CN111068670B - 酸性产氧电催化剂含有拉伸应变的钌@二氧化钌核壳纳米球的制备方法 - Google Patents
酸性产氧电催化剂含有拉伸应变的钌@二氧化钌核壳纳米球的制备方法 Download PDFInfo
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Abstract
本发明涉及酸性产氧电催化剂含有拉伸应变的钌@二氧化钌核壳纳米球的制备方法。将二氧化钌粉末置于超纯水中超声分散至没有沉淀的悬浊液;将悬浊液在室温持续搅拌下,用纳秒平行脉冲激光辐照,得到黑色溶液;将黑色溶液置于冰箱中冷冻成固体,之后将冷冻的固体放置于冻干机中进行冻干,得到含有应变的钌@二氧化钌核壳纳米球。本发明制备的样品,10mA cm‑2处过电势仅为191mV,比商用二氧化钌降低了100mV以上,是目前性能最优的不引入其他原子的钌基催化剂。本发明的合成方法工艺简单、操作方便、易于控制,为设计和合成高效电催化剂提供了一条有用的途径。
Description
技术领域
本发明属于核壳结构构造技术领域,涉及激光辐照商用二氧化钌粉末制备含应变的钌@二氧化钌核壳纳米球,利用二氧化钌外壳中的拉应变产生RuX+(4<x<5)增加本征活性及钌核增加导电性来提升酸性环境中的电催化产氧性能。特别是提出酸性产氧电催化剂含有拉伸应变的钌@二氧化钌核壳纳米球的制备方法。
背景技术
水作为一种储量巨大且可循环利用的资源,可以被电解槽电化学分解为清洁的氢能和化学品氧气,来实现环境友好的能源循环。与碱性电解槽相比,质子交换膜(PEM)电解槽具有明显的优势,例如更高的电流密度、更高的电压效率、更低的欧姆损耗和更少的不利反应,使其成为生产氢能和氧气的最有希望的装置。作为电化学水分解的半反应之一,氧析出反应(OER)过程是一个四电子和四质子耦合的多步电化学反应,与双电子转移的氢析出发应(HER)相比,需要更高的能量来补偿缓慢的动力学过程。PEM电解槽中高的阳极电势和苛刻的腐蚀环境,为阳极电催化剂设定了更高的选择标准,同时由于缺乏高活性和高稳定性的阳极电催化剂,限制了PEM电解槽的广泛应用。在这种条件下,适用的阳极电催化剂主要限于钌(Ru)和铱(Ir)及其衍生物,因为其固有的电子结构而具有较高的催化活性。然而由于Ir的低地球丰度和高成本,我们更希望开发RuO2基电催化剂。遗憾的是,商业RuO2电催化剂在酸性介质中的OER过电位仍然过高,稳定性也比在碱性介质中低得多,无法满足实际应用的要求。此外,从实用的角度出发,我们始终希望提高贵金属Ru基电催化剂的本征活性以减少实际应用所需的催化剂量。因此,迫切需要改性RuO2基电催化剂以提升其在酸性介质中的析氧反应催化活性。
迄今为止,研究已经证实活性中间体*OOH的形成是酸性介质中OER的速控步(RDS),但是RuO2基催化剂中Ru4+活性位点对活性中间体*OOH的吸附过强,导致商用RuO2具有约300mV的过电势(10mAcm-2)。参见:Reier T,Nong H N,Teschner D,et al.Adv.EnergyMater.,2017,7(1),1601275.为了减弱*OOH在Ru4+活性位点上的吸附能并降低RDS能垒,研究人员做了大量的试验来调节Ru4+活性位点的电子结构,包括杂原子掺杂和制备Ru基固溶体。Retuerto等制备了Na掺杂的Sr1-xNaxRuO3,在酸性介质中具有优异的OER活性,Na掺杂增加了Ru4+的价态,使O p带和Ru d带中心正位移,削弱了Ru-吸附剂键。参见:Retuerto M,Pascual L,Calle-Vallejo F,et al.Nat.Commun.,2019,10(1),2041.Lin等合成了Cr0.6Ru0.4O2固溶体,Cr能够吸Ru的电子,使Ru位点处的电荷密度降低,Cr位点处的电荷密度升高,Ru的高度氧化状态有利于降低RDS形成*OOH的能垒,提高了水氧化为氧的能力。参见:Lin Y,Tian Z,Zhang L,et al.Nat.Commun.,2019,10(1),162.以上研究都是通过引入杂原子实现对Ru4+活性位点电子结构进行调整,目前还没有一种不引入杂原子的简便的方法去调整Ru4+活性位点的电子结构的研究出现。
为了解决这一难题,通过简单的激光辐照商用RuO2粉末,我们成功地制备了含应变的Ru@RuO2核壳纳米球,RuO2外壳中存在拉应变,倾向于向内收缩,Ru核存在压应变,倾向于向外膨胀,二者相互对抗,使得应变稳定存在。利用RuO2外壳中的拉应变创造RuX+(4<x<5)增加本征活性及Ru核增加导电性来提升酸性环境中的OER电催化活性。
发明内容
针对目前还未有在不引入杂原子的情况下来调整Ru4+活性位点的电子结构进而改性二氧化钌基催化剂的问题,通过调整激光的辐照能量和时间,合成含有应变稳定存在的钌@二氧化钌核壳纳米球,利用二氧化钌外壳中的拉伸应变创造RuX+(4<x<5)增加本征活性,以及钌核增加材料整体导电性,来提升酸性环境中的OER电催化活性。该发明绿色环保、安全易控、工艺简单。
本发明的技术方案是:
一种酸性产氧电催化剂含有拉伸应变的钌@二氧化钌核壳纳米球的制备方法,包括如下步骤:
(1)将二氧化钌粉末置于超纯水中超声分散至没有沉淀的悬浊液;
(2)将步骤(1)制得的悬浊液在室温持续搅拌下,用纳秒平行脉冲激光辐照,得到黑色溶液;
(3)将步骤(2)所得的黑色溶液置于冰箱中冷冻成固体,之后将冷冻的固体放置于冻干机中进行冻干,得到含有应变的钌@二氧化钌核壳纳米球。
所述步骤(1)二氧化钌粉末和超纯水的配制浓度为0.5-2.0mg/mL。
所述步骤(2)纳秒脉冲激光作用辐照时,激光的能量为185~518mJ,时间10~60min,波长为1064nm,激光重复频率为10Hz。
所述步骤(2)激光辐照过程中搅拌速度为300-500转/分钟。
所述步骤(2)激光辐照过程中容器为锥形瓶或其他容器。
所述步骤(3)冻干过程中,冰箱温度为-4℃至-20℃,冻干机温度为-10至-50℃,真空度为20-50Pa。
在脉冲激光辐照下,RuO2粉末吸收激光能量并迅速加热,从而导致Ru-O键断裂。在随后的快速冷却过程中,一部分O原子聚集在一起形成O-O键,然后以O2的形式逸出,同时Ru原子迅速聚集形成含有压缩应变的Ru纳米晶体。其余的O和Ru原子形成Ru-O键,并继续吸收下一个激光脉冲能量,从而增加了Ru-O键的长度。最后,在Ru核的外部形成含有拉伸应变的RuO2外壳,从而得到含应变的Ru@RuO2核壳结构。
整个实验过程都在暴露的环境中进行,无需通入保护气,辐照过后直接将样品冻干即可,操作简单。
本发明的钌@二氧化钌核壳纳米球电化学性能测试:称取5mg制备的Ru@RuO2核壳纳米球和5mg炭黑,加入800μL去离子水、200μL异丙醇,和8μL Nafion溶液,超声混匀后制成催化剂浆液。用移液枪取适量的催化剂浆液涂在抛光的L型电极上,保证负载量为0.3mgcm-2,待自然风干。在氧气饱和的0.5M H2SO4中,使用三电极***进行电化学性能测试。主要比较10mA cm-2处过电势、Tafel斜率、界面转移电阻、比活性和质量活性。
我们制备的样品,10mA cm-2处过电势仅为191mV,比商用二氧化钌降低了100mV以上,是目前性能最优的不引入其他原子的钌基催化剂。其具有较低的Tafel斜率(48.90mVdec-1)和较小的界面转移电阻,说明显著改善的动力学和界面转移速率。同时,面积比活性和质量比活性显著提高,质量比活性比商用二氧化钌提高了18倍。
本发明的合成方法工艺简单、操作方便、易于控制,是一种环境友好的绿色合成工艺,为设计和合成高效电催化剂提供了一条有用的途径。
附图说明
图1为利用纳秒激光辐照制备含应变的钌@二氧化钌核壳纳米球的工艺装置图。
图2(a)为含应变的钌@二氧化钌核壳纳米球(Ru@RuO2-L)和商用二氧化钌(RuO2-C)的X射线衍射图;(b)为含应变的钌@二氧化钌核壳纳米球(Ru@RuO2-L)的扫描电子显微镜照片,插图:钌@二氧化钌核壳纳米球(Ru@RuO2-L)的粒径分布图;(c)为含应变的钌@二氧化钌核壳纳米球(Ru@RuO2-L)的高倍透射电子显微镜照片;(d)为商用二氧化钌(RuO2-C)的高倍透射电子显微镜照片。
图3(a)为含应变的钌@二氧化钌核壳纳米球(Ru@RuO2-L)和商用二氧化钌(RuO2-C)的扩展Ru K-edge X射线吸收精细结构图;(b)为含应变的钌@二氧化钌核壳纳米球(Ru@RuO2-L)和商用二氧化钌(RuO2-C)的Ru 3p轨道X射线光电子能谱分析图;(c)为含应变的钌@二氧化钌核壳纳米球(Ru@RuO2-L)和商用二氧化钌(RuO2-C)的Ru M-edge电子能量损失谱。
图4为含应变的钌@二氧化钌核壳纳米球(Ru@RuO2-L)和商用二氧化钌(RuO2-C)在0.5M硫酸溶液中的电催化产氧性能对比图。
具体实施方式
整个制备过程均在实验室自然条件下进行。
实施例1:
(1)将商用二氧化钌粉末置于超纯水中以1.0mg/mL的浓度超声分散至没有沉淀的悬浊液;
(2)将步骤(1)制得的悬浊液,室温持续搅拌,搅拌速度为400转/分钟,用纳秒平行脉冲激光辐照,用纳秒平行脉冲激光辐照20min,激光器能量为518mJ,得到黑色溶液;
(3)将步骤(2)所得的黑色溶液置于冰箱中在-4℃冷冻成固体,之后将冷冻的固体放置于冻干机中,在-50℃和50Pa进行冻干,得到含有应变的钌@二氧化钌核壳纳米球。
利用纳秒激光辐照制备含应变的钌@二氧化钌核壳纳米球的工艺装置图如图1所示,装有RuO2水分散液的容器置于磁力搅拌器上,脉冲激光平行光辐照。
利用纳秒平行脉冲激光(20min、518mJ)辐照后制得的含应变的钌@二氧化钌核壳纳米球(Ru@RuO2-L)的形貌和物相表征如图2所示。图2(a)XRD图谱说明Ru@RuO2-L是由RuO2和Ru两相组成的,结晶性也较好。图2(b)说明激光辐照后得到的纳米球尺寸均匀,同时由插图中的粒径统计分布可知,纳米球的尺寸较小,约为21.7nm。图2(c)和(d)是Ru@RuO2-L和RuO2-C的高倍透射电镜图,清楚地显示了Ru@RuO2-L的核壳结构,壳厚度为2-3nm,外壳的晶格对应于RuO2(PDF#88-0322)的(110)晶面,晶格间距为0.338nm,大于图2(d)中RuO2-C(110)晶面的0.318nm,说明了在RuO2外壳中拉伸应变的存在。
对Ru@RuO2-L的应变及Ru价态表征如图3所示。由图3(a)R空间谱图,RuO2-C在处的峰归因于Ru-O键,而Ru@RuO2-L中的Ru-O键长度略微延长至表明在Ru@RuO2-L样品中,Ru-O键拉伸6%,即RuO2外壳中存在6%的拉伸应变;图3(b)显示,与RuO2-C相比,Ru@RuO2-L的Ru4+的峰向更高结合能偏移;图3(c)显示,与RuO2-C相比,Ru@RuO2-L的M2、M3峰向更高能量损失偏移,XPS和EELS结果一同说明Ru@RuO2-L中Ru4+位点电荷密度降低,产生RuX+(4<x<5)。
Ru@RuO2-L的酸性电催化产氧性能如图4所示。10mAcm-2处过电势为191mV,比RuO2-C降低了100多mV,具有较低的Tafel斜率(48.90mV dec-1)和较小的界面转移电阻,同时,面积比活性和质量比活性显著提高,质量比活性比RuO2-C提高了18倍。
实施例2:
(1)将商用二氧化钌粉末置于超纯水中以0.5mg/mL的浓度超声分散至没有沉淀的悬浊液。
(2)将步骤(1)制得的悬浊液,室温持续搅拌,搅拌速度为500转/分钟,用纳秒平行脉冲激光辐照,用纳秒平行脉冲激光辐照60min,激光器能量为185mJ,得到黑色溶液;
(3)将步骤(2)所得的黑色溶液置于冰箱中在-20℃冷冻成固体,之后将冷冻的固体放置于冻干机中,在-10℃和20Pa进行冻干,得到含有应变的钌@二氧化钌核壳纳米球。
实施例3:
(1)将商用二氧化钌粉末置于超纯水中以0.5mg/mL的浓度超声分散至没有沉淀的悬浊液。
(2)将步骤(1)制得的悬浊液,室温持续搅拌,搅拌速度为300转/分钟,用纳秒平行脉冲激光辐照,用纳秒平行脉冲激光辐照10min,激光器能量为409mJ,得到黑色溶液;
(3)将步骤(2)所得的黑色溶液置于冰箱中在-10℃冷冻成固体,之后将冷冻的固体放置于冻干机中,在-20℃和40Pa进行冻干,得到含有应变的钌@二氧化钌核壳纳米球。
实施例4:
(1)将商用二氧化钌粉末置于超纯水中以2.0mg/mL的浓度超声分散至没有沉淀的悬浊液。
(2)将步骤(1)制得的悬浊液,室温持续搅拌,搅拌速度为300转/分钟,用纳秒平行脉冲激光辐照,用纳秒平行脉冲激光辐照30min,激光器能量为518mJ,得到黑色溶液;
(3)将步骤(2)所得的黑色溶液置于冰箱中在-10℃冷冻成固体,之后将冷冻的固体放置于冻干机中,在-30℃和30Pa进行冻干,得到含有应变的钌@二氧化钌核壳纳米球。
我们制备的所有实施例样品,10mA cm-2处过电势仅为191mV,比商用二氧化钌降低了100mV以上,是目前性能最优的不引入其他原子的钌基催化剂。其具有较低的Tafel斜率(48.90mV dec-1)和较小的界面转移电阻,说明显著改善的动力学和界面转移速率。同时,面积比活性和质量比活性显著提高,质量比活性比商用二氧化钌提高了18倍。
本发明公开和提出的技术方案,本领域技术人员可通过借鉴本文内容,适当改变条件路线等环节实现,尽管本发明的方法和制备技术已通过较佳实施例子进行了描述,相关技术人员明显能在不脱离本发明内容、精神和范围内对本文所述的方法和技术路线进行改动或重新组合,来实现最终的制备技术。特别需要指出的是,所有相类似的替换和改动对本领域技术人员来说是显而易见的,他们都被视为包括在本发明精神、范围和内容中。
Claims (4)
1.一种酸性产氧电催化剂含有拉伸应变的钌@二氧化钌核壳纳米球的制备方法,包括如下步骤:
(1)将二氧化钌粉末置于超纯水中超声分散至没有沉淀的悬浊液;
(2)将步骤(1)制得的悬浊液在室温持续搅拌下,用纳秒平行脉冲激光辐照,得到黑色溶液;纳秒脉冲激光作用辐照时,激光的能量为185~518mJ,时间10~60min,波长为1064nm,激光重复频率为10Hz;
(3)将步骤(2)所得的黑色溶液置于冰箱中冷冻成固体,之后将冷冻的固体放置于冻干机中进行冻干,得到含有应变的钌@二氧化钌核壳纳米球。
2.如权利要求1所述的方法,其特征是所述步骤(1)二氧化钌粉末和超纯水的配制浓度为0.5-2.0mg/mL。
3.如权利要求1所述的方法,其特征是所述步骤(2)激光辐照过程中搅拌速度为300-500转/分钟。
4.如权利要求1所述的方法,其特征是所述步骤(3)冻干过程中,冰箱温度为-4℃至-20℃,冻干机温度为-10至-50℃,真空度为20-50Pa。
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