CN115090288B - 一种磁控合成金属钴催化剂的方法 - Google Patents
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Abstract
本发明公布了一种磁控合成金属钴催化剂的方法,属于新材料领域。所述方法通过改变外磁场的强度和作用时间磁控合成不同形貌、不同结构的钴微米花、钴微米棒。所述金属钴对以过硫酸盐、双氧水、芬顿试剂为氧化剂的反应过程具有高催化活性,可以对染料、抗生素、农业、表面活性剂等难降解有机物进行高效催化降解。本发明方法可实现金属钴催化剂的绿色高效制备,工艺简单,经改造后适于工业生产。由于所述金属钴催化剂催化活性高、抗无机盐、添加量少、可高效磁分离,因此适于处理各种难降解工业污水,运行成本低,满足工业生产实际的要求。
Description
一、技术领域
本发明涉及新材料领域,涉及一种磁控合成金属钴催化剂的方法,具体地说是一种利用不同磁场强度制备不同结构钴微米花催化剂的方法。
二、背景技术
目前,金属钴催化剂由于其降解污水效果好而广受研究学者欢迎,但其制备方法各有难点,且制备数量不大。钴作为一种铁磁性过渡金属,由于具有高饱和磁感应强度和高磁导率等独特的性能,在电磁吸收和催化降解等众多领域具有广泛的应用。通常钴颗粒的物理化学性质与其微观形貌有着密切关系,使得制备具有不同形貌的金属钴成为研究学者关注的热点。公开号为CN113059179A的专利采用溶剂热法一步制备出具有海胆状和多孔状形貌的磁性钴颗粒,但其合成过程中并未研究外加磁场对其形貌的影响,且对其催化降解性能并未做研究。文献(DOI:10.3969/j.issn.1001—9731.2017.11.033)采用无模板液相还原法制备得到钴纳米线,并探究了不同温度和pH值以及磁场对其形貌的影响。公开号为CN103055869A的专利采用真空电弧炉熔炼钴铝合金,并利用氢等离子体金属反应法制备钴铝纳米颗粒,然后利用去合金化反应制备多孔钴纳米颗粒,该方法反应过程繁琐,对设备即研究人员的操作要求较高,且所制备出的多孔钴为面心立方结构钴和氧化钴的混合物。公开号为CN113122878A专利采用水热反应获得氮掺杂碳复合石墨烯前驱体,再将钴盐及获得的氮掺杂碳复合石墨烯前驱体经络合反应获得氮掺杂碳复合石墨烯包覆金属钴前驱体,最后将获得氮掺杂碳复合石墨烯包覆金属前驱体,在氢气与氩气的混合氛围下,于300~600℃反应1~6h,即得所述氮掺杂碳复合石墨烯包覆金属钴催化剂。这些方法制备过程较为复杂、反应温度要求较高、周期长、不适合工业快速生产。
三、发明内容
本发明是为弥补用过硫酸氢钾降解染料污水速度的不足,提供一种高效的利用磁控合成金属钴催化剂催化降解的方法;再加上可方便的利用磁分离进行固液分离回收,因此可大大提升催化剂的循环利用性能。
一种磁控合成金属钴催化剂的方法,包括如下步骤:
步骤1:取适量聚乙烯吡咯烷酮溶于无水乙醇中,超声震荡并充分搅拌后制备成浓度为2~6g·L-1的聚乙烯吡咯烷酮混合液。按照钴含量5~15g·L-1的配比称取溶解性钴盐,放入聚乙烯吡咯烷酮混合液中,充分搅拌使其完全反应,生成蓝色絮状溶液。
步骤2:按一定量取水合肼溶液并用碱溶液调节pH至10以上。将钴盐溶液缓慢与水合肼在玻璃或聚四氟乙烯反应釜中混合,搅拌均匀后放入水浴锅中。
步骤3:60℃-90℃水浴3-30分钟,待溶液完全变为粉紫色并有微量汽包产生时,转移烧杯或反应釜等容器至匀强磁场中。
步骤4:依据对金属Co产物形貌的要求,调控匀强磁场的场强在20-600mT之间,并控制磁场作用时间,当反应全部完成后产生黑色钴絮状沉淀,溶液由粉紫色转变为无色透明。
步骤5:将黑色钴絮状沉淀用磁铁分离出来后反复用无水乙醇和去离子水清洗后,在真空烘箱中烘干。经简单研磨后,即获得金属钴催化剂。
优选地,所述碱溶液是指氢氧化钠或氨水溶液。
优选地,所述溶解性钴盐是指CoCl2·6H2O、乙酸钴等无机钴盐和环烷酸钴、硬脂酸钴、新癸酸钴等有机钴盐。
优选地,所述匀强磁场由永磁体或电磁铁产生,永磁体产生的场强为固定值,其大小通过调节两磁极间的距离控制。电磁铁磁场分为直流场和交流场两种,其场强值可以是固定值也可以是连续变化值,其大小通过调节电流强度控制。
技术效果
与已有技术相比,本发明技术方法具有以下优势:
1、本发明一种磁控合成金属钴催化剂的方法,利用磁场控制合成制备金属钴微米结构材料,不但能控制金属钴的形貌,而且可以控制其晶体结构,可以较大范围的调控金属钴的催化性能。
2、本发明一种磁控合成金属钴催化剂的方法,可以大大提升反应效率,同等条件下金属钴生成速度是不加磁场的3倍以上,制备工艺简单,成本低廉,有利于实现工业生产。
2、获得的金属钴催化剂催化活性高、抗无机盐、添加量少,可高效磁分离,因此适于处理各种难降解工业污水,运行成本低。
3、制备的金属钴催化剂具有强磁性,因此易于回收,可循环利用30次以上。
四、附图说明
下面结合附图和实施例对本发明进一步说明。
图1为不同磁场强度下的钴微米花SEM图。
图2为不同磁场下所制备样品的XRD图谱。
图3为不同磁场下钴纳米花比表面积的分析结果一。
图4为不同磁场下钴纳米花比表面积的分析结果二。
图5为不同含量钴微米花的活化效果图。
五、具体实施方式
以下结合附图及实施例对本发明做进一步详细描述。
实施例1:
1、金属钴催化剂的制备
将0.1g聚乙烯吡咯烷酮于适量无水乙醇中超声波振动完全溶解。称取1g CoCl2·6H2O于无水乙醇混合液中搅拌20分钟使其完全反应生成蓝色絮状溶液。
量取水合肼溶液用氢氧化钠溶液调节pH至10~12。将钴盐溶液缓慢与水合肼在聚四氟乙烯反应釜中混合,搅拌均匀后放入水浴锅中。
放入水浴锅中,60℃下水浴5分钟,待溶液完全变为粉红色并有微量汽包产生时,转移反应釜于80mT匀强磁场中使产生的黑色沉淀在匀强磁场中生长。
待反应完全之后,溶液由粉红色转变为无色透明状并生成黑色钴絮状沉淀。将沉淀用磁铁分离出来后反复用无水乙醇清洗多次,再用去离子水清洗干净后放入真空烘箱中烘干。
2、降解浓度为100mg/L的亚甲基蓝染料污水
取100mg亚甲基蓝于烧杯中加去离子水充分溶解。转移亚甲基蓝溶液于1L的容量瓶中加去离子水定容,此时溶液的浓度为100mg/L。取100mL的亚甲基蓝溶液加入适量的钴纳米花,再加入一定量的过硫酸氢钾,搅拌均匀后再放入恒温振荡器中。反应每隔一段时间后在664nm波长下测定溶液的吸光度。根据标准曲线计算出此时溶液中亚甲基蓝的浓度。
实施例2:
同样的方法制备金属钴催化剂,降解浓度为100mg/L的甲基橙染料污水。探讨不同结构催化剂对染料污水催化降解的影响,选出最佳方案。
参阅图1-5,图1为不同磁场强度下的钴微米花SEM图((a)0mT,(b)25mT,(c)50mT,(d)200mT,(e)400mT)。当外界磁场强度为零时,钴微米花呈放射状均匀地在空间中生长,随着磁场强度的增加,钴微米花由空间放射状结构向平面结构转变,同时微米花原有的尖端明显钝化,钴微米花变为边形雪花平面结构,接着又向棒状转变,样品的团聚开始出现。结果表明外磁场对金属钴微米花的形貌具有显著影响。
图2为不同磁场下所制备样品的XRD图谱((a)为0mT下的产物,(b)为25mT下的产物,(c)为50mT下的产物,(d)为200mT下的产物,(e)为400mT下的产物),样品在有无磁场条件下都为金属钴晶体结构,但其晶型因外加磁场强度变化而不同。
图3和图4为不同磁场下钴纳米花比表面积的分析结果。BET结果分析,高强度磁场下钴微米花的介孔比例大幅升高。在低强度磁场下,介孔会有优先随着磁场强度增长而增长,当磁场达到一定强度,介孔比例会维持稳定,而微孔会继续增加。在强磁作用下钴微米花的吸附量会大幅增长,这和钴微米花在磁场作用下团聚后微孔与介孔分布比例提高有关。
图5为不同含量钴微米花的活化效果,当催化剂的添加量大于0.004g时,反应在10分钟内基本可以达到90%以上。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (4)
1.一种磁控合成金属钴催化剂的方法,其特征在于,包括如下步骤:
步骤1:取适量聚乙烯吡咯烷酮溶于无水乙醇中,超声震荡并充分搅拌后制备成浓度为2~6g·L-1的聚乙烯吡咯烷酮混合液;按照钴含量5~15g·L-1的配比称取溶解性钴盐,放入聚乙烯吡咯烷酮混合液中,充分搅拌使其完全反应,生成蓝色絮状溶液;
步骤2:按一定量取水合肼溶液并用碱溶液调节pH至10~12;将钴盐溶液缓慢与水合肼在玻璃或聚四氟乙烯反应釜中混合,搅拌均匀后放入水浴锅中;
步骤3:60℃-90℃水浴3-30分钟,待溶液完全变为粉紫色并有微量汽包产生时,转移烧杯或反应釜至匀强磁场中;
步骤4:依据对金属Co产物形貌的要求,调控匀强磁场的场强在400-600 mT之间,并控制磁场作用时间,当反应全部完成后产生黑色钴絮状沉淀,溶液由粉紫色转变为无色透明;
步骤5:将黑色钴絮状沉淀用磁铁分离出来后反复用无水乙醇和去离子水清洗后,在真空烘箱中烘干;经简单研磨后,即获得金属钴催化剂;
在低强度磁场下,介孔会随着磁场强度增长而增长,当磁场达到一定强度,介孔比例会维持稳定,而微孔会继续增加;在强磁作用下钴微米花的吸附量会大幅增长,钴微米花在磁场作用下团聚后微孔与介孔分布比例提高;
利用磁场控制合成制备金属钴微米结构材料,不但能控制金属钴的形貌,而且控制其晶体结构。
2.根据权利要求1所述的方法,其特征在于:所述碱溶液是指氢氧化钠或氨水溶液。
3.根据权利要求1所述的方法,其特征在于:所述溶解性钴盐是指CoCl2∙6H2O的无机钴盐和环烷酸钴、硬脂酸钴、新癸酸钴、乙酸钴的有机钴盐。
4.根据权利要求1所述的方法,其特征在于:所述匀强磁场由永磁体或电磁铁产生,永磁体产生的场强为固定值,其大小通过调节两磁极间的距离控制;
电磁铁磁场分为直流场和交流场两种,其场强值是固定值或是连续变化值,其大小通过调节电流强度控制。
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