CN106513029A - 一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法 - Google Patents
一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法 Download PDFInfo
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Abstract
本发明属于碳材料技术领域,具体涉及一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法,该方法将金属前驱体、致孔剂过氧化氢、氮源氨加入到氧化石墨烯水溶液中,再将混合溶液加热至100‑220℃进行水热反应一步即可制得负载金属纳米粒子的氮掺杂多孔石墨烯复合材料。该方法在构建石墨烯多孔结构的同时实现氮掺杂和金属纳米粒子的负载,整个工艺简单,对设备要求低,反应条件较为温和,生产成本低,所制备的金属纳米粒子/氮掺杂多孔石墨烯具有比表面积大、催化性能优异、负载的金属纳米粒子分布均匀等特点,可用于电催化、超级电容器、锂离子电池和有机催化等领域。
Description
技术领域
本发明属于碳材料与有机催化技术领域,具体涉及一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法。
背景技术
石墨烯因具有独特的石墨化平面结构、高比表面积和良好的导电性等众多优异性质,成为催化剂的理想载体。邱建丁等[CN201010523363.5]将Pt纳米粒子负载于功能化的石墨烯上,用于电催化领域。对石墨烯进行N掺杂,一方面可以实现对石墨烯碳材料表面电荷分布及表面缺陷程度的有效调控[ACS Nano2012,6,7084-7091],另一方面掺杂的N还对石墨烯负载的金属(如M=Pt,Pd,Co等)催化剂纳米粒子的成核和生长以及M―C之间的相互作用产生影响,从而进一步改变石墨烯基负载型催化剂的性能[Acta Phys.-Chim.Sin.2014,30,1267-1273]。因此,N掺杂石墨烯作为催化剂的载体显示出很大的应用潜力,在氮掺杂石墨烯上负载金属纳米粒子则可以进一步拓展其应用。
然而,石墨烯片层之间有较强的π-π作用力,容易导致堆叠,降低其比表面积而影响催化性能[Angew.Chem.Int.Ed.2013,126,254-258],而利用活化造孔的方法来提高其比表面积并加强传质[Nat.Commun.2014,5,4554],可以有效增强其催化活性。因此,通过在氮掺杂石墨烯上构建多孔结构是提高氮掺杂石墨烯基比表面积的有效手段,同时可以提高负载金属纳米粒子氮掺杂石墨烯的催化剂活性。
目前,负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法还未见报道。因而,发展一种简易、高效的负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法,在催化领域无疑具有十分重要的应用价值。
发明内容
为克服现有技术存在的上述不足,本发明的首要目的在于提供一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法,该方法在构建石墨烯多孔结构的同时实现了氮掺杂和金属纳米粒子的负载,工艺简单,对设备要求低。为实现上述目的,本发明的技术方案如下:
一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法,包括以下步骤:配制氧化石墨烯水溶液,分别向其中加入金属前驱体、致孔剂和氮源,将溶液混合均匀,水热反应后得负载金属纳米粒子的氮掺杂多孔石墨烯复合材料。
上述方案中,所述氧化石墨烯水溶液的浓度为3-10mg/mL。
上述方案中,所述金属前驱体为金、银、铂、钯、钌、铑、铁、钴、镍、锰、锌、铜、钛、锡、钼、镉、钨、铋、铈的水溶性盐类化合物中的一种及其组合。
上述方案中,所述致孔剂为过氧化氢,其水溶液质量分数为0.2-30%。
上述方案中,所述氮源为氨,其水溶液质量分数为28-30%。
上述方案中,氧化石墨烯与金属前驱体、致孔剂、氮源的质量比为1:0.001-1:0.05-5:0.05-30。
上述方案中,水热反应时的温度为100-220℃,反应时间为5-24h。
与现有技术相比,本发明具有以下有益效果:(1)工艺简单,制备过程无需还原剂,生产效率更高;(2)反应条件温和,所需原料简单易得,无需特殊或复杂反应设备,成本更低;(3)制备出的负载金属纳米粒子的氮掺杂多孔石墨烯复合材料具有比表面积大、催化性能优异等特点,可用于电催化、超级电容器、锂离子电池和有机催化等领域。
附图说明
图1为本发明实施例1制备的负载钯纳米粒子的氮掺杂多孔石墨烯扫描电镜图。
图2为本发明实施例1制备的负载钯纳米粒子的氮掺杂多孔石墨烯透射电镜图。
图3为本发明实施例1制备的负载钯纳米粒子的氮掺杂多孔石墨烯的X-射线光电子能谱测试结果图。
图4为本发明实施例1制备的负载钯纳米粒子的氮掺杂多孔石墨烯的N2吸附脱附曲线图(A)和孔径分布图(B)。
具体实施方式
为使本领域普通技术人员充分理解本发明的技术方案和有益效果,以下结合具体实施例进行进一步充分说明。
一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法,首先配制氧化石墨烯水溶液,向其中加入金属前驱体(金、银、铂、钯、钌、铑、铁、钴、镍、锰、锌、铜、钛、锡、钼、镉、钨、铋、铈的水溶性盐类化合物中的一种及其组合)、浓度为0.2-30wt%的过氧化氢、浓度为28-30wt%的氨水并混合均匀,将混合物加热至100-220℃进行水热反应5-24h,最终得到负载金属纳米粒子的氮掺杂多孔石墨烯复合材料。氧化石墨烯与金属前驱体、过氧化氢、氨三者纯物质的质量比为1:0.001-1:0.05-5:0.05-30
实施例1
按氧化石墨烯、金属前驱体、过氧化氢、氨1:0.033:0.05:30的质量比投料。取50mL浓度为6mg/mL的氧化石墨烯水溶液,将其装入100mL聚四氟乙烯反应釜内胆中,在搅拌条件下加入5mL质量分数为0.3%的过氧化氢溶液和30mL质量分数为28-30%的氨水溶液以及10mg氯亚钯酸钾。将混合均匀的反应物,装入水热反应釜中,在180℃烘箱中水热反应6h,得负载钯纳米粒子的氮掺杂多孔石墨烯。
为了更充分的了解本实施例制得的负载钯纳米粒子的氮掺杂多孔石墨烯的结构特征及其性能,分别对其进行了SEM、TEM、XPS、吸附脱附以及孔径分布测试。
如图1所示,本实施例制备的负载钯纳米粒子的氮掺杂多孔石墨烯呈片状褶皱;由图2可以看到,片状石墨烯被刻蚀成为多孔结构且石墨烯纳米片上负载有大量分布均匀的纳米粒子;图3 XPS分析表明,制备的负载钯纳米粒子的氮掺杂多孔石墨烯中含有C,O,N,Pd元素,其中掺杂氮元素含量为5.49wt.%,钯的负载量为1.64wt.%;图4显示制备的负载钯纳米粒子的氮掺杂多孔石墨烯比表面积为191.1m2/g,孔径分布在微孔和介孔范围。
实施例2
按氧化石墨烯与金属前驱体、过氧化氢、氨1:0.001:0.05:0.05的质量比投料。取75mL浓度为4mg/mL氧化石墨烯水溶液,装入100mL聚四氟乙烯反应釜内胆中,在搅拌条件下加入5mL质量分数为0.3%的过氧化氢溶液和0.05mL质量分数为28-30%的氨水溶液以及0.3mg氯亚铂酸钾。将混合均匀的反应物,装入水热反应釜中,在120℃烘箱中水热反应24h,得负载铂纳米粒子的氮掺杂多孔石墨烯。
实施例3
按氧化石墨烯与金属前驱体、过氧化氢、氨1:0.008:0.05:24的质量比投料。取50mL浓度为5mg/mL氧化石墨烯水溶液,装入100mL聚四氟乙烯反应釜内胆中,在搅拌条件下加入5mL质量分数为0.3%的过氧化氢溶液和20mL质量分数为28-30%的氨水溶液以及2mg氯金酸钾。将混合均匀的反应物,装入水热反应釜中,在180℃烘箱中水热反应10h,得负载金纳米粒子的氮掺杂多孔石墨烯。
实施例4
按氧化石墨烯与金属前驱体、过氧化氢、氨1:0.028:0.05:8.333的质量比投料。取36mL浓度为10mg/mL氧化石墨烯水溶液,装入100mL聚四氟乙烯反应釜内胆中,在搅拌条件下加入9mL质量分数为0.2%的过氧化氢溶液和10mL质量分数为28-30%的氨水溶液以及10mg氯钯酸钾。将混合均匀的反应物,装入水热反应釜中,在180℃烘箱中水热反应5h,得负载钯纳米粒子的氮掺杂多孔石墨烯。
实施例5
按氧化石墨烯与金属前驱体、过氧化氢、氨1:0.05:0.2:7.5的质量比投料。取60mL浓度6mg/mL氧化石墨烯水溶液,装入100mL聚四氟乙烯反应釜内胆中,在搅拌条件下加入9mL质量分数为0.8%的过氧化氢溶液和9mL质量分数为28-30%的氨水溶液以及8mg氯铂酸钾。将混合均匀的反应物,装入水热反应釜中,在180℃烘箱中水热反应6h,得负载铂纳米粒子的氮掺杂多孔石墨烯。
实施例6
按氧化石墨烯与金属前驱体、过氧化氢、氨1:1:5:30的质量比投料。取60mL浓度5mg/mL氧化石墨烯水溶液,装入100mL聚四氟乙烯反应釜内胆中,在搅拌条件下加入1mL质量分数为30%的过氧化氢溶液和30mL质量分数为28-30%的氨水溶液以及300mg氯铂酸钾。将混合均匀的反应物,装入水热反应釜中,在180℃烘箱中水热反应6h,得负载铂纳米粒子的氮掺杂多孔石墨烯。
以上所述仅为本发明的部分实施例,并非限制本发明的保护范围。凡是利用本发明技术方案所进行的修改,或者对其中部分或全部技术特征进行等同替换,均应落入本发明的保护范围之内。
Claims (7)
1.一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法,其特征在于,包括以下步骤:配制氧化石墨烯水溶液,分别向其中加入金属前驱体、致孔剂和氮源,将溶液混合均匀,水热反应后得负载金属纳米粒子的氮掺杂多孔石墨烯复合材料。
2.如权利要求1所述的一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法,其特征在于:所述氧化石墨烯水溶液的浓度为3-10mg/mL。
3.如权利要求1所述的一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法,其特征在于:所述金属前驱体为金、银、铂、钯、钌、铑、铁、钴、镍、锰、锌、铜、钛、锡、钼、镉、钨、铋、铈的水溶性盐类化合物中的一种及其组合。
4.如权利要求1所述的一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法,其特征在于:所述致孔剂为过氧化氢,其水溶液质量分数为0.2-30%。
5.如权利要求1所述的一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法,其特征在于:所述氮源为氨,其水溶液质量分数为28-30%。
6.如权利要求1所述的一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法,其特征在于:氧化石墨烯与金属前驱体、致孔剂、氮源的质量比为1:0.001-1:0.05-5:0.05-30。
7.如权利要求1所述的一种负载金属纳米粒子的氮掺杂多孔石墨烯的制备方法,其特征在于:水热反应时的温度为100-220℃,反应时间为5-24h。
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