CN105833889A - 一种基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂及其制备方法 - Google Patents
一种基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂及其制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
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- 238000000231 atomic layer deposition Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000004108 freeze drying Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
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- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 claims description 3
- FSKLOGLSYZIRMP-UHFFFAOYSA-N carbanide 2-methylcyclopenta-1,3-diene platinum(4+) Chemical compound [CH3-].[CH3-].[CH3-].[Pt+4].CC=1C=C[CH-]C=1 FSKLOGLSYZIRMP-UHFFFAOYSA-N 0.000 claims description 3
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 4
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 4
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- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂及其制备方法。其包括具有三明治结构的多孔石墨烯/纳米陶瓷载体和均匀地沉积在载体表面的纳米铂颗粒;所述具有三明治结构的多孔石墨烯/纳米陶瓷载体由多孔石墨烯作为面层,以纳米陶瓷作为芯材插入到多孔石墨烯片层间形成。其中的多孔石墨烯中的纳米孔有利于水和反应气体的轴向运输和电子、质子的传导,提高催化剂组分利用率,从而降低铂的用量;多孔石墨烯/纳米陶瓷三明治结构有效地提供了载铂的位点,限制了铂纳米颗粒在载体表面的迁移团聚,提高了催化剂的稳定性。
Description
技术领域
本发明属于催化剂制备技术领域,具体涉及一种基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂及其制备方法。
技术背景
铂(Pt)基催化剂因其优良的氧还原催化活性、高选择性和良好的电化学稳定性,而被广泛应用于燃料电池电极催化剂、石油化工中的催化重整以及各种精细化学品的催化合成等领域。但Pt的成本较高,导致Pt基催化剂造价高,且在长期的催化过程中催化剂的活性和稳定性会降低,这些都与载体的比表面积、电导率和电化学稳定性相关。目前应用最广泛的载体是传统的Vulcan XC-72,但由于这种碳材料在工作环境下容易被腐蚀,使金属粒子很容易发生迁移、脱落和团聚的现象,导致催化剂活性明显下降。而增强载体与活性粒子之间的结合力和载体稳定性,可以有效防止金属粒子的迁移,因此对载体材料进行改进是保持催化剂活性和提高其稳定性的重要途径之一。
目前载体材料的改进工作主要集中在以下三个方面:一是选用新型纳米碳材料,比如碳纳米管、富勒烯、碳纳米纤维以及石墨烯材料。它们具有比表面积大、导电性好以及催化效率高等优点,有利于降低铂的载量。石墨化的纳米碳材料既可以克服碳黑载体本身不稳定以及表面微孔发达的问题,也使催化剂的稳定性与活性都得到一定程度的增加。但由于石墨化惰性表面,限制了Pt纳米颗粒的均匀分散。而石墨烯作为载体不仅利于电子转移、可用表面积最大化、并能减少Pt颗粒团聚。但石墨烯晶体表面呈石墨化惰性状态,并且石墨片层之间因为存在π-π键,而具有较强的范德华力,容易产生堆叠和团聚。
二是选用抗化学腐蚀性能好的陶瓷材料,纳米陶瓷由于其优异的热稳定性、出色的抗氧化、耐酸腐蚀和独特的机械性能,作为载体材料能够在一定程度提高催化剂的稳定性。本发明人所在课题组分别采用导电陶瓷TiB2[J.Power Sources,2011,96:7931-7936]、SiC[Appl.Catal.B,2010,100:190-196]制备出稳定性显著提高的燃料电池催化剂。但陶瓷材料的导电性不高,特别是在常温下其大部分为半导体材料,而且它们在比表面积方面还不太理想,均低于现有的载体材料。
三是制备复合载体材料,Zhang等[Zhang Q,Zhao M,Liu Y,et.al.Adv.Mater.,2009,21:2876-2880]在石墨烯片层间植入用于碳纳米管生长的催化剂,再利用气相沉积的方法制备出石墨烯/碳纳米管复合材料。石墨烯片层间插入的碳纳米管能够很好的阻止石墨烯片层的团聚。然而,这种方法操作起来比较复杂,制备成本也过于昂贵。
发明内容
本发明所要解决的技术问题是针对现有技术的不足提供一种基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂及其制备方法。
基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂,包括具有三明治结构的多孔石墨烯/纳米陶瓷载体和均匀地沉积在载体表面的纳米铂颗粒;所述具有三明治结构的多孔石墨烯/纳米陶瓷载体由多孔石墨烯作为面层,以纳米陶瓷作为芯材插入到多孔石墨烯片层间形成。
按上述方案,所述具有三明治结构的多孔石墨烯/纳米陶瓷载体是将多孔石墨烯加入到去离子水中超声,使其均匀分散;然后加入纳米陶瓷颗粒,充分混合搅拌,冷冻干燥而得。
按上述步骤,所述纳米铂颗粒采用原子层沉积方法沉积而得,所述的原子层沉积方法是以三甲基(甲基环戊二烯基)铂(IV)和氧气为前驱体,将气相前驱体脉冲交替地通入反应室的反应腔体中,并控制原子层沉积的循环次数获得沉积铂纳米颗粒。
按上述步骤,所述铂纳米颗粒的沉积过程中,沉积反应温度为250-275℃,沉积循环次数100-120次。
按上述方案,整个原子沉积反应过程中持续通入高纯氮作为载气,反应腔体内的压强控制在4mbar以下。
按上述方案,所述多孔石墨烯中的纳米孔由微孔、大孔、介孔组成,尺寸大小为1-100nm。
按上述方案,所述的多孔石墨烯为将氧化石墨烯水溶液经浓硝酸超声刻蚀后,600-800℃加热还原制得。
按上述方案,其中:氧化石墨烯水溶液为0.05-0.1wt.%;氧化石墨烯水溶液与浓硝酸的体积比为1:7.5-1:12.5。
按上述方案,超声功率为100-200W,超声刻蚀时间1-2h,还原时间为1-2h。
按上述方案,所述纳米陶瓷颗粒选自金属碳化物、金属氧化物、金属氮化物、金属硼化物,优选为SiC、WC、B4C、Mo2C、TiC、TiO2、SiO2、WO3、CeO2、ZrO2、TiN、ZrN、VN、ZrB2、TiB2中的一种或多种。
按上述方案,所述纳米陶瓷颗粒尺寸为10-100nm,优选为10-50nm;所述的铂纳米颗粒尺寸为1-5nm,优选为2-3nm。
基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂的制备方法,其特征在于:包括以下步骤:将多孔石墨烯加入到去离子水中超声,使其均匀分散;加入纳米陶瓷颗粒,充分混合搅拌,冷冻干燥后得到三明治结构的多孔石墨烯/纳米陶瓷载体;使用原子层沉积方法在载体表面沉积铂纳米颗粒,形成载铂催化剂。
按上述步骤,所述多孔石墨烯与纳米陶瓷颗粒的质量比为0.1-10:1,优选为1-5:1。
按上述步骤,所述超声分散频率为100-150W,超声时间为30-90min。
按上述步骤,所述混合搅拌温度为60-80℃,搅拌时间为4-6h。
本发明的有益效果:
石墨烯具有很高的理论比表面积,但由于π-π电子的作用,石墨烯容易产生团聚,这种团聚不仅降低比表面积,还会阻碍其它物质如电解质离子进入到石墨烯片层。本发明中采用的多孔石墨烯不仅保留了石墨烯优良的性质,而且由于石墨烯内不同尺寸孔的引入,避免了团聚造成的不利影响;与惰性的石墨烯表面相比,介孔和大孔可以促进物质的渗透和轴向运输,如水和反应气体的轴向运输和电子、质子的传导,起到筛分不同尺寸的离子、分子的作用,最大化提高催化剂活性,降低铂载量,而微孔则有利于比表面积的提高。同时多孔石墨烯表面上的孔隙可以增强石墨烯和锚定的铂团簇之间的相互作用,一定程度上提高催化剂稳定性。另外多孔石墨烯与石墨烯相比,孔的引入可引起石墨烯表面电学性质的改变,削弱石墨烯片层间引起石墨烯团聚的π-π电子的作用,因此多孔石墨烯不易团聚,更易被纳米陶瓷颗粒插层形成三明治结构,同时三明治结构的形成有效地提供了载铂的位点,且纳米陶瓷颗粒具有良好的抗电化学腐蚀、化学腐蚀性能,而且限制了铂纳米颗粒在载体表面的迁移团聚,提高了催化剂的稳定性。
在合成方法方面,本发明基于多孔石墨烯的特性采用简单的液相混合方法在多孔石墨烯片层之间引入纳米陶瓷颗粒,即可合成出具有纳米三明治结构的多孔石墨烯/纳米陶瓷三维复合材料。然后采用原子层沉积方法在载体表面沉积铂纳米颗粒可在保证多孔石墨烯/纳米陶瓷载体的插层结构不被破坏的同时,因其工艺的非连续性以及自身反应的自限制性,控制铂颗粒纳米粒径和均匀性,获得在载体上粒径均一,沉积均匀的铂纳米颗粒。
附图说明
图1为多孔石墨烯/碳化硅载铂催化剂的扫描电子显微镜图(SEM)。
图2为图1中黄色方框部分表示的多孔石墨烯/碳化硅载铂催化剂中多孔石墨烯的扫描电子显微镜图(SEM)。
图3为多孔石墨烯/碳化硅载铂催化剂的X射线衍射图(XRD)。其中a Pt-RGO;b Pt-PG/SiC。
图4为多孔石墨烯/碳化硅载铂催化剂的氧化还原性能图,其中a Pt/C;b Pt-PG/SiC。
具体实施方式
为了更好地理解本发明的内容,以下将结合具体实例来进一步说明。但是应该指出,本发明的实施并不限于以下几种实施方式。
实施例1多孔石墨烯/碳化硅载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在150W下,超声分散30min;加入0.25g碳化硅(SiC,40nm),在60℃下充分混合搅拌4h后,冷冻干燥后得到三明治结构的多孔石墨烯/碳化硅载体;
(2)将(1)中的载体放入原子层沉积设备中,使用三甲基(甲基环戊二烯基)铂(IV)作为铂源和氧气在载体表面沉积铂纳米颗粒。整个原子沉积反应过程中持续通入高纯氮作为载气,腔体内的压强控制在4mbar以下。原子层沉积反应温度为250℃。为保证足够的蒸汽压,将铂源加热到65℃,为防止管路冷凝,管路被加热到100℃,铂前驱体脉冲时间为1s,氧气前驱体脉冲时间为1s,氮气清洗时间为20s。重复100次循环,即获得多孔石墨烯/碳化硅载铂催化剂。
图1为本发明实施例1中步骤(2)所制备的多孔石墨烯/碳化硅载铂催化剂的扫描电子显微镜图(SEM),从图中可看出陶瓷插入多孔石墨烯片层间。图2为本发明实施例1中步骤(2)所述的多孔石墨烯/碳化硅载铂催化剂中多孔石墨烯的扫描电子显微镜图(SEM)。如图2所示,制备得到的多孔石墨烯中孔分布比较均匀。图3为多孔石墨烯/碳化硅载铂(Pt-PG/SiC)催化剂的X射线衍射图(XRD),从中可以看出石墨烯、碳化硅和铂催化剂物相的存在,并且通过与石墨烯载铂(Pt-RGO)催化剂进行对比,可看出Pt-PG/SiC与Pt-RGO相比石墨材料C(002)特征峰明显向一个低角度偏移,这表明SiC的插入导致片层间距增大。图4为多孔石墨烯/碳化硅载铂催化剂的氧化还原性能图,从图中可看出多孔石墨烯/碳化硅载铂催化剂(Pt-PG/SiC)半波电势为0.89V,明显高于商业Pt/C(Pt含量30%,E-TEK公司)的半波电势0.79V。
实施例2多孔石墨烯/碳化钨载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在100W下,超声分散90min;加入0.05g碳化钨(WC,50nm),在80℃下充分混合搅拌6h后,冷冻干燥后得到三明治结构的多孔石墨烯/碳化钨载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为275℃,重复120次循环,即获得多孔石墨烯/碳化钨载铂催化剂。
实施例3多孔石墨烯/碳化硼载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在120W下,超声分散60min;加入0.1g碳化硼(B4C,50nm),在80℃下充分混合搅拌6h后,冷冻干燥后得到三明治结构的多孔石墨烯/碳化硼载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为260℃,重复110次循环,即获得多孔石墨烯/碳化硼载铂催化剂。
实施例4多孔石墨烯/碳化钼载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在150W下,超声分散30min;加入0.05g碳化硼(Mo2C,50nm),在80℃下充分混合搅拌6h后,冷冻干燥后得到三明治结构的多孔石墨烯/碳化钼载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为250℃,重复100次循环,即获得多孔石墨烯/碳化钼载铂催化剂。
实施例5多孔石墨烯/碳化钛载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在120W下,超声分散60min;加入0.05g碳化钛(TiC,50nm),在80℃下充分混合搅拌5h后,冷冻干燥后得到三明治结构的多孔石墨烯/碳化钛载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为275℃,重复110次循环,即获得多孔石墨烯/碳化钛载铂催化剂。
实施例6多孔石墨烯/二氧化硅载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在150W下,超声分散30min;加入0.05g二氧化硅(SiO2,30nm),在60℃下充分混合搅拌6h后,冷冻干燥后得到三明治结构的多孔石墨烯/二氧化硅载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为250℃,重复100次循环,即获得多孔石墨烯/二氧化硅载铂催化剂。
实施例7多孔石墨烯/二氧化钛载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在150W下,超声分散30min;加入0.25g二氧化钛(TiO2,10nm),在80℃下充分混合搅拌4h后,冷冻干燥后得到三明治结构的多孔石墨烯/二氧化钛载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为275℃,重复120次循环,即获得多孔石墨烯/二氧化钛载铂催化剂。
实施例8多孔石墨烯/三氧化钨载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在120W下,超声分散60min;加入0.1g三氧化钨(WO3,40nm),在80℃下充分混合搅拌5h后,冷冻干燥后得到三明治结构的多孔石墨烯/三氧化钨载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为250℃,重复100次循环,即获得多孔石墨烯/三氧化钨载铂催化剂。
实施例9多孔石墨烯/氧化铈载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在120W下,超声分散60min;加入0.25g氧化铈(CeO2,20nm),在80℃下充分混合搅拌4h后,冷冻干燥后得到三明治结构的多孔石墨烯/氧化铈载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为275℃,重复110次循环,即获得多孔石墨烯/氧化铈载铂催化剂。
实施例10多孔石墨烯/氧化锆载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在150W下,超声分散30min;加入0.1g氧化锆(ZrO2,10nm),在60℃下充分混合搅拌4h后,冷冻干燥后得到三明治结构的多孔石墨烯/氧化锆载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为275℃,重复110次循环,即获得多孔石墨烯/氧化锆载铂催化剂。
实施例11多孔石墨烯/氮化钛载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在100W下,超声分散90min;加入0.05g氮化钛(TiN,20nm),在60℃下充分混合搅拌6h后,冷冻干燥后得到三明治结构的多孔石墨烯/氮化钛载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为250℃,重复120次循环,即获得多孔石墨烯/氮化钛载铂催化剂。
实施例12多孔石墨烯/氮化锆载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在120W下,超声分散60min;加入0.05g氮化锆(ZrN,50nm),在80℃下充分混合搅拌6h后,冷冻干燥后得到三明治结构的多孔石墨烯/氮化锆载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为275℃,重复100次循环,即获得多孔石墨烯/氮化锆载铂催化剂。
实施例13多孔石墨烯/氮化钒载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在100W下,超声分散90min;加入0.1g氮化钒(VN,40nm),在80℃下充分混合搅拌5h后,冷冻干燥后得到三明治结构的多孔石墨烯/氮化钒载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为250℃,重复120次循环,即获得多孔石墨烯/氮化钒载铂催化剂。
实施例14多孔石墨烯/硼化锆载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在150W下,超声分散30min;加入0.05g硼化锆(ZrB2,45nm),在80℃下充分混合搅拌6h后,冷冻干燥后得到三明治结构的多孔石墨烯/硼化锆载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为275℃,重复110次循环,即获得多孔石墨烯/硼化锆载铂催化剂。
实施例15多孔石墨烯/硼化钛载铂催化剂的制备
(1)称取0.25g多孔石墨烯(PG),加入100mL去离子水中,在120W下,超声分散60min;加入0.05g硼化钛(TiB2,50nm),在80℃下充分混合搅拌6h后,冷冻干燥后得到三明治结构的多孔石墨烯/硼化钛载体;
(2)将(1)中的载体放入原子层沉积设备中,整个原子沉积反应过程与实施例1中步骤(2)相同,不同之处在于原子层沉积反应温度为250℃,重复100次循环,即获得多孔石墨烯/硼化钛载铂催化剂。
本发明中使用的原子层沉积设备为美国Cambridge Nano Tech公司生产,型号为Savannah-100。上述的多孔石墨烯可将氧化石墨烯水溶液与浓硝酸以一定比例混合后;超声刻蚀,超声后的混合物进行过滤,过滤产物真空干燥;最后在还原气氛中升温还原,即得多孔石墨烯(PG)。
其中:氧化石墨烯水溶液为0.05-0.1wt.%;氧化石墨烯水溶液与浓硝酸的体积比为1:7.5-1:12.5;超声功率为100-200W,超声刻蚀时间1-2h;采用阳极膜过滤,真空干燥温度为60-80℃,时间8-12h;还原气氛:5%氢气/95%氮气混合气,以3-8℃/min升温至600-800℃后保温1-2h。
Claims (10)
1.一种基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂,其特征在于:包括具有三明治结构的多孔石墨烯/纳米陶瓷载体和均匀地沉积在载体表面的纳米铂颗粒;所述具有三明治结构的多孔石墨烯/纳米陶瓷载体由多孔石墨烯作为面层,以纳米陶瓷作为芯材插入到多孔石墨烯片层间形成。
2.根据权利要求1所述的基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂,其特征在于:所述具有三明治结构的多孔石墨烯/纳米陶瓷载体是将多孔石墨烯加入到去离子水中超声,使其均匀分散;然后加入纳米陶瓷颗粒,充分混合搅拌,冷冻干燥而得;
所述纳米铂颗粒采用原子层沉积方法沉积而得,所述的原子层沉积方法是以三甲基(甲基环戊二烯基)铂(IV)和氧气为前驱体,将气相前驱体脉冲交替地通入反应室的反应腔体中,并控制原子层沉积的循环次数获得沉积铂纳米颗粒。
3.根据权利要求1所述的基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂,其特征在于:所述铂纳米颗粒的沉积过程中,沉积反应温度为250-275℃,沉积循环次数100-120次。
4.根据权利要求1所述的基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂,其特征在于:所述多孔石墨烯中的纳米孔由微孔、大孔、介孔组成,尺寸大小为1-100nm;所述纳米陶瓷颗粒尺寸为10-100nm;所述的铂纳米颗粒尺寸为1-5nm。
5.根据权利要求1所述的基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂,其特征在于:所述的多孔石墨烯为将氧化石墨烯水溶液经浓硝酸超声刻蚀后,600-800℃加热还原制得。
6.根据权利要求1所述的基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂,其特征在于:所述纳米陶瓷颗粒选自金属碳化物、金属氧化物、金属氮化物、金属硼化物,优选为SiC、WC、B4C、Mo2C、TiC、TiO2、SiO2、WO3、CeO2、ZrO2、TiN、ZrN、VN、ZrB2、TiB2中的一种或多种。
7.权利要求1所述的基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂的制备方法,其特征在于:包括以下步骤:将多孔石墨烯加入到去离子水中超声,使其均匀分散;加入纳米陶瓷颗粒,充分混合搅拌,冷冻干燥后得到三明治结构的多孔石墨烯/纳米陶瓷载体;使用原子层沉积方法在载体表面沉积铂纳米颗粒,形成载铂催化剂。
8.根据权利要求7所述的基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂的制备方法,其特征在于:所述多孔石墨烯与纳米陶瓷颗粒的质量比为0.1-10:1。
9.根据权利要求7所述的基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂的制备方法,其特征在于:所述超声分散频率为100-150W,超声时间为30-90min。
10.根据权利要求7所述的基于多孔石墨烯/纳米陶瓷三明治结构的载铂催化剂的制备方法,其特征在于:所述混合搅拌温度为60-80℃,搅拌时间为4-6h。
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