CN113941346A - 一种具有膜包覆层的负载型纳米催化剂及其制备方法 - Google Patents
一种具有膜包覆层的负载型纳米催化剂及其制备方法 Download PDFInfo
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- CN113941346A CN113941346A CN202111111917.5A CN202111111917A CN113941346A CN 113941346 A CN113941346 A CN 113941346A CN 202111111917 A CN202111111917 A CN 202111111917A CN 113941346 A CN113941346 A CN 113941346A
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Abstract
本发明公开了一种具有膜包覆层的负载型纳米催化剂,催化剂以磷酸盐B(PO4)a为载体,在磷酸盐B(PO4)a载体上负载有金属磷化物APb颗粒,在金属磷化物APb颗粒表面包覆有BOc膜包覆层,B为钇、钛、锰、铝、铬、铅、钙、镁、锆、镧、铈中的一种,A为钯、铱、铂、钌、铑、银、金、镍、铜、钴、铁中的一种。本发明相比现有技术具有以下优点:在盐载体表面形成膜包覆结构,形成了强烈的金属‑载体强相互作用,防止金属团聚、浸出,在形成膜包覆结构的同时将磷酸盐载体中的磷引入金属纳米颗粒中,从而达到稳定金属物种状态、调控金属纳米颗粒电子态的效果,使其活性与稳定性兼备。
Description
技术领域
本发明涉及金属-载体强相互作用领域,尤其涉及的是一种利用金属-载体强相互作用制备氧化物膜包覆结构催化剂的方法。
背景技术
负载型纳米颗粒催化剂作为多相催化剂在工业催化中得到了广泛的应用,其能够将金属均匀分散在载体表面上,可节省催化剂金属用量,显著的提升金属原子利用率,从而降低催化剂的成本。但相应的,由于金属以纳米级的小尺寸均匀分散在载体表面上,在使用过程中,其金属团聚、浸出、烧结现象尤为严重,严重限制了负载型纳米颗粒催化剂的大规模工业化。
上述问题的一种主要解决办法,就是使用氧化物或碳层对金属纳米颗粒进行包覆,包覆层可以作为阻碍金属聚合的物理屏障,利用其产生的限域效应来封装金属纳米颗粒,从而防止金属的烧结长大以及催化反应时的金属流失的现象发生。
其中,采用碳层对金属纳米颗粒进行包覆,在加氢反应中,还原性气氛H2和高温存在下,及在催化剂去除积碳的过程中,碳层易被去除,而无法达到保护金属的作用。而采用氧化物对金属纳米颗粒进行包覆的方法主要有原子层沉积、分子层沉积和金属-载体强相互作用。原子层沉积、分子层沉积具有设备投资巨大,能耗大,不易大规模制备催化剂的缺点。相对于原子层沉积、分子层沉积,传统的金属-载体强相互作用制备条件及方法简单易行,通常具有促进负载型纳米颗粒催化剂上载体的金属分散、促进电荷转移、形成氧化物膜包覆等多种功能。它通过载体表面的覆盖层对纳米粒子进行几何和电子修饰,最终调节其催化活性和稳定性。尽管传统的金属-载体强相互作用产生的氧化物覆盖层可以稳定金属,但活性位点的覆盖总是导致催化活性的丧失,以牺牲活性的代价增强了其稳定性。
发明内容
本发明通过引入新的催化活性中心,提供了一种具有膜包覆层的负载型纳米催化剂及其制备方法。
本发明是通过以下技术方案实现的:一种具有膜包覆层的负载型纳米催化剂,催化剂以磷酸盐B(PO4)a为载体,在磷酸盐B(PO4)a载体上负载有金属磷化物APb颗粒,在金属磷化物APb颗粒表面包覆有BOc膜包覆层,其中,A为元素周期表中VIIIB、IB和IIB族中过渡金属元素的一种或多种,具体为钯(Pd)、铱(Ir)、铂(Pt)、钌(Ru)、铑(Rh)、银(Ag)、金(Au)、镍(Ni)、铜(Cu)、钴(Co)、铁(Fe)中的一种或多种,B为钇(Y)、钛(Ti)、锰(Mn)、铝(Al)、铬(Cr)、铅(Pb)、钙(Ca)、镁(Mg)、锆(Zr)、镧(La)、铈(Ce)中的一种或多种,a、b和c在化学式的价键平衡的条件下各自独立地取值。
作为对上述方案的进一步改进,金属元素A在磷酸盐B(PO4)a载体上的负载量为0.5-20wt%。
作为对上述方案的进一步改进,催化剂用于催化加氢反应、催化氧化反应、催化加氢脱氧反应。
本法米还提供一种上述具有膜包覆层的负载型纳米颗粒催化剂的制备方法,其特征在于包括如下步骤:
步骤一、预盐载体制备,使用B的可溶性盐、柠檬酸、尿素和磷酸氢二铵依次混合均匀,经过水热处理后干燥煅烧获得预盐载体;
步骤二、负载,使用A的硝酸盐或醋酸盐溶于丙酮中,制备成A的丙酮溶液,将步骤一制备的预盐载体浸渍于A的丙酮溶液中;
步骤三、干燥、煅烧、还原,将经过步骤二处理后的预盐载体取出后干燥,再进行煅烧,然后在氢气氛围下还原获得一种具有膜包覆层的负载型纳米催化剂。
作为对上述方案的进一步改进,A的丙酮溶液浓度为3-12mmol/L。
作为对上述方案的进一步改进,步骤二中浸渍时间为12-24小时。
作为对上述方案的进一步改进,步骤三中干燥温度为20-120℃,干燥时间为6-12小时,煅烧温度为600℃,煅烧时间为2小时,还原温度为600-800℃,还原时间为1-6小时。
作为对上述方案的进一步改进,步骤一预盐载体的制备具体方法为:先将B的可溶性盐加入水热釜中加水搅拌使其溶解,而后在搅拌状态下依次加入柠檬酸、尿素和磷酸氢二氨,搅拌完成后将水热釜转移到烘箱中进行水热反应,水热反应结束后过滤、干燥、煅烧得到盐载体;B的可溶性盐、柠檬酸、尿素、磷酸氢二氨用量的摩尔比为1:3:6:1~5。
作为对上述方案的进一步改进,步骤一盐载体的制备具体方法中,依次加入每种物质的搅拌间隔时间为15分钟,加入磷酸氢二氨后继续搅拌15分钟后再移入烘箱进行水热反应,水热反应的温度为160℃,时间为13小时,干燥温度为105℃,煅烧温度为550℃,煅烧时间为2小时。
本发明相比现有技术具有以下优点:本发明采用负载后煅烧再还原的方案来制备催化剂,使得磷酸盐载体中的磷引入金属纳米颗粒中,从而达到稳定金属物种状态、调控金属纳米颗粒电子态的效果。且包覆于磷酸盐载体表面形成膜包覆结构,形成了强烈的金属-载体的强相互作用,包覆层能够能有效防止金属团聚,能够有效避免催化剂流失的问题。
由于磷酸盐载体呈现弱酸性,可以明显促进反应过程中底物的吸附和活化;磷酸盐载体具有很强的金属离子吸附能力,可以使负载金属分散效果非常好而使其表现出较高的催化活性。
附图说明
图1为实施例3中焦磷酸锰预盐载体的SEM照片;
图2为实施例3中Co/MnP-3的SEM照片;
图3为实施例3中Co/MnP-3膜包覆结构的HRTEM照片;
图4为实施例3中Co/MnP-3的XRD图;
图5为实施例3中Co/YPO4膜包覆结构的HRTEM照片;
图6为实施例3中Co/Ti3(PO4)4膜包覆结构的HRTEM照片;
图7为实施例3中Co/AlPO4膜包覆结构的HRTEM片;
图8为实施例3中Co/CrPO4膜包覆结构的HRTEM照片;
图9为实施例3中Co/LaPO4膜包覆结构的HRTEM照片;
图10为实施例3中Ni/MnP-3膜包覆结构的HRTEM照片;
图11为实施例3中Ni/Ti3(PO4)4膜包覆结构的HRTEM照片;
图12为实施例3中Ni/LaPO4膜包覆结构的HRTEM片;
图13为实施例3中Pd/MnP-3膜包覆结构的HRTEM照片;
图14为实施例3中Ru/MnP-3膜包覆结构的HRTEM照片;
图15为实施例3中Co/MnP-3的EDS元素映射图;
图16为本发明提供的催化剂上负载的具有膜包覆结构的纳米颗粒的模型图。
具体实施方式
下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1
一种具有膜包覆层的负载型纳米催化剂,催化剂以磷酸盐B(PO4)a为载体,在磷酸盐B(PO4)a载体上负载有金属磷化物APb颗粒,在金属磷化物APb颗粒表面包覆有BOc膜包覆层,其中,A为钯(Pd)、铱(Ir)、铂(Pt)、钌(Ru)、铑(Rh)、银(Ag)、金(Au)、镍(Ni)、铜(Cu)、钴(Co)、铁(Fe)中的一种或多种,B为钇(Y)、钛(Ti)、锰(Mn)、铝(Al)、铬(Cr)、铅(Pb)、钙(Ca)、镁(Mg)、锆(Zr)、镧(La)、铈(Ce)中的一种或多种,a、b和c在化学式的价键平衡的条件下各自独立地取值。
金属元素A在磷酸盐B(PO4)a为载体上的负载量为0.5-20wt%。
该催化剂可用于催化加氢反应、催化氧化反应、催化加氢脱氧反应等。
附图16为催化剂上负载的具有膜包覆结构的纳米颗粒的模型图,外壳是磷酸盐载体通过金属-载体强相互作用形成的包覆层;核为金属与磷酸盐载体中的磷结合形成的金属磷化物,例如Co2P,Ni2P,RuP等。
实施例2
一种具有膜包覆层的负载型纳米催化剂,该催化剂以磷酸锰为载体,在磷酸锰载体上负载有金属磷化物Co2P颗粒,在金属磷化物Co2P颗粒表面包覆有MnOx膜包覆层,Co在磷酸锰载体上的负载量为10wt%。该催化剂可用于催化加氢反应、催化氧化反应、催化加氢脱氧反应等。
实施例3
一种具有膜包覆层的负载型纳米催化剂的制备方法
步骤一、预盐载体的制备。
按顺序将1964mg四水乙酸锰、5043mg柠檬酸、2882mg尿素、3169.4mg磷酸氢二铵分别加入100mL水热釜中,依次加入每种物质的搅拌间隔时间为15分钟,随后再移入烘箱进行水热反应,水热反应的温度为160℃,时间为13小时,待水热釜完全冷却后过滤洗涤、于105℃下干燥、550℃下煅烧2h得到焦磷酸锰预盐载体。附图1为磷酸锰预盐载体的SEM照片。
步骤二、负载。
采用含有质量为871.5mg Co(NO3)2的丙酮溶液100mL,浸渍1.00g的焦磷酸锰预盐载体,搅拌24h待达到吸附平衡。
步骤三、干燥、煅烧、还原。
将吸附后的预盐载体过滤并用丙酮洗涤,在105℃条件下干燥10h,在600℃的空气中煅烧2h,然后在800℃下用氢气还原3h,得到负载钴质量分数为15%的Co催化剂,简写为Co/MnP-3。图2为Co/MnP-3的SEM照片,图中圆形颗粒即为Co2P颗粒。
对比图1和图2发现,经过煅烧和还原焦磷酸锰还原为磷酸锰后形貌更为致密,Co负载到载体上之后,形成类似球状物附着在载体表面,Co物种均匀分散在载体上,这说明钴物种分散性良好。经计算,钴物种的平均颗粒只有61.9nm,钴物种在载体MnP-3上分散非常均匀。经过对产物的X射线衍射分析可以知道,负载金属后的XRD谱图(图4)上观察到了Co2P衍射峰的出现,这说明Co2P物种在载体上的出现,说明Co物种是以Co2P的形式负载在载体上的。图3是该催化剂中球形颗粒的边缘所做的HRTEM照片,通过图3能够发现在Co颗粒的表面包覆膜包覆结构。通过EDS元素映射图(图15)可以清晰的看出Co/MnP-3的元素分布,结合XRD及HRTEM,我们可以得出Co2P被MnOx结构的膜紧紧包覆的结论。
焦磷酸锰预盐载体与金属Co结合后,氢气还原的条件明显的促进金属Co向Co2P物种转变,在盐载体的表面形成了包覆膜结构,从而形成了强烈的金属-载体的强相互作用,可以防止金属团聚、浸出,这些都会导致催化剂表现出较好的催化活性与稳定性。
将金属Pd、Ir、Pt、Ru、Rh、Ag、Au、Ni、Cu、Co、Fe分别负载到YPO4、Ti3(PO4)4、AlPO4、CrPO4、Pb(PO4)2载体上,得到不同载体的负载型化剂。我们从中选取Co,制备了不同载体的负载型催化剂Co/YPO4、Co/Ti3(PO4)4、Co/AlPO4、Co/CrPO4、Co/LaPO4,制备方法同Co/MnP-3。对它们分别进行了HRTEM表征,如图5~9所示。从图5~9中可以看出,在YPO4、Ti3(PO4)4、AlPO4、CrPO4、LaPO4载体上也出现了膜包覆结构的现象。
我们还尝试选取不同金属负载,如选取了非贵金属Ni,制备了不同载体的负载型催化剂Ni/MnP-3、Ni/Ti3(PO4)4、Ni/LaPO4,选取了贵金属Pd、Ru,制备了不同载体的负载型催化剂Pd/MnP-3、Ru/MnP-3。对它们也分别进行了HRTEM表征,如图10~14所示。从图10~14中可以看出,更换了负载金属后,负载Ni、Pd、Ru也均出现了膜包覆结构的现象。
性能测试实施例1-10
按照实施例3中Co/Mn3(PO4)2的制备方法制备如表1所示的不同金属负载量的Co/YPO4、Co/Ti3(PO4)4、Co/AlPO4、Co/CrPO4、Co/LaPO4、Ni/MnP-3、Ni/Ti3(PO4)4、Ni/LaPO4、Pd/MnP-3和Ru/MnP-3,
在25mL的反应釜中加入100mg底物、加入如表1中所示的的金属催化剂50mg,加入10mL纯净水,即反应底物浓度为1wt%(质量分数),向反应釜内先冲入H2后排出(重复至少5次),以排净内部的空气,搅拌条件下反应。反应指定时间后,冷却、放气、过滤,使催化剂与反应液分离,反应液用乙醇稀释后,用气相色谱分析。
气相色谱条件如下:GC1690气相色谱FID检测器,毛细管色谱柱(Innowax,30m×0.250mm×0.25μm),采取程序升温,起始柱温为40℃,以10℃/min的升温速率升至250℃保持10分钟。载气为99.99%的高纯N2,流速为1mL/min。
按照表1的测试条件进行肉桂醛加氢制备苯丙醇反应测试,结果记录进表1,氢压均为2.5MPa。
表1性能测试实施例1-10制备苯丙醇的条件和结果
性能测试实施例12-21
按照实施例3中Co/Mn3(PO4)2的制备方法制备如表2所示的不同金属负载量的Co/YPO4、Co/Ti3(PO4)4、Co/AlPO4、Co/CrPO4、Co/LaPO4、Ni/MnP-3、Ni/Ti3(PO4)4、Ni/LaPO4、Pd/MnP-3和Ru/MnP-3,并在性能测试实施例1-10的测试环境下按照表2的测试条件进行顺丁烯二酸加氢制备丁二酸反应测试,结果记录进表2,氢压均为3MPa。
表2性能测试实施例11-20顺丁烯二酸加氢的条件和结果
性能测试实施例22-31
按照实施例3中Co/Mn3(PO4)2的制备方法制备如表3所示的不同金属负载量的Co/YPO4、Co/Ti3(PO4)4、Co/AlPO4、Co/CrPO4、Co/LaPO4、Ni/MnP-3、Ni/Ti3(PO4)4、Ni/LaPO4、Pd/MnP-3和Ru/MnP-3,并在性能测试实施例1-10的测试环境下按照表3的测试条件进行富马酸加氢制备丁二酸反应测试,结果记录进表3,氢压均为3MPa。
表3性能测试实施例21-30富马酸加氢的条件和结果
性能测试实施例32-41
按照实施例3中Co/Mn3(PO4)2的制备方法制备如表4所示的不同金属负载量的Co/YPO4、Co/Ti3(PO4)4、Co/AlPO4、Co/CrPO4、Co/LaPO4、Ni/MnP-3、Ni/Ti3(PO4)4、Ni/LaPO4、Pd/MnP-3和Ru/MnP-3,并在实施例1-10的测试环境下按照表4的测试条件进行香草醛加氢制备香草醇反应测试,结果记录进表4,氢压均为2.5MPa。
表4性能测试实施例31-40香草醛加氢的条件和结果
因此,从以上实施例实验结果表明,本发明主要使载体Mn3(PO4)2、YPO4、Ti3(PO4)4、AlPO4、CrPO4、LaPO4等与Pd、Ir、Pt、Ru、Rh、Ag、Au、Ni、Cu、Co、Fe等金属通过浸渍的方法制备出磷酸盐类催化剂,采用本发明方法,催化剂制备设备简单,操作简便,产物与催化剂易分离,催化剂廉价易得且有膜包覆保护,在催化加氢、催化氧化、催化加氢脱氧、催化加氢脱硫等领域具有非常广泛的应用前景。
以上仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种具有膜包覆层的负载型纳米催化剂,其特征在于:所述催化剂以磷酸盐B(PO4)a为载体,在磷酸盐B(PO4)a载体上负载有金属磷化物APb颗粒,在金属磷化物APb颗粒表面包覆有BOc膜包覆层,其中,A为元素周期表中VIIIB、IB和IIB族中过渡金属元素的一种或多种,B为钇(Y)、钛(Ti)、锰(Mn)、铝(Al)、铬(Cr)、铅(Pb)、钙(Ca)、镁(Mg)、锆(Zr)、镧(La)、铈(Ce)中的一种或多种,a、b和c在化学式的价键平衡的条件下各自独立地取值。
2.如权利要求1所述一种具有膜包覆层的负载型纳米催化剂,其特征在于:A为钯(Pd)、铱(Ir)、铂(Pt)、钌(Ru)、铑(Rh)、银(Ag)、金(Au)、镍(Ni)、铜(Cu)、钴(Co)、铁(Fe)中的一种或多种。
3.如权利要求1所述一种具有膜包覆层的负载型纳米催化剂,其特征在于:金属元素A在磷酸盐B(PO4)a载体上的负载量为0.5-20wt%。
4.如权利要求1所述一种具有膜包覆层的负载型纳米催化剂,其特征在于:所述催化剂用于催化加氢反应、催化氧化反应、催化加氢脱氧反应。
5.一种权利要求1所述一种具有膜包覆层的负载型纳米催化剂的制备方法,其特征在于包括如下步骤:
步骤一、预盐载体制备,使用B的可溶性盐、柠檬酸、尿素和磷酸氢二铵依次混合均匀,经过水热处理后干燥煅烧获得预盐载体;
步骤二、负载,使用A的硝酸盐或醋酸盐溶于丙酮中,制备成A的丙酮溶液,将步骤一制备的预盐载体浸渍于所述A的丙酮溶液中;
步骤三、干燥、煅烧、还原,将经过步骤二处理后的预盐载体取出后干燥,再进行煅烧,然后在氢气氛围下还原获得所述一种具有膜包覆层的负载型纳米催化剂。
6.如权利要求5所述的一种具有膜包覆层的负载型纳米催化剂的制备方法,其特征在于:所述A的丙酮溶液浓度为3-12mmol/L。
7.如权利要求5所述的一种具有膜包覆层的负载型纳米催化剂的制备方法,其特征在于:所述步骤二中浸渍时间为12-24小时。
8.如权利要求5所述的一种具有膜包覆层的负载型纳米催化剂的制备方法,其特征在于:所述步骤三中干燥温度为20-120℃,干燥时间为6-12小时,煅烧温度为600℃,煅烧时间为2小时,还原温度为600-800℃,还原时间为1-6小时。
9.如权利要求5所述的一种具有膜包覆层的负载型纳米催化剂的制备方法,其特征在于:步骤一预盐载体的制备具体方法为:先将B的可溶性盐加入水热釜中加水搅拌使其溶解,而后在搅拌状态下依次加入柠檬酸、尿素和磷酸氢二氨,搅拌完成后将水热釜转移到烘箱中进行水热反应,水热反应结束后过滤、干燥、煅烧得到所述盐载体;B的可溶性盐、柠檬酸、尿素、磷酸氢二氨用量的摩尔比为1:3:6:1~5。
10.如权利要求9所述的一种具有膜包覆层的负载型纳米催化剂的制备方法,其特征在于:步骤一盐载体的制备具体方法中,依次加入每种物质的搅拌间隔时间为15分钟,加入磷酸氢二氨后继续搅拌15分钟后再移入烘箱进行水热反应,水热反应的温度为160℃,时间为13小时,干燥温度为105℃,煅烧温度为550℃,煅烧时间为2小时。
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