CN109603800B - 一种超薄多金属纳米片堆叠组装材料的制备方法及其应用 - Google Patents
一种超薄多金属纳米片堆叠组装材料的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种超薄多金属纳米片堆叠组装材料的制备方法及其应用，包括如下步骤：(1)将十六烷基三甲基氯化铵、聚乙烯吡咯烷酮、钯前驱盐、铂前驱盐、可选金属前驱盐、三氯化铁和六羧基钨用乙醇溶解并搅拌混合均匀；(2)将步骤(1)所得的物料由室温升至175‑185℃，恒温反应30‑90min，然后冷却至室温；(3)将步骤(2)所得的物料用乙醇充分洗涤后，获得所述超薄多金属纳米片堆叠组装材料。本发明通过一步法制备得到超薄多金属纳米片堆叠组装材料，其产品能够用于小分子燃料的电催化反应中。
Description
技术领域
本发明属于电催化技术领域，具体涉及一种超薄多金属纳米片堆叠组装材料的制备方法及其应用。
背景技术
近年来，由于贵金属纳米材料在催化、能源、生物医药等各个领域都体现出重要的应用前景，发展制备具有特定结构和特殊功能的贵金属基纳米结构的方法极为重要。其中，铂系贵金属在电催化领域方面的应用尤为突出。比如，目前众多的电催化材料中，铂基(Pt-)材料是许多燃料小分子电催化氧化反应的优良催化剂。然而Pt的价格昂贵、储量稀少，同时易产生类CO有毒中间体，极大地制约了其在工业生产上的进一步推广应用。为了提高Pt材料的催化活性和电池性能，主要的研究途径是添加其他金属元素(如Pd、Ru、Rh、Ir、Cu、Co和Ni等)以形成合金，通过元素之间的电子效应和协同效应增强催化性能。例如，杜玉扣团队合成的PtRu双金属纳米颗粒用于乙醇的电催化氧化，发现其催化活性和稳定性相比于商业化Pt/C都得到了很大的提高(Gu，Z.L.；Li，S.M.；Xiong，Z.P.；Xu，H..；Gao，F.；Du，Y.K.J.Colloid Interface Sci.2018，521，118.)；王训课题组将Pd、Rh与Pt合金化，得到三元纳米晶，并发现其对多个醇类氧化(乙二醇、甘油、甲醇和乙醇)都有较好的催化活性(Huang，D.B.；Yuan，Q.；He，P.P.；Wang，K.；Wang，X.Nanoscale.2016，8，14705)。另一方面，Pt-基催化剂的形貌结构会直接影响其表面性质，进而表现出不同的催化活性。近年来，二维(2D)材料表现出优异的催化性能，这是由于纳米片拥有较大的比表面积和丰富的配位不饱和位点。有文献报道，PdPtAg纳米片通过促进OHads的形成和提高抗CO毒害能力而对乙醇电催化氧化表现出较好的催化活性(Hong，J.W.；Kim，Y.；Wi，D.H.；Lee，S.；Lee，S.-U.；Lee，Y.W.；Choi，S.-I.；Han，S.W.Angew.Chem.Int.Ed.2016，55，2753)。然而，超薄二维纳米结构高度的分散性往往导致材料的稳定性下降，也为材料的回收和重复利用带来极大不便。因此，发展制备二维超薄多金属纳米片的组装结构的方法及研究其在电催化方面的应用，对于提高小分子醇类电催化活性和燃料电池性能来说是非常重要的。
发明内容
本发明的目的在于克服现有技术缺陷，提供一种超薄多金属纳米片堆叠组装材料的制备方法。
本发明的另一目的在于提供上述超薄多金属纳米片堆叠组装材料的应用
本发明的技术方案如下：
一种超薄多金属纳米片堆叠组装材料的制备方法，包括如下步骤：
(1)将十六烷基三甲基氯化铵、聚乙烯吡咯烷酮、钯前驱盐、铂前驱盐、可选金属前驱盐、三氯化铁和六羧基钨用乙醇溶解并搅拌混合均匀；
(2)将步骤(1)所得的物料由室温升至175-185℃，恒温反应30-90min，然后冷却至室温；
(3)将步骤(2)所得的物料用乙醇充分洗涤后，获得所述超薄多金属纳米片堆叠组装材料。
在本发明的一个优选实施方案中，所述钯前驱盐为乙酰丙酮钯。
在本发明的一个优选实施方案中，所述铂前驱盐为乙酰丙酮铂。
在本发明的一个优选实施方案中，可选金属前驱盐为三氯化钌、无水氯化镍、三氯化铑和氯化铱中的至少一种。
在本发明的一个优选实施方案中，所述步骤(2)为：将步骤(1)所得的物料由室温升至180℃，恒温反应30-90min，然后冷却至室温。
在本发明的一个优选实施方案中，所述十六烷基三甲基氯化铵、聚乙烯吡咯烷酮、钯前驱盐、铂前驱盐、可选金属前驱盐、三氯化铁和六羧基钨的质量比为90-110∶90-110∶7-9∶8-12∶3-55∶1.2-8.5∶45-55。
进一步优选的，所述十六烷基三甲基氯化铵、聚乙烯吡咯烷酮、钯前驱盐、铂前驱盐、可选金属前驱盐、三氯化铁和六羧基钨的质量比为100∶100∶8∶10∶3-52.5∶1.35-8.1∶50。
本发明的另一技术方案如下：
一种电催化材料，其原料包括上述制备方法制得的超薄多金属纳米片堆叠组装材料。
本发明的再一技术方案如下：
上述制备方法制得的超薄多金属纳米片堆叠组装材料在制备电催化材料中的应用。
本发明的有益效果是：本发明通过一步法制备得到超薄多金属纳米片堆叠组装材料，其产品能够用于小分子燃料的电催化反应中。
附图说明
图1为本发明实施例1制得的PdPtRu三金属纳米片堆叠组装材料的(A)低倍透射电子显微镜(TEM)图片及(B)高倍透射电子显微镜(HRTEM)图片。
图2为本发明实施例制得的PdPtRu三金属纳米片堆叠组装材料能谱分析面扫描图，其中(A)Pd，(B)Pt，(C)Ru，(D)Pd+Pt+Ru。
图3为本发明实施例制得的PdPtRu三金属纳米片堆叠组装材料的(A)X射线粉末衍射(XRD)图片及(B)扫描电子显微镜-能谱分析(SEM-EDS)图片；
图4为本发明实施例2制得的PdPtNi三金属纳米片堆叠组装材料(A，B)的低倍透射电子显微镜(TEM)图片；
图5为本发明实施例3制得的PdPtRh三金属纳米片堆叠组装材料(A，B)的低倍透射电子显微镜(TEM)图片；
图6为本发明实施例4制得的PdPtIr三金属纳米片堆叠组装材料(A，B)低倍透射电子显微镜(TEM)图片。
图7四金属纳米片堆叠组装材料的低倍透射电子显微镜(TEM)图片，其中，(A)PdPtRuRh，(B)PdPtRuNi，(C)PdPtRhNi。
图8三金属PdPtRu纳米片堆叠组装结构和商业化Pt/C催化剂在碱性条件下对乙醇的电催化氧化性能比较图片。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1：
在25mL聚四氟乙烯反应釜内胆中，加入100mg的十六烷基三甲基氯化铵、100mg的聚乙烯吡咯烷酮、8mg的乙酰丙酮钯、10mg的乙酰丙酮铂、3-13mg的三氯化钌、1.35-8.1mg的三氯化铁、50mg的六羰基钨和12mL的无水乙醇。室温下以600rpm的转速搅拌30min，放烘箱里，从30℃升温至180℃(升温速率：5℃/min)，并保持180℃30-90min，然后自然冷却至室温，最后用乙醇清洗数次并保存在乙醇备用，即得超薄PdPtRu三金属纳米片堆叠组装材料。
该超薄PdPtRu三金属纳米片堆叠组装材料经TEM、HRTEM、SEM-EDS等现代纳米测试分析技术对其形貌、成分、微结构进行系统的研究。TEM、HRTEM(图1A、B)表征为二维纳米片堆叠组装结构；能谱分析面扫描图(EDS-mapping)(图2A、B、C、D)表征纳米片堆叠组装结构为PdPtRu合金，其中Pd的信号最强，Pt信号强度次之，Ru含量最少；XRD谱图表征PdPtRu三金属纳米片堆叠组装材料为合金结构；SEM-EDS表征超枝状纳米晶Pd、Pt、Ru的含量，本实施例制得的超薄PdPtRu三金属纳米片堆叠组装材料和商业化Pt/C催化剂在碱性条件下对乙醇的电催化氧化性能比较结果如图8所示。
实施例2：
在25mL聚四氟乙烯反应釜内胆中，加入100mg的十六烷基三甲基氯化铵、100mg的聚乙烯吡咯烷酮、8mg的乙酰丙酮钯、10mg的乙酰丙酮铂、8mg的无水氯化镍、1.35-8.1mg的三氯化铁、50mg的六羰基钨和12mL的无水乙醇。室温下以600rpm的转速搅拌30min，放烘箱里，从30℃升温至180℃(升温速率：5℃/min)，并保持180℃30-90min，然后自然冷却至室温，最后用乙醇清洗数次并保存在乙醇中备用，即得超薄PdPtRh三金属纳米片堆叠组装材料。
TEM表征如图4A、B，三金属PdPtNi纳米晶为二维六角环组装结构。
实施例3：
在25mL聚四氟乙烯反应釜内胆中，加入100mg的十六烷基三甲基氯化铵、100mg的聚乙烯吡咯烷酮、8mg的乙酰丙酮钯、10mg的乙酰丙酮铂、13mg的三氯化铑、1.35-8.1mg的三氯化铁、50mg的六羰基钨和12mL的无水乙醇。室温下以600rpm的转速搅拌30min，放烘箱里，从30℃升温至180℃(升温速率：5℃/min)，并保持180℃30-90min，然后自然冷却至室温，最后用乙醇清洗数次并保存在乙醇中备用，即得超薄PdPtRh三金属纳米片堆叠组装材料。
TEM表征如图5A、B，三金属PdPtRh纳米晶为六角片组装结构。
实施例4：
在25mL聚四氟乙烯反应釜内胆中，加入100mg的十六烷基三甲基氯化铵、100mg的聚乙烯吡咯烷酮、8mg的乙酰丙酮钯、10mg的乙酰丙酮铂、18.5mg的氯化铱、1.35-8.1mg的三氯化铁、50mg的六羰基钨和12mL的无水乙醇。室温下以600rpm的转速搅拌30min，放烘箱里，从30℃升温至180℃(升温速率：5℃/min)，并保持180℃30-90min，然后自然冷却至室温，最后用乙醇清洗数次并保存在乙醇中备用，即得超薄PdPtIr三金属纳米片堆叠组装材料。
TEM表征如图6A、B，三金属PdPtIr纳米晶为六角片组装结构。
实施例5：
在25mL聚四氟乙烯反应釜内胆中，加入100mg的十六烷基三甲基氯化铵，100mg的聚乙烯吡咯烷酮、8mg的乙酰丙酮钯、10mg的乙酰丙酮铂、3-13mg的三氯化钌、8mg的无水氯化镍/13mg的三氯化铑/18.5mg的氯化铱、1.35-8.1mg的三氯化铁、50mg的六羰基钨和12mL的无水乙醇。室温下以600rpm的转速搅拌30min，放烘箱里，从30℃升温至180℃(升温速率：5℃/min)，并保持180℃ 30-90min，然后自然冷却至室温，最后用乙醇清洗数次并保存在乙醇中备用，即得超薄PdPtRuRh/PdPtRuRh/PdPtRuRh四金属纳米片堆叠组装材料
TEM表征如图7，四金属(A)PdPtRuRh，(B)PdPtRuRh，(C)PdPtRuRh纳米晶为六角片组装结构。
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。
Claims (6)
1.一种超薄多金属纳米片堆叠组装材料的制备方法，其特征在于：包括如下步骤：
（1）将十六烷基三甲基氯化铵、聚乙烯吡咯烷酮、钯前驱盐、铂前驱盐、可选金属前驱盐、三氯化铁和六羰基钨用乙醇溶解并搅拌混合均匀；
（2）将步骤（1）所得的物料由室温升至175-185 ℃，恒温反应30-90min，然后冷却至室温；
（3）将步骤（2）所得的物料用乙醇充分洗涤后，获得所述超薄多金属纳米片堆叠组装材料；
其中，钯前驱盐为乙酰丙酮钯，所述铂前驱盐为乙酰丙酮铂，可选金属前驱盐为三氯化钌、无水氯化镍、三氯化铑和氯化铱中的至少一种。
2.如权利要求1所述的制备方法，其特征在于：所述步骤（2）为：将步骤（1）所得的物料由室温升至180 ℃，恒温反应30-90min，然后冷却至室温。
3.如权利要求1或2所述的制备方法，其特征在于：所述十六烷基三甲基氯化铵、聚乙烯吡咯烷酮、钯前驱盐、铂前驱盐、可选金属前驱盐、三氯化铁和六羰基钨的质量比为90-110:90-110:7-9:8-12:3-55:1.2-8.5:45-55。
4.如权利要求3所述的制备方法，其特征在于：所述十六烷基三甲基氯化铵、聚乙烯吡咯烷酮、钯前驱盐、铂前驱盐、可选金属前驱盐、三氯化铁和六羰基钨的质量比为100:100:8:10:3-52.5:1.35-8.1:50。
5.一种电催化材料，其特征在于：其原料包括权利要求1至4中任一权利要求所述的制备方法制得的超薄多金属纳米片堆叠组装材料。
6.权利要求1至4中任一权利要求所述的制备方法制得的超薄多金属纳米片堆叠组装材料在制备电催化材料中的应用。
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