CN116212907A - 一种钯/磷催化剂及其制备方法和应用 - Google Patents
一种钯/磷催化剂及其制备方法和应用 Download PDFInfo
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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Abstract
本发明公开了一种钯/磷催化剂及其制备方法和应用，钯/磷催化剂的制备方法，包括以下步骤：1)钯基催化剂的合成：将钯盐与第一溶剂超声混合均匀，然后加入载体进行反应得到钯基催化剂；2)钯基催化剂的磷化：在第二溶剂中加入步骤1)中制备得到的钯基催化剂和磷源，然后反应得到所述钯/磷催化剂。和现有技术相比，本发明所公开的制备方法可快速调控金属钯表面电子结构，从而得到一种合成简易、成本低廉的高效蒽醌加氢反应催化剂。
Description
技术领域
本发明属于催化剂材料技术领域，具体涉及一种钯/磷催化剂及其制备方法和应用。
背景技术
当前众多的催化剂中，钯基纳米催化剂在化工、医药、环保等领域都存在着至关重要的作用。此外，石油化工重整催化以及各种精细化工品的合成都大量依赖于高效的负载型钯催化剂。然而钯在地壳中的含量极低，相对于其高需求量，钯金属资源严重匮乏。因此，开发一种成本低廉、高催化活性的钯基催化剂具有重要意义。
发明内容
为了解决上述背景技术中所提出的问题，本发明的目的在于提供一种钯/磷催化剂及其制备方法和应用。本发明设计的钯/磷催化剂通过磷元素与钯元素的高吸附能，钯纳米颗粒与磷元素发生表面合金化，形成钯磷键，达到调控钯纳米颗粒表面电子结构状态从而达到调控其催化活性的目的。
为了达到上述目的，本发明所采取的技术方案是：一方面，本发明提供了一种钯/磷催化剂的制备方法，包括以下步骤：
1)钯基催化剂的合成：将钯盐与第一溶剂超声混合均匀，然后加入载体进行反应得到钯基催化剂；
2)钯基催化剂的磷化：在第二溶剂中加入步骤1)中制备得到的钯基催化剂和磷源，然后反应得到所述钯/磷催化剂。
进一步地，步骤1)中所述钯盐包括硝酸钯、氯化钯、溴化钯、四氯钯酸钠、氯钯酸钾、四溴钯(II)酸钾、氯钯酸铵、四氯钯酸铵、乙酰丙酮钯、三甲基醋酸钯(II)、三苯基膦醋酸钯、四(三苯基膦)钯(0)、双(甲基二苯膦)二氯化钯(II)中的至少一种；
优选地，步骤1)中所述第一溶剂包括N,N-二甲基甲酰胺、N-甲基吡咯烷酮、甲苯、乙醇中的至少一种；
优选地，步骤1)中所述载体包括石墨、石墨烯、炭黑、活性炭、氧化铝、硅胶、硅藻土和浮石中的至少一种。
进一步地，步骤1)中所述钯盐、第一溶剂、载体的质量比为(0.01-0.5)：(10-500)：1。
进一步地，步骤1)中所述反应具体为：在高压反应釜中先进行反复排气除氧操作，充入2-6MPa氢气，然后加热至反应温度为80-180℃，反应2-10h。
进一步地，步骤2)中所述第二溶剂包括醇类溶剂、醚类溶剂、酯类溶剂、酮类溶剂、酰胺类溶剂中的至少一种；
优选地，步骤2)中所述磷源包括单质磷、无机磷酸盐、三辛基磷、三苯基磷、氧化磷中的至少一种；更优选地，所述单质磷包括黑磷、红磷、橙磷、紫磷、白磷；更优选地，所述氧化磷包括五氧化二磷、三氧化二磷。
进一步地，所述钯基催化剂中的钯、磷源中的磷的质量比为1：(0.01-1.0)。
进一步地，步骤2)中所述反应具体为：常温常压超声处理0.5min-20min或者0-200℃低温下搅拌反应1-48h。
另一方面，本发明提供了一种钯/磷催化剂，由上述任一所述的钯/磷催化剂的制备方法制备得到。
另一方面，本发明提供了一种上述所述的钯/磷催化剂在电催化氧还原反应中的应用。
另一方面，本发明提供了一种上述所述的钯/磷催化剂在蒽醌加氢制双氧水中的应用。本发明的有益效果为：本发明通过磷元素与钯元素所形成钯磷键，达到调控钯纳米颗粒表面电子结构状态的目的；
本发明可在温和实验条件下实现磷元素在金属钯表面合金化，达到调控金属钯表面电子结构的作用，以达到促进反应吸附平衡，提升催化活性的作用；
本发明钯/磷催化剂的制备方法简单，成本低廉，催化活性高。
附图说明
图1(a)为本发明实施例1制备得到的钯基催化剂的透射电镜图，图1(b)为本发明实施例1制备得到的钯/磷催化剂的透射电镜图；
图2(a)为本发明实施例1制备得到的钯基催化剂的XPS图，图1(b)为本发明实施例1制备得到的钯/磷催化剂的XPS图；
图3为本发明实施例1制备得到的钯基催化剂与钯/磷催化剂的蒽醌加氢性能对比数据图。
具体实施方式
为了更好地理解本发明的内容，下面结合具体实施方法对本发明内容作进一步说明，但本发明的保护内容不局限以下实施例。
实施例中所用的原料如无特殊说明，均可从常规商业途径得到。
实施例1
一种钯/磷催化剂的制备方法，包括以下步骤：
1)钯基催化剂的合成：在常温下将38mg氯化钯溶解在10mL N,N-二甲基甲酰胺中，超声混合均匀，加入100mg石墨烯，加入磁子搅拌，在高压反应釜中反应，反复充入氢气和抽真空，尽可能排除体系中的氧气，充入4.5MPa的氢气，保持体系压力不变后，开始升温至120℃，反应4h后反应结束。离心收集固体产物，用丙酮洗涤一次后，用乙醇、水洗涤三次，得到钯碳催化剂。
2)钯基催化剂的磷化：将得到的钯碳催化剂分散在乙醇中，通过ICP测定钯的含量为1mg/mL。取1mL钯碳催化剂溶液，加入0.2mL黑磷纳米片乙醇分散液(0.1mg/mL)，然后常温常压超声处理2-5分钟，得到的固体产物为钯/磷催化剂。
本发明实施例1制备得到的钯/碳催化剂和钯/磷催化剂的透射电镜图如图1所示，从图1可以看出，在两种催化剂基底的表面均均匀的分布着钯颗粒，且粒径约为3-4nm。
本发明实施例1制备得到的钯基催化剂和钯/磷催化剂的XPS图如图2所示，从图2可以看出，经过磷化后的钯基催化剂其X射线光电子能谱(XPS)在337eV出现新的Pd 3d锋，同样说明了钯磷键的形成。
蒽醌加氢应用：采用带有聚四氟乙烯内胆的不锈钢高压液相反应釜对其(实施例1制备得到的钯基催化剂与钯/磷催化剂)蒽醌加氢性能进行评价，反应釜带有磁力搅拌和加热系统。量取60mL蒽醌工作液(蒽醌含量80g/L，磷酸三辛酯：三甲苯＝1:1)，称取25mg催化剂(钯基催化剂或钯/磷催化剂)加入到100mL内胆中并密封。通入氢气以置换反应釜中的空气，重复5次。升温至50℃后使氢气压力达到0.23MPa。从反应器出口阀釆集反应样品进行活性评价。反应结束后，收集反应后催化剂，经丙酮洗涤、干燥。实施例1制备得到的钯基催化剂与钯/磷催化剂的蒽醌加氢性能对比数据图如图3所示，从图3可知，经过磷化后，钯/磷催化剂相比钯碳催化剂的加氢效率有提升，平均氢效约高0.6g/L。
以上所述仅为本发明的具体实施方式，不是全部的实施方式，本领域普通技术人员通过阅读本发明说明书而对本发明技术方案采取的任何等效的变换，均为本发明的权利要求所涵盖。
Claims (10)
1.一种钯/磷催化剂的制备方法，其特征在于，包括以下步骤：
1)钯基催化剂的合成：将钯盐与第一溶剂超声混合均匀，然后加入载体进行反应得到钯基催化剂；
2)钯基催化剂的磷化：在第二溶剂中加入步骤1)中制备得到的钯基催化剂和磷源，然后反应得到所述钯/磷催化剂。
2.根据权利要求1所述的钯/磷催化剂的制备方法，其特征在于，步骤1)中所述钯盐包括硝酸钯、氯化钯、溴化钯、四氯钯酸钠、氯钯酸钾、四溴钯(II)酸钾、氯钯酸铵、四氯钯酸铵、乙酰丙酮钯、三甲基醋酸钯(II)、三苯基膦醋酸钯、四(三苯基膦)钯(0)、双(甲基二苯膦)二氯化钯(II)中的至少一种；
优选地，步骤1)中所述第一溶剂包括N,N-二甲基甲酰胺、N-甲基吡咯烷酮、甲苯、乙醇中的至少一种；
优选地，步骤1)中所述载体包括石墨、石墨烯、炭黑、活性炭、氧化铝、硅胶、硅藻土和浮石中的至少一种。
3.根据权利要求1所述的钯/磷催化剂的制备方法，其特征在于，步骤1)中所述钯盐、第一溶剂、载体的质量比为(0.01-0.5)：(10-500)：1。
4.根据权利要求1所述的钯/磷催化剂的制备方法，其特征在于，步骤1)中所述反应具体为在高压反应釜中先进行反复排气除氧操作，充入2-6MPa氢气，然后加热至反应温度为80-180℃，反应2-10h。
5.根据权利要求1所述的钯/磷催化剂的制备方法，其特征在于，步骤2)中所述第二溶剂包括醇类溶剂、醚类溶剂、酯类溶剂、酮类溶剂、酰胺类溶剂中的至少一种；
优选地，步骤2)中所述磷源包括单质磷、无机磷酸盐、三辛基磷、三苯基磷、氧化磷中的至少一种；更优选地，所述单质磷包括黑磷、红磷、橙磷、紫磷、白磷；更优选地，所述氧化磷包括五氧化二磷、三氧化二磷。
6.根据权利要求1所述的钯/磷催化剂的制备方法，其特征在于，所述钯基催化剂中的钯、磷源中的磷的质量比为1：(0.01-1.0)。
7.根据权利要求1所述的钯/磷催化剂的制备方法，其特征在于，步骤2)中所述反应具体为常温常压超声处理0.5min-20min或者0-200℃低温下搅拌反应1-48h。
8.一种钯/磷催化剂，其特征在于，由权利要求1-7任一项所述的钯/磷催化剂的制备方法制备得到。
9.权利要求8所述的钯/磷催化剂在电催化氧还原反应中的应用。
10.权利要求8所述的钯/磷催化剂在蒽醌加氢制双氧水中的应用。
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