CN115301270B - 一种催化剂及其制备方法和应用 - Google Patents

一种催化剂及其制备方法和应用 Download PDF

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CN115301270B
CN115301270B CN202210875582.2A CN202210875582A CN115301270B CN 115301270 B CN115301270 B CN 115301270B CN 202210875582 A CN202210875582 A CN 202210875582A CN 115301270 B CN115301270 B CN 115301270B
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杨世和
洪梅
袁海丰
钱微
王高鹏
鞠敏
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Peking University Shenzhen Graduate School
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Abstract

本发明属于催化剂技术领域，公开了一种催化剂及其制备方法和应用。该催化剂包括活性组分和用于负载所述活性组分的载体；载体为N掺杂分级碳，所述活性组分为稀合金纳米粒子；稀合金纳米粒子包括贵金属M和贱金属Co；M选自Pd、Pt、Ru、Au、Ir和Rh中的任意一种。该催化剂具有良好的底物普适性，当底物为醛酮化合物、喹啉类化合物、硝基化合物、酚类化合物、烯或炔类化合物、或杂环化合物及苄醇中的任意一类时，催化剂均显示出优异的催化活性和高的目标产物收率。

Description

一种催化剂及其制备方法和应用
技术领域
本发明属于催化剂技术领域，特别涉及一种催化剂及其制备方法和应用。
背景技术
稀合金(Dilute Alloys)是指少量异类单分散金属添加到一个给定的主体元素的组装材料。过渡金属催化剂(transition metals，TM)具有不完全填充的d轨道，容易提供和接受电子，在现代有机合成中必不可少。与均相催化剂相比，负载的多相过渡金属催化剂具有稳定且易于从反应混合物中分离的优点，但存在原子效率不足和选择性较低的问题。
现有技术中的催化剂对醛酮化合物、喹啉类化合物、硝基化合物、酚类化合物、烯或炔类化合物、芳香杂环化合物的定向氢化反应及苄醇的选择性氧化反应催化活性低，选择性差，且催化反应的条件较为严苛，不利于催化剂的工业应用。
因此，亟需提供一种新的催化剂，该催化剂不仅制备成本相对较低，而且可在温和的水相条件下对于醛酮化合物、喹啉类化合物、硝基化合物、酚类化合物、烯或炔类化合物、芳香杂环化合物的定向氢化反应及苄醇的选择性氧化反应具有非常高的催化活性、选择性及稳定性，这将十分有利于该催化剂的工业应用。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种催化剂及其制备方法和应用。所述催化剂更好地利用了稀缺的贵金属资源，作为一种高效水相催化剂，可在温和的水相条件下对于醛酮化合物、喹啉类化合物、硝基化合物、酚类化合物、芳香杂环化合物的定向氢化反应及苄醇的选择性氧化反应具有非常高的催化活性、选择性及稳定性。本发明所述催化剂及其制备方法很好地解决了多相过渡金属催化剂原子效率不足和选择性较低的技术问题。
本发明的发明构思为：本发明催化剂使用海胆状的N掺杂分级碳(CN)为载体，负载由痕量贵金属和主体贱金属Co组成的稀合金纳米粒子。所述催化剂的制备过程简便，适合于大规模生产，并且能够在环境友好的水相温和条件下实现多种底物高效(转化率＞81.5％)定向(选择性＞75.5％)转化为目标产物。
本发明是通过调节痕量过渡贵金属与贱金属主体及N掺杂分级碳(CN)的相互作用，以调整孤立的少数金属物种的几何和电子结构，继而赋予催化剂高催化活性和反应普遍性。
本发明的第一方面提供一种催化剂。
具体的，一种催化剂，所述催化剂包括活性组分和用于负载所述活性组分的载体；所述载体为N掺杂分级碳，所述活性组分为稀合金纳米粒子；
所述稀合金纳米粒子包括贵金属M和贱金属Co；
所述M选自Pd、Pt、Ru、Au、Ir和Rh中的任意一种。
优选的，以所述载体质量为基准，所述贵金属M的质量为载体质量的0.1-1.5％。在稀合金纳米粒子中，贵金属M是痕量的，贱金属Co是主体，可大大降低催化剂的制备成本。
进一步优选的，以所述载体质量为基准，所述贵金属M的质量为载体质量的0.1-1.2％；进一步优选的，以所述载体质量为基准，所述贵金属M的质量为载体质量的0.1-0.6％。
优选的，以所述载体质量为基准，所述贱金属Co的质量为载体质量的25-45％，优选30-36％。
优选的，所述N掺杂分级碳具有孔或管状空腔，所述稀合金纳米粒子封装于所述N掺杂分级碳的孔或管状空腔中。
优选的，所述N掺杂分级碳的外形呈海胆状。
本发明的第二方面提供一种催化剂的制备方法。
具体的，一种催化剂的制备方法，包括以下步骤：
(1)将碳氮化合物加热，发生反应生成富氮化合物，然后通过所述富氮化合物、钴盐、咪唑类物质反应，制得纳米复合材料，再进行加热反应，所述加热反应的温度为700-800℃，生成负载Co的载体；
(2)将步骤(1)制得的负载Co的载体与贵金属M的盐反应，得到的产物进行热处理，制得所述催化剂。
优选的，步骤(1)中，所述碳氮化合物选自尿素、三聚氰胺或者双氰胺中的至少一种。
优选的，步骤(1)中，所述对碳氮化合物加热的温度为500-600℃，发生反应的时间为2-5小时。
优选的，步骤(1)中，所述钴盐为硝酸钴或六水合硝酸钴。
优选的，步骤(1)中，所述咪唑类物质为2-甲基咪唑。
优选的，步骤(1)中，富氮化合物、钴盐、咪唑类物质的质量比为0.1-0.5∶(0.2-1)∶(0.3-1)。
优选的，步骤(1)中，所述富氮化合物、钴盐、咪唑类物质反应的过程中，是先将富氮化合物、钴盐溶解于甲醇中，获得溶液A；然后将咪唑类物质溶解于溶剂中，获得溶液B，再在1000-2000转/分钟的搅拌速度下，将溶液B倒入溶液A中，搅拌12-24小时，得到悬浮液，洗涤，离心，干燥，制得纳米复合材料(记为Co@CN)。
优选的，步骤(1)中，所述加热反应是在保护气氛下进行，例如在Ar氛围下进行，加热反应的时间为1-3小时。
优选的，步骤(1)中，所述溶剂选自丙酮、甲苯或正己烷中的任意一种或两种。
优选的，步骤(2)中，所述贵金属M的盐选自氯化钯、硝酸钯、氯铂酸、氯化钌、氯金酸、二羰基乙酰丙酮铱或二羰基乙酰丙酮铑中的任意一种。
优选的，步骤(2)的具体过程为：将负载Co的载体与正己烷混合，制得悬浮液，然后加入贵金属M的盐，在800-1200转/分钟的搅拌速度下搅拌10-14小时，离心获得沉淀物，洗涤，烘干，获得的产物在H2/Ar的流动氛围下，在150-300℃(升温至150-300℃的升温速率为1-6℃/分钟)下处理1-3小时，制得所述催化剂(记为MxCoy@CN，其中x，y为正数)。
优选的，步骤(2)中，所述负载Co的载体与贵金属M的盐的质量比为1∶(0.01-0.05)。
本发明的第三方面提供上述催化剂的应用。
具体的，上述催化剂在醛酮化合物、喹啉类化合物、硝基化合物、酚类化合物、烯或炔类化合物、或杂环化合物的定向氢化反应，以及在苄醇的选择性氧化反应中的应用。
优选的，所述应用中，用于醛酮化合物、喹啉类化合物、硝基化合物、酚类化合物、烯或炔类化合物、或杂环化合物的定向氢化反应的具体过程为：将5-15mL的去离子水加入到50mL高压反应釜中，再加入底物和催化剂，底物与催化剂的优选摩尔比为(200-6000)∶1，高压反应釜中充入0.2-1.0MPa的H2，在25-100℃下搅拌30-360min，冷却，将剩余氢气排除，离心分离催化剂。离心分离催化剂后，剩余的反应溶液利用GC和GC-MS分析。
优选的，所述应用中，用于苄醇的选择性氧化反应的具体过程为：将5-15mL的溶剂加入到50mL高压反应釜中，再加入苄醇和催化剂，苄醇与催化剂优选摩尔比为(5000-15000)∶1，高压反应釜中加入5-15mL的H2O2或0.5-1.5MPa的O2，在70-110℃下搅拌90-360min，冷却，将剩余氢气排除，离心分离催化剂。
底物、离心分离催化剂后剩余的反应溶液、和纯化产物利用气相色谱仪(GC)和气相色谱-质谱联用仪(GC-MS)定性和定量，底物的转化率在81.5％以上，目标产物选择性均大于75.5％。
相对于现有技术，本发明的有益效果如下：
(1)本发明所述催化剂分别以N掺杂分级多孔碳和贵金属盐为载体和活性组分的前驱体，通过电置换和简单热处理得到富含稀合金纳米粒子的高效水相催化剂，过程简便，适合大规模批量生产。
(2)本发明所述催化剂具有优异的催化性能，可在温和的水相条件下将肉桂醛还原为氢化肉桂醛，转化率高达93.6％，产率高达92.6％，转化频率(TOF)高达1656h-1；其循环套用6次，催化性能无明显下降，催化剂稳定性极高，工业价值极高，具有重要的应用意义。
(3)本发明所述催化剂具有良好的底物普适性。当底物为醛酮化合物、喹啉类化合物、硝基化合物、酚类化合物、烯或炔类化合物、或杂环化合物及苄醇中的任意一类时，催化剂也显示出优异的催化活性和高的目标产物收率。
附图说明
图1为本发明实施例1制得的PdxCoy@CN催化剂的XRD(X射线衍射)图；
图2为本发明实施例1制得的PdxCoy@CN催化剂的Raman(拉曼)图；
图3为本发明实施例1制得的PdxCoy@CN催化剂的XPS(X射线光电子能谱)图；
图4为本发明实施例1制得的PdxCoy@CN催化剂的SEM(扫描电子显微镜)图和TEM(透射电子显微镜)图；
图5为本发明实施例1制得的PdxCoy@CN催化剂在肉桂醛选择性加氢反应中的循环使用性能图；
图6为1#-7#催化剂对肉桂醛选择加氢性能效果图。
具体实施方式
为了让本领域技术人员更加清楚明白本发明所述技术方案，现列举以下实施例进行说明。需要指出的是，以下实施例对本发明要求的保护范围不构成限制作用。
以下实施例中所用的原料、试剂或装置如无特殊说明，均可从常规商业途径得到，或者可以通过现有已知方法得到。
实施例1
一种催化剂，催化剂包括活性组分和用于负载所述活性组分的载体；载体为N掺杂分级碳，活性组分为稀合金纳米粒子；
稀合金纳米粒子包括贵金属M和贱金属Co；
M为Pd，以载体的质量为基准，Pd的质量百分含量为0.15％。
N掺杂分级碳具有管状空腔，稀合金纳米粒子封装于所述N掺杂分级碳的管状空腔中。
一种催化剂的制备方法，包括以下步骤：
(1)称取6g尿素置于坩埚后，在马弗炉中经550℃热聚4h得到淡黄色粉末富氮化合物(g-C3N4)，然后将0.2g富氮化合物、0.45g六水合硝酸钴溶解于40mL甲醇中，获得溶液A；然后将5.5g 2-甲基咪唑溶解于40mL甲醇中，获得溶液B，再在1500转/分钟的搅拌速度下，将溶液B缓慢倒入溶液A中，搅拌24小时，得到悬浮液，用甲醇洗涤5次，离心，收集固体物质，在60℃真空烘箱中干燥过夜，制得纳米复合材料(记为ZIF-67@C3N4)，再进行加热反应，加热反应的过程是在Ar氛围的管式炉中，以5℃/min的速率从室温20℃升到750℃，保温2小时，然后自然冷却至室温，生成负载Co的载体(记为Co@CN)；
(2)将1.0g步骤(1)制得的负载Co的载体与60mL正己烷添加到100mL烧杯中，磁力搅拌混合3小时，制得悬浮液，然后加入0.05g硝酸钯(II)溶液(硝酸钯(II)溶液中，溶剂为水，以Pd为基准，质量浓度为4.5％)，在1000转/分钟的搅拌速度下搅拌12小时，离心收集获得沉淀物，用超纯水洗涤沉淀物，并在真空烘箱中于60℃下干燥过夜，获得的黑色粉末产物在H2/Ar(H2体积分数为5％)的流动氛围下在300℃(升温至300℃的升温速率为5℃/分钟)下处理2小时，制得催化剂(记为PdxCoy@CN，其中x，y为正数，实施例1制得的催化剂标记为1#催化剂)。
实施例2
与实施例1相比，实施例2的区别仅在于步骤(2)中硝酸钯溶液的质量为0.11g，所得催化剂以载体质量为基准，Pd的质量百分含量为0.35％，标记为2#催化剂。
实施例3
与实施例1相比，实施例3的区别仅在于步骤(2)中硝酸钯溶液的质量为0.20g，所得催化剂以载体质量为基准，Pd的质量百分含量为0.65％，标记为3#催化剂。
实施例4
与实施例1相比，实施例4的区别仅在于步骤(2)中硝酸钯溶液的质量为0.30g，所得催化剂以载体质量为基准，Pd的质量百分含量为0.95％。
实施例5
与实施例1相比，实施例5的区别仅在于将步骤(2)中硝酸钯溶液替换为0.6mL0.0125mol/L四氯金酸溶液，所得催化剂以载体质量为基准，Au的质量百分含量为0.15％。
实施例6
与实施例1相比，实施例6的区别仅在于将步骤(2)中硝酸钯溶液替换为0.6mL0.0125mol/L六氯合铂溶液，所得催化剂以载体质量为基准，Pt的质量百分含量为0.15％。
实施例7
与实施例1相比，实施例7的区别仅在于将步骤(2)中硝酸钯溶液替换为0.6mL0.0125mol/L三氯化钌溶液，所得催化剂以载体质量为基准，Ru的质量百分含量为0.15％。
对比例1
与实施例1相比，对比例1的区别仅在于步骤(1)中，以5℃/min的速率从室温20℃升到950℃，保温2小时，然后自然冷却至室温，生成负载Co的载体；其余过程与实施例1相同。制得的催化剂标记为4#催化剂。
对比例2
与实施例1相比，对比例2的区别仅在于步骤(1)中，制备溶液A时，未添加富氮化合物；其余过程与实施例1相同。制得的催化剂标记为5#催化剂。
对比例3
与实施例1相比，对比例3的区别仅在于步骤(1)中，生成负载Co的载体后用硝酸(6mol/L)溶液刻蚀掉Co，然后进行步骤(2)的操作；其余过程与实施例1相同。制得的催化剂标记为6#催化剂(即为Pd@CN催化剂)。
对比例4
与实施例1相比，对比例4的区别仅在于没有进行步骤(2)的处理；其余过程与实施例1相同。制得的催化剂标记为7#催化剂(即为Co@CN催化剂)。
图1为本发明实施例1制得的PdxCoy@CN催化剂的XRD(X射线衍射)图；图1中的“Ref.Pattern；PdCo；PDF#65-6075”表示PdCo合金的标准XRD卡片；“Ref.Pattern；Pd；PDF#65-2876”表示Pd的标准XRD卡片；“Ref.Pattern；Co；PDF#15-0806”表示Co合金的标准XRD卡片；“Ref.Pattern；graphite；PDF#65-6212”表示石墨碳的标准XRD卡片。
图2为本发明实施例1制得的PdxCoy@CN催化剂的Raman(拉曼)图；图2中的ID、IG分别表示C原子晶格的缺陷和C原子sp2杂化的面内伸缩振动。
图3为本发明实施例1制得的PdxCoy@CN催化剂的XPS(x射线光电子能谱)图，Sat.指代XPS测试过程中卫星峰(伴峰)。
图4为本发明实施例1制得的PdxCoy@CN催化剂的SEM(扫描电子显微镜)图和TEM(透射电子显微镜)图；图a：SEM；图b-f：TEM，其中，b图(b图中的“Carbon layer”表示碳层)表示单个PdxCoy稀合金的HRTEM(高分辨TEM)图像；c图表示b中区域相应逆FFT(快速傅立叶变换(Fast Fourier Transform))模式；d图(d图中“Frequency”表示频率，“Size”表示尺寸，“Gaussian Fitting”表示高斯拟合)表示HAADF-STEM(高角环形暗场像)图像；e图表示相应元素的EDS(能量色散X射线光谱)映射，f图(f图中“Distance”表示距离)沿绿色线标记的方向的元素线扫描图。
图5为本发明实施例1制得的PdxCoy@CN催化剂在肉桂醛选择性加氢反应中的循环使用性能图；从图5中可以看出，本发明实施例1制得的PdxCoy@CN催化剂在肉桂醛选择性加氢反应中具有良好的循环稳定性。
图6为1#-7#催化剂对肉桂醛选择加氢性能效果图。
在盛有10mL去离子水的50mL高压反应釜中，分别加入适量的肉桂醛和1#-7#催化剂(肉桂醛与钯的摩尔比为2661)，空气排尽后通入0.5MPa H2，在50℃下反应1.5h，产物利用GC和GC-MS来进行定性和定量分析。结果见表1和图6所示。
从图6可以看出本发明实施例制得的催化剂(负载双金属稀合金催化剂)的活性明显优于对比例制得的催化剂的催化活性。
表1：1#-7#催化剂的肉桂醛选择加氢性能
序号 转化率(％) 选择性(％)
1# 93.6 98.9
2# 85.6 95.5
3# 78.5 99.1
4# 21.6 79.8
5# 61.8 92.5
6# 7.88 32.27
7# 19.1 92.6
从表1可以看出，本发明实施例制得的1#-3#催化剂对肉桂醛选择加氢的转化率和选择性明显优于对比例制得的4#-7#催化剂。
在盛有10mL去离子水的50mL高压反应釜中，加入适量的1#催化剂和其它底物，空气排尽后通入0.5MPa H2或10mL H2O2，在一定温度下反应一段时间，底物和产物利用GC和GC-MS来进行定性和定量分析。结果见表2、表3、表4、表5和表6(表中的n(底物)/n(钯)表示底物与催化剂中钯的摩尔比)。
表2：1#催化剂用于其他醛、酯类化合物的选择性催化
表3：1#催化剂用于酮类化合物的选择性催化
表4：1#催化剂用于N-杂环化合物的选择性催化
表5：1#催化剂用于硝基类化合物的选择性催化
表6：1#催化剂用于酚类化合物选择性氢化还原反应和苄醇的选择性催化氧化反应
从表2-6可以看出，本发明实施例制得的催化剂在醛酮化合物、喹啉类化合物、硝基化合物、酚类化合物或杂环化合物的定向氢化反应，以及在苄醇的选择性氧化反应中具有良好的催化活性。
在盛有10mL去离子水的50mL高压反应釜中，加入适量的1#催化剂和肉桂醛，空气排尽后通入0.5MPa H2，在50℃下反应一段时间。反应结束后，通过离心将催化剂与反应液分离，离心液用GC和GC-MS分析。将使用过的催化剂移入高压釜中，加入一定量的新鲜的去离子水和肉桂醛，进行下一轮实验。连续重复使用5次，结果见图5。
以上所述，只是本发明的较佳实施例而已，本发明并不局限于上述实施方式，只要其以相同的手段达到本发明的技术效果，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明保护的范围之内，都应属于本发明的保护范围。在本发明的保护范围内其技术方案和/或实施方式可以有各种不同的修改和变化。

Claims (9)

1.一种催化剂，其特征在于，所述催化剂包括活性组分和用于负载所述活性组分的载体；所述载体为N掺杂分级碳，所述活性组分为稀合金纳米粒子；
所述稀合金纳米粒子由贵金属M和贱金属Co组成；
所述M选自Pd、Pt、Ru、Au、Ir和Rh中的任意一种；
所述催化剂的制备方法，包括以下步骤：
(1)将碳氮化合物加热，发生反应生成富氮化合物，然后通过所述富氮化合物、钴盐、咪唑类物质反应，制得纳米复合材料，再进行加热反应，所述加热反应的温度为700-800℃，生成负载Co的载体；
(2)将步骤(1)制得的负载Co的载体与贵金属M的盐反应，得到的产物进行热处理，制得所述催化剂。
2.根据权利要求1所述的催化剂，其特征在于，以所述载体质量为基准，所述贵金属M的质量为载体质量的0.1-1.5％。
3.根据权利要求1所述的催化剂，其特征在于，所述N掺杂分级碳具有孔或管状空腔，所述稀合金纳米粒子封装于所述N掺杂分级碳的孔或管状空腔中。
4.权利要求1-3任一项所述的催化剂的制备方法，其特征在于，包括以下步骤：
(1)将碳氮化合物加热，发生反应生成富氮化合物，然后通过所述富氮化合物、钴盐、咪唑类物质反应，制得纳米复合材料，再进行加热反应，所述加热反应的温度为700-800℃，生成负载Co的载体；
(2)将步骤(1)制得的负载Co的载体与贵金属M的盐反应，得到的产物进行热处理，制得所述催化剂。
5.根据权利要求4所述的制备方法，其特征在于，步骤(1)中，所述碳氮化合物选自尿素、三聚氰胺或者双氰胺中的至少一种；步骤(1)中，对碳氮化合物加热的温度为500-600℃，发生反应的时间为2-5小时；步骤(1)中，富氮化合物、钴盐、咪唑类物质的质量比为(0.1-0.5)∶(0.2-1)∶(0.3-1)。
6.根据权利要求4所述的制备方法，其特征在于，步骤(1)中，所述富氮化合物、钴盐、咪唑类物质反应的过程中，是先将富氮化合物、钴盐溶解于溶剂中，获得溶液A；然后将咪唑类物质溶解于溶剂中，获得溶液B，再在1000-2000转/分钟的搅拌速度下，将溶液B倒入溶液A中，搅拌12-24小时，得到悬浮液，洗涤，离心，干燥，制得纳米复合材料。
7.根据权利要求4所述的制备方法，其特征在于，步骤(2)的具体过程为：将负载Co的载体与溶剂混合，制得悬浮液，然后加入贵金属M的盐，在800-1200转/分钟的搅拌速度下搅拌10-14小时，离心获得沉淀物，洗涤，烘干，获得的产物在H2 /Ar的流动氛围下在150-300℃下处理1-3小时，制得所述催化剂。
8.权利要求1-3中任一项所述的催化剂在醛酮化合物、喹啉类化合物、硝基化合物、酚类化合物、烯或炔类化合物、或杂环化合物的定向氢化反应，以及在苄醇的选择性氧化反应中的应用。
9.根据权利要求8所述的应用，其特征在于，所述应用中，用于醛酮化合物、喹啉类化合物、硝基化合物、酚类化合物、烯或炔类化合物、或杂环化合物的定向氢化反应的具体过程为：将5-15mL的去离子水加入到50mL高压反应釜中，再加入底物和催化剂，底物与催化剂的摩尔比为(200-6000)∶1，高压反应釜中充入0.2-1.0MPa的H2 ，在25-100℃下搅拌30-360min，冷却，将剩余氢气排除，离心分离催化剂。
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