CN111349245A - 一种交叠结构纳米片层材料及其制备方法和应用 - Google Patents
一种交叠结构纳米片层材料及其制备方法和应用 Download PDFInfo
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- CN111349245A CN111349245A CN201811569690.7A CN201811569690A CN111349245A CN 111349245 A CN111349245 A CN 111349245A CN 201811569690 A CN201811569690 A CN 201811569690A CN 111349245 A CN111349245 A CN 111349245A
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Abstract
本发明涉及一种交叠结构纳米片层材料,由金属有机框架纳米片层和石墨烯基材料片层叠合或交替叠合而成的复合片层结构;每层金属有机框架纳米片层的厚度为1‑5nm;每层石墨烯基材料片层的厚度为1‑10nm;复合片层的厚度为2‑100nm。复合材料可用于电催化反应、物质吸收释放以及气体分离。
Description
技术领域
本发明涉及一种交叠结构纳米片层材料,具体的说是一种可用于电催化反应、物质吸收释放以及气体分离的复合材料。
本发明还涉及上述交叠结构纳米片层材料的制备方法。
背景技术
具有复合纳米结构的层状材料,在生物、医疗、电子、能源等领域具有十分广阔的应用前景。特别是基于片层材料的电化学催化材料在能源技术、分析表征技术、电子与信息技术以及材料合成技术等国民经济重要领域具有不可替代的作用。电化学催化剂的结构设计与材料合成是该领域的核心技术之一。随着纳米技术的不断发展与在能源材料领域的深入研究,具有纳米尺度的新材料及其具有的特殊物化性质得到了广泛的应用。其中,金属有机框架结构(MOFs)作为近年来发展起来的新型纳米多孔材料,由于其具有有序孔结构、高化学活性、高比表面积等优异的性质,在电化学催化领域具有极大的应用潜力。基于MOFs材料的电化学催化研究,目前开拓出了包括氧还原反应(ORR)、氧析出反应(OER)等能源器件密切相关的催化反应体系,以及有机小分子合成、二氧化碳电还原等材料环境相关的催化体系等。但与此同时,我们也发现MOFs材料由于其自身的不稳定性、导电性能不足等缺陷,在电催化领域的应用仍旧面临着活性、稳定性的严峻挑战。以石墨烯为代表的片层结构碳材料,在电催化与储能等领域具有极高的应用价值。然而由于其结构相对单一,对其原位的修饰与调控相对困难,基于片层结构的碳材料开发复合结构新型材料是一条有效的制备多功能材料与器件的方法。
鉴于此,基于MOFs材料与碳材料开发一种具有高活性、高稳定性,且结构可控的复合纳米片层结构材料,是未来MOFs材料与二维纳米碳材料实现其应用价值的关键步骤之一,也可能在电化学催化、储能、物质分离等领域开拓全新的研究应用方向。
发明内容
本发明的目的在于提供一种新型的复合纳米片层结构材料,该材料具有均匀交叠复合的纳米级厚度的金属有机框架片层与石墨烯基材料片层,两种片层结构间通过静电相互作用力实现有序耦合。该材料具有相对较高的导电性、比表面积与高密度金属活性位点等优点,可广泛应用于电化学催化、燃料电池、储能电池、气体分离等领域。
为实现上述目的,本发明采用以下方案来实现:
一种交叠结构纳米片层,包括一种或一种以上金属有机框架纳米片层和石墨烯基材料片层,以及这两类材料之间形成的交叠复合片层结构。
所述金属有机框架纳米片层的金属种类为铁、钴、镍、铜、锌、锆中的一种或几种,所述金属框架纳米片层的配体分子为对苯二甲酸、苯甲酸、联吡啶中的一种;
所述石墨烯基材料为氧化石墨烯、氮掺杂石墨烯、硼掺杂石墨烯、硫掺杂石墨烯、磷掺杂石墨烯、石墨烯负载金属纳米粒子中的一种或几种;
所述石墨烯负载金属纳米粒子为为金、铂、银、钌、钯、铁、钴、镍中的一种或两种以上合金材料;
所述交叠结构纳米片层材料的制备,包括以下步骤:
a,石墨烯基材料的制备
石墨烯基材料均采用Hummer法制备的氧化石墨作为前体,将所制备的氧化石墨以0.1-10毫克每毫升的浓度分散于去离子水中,并持续超声搅拌2-8小时;通过化学热解、水热合成等方法中的一种,制备含有掺杂元素的氧化石墨烯或负载有金属纳米粒子前体的氧化石墨烯;将上述中间产物以10-50毫克每毫升的浓度分散于去离子水中,并用液氮冷凝至固态,置于冷冻干燥机中进行24-48小时的冷冻干燥过程,直至溶剂完全除尽;将上述干燥样品置于管式炉中,在150至500摄氏度含5%氢气的氢氩混合气中化学还原2-8小时,即得到所述石墨烯基材料。
b,金属有机框架片层与石墨烯基片层的交叠制备
将上述石墨烯基材料分散于二甲基甲酰胺中,浓度为0.5-5毫克每毫升,超声分散2-8小时制得均匀分散的胶体溶液;在上述胶体溶液中加入过渡金属盐,浓度为0.01-0.5毫摩尔每毫升,超声分散均匀;加入与过渡金属盐同等物质的量的配体,超声分散均匀;上述混合物加入一定量的乙醇/水一比一的混合溶剂,使其占混合物总体积的5-20%;将上述混合物超声分散2-8小时;将上述混合物在氮气保护条件下,迅速加入占混合物总体积1-4%的三乙胺沉淀剂,并迅速将容器密封,置于功率为50-500W的超声清洗机温度为-10至10摄氏度反应6-24小时;将上述混合物进行转速为3000-10000转的离心分离,并将所得沉淀继续采用离心方法乙醇清洗4-6次,所得沉淀冷冻干燥即得所述复合结构材料样品。
所述步骤b中所采用的溶剂目的是保证石墨烯基材料形成分散均匀的胶体溶液,使得金属前体盐可有效地附着于石墨烯基材料的表面,进而形成稳定交联的交叠片层结构;
所述步骤b中将金属有机框架结构片层的前体材料与石墨烯基材料的混合与超声分散步骤与低温生长步骤,是使其两者形成交联结构以及形成交叠良好的层状结构的关键环节,过短的分散时间与过高的生长温度将使纳米片层形成各自游离堆叠的结构;
所述复合材料中石墨烯基材料若为氧化石墨烯,则所述步骤a中可将超声分散的氧化石墨样品冷冻干燥后直接进行步骤b的操作;
所述石墨烯基材料若为氮、硼、硫、磷掺杂石墨烯片层,则所述步骤a中采用化学热解法,将掺杂元素前体与上述冷冻干燥后的氧化石墨烯样品混合均匀,在管式炉中氮气气氛下400-900摄氏度反应2-8小时;
所述掺杂元素前体为三聚氰胺、硼酸、硫代硫酸钠、五氧化二磷中的一种,分别制备掺杂氮、硼、硫、磷元素的石墨烯材料;
所述石墨烯基材料若为石墨烯负载金属纳米粒子片层材料,则所述步骤a中采用水热合成法将金属前体盐按照金属占石墨烯质量比例为1-40%加入氧化石墨烯的乙二醇分散溶液中,金属前体盐和氧化石墨烯总质量百分浓度为1-10%,用氢氧化钠调节pH值至11-14左右,120-150摄氏度水浴反应1-6小时,充分还原后过滤洗涤;
所述金属前体盐为氯铂酸、氯钯酸、氯化钌、氯金酸、硝酸银、氯化镍、氯化钴、氯化铁中的一种或几种;
所述有机金属框架结构的金属前体盐为氯化镍、氯化钴、氯化铁、氯化锌、氯化铜、氯化锆中的一种或几种;
所述有金金属框架结构的配体为对苯二甲酸、均苯三甲酸、吡啶、2-2‘联吡啶中的一种或几种;
所述复合结构材料可用于氧还原电催化、氧析出电催化、甲醇氧化、二氧化碳电还原等电催化反应中,以及气体吸附、药物释放、物质分离等领域。与现有技术相比,本发明具有以下优点:
1,具有多功能活性:本发明所制备的交叠结构材料相比单一组分材料可同时发挥两种或两种以上的物性特征;
2,具有高活性特征:本发明所制备的复合材料基于多种组分间的电子调控等相互作用,可提升材料的物化活性;
3,高活性表面积:本发明所制备的片层结构具有较高的比表面积,且大部分暴露于介孔与大孔中,更有利于活性表面的充分暴露;
4,实用性强:本发明制备过程无需采用苛刻的条件,可根据应用目标的要求调变其中的组分,可应用的范围广泛。
附图说明
图1为本发明所述交叠复合片层材料的合成路线示意图。
图2为一种采用本发明所述方法制备的交叠复合片层材料的透射电镜照片(实施例1)。如图所示,石墨烯基材料担载有均匀的Pt纳米颗粒,平均粒径2纳米左右,金属有机框架结构薄层以50纳米左右的尺寸均匀叠层于石墨烯基片层表面。
图3为一种采用本发明所述方法制备的交叠复合片层材料应用于氧还原反应(a)与氧析出反应(b)电化学测试结果曲线(实施例1、对比例1与对比例2)。由图可以看出,采用本发明方法制备的交叠复合片层材料氧还原与氧析出催化性能明显提升。
具体实施方式
以下通过实例对本发明作详细描述,但本发明不仅限于以下实施例。
实施例1:
a,石墨烯基材料的制备
石墨烯基材料均采用Hummer法制备的氧化石墨作为前体,将所制备的氧化石墨以1毫克每毫升的浓度分散于去离子水中,并持续超声搅拌4小时;通过水热合成制备负载有金属Pt纳米粒子前体的氧化石墨烯:将氯铂酸按照金属Pt占石墨烯质量比例为10%加入氧化石墨烯的乙二醇分散溶液中,金属前体盐和氧化石墨烯总质量百分浓度为2%,用氢氧化钠调节pH值至11-14左右,140摄氏度油浴反应2小时,充分还原后过滤洗涤;将上述中间产物以20毫克每毫升的浓度分散于去离子水中,并用液氮冷凝至固态,置于冷冻干燥机中进行24小时的冷冻干燥过程,直至溶剂完全除尽;将上述干燥样品置于管式炉中,在200摄氏度含5%氢气的氢氩混合气中化学还原4小时,即得到所述石墨烯基材料。
b,金属有机框架片层与石墨烯基片层的交叠制备
将上述石墨烯基材料分散于二甲基甲酰胺中,浓度为1毫克每毫升,超声分散6小时制得均匀分散的胶体溶液;在上述胶体溶液中加入氯化镍,浓度为0.05毫摩尔每毫升,超声分散均匀;加入与过渡金属盐同等物质的量的对苯二甲酸,超声分散均匀;上述混合物加入一定量的乙醇/水一比一体积比的混合溶剂,使其占混合物总体积的10%;将上述混合物超声分散6小时;将上述混合物在氮气保护条件下,迅速加入占混合物总体积2%的三乙胺沉淀剂,并迅速将容器密封,置于功率为200W的超声清洗机中温度为-10摄氏度反应8小时;将上述混合物进行转速为6000转的离心分离,并将所得沉淀继续采用离心方法乙醇清洗4次,所得沉淀冷冻干燥即得所述复合结构材料样品。由透射电子显微镜结果可见,所制备样品呈现出良好的片层堆叠结构,金属有机框架结构片层直径约为50纳米,石墨烯材料上所负载的铂纳米粒子粒径约为2纳米。
对比例1:
石墨烯基片层材料的制备,采用Hummer法制备的氧化石墨作为前体,将所制备的氧化石墨以1毫克每毫升的浓度分散于去离子水中,并持续超声搅拌4小时;通过水热合成制备负载有金属Pt纳米粒子前体的氧化石墨烯:将氯铂酸按照金属Pt占石墨烯质量比例为10%加入氧化石墨烯的乙二醇分散溶液中,金属前体盐和氧化石墨烯总质量百分浓度为2%,用氢氧化钠调节pH值至11-14左右,140摄氏度油浴反应2小时,充分还原后过滤洗涤;将上述中间产物以20毫克每毫升的浓度分散于去离子水中,并用液氮冷凝至固态,置于冷冻干燥机中进行24小时的冷冻干燥过程,直至溶剂完全除尽;将上述干燥样品置于管式炉中,在200摄氏度含5%氢气的氢氩混合气中化学还原4小时,即得到所述石墨烯基材料。
对比例2:
金属有机框架结构薄层材料的制备,在二甲基甲酰胺溶液中加入氯化钴,浓度为0.1毫摩尔每毫升,超声分散均匀;加入与过渡金属盐同等物质的量的对苯二甲酸,超声分散均匀;上述混合物加入一定量的乙醇/水一比一的混合溶剂,使其占混合物总体积的20%;将上述混合物超声分散8小时;将上述混合物在氮气保护条件下,迅速加入占混合物总体积1%的三乙胺沉淀剂,并迅速将容器密封,置于功率为500W的超声清洗机中反应6小时;将上述混合物进行转速为10000转的离心分离,并将所得沉淀继续采用离心方法乙醇清洗4次,所得沉淀冷冻干燥即得金属有机框架结构薄层材料样品。
对比例3:
a,石墨烯基材料的制备
石墨烯基材料均采用Hummer法制备的氧化石墨作为前体,将所制备的氧化石墨以1毫克每毫升的浓度分散于去离子水中,并持续超声搅拌4小时;通过水热合成制备负载有金属Pt纳米粒子前体的氧化石墨烯:将氯铂酸按照金属Pt占石墨烯质量比例为10%加入氧化石墨烯的乙二醇分散溶液中,金属前体盐和氧化石墨烯总质量百分浓度为2%,用氢氧化钠调节pH值至11-14左右,140摄氏度油浴反应2小时,充分还原后过滤洗涤;将上述中间产物以20毫克每毫升的浓度分散于去离子水中,并用液氮冷凝至固态,置于冷冻干燥机中进行24小时的冷冻干燥过程,直至溶剂完全除尽;将上述干燥样品置于管式炉中,在200摄氏度含5%氢气的氢氩混合气中化学还原4小时,即得到所述石墨烯基材料。
b,金属有机框架片层与石墨烯基片层的交叠制备
将上述石墨烯基材料分散于水溶液中,浓度为1毫克每毫升,超声分散6小时制得均匀分散的胶体溶液;在上述胶体溶液中加入氯化镍,浓度为0.05毫摩尔每毫升,超声分散均匀;加入与过渡金属盐同等物质的量的对苯二甲酸,超声分散均匀;上述混合物加入一定量的乙醇/水一比一的混合溶剂,使其占混合物总体积的10%;将上述混合物超声分散6小时;将上述混合物在氮气保护条件下,迅速加入占混合物总体积2%的三乙胺沉淀剂,并迅速将容器密封,置于功率为200W的超声清洗机中温度为-10摄氏度反应8小时;将上述混合物进行转速为6000转的离心分离,并将所得沉淀继续采用离心方法乙醇清洗4次,所得沉淀冷冻干燥即得所述样品。在水溶液中分散的制备过程石墨烯基材料难以形成良好的胶体溶液,所得材料交联堆叠结构不显著。
对比例4:
a,石墨烯基材料的制备
石墨烯基材料均采用Hummer法制备的氧化石墨作为前体,将所制备的氧化石墨以1毫克每毫升的浓度分散于去离子水中,并持续超声搅拌4小时;通过水热合成制备负载有金属Pt纳米粒子前体的氧化石墨烯:将氯铂酸按照金属Pt占石墨烯质量比例为10%加入氧化石墨烯的乙二醇分散溶液中,金属前体盐和氧化石墨烯总质量百分浓度为2%,用氢氧化钠调节pH值至11-14左右,140摄氏度油浴反应2小时,充分还原后过滤洗涤;将上述中间产物以20毫克每毫升的浓度分散于去离子水中,并用液氮冷凝至固态,置于冷冻干燥机中进行24小时的冷冻干燥过程,直至溶剂完全除尽;将上述干燥样品置于管式炉中,在200摄氏度含5%氢气的氢氩混合气中化学还原4小时,即得到所述石墨烯基材料。
b,金属有机框架片层与石墨烯基片层的交叠制备
将上述石墨烯基材料分散于二甲基甲酰胺中,浓度为1毫克每毫升,超声分散6小时制得均匀分散的胶体溶液;在上述胶体溶液中加入氯化镍,浓度为0.05毫摩尔每毫升,超声分散均匀;加入与过渡金属盐同等物质的量的对苯二甲酸,超声分散均匀;上述混合物加入一定量的乙醇/水一比一的混合溶剂,使其占混合物总体积的10%;将上述混合物超声分散0.5小时;将上述混合物在氮气保护条件下,迅速加入占混合物总体积2%的三乙胺沉淀剂,并迅速将容器密封,置于功率为200W的超声清洗机中常温下反应8小时;将上述混合物进行转速为6000转的离心分离,并将所得沉淀继续采用离心方法乙醇清洗4次,所得沉淀冷冻干燥即得所述样品。由于步骤b中超声分散时间过短,以及生长温度过高,导致金属有机框架结构片层与石墨烯基底之间难以形成有效的交联结构,两类片层呈现出游离的分布状态。
实施例2:
a,石墨烯基材料的制备
石墨烯基材料均采用Hummer法制备的氧化石墨作为前体,将所制备的氧化石墨以1毫克每毫升的浓度分散于去离子水中,并持续超声搅拌4小时;通过化学热解法制备掺杂有氮元素的氧化石墨烯:将占氧化石墨烯质量比例为20%的三聚氰胺与上述冷冻干燥后的氧化石墨烯样品混合均匀,在管式炉中氮气气氛下800摄氏度反应3小时;将上述中间产物以10毫克每毫升的浓度分散于去离子水中,并用液氮冷凝至固态,置于冷冻干燥机中进行48小时的冷冻干燥过程,直至溶剂完全除尽;将上述干燥样品置于管式炉中,在500摄氏度含5%氢气的氢氩混合气中化学还原6小时,即得到所述石墨烯基材料。
b,金属有机框架片层与石墨烯基片层的交叠制备
将上述石墨烯基材料分散于二甲基甲酰胺中,浓度为2毫克每毫升,超声分散4小时制得均匀分散的胶体溶液;在上述胶体溶液中加入氯化钴,浓度为0.1毫摩尔每毫升,超声分散均匀;加入与过渡金属盐同等物质的量的均苯三甲酸,超声分散均匀;上述混合物加入一定量的乙醇/水一比一体积比的混合溶剂,使其占混合物总体积的20%;将上述混合物超声分散8小时;将上述混合物在氮气保护条件下,迅速加入占混合物总体积1%的三乙胺沉淀剂,并迅速将容器密封,置于功率为500W的超声清洗机中温度为-5摄氏度反应6小时;将上述混合物进行转速为10000转的离心分离,并将所得沉淀继续采用离心方法乙醇清洗4次,所得沉淀冷冻干燥即得所述复合结构材料样品。由透射电子显微镜结果可见,所制备样品呈现出良好的片层堆叠结构,金属有机框架结构片层直径约为100纳米。
实施例3:
a,石墨烯基材料的制备
石墨烯基材料均采用Hummer法制备的氧化石墨作为前体,将所制备的氧化石墨以1毫克每毫升的浓度分散于去离子水中,并持续超声搅拌6小时;通过水热合成制备负载有金属Pd纳米粒子前体的氧化石墨烯:将氯钯酸按照金属Pd占石墨烯质量比例为10%加入氧化石墨烯的乙二醇分散溶液中,金属前体盐和氧化石墨烯总质量百分浓度为2%,用氢氧化钠调节pH值至11-14左右,140摄氏度油浴反应2小时,充分还原后过滤洗涤;将上述中间产物以20毫克每毫升的浓度分散于去离子水中,并用液氮冷凝至固态,置于冷冻干燥机中进行24小时的冷冻干燥过程,直至溶剂完全除尽;将上述干燥样品置于管式炉中,在300摄氏度含5%氢气的氢氩混合气中化学还原6小时,即得到所述石墨烯基材料。
b,金属有机框架片层与石墨烯基片层的交叠制备
将上述石墨烯基材料分散于二甲基甲酰胺中,浓度为1毫克每毫升,超声分散6小时制得均匀分散的胶体溶液;在上述胶体溶液中加入氯化铜,浓度为0.05毫摩尔每毫升,超声分散均匀;加入与过渡金属盐同等物质的量的2-2‘联吡啶,超声分散均匀;上述混合物加入一定量的乙醇/水一比一体积比的混合溶剂,使其占混合物总体积的10%;将上述混合物超声分散6小时;将上述混合物在氮气保护条件下,迅速加入占混合物总体积2%的三乙胺沉淀剂,并迅速将容器密封,置于功率为200W的超声清洗机中温度为0摄氏度反应4小时;将上述混合物进行转速为6000转的离心分离,并将所得沉淀继续采用离心方法乙醇清洗4次,所得沉淀冷冻干燥即得所述复合结构材料样品。由透射电子显微镜结果可见,所制备样品呈现出良好的片层堆叠结构,金属有机框架结构片层直径约为50纳米,石墨烯材料上所负载的钯纳米粒子粒径约为5纳米。
Claims (10)
1.一种交叠结构纳米片层材料,其特征在于:
由金属有机框架纳米片层和石墨烯基材料片层叠合或交替叠合而成的复合片层结构;
每层金属有机框架纳米片层的厚度为1-5nm;每层石墨烯基材料片层的厚度为1-10nm;
复合片层的厚度为2-100nm。
2.按照权利要求1所述的材料,其特征在于:
所述金属有机框架纳米片层由金属配合物构成,金属为铁、钴、镍、铜、锌、锆中的一种或二种以上,配体分子为对苯二甲酸、均苯三甲酸、苯甲酸、联吡啶中的一种或二种以上。
3.按照权利要求2所述的材料,其特征在于:
所述石墨烯基材料为氧化石墨烯、掺杂石墨烯、负载金属纳米粒子的石墨烯中的一种或二种以上;
石墨烯负载金属纳米粒子中金属纳米粒子的质量负载量为0.5-60%;
所述掺杂石墨烯中的掺杂元素为氮、硼、硫或磷中的一种或两种以上,所述掺杂元素的质量掺杂量为0.1-10%;
所述石墨烯负载金属纳米粒子为金、铂、银、钌、钯、铁、钴、镍中的一种或两种以上合金材料。
4.一种权利要求1-3任一所述材料的制备方法,其特征在于:包括以下步骤,
a,石墨烯基材料的制备:采用Hummer法制备氧化石墨烯,进行或不进行采用氧化石墨烯制备掺杂石墨烯的过程,进行或不进行负载金属纳米粒子的石墨烯的过程;
b,金属有机框架片层与石墨烯基片层的交叠制备:
将石墨烯基材料分散于二甲基甲酰胺、二甲基乙酰胺或二甲基亚砜中的一种或两种以上溶液中,浓度为0.5-5毫克每毫升,分散制得胶体溶液;于所得胶体溶液中加入过渡金属盐,浓度为0.01-0.5毫摩尔每毫升,超声分散均匀;加入与过渡金属盐同等物质的量的配体,再次超声分散均匀得混合物;上述混合物加入乙醇和水(体积比例为1:5至5:1)的混合溶剂,使混合溶剂占混合物总体积的5-20%,再次分散;在惰性气体保护条件下,加入占混合物料总体积1-4%的三乙胺沉淀剂,并迅速将容器密封,并置于超声条件下反应;重复进行分离、清洗后,将沉淀冷冻干燥得所述复合结构材料样品。
5.按照权利要求4所述材料的制备方法,其特征在于:
步骤b中,所述过渡金属盐为氯化镍、氯化钴、氯化铁、氯化锌、氯化铜、氯化锆中的一种或两种以上;配体为对苯二甲酸、均苯三甲酸、吡啶、2-2‘联吡啶中的一种或两种以上。
所述乙醇和水的混合溶剂的体积比为1:2-2:1;
所述分散方法为超声分散;
所述惰性气体为氮气、氩气、氦气中的一种或两种以上;
所述超声反应条件为功率为50-500W的超声清洗机中温度为-10至10摄氏度反应6-24小时;
所述分离条件为3000-10000转离心分离,清洗溶剂为乙醇,重复次数为4-6次。
6.按照权利要求4所述材料的制备方法,其特征在于:
步骤a采用Hummer法制备石墨烯基材料,具体为,
石墨烯基材料均采用Hummer法制备的氧化石墨作为前体,将所制备的氧化石墨以0.1-10毫克每毫升的浓度分散于去离子水中,并持续超声搅拌2-8小时,并用液氮冷凝至固态,置于冷冻干燥机中进行24-48小时的冷冻干燥过程,直至溶剂完全除尽,得氧化石墨烯;
石墨烯基材料均采用Hummer法制备的氧化石墨作为前体,将所制备的氧化石墨以0.1-10毫克每毫升的浓度分散于去离子水中,并持续超声搅拌2-8小时,加入掺杂元素前体,通过化学热解或水热合成等方法中的一种,制备含有掺杂元素的氧化石墨烯或负载有金属纳米粒子前体的氧化石墨烯,得中间产物;将上述中间产物以10-50毫克每毫升的浓度分散于去离子水中,并用液氮冷凝至固态,置于冷冻干燥机中进行24-48小时的冷冻干燥过程,直至溶剂完全除尽;将上述干燥样品置于管式炉中,在150至500摄氏度含体积含量3-5%氢气的氢氩混合气中化学还原2-8小时,即得到所述负载金属纳米粒子的石墨烯。
7.按照权利要求6所述材料的制备方法,其特征在于:
所述石墨烯基材料若为含氮、硼、硫或磷掺杂石墨烯片层,则所述步骤a中采用化学热解法,将掺杂元素前体与上述冷冻干燥后的氧化石墨烯样品混合均匀,在管式炉中惰性气氛下400-900摄氏度反应2-8小时;所述惰性气体为氮气、氩气、氦气中的一种或两种以上;所述掺杂元素前体为三聚氰胺、硼酸、硫代硫酸钠、五氧化二磷中的一种或两种以上,分别制备掺杂氮、硼、硫、磷元素中的一种或两种以上的石墨烯材料。
8.按照权利要求4-6任一所述材料的制备方法,其特征在于:
所述石墨烯基材料若为石墨烯负载金属纳米粒子片层材料,则所述步骤中采用水热合成法将金属前体盐按照金属占石墨烯质量比例为1-40%加入氧化石墨烯的乙二醇分散溶液中,金属前体盐和氧化石墨烯总质量百分浓度为1-10%,用氢氧化钠调节pH值至11-14左右,120-150摄氏度水浴反应1-6小时,充分还原后过滤洗涤。
9.按照权利要求8所述材料的制备方法,其特征在于:
所述金属前体盐为氯铂酸、氯钯酸、氯化钌、氯金酸、硝酸银、氯化镍、氯化钴、氯化铁中的一种或几种。
10.一种权利要求1-3任一所述交叠结构纳米片层材料作为催化剂的应用,其特征在于:可用于氧还原电催化、氧析出电催化、甲醇氧化或二氧化碳电还原等电催化反应中,或气体吸附材料、药物释放材料、或物质分离材料。
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