CN111729678A - 一种负载铜钯的介孔碳化硅基催化剂及其制备方法与应用 - Google Patents

一种负载铜钯的介孔碳化硅基催化剂及其制备方法与应用 Download PDF

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CN111729678A
CN111729678A CN202010622992.7A CN202010622992A CN111729678A CN 111729678 A CN111729678 A CN 111729678A CN 202010622992 A CN202010622992 A CN 202010622992A CN 111729678 A CN111729678 A CN 111729678A
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copper
mesoporous silicon
silicon carbide
palladium
based catalyst
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范建伟
王玥
张伟贤
滕玮
冉献强
余备
陈小倩
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Tongji University
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Abstract

本发明公开了一种负载铜钯的介孔碳化硅基催化剂及其制备方法与应用，首先以介孔二氧化硅为硬模板制备介孔碳化硅材料；随后将介孔碳化硅材料与钯和铜的前驱体混合溶液混合，溶剂完全挥发后干燥；干燥后的粉末先后经N2煅烧、H2还原，最终得到负载钯铜的介孔碳化硅基催化剂。将该催化剂制成电极，通过电化学法催化还原水体中的硝酸盐。本发明的催化剂制备方法简单，在低金属负载量下该催化剂即可实现高效催化脱氮，产物氮气选择性高，具备活性高、稳定性好、适用范围广、成本低的优势。

Description

一种负载铜钯的介孔碳化硅基催化剂及其制备方法与应用
技术领域
本发明涉及催化剂制备及应用的技术领域，尤其涉及一种负载铜钯的介孔碳化硅基催化剂及其制备方法与应用。
背景技术
化石燃料、植物和垃圾的燃烧，生活污水、工业废水和畜牧废水的未处理排放以及含氮化肥的大量合成和过量使用等人类活动造成了水体硝酸盐污染。水体硝酸盐污染严重危害生态环境和人体健康。传统的脱氮处理技术(物理法、生物法、活泼金属还原法、化学催化加氢法)，存在操作复杂、需要后续处理、造成二次污染、潜在安全隐患等局限。与之相比，电催化技术更加简便、高效、安全、经济，可应用于水体脱氮。钯铜催化体系具备催化还原硝态氮的活性，但其脱氮效率和产物氮气选择性仍需进一步提高。
发明内容
针对上述现有技术的缺陷与不足，提供一种负载铜钯的介孔碳化硅基催化剂的制备方法，包括如下步骤：S1、将P123、去离子水、盐酸、正四硅酸乙酯进行混合搅拌，得到均匀溶液，将所述均匀溶液在40C的水浴中搅拌24h后倒入水热釜，进行进行晶化，再经冷却、过滤、干燥后置于马弗炉中进行煅烧，得到介孔二氧化硅，介孔二氧化硅为制备介孔碳化硅的硬模板；S2、将聚碳硅烷溶于二甲苯中得到聚碳硅烷溶液，聚碳硅烷的数均分子量为1500～2500，将介孔二氧化硅与聚碳硅烷溶液混合搅拌，待二甲苯溶剂完全挥发后进行干燥，干燥后的粉末经煅烧、刻蚀、洗涤、干燥，得到介孔碳化硅；S3、将PdCl2和Cu(NO3)2·3H2O进行混合得到铜钯前驱体混合溶液；S4、向所述铜钯前驱体混合溶液中加入所述介孔碳化硅，待溶剂完全挥发后干燥，干燥后的粉末于管式炉中先后经氮气气氛煅烧、氢气气氛还原，得到所述负载钯铜的介孔碳化硅基催化剂。
较佳地，步骤S1中，所述均匀溶液的各组分的配方为：每2g P123，水的用量为63.95ml，盐酸的用量为10ml，正四硅酸乙酯的用量为4.25g；将P123、水、盐酸进行混合搅拌，再滴加正四硅酸乙酯，得到所述均匀溶液。
较佳地，步骤S1中：晶化温度为130C，时间为72h；煅烧条件为：以空气为气氛，煅烧要求温度为550C，升温速率1C/min，煅烧时间6h。
较佳地，聚碳硅烷溶液中聚碳硅烷的浓度为10wt％，介孔二氧化硅和聚碳硅烷按质量比1:(1～1.2)混合。
较佳地，步骤S2中：干燥温度为80℃，干燥时间为12h；刻蚀为与过量4wt％HF水溶液混合搅拌24h。
较佳地，步骤S2中的煅烧过程为：以氮气为气氛，首先以2℃/min的速率升温至350℃，保温5h；随后以0.5℃/min的速率升温至700℃；继而以2℃/min的速率升温至1200～1400℃，保温2h；最后在氮气保护下自然冷却至室温。
较佳地，所述铜钯前驱体混合溶液中：钯的质量体积浓度为0.1～5g/L；铜的质量体积浓度为0.05～2.5g/L；钯铜的质量比为2:1。
较佳地，步骤S4中：所述的介孔碳化硅在所述铜钯前驱体混合溶液中的质量体积浓度为100g/L；干燥温度为80℃，时间为12h；煅烧、还原条件为：要求温度400℃，升温速率1℃/min；氮气气氛煅烧时间为3h，氢气气氛还原时间为1h。
本发明还提供了一种负载铜钯的介孔碳化硅基催化剂，采用所述负载铜钯的介孔碳化硅基催化剂的制备方法制备而成。
本发明还提供了一种负载铜钯的介孔碳化硅基催化剂的应用，采用所述负载铜钯的介孔碳化硅基催化剂，
本发明由于采用以上技术方案，使之与现有技术相比，具有以下的优点和积极效果：
1、本发明提供的负载铜钯的介孔碳化硅基催化剂及其制备方法与应用，将钯、铜作为催化脱氮的活性组分，介孔碳化硅既为催化剂载体又为产氢催化剂；且催化剂制备方法简单，制备得到的催化剂即使在低负载量时也可高效催化还原硝态氮，产物氮气选择性高，可用于多种初始浓度、pH的硝态氮污染水的电催化脱氮反应。
2、本发明提供的负载铜钯的介孔碳化硅基催化剂及其制备方法与应用，以介孔碳化硅基材料作为催化剂载体，一方面，介孔碳化硅能够将钯铜稳定分散在介孔孔道中，防止钯铜活性组分团聚，并提供更多的活性位点，从而提高钯铜的催化脱氮活性；另一方面，介孔碳化硅具备热稳定性、化学稳定性和高机械强度，且能自催化水电解产氢，氢气可以促进脱氮反应，从而使得本发明所制备的负载钯铜的介孔碳化硅基催化剂的催化效果优于其他负载钯铜的催化剂。
附图说明
图1为本发明的第一实施例中负载铜钯的介孔碳化硅基材料的SEM照片；
图2为本发明的第二实施例中负载铜钯的介孔碳化硅基材料的SEM照片；
图3为本发明的第三实施例中负载铜钯的介孔碳化硅基材料的SEM照片；
图4为本发明的第一实施例中负载铜钯的介孔碳化硅基材料的TEM照片；
图5为本发明的第二实施例中负载铜钯的介孔碳化硅基材料的TEM照片；
图6为本发明的第三实施例中负载铜钯的介孔碳化硅基材料的TEM照片；
图7为本发明的第一实施例、第二实施例、第三实施例和现有技术对比例中催化剂催化反应体系的硝态氮去除率和产物氮气选择性；
图8为本发明的第一实施例中催化剂在NO3 --N的浓度为100～500mg/L的中性反应体系中的硝态氮去除率和产物氮气选择性；
图9为本发明的第一实施例中催化剂在NO3 --N的浓度为100mg/L、初始pH为3～11的反应体系中的硝态氮去除率和产物氮气选择性。
具体实施方式
以下参见示出的本发明实施例的附图，下文将更详细地描述本发明。然而，本发明可以以许多不同形式实现，并且不应解释为受在此提出之实施例的限制。相反，提出这些实施例是为了达成充分及完整公开，并且使本技术领域的技术人员完全了解本发明的范围。这些附图中，为清楚起见，可能放大了层及区域的尺寸及相对尺寸。
下面通过三个实施例和一个现有技术对比例来具体说明。
第一实施例，负载钯铜的介孔碳化硅基催化剂的制备方法，包括以下步骤：
(1)取2g表面活性剂P123、63.95ml去离子水和10ml盐酸(12M)放入烧杯中，搅拌至完全溶解后，向其中滴加4.25g正四硅酸乙酯，在40℃水浴中进行机械搅拌24h后倒入水热釜；随后将水热釜置于130℃的烘箱中静止晶化72h，经冷却、过滤、干燥后置于550℃的马弗炉中煅烧6h，得到介孔二氧化硅；
(2)取5g介孔二氧化硅加入到含有6g聚碳硅烷的10wt％聚碳硅烷的二甲苯溶液中，混合搅拌至二甲苯溶剂完全挥发，随后置于80℃的烘箱中进行干燥12h；干燥后置于管式炉中，在氮气气氛下煅烧，首先以2℃/min的速率升温至350℃并保温5h，随后以0.5℃/min的速率升温至700℃，继而以2℃/min的速率升温至1400℃并保温2h，最后在氮气保护下自然冷却至室温；取冷却后的粉末加入到过量的4wt％HF水溶液中，在室温下搅拌24h后，经反复洗涤、过滤、干燥后得到介孔碳化硅，干燥条件为80℃，时间为12h；
(3)将PdCl2和Cu(NO3)2·3H2O进行混合得到铜钯前驱体混合溶液，铜钯前驱体混合溶液中钯的质量体积浓度为0.1g/L，铜的质量体积浓度为0.05g/L；
(4)取1g介孔碳化硅加入到10ml的铜钯前驱体混合溶液中，混合搅拌至溶剂完全挥发后，于80C的烘箱中干燥12h，干燥后置于管式炉中，以1C/min升温至400C，在氮气气氛下煅烧3h，氢气气氛下还原1h，得到负载钯(0.1％)铜(0.05％)的介孔碳化硅基催化剂，表面形貌如图1和图4所示。
取4mg负载钯(0.1％)铜(0.05％)的介孔碳化硅基催化剂涂在镍网上制成工作电极，铂电极作为对电极，饱和甘汞电极作为参比电极。把三电极放在体积为20ml、NO3 --N的浓度为100mg/L的中性溶液中，施加-1.5V电压，反应24h，然后测反应后硝态氮浓度，计算硝态氮去除率和产物氮气选择性，结果如图7所示。
把三电极放在NO3 --N的浓度分别为200mg/L、300mg/L、500mg/L的中性溶液中，施加-1.5V电压，反应24h，然后测反应后硝态氮浓度，计算硝态氮去除率和产物氮气选择性，结果如图8所示，可以看出，本发明所制备的负载钯铜的介孔碳化硅基催化剂可用于多种初始浓度的硝态氮污染水的电催化脱氮反应。
把三电极放在NO3 --N的浓度为100mg/L、初始pH分别为3-11的溶液中，施加-1.5V电压，反应24h，然后测反应后硝态氮浓度，计算硝态氮去除率和产物氮气选择性，结果如图9所示，可以看出，本发明所制备的负载钯铜的介孔碳化硅基催化剂可用于多种初始pH的硝态氮污染水的电催化脱氮反应。
第二实施例，负载钯铜的介孔碳化硅基催化剂的制备方法，包括以下步骤：
(1)取2g表面活性剂P123、63.95ml去离子水和10ml盐酸(12M)放入烧杯中，搅拌至完全溶解后向其中滴加4.25g正四硅酸乙酯，在40C水浴中进行机械搅拌24h后倒入水热釜，随后将水热釜置于烘箱中130C静止晶化72h，经冷却、过滤、干燥后置于马弗炉中550C煅烧6h，得到介孔二氧化硅；
(2)取5g介孔二氧化硅加入到含有6g聚碳硅烷的10wt％聚碳硅烷的二甲苯溶液中，混合搅拌至二甲苯溶剂完全挥发，置于80C的烘箱中干燥12h；干燥后置于管式炉中，在氮气气氛下煅烧，首先以2C/min的速率升温至350C并保温5h，随后以0.5C/min的速率升温至700C，继而以2C/min的速率升温至1400C并保温2h，最后在氮气保护下自然冷却至室温；取冷却后的粉末加入到过量的4wt％HF水溶液中，在室温下搅拌24h后，经反复洗涤、过滤、干燥后得到介孔碳化硅，干燥条件为80℃，时间为12h；
(3)将PdCl2和Cu(NO3)2·3H2O进行混合得到铜钯前驱体混合溶液，铜钯前驱体混合溶液中钯的质量体积浓度为1g/L，铜的质量体积浓度为0.5g/L；
(4)取1g介孔碳化硅加入到10ml的铜钯前驱体混合溶液中，混合搅拌至溶剂完全挥发，于80C的烘箱中干燥12h，干燥后置于管式炉中，以1C/min升温至400C，在氮气气氛下煅烧3h，氢气气氛下还原1h，得到负载钯(1％)铜(0.5％)的介孔碳化硅基催化剂，表面形貌如图2和图5所示。
取4mg负载钯(1％)铜(0.5％)的介孔碳化硅基催化剂涂在镍网上制成工作电极，铂电极作为对电极，饱和甘汞电极作为参比电极，把三电极放在体积为20ml、NO3 --N的浓度为100mg/L的中性溶液中，施加-1.5V电压，反应24h，然后测反应后硝态氮浓度，计算硝态氮去除率和产物氮气选择性，结果如图7所示。
第三实施例，负载钯铜的介孔碳化硅基催化剂的制备方法，包括以下步骤，
(1)取2g表面活性剂P123、63.95ml去离子水和10ml盐酸(12M)放入烧杯中，搅拌至完全溶解后向其中滴加4.25g正四硅酸乙酯TEOS，在40C水浴中机械搅拌24h后倒入水热釜，随后将水热釜置于烘箱中130C静止晶化72h，经冷却、过滤、干燥后置于马弗炉中550C煅烧6h，得到介孔二氧化硅；
(2)取5g介孔二氧化硅加入到含有6g聚碳硅烷的10wt％聚碳硅烷的二甲苯溶液中，混合搅拌至二甲苯溶剂完全挥发，于80C的烘箱中干燥12h；干燥后置于管式炉中，在氮气气氛下煅烧，首先以2C/min的速率升温至350C并保温5h，随后以0.5C/min的速率升温至700C，继而以2C/min的速率升温至1400C并保温2h，最后在氮气保护下自然冷却至室温；取冷却后的粉末加入到过量的4wt％HF水溶液中，在室温下搅拌24h后，经反复洗涤、过滤、干燥后得到介孔碳化硅，干燥条件为80℃，时间为12h；
(3)将PdCl2和Cu(NO3)2·3H2O进行混合得到铜钯前驱体混合溶液，铜钯前驱体混合溶液中钯的质量体积浓度为5g/L，铜的质量体积浓度为2.5g/L；
(4)取1g介孔碳化硅加入到10ml的铜钯前驱体混合溶液中，混合搅拌至溶剂完全挥发，于烘箱中80C干燥12h将干燥后置于管式炉中，以1C/min升温至400C，在氮气气氛下煅烧3h，氢气气氛下还原1h，得到负载钯(5％)铜(2.5％)的介孔碳化硅基催化剂，表面形貌如图3和图6所示。
取4mg负载钯(5％)铜(2.5％)的介孔碳化硅基催化剂涂在镍网上制成工作电极，铂电极作为对电极，饱和甘汞电极作为参比电极，把三电极放在体积为20ml、NO3 --N的浓度为100mg/L的中性溶液中，施加-1.5V电压，反应24h，然后测反应后硝态氮浓度，计算硝态氮去除率和产物氮气选择性，结果如图7所示。
现有技术对比例，制备负载钯铜的氮掺杂介孔碳基催化剂，将其应用于电催化去除水体中的硝酸盐，具体，取4mg催化剂涂在镍网上制成工作电极，铂电极作为对电极，饱和甘汞电极作为参比电极，把三电极放在体积为20ml、NO3 --N的浓度为100mg/L的中性溶液中，施加-1.5V电压，反应24h，然后测反应后硝态氮浓度，计算硝态氮去除率和产物氮气选择性，结果如图7所示。
从图7可以看出，本发明所制备的负载钯铜的介孔碳化硅基催化剂在低负载量时即具有较高的催化活性。相比现有钯铜催化体系，本发明催化剂在电催化去除水体中的硝酸氮时，去除率更高，产物氮气选择性显著提高；尤其是第一实施例中的钯铜负载量分别为0.1％和0.05％时，硝态氮的去除率为94.5％，产物氮气选择性高达91.2％。
因本技术领域的技术人员应理解，本发明可以以许多其他具体形式实现而不脱离其本身的精神或范围。尽管已描述了本发明的实施案例，应理解本发明不应限制为这些实施例，本技术领域的技术人员可如所附权利要求书界定的本发明的精神和范围之内做出变化和修改。

Claims (10)

1.一种负载铜钯的介孔碳化硅基催化剂的制备方法，其特征在于，包括如下步骤：
S1、将P123、水、盐酸、正四硅酸乙酯进行混合搅拌，得到均匀溶液，将所述均匀溶液水浴搅拌后进行晶化，再经冷却、过滤、干燥后进行煅烧，得到介孔二氧化硅；
S2、将聚碳硅烷溶于二甲苯中得到聚碳硅烷溶液，聚碳硅烷的数均分子量为1500～2500；将介孔二氧化硅与聚碳硅烷溶液混合搅拌，待二甲苯溶剂完全挥发后进行干燥，干燥后的粉末经煅烧、刻蚀、洗涤、干燥，得到介孔碳化硅；
S3、将PdCl2和Cu(NO3)2·3H2O进行混合得到铜钯前驱体混合溶液；
S4、向所述铜钯前驱体混合溶液中加入所述介孔碳化硅，待溶剂完全挥发后干燥，干燥后的粉末先后经氮气气氛煅烧、氢气气氛还原，得到所述负载钯铜的介孔碳化硅基催化剂。
2.根据权利要求1所述的负载铜钯的介孔碳化硅基催化剂的制备方法，其特征在于，步骤S1中，所述均匀溶液的各组分的配方为：每2g P123，水的用量为63.95ml，盐酸的用量为10ml，正四硅酸乙酯的用量为4.25g；将P123、水、盐酸进行混合搅拌，再滴加正四硅酸乙酯，得到所述均匀溶液。
3.根据权利要求1或2所述的负载铜钯的介孔碳化硅基催化剂的制备方法，其特征在于，步骤S1中：
晶化温度为130℃，时间为72h；
煅烧条件为：以空气为气氛，煅烧要求温度为550℃，升温速率1C/min，煅烧时间6h。
4.根据权利要求1所述的负载铜钯的介孔碳化硅基催化剂的制备方法，其特征在于，聚碳硅烷溶液中聚碳硅烷的浓度为10wt％，介孔二氧化硅和聚碳硅烷按质量比1:(1～1.2)混合。
5.根据权利要求1或4所述的负载铜钯的介孔碳化硅基催化剂的制备方法，其特征在于，步骤S2中：
干燥温度为80℃，干燥时间为12h；
刻蚀为与过量4wt％HF水溶液混合搅拌24h。
6.根据权利要求1所述的负载铜钯的介孔碳化硅基催化剂的制备方法，其特征在于，步骤S2中的煅烧过程为：以氮气为气氛，首先以2℃/min的速率升温至350℃，保温5h；随后以0.5℃/min的速率升温至700℃；继而以2℃/min的速率升温至1200～1400℃，保温2h；最后在氮气保护下自然冷却至室温。
7.根据权利要求1所述的负载铜钯的介孔碳化硅基催化剂的制备方法，其特征在于，所述铜钯前驱体混合溶液中：钯的质量体积浓度为0.1～5g/L；铜的质量体积浓度为0.05～2.5g/L；钯铜的质量比为2:1。
8.根据权利要求1所述的负载铜钯的介孔碳化硅基催化剂的制备方法，其特征在于，步骤S4中：
所述的介孔碳化硅在所述铜钯前驱体混合溶液中的质量体积浓度为100g/L；
干燥温度为80℃，时间为12h；
煅烧、还原条件为：要求温度400℃，升温速率1℃/min；氮气气氛煅烧时间为3h，氢气气氛还原时间为1h。
9.一种负载铜钯的介孔碳化硅基催化剂，采用上述权利要求1-8所述的负载铜钯的介孔碳化硅基催化剂的制备方法制备而成。
10.一种负载铜钯的介孔碳化硅基催化剂的应用，采用权利要求9所述的负载铜钯的介孔碳化硅基催化剂，其特征在于，将所述负载钯铜的介孔碳化硅基催化剂作为工作电极，铂电极作为对电极，饱和甘汞电极作为参比电极；
将工作电极、对电极和参比电极置于硝酸盐溶液中，得到进行脱氮反应的电催化系统，所述脱氮反应时间为24h、反应温度为室温、工作电极的电压为-1.5V；
所述硝酸盐溶液中NO3 --N的浓度为100～500mg/L，初始pH为3～11；
电催化体系中：硝酸盐溶液体积为20ml、所述负载铜钯的介孔碳化硅基催化剂为4mg。
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