CN111359670A - 一种Au-Pd/NH2-MIL-101(Cr)催化剂及其制备与应用 - Google Patents
一种Au-Pd/NH2-MIL-101(Cr)催化剂及其制备与应用 Download PDFInfo
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Abstract
本发明提供了一种Au‑Pd/NH2‑MIL‑101(Cr)催化剂及其制备方法，以及在光催化苯甲醇无溶剂液相氧化制备苯甲醛的反应中的应用；本发明首次将侧柏还原制备的Au‑Pd合金纳米颗粒负载于NH2‑MIL‑101(Cr)材料上，成功制备出Au‑Pd合金负载型NH2‑MIL‑101(Cr)催化剂，与现有技术相比，本发明制备的催化剂表现出更优异的光催化稳定性能。
Description
技术领域
本发明涉及一种Au-Pd合金催化剂，尤其是涉及一种用于光催化苯甲醇氧化制备苯甲醛的 Au-Pd/NH2-MIL-101(Cr)催化剂及其制备方法。
背景技术
金属有机骨架材料(MOFs)是一种由金属离子和有机配体组成的新型多孔骨架材料。金属有机骨架(MOF)复合材料作为一种新型功能材料正在迅速发展，广泛应用于气体吸附、分离与储存、催化、气体传感、药物转运等领域(Journal of Chromatography A，2018，1574)。MOF材料种类繁多，而MIL-101(Cr)在催化氧化反应中表现出优异的性能。具有比表面积大、孔隙率高、热稳定性好、水稳定性好、有机溶剂稳定性好等优点。这些优异的性能使其在多相催化领域具有良好的应用前景，并得到了广泛的研究。
而贵金属Au和Pd拥有着的特殊的物理化学性质，使其在石化工业中起到有效的催化氧化作用(Journal of Physical Chemistry C，2010，13362)。随着MOFs的发展，Au和Pd的纳米粒子因为具有较高的表面积，而被证明其有着很好的氧化活性，使得负载Au/Pd催化剂成为催化领域研究的重点。
目前贵金属负载型催化剂在制备过程中，贵金属纳米颗粒容易发生团聚而导致催化剂失去催化性能，其次催化剂在使用过程中贵金属纳米颗粒可能容易脱落，而导致催化剂的稳定性能下降。本发明将Au、Pd合金纳米颗粒负载于MIL-101(Cr)材料内，并用于光催化苯甲醇氧化。MIL-101(Cr) 材料可以提供有限的孔道空间，防止在催化剂的制备过程中金属颗粒的团聚，以及催化剂在使用过程中阻止贵金属纳米颗粒的流失。
发明内容
本发明旨在提供一种用于光催化苯甲醇氧化制备苯甲醛的Au-Pd/NH2-MIL-101(Cr)催化剂及其制备方法。
本发明的技术方案如下：
一种Au-Pd/NH2-MIL-101(Cr)催化剂，按如下方法制备得到：
(1)NH2-MIL-101(Cr)的制备：将Cr(NO)3·9H2O、2-氨基对苯二甲酸、碱液混合均匀，升温至100～200℃反应10～24h，之后反应液经后处理，得到NH2-MIL-101(Cr)；
所述Cr(NO)3·9H2O和2-氨基对苯二甲酸的质量比为1：0.3～3；
所述碱液由碱性物质溶于水而得，所述碱性物质例如氢氧化钠，所述碱液的浓度为0.1～1M，碱液的体积用量以Cr(NO)3·9H2O的质量计为15～20mL/g；
所述后处理的方法为：反应结束后，待反应液冷却至室温(20～30℃)，离心(7000rpm)收集固体产物，分别用水、DMF、甲醇洗涤，100℃下干燥过夜，得到NH2-MIL-101(Cr)；
(2)Au-Pd双金属纳米颗粒的制备：将侧柏(学名：Platycladus orientalis)提取液用去离子水稀释后，加入钯前驱体溶液和金前驱体溶液，升温至60～90℃反应0.5～4h，得到Au-Pd双金属纳米颗粒溶胶；
所述侧柏提取液的制备方法为：取侧柏粉按料液质量比1：100与去离子水混合均匀，用保鲜膜密封，于30～100℃下搅拌0.5～4h，之后过滤，收集滤液即为侧柏提取液；
所述钯前驱体与金前驱体的物质的量之比为1：0.1～10，优选1：0.5～1，所述钯前驱体溶液的浓度为0.01～0.5M，所述金前驱体溶液的浓度为0.01～0.5M，所述钯前驱体为可溶性钯盐，例如氯化钯、硝酸钯等，所述金前驱体例如氯金酸等；
所述侧柏提取液的体积用量以钯前驱体的物质的量计为500～2500mL/mmol；
(3)Au-Pd/NH2-MIL-101(Cr)催化剂的制备：将步骤(1)制备的NH2-MIL-101(Cr)加入步骤(2) 制备的Au-Pd双金属纳米颗粒溶胶中，于60～90℃下搅拌0.5～4h，之后过滤，滤饼于60～100℃下真空干燥，得到粉末状的Au-Pd/NH2-MIL-101(Cr)催化剂；
本发明制备的催化剂中Au-Pd双金属纳米颗粒的负载量在0.05～6wt％，优选2～4wt％。
本发明所述Au-Pd/NH2-MIL-101(Cr)催化剂可用于光催化苯甲醇无溶剂液相氧化制备苯甲醛的反应中，具体应用的方法为：
将所述催化剂加入装有苯甲醇的反应瓶中，90℃下预热5min并回流，以90mL/min的速度通入氧气，打开150W的金卤灯光源照射反应瓶进行光催化反应，反应结束后，获得含苯甲醛的反应液，经分离纯化，获得氧化产物苯甲醛。
本发明首次将侧柏还原制备的Au-Pd合金纳米颗粒负载于NH2-MIL-101(Cr)材料上，成功制备出Au-Pd合金负载型NH2-MIL-101(Cr)催化剂。与现有技术相比，本发明制备的催化剂表现出更优异的光催化稳定性能。
附图说明
图1为实施例3制备的Au-Pd/NH2-MIL-101(Cr)催化剂的TEM图。
具体实施方式
下面通过具体实施例对本发明作进一步说明，但本发明的保护范围并不仅限于此。
实施例1
将3.2g Cr(NO)3·9H2O和1.44g 2-氨基对苯二甲酸缓慢加入到60mL含有0.8克NaOH的水溶液中。然后将在室温下搅拌30min的混合物转移到100mL水热反应釜中并在150℃下保持12h。自然冷却后，通过在7000rpm下离心收集所得混合物。将得到的绿色粉末分别用水，DMF和甲醇洗涤数次，并在100℃下干燥过夜。获得活化的NH2-MIL-101(Cr)。
取侧柏粉2g，去离子水200mL，置于250mL锥形瓶中，用保鲜膜封好，置于30℃油浴中加热搅拌。充分搅拌2小时后，停止加热搅拌，取出锥形烧瓶，用循环水多用途真空泵对溶液进行真空过滤得到透明土黄色侧柏提取液。取30mL的去离子水和30mL的侧柏提取液混合，然后加入190微升浓度为0.075M的硝酸钯水溶液和156微升浓度为0.049M的氯金酸水溶液，置于油浴90℃加热和搅拌，1h后即可得到Au-Pd双金属纳米颗粒溶胶。
向Au-Pd双金属纳米颗粒溶胶中加入0.3g已制备好的NH2-MIL-101(Cr)载体，继续加热搅拌1小时，过滤，并置于60℃真空干燥箱内烘干。即可得到粉末状的Au-Pd/MIL-101催化剂A。
催化剂A用于光催化苯甲醇氧化反应，50mL三口烧瓶中加入0.1g催化剂A，并加入10mL苯甲醇，之后将三口烧瓶置于90℃油浴锅中预热5min并回流，之后通入90mL/min的氧气，打开150W的金卤灯光源开始光催化反应，反应4h后，取样分析。催化反应结果见表1。
实施例2
取30mL的去离子水和30mL实施例1中制备的侧柏提取液混合，然后加入380微升浓度为0.075 M的硝酸钯水溶液和312微升浓度为0.049M的氯金酸水溶液，置于油浴90℃加热和搅拌，1h后即可得到Au-Pd双金属纳米颗粒溶胶。
向溶胶中加入放入0.3g实施例1中制备的NH2-MIL-101(Cr)载体，继续加热搅拌1小时，过滤，并置于60℃真空干燥箱内烘干。即可得到粉末状的Au-Pd/MIL-101催化剂B。催化剂评价条件同实施例1，催化反应结果见表1。
实施例3
取30mL的去离子水和30mL实施例1中制备的侧柏提取液混合，然后加入570微升浓度为0.075 M的硝酸钯水溶液和468微升浓度为0.049M的氯金酸水溶液，置于油浴90℃加热和搅拌，1h后即可得到Au-Pd双金属纳米颗粒溶胶。
向溶胶中加入放入0.3g实施例1中制备的NH2-MIL-101(Cr)载体，继续加热搅拌1小时，过滤，并置于60℃真空干燥箱内烘干。即可得到粉末状的Au-Pd/MIL-101催化剂C。催化剂评价条件同实施例1，催化反应结果见表1。
实施例4
取30mL的去离子水和30mL实施例1中制备的侧柏提取液混合，然后加入760微升浓度为0.075 M的硝酸钯水溶液和624微升浓度为0.049M的氯金酸水溶液，置于油浴90℃加热和搅拌，1h后即可得到Au-Pd双金属纳米颗粒溶胶。
向溶胶中加入放入0.3g实施例1中制备的NH2-MIL-101(Cr)载体，继续加热搅拌1小时，过滤，并置于60℃真空干燥箱内烘干。即可得到粉末状的Au-Pd/MIL-101催化剂D。催化剂评价条件同实施例1，催化反应结果见表1。
实施例5
取30mL的去离子水和30mL实施例1中制备的侧柏提取液混合，然后加入312微升浓度为0.049 M的氯金酸水溶液，置于油浴90℃加热和搅拌，1h后即可得到Au纳米颗粒溶胶。
向溶胶中加入放入0.3g实施例1中制备的NH2-MIL-101(Cr)载体，继续加热搅拌1小时，过滤，并置于60℃真空干燥箱内烘干。即可得到粉末状的Au/MIL-101催化剂E。催化剂评价条件同实施例1，催化反应结果见表1。
实施例6
取30mL的去离子水和30mL实施例1中制备的侧柏提取液混合，然后加入380微升浓度为0.075 M的硝酸钯水溶液，置在油浴90℃加热和搅拌，1h后即可得到Pd纳米颗粒溶胶。
向溶胶中加入放入0.3g实施例1中制备的NH2-MIL-101(Cr)载体，继续加热搅拌1小时，过滤，并置于60℃真空干燥箱内烘干。即可得到粉末状的Pd/MIL-101催化剂E。催化剂评价条件同实施例1，催化反应结果见表1。
表1 Au-Pd/MIL-101催化剂光催化苯甲醇氧化反应性能
结论：相比较单金属Au和Pd催化剂，Au-Pd合金双金属催化的光催化性能得到显著提升，其中Au和Pd负载量都为1.5wt％，合金催化剂达到最佳的光催化性能。
Claims (9)
1.一种Au-Pd/NH2-MIL-101(Cr)催化剂，其特征在于，按如下方法制备得到：
(1)NH2-MIL-101(Cr)的制备：将Cr(NO)3·9H2O、2-氨基对苯二甲酸、碱液混合均匀，升温至100～200℃反应10～24h，之后反应液经后处理，得到NH2-MIL-101(Cr)；
所述Cr(NO)3·9H2O和2-氨基对苯二甲酸的质量比为1：0.3～3；
(2)Au-Pd双金属纳米颗粒的制备：将侧柏提取液用去离子水稀释后，加入钯前驱体溶液和金前驱体溶液，升温至60～90℃反应0.5～4h，得到Au-Pd双金属纳米颗粒溶胶；
所述钯前驱体与金前驱体的物质的量之比为1：0.1～10；
(3)Au-Pd/NH2-MIL-101(Cr)催化剂的制备：将步骤(1)制备的NH2-MIL-101(Cr)加入步骤(2)制备的Au-Pd双金属纳米颗粒溶胶中，于60～90℃下搅拌0.5～4h，之后过滤，滤饼于60～100℃下真空干燥，得到粉末状的Au-Pd/NH2-MIL-101(Cr)催化剂。
2.如权利要求1所述Au-Pd/NH2-MIL-101(Cr)催化剂，其特征在于，步骤(1)中，所述碱液由碱性物质溶于水而得，所述碱性物质为氢氧化钠，所述碱液的浓度为0.1～1M，碱液的体积用量以Cr(NO)3·9H2O的质量计为15～20mL/g。
3.如权利要求1所述Au-Pd/NH2-MIL-101(Cr)催化剂，其特征在于，步骤(1)中，所述后处理的方法为：反应结束后，待反应液冷却至室温，离心收集固体产物，分别用水、DMF、甲醇洗涤，100℃下干燥过夜，得到NH2-MIL-101(Cr)。
4.如权利要求1所述Au-Pd/NH2-MIL-101(Cr)催化剂，其特征在于，步骤(2)中，所述侧柏提取液的制备方法为：取侧柏粉按料液质量比1：100与去离子水混合均匀，用保鲜膜密封，于30～100℃下搅拌0.5～4h，之后过滤，收集滤液即为侧柏提取液。
5.如权利要求1所述Au-Pd/NH2-MIL-101(Cr)催化剂，其特征在于，步骤(2)中，所述钯前驱体溶液的浓度为0.01～0.5M，所述金前驱体溶液的浓度为0.01～0.5M，所述钯前驱体为氯化钯或硝酸钯，所述金前驱体为氯金酸。
6.如权利要求1所述Au-Pd/NH2-MIL-101(Cr)催化剂，其特征在于，步骤(2)中，所述侧柏提取液的体积用量以钯前驱体的物质的量计为500～2500mL/mmol。
7.如权利要求1所述Au-Pd/NH2-MIL-101(Cr)催化剂，其特征在于，步骤(3)中，所得催化剂中Au-Pd双金属纳米颗粒的负载量在0.05～6wt％。
8.如权利要求1所述Au-Pd/NH2-MIL-101(Cr)催化剂在光催化苯甲醇无溶剂液相氧化制备苯甲醛的反应中的应用。
9.如权利要求8所述的应用，其特征在于，所述应用的方法为：
将所述催化剂加入装有苯甲醇的反应瓶中，90℃下预热5min并回流，以90mL/min的速度通入氧气，打开150W的金卤灯光源照射反应瓶进行光催化反应，反应结束后，获得含苯甲醛的反应液，经分离纯化，获得氧化产物苯甲醛。
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