CN101038969A - 具有高催化活性的钌核铂壳纳米薄膜的制备方法 - Google Patents

具有高催化活性的钌核铂壳纳米薄膜的制备方法 Download PDF

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CN101038969A
CN101038969A CNA2007100396475A CN200710039647A CN101038969A CN 101038969 A CN101038969 A CN 101038969A CN A2007100396475 A CNA2007100396475 A CN A2007100396475A CN 200710039647 A CN200710039647 A CN 200710039647A CN 101038969 A CN101038969 A CN 101038969A
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蔡文斌
李巧霞
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Abstract

本发明属薄膜电极制备技术领域，具体为一种具有超低Pt含量，且对CO和CH3OH有较高催化活性的钌核铂壳纳米薄膜的制备方法。其步骤是先在半圆硅柱反射底面化学镀金，采用两步湿法在金上电沉积5－6纳米厚的Ru膜，再在Ru膜上采用自发沉积法覆盖Pt层，重复上述还原/沉积步骤1－4次，即得所需Ru@Pt纳米薄膜电极。该薄膜电极兼有Pt－Ru合金催化剂的优点，而且可以直接用于现场ATR－SEIRAS研究电催化吸附与效应。

Description

具有高催化活性的钌核铂壳纳米薄膜的制备方法
技术领域
本发明属薄膜电极制备技术领域，具体涉及一种具有超低Pt含量且对CO和CH3OH有较高的催化活性的钌核铂壳纳米薄膜的制备方法。该薄膜可用于衰减全反射表面增强红外光谱(ATR-SEIRAS)现场研究电催化过程。
背景技术
面向燃料电池催化剂的表面电化学一直是电催化研究的主要内容，其相关研究也从较早的单晶电极为主，逐步向纳米结构的薄膜电极过渡，其驱动力是最终设计研制高活性、低Pt载量的阳极和阴极催化剂[1，2]。近来，新型高效的电催化表面体系已从传统的双金属合金(阳极如Pt-Ru和阴极如Pt-Cr等)逐步发展到了表面(亚)单层修饰的双元金属：一类是亚单层Ru修饰的Pt电极(Pt@Ru)，它对CO和甲醇电催化氧化具有很好的催化活性；另一类是亚单层Pt修饰的Ru电极(Ru@Pt)，它对含CO的H2氧化，以及(亚)单层Pt修饰的Pd电极(Pd@Pt或Pd@Pt-Ru)对O2还原有超高的活性[3]。因此探索上述纳米结构薄膜表面的制备、表面增强红外效应及其在电催化研究中的应用，对指导新型高效催化材料的研发具有十分现实意义。
金属的自沉积是制备Ru@Pt或Pt@Ru超薄外层结构一种新型的方法[4]。采用此方法，可以在不加外界电压的情况下，使一种贵金属在另一种贵金属表面沉积下来。此方法的优点在于可以控制价格昂贵的金属的含量，使Pt的含量降低，同时又利用了Pt-Ru的协同催化效应。尤其是Pt自沉积在Ru基上可以提高Pt的抗CO中毒性，大大降低了催化剂中Pt的使用量。下列用简单的公式表明自沉积发生的原理
ΔU = Δ E Pt / Pt Cl 6 2 - - Δ E R u 0 / Ru ( oxidized ) > 0
[PtCl6]2-+4e-＝Pt0+6Cl-
Ru0+x(H2O)＝RuOxHx+(2x-y)H++(2x-y)e-
文献报道的自沉积发生的过程都是在单晶电极上发生。例如在Ru单晶上自沉积Pt，需要在高温下H2气还原、退火，再迅速转入除去氧气的H2PtCl6溶液中。所用设备比较昂贵，操作麻烦，并且研究体系与实际的催化剂相距甚远；Tong[5]小组在水溶液中在本体Au电极电镀Ru膜，在此基础上进行自沉积Pt，电化学测量表明所制的Ru@Pt膜对CO及CH3OH具有电催化氧化活性。
另一方面，表面增强红外光谱(SEIRAS)[6]是一种研究电极界面分子结构信息的重要分析工具。配以衰减全反射(ATR)模式的表面增强红外吸收光谱(ATR-SEIRAS)具有表面信号强、表面选律简单，可避免传统外反射红外吸收光谱(IRAS)面临的问题，如表面信号不够强、电场分布不均匀、传质补充滞后、溶液背景的干扰等。电化学ATR-SEIRAS可方便检测所制备的PtRu膜电极对CO及CH3OH电催化氧化特性。值得一提是，前述制备的Ru@Pt结构都无法用于现场ATR-SEIRAS研究，本发明将解决这个问题。
参考文献：
1.(a)K.Sasaki，Y.Mo，J.X.Wang，M.Balasubramanian，F.Uribe，J.McBreen，R.R.Adzic，Electrochim.Acta 48(2003)3841.(b)J.X.Wang，S.R.Brankovic，Y.Zhu，J.C.Hanson，R.R.Adzic，J.Electrochem.Soc.，150(2003)A1108.(c)J.Zhang，M.B.Vukmirovic，Y.Xu，M.Mavrikakis，R.R.Adzic，Angew.Chem.Int.Ed.44(2005)2132.(d)J.Zhang，M.B.Vukmirovic，K.Sasaki A.U.Nilekar M.Mavrikakis，R.R.Adzic，J.Am.Chem.Soc.127(2005)12480
2.F.Maillard，G.-Q.Lu，A.Wieckowski，U.Stimming，J.Phys.Chem.B.109(2005)16230(feature article)
3.F.Maillard，E.R.Savinova，P.A.Simonov，V.I.Zaikovskii，U.Stimming J.Phys.Chem.B，108(2004)17893.
4.Brankovic，S.R.；McBreen，J.；Adzic，R.R.J.Electroanal.Chem.2001，503，99
5.Bingchen，Du.，Yuye，Tong，J.Phys.Chem.B 2005，109，17775
6.M.Osawa，In Handbook of Vibrational Spectroscopy；Chalmers J.M.，Griffiths，P.R.，Eds.；John Wiley & Sons：Chichester，UK，2002；Vol.1，p.785.
发明内容
针对现有Pt-Ru二元催化材料Pt含量高以及无法直接应用于现场ATR-SEIRAS测量的问题，本发明提供一种新方法在ATR红外窗口Si基底制备超低Pt含量且具有SEIRA效应的Ru@Pt纳米薄膜，根据Pt能够在Ru上自发沉积这一特点，可以在Ru纳米颗粒上覆盖亚单层到数单层的Pt外壳，从而降低催化剂中二元催化剂中Pt的含量，同时兼具Pt-Ru合金催化剂的优点，可以直接应用于现场ATR-SEIRAS研究电催化吸附与反应。
本发明解决其技术问题所采用的技术方案是：
首先，在半圆硅柱反射底面化学镀金，采用两步湿法在金基底上电沉积5-6纳米厚的Ru膜；然后在Ru电极上采用自发沉积法覆盖Pt层，重复还原/沉积步骤n次，可得到具有抗CO中毒、高催化活性、超低Pt含量的Ru@Pt纳米薄膜电极；这里n为1-4，Pt层的厚度为亚单层到数个单层。将制备的工作电极组装到光谱电解池上，进行电化学及红外光谱实验。
本发明的有益效果：代替文献上使用的高温，H2氛还原的苛刻条件，而且还可以在除单晶之外的纳米薄膜上自沉积出具有催化活性Ru@Pt纳米薄膜，可应用于现场ATR-SEIRAS研究，获得了明显的吸附物种的比表面红外光谱信号，显示了Pt-Ru催化剂的协同效应。
附图说明
下面结合附图和具体实例对本发明Ru@Pt催化剂进一步说明。
图1是Ru膜电极及经过1次(2次)还原/自沉积循环的Ru@Pt1(Ru@Pt2)膜在0.1M HClO4溶液中的循环伏安(CV)曲线。图中表明随着Pt含量的增加，CV曲线逐渐表现出Pt上H的吸脱附电流峰，明显不同于纯Ru的CV曲线。
图2是Ru膜、Pt膜与Ru@Pt膜在饱和CO的HClO4中的循环伏安曲线(50mV/s)。图中表明CO在Ru@Pt膜的起始电位介于纯的Pt，Ru之间，说明所制的Ru@Pt膜具有类似Pt-Ru合金的催化活性。
图3是经过还原/沉积二个循环后的Ru@Pt膜在含饱和CO的HClO4溶液中的红外光谱图。参比谱采于-0.2V的0.1M HClO4溶液中。图中可看到有两个红外吸收峰，分别位于2029，2028cm-1左右。根据文献分别对应于Pt-CO和Ru-CO的线性振动。用拟合的方法分出这两个峰，计算出Stark效应分别是33和28cm-1V-1。
图4是Ru@Pt膜在0.1M HCLO4中加入甲醇前后的循环伏安曲线(50mV/s)。从图上可以看到，加入甲醇后，有明显的甲醇氧化峰的出现，表明所制的PtRu膜对甲醇有催化作用，此结论与溅射的PtRu合金性质相似，但此种制备方法大大降低了贵金属Pt的含量。
具体实施方式
Ru基/Pt外壳工作电极制备：首先，在半圆硅柱反射底面化学镀金，采用两步湿法可在金基底上电沉积5-6纳米厚的Ru膜；在Ru电极上采用自发沉积法覆盖Pt层，即在0.01-0.2M HClO4中于-0.5V至0V(SCE)电还原Ru电极表面上的氧化物，然后断开电位控制注入0.01-5mL 0.1-2g/10mL H2PtCl6溶液(计算出最终的H2PtCl6的浓度为0.1-10mM)中，浸泡1-2小时。重复上述还原/沉积步骤1-4次，可得到具有抗CO中毒、高催化活性、超低Pt含量的Ru@Pt纳米薄膜电极。
电化学及红外实验准备：在0.1M HCLO4中，控-0.2V电位，通CO 30min(或注入0.5M CH3OH)，扫循环伏安图；采用多步(或动)电位模式实时测量ATR-SEIRAS光谱。检测结果见图1-图4。

Claims (2)

1、一种具有高催化活性的钌核铂壳纳米薄膜的制备方法，其特征在于具体步骤如下：首先，在半圆硅柱反射底面化学镀金，采用两步湿法在金基底上电沉积5-6纳米厚的Ru膜；然后在Ru电极上采用自发沉积法覆盖Pt层，重复还原/沉积步骤1-4次，可得到具有抗CO中毒、高催化活性、超低Pt含量的Ru@Pt纳米薄膜电极。
2、根据权利要1所述的具有高催化活性的钌核铂壳纳米薄膜的制备方法，其特征在于所述在Ru电极上采用自发沉积法覆盖Pt层，其步骤为：在0.01-0.2M HClO4中，于-0.5V至0V电位下电还原Ru电极表面上的氧化物，然后断开电位，注入0.01-5mL的0.1-2g/10mL H2PtCl6溶液，浸泡1-2小时；重复上述还原/沉积步骤1-4次。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101841043B (zh) * 2010-01-25 2012-05-23 上海电力学院 一种燃料电池用Ru基/Pt肤膜纳米薄膜电极制备方法
WO2018122569A1 (en) * 2016-12-30 2018-07-05 The Hong Kong University Of Science And Technology Core-shell nanoparticle catalysts

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101841043B (zh) * 2010-01-25 2012-05-23 上海电力学院 一种燃料电池用Ru基/Pt肤膜纳米薄膜电极制备方法
WO2018122569A1 (en) * 2016-12-30 2018-07-05 The Hong Kong University Of Science And Technology Core-shell nanoparticle catalysts
CN110114918A (zh) * 2016-12-30 2019-08-09 香港科技大学 核壳纳米颗粒催化剂

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