CN111346677A - 一种用于催化甲酸自分解制取氢气的钯/富氨基多孔聚合物催化剂的制备方法 - Google Patents
一种用于催化甲酸自分解制取氢气的钯/富氨基多孔聚合物催化剂的制备方法 Download PDFInfo
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Abstract
本发明涉及提供一种室温条件下催化甲酸自分解制取纯氢气的富氨基聚合物负载的钯催化剂的制备方法，属于能源催化材料、氢气制备技术领域。本方法首先制备一种共价氨基吡啶类多孔聚合物（APPOPs），然后利用浸渍还原法将钯离子还原成纳米颗粒沉积到APPOPs表面，由于钯粒子与聚合物表面的大量氨基的相互作用，一方面使得钯粒子可稳定地附着在APPOPs表面，另一方面还有效调制了钯催化剂的电子结构，大幅改善了催化剂对甲酸分解制氢的活性。在100 kPa、303 K下，5 wt%Pd载量的催化剂对1.1 mol/L甲酸水溶液的催化制氢TOF值（10分钟）达到494 h‑1，是同等条件下商业钯催化剂的2.4倍。本发明操作简单，便于扩大生产和工业化应用。
Description
技术领域
本发明涉及提供一种室温条件下催化甲酸自分解制取纯氢气的富氨基聚合物负载的钯催化剂（Pd/APPOPs）的制备方法，属于能源催化材料、氢气制备技术领域。
背景技术
在全球能源短缺与环境污染问题日益突出的背景下，亟需发展可持续的清洁低碳能源。氢气能量密度高，是高效绿色的能源供给者。然而，氢气的安全可控生产、储运仍然是氢能经济面临的严峻挑战。
甲酸在常温常压下可被催化直接分解产出氢气，是一种安全可控的氢气制取方案，目前已成为制氢领域的研究热点。
钯（Pd）是目前公认最优的室温条件下高效甲酸制氢催化剂之一，为提高Pd基催化剂的甲酸制氢活性，以合金化和载体改性为主要手段的研究工作被陆续报道。利用元素掺杂，将Pd与其他元素形成合金，可有效调节Pd的电子结构，从而提高催化活性。Tsang课题组(Nat. Nanotechnol. 2011, 6, 302-307)制备的Pd-Ag合金催化剂对甲酸制氢的催化活性比纯Pd有大幅度提高。另一方面，改变催化剂载体，如利用碳纳米管(J. Col. & Inter.Sci. 2019, 538, 474-480.)，金属有机框架材料(Chem. Eng. J. 2019, 361, 953-959)，金属氧化物(J. Mater. Chem. A 2019, 7, 21438-21446)作为载体，利用Pd纳米颗粒与载体之间的强相互作用，提高催化剂的活性和稳定性。
然而，上述方案虽然能有效提高Pd对甲酸制氢的催化活性，但催化材料制备工艺复杂、成本高。因此,如何简便而经济地调控Pd的催化性能是一个亟待解决的问题。
发明内容
针对以上技术问题，本发明的目的在于提供一种富氨基多孔聚合物为载体的Pd基催化剂（Pd/APPOPs）的制备方法。所述方法以共价氨基吡啶类多孔有机聚合物(APPOPs)为载体，氯化钯为金属前驱体，以硼氢化钠为还原剂，浸渍还原合成负载型Pd/APPOPs催化剂。该催化剂制备简单、催化效率高、易于扩大生产，有一定的商业应用前景。
本发明采用的技术方案是：
1) 酰胺化法合成共价氨基吡啶类多孔聚合物材料(APPOPs)；
2) 将步骤1)制得的APPOPs和适量钯盐溶液加入有机溶剂中，超声分散后在油浴中搅拌回流12小时。然后加入过量的NaBH4还原钯盐，将反应后的悬浊液以乙醇洗涤，后抽滤、真空干燥，制得Pd/APPOPs催化剂；
3) 将步骤2)制得的Pd/APPOPs催化剂加入甲酸溶液中，在298 K～323 K条件下催化甲酸产生氢气。
本发明所述技术方案的步骤1)中共价氨基吡啶类多孔聚合物材料的制备方法参照文献（Chem2019, 5 , 693-705），过程如下：将定量2，6-二氨基吡啶（DAP）、三乙胺(TEA)加入二氯甲烷溶液中，在氩气保护和冰浴条件下，逐滴滴加1，3，5-苯三甲酰氯和二氯甲烷混合液，完成后在室温下搅拌12小时，然后在70 ℃回流12小时，洗涤烘干。
本发明所述技术方案的步骤2)中所述有机溶剂为甲醇、N, N-二甲基酰胺和二氯甲烷。
本发明所述技术方案的步骤2)中所述油浴的温度为65 ℃～75 ℃。
本发明所述技术方案的步骤2)中所述的NaBH4摩尔量为Pd盐摩尔量的20倍。
本发明所述技术方案的步骤2)中所述的钯盐为氯化钯。
本发明所述技术方案的步骤2)中NaBH4还原钯盐的温度为0摄氏度，还原时间为4小时。
本发明所述技术方案所得Pd/APPOPs催化剂中贵金属Pd的负载量为催化剂质量的1 %～5 %。
进一步地，在上述方案步骤3)中，每10 ml甲酸溶液所添加的催化剂的使用量为100 mg。
进一步地，在上述方案步骤3)中，甲酸初始浓度优选为0.5 mol/L～2 mol/L。
本发明的有益效果：
(1) 以一种共价氨基吡啶类多孔有机聚合物材料 (APPOPs)作为Pd基催化剂的载体，载体表面大量氨基与Pd原子的相互作用，改变Pd的价电子结构，显著提升了催化活性。5wt%Pd载量的催化剂在常压、303 K下对1.1 mol/L甲酸水溶液的催化TOF值（10分钟）达到494 h-1，是同等条件下商业钯催化剂的2.4倍；
(2) 本发明与现有技术相比，制备方法安全简单，易于扩大生产，具有较好的大规模应用前景。
附图说明
图1是本发明最佳案例催化剂（实施案例1）的透射电镜表征图。
图2是本发明最佳案例催化剂（实施案例1）的X射线光电子能谱分析图。
图3是本发明最佳案例催化剂（实施案例1）的X射线衍射表征图。
图4是本发明实施案例1与同条件下商业碳载钯催化剂甲酸制氢的活性对比图。
图5是本发明实施案例1、实施案例2以及实施案例3中催化剂的TOF值对比图。
具体实施方式
下面对本发明的具体实施方式进行详细说明，但是需要指出的是，本发明的保护范围并不受这些具体实施方式的限制，而是由权利要求书来确定。
实施案例1
步骤一：合成APPOPs载体。将2.7 g 2，6-二氨基吡啶（DAP）和6.0 g三乙胺(TEA)加入120 mL二氯甲烷溶液中，在氩气保护和冰浴条件下，45分钟内逐滴滴加4.3 g 1,3,5-苯三甲酰氯和80 mL二氯甲烷混合液，室温下搅拌12小时，再回流12小时;
步骤二：合成Pd/APPOPs催化剂。将步骤一制得的190 mg APPOPs加入70 mL甲醇溶液中，然后加入1.67 mL的56.4 mmol/L PdCl2溶液，超声分散15分钟，70 ℃油锅中加热搅拌回流12小时，待反应完成后，加入过量20倍的NaBH4 溶液（127 mg无水碳酸钠、72 mg NaBH4粉末与24 mL水混合配制）还原，然后洗涤、抽滤、真空干燥;
步骤三：催化甲酸制氢。由上述方法制得5 wt%负载量的Pd/APPOPs为催化剂用于催化甲酸制氢反应。将所述的催化剂加入10 ml甲酸溶液中，催化剂使用量为100 mg、甲酸溶液的初始浓度为1.1 mol/L，反应温度为303 K，随着反应时间的增长，产生氢气体积逐渐增加。
对上述方法制得的5 wt% Pd含量的负载型钯催化剂进行表征，其表征结果如下：
由图1可知，Pd纳米粒子均匀分布在聚合物APPOPs表面，粒径约为2.1 nm;
由图2可知，5 wt% Pd/APPOPs的表面具有Pd元素;
由图3可得，所得催化剂纳米粒子中Pd原子呈现典型的面心立方排布；
由图4可以看出，将5 wt% Pd/APPOPs用于催化甲酸产氢，催化反应10分钟时，产生气体量为195 mL。反应过后计算转化效率(TOF)值为494 h-1。
实施案例2
步骤一：合成APPOPs载体。将2.7 g 2，6-二氨基吡啶（DAP）和6.0 g三乙胺(TEA)加入120 mL二氯甲烷溶液中，在氩气保护和冰浴下，45分钟内逐滴滴加4.3 g 1, 3, 5-苯三甲酰氯和80 mL二氯甲烷混合液，室温下搅拌12小时，再回流12小时;
步骤二：合成Pd/APPOPs催化剂。将步骤一制得的190 mg APPOPs加入70 mL甲醇溶液中，然后加入1.0 mL的56.4 mmol/L PdCl2溶液，超声分散15分钟，70 ℃油锅中加热搅拌回流12 小时，待反应完成后，加入过量20倍的NaBH4 溶液（76 mg无水碳酸钠、43 mg NaBH4粉末和14 mL水混合配制）还原，后洗涤、抽滤、真空干燥;
步骤三：催化甲酸制氢。由上述方法制得3 wt%负载量的Pd/APPOPs为催化剂用于催化甲酸制氢反应。将所述的催化剂加入10 ml甲酸溶液中，催化剂使用量为100 mg、甲酸溶液的初始浓度为1.1 mol/L，反应温度为303 K，随着反应时间的增长，产生氢气体积逐渐增加，3 wt% Pd/APPOPs用于催化甲酸产氢，催化反应10分钟时，产生气体量为116 ml。反应过后计算转化效率 (TOF)值为288 h-1。
实施案例3
步骤一： 合成APPOPs载体。将2.7 g 2, 6-二氨基吡啶（DAP）和6.0 g三乙胺(TEA)加入120 mL二氯甲烷溶液中，在氩气保护和冰浴下，45分钟内逐滴滴加4.3 g 1, 3, 5-苯三甲酰氯和80 mL二氯甲烷混合液，室温下搅拌12小时，再回流12小时;
步骤二：合成Pd/APPOPs催化剂。将步骤一制得的190 mg APPOPs加入70 mL甲醇溶液中，然后加入0.5 mL的56.4 mmol/L PdCl2溶液，超声分散15分钟，70 ℃油锅中加热搅拌回流12小时，待反应完成后，加入过量20倍的NaBH4 溶液（38 mg Na2CO3、21 mg NaBH4粉末和7ml H2O混合配制）还原，后洗涤、抽滤、真空干燥;
步骤三：催化甲酸制氢。 由上述方法制得1.5 wt%负载量的Pd/APPOPs为催化剂用于催化甲酸制氢反应。将所述的催化剂加入10 ml甲酸溶液中，催化剂使用量为100 mg、甲酸溶液的初始浓度为1.1 mol/L，反应温度为303 K，随着反应时间的增长，产生氢气体积逐渐增加，1.5 wt% Pd/APPOPs用于催化甲酸产氢，催化反应10分钟时，产生气体量为25 ml。反应过后计算转化效率(TOF)值为66 h-1。
Claims (9)
1.一种甲酸制氢的富氨基聚合物负载的钯催化剂（Pd/APPOPs）的制备方法，包括以下步骤：
1) 酰胺化法合成共价氨基吡啶类多孔聚合物材料(APPOPs)；
2) 将步骤1)制得的APPOPs和适量钯盐溶液加入有机溶剂中，超声分散后在油浴中搅拌回流12小时；然后加入过量的NaBH4溶液在0摄氏度反应4 小时，将反应后的悬浊液以乙醇洗涤，后抽滤、真空干燥，制得Pd/APPOPs催化剂。
2.根据权利要求1所述的方法，其特征在于，步骤1)涉及的共价氨基吡啶类多孔聚合物材料的制备方法参照文献（Chem2019, 5 , 693-705），过程如下：将定量2，6-二氨基吡啶（DAP）、三乙胺(TEA)加入二氯甲烷溶液中，在氩气保护和冰浴条件下，逐滴滴加1，3，5-苯三甲酰氯和二氯甲烷混合液，完成后在室温下搅拌12小时，然后在70 ℃回流12小时，洗涤烘干。
3.根据权利要求1所述的方法，其特征在于，步骤2)制备的催化剂的钯纳米颗粒的粒径范围为1.8 nm～2.5 nm。
4.根据权利要求1所述的一种室温条件下甲酸制氢的富氨基聚合物负载的钯催化剂（Pd/APPOPs）的制备方法，其特征在于，步骤2)中所述有机溶剂为甲醇、N, N-二甲基酰胺和二氯甲烷。
5.根据权利要求1所述方法，其特征在于，步骤2)中所述油浴的温度为65 ℃～75 ℃。
6.根据权利要求1所述方法，其特征在于，步骤2)中所述的NaBH4摩尔量为Pd盐摩尔量的20倍。
7.根据权利要求1所述方法，其特征在于，Pd/APPOPs催化剂中贵金属Pd的负载量为催化剂质量的1 %～5 %。
8.根据权利要求1所述方法，其特征在于，步骤2)中所述的钯盐为氯化钯。
9.根据权利要求1所述方法，其特征在于，所得5 wt%Pd载量的催化剂在常压、303 K下对甲酸分解制氢的TOF值（10分钟）能达到494 h-1，是同等条件下商业钯催化剂的2.4倍。
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