存在,为单独考察RuOxHy的助催化作用提供了基础。对比考察了经窄电势(-0.20～0.46 V vs.SCE)和扩展电势区间(-0.20～0.96 V vs.SCE)循环伏安预处理的电极催化剂的催化性能,发现RuOxHy能有效促进CO在Pt催化剂上氧化脱除,但同时也会导致Pt电化学活性面积的下降。窄电势区间预处理不会导致RuOxHy的溶解流失,Pt-(RuOxHy)0.10／MWCNTs显示出最高的甲醇电氧化活性,为相应Pt/MWCNTs的9～10倍。扩展电势区间预处理会造成RuOxHy明显溶解,使Pt-RuOxHy催化剂性能显著下降。文中还通过调变制备条件(如：MWCNTs的预处理方式,钌前体溶液浓度及RuOxHy的干燥温度等),对影响Pt-RuO-Hy催化剂性能及RuOxHy稳定性的因素进行了讨论。
2)发现过渡金属氧化物(WOm或MoOm)的存在可有效提高Pt-(RuOxHy)0.10／MWCNTs催化剂中RuOxHy的稳定性。在扩展电势区间预处理过程中,RuOxHy的溶解程度由Pt-RuOxHy/MWCNTs中70%显著降至Pt-RuOxHy-WOm/MWCNTs和Pt-RuOxHy-MoOm/MWCNTs样品中的约15%,Pt-RuOxHy-WOm／MWCNTs和Pt-RuOxHy-MoOm/MWCNTs中Pt的抗CO毒化性能明显优于Pt-RuOxHy/MWCNTs,其甲醇电氧化的本征活性为Pt-RuOxHy／MWCNTs的2倍以上。
3)发现XC-72炭黑负载的Pt-RuOxHy样品中RuOxHy在酸性电解质中的稳定性明显优于MWCNTs负载的Pt-RuOxHy样品。但将WOm或MoOm引入Pt-RuOxHy/XC对进一步提高RuOxHy在酸性电解质中的稳定性作用并不显著。以上结果表明,RuOxHy在酸性电解质中的稳定性以及WOm或MoOm对RuOxHy的稳定效果同载体的类型密切相关。
PtRu electrocatalyst is so far the most effective anode catalyst for direct methanol fuel cell (DMFC). However, the exact state of the active ruthenium component that takes effect in promoting the catalytic performance of Pt is still a point of discussion. A comprehensive investigation of the actual chemical state and the corresponding promotional effect of ruthenium would be of great significance for improving the electrocatalytic activity of Pt catalyst as well as the performance of DMFC. In the present dissertation, a series of Pt-(RuOxHy)m electrocatalysts with RuOxHy as the exclusive ruthenium species were carefully prepared. The influence of catalyst composition (atomic Ru/Pt ratio) and pretreatment potential range on the promotional effect of RuOxHy was systematically investigated, and further, various approaches were studied in depth in a hope to efficiently stabilize the RuOxHy species. The results obtained are as follows:
1) Multi-walled carbon nanotube supported Pt-(RuOxHy)m electrocatalysts (m is atomic Ru/Pt ratio), in which amorphous hydrous ruthenium oxide (RuOxHy) is the exclusive Ru-containing species, were prepared and comprehensively characterized by X-ray diffraction, X-ray photoelectron spectroscopy, temperature programmed reduction, thermogravimetric analysis and transmission electron microscopy techniques. Before the electrochemical measurement, the electrode catalyst was pretreated in H2SO4 by cyclic voltammetric scanning over two different potential ranges:narrow (-0.20-0.46 V vs. SCE) and extended (-0.20～0.96 V vs. SCE) potential ranges. The results show that RuOxHy can effectively promote the oxidative removal of CO on Pt surface, but also lead to a loss of electrochemically active surface area of Pt. When the electrode catalysts were pretreated in the narrow potential range, Pt-(RuOxHy)0.10/MWCNTs exhibited the highest activity for methanol oxidation among all the investigated samples, with both mass-specific activity (MSA) and intrinsic activity (IA) one order of magnitude higher than those of the reference Pt/MWCNT catalyst, which further verified the significant promotion effect of RuOxHy. After being subjected to electrochemical pretreatment over the extended potential range, however, the activity for methanol oxidation of Pt-(RuOxHy)m/MWCNTs decreased remarkably relative to their counterparts pretreated in narrow potential range duing to the dissolution of RuOxHy. The effects of preparation conditions on the electrochemical behavior of Pt-RuOxHy catalyst and the stability of RuOxHy were also studied.
2) It was found that the doping of transition metal oxides (WOm and MoOm) could effectively improve the stability of RuOxHy in Pt-(RuOxHy)0.10/MWCNTs. The dissolution of RuOxHy in Pt-(RuOxHy)0.10/MWCNT catalyst could be reduced from 70% to ca.15% by the addition of WOm or MoOm. Furthermore, the resultant Pt-RuOxHy-WOm/MWCNT and Pt-RuOxHy-MoOm/MWCNT catalysts showed enhanced CO tolerance, and also more than double in IA value of Pt for methanol electro-oxidation, as compared with Pt-RuOxHy/MWCNT catalyst.
3) The effects of the carbon support properties on Pt-RuOxHy were also investigated. The stability of RuOxHy in Pt-RuOxHy catalysts supported on XC-72 was significantly higher than that in the catalysts supported on MWCNTs. The introduction of WOm or MoOm into Pt-RuOxHy/MWCNTs could induce an enhanced stability of RuOxHy, while it was not applicable for Pt-RuOxHy/XC catalyst. These results showed that the effects of WOm and MoOm on the the stability of RuOxHy were closely related with the type of carbon support.
1)采用分步负载法制备了Pt-(RuOxHy)m/MWCNTs系列电催化剂,使用X射线衍射,X射线光电子能谱,透射电子显微镜,程序升温还原和热重分析等手段对催化剂的结构和组成进行了系统表征。结果显示,所合成样品中的钉物种均以RuOxHy状态存在,为单独考察RuOxHy的助催化作用提供了基础。对比考察了经窄电势(-0.20～0.46 V vs.SCE)和扩展电势区间(-0.20～0.96 V vs.SCE)循环伏安预处理的电极催化剂的催化性能,发现RuOxHy能有效促进CO在Pt催化剂上氧化脱除,但同时也会导致Pt电化学活性面积的下降。窄电势区间预处理不会导致RuOxHy的溶解流失,Pt-(RuOxHy)0.10／MWCNTs显示出最高的甲醇电氧化活性,为相应Pt/MWCNTs的9～10倍。扩展电势区间预处理会造成RuOxHy明显溶解,使Pt-RuOxHy催化剂性能显著下降。文中还通过调变制备条件(如：MWCNTs的预处理方式,钌前体溶液浓度及RuOxHy的干燥温度等),对影响Pt-RuO-Hy催化剂性能及RuOxHy稳定性的因素进行了讨论。
2)发现过渡金属氧化物(WOm或MoOm)的存在可有效提高Pt-(RuOxHy)0.10／MWCNTs催化剂中RuOxHy的稳定性。在扩展电势区间预处理过程中,RuOxHy的溶解程度由Pt-RuOxHy/MWCNTs中70%显著降至Pt-RuOxHy-WOm/MWCNTs和Pt-RuOxHy-MoOm/MWCNTs样品中的约15%,Pt-RuOxHy-WOm／MWCNTs和Pt-RuOxHy-MoOm/MWCNTs中Pt的抗CO毒化性能明显优于Pt-RuOxHy/MWCNTs,其甲醇电氧化的本征活性为Pt-RuOxHy／MWCNTs的2倍以上。
3)发现XC-72炭黑负载的Pt-RuOxHy样品中RuOxHy在酸性电解质中的稳定性明显优于MWCNTs负载的Pt-RuOxHy样品。但将WOm或MoOm引入Pt-RuOxHy/XC对进一步提高RuOxHy在酸性电解质中的稳定性作用并不显著。以上结果表明,RuOxHy在酸性电解质中的稳定性以及WOm或MoOm对RuOxHy的稳定效果同载体的类型密切相关。
PtRu electrocatalyst is so far the most effective anode catalyst for direct methanol fuel cell (DMFC). However, the exact state of the active ruthenium component that takes effect in promoting the catalytic performance of Pt is still a point of discussion. A comprehensive investigation of the actual chemical state and the corresponding promotional effect of ruthenium would be of great significance for improving the electrocatalytic activity of Pt catalyst as well as the performance of DMFC. In the present dissertation, a series of Pt-(RuOxHy)m electrocatalysts with RuOxHy as the exclusive ruthenium species were carefully prepared. The influence of catalyst composition (atomic Ru/Pt ratio) and pretreatment potential range on the promotional effect of RuOxHy was systematically investigated, and further, various approaches were studied in depth in a hope to efficiently stabilize the RuOxHy species. The results obtained are as follows:
1) Multi-walled carbon nanotube supported Pt-(RuOxHy)m electrocatalysts (m is atomic Ru/Pt ratio), in which amorphous hydrous ruthenium oxide (RuOxHy) is the exclusive Ru-containing species, were prepared and comprehensively characterized by X-ray diffraction, X-ray photoelectron spectroscopy, temperature programmed reduction, thermogravimetric analysis and transmission electron microscopy techniques. Before the electrochemical measurement, the electrode catalyst was pretreated in H2SO4 by cyclic voltammetric scanning over two different potential ranges:narrow (-0.20-0.46 V vs. SCE) and extended (-0.20～0.96 V vs. SCE) potential ranges. The results show that RuOxHy can effectively promote the oxidative removal of CO on Pt surface, but also lead to a loss of electrochemically active surface area of Pt. When the electrode catalysts were pretreated in the narrow potential range, Pt-(RuOxHy)0.10/MWCNTs exhibited the highest activity for methanol oxidation among all the investigated samples, with both mass-specific activity (MSA) and intrinsic activity (IA) one order of magnitude higher than those of the reference Pt/MWCNT catalyst, which further verified the significant promotion effect of RuOxHy. After being subjected to electrochemical pretreatment over the extended potential range, however, the activity for methanol oxidation of Pt-(RuOxHy)m/MWCNTs decreased remarkably relative to their counterparts pretreated in narrow potential range duing to the dissolution of RuOxHy. The effects of preparation conditions on the electrochemical behavior of Pt-RuOxHy catalyst and the stability of RuOxHy were also studied.
2) It was found that the doping of transition metal oxides (WOm and MoOm) could effectively improve the stability of RuOxHy in Pt-(RuOxHy)0.10/MWCNTs. The dissolution of RuOxHy in Pt-(RuOxHy)0.10/MWCNT catalyst could be reduced from 70% to ca.15% by the addition of WOm or MoOm. Furthermore, the resultant Pt-RuOxHy-WOm/MWCNT and Pt-RuOxHy-MoOm/MWCNT catalysts showed enhanced CO tolerance, and also more than double in IA value of Pt for methanol electro-oxidation, as compared with Pt-RuOxHy/MWCNT catalyst.
3) The effects of the carbon support properties on Pt-RuOxHy were also investigated. The stability of RuOxHy in Pt-RuOxHy catalysts supported on XC-72 was significantly higher than that in the catalysts supported on MWCNTs. The introduction of WOm or MoOm into Pt-RuOxHy/MWCNTs could induce an enhanced stability of RuOxHy, while it was not applicable for Pt-RuOxHy/XC catalyst. These results showed that the effects of WOm and MoOm on the the stability of RuOxHy were closely related with the type of carbon support.
引文
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