CN114073951A - 具有薄壁球壳结构的低密度漂浮型复合微球催化剂及其制备方法和应用 - Google Patents
具有薄壁球壳结构的低密度漂浮型复合微球催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000007667 floating Methods 0.000 title claims abstract description 25
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
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- 238000001035 drying Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种具有薄壁球壳结构的低密度漂浮型复合微球催化剂,所述催化剂由载体及组装在所述载体表面的微纳米颗粒组成;其中,所述载体为中空微球,所述微纳米颗粒为铜微纳米颗粒。该催化剂克服了传统铜及其化合物催化剂易团聚、密度高、难分离等不足。本发明还公开了该催化剂的制备方法和应用。
Description
技术领域
本发明涉及粉体材料技术领域。更具体地,涉及一种具有薄壁球壳结构的低密度漂浮型复合微球催化剂及其制备方法和应用。
背景技术
在环境污染物治理和化学合成中,通常需借助高效催化剂加速反应过程,提高化学反应过程的经济性。为获得优异的催化活性,常用的方法是将催化活性材料设计成纳米尺寸,并结合一定的形貌控制来获得高活性和选择性。然而,纳米级的外形尺度在赋予催化剂材料高活性的同时,其高表面能也会带来易团聚、难分离等不足。
作为一类重要的非贵金属催化剂,铜及其化合物纳米材料以其价廉易得、结构可控性强、无毒、来源丰富等优点得到广泛应用。根据金属价态和化合元素的不同,铜及其化合物可以实现热催化、光催化、电催化等多种活性,在催化领域具有广泛的适用性。例如铜单质纳米颗粒可以用作高效的加氢还原催化剂;而其氧化物或硫化物因具有不同的禁带宽度,可作为对不同波段的光有响应的光催化剂。另外,通过构建铜-铜化合物异质结构,除了可以通过不同价态和化合元素的选择提高光的利用率外,还可以利用铜的高电导性将光激发电子和空穴有效地转移和分离,从而提高量子效率。然而,尽管铜及其化合物在催化领域有其独特的性能优势,但独立存在的铜单质及其化合物仍存在与其他纳米催化剂相同的缺点——密度高、易团聚且难以高效分离。而传统的负载型复合催化剂虽可解决团聚问题,但仍无法克服密度偏高且分离回收困难的不足。因此,为进一步促进铜及其化合物催化活性材料的性能稳定性和适用性,仍需设计新颖结构,开发新型的铜基负载型复合催化剂材料。
发明内容
为克服传统铜及其化合物催化剂易团聚、密度高、难分离等不足,本发明的第一个目的在于提供一种具有薄壁球壳结构的低密度漂浮型复合微球催化剂。
本发明的第二个目的在于提供一种具有薄壁球壳结构的低密度漂浮型复合微球催化剂的制备方法。
本发明的第三个目的在于提供一种具有薄壁球壳结构的低密度漂浮型复合微球催化剂的应用。
为达到上述第一个目的,本发明采用下述技术方案:
一种具有薄壁球壳结构的低密度漂浮型复合微球催化剂,所述催化剂由载体及组装在所述载体表面的微纳米颗粒组成;其中,所述载体为中空微球,所述微纳米颗粒为铜微纳米颗粒。
进一步地,所述催化剂的密度小于水。
进一步地,所述催化剂中,所述微纳米颗粒的负载量为0.01-30%。本发明中,负载量是微纳米颗粒质量占复合催化剂总质量的百分比。示例性的,所述微纳米颗粒的负载量为7.5-20%、8-19%、8-18.5%等。
进一步地,所述中空微球的密度为0.05-0.95g/cm3。示例性的,所述中空微球的密度包括但不限于为0.15-0.95g/cm3、0.2-0.55g/cm3、0.25-0.45g/cm3、0.3-0.4g/cm3等。
进一步地,所述中空微球的球壳材质为可形成球壳结构的玻璃、二氧化硅、聚合物或碳。
进一步地,所述聚合物包括但不局限于酚醛聚合物、聚酯聚合物等。
进一步地,所述铜微纳米颗粒的组成选自铜、氧化亚铜(Cu2O)、氧化铜(CuO)中的一种或两种或三种的混合。
进一步地,所述铜微纳米颗粒的粒径为0.001-2μm,优选为0.01-0.5μm。
进一步地,当所述铜微纳米颗粒的组成选自铜、氧化亚铜、氧化铜中的两种或三种的混合时,各组分间的结合方式为无序混合或分层混合。可以理解,当各组分间为分层结合时,此时的复合微球催化剂为三层过多层球壳结构。
本发明中提供的该复合微球催化剂采用低密度中空微球为载体,将微纳米级的催化活性材料组装在中空微球的表面,提高活性物质的分散性;同时由于中空微球的限域和锚定作用,有效防止了催化活性颗粒的团聚。第二,选用的中空微球具有低密度(低于水,介于0.01-0.8g/cm3之间),通过控制催化活性物质和中空微球载体的比例,可以使所得的复合微球催化剂仍具有低于水的密度,实现在水溶液体系中的漂浮,便于提高性能和分离回收。特别的,对于光催化体系,中空复合微球催化剂的漂浮性还利于反应液、催化剂、光线三者之间的充分接触,实现对光能的高效利用。
为达到上述第二个目的,本发明采用下述技术方案:
一种具有薄壁球壳结构的低密度漂浮型复合微球催化剂的制备方法,包括如下步骤:
将中空微球进行偶联处理,得中空微球A;
将上述中空微球A进行活化处理,得中空微球B;
在上述中空微球B表面组装金属铜;
对组装金属铜后的中空微球B进行后处理。
进一步地,所述偶联处理的方法包括如下步骤:将中空微球与偶联溶液混合搅拌,之后过滤、清洗、烘干;筛分除去团聚颗粒,即可。
进一步地,所述偶联溶液中溶剂为水或乙醇和水以体积比1:20-10:1的比例的混合物。其中,偶联溶液中,溶质为偶联剂,所述偶联剂为常规市售偶联剂。
进一步地,所述偶联处理在搅拌下进行,温度为0-80℃,优选为30-50℃。
进一步地,所述活化处理的方法包括如下步骤:将中空微球A与活化溶液混合搅拌,之后过滤、清洗、烘干;筛分除去团聚颗粒,即可。
进一步地,所述活化溶液为水溶液;活性离子浓度为0.001-0.5mol/L;所述活化溶液中的活性离子选自银、钯、金、铂离子中的一种或几种。
进一步地,在中空微球B表面组装金属铜的方法包括如下步骤:
将中空微球B与组装反应液混合搅拌,之后过滤、清洗、烘干;筛分除去团聚颗粒,即可。
进一步地,所述组装反应液组成:铜离子0.001-2mol/L、络合剂0.005-0.5mol/L、pH至调节剂0.1-1mol/L、还原剂0.001-2mol/L。
进一步地,所述铜离子来源为无机铜盐,选自硝酸铜、硫酸铜、氯化铜中的一种或几种,所述无机铜盐为水合或无水铜盐。
进一步地,所述络合剂选自酒石酸钾钠、柠檬酸钠、EDTA中的一种或几种。
进一步地,所述pH调节剂选自碱金属氢氧化物。
进一步地,所述还原剂选自甲醛、水合肼、次亚磷酸钠、硼氢化钠中的一种或几种。
进一步地,所述后处理的方法包括如下步骤:
将组装金属铜后的中空微球B进行热处理氧化或溶液氧化,之后筛分除去团聚颗粒;浮选除去碎片和高密度颗粒,即可。
进一步地,所述热处理氧化过程在空气或氧气气氛中进行,视氧化程度和中空微球的耐温性选择处理温度为200-800℃,处理时间1-600min。
进一步地,所述溶液氧化过程使用水溶液;溶液中含氢氧化钠:0.1-2mol/L、过氧化氢:0.01-2mol/L。
进一步地,所述溶液氧化过程在水热釜或常压下进行,处理时间0.5-48小时。
进一步地,中空微球在进行偶联处理之前,先依次进行浮选处理和清洗处理。
进一步地,所述浮选处理的方法包括如下步骤:将中空微球与乙醇或水或二者任意比例的混合物以体积比1:1-1:10,搅拌混合均匀,静置分层后取上层漂浮物,过滤,干燥。
进一步地,所述清洗处理的方法包括如下步骤:所述清洗处理为酸洗或碱洗处理;过程为:将中空微球与清洗溶液混合搅拌,之后过滤、清洗、烘干;筛分除去团聚颗粒。酸洗溶液为水溶液,其中的酸选自有机或无机酸;更优选无机酸,浓度0.01-1mol/L。碱洗溶液为水溶液,其中的碱选自无机碱,浓度0.01-1mol/L。
为达到上述第三个目的,本发明采用下述技术方案:
一种具有薄壁球壳结构的低密度漂浮型复合微球催化剂在催化氢化和光催化转化中的应用。
本发明的有益效果如下:
本发明中提供的复合微球催化剂中,具有内部空腔的薄壁球壳结构一方面对铜基催化活性物质起到支撑和分散作用,避免团聚;另一方面,复合微球催化剂内部的空腔使得该催化剂具有低密度,从而使得催化剂具有漂浮特性,便于提升催化剂性能和使用后的分离。
另外,本发明提供的漂浮型复合微球催化剂可通过控制制备条件将铜单质成分适当保留,利用其良好的导电性提升催化活性,能够代替传统的贵金属掺杂,进而有效提升催化效果。
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示出实施例1制备得到的复合微球催化剂的SEM图。
图2示出实施例1制备得到的复合微球催化剂的局部SEM图。
图3示出示出实施例1所示的具有薄壁球壳结构的低密度漂浮型复合微球催化剂漂浮特性图。
图4示出实施例2、6、7制备得到的复合微球催化剂对应样品的XRD曲线图。
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
具有薄壁球壳结构的低密度漂浮型复合微球催化剂,具体实施方案如下:
将30g中空玻璃微球(密度0.38g/cm3)分散于100ml蒸馏水和200ml无水乙醇的混合溶剂中,搅拌均匀,静置分层后取上层漂浮物,过滤,80℃干燥10h。筛分除去团聚颗粒。再用0.05mol/L稀盐酸清洗,过滤收集,80℃干燥10h。
将上述清洗后的15g中空玻璃微球分散于盛有100ml蒸馏水、200ml无水乙醇、10mlKH550的烧杯中,室温搅拌30min,过滤,80℃干燥10h。筛分除去团聚颗粒。然后,将所得微球按1g/20ml依次处理于200ml溶液A:盐酸1.2mol/L,氯化亚锡33g/L;200ml溶液B:盐酸0.4mol/L,氯化钯1.33g/L;200ml溶液C:次亚磷酸钠0.28mol/L,50℃水浴加热,搅拌,30min后过滤收集微球,60℃干燥过夜。
将3g上述所得活化微球分散于0.08mol/L硫酸铜、0.05mol/L酒石酸钾钠、0.07mol/L EDTA、0.5mol/L氢氧化钠、1.5ml/L甲醛的50ml混合溶液中,30℃水浴中搅拌,待反应结束后分离粉末,洗涤干燥收集;
将1g上述组装铜后的微球分散于盛有30ml 3ml/L过氧化氢和0.8mol/L氢氧化钠混合溶液的50ml水热釜中,120℃处理10h,分离洗涤,收集干燥。
上述所得复合微球密度为0.45g/cm3,表面组装纳米颗粒负载量为8.1%。所得复合微球催化剂的整体和局部形貌如附图1和2所示。
实施例2-7
实施步骤同实施例1中,具体区别条件如表1所示:
表1具有薄壁球壳结构的低密度漂浮型复合微球催化剂合成条件
注:表中HMS指中空微球;表中除已标注热处理方式外,其余均指水热处理;表中负载量的计量方式为表面组装的微纳米颗粒质量占复合催化剂总质量的百分比。
实施例11催化-分离实验
对硝基苯酚催化转化: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下表2所示。
光催化性能实验:配制10ml 0.1ppm甲基橙(MO)水溶液,添加10mg催化剂样品,搅拌,并在暗箱中用440nm LED灯照射2h,用紫外可见分光光度计监测反应后溶液在465nm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光催化转化率如下表2所示。
复合催化剂漂浮分离:待上述催化反应结束之后,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4所示。
表2各实施例所得催化剂催化4-NP转化和光催化MO转化的数据表
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 (10)
1.一种具有薄壁球壳结构的低密度漂浮型复合微球催化剂,其特征在于,所述催化剂由载体及组装在所述载体表面的微纳米颗粒组成;其中,所述载体为中空微球,所述微纳米颗粒为铜微纳米颗粒。
2.根据权利要求1所述的具有薄壁球壳结构的低密度漂浮型复合微球催化剂,其特征在于,所述催化剂的密度小于水;
优选地,所述催化剂中,所述微纳米颗粒的负载量为0.01-30%。
3.根据权利要求1所述的具有薄壁球壳结构的低密度漂浮型复合微球催化剂,其特征在于,所述中空微球的密度为0.05-0.95g/cm3;
优选地,所述中空微球的材质为玻璃、氧化硅、聚合物或碳。
4.根据权利要求1所述的具有薄壁球壳结构的低密度漂浮型复合微球催化剂,其特征在于,所述铜微纳米颗粒的组成选自铜、氧化亚铜、氧化铜中的一种或两种或三种的混合;
优选地,所述铜微纳米颗粒的粒径为0.001-2μm,更优选为0.01-0.5μm;
优选地,当所述铜微纳米颗粒的组成选自铜、氧化亚铜、氧化铜中的两种或三种的混合时,各组分间的结合方式为无序混合或分层混合。
5.如权利要求1-4任一项所述的具有薄壁球壳结构的低密度漂浮型复合微球催化剂的制备方法,其特征在于,包括如下步骤:
将中空微球进行偶联处理,得中空微球A;
将上述中空微球A进行活化处理,得中空微球B;
在上述中空微球B表面组装金属铜;
对组装金属铜后的中空微球B进行后处理。
6.根据权利要求5所述的制备方法,其特征在于,所述偶联处理的方法包括如下步骤:将中空微球与偶联溶液混合搅拌,之后过滤、清洗、烘干;筛分除去团聚颗粒,即可;
优选地,所述偶联溶液中溶剂为水或乙醇和水以体积比1:20-10:1的比例的混合物;优选地,所述偶联处理在搅拌下进行,温度为0-80℃,优选为30-50℃。
7.根据权利要求5所述的制备方法,其特征在于,所述活化处理的方法包括如下步骤:将中空微球A与活化溶液混合搅拌,之后过滤、清洗、烘干;筛分除去团聚颗粒,即可;
优选地,所述活化溶液为水溶液;活性离子浓度为0.001-0.5mol/L;所述活化溶液中的活性离子选自银、钯、金、铂离子中的一种或几种。
8.根据权利要求5所述的制备方法,其特征在于,在中空微球B表面组装金属铜的方法包括如下步骤:
将中空微球B与组装反应液混合搅拌,之后过滤、清洗、烘干;筛分除去团聚颗粒,即可;
优选地,所述组装反应液组成:铜离子0.001-2mol/L、络合剂0.005-0.5mol/L、pH至调节剂0.1-1mol/L、还原剂0.001-2mol/L;
优选地,所述铜离子来源为无机铜盐,选自硝酸铜、硫酸铜、氯化铜中的一种或几种,所述无机铜盐为水合或无水铜盐;
优选地,所述络合剂选自酒石酸钾钠、柠檬酸钠、EDTA中的一种或几种;
优选地,所述pH调节剂选自碱金属氢氧化物;
优选地,所述还原剂选自甲醛、水合肼、次亚磷酸钠、硼氢化钠中的一种或几种。
9.根据权利要求5所述的制备方法,其特征在于,所述后处理的方法包括如下步骤:
将组装金属铜后的中空微球B进行热处理氧化或溶液氧化,之后筛分除去团聚颗粒;浮选除去碎片和高密度颗粒,即可;
优选地,所述热处理氧化过程在空气或氧气气氛中进行,处理温度为200-800℃,处理时间1-600min;
优选地,所述溶液氧化过程使用水溶液;溶液中含氢氧化钠:0.1-2mol/L、过氧化氢:0.01-2mol/L;
优选地,所述溶液氧化过程在水热釜或常压下进行,处理时间0.5-48小时。
10.如权利要求1-4任一项所述的具有薄壁球壳结构的低密度漂浮型复合微球催化剂在催化氢化和光催化转化中的应用。
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