CN114425334B - CeO2微米花负载的Ru纳米颗粒复合物及其制法 - Google Patents
CeO2微米花负载的Ru纳米颗粒复合物及其制法 Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 10
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- 239000003054 catalyst Substances 0.000 abstract description 7
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Abstract
该发明专利名称为：“CeO2微米花负载的Ru纳米颗粒复合物及其制法”，所属领域：电催化剂与制备。通过两步法制备Ru/CeO2(3wt％)复合物，Ru在复合物中质量分数为3wt％：首先，制备CeO2微米花前驱体，其次将适量的CeO2前驱体配成悬浊液，然后添加适量的Ru3+离子溶液，使Ru在Ru/CeO2复合物中质量分数为3wt％，用NaBH4还原Ru3+为金属纳米颗粒，经洗涤烘干处理，成为Ru/CeO2复合物。该复合物是很好的碱性电解水析氢催化剂，性能超过商用Pt/C(20wt％)，具有很好的应用前景。本发明公开了这种材料及其制法。
Description
技术领域
本发明涉及CeO2微米花负载的Ru纳米颗粒复合材料及其制法。具体地说，两步法制备出CeO2微米花上负载Ru纳米颗粒的复合材料Ru/CeO2(3wt％)，Ru在复合物中质量分数为3wt％，在碱性条件下具有良好的电催化析氢作用。
背景技术
目前，Pt基材料被认为是最好的析氢电催化剂，由于Pt具有最优的H吸附能。但是，因为Pt的储量较低、价格昂贵，从而限制了Pt基催化剂的商业化[参见：(a)Li，Y.；Zhang，H.；Xu，T.Adv.Funct.Mater.2015，25，1737-1744.(b)Cao，B.；Veith，G.M.；Neuefeind，J.C.J.Am.Chem.Soc.2014，45，19186-19190.(c)Yan，Y.；Xia，B.Y.；Xu，Z.C.；Wang，Xi.ACSCatal.2014，4，1693-1705.]。因此，发展高效稳定的非Pt基催化剂成为了一项重要任务。Ru作为一种比Pt便宜的贵金属，也具有一定的HER性能。Qiao等人发现H2O在Ru(111)上解离成H和OH所要跨越的动力学势垒比Pt(111)要小，这与实验中Ru在碱性溶液中HER性能高于Pt的结论一致[参见：Zheng，Y.；Jiao，Y.；Zhu，Y.H.；Li，L.H.；Han，Y.；Chen，Y.；Jaroniec，M.；Qiao，S.Z.J.Am.Chem.Soc.2016，138，16174-16181.]。另外，Wu等人研究了二维超薄Ru纳米片，可以高效的进行析氢反应，由于二维纳米片层能够最大陬度的暴露出Ru原子，提供更多的活性位点，进而加速电荷转移，提高催化反应速率[参见：Kong，X.；Xu，K.；Zhang，C.；Dai，J.；Oliaee，S.N.；Li，L.；Zeng，X.；Wu，C.；Peng，Z.ACS Catal.，2016，6，1487-1492.]。尽管这些研究明确碱性条件下Ru有比Pt具有更好的HER活性，但是，他们所需要的Ru载量仍然很多，毕竟Ru也是一种贵金属，所以，如何降低Ru的载量同时又能表现出良好的催化活性，成为了Ru基HER催化剂的一大难题。本发明通过CeO2微米花作为载体负载少量金属Ru，当Ru的负载量达催化剂总质量的3％时(即Ru/CeO2(3wt％))，这种催化剂在碱性条件下的析氢(HER)性能优于商业Pt/C(20％)并表现良好的稳定性。
发明内容
本发明的目的是提供CeO2微米花负载的Ru纳米颗粒复合物及其制备方法。
本发明的技术方案如下：
一种CeO2微米花负载的Ru纳米颗粒复合物(Ru/CeO2)，Ru在复合物中质量分数仅为3wt％。
制备方法分两步进行：(1)CeO2微米花载体的制备：称取一定量的Ce3+的可溶性盐和0.75g的NH4HCO3分别溶解在200ml的去离子水中，溶解的过程保持温度为0℃，然后将0℃的NH4HCO3溶液迅速地转移到Ce3+的溶液中，0℃恒温搅拌30min，最后将反应得到的悬浊物放入冰箱冷藏室里老化15h。老化后的前驱体悬浊液被过滤并且用去离子水和无水乙醇分别洗涤几次，然后，放入80℃烘箱中干燥。最后，将干燥物置于马弗炉中，在空气气氛下，450℃锻烧4h，得到CeO2样品；(2)Ru/CeO2(3wt％)复合物的制备：称取0.03g上述合成的CeO2粉末于圆底烧瓶中，加入10mL乙醇和25mL去离子水，搅拌形成均匀的悬浊液，然后向体系中注入0.2mL，10mg/mL的Ru3+溶液，30℃条件下，继续搅拌12h。接着，向上述体系中缓慢滴入1mLNaBH4水溶液(NaBH4∶Ru＝3∶1mol/mol)，滴加完毕后继续搅拌反应1h。最后，用去离子水和乙醇多次离心洗涤，收集后的产物在60℃真空烘箱中干燥2h，并标记为Ru/CeO2(3wt％)。
本发明的Ru/CeO2复合物经XRD测定，呈现了明显的CeO2立方萤石结构的衍射峰以及微弱的金属Ru特征衍射峰(图1)。
CeO2载体为立方萤石结构，微花由纳米片自组装而成，直径约为2.5-3.0μm(SEM，图2)。Ru纳米颗粒可以附着在CeO2纳米片上，粒径约为5-10nm(SEM，图2)。TEM也能观察到Ru颗粒分散在CeO2的纳米片上(图3a)，HRTEM检测到晶格条纹间距为0.207nm，归属于六方晶系金属Ru(101)晶面(图3b)。CeO2纳米片是由尺寸约为5nm的微晶组成，清晰的晶格条纹(间距为0.312nm)归属于立方萤石结构CeO2(111)晶面(图3b)。
从电化学极化曲线(LSV，图4A))中可以看出，Ru/CeO2(3wt％)复合物具有较低的电催化析氢(HER)过电势，并且活性优于商业Pt/C(20wt％)催化剂，同时，Ru/CeO2(3wt％)复合物也具有良好的稳定性(见图4B)，因此，Ru/CeO2(3wt％)复合物在电催化析氢方面有很好的应用前景。
本发明的制备Ru/CeO2(3wt％)复合物，方法原料简单易得、条件简便易行。
附图说明
图1为本发明Ru/CeO2(3wt％)复合物的XRD图；
图2为本发明Ru/CeO2(3wt％)复合物的SEM照片：(a)低倍像，(b)高倍像；
图3为本发明Ru/CeO2(3wt％)复合物的(a)TEM照片和(b)HRTEM图；
图4为本发明Ru/CeO2(3wt％)复合物与相关材料的HER活性图(LSV)和稳定性图。(A)HER活性图：(a)Pt/C(20wt％)，(b)Ru/CeO2(3wt％)，(c)Ru+CeO2，(d)Ru，(e)CeO2；(B)Ru/CeO2(3wt％)的稳定性图。
具体实施方式
实施例1.Ru/CeO2(3wt％)复合材料的制备
整个制备方法分两步：
(1)CeO2微米花载体的制备：称取1.3205g Ce(NO3)3·6H2O和0.75g的NH4HCO3分别溶解在200ml的去离子水中，溶解的过程保持温度为0℃，然后将0℃的NH4HCO3溶液迅速地转移到金属硝酸盐溶液中，0℃恒温搅拌30min，最后将反应得到的悬浊物放入冰箱冷藏室里老化15h。老化后的前驱体悬浊液被过滤并且用去离子水和无水乙醇分别洗涤三次，然后，放入80℃烘箱中干燥12h。最后，将干燥物置于马弗炉中，在空气气氛下，450℃锻烧4h，得到CeO2样品。
(2)Ru/CeO2(3wt％)复合物的制备：称取0.03g上述合成的CeO2粉末于圆底烧瓶中，加入10mL乙醇和25mL去离子水，搅拌形成均匀的悬浊液，然后向体系中注入0.2mL，10mg/mL的RuCl3溶液，30℃条件下，继续搅拌12h。接着，向上述体系中缓慢滴入1mL NaBH4水溶液(NaBH4∶Ru＝3∶1mol/mol)，滴加完毕后继续搅拌反应1h。最后，用去离子水和乙醇多次离心洗涤，收集后的产物在60℃真空烘箱中干燥2h，得到Ru/CeO2(3wt％)。
实施例2.Ru/CeO2(3wt％)复合材料的制备
整个制备方法分两步：
(1)CeO2微米花载体的制备：称取1.0531g CeCl3·6H2O(或1.1066g CeCl3·7H2O)和0.75g的NH4HCO3分别溶解在200ml的去离子水中，溶解的过程保持温度为0℃，然后将0℃的NH4HCO3溶液迅速地转移到金属硝酸盐溶液中，0℃恒温搅拌30min，最后将反应得到的悬浊物放入冰箱冷藏室里老化15h。，其余操作同实例1(1)。
(2)Ru/CeO2(3wt％)复合物的制备：操作同实例1(2)。
实施例3.Ru/CeO2(3wt％)复合材料的制备
整个制备方法分两步：
(1)CeO2微米花载体的制备：操作同实例1(1)。
(2)Ru/CeO2(3wt％)复合物的制备：称取0.03g上述合成的CeO2粉末于圆底烧瓶中，加入10mL乙醇和25mL去离子水，搅拌形成均匀的悬浊液，然后向体系中注入0.2mL，10mg/mL的Ru(NO3)3溶液，30℃条件下，继续搅拌12h。其余操作同实例1(2)。
实施例4.Ru/CeO2(3wt％)复合材料的制备
整个制备方法分两步：
(1)CeO2微米花载体的制备：操作同实例2(1)。
(2)Ru/CeO2(3wt％)复合物的制备：操作同实例3(2)。
Claims (1)
1.一种CeO2微米花负载的Ru纳米颗粒复合物在电催化分解水析氢中的应用，其特征在于：所述复合物中CeO2微米花直径2.5-3.0μm，花瓣由CeO2纳米片组成，Ru纳米颗粒附着在CeO2纳米片上，Ru纳米颗粒的粒径为5-10nm，Ru在复合物中质量分数为3wt％；所述复合物的制备方法为：
(1)CeO2微米花的制备：称取一定量的Ce3+的可溶性盐和0.75g的NH4HCO3分别溶解在200ml的去离子水中，溶解的过程保持温度为0℃，然后将0℃的NH4HCO3溶液迅速地转移到Ce3+溶液中，0℃恒温搅拌30min，将反应得到的悬浊物放入冰箱冷藏室里老化15h，老化后的前驱体悬浊液被过滤并且用去离子水和无水乙醇分别洗涤几次，放入80℃烘箱中干燥，最后，将干燥物置于马弗炉中，在空气气氛下，450℃锻烧4h，得到CeO2微米花；
(2)CeO2微米花负载Ru纳米颗粒复合物的制备：称取0.03g上述合成的CeO2微米花于圆底烧瓶中，加入10mL乙醇和25mL去离子水，搅拌形成均匀的悬浊液，然后向其中注入0.2mL，10mg/mL的Ru3+溶液，30℃条件下，继续搅拌12h，再缓慢滴入1mL NaBH4水溶液，NaBH4∶Ru＝3mol∶1mol，滴加完毕后继续搅拌反应1h，最后，用去离子水和乙醇多次离心洗涤，收集后的产物在60℃真空烘箱中干燥2h，得到CeO2微米花负载Ru纳米颗粒复合物。
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