CN114073973B - 一种轻质负载型磁性金属复合催化剂及其制备方法和应用 - Google Patents
一种轻质负载型磁性金属复合催化剂及其制备方法和应用 Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
本发明公开了一种轻质负载型磁性金属复合催化剂,包括载体以及负载在所述载体上的纳米颗粒,其中,所述载体为微米级空心球体;所述纳米颗粒为磁性催化剂纳米颗粒。该复合催化剂中纳米颗粒粒径可调、负载量可调、成分可调,且该复合催化剂利用空间效应有效阻止了纳米颗粒的团聚、通过成分调控实现了催化活性的提升、提高了纳米颗粒负载量、集合了自漂浮分离和磁分离的双重分离特性。本发明还公开了该复合催化剂的制备方法和应用。
Description
技术领域
本发明涉及功能材料技术领域。更具体地,涉及一种轻质负载型磁性金属复合催化剂及其制备方法和应用。
背景技术
近年间,纳米催化剂的研究备受青睐。纳米粒子表面缺陷和配位不饱和度,使其活性中心密度高于相应的本体大尺寸材料,从而具有更高的催化活性。然而,纳米粒子在合成和应用过程中的易聚集和难分离的问题,制约了纳米催化剂的性能稳定性和经济高效的应用。为了避免活性纳米颗粒团聚,构建大尺寸载体负载型结构是可行的策略,该结构可通过空间阻隔效应有效阻止纳米颗粒的聚集。已报道的载体有石墨烯类、活性炭、多孔氧化物、(多层)核壳结构、金属氧化物纳米颗粒等,这些结构在一定程度上缓解了纳米颗粒的团聚,但是其本身存在的一些局限性带来了新的问题。如具有多孔结构型复合催化剂,丰富的孔洞和空腔结构提供较大负载表面的同时,阻碍了活性组分的高效利用;石墨烯、金属氧化物纳米颗粒型复合催化剂因自身的表面能高或者本征磁性而存在自发聚集的问题;活性炭类和多孔二氧化硅类负载型复合催化剂存在分离回收困难的问题。因此,需要开发出组成和结构易于调整、分离回收便捷、不影响传质的负载型复合纳米催化剂。
空心微球是一种微米级球形粉体材料,微米级尺寸使其具有很强的表面可操控性,且自身聚集倾向小,是负载型复合催化剂载体的优良候选。近年,基于微米级空心微球载体合成复合催化剂材料的报道较少。对于以空心微球为载体的负载型磁性金属催化剂而言,催化活性物质的种类、组成配比、颗粒大小、负载量、微观结构等因素对其催化活性、操作方便性和应用经济性发挥着决定性作用。但是,目前在中空微球负载型催化剂的结构和组成设计以及制备方法开发方面存在不足,严重制约了轻质微球负载型金属催化剂的设计、制备与应用开发。
发明内容
基于以上问题,本发明的一个目的在于提供一种轻质负载型磁性金属复合催化剂,以克服常用纳米催化剂颗粒易团聚和难回收、贵金属成本高以及载体局限性、负载量低等缺点。
本发明的第二个目的在于提供一种轻质负载型磁性金属复合催化剂的制备方法。
本发明的第三个目的在于提供一种轻质负载型磁性金属复合催化剂的应用。
为达到上述第一个目的,本发明采用下述技术方案:
一种轻质负载型磁性金属复合催化剂,包括载体以及负载在所述载体上的纳米颗粒,其中,所述载体为微米级空心球体;所述纳米颗粒为磁性催化剂纳米颗粒。
进一步地,所述复合催化剂的密度小于水。
进一步地,所述纳米颗粒在所述载体表面呈岛状分布。
进一步地,所述复合催化剂中,纳米颗粒的负载量为0.02-30wt%,优选为1-10wt%。示例性的为1.5-10wt%、1.5-9wt%、1.8-8.5wt%等。
如无特殊说明,本发明中的负载量均是指纳米颗粒质量占复合催化剂总质量的百分比。
进一步地,所述磁性催化剂纳米颗粒的组成选自:铁、钴、镍、磷、硼中的一种或其中的两种形成的二元合金或其中的三种形成的三元合金。可以理解,当该纳米颗粒为合金(二元合金、三元合金)时,其组成中至少包含前述金属(铁、钴、镍)中的一种。优选地,合金中,金属成分比例可控,金属摩尔比范围0.1-10。
进一步地,所述纳米颗粒的粒径为10-500nm,优选为10-50nm。
进一步地,所述空心球体的材质为玻璃、聚合物、碳中的一种。可以理解,所述空心球体也即空心微球。空心球体包括但不限于选自空心玻璃微球、空心酚醛聚合物微球、表面包覆二氧化硅的空心微球、表面包覆聚合物的空心微球等。
进一步地,所述空心球体的密度为0.05-0.95g/cm3。示例性的,所述空心球体的密度包括但不限于为0.1-0.9g/cm3、0.2-0.8g/cm3等。
进一步地,所述空心球体的粒径为5-300μm。
为达到上述第二个目的,本发明采用下述技术方案:
一种轻质负载型磁性金属复合催化剂的制备方法,包括如下步骤:
将所述载体进行表面官能团化处理,得表面官能团化的载体;
对上述表面官能团化的载体进行种核锚定;
对上述经种核锚定后的载体辅助沉积纳米颗粒。
进一步地,将所述载体进行表面官能团化处理的方法为:对所述载体进行表面偶联处理。
进一步地,进行表面偶联处理的方法包括如下步骤:
在偶联处理混合溶液中加入所述载体,混合均匀,过滤,干燥,筛除团聚物,得到表面官能团化的载体。
进一步地,所述偶联处理混合溶液中的溶剂为无水乙醇和蒸馏水的混合液,可以是任意体积比,优选为无水乙醇和蒸馏水的体积比为1:1-1:5。
进一步地,所述偶联处理剂为常规市售硅烷偶联剂。
进一步地,所述载体添加量为1g/5ml-1g/20ml。
进一步地,所述表面偶联处理的条件为温度20-70℃,更优选30-50℃。
进一步地,所述种核锚定包括如下步骤:在锚定溶液中加入所述表面官能团化的载体,混合均匀,过滤,干燥,即得。
进一步地,所述锚定溶液为水溶液,更优选为酸性水溶液。其中,酸性水溶液中的酸优选为无机酸,浓度为0.1-2mol/L。
进一步地,所述锚定溶液离子包括钯、银、金中的一种或几种,离子浓度为1-10g/L。
进一步地,所述表面官能团化的载体的添加量为1g/5ml-1g/150ml。
进一步地,所述种核锚定的温度为0-100℃,更优选40-70℃。
进一步地,所述辅助沉积纳米颗粒包括如下步骤:在辅助沉积溶液中加入经种核锚定后的载体,均匀搅拌,过滤,烘干。
进一步地,所述辅助沉积溶液为水溶液。
进一步地,所述辅助沉积溶液组成为离子源盐、稳定剂、还原剂、pH调节剂。
进一步地,所述离子源盐包括铁盐、镍盐、钴盐,可以是无机盐或有机盐,浓度为0.01-20g/L。
进一步地,所述稳定剂包括硫酸铵、酒石酸钾钠、EDTA,浓度为20-80g/L。
进一步地,所述还原剂包括次亚磷酸钠、水合肼、甲醛、硼氢化钠,浓度为0.1-150g/L。
进一步地,所述辅助沉积溶液pH优选9-11,调节剂优选无机碱。
进一步地,所述种核锚定后空心微球添加量为1g/5ml-1g/150ml,更优选为1g/5ml-1g/20ml。
进一步地,所述辅助沉积的温度为0-100℃,更优选为50-70℃。
为达到上述第三个目的,本发明采用下述技术方案:
一种轻质负载型磁性金属复合催化剂的应用,在还原剂的存在下,将所述复合催化剂用于催化污染物转化过程、催化加氢反应。
本发明的有益效果如下:
本发明提供的复合催化剂中纳米颗粒粒径可调、负载量可调、成分可调,且该复合催化剂利用空间效应有效阻止了纳米颗粒的团聚、通过成分调控实现了催化活性的提升、提高了纳米颗粒负载量。该复合催化剂可很好的用于催化污染物转化过程、催化加氢反应中。
本发明提供的复合催化剂既能通过自身低密度性从溶液体系中漂浮分离,亦能通过磁性中空微球的磁性从体系中磁分离出来。
本发明提供的复合催化剂的制备方法可在多种微球或载体表面实现磁性纳米颗粒的可控组装。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1中,(a)示出实施例1所得复合催化剂微球的整体形貌;(b)示出实施例1所得复合催化剂微球表面的纳米颗粒形貌;
图2中,(a)示出实施例3所得复合催化剂微球的整体形貌;(b)示出实施例3所得复合催化剂微球表面的纳米颗粒形貌;
图3示出实施例1所得轻质负载型磁性金属复合微球的镍元素分布图;
图4示出实施例1所得轻质负载型磁性金属复合催化剂催化4-NP转化的吸光度随时间变化图;
图5示出实施例1所得轻质负载型磁性金属复合催化剂催化转化(a)对硝基苯酚,4-NP(b)亚甲基蓝,MB(c)罗丹明B,RhB(d)甲基橙,MO(e)茜素红S,ArS的实物图;
图6示出实施例1所得负载型磁性轻质复合催化剂(a)自漂浮分离和磁分离图(b)循环稳定性。
具体实施方式
为了更清楚地说明本发明,下面结合优选实施例和附图对本发明做进一步的说明。附图中相似的部件以相同的附图标记进行表示。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
实施例1
一种轻质负载型磁性金属复合催化剂的制备方法,包括如下步骤:
(1)前处理:用无水乙醇搅拌洗涤空心玻璃微球(密度0.38g/cm3),进行表面除污;接着,200ml无水乙醇和200ml蒸馏水的混合溶液中加10ml 3-氨丙基三乙氧基硅烷,加入50g空心玻璃微球,进行表面氨基化;
(2)种核锚定:将50g(1)所得微球依次分散于500ml溶液A:盐酸1.2mol/L,氯化亚锡33g/L;500ml溶液B:盐酸0.4mol/L,氯化钯1.33g/L;500ml溶液C:次亚磷酸钠0.28mol/L,分别加热至50℃,搅拌,30min后过滤收集微球,60℃干燥过夜,得到锚定空心微球(AHMs)。
(3)载体辅助沉积纳米颗粒:配制辅助沉积溶液50ml:14g/L硫酸镍、14g/L硫酸钴、60g/L次亚磷酸钠、60g/L酒石酸钾钠、40g/L硫酸铵、浓氨水调节pH≈10,70℃水浴保温。加入上述5g AHMs,搅拌,待反应结束,收集粉末、洗涤烘干。
所得复合催化剂微球密度为0.38g/cm3,表面纳米颗粒负载量为5.7%。图3所示为本实施例所得复合微球中镍元素分布图,表明镍元素均匀的分布在载体表面,进一步说明NiCoP纳米颗粒在复合微球中的可控均匀沉积。
实施例2-5
前处理和种核锚定实施步骤按实施例1进行,具体区别条件如表1所示:
表1空心微球表面沉积不同成分纳米颗粒条件变化表
实施例6
前处理和种核锚定实施步骤按实施例1进行,具体区别条件如表2所示:
表2不同种类空心微球表面沉积纳米颗粒
实施例7-8
前处理和种核锚定实施步骤按实施例1进行,具体区别条件如表3所示:
表3空心微球表面沉积不同粒径纳米颗粒条件变化表
实施例9-10
前处理和种核锚定实施步骤按实施例1进行,具体区别条件如表4所示:
表4空心微球表面纳米颗粒负载量变化表
实施例11-12
前处理和种核锚定实施步骤按实施例1进行,具体区别条件如表5所示:
表5空心微球表面纳米颗粒中金属比例条件变化表
实施例13催化-分离实验
配制200ml溶液(25mM NaBH4,0.25mM 4-NP),添加0.10g催化剂样品,并用紫外可见分光光度计监测400nm处吸光度值随时间的变化。根据朗伯比尔定律评估反应前后反应物浓度的变化。各催化剂样品对应的表观速率常数如表6所示。保证其他条件一致,将4-NP分别替换为亚甲基蓝(MB)、罗丹明B(RhB)、甲基橙(MO)、茜素红S(ArS),进行多种染料的催化氢化,结果如图4所示,催化反应后,各种染料的溶液军由其初始颜色转变为无色,溶液的脱色效果表明有效地发生了催化反应。
复合催化剂分离:待上述催化反应结束后,静置,复合微球催化剂因自身低密度(小于水)特性,与水溶液体系迅速分离,漂浮于液体表面,如图5(a);或待反应结束后,用磁铁吸附,实现复合催化剂与溶液体系的分离,如图5(a)。将分理出的样品进行重复利用,可保持其催化活性(图5(b)为六个循环内的催化活性保持率)。
表6各实施例所得催化剂样品的催化反应表观速率常数。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (13)
1.一种用于催化加氢反应的轻质负载型磁性金属复合催化剂,其特征在于,包括载体以及负载在所述载体上的纳米颗粒,其中,所述载体为微米级空心球体;所述纳米颗粒为磁性催化剂纳米颗粒;
所述复合催化剂的密度小于水;
所述纳米颗粒在所述载体表面呈岛状分布;
所述复合催化剂中,纳米颗粒的负载量为0.02-30wt%;
所述磁性催化剂纳米颗粒的组成为钴、镍、硼形成的三元合金;
所述纳米颗粒的粒径为10-500nm;
所述轻质负载型磁性金属复合催化剂按照如下步骤制备得到:
将所述载体进行表面官能团化处理,得表面官能团化的载体;
对上述表面官能团化的载体进行种核锚定;
对上述经种核锚定后的载体辅助沉积纳米颗粒;
将所述载体进行表面官能团化处理的方法为:对所述载体进行表面偶联处理;
所述种核锚定包括如下步骤:在锚定溶液中加入所述表面官能团化的载体,混合均匀,
过滤,干燥,即得;
所述锚定溶液为酸性水溶液;
所述锚定溶液中离子包括钯、银、金中的一种或几种,离子浓度为1-10 g/L;
所述辅助沉积包括如下步骤:在辅助沉积溶液中加入经种核锚定后的载体,均匀搅拌
过滤,烘干;
所述辅助沉积溶液为水溶液;所述辅助沉积溶液组成为离子源盐、稳定剂、还原剂、pH调节剂;
所述离子源盐包括镍盐、钴盐的无机盐或有机盐;
所述稳定剂包括硫酸铵、酒石酸钾钠、EDTA;
所述还原剂选自硼氢化钠;
所述辅助沉积溶液pH为9-11,调节剂无机碱。
2.根据权利要求1所述的轻质负载型磁性金属复合催化剂,其特征在于,纳米颗粒的负载量为1-10wt%,所述纳米颗粒的粒径为10-50nm。
3.根据权利要求1所述的轻质负载型磁性金属复合催化剂,其特征在于,所述空心球体的材质为玻璃、聚合物、碳中的一种。
4.根据权利要求 1 所述的轻质负载型磁性金属复合催化剂,其特征在于,所述空心球体的密度为0.05-0.95 g/cm3。
5.根据权利要求1所述的轻质负载型磁性金属复合催化剂,其特征在于,所述空心球体的粒径为5-300μm。
6.如权利要求1-5任一项所述的用于催化加氢反应的轻质负载型磁性金属复合催化剂的制备方法,其特征在于,包括如下步骤:
将所述载体进行表面官能团化处理,得表面官能团化的载体;
对上述表面官能团化的载体进行种核锚定;
对上述经种核锚定后的载体辅助沉积纳米颗粒;
将所述载体进行表面官能团化处理的方法为:对所述载体进行表面偶联处理;
所述种核锚定包括如下步骤:在锚定溶液中加入所述表面官能团化的载体,混合均匀,
过滤,干燥,即得;
所述锚定溶液为酸性水溶液;
所述锚定溶液中离子包括钯、银、金中的一种或几种,离子浓度为1-10 g/L;
所述辅助沉积包括如下步骤:在辅助沉积溶液中加入经种核锚定后的载体,均匀搅拌
过滤,烘干;
所述辅助沉积溶液为水溶液;所述辅助沉积溶液组成为离子源盐、稳定剂、还原剂、pH调节剂;
所述离子源盐包括镍盐、钴盐的无机盐或有机盐;
所述稳定剂包括硫酸铵、酒石酸钾钠、EDTA;
所述还原剂选自硼氢化钠;
所述辅助沉积溶液pH为9-11,调节剂无机碱。
7.根据权利要求6所述的制备方法,其特征在于,所述表面偶联处理的方法包括如下步骤:
在偶联处理混合溶液中加入所述载体,混合均匀,过滤,干燥,筛除团聚物,得到表面官能团化的载体。
8.根据权利要求6所述的制备方法,其特征在于,所述表面官能团化的载体的添加量为1g/5ml-1g/150ml。
9.根据权利要求6所述的制备方法,其特征在于,所述种核锚定的温度为0-100℃。
10.根据权利要求9所述的制备方法,其特征在于,所述种核锚定的温度为40-70℃。
11.根据权利要求6所述的制备方法,其特征在于,所述辅助沉积的温度为0-100℃。
12.根据权利要求11所述的制备方法,其特征在于,所述辅助沉积的温度为50-70℃。
13.如权利要求1-5任一项所述的用于催化加氢反应的轻质负载型磁性金属复合催化剂的应用,其特征在于,在还原剂的存在下,将所述复合催化剂用于催化加氢反应。
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