CN109395783B - 一种四氧化三钴@聚多巴胺催化剂及其制备方法 - Google Patents
一种四氧化三钴@聚多巴胺催化剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种用于CO催化氧化的高抗水性四氧化三钴@聚多巴胺催化剂及其制备方法,制备方法包括以下步骤:在水和乙醇反应介质中,以六水硝酸钴为钴源,采用水热法合成制得Co(OH)2前驱体;在一定条件下,通过焙烧将前驱体转变为四氧化三钴纳米线;于一定pH值的三羟甲基氨基甲烷缓冲溶液中,在四氧化三钴纳米线表面包裹一层聚多巴胺,即得到产品。本发明的优点是:制备工艺简单,原材料易得、价格低廉、对环境无污染,成本低、产率高,适合工业化生产,解决了催化有毒气体CO氧化过程中遇到水汽容易失活的缺点。
Description
技术领域
本发明涉及纳米材料制备领域,具体涉及一种用于CO催化氧化的高抗水性四氧化三钴@聚多巴胺催化剂及其制备方法。
背景技术
CO是一种无色无味的有毒气体,其排放量远远高于氮氧化合物和碳氢化合物。CO与人体内的血红蛋白结合后,轻者产生头疼、头昏、心悸、恶心、呕吐症状,加重时出现不同意识障碍,如神志恍惚、全身无力、意识模糊、嗜睡或突然昏倒,严重者呈深昏迷、强直性抽搐、呼吸循环衰竭。因此,如何消除或者降低CO排放量尤为必要。
通过催化氧化消除CO的传统催化剂以贵金属为主,包括Au和Pt。但其价格昂贵,资源有限,尤其是金属纳米颗粒在高温环境中或者放热反应条件下容易团聚长大造成失活。以Co3O4为代表的非贵金属氧化物是一类非常有潜力的替代催化剂,其对CO催化氧化的活性甚至优异于贵金属,但是在应用过程中遇到的一个重要问题是反应体系中存在少量的水或者水汽,即使2ppm的水氛,也会造成催化剂的失活。
发明内容
为了克服现有技术的不足,本发明提供一种用于CO催化氧化的高抗水性四氧化三钴@聚多巴胺催化剂及其制备方法,该制备方法步骤简单、成本低廉、可大规模生产四氧化三钴@聚多巴胺。
本发明的目的通过以下技术方案实现:
一种用于CO催化氧化的高抗水性四氧化三钴@聚多巴胺催化剂的制备方法,该制备方法为:
(1)在水和乙醇反应介质中,加入钴源,采用水热法合成制得Co(OH)2前驱体,通过焙烧,将Co(OH)2前驱体转变为Co3O4纳米线;
(2)将Co3O4纳米线加入三羟甲基氨基甲烷缓冲溶液中,再加入多巴胺,在Co3O4纳米线表面包裹一层聚多巴胺,即得到产品。
进一步地,具体步骤为:
(1)将高纯水和乙醇等体积混合,加入钴源和尿素,进行超声分散,得到混合液;
(2)将混合液在设定温度下进行恒温反应,反应结束后,将反应液冷却至室温得到固体产物,经离心分离、洗涤、干燥,即得Co(OH)2前驱体;
(3)将Co(OH)2前驱体以一定升温速率升至设定温度并保持一段时间,得Co3O4纳米线;
(4)将Co3O4纳米线置于pH=8.5的三羟甲基氨基甲烷缓冲溶液中,超声完全后,取多巴胺置于上述缓冲液中,搅拌、离心、真空干燥,即得四氧化三钴@聚多巴胺催化剂。
进一步地,所述钴源为六水合硝酸钴。
进一步地,所述六水合硝酸钴的质量与乙醇的体积比为0.01-0.04g/ml,优选为0.02g/ml。
进一步地,所述尿素与六水合硝酸钴的质量比为1:1-1.3。
进一步地,步骤(2)所述混合液反应温度为60-120℃,反应时间为6-10小时,优选反应温度为90℃,反应时间为8小时。
进一步地,步骤(3)升温速率为1-5℃/分钟,设定温度为200-400℃,保持时间2-4小时,优选升温速率为2℃/分钟,设定温度为300℃,保持时间3小时。
进一步地,步骤(4)所述多巴胺与Co3O4纳米线的质量比为0.2-2。
进一步地,步骤(4)所述多巴胺与Co3O4纳米线的质量比为0.4-1。
一种用于CO催化氧化的高抗水性四氧化三钴@聚多巴胺催化剂,采用上述制备方法制备得到。
与现有技术相比,本发明所采用的工艺步骤制简单,原材料易得、所使用原料之间无相互反应,价格低廉、对环境无污染,产率高,适合工业化生产。在Co3O4纳米线表面包裹一层聚多巴胺的过程,是比较关键的反应步骤,利用高分子多巴胺的疏水性能,创造性地解决了Co3O4催化有毒气体CO氧化过程中遇到水汽容易失活的缺点,使得Co3O4纳米线替代传统意义上的Pt、Au等贵金属催化剂提供了宝贵方案。总之,此研究结果为企业,科研工作者等都提供了很好设计材料的思路,以及对该材料应用的开展。
附图说明
图1为实施例1中Co3O4纳米线的透射电子显微镜照片;
图2为实施例2中Co3O4@聚多巴胺-200的透射电子显微镜照片;
图3为实施例3中Co3O4@聚多巴胺-300的透射电子显微镜照片;
图4为实施例4中Co3O4@聚多巴胺-400的透射电子显微镜照片;
图5为实施例5中Co3O4@聚多巴胺-500的透射电子显微镜照片;
图6为实施例2-5中Co3O4@聚多巴胺-200、Co3O4@聚多巴胺-300、Co3O4@聚多巴胺-400和Co3O4@聚多巴胺-500的氮气吸-脱附等温线;
图7为实施例2-5中Co3O4@聚多巴胺-200、Co3O4@聚多巴胺-300、Co3O4@聚多巴胺-400和Co3O4@聚多巴胺-500的X射线衍射图谱;
图8为实施例1中制得的Co3O4纳米线和实施例5中制得的Co3O4@聚多巴胺-500催化剂分别在水汽浓度为20000ppm时催化CO氧化稳定性的测试结果。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
将0.87g六水合硝酸钴和0.72g尿素溶于40ml超纯水和40ml乙醇中,置于容量为100mL带有聚四氟乙烯的水热反应釜中,超声5分钟。再将水热反应釜拧紧密封,置于90℃恒温烘箱中静置8小时。生成的固体产物用去离子水洗涤三次,置于80℃恒温烘箱中静置12小时,即得Co(OH)2前驱体。将Co(OH)2前驱体置于管式炉中,在空气氛围下以2℃/分钟的升温速率升至300℃,并在300℃保持3个小时,即得Co3O4纳米线。图1为Co3O4纳米线的透射电子显微镜照片。
实施例2
取200mg实施例1中制得的Co3O4纳米线,置于pH=8.5的三羟甲基氨基甲烷缓冲溶液中,超声20分钟。将500mg多巴胺加入上述悬浊液中,搅拌24小时,离心,真空干燥,即得到Co3O4@聚多巴胺-200。图2为Co3O4@聚多巴胺-200的透射电子显微镜照片,图6中有Co3O4@聚多巴胺-200的氮气吸-脱附等温线,图7中有Co3O4@聚多巴胺-200的X射线衍射图谱。
实施例3
取300mg实施例1中制得的Co3O4纳米线,置于pH=8.5的三羟甲基氨基甲烷缓冲溶液中,超声20分钟。将500mg多巴胺加入上述悬浊液中,搅拌24小时,离心,真空干燥,即得到Co3O4@聚多巴胺-300。图3为Co3O4@聚多巴胺-300的透射电子显微镜照片,图6中有Co3O4@聚多巴胺-300的氮气吸-脱附等温线,图7中有Co3O4@聚多巴胺-300的X射线衍射图谱。
实施例4
取400mg实施例1中制得的Co3O4纳米线,置于pH=8.5的三羟甲基氨基甲烷缓冲溶液中,超声20分钟。将500mg多巴胺加入上述悬浊液中,搅拌24小时,离心,真空干燥,即得到Co3O4@聚多巴胺-400。图4为Co3O4@聚多巴胺-400的透射电子显微镜照片,图6中有Co3O4@聚多巴胺-400的氮气吸-脱附等温线,图7中有Co3O4@聚多巴胺-400的X射线衍射图谱。
实施例5
取500mg实施例1中制得的Co3O4纳米线,置于pH=8.5的三羟甲基氨基甲烷缓冲溶液中,超声20分钟。将500mg多巴胺加入上述悬浊液中,搅拌24小时,离心,真空干燥,即得到Co3O4@聚多巴胺-500。图5为Co3O4@聚多巴胺-500的透射电子显微镜照片,图6中有Co3O4@聚多巴胺-500的氮气吸-脱附等温线,图7中有Co3O4@聚多巴胺-500的X射线衍射图谱。
催化剂性能测试:
将实施例1中制得的Co3O4纳米线和实施例5中制得的Co3O4@聚多巴胺-500催化剂分别用于有水汽氛围中的CO氧化,具体实验步骤:
在固定床中对催化剂的稳定性进行测试,首先将催化剂装填在反应管中,用热电偶检测催化剂床层的温度,然后通入水汽浓度为20000ppm的反应气(1%CO,20%O2,其余为氦气)。
图8为实施例1中制得的Co3O4纳米线和实施例5中制得的Co3O4@聚多巴胺-500催化剂分别在水汽浓度为20000ppm时催化CO氧化稳定性的测试结果。可以看出,在20000ppm水汽气氛中,Co3O4纳米线迅速失活,而Co3O4@聚多巴胺-500催化剂具有高稳定性,CO转化率始终稳定在100%,并可稳定运行100h以上。
以上所述为本发明较佳实例而已,但本发明不应该局限于该实例所公开的内容。所以凡是不脱离本发明所公开的精神下完成的等效或修改,都落入本发明保护的范围。
Claims (6)
1.一种用于CO催化氧化的高抗水性Co3O4@聚多巴胺催化剂的制备方法,其特征在于,该制备方法为:
(1)将高纯水和乙醇等体积混合,加入钴源和尿素,进行超声分散,得到混合液;
(2)将混合液在设定温度下进行恒温反应,反应结束后,将反应液冷却至室温得到固体产物,经离心分离、洗涤、干燥,即得Co(OH)2前驱体;
(3)将Co(OH)2前驱体以一定升温速率升至设定温度并保持一段时间,得Co3O4纳米线;
(4)将Co3O4纳米线置于pH=8.5的三羟甲基氨基甲烷缓冲溶液中,超声完全后,取多巴胺置于上述缓冲液中,搅拌、离心、真空干燥,即得Co3O4@聚多巴胺催化剂;
所述钴源为六水合硝酸钴;
所述六水合硝酸钴的质量与乙醇的体积比为0.01-0.04g/ml;
所述尿素与六水合硝酸钴的质量比为1:1-1.3;
步骤(2)所述混合液反应温度为60-120℃,反应时间为6-10小时;
步骤(3)升温速率为1-5℃/分钟,设定温度为200-400℃,保持时间2-4小时;
步骤(4)所述多巴胺与Co3O4纳米线的质量比为0.2-2。
2.根据权利要求1所述的一种用于CO催化氧化的高抗水性Co3O4@聚多巴胺催化剂的制备方法,其特征在于,所述六水合硝酸钴的质量与乙醇的体积比为0.02g/ml。
3.根据权利要求1所述的一种用于CO催化氧化的高抗水性Co3O4@聚多巴胺催化剂的制备方法,其特征在于,步骤(2)所述混合液反应温度为90℃,反应时间为8小时。
4.根据权利要求1所述的一种用于CO催化氧化的高抗水性Co3O4@聚多巴胺催化剂的制备方法,其特征在于,步骤(3)升温速率为2℃/分钟,设定温度为300℃,保持时间3小时。
5.根据权利要求1所述的一种用于CO催化氧化的高抗水性Co3O4@聚多巴胺催化剂的制备方法,其特征在于,步骤(4)所述多巴胺与Co3O4纳米线的质量比为0.4-1。
6.一种用于CO催化氧化的高抗水性Co3O4@聚多巴胺催化剂,其特征在于,采用如权利要求1所述的制备方法制备得到。
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