CN108057446A - 氨硼烷水解制氢Co-Mo-B纳米催化剂及制备方法 - Google Patents
氨硼烷水解制氢Co-Mo-B纳米催化剂及制备方法 Download PDFInfo
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Abstract
本发明属于无机纳米材料领域，涉及一种氨硼烷水解制氢Co‑Mo‑B纳米催化剂及制备方法，以金属或非金属基底为载体，将基底依次用热碱溶液、酸侵蚀液、敏化液和活化液处理后，浸入化学镀液中进行化学镀，再经洗涤、干燥，即得以基底为载体的、具有多种形貌的Co‑Mo‑B纳米催化剂。该方法过程简单、成本低廉、易重复、纯度高、适宜大规模制备，且制备的纳米催化材料在催化氨硼烷水解制氢上具有较高的催化活性和较好的循环稳定性，这为氨硼烷水解制氢在质子交换膜燃料电池方面的应用提供了有效的技术支撑，加快了其实用化进程。
Description
技术领域
本发明涉及一种氨硼烷水解制氢Co-Mo-B纳米催化剂及制备方法，属于无机纳米材料领域。
背景技术
随着全球经济的迅猛发展，煤、石油和天然气等化石能源的不断消耗，氢能成为解决当前能源危机的一种新能源。氢能由于具有清洁高效的优点而能够应用于生产生活多个方面，而成为具有开发潜力的能源之一。然而，怎样制氢？靠什么来制氢？这些问题一直是广大科研工作者极为关注的研究领域。在众多的储氢材料中，氨硼烷(NH3BH3,AB)以其高质量储氢量(19.6wt.％)、相对成本较低等优点成为较有潜力的储氢材料之一。水解是氨硼烷与水反应放出氢气的过程，此反应无催化剂在室温下不反应，加入催化剂后均可实现室温快速、大量放氢(见式(1))。水解制氢的关键在于研制高效廉价催化剂。
NH3BH3+2H2O→NH4 ++BO2 －+3H2 (1)
氨硼烷可以为便携式电源、燃料电池以及电动汽车等提供氢源，引起了人们的广泛关注。上述制氢反应可通过催化剂来调节，因此催化剂开发成为氨硼烷制氢领域亟待解决的关键问题之一。
在氨硼烷水解放氢反应中，Pt、Ru、Pd、Ir、Rh等贵金属材料催化剂的使用(Q.Yao,Z.H.Lu,Y.Jia,X.Chen,X.Liu,Int.J.Hydrogen Energy,40(2015)2207-2215；B.L.Conley,D.Guess,T.J.Williams,J.Am.Chem.Soc.,133(2011)14212-14215.)均可有效提高氨硼烷的放氢速率，但高昂的成本不适合工业生产和生活需要，阻碍其广泛应用。因此，为了在提高催化剂催化速率的同时降低材料成本，非贵金属基催化剂则成为了又一研究热点。主要包含Ni，Co，Co–P，Co–B，Cu–B，Co–Ni–B，Ni–B，Co–Mo–B以及Co–Ni–P等Co基和Ni基催化剂。随着研究的不断深入，三元非贵金属催化剂材料被广泛关注，这可能是三种元素之间的协同效应，可有效提高催化效率，增强催化剂的稳定性，尤其是三元非贵金属Co–Mo–B催化剂材料因具有较好的催化活性而备受关注。
传统的Co–Mo–B材料多采用液相还原法制备成粉状，但是粉体材料存在一定的问题，如易于团聚，在循环使用过程难于从体系中分离，这在很大程度上影响了其催化氨硼烷水解制氢的活性和循环稳定性。实际上，材料的性质不仅与其元素组成、纯度有关，还与材料本身的形貌、结构以及颗粒尺寸等因素有很大关系，因此，这就为Co–Mo–B材料的制备过程提出了更高的要求，不仅能制备出Co–Mo–B纳米材料，而且还要重视材料本身的微观形貌以及颗粒尺寸。目前，采用化学镀一步合成形貌可控的Co–Mo–B纳米催化材料还未见报道。
发明内容
本发明以解决上述粉体材料中遇到的问题为目的，旨在提供一种粒径可控的Co–Mo–B纳米催化材料及制备方法。
本发明是这样实现的，提供一种氨硼烷水解制氢Co-Mo-B纳米催化剂的制备方法，以金属或非金属基底为载体，将基底依次用热碱溶液、酸侵蚀液、敏化液和活化液处理后，浸入化学镀液中进行化学镀，再经洗涤、干燥，即得以金属或非金属基底为载体的、具有多种形貌的Co-Mo-B纳米催化剂。
具体的，上述方法包括如下步骤:
1)配制热碱溶液、酸侵蚀液、敏化液以及活化液：
称取5-10g氢氧化钠溶于100mL水中，并在40-80℃的恒温水浴中恒温配制成热碱溶液；由30-60mL磷酸、30-50mL醋酸和5-20mL硝酸配制成的混合液为酸侵蚀液；由1g二水氯化亚锡超声分散在5mL盐酸中，加蒸馏水定容至1L配制成敏化液；由0.1g氯化钯超声溶解在1mL盐酸中，加蒸馏水定容至1L配制成活化液；
2)配制化学镀液：
a)将一定量的钴盐和钼酸盐先后溶于80mL蒸馏水中配成0.05～1.0mol/L主盐溶液；b)将一定量的的甘氨酸加入到所述主盐溶液中，使主盐与甘氨酸均匀混合；c)将5-15g次磷酸钠作为还原剂加入到步骤b)配好的混合溶液中，用一定浓度的氢氧化钠溶液调节体系pH至10-13之间，即为化学镀液；d)将化学镀液置于50～90℃的恒温水浴中恒温待用；
3)制备Co-Mo-B纳米催化剂：
将一定面积的金属或非金属基底依次用上述步骤1)中配制好的热碱溶液、酸侵蚀液、敏化液以及活化液处理后，侵入步骤2)中配好的化学镀液中进行化学镀，施镀时间为5min，最后将镀好的催化剂材料取出，依次用蒸馏水和无水乙醇清洗干净后，室温下真空干燥24h，得到Co-Mo-B纳米催化剂。
进一步地，，所述基底为碳布、Cu片、Ni片、泡沫Cu、泡沫Ni或泡沫海绵中的一种。
本发明还提供了一种利用上述方法制备的氨硼烷水解制氢Co-Mo-B纳米催化剂，制得的Co-Mo-B纳米催化剂的形貌为由纳米尺寸的颗粒堆积而成的球状、类珊瑚状、类冰淇淋状。
利用上述方法制备而得的Co-Mo-B纳米催化剂在催化氨硼烷水解制氢过程中放氢速率为5100mLmin-1g-1，经过五次循环利用后，催化效率为3159.1mLmin-1g-1。
与现有技术相比，本发明的优点在于：
使用低成本的反应物，通过调节基底材料、体系的pH值，还原剂浓度，施镀时间，在室温下采用化学镀法制备了形貌可控Co–Mo–B纳米催化材料，主要包括球状、类珊瑚状、类冰淇淋状。条件的调节改变了化学镀过程中金属Co、Mo和非金属B的沉积速度，改变了晶核生长速度以及生长方向，最终实现了Co–Mo–B催化材料的形貌可控制备，这在一定程度上实现了材料的有效筛选，降低颗粒尺寸，增加材料的比表面积，提高了其催化活性。尤其是在泡沫海绵上制备的球形纳米级该催化剂材料在催化氨硼烷水解制氢体系中表现了较好的催化活性，其放氢速率高达5100.0mL·min-1·g-1，该速率其活化能为41.7kJ·mol-1，该催化活性明显优于多数非贵金属催化材料，甚至远远超过贵金属催化材料，这在质子交换膜燃料电池方面将具有广泛的应用前景。
附图说明
图1为化学镀制备的三元非贵金属Co–Mo–B纳米催化材料CMB-A的扫描电镜(SEM)图；
图2化学镀制备的三元非贵金属Co–Mo–B纳米催化材料CMB-B的扫描电镜(SEM)图；
图3化学镀制备的三元非贵金属Co–Mo–B纳米催化材料CMB-C的扫描电镜(HRSEM)图；
图4为制备的三元非贵金属Co–Mo–B纳米催化材料CMB-E催化氨硼烷水解(25℃)放氢速率曲线图；
图5制备的三元非贵金属Co–Mo–B纳米催化材料CMB-E催化氨硼烷水解放氢的循环性能测试曲线。
具体实施方式
下面结合实施例进一步说明本发明方法的过程和效果。
实施例1
碳布负载的Co–Mo–B纳米催化材料的制备：
1)配制热碱溶液、酸侵蚀液、敏化液以及活化液(以下实施例均使用该热碱溶液、酸侵蚀液、敏化液以及活化液)：
称取9g氢氧化钠溶于100mL水中，并在60℃的恒温水浴中恒温配制成热碱溶液；量取48mL磷酸、33mL醋酸、19mL硝酸混合配成100mL的酸侵蚀液；称取1g二水氯化亚锡超声溶解在5mL盐酸中，加蒸馏水定容至1L，配成敏化液；配制活化液：称取0.1g氯化钯超声溶解在1mL盐酸中，加蒸馏水定容至1L，配成活化液。
2)配制化学镀液：①取1.1884g六水合氯化钴溶于80mL蒸馏水中配成钴盐溶液；②取1.2099g的钼酸钠溶于上述配制好的钴盐溶液中，搅拌溶解，配制成主盐溶液；③将4.5022g甘氨酸加入到上述主盐溶液中，使主盐与甘氨酸混合均匀；④将2.2735g硼氢化钠作为还原剂加入到上述混合溶液中，并通过一定氢氧化钠溶液调节体系pH至11.5，置于25℃的恒温水浴中恒温待用。
3)碳布负载的Co–Mo–B纳米催化材料的制备：将面积为1×1cm2的碳布依次用上述步骤1中配制好的热碱溶液、酸侵蚀液、敏化液以及活化液处理后，浸入步骤2中配好的镀液中进行化学镀，施镀时间为5min。最后将镀好的催化剂材料取出，依次用蒸馏水和无水乙醇清洗干净后，室温下真空干燥24h，所得催化材料记为CMB-A。图1为对应条件下制备的Co–Mo–B催化材料CMB-A的扫面电镜(SEM)图。从图可以看出，制备的Co–Mo–B表现90-110nm之间的球形颗粒结构。
实施例2
1)配制热碱溶液、酸侵蚀液、敏化液以及活化液同实施例1步骤1。
2)配制化学镀液：①取1.1890g六水合氯化钴溶于80mL蒸馏水中配成钴盐溶液；②取1.2073g的钼酸钠溶于上述配制好的钴盐溶液中，搅拌溶解，配制成主盐溶液；③将4.5000g甘氨酸加入到上述主盐溶液中，使主盐与甘氨酸混合均匀；④将1.5399g硼氢化钠作为还原剂加入到上述混合溶液中，并通过一定氢氧化钠溶液调节体系pH至12，置于25℃的恒温水浴中恒温待用。
3)泡沫镍负载的Co–Mo–B纳米催化材料的制备：将面积为1×1cm2的泡沫镍依次用上述步骤1中配制好的热碱溶液、酸侵蚀液、敏化液以及活化液处理后，浸入步骤2中配好的镀液中进行化学镀，施镀时间为5min。最后将镀好的催化剂材料取出，依次用蒸馏水和无水乙醇清洗干净后，室温下真空干燥24h，所得催化材料记为CMB-B。图2为对应条件下制备的Co–Mo–B催化材料CMB-B的扫面电镜(SEM)图。从图可以看出，制备的Co–Mo–B是由60-80nm的小颗粒纠结在一起的珊瑚状结构。
实施例3
1)配制热碱溶液、酸侵蚀液、敏化液以及活化液同实施例1步骤1。
2)配制化学镀液：①取1.1858g六水合氯化钴溶于80mL蒸馏水中配成钴盐溶液；②取1.2056g的钼酸钠溶于上述配制好的钴盐溶液中，搅拌溶解，配制成主盐溶液；③将4.5027g甘氨酸加入到上述主盐溶液中，使主盐与甘氨酸混合均匀；④将1.5350g硼氢化钠作为还原剂加入到上述混合溶液中，并通过一定氢氧化钠溶液调节体系pH至11，置于25℃的恒温水浴中恒温待用。
3)泡沫镍负载的Co–Mo–B纳米催化材料的制备：将面积为1×1cm2的泡沫镍依次用上述步骤1中配制好的热碱溶液、酸侵蚀液、敏化液以及活化液处理后，浸入步骤2中配好的镀液中进行化学镀，施镀时间为5min。最后将镀好的催化剂材料取出，依次用蒸馏水和无水乙醇清洗干净后，室温下真空干燥24h，所得催化材料记为CMB-C。图3为对应条件下制备的Co–Mo–B催化材料CMB-C的扫面电镜(SEM)图。从图可以看出，制备的Co–Mo–B是由40-85nm的小颗粒堆积在一起的类冰淇淋状结构。
实施例4
1)配制热碱溶液、酸侵蚀液、敏化液以及活化液同实施例1步骤1。
2)配制化学镀液：①取1.1927g六水合氯化钴溶于80mL蒸馏水中配成钴盐溶液；②取1.2081g的钼酸钠溶于上述配制好的钴盐溶液中，搅拌溶解，配制成主盐溶液；③将4.5081g甘氨酸加入到上述主盐溶液中，使主盐与甘氨酸混合均匀；④将1.5392g硼氢化钠作为还原剂加入到上述混合溶液中，并通过一定氢氧化钠溶液调节体系pH至11，置于25℃的恒温水浴中恒温待用。
3)铜片负载的Co–Mo–B纳米催化材料的制备：将面积为1×1cm2的铜片依次用上述步骤1中配制好的热碱溶液、酸侵蚀液、敏化液以及活化液处理后，浸入步骤2中配好的镀液中进行化学镀，施镀时间为5min。最后将镀好的催化剂材料取出，依次用蒸馏水和无水乙醇清洗干净后，室温下真空干燥24h，所得催化材料记为CMB-D。
实施例5
1)配制热碱溶液、酸侵蚀液、敏化液以及活化液同实施例1步骤1。
2)配制化学镀液：①取1.1899g六水合氯化钴溶于80mL蒸馏水中配成钴盐溶液；②取1.2104g的钼酸钠溶于上述配制好的钴盐溶液中，搅拌溶解，配制成主盐溶液；③将4.5020g甘氨酸加入到上述主盐溶液中，使主盐与甘氨酸混合均匀；④将2.2713g硼氢化钠作为还原剂加入到上述混合溶液中，并通过一定氢氧化钠溶液调节体系pH至11，置于25℃的恒温水浴中恒温待用。
3)泡沫海绵负载的Co–Mo–B纳米催化材料的制备：将面积为1×1cm2的泡沫海绵依次用上述步骤1中配制好的热碱溶液、酸侵蚀液、敏化液以及活化液处理后，浸入步骤2中配好的镀液中进行化学镀，施镀时间为5min。最后将镀好的催化剂材料取出，依次用蒸馏水和无水乙醇清洗干净后，室温下真空干燥24h，所得催化材料记为CMB-E。
实施例5
将催化剂CMB-E加入到氨硼烷水溶液溶液中，进行放氢动力学性能测试实验，具体为：称取0.0400g固体氨硼烷溶解于8mL蒸馏水中配成澄清的氨硼烷水溶液，待完全溶解后，转移至25mL单口瓶中，立即加入一定量的上述制备好的催化剂，计时开始，测试温度为25℃。
依上述方法对催化剂CMB-E进行催化氨硼烷水解制氢动力学性能测试的实验结果如图4示。可见，该催化剂催化氨硼烷水解的放氢速率(以单位质量催化剂的用量计算)为5100mLmin-1g-1。
重复上述操作4次，测得催化剂CMB-E催化氨硼烷水解制氢的循环性能曲线如图5示。可以看出：催化剂CMB-E催化氨硼烷水解制氢的放氢速率第一次为5100mLmin-1g-1，第五次为3159.1mLmin-1g-1，也就是说，经过五次循环利用后，其催化效率仍保持在第一次的61.9％。通过与文献进行对比，可以发现，即使经过五次吸放氢循环后，第五次的放氢速率也远远高于多数非贵金属催化剂材料(Paladini M,Arzac GM,Godinho V,et al.AppliedCatalysis B:Environmental.2014；158-159:400-9)，甚至是贵金属催化剂材料(Basu S,Brockman A,Gagare P,et al.J Power Sources.2009；188:238-43)，这说明该催化剂具有较高的催化氨硼烷水解制氢的催化活性。
结果表明，本发明提供的一种氨硼烷水解制氢Co-Mo-B纳米催化剂及其制备方法，通过调节基底材料、体系的pH值，还原剂浓度，施镀时间，在室温下采用化学镀法制备了形貌可控Co–Mo–B纳米催化材料，主要包括球状、类珊瑚状、类冰淇淋状。条件的调节改变了化学镀过程中金属Co、Mo和非金属B的沉积速度，改变了晶核生长速度以及生长方向，最终实现了Co–Mo–B催化材料的形貌可控制备，这在一定程度上实现了材料的有效筛选，降低颗粒尺寸，增加材料的比表面积，提高了其催化活性。，这为氨硼烷水解制氢在质子交换膜燃料电池方面的应用提供了有效的技术支撑，加快了其实用化进程。
Claims (5)
1.氨硼烷水解制氢Co-Mo-B纳米催化剂的制备方法，其特征在于，以金属或非金属基底为载体，将基底依次用热碱溶液、酸侵蚀液、敏化液和活化液处理后，浸入化学镀液中进行化学镀，再经洗涤、干燥，即得以金属或非金属基底为载体的、具有多种形貌的Co-Mo-B纳米催化剂。
2.氨硼烷水解制氢Co-Mo-B纳米催化剂的制备方法，其特征在于，包括如下步骤:
1)配制热碱溶液、酸侵蚀液、敏化液以及活化液：
称取5-10g氢氧化钠溶于100mL水中，并在40-80℃的恒温水浴中恒温配制成热碱溶液；由30-60mL磷酸、30-50mL醋酸和5-20mL硝酸配制成的混合液为酸侵蚀液；由1g二水氯化亚锡超声分散在5mL盐酸中，加蒸馏水定容至1L配制成敏化液；由0.1g氯化钯超声溶解在1mL盐酸中，加蒸馏水定容至1L配制成活化液；
2)配制化学镀液：
a)将一定量的钴盐和钼酸盐先后溶于80mL蒸馏水中配成0.05～1.0mol/L主盐溶液；b)将一定量的的甘氨酸加入到所述主盐溶液中，使主盐与甘氨酸均匀混合；c)将5-15g次磷酸钠作为还原剂加入到步骤b)配好的混合溶液中，用一定浓度的氢氧化钠溶液调节体系pH至10-13之间，即为化学镀液；d)将化学镀液置于50～90℃的恒温水浴中恒温待用；
3)制备Co-Mo-B纳米催化剂：
将一定面积的金属或非金属基底依次用上述步骤1)中配制好的热碱溶液、酸侵蚀液、敏化液以及活化液处理后，侵入步骤2)中配好的化学镀液中进行化学镀，施镀时间为5min，最后将镀好的催化剂材料取出，依次用蒸馏水和无水乙醇清洗干净后，室温下真空干燥24h，得到Co-Mo-B纳米催化剂。
3.如权利要求1或2任一所述的氨硼烷水解制氢Co-Mo-B纳米催化剂的制备方法，其特征在于，所述基底为碳布、Cu片、Ni片、泡沫Cu、泡沫Ni或泡沫海绵中的一种。
4.利用如权利要求1或2任一所述的氨硼烷水解制氢Co-Mo-B纳米催化剂的制备方法制备而得的Co-Mo-B纳米催化剂，其特征在于，制得的Co-Mo-B纳米催化剂的形貌为由纳米尺寸的颗粒堆积而成的球状、类珊瑚状、类冰淇淋状。
5.利用如权利要求1或2任一所述的氨硼烷水解制氢Co-Mo-B纳米催化剂的制备方法制备而得的Co-Mo-B纳米催化剂，其特征在于，制得的Co-Mo-B纳米催化剂在催化氨硼烷水解制氢过程中放氢速率为5100mLmin-1g-1，经过五次循环利用后，催化效率为3159.1mLmin-1g-1。
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| CN111495370A (zh) * | 2020-05-08 | 2020-08-07 | 沈阳师范大学 | 扭结的纳米带状Co-Fe-B催化剂、制备方法及其应用 |
| CN111569933A (zh) * | 2020-06-22 | 2020-08-25 | 中认英泰检测技术有限公司 | 基于多孔碳的金属催化剂、其制备方法及应用 |
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| CN114225955A (zh) * | 2021-12-24 | 2022-03-25 | 沈阳师范大学 | 一种双载体修饰三元合金纳米腔催化剂及其制备方法与应用 |
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