CN115487866B - 一种共价有机框架材料耦合纳米金属催化剂及其制备方法 - Google Patents
一种共价有机框架材料耦合纳米金属催化剂及其制备方法 Download PDFInfo
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- CN115487866B CN115487866B CN202110677474.XA CN202110677474A CN115487866B CN 115487866 B CN115487866 B CN 115487866B CN 202110677474 A CN202110677474 A CN 202110677474A CN 115487866 B CN115487866 B CN 115487866B
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- FWBJGIGJPTUMLG-UHFFFAOYSA-N diethyl 2-phenylethynyl phosphate Chemical compound CCOP(=O)(OCC)OC#CC1=CC=CC=C1 FWBJGIGJPTUMLG-UHFFFAOYSA-N 0.000 description 1
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- 239000012362 glacial acetic acid Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
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- LFGRDRAXRZFPAB-UHFFFAOYSA-N selanylideneplatinum Chemical compound [Pt]=[Se] LFGRDRAXRZFPAB-UHFFFAOYSA-N 0.000 description 1
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- 239000011669 selenium Substances 0.000 description 1
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- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种共价有机框架材料耦合纳米金属催化剂及其制备方法。该催化剂利用共价有机框架材料对负载于载体上的纳米金属的表面进行包覆。该共价有机框架材料耦合纳米金属催化剂具有优异的热稳定性与化学稳定性。本发明提供的制备方法工艺简单,制得的材料孔径、表面积以及共价有机框架材料和金属的比例可调,在反应中展现优异的催化活性、选择性和稳定性,具有很高的工业价值。
Description
技术领域
本发明涉及一种共价有机框架耦合纳米金属催化剂及其制备方法,该催化剂利用共价有机框架材料对负载于载体上的纳米金属的表面进行包覆。该共价有机框架材料耦合纳米金属催化剂具有优异的热稳定性与化学稳定性。
背景技术
在化学与化工领域,多相催化有着广泛的应用,其中超过80%的产品需应用多相催化反应。多相催化剂的设计影响催化反应进程,从而影响工业生产的效率和产品质量。多相催化剂表面的孔道结构与活性中心的分布对反应产物的分布与催化剂本身活性、稳定性有重要影响。随着对环境保护的要求,研发高活性、高选择性和高稳定性的多相催化剂成为当今研究的重点及难点。
共价有机框架材料(COF)是一类由轻质元素(C,O,N,B等)通过共价键连接的有机多孔晶态材料,是继金属有机框架材料(MOF)之后又一重要的二维或三维有序材料,其具有其他传统多孔材料如分子筛、多孔聚合物、金属有机框架材料(MOF)等无法比拟的优点,诸如官能团可修饰性,高比表面积,孔道尺寸可控制性,优异热稳定性和化学稳定性等。因此,目前COF材料在非均相催化和光电催化等领域已经有了广泛的研究并展现出优异的应用前景。2019年邹建平课题组(Wang,Dengke,et al."Size-controlled synthesis of CdSnanoparticles confined on covalent triazine-based frameworks for durablephotocatalytic hydrogen evolution under visible light."Nanoscale 10.41(2018):19509-19516),在共价有机框架(CTF-1)材料上沉积CdS纳米粒子,CTF-1材料不仅作为载体,还作为光催化剂和电子给体,CdS-CTF-1具有较高的光催化水制氢能力。凭借大比表面积和可控孔道结构,以COF材料为载体担载金属组分的多相催化剂在多种反应中展现出优异的催化性能。2011年王为课题组(Ding,San-Yuan,et al."Construction of covalentorganic framework for catalysis:Pd/COF-LZU1 in Suzuki–Miyaura couplingreaction."Journal of the American Chemical Society 133.49(2011):19816-19822),首次合成以COF-LZU1为载体担载金属钯的多相催化剂,并应用于形成碳碳连接键的重要反应(Suziki-Miyaura反应)。该催化剂具有高活性、高稳定性和高可回收性。然而,COF造价昂贵,很难进行规模化放大生产。此外,进行COF放大生产过程中会产生大量有机废液,对环境污染严重。这些缺点都限制了COF材料在实际应用中的发展。而解决这些难题的一种有效方法是将COF材料与传统多相催化剂相结合,综合利用COF材料的功能结构和传统催化剂的廉价易得性。
尽管目前COF材料在多相催化剂方面的研究日渐深入,但目前合成工艺复杂,且催化性能也有待提高。
此外,COF材料在多相催化剂方面的研究还比较薄弱,所以COF耦合纳米催化剂在化学化工反应具有很高的价值。
发明内容
本发明的目的在于提供一种共价有机框架材料耦合纳米金属催化剂,该催化剂利用共价有机框架材料对负载于载体上的纳米金属的表面进行包覆。
本发明还提供了一种制备上述共价有机框架材料耦合纳米金属催化剂的合成方法。
本发明通过提供COF耦合纳米催化剂及其制备方法,将COF材料与传统多相催化剂相结合,综合利用COF材料的功能结构和传统催化剂的廉价易得性,有效解决了现有技术中存在的以上问题。该制备方法合成的催化剂在化学化工反应中展现出优异的催化性能,可提高催化剂的活性、选择性和稳定性,且其制备方法简单,生产成本低,对设备的要求不高。
为实现上述目的,本发明提供了一种共价有机框架材料耦合纳米金属催化剂的合成方法,其包括如下步骤:
1)利用沉淀、浸渍、超声、溶胶凝胶等方法中的一种或者几种将纳米金属负载于载体上,得到负载于载体上的纳米金属,
2)将COF单体A和COF单体B溶解或分散在有机溶剂中,加入控制剂AP和控制剂BP,得到COF反应液,基于有机溶剂的体积计,所述单体A和单体B的浓度为0.001-100M,控制剂AP和控制剂BP浓度为0-1000M,
3)将获自步骤1)的负载于载体上的纳米金属均匀分散到获自步骤2)的COF反应液中,加入COF催化剂,在0-200℃下反应耦合0.1-96h,得到共价有机框架耦合纳米金属材料分散液,基于COF反应液的体积计,所述负载于载体上的纳米金属浓度为0.1-4000mg/mL,所述COF催化剂浓度为0.001-100mM/mL,
4)将获自步骤3)的共价有机框架耦合纳米金属材料分散液过滤,用有机溶剂洗涤沉淀,在20-180℃下,在氮气、氩气或氦气保护下,常压或真空干燥0.1-48h,得到共价有机框架耦合纳米金属材料。
COF单体A是本领域已知的用于制备共价有机框架材料的单体。例如,其可选自芳香胺类及其衍生物、芳香酰肼类及其衍生物、芳香硼酸类及其衍生物、和芳香腈类及其衍生物。单体A的实例包括但不限于1,4-苯二胺、2,5-二甲基-1,4-苯二胺、四甲基对苯二胺、联苯胺、3,3’,5,5’-四甲基联苯-4,4’-二胺、3,3'-二硝基联苯胺、4,4'-二氨基三连苯、4,4'-二氨基二苯乙烯、对二氨基偶氮苯、2,6蒽二胺、3,4-二氨基四氢呋喃、肼、1,2-环己二胺、1,2,4,5-二(二酰肼)苯、1,3,5-三(4-氨苯基)苯、2,4,6-三(4-氨基苯基)-1,3,5-三嗪、三聚氰胺、5,10,15,20-四(4-氨基苯基)卟啉、1,2,4,5-苯四胺、六氨基苯、1,6-二氨基芘、2,3,6,7,10,11-六氨基三亚苯、1,4-苯二硼酸、均苯三硼酸、1,4-苯二硼酸二频哪酯、4,7-双硼酸-2,1,3-苯并噻二唑、4,7-双(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)-2,1,3-苯并噻二唑、2,7-双硼酸芘、2,7-双(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)芘、4,4'-联苯基二硼酸、4,4'-联苯二硼酸二频哪醇酯、5,10,15,20-四(4-硼酸基苯基)卟啉、对苯二腈、2,6蒽二腈、对苯二甲酰肼、2,5-二甲氧基对苯二甲酰肼、2,5-二乙氧基对苯二甲酰肼、及其组合。
优选的单体A选自1,4-苯二胺、1,3,5-三(4-氨苯基)苯、2,4,6-三(4-氨基苯基)-1,3,5-三嗪、5,10,15,20-四(4-氨基苯基)卟啉、1,4-苯二硼酸、均苯三硼酸、5,10,15,20-四(4-硼酸基苯基)卟啉、对苯二甲酰肼、及其组合。
以上单体A均可商购或通过已知的方法制备得到。
COF单体B是本领域已知的用于制备COF材料的共价有机框架材料单体。例如,其可选自芳香醛类及其衍生物、芳香硼酸类及其衍生物、酚类及其衍生物、醇类及其衍生物、和芳香腈类及其衍生物。单体B的实例包括但不限于对苯二甲醛、联苯二甲醛、2,5-二羟基对苯二甲醛、2,5-二甲氧基对苯二甲醛、2,3-二羟基对苯二甲醛、2,3-二甲氧基对苯二甲醛、2,5-二炔氧基对苯二甲醛、乙二醛、均苯三甲醛、2,4,6-三羟基均苯三甲醛、1,3,5-三(4-醛基苯基)苯、2,4,6-三(4-醛基苯基)-1,3,5-三嗪、环己六酮、1,4-苯二硼酸、均苯三硼酸、1,4-苯二硼酸二频哪酯、4,7-双硼酸-2,1,3-苯并噻二唑、4,7-双(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)-2,1,3-苯并噻二唑、2,7-双硼酸芘、2,7-双(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)芘、4,4'-联苯基二硼酸、4,4'-联苯二硼酸二频哪醇酯、5,10,15,20-四(4-硼酸基苯基)卟啉、1,2,4,5-苯四酚、3,6-二甲基-1,2,4,5-苯四酚、3,6-二乙基-1,2,4,5-苯四酚、3,6-二丙基-1,2,4,5-苯四酚、2,3,6,7-萘四酚、2,3,6,7-蒽四酚、3,6,7,10,11-六羟基三亚苯、对苯二腈、2,6蒽二腈、及其组合。
优选的单体B选自对苯二甲醛、联苯二甲醛、2,4,6-三羟基均苯三甲醛、1,2,4,5-苯四酚、3,6,7,10,11-六羟基三亚苯、1,4-苯二硼酸、均苯三硼酸、及其组合。
以上单体B均可通过商购或通过已知的方法制备得到。
控制剂AP选自单醛类及其衍生物、单硼酸类及其衍生物、酚类及其衍生物、醇类及其衍生物、和单腈类及其衍生物。控制剂AP的实例包括但不限于苯甲醛、2-氯苯甲醛、3-氯苯甲醛、4-氯苯甲醛、2-硝基苯甲醛、3-硝基苯甲醛、4-硝基苯甲醛、2-甲基苯甲醛、3-甲基苯甲醛、4-甲基苯甲醛、4-叔丁基苯甲醛、4-氟苯甲醛、1-萘甲醛、2-萘甲醛、甲醛、乙醛、丙醛、丁醛、戊醛、己醛、庚醛、辛醛、苯硼酸、4-叔丁基苯硼酸、正丙基硼酸、环己基硼酸、邻苯二酚、2,3-二羟基萘、乙二醇、2,3-二甲基-2,3-丁二醇、1,2-环己二醇、苯腈、萘腈、乙腈、环己腈、及其组合。
优选的控制剂AP选自苯甲醛、4-叔丁基苯甲醛、丁醛、苯硼酸、邻苯二酚、乙二醇、苯腈、及其组合。
所述控制剂AP可通过商购或通过已知的方法制备得到。
控制剂BP选自单胺类及其衍生物、单酰肼类及其衍生物、单硼酸类及其衍生物、和单腈类及其衍生物。控制剂BP的实例包括但不限于苯胺、2-氯苯胺、3-氯苯胺、4-氯苯胺、1,3-苯并噻唑-5-胺、2-硝基苯胺、3-硝基苯胺、4-硝基苯胺、2-甲基苯胺、3-甲基苯胺、4-甲基苯胺、4-叔丁基苯胺、4-氟苯胺、1-萘胺、2-萘胺、甲胺、乙胺、丙胺、丁胺、戊胺、己胺、庚胺、辛胺、环己胺、苯硼酸、4-叔丁基苯硼酸、正丙基硼酸、环己基硼酸、2,3-二羟基萘、乙二醇、2,3-二甲基-2,3-丁二醇、1,2-环己二醇、苯腈、萘腈、乙腈、环己腈、苯甲酰肼、4-氯苯甲酰肼、3-吡啶甲酰肼、甲酸酰肼、乙酸酰肼、丙酸酰肼、环己甲酰肼、及其组合。
优选的控制剂BP选自苯胺、4-叔丁基苯胺、丁胺、苯硼酸、苯腈、苯甲酰肼、及其组合。
所述控制剂均BP可通过商购或通过已知的方法制备得到。
COF催化剂是本领域已知的用于制备共价有机框架材料的共价有机框架材料催化剂,其可相同或者不同,可选自羧酸及其盐、磺酸及其盐、以及它们的衍生物。其实例包括但不限于甲酸、乙酸、三氟乙酸、苯磺酸、甲基苯磺酸、三氟甲磺酸钪、三氟甲磺酸铕、三氟甲磺酸铟、三氟甲磺酸镱、三氟甲磺酸钇、三氟甲磺酸锌、及其组合。
某些催化剂,例如甲酸,可在本发明的方法中同时充当溶剂,在这种情况下,催化剂的浓度可以是较高的。
负载于载体上的纳米金属催化剂是本领域已知的纳米金属催化剂,可选自单金属纳米颗粒或金属合金纳米颗粒。其实例包括纳米金、纳米铜、纳米钯、纳米铂、纳米镍、纳米银、纳米铱、纳米钴、纳米锌、纳米铈、纳米硒、或纳米合金催化剂如钯铜纳米合金、铂铜纳米合金、铂硒纳米合金、金铜纳米合金、镍硼纳米合金、铂钌纳米合金、钯镍纳米合金、钴硼纳米合金、银铜钯纳米合金、镍铜纳米合金及其组合。
用于负载纳米金属催化剂的载体是本领域已知的纳米金属载体。其实例包括活性炭、二氧化硅、硅藻土、树脂、多孔氧化铝、分子筛、ZSM-5、SAPO-34、SAPO-11、MCM-41、SSZ-13、TM-5、TNU-9、SBA-15、多孔氮化碳、多孔碳化硅及其组合。
本发明的共价有机框架耦合纳米金属材料用于催化合成领域,可用于工业反应器,参与工业反应。
本发明的共价有机框架耦合纳米金属催化剂所应用的反应是本领域已知的反应,可选自加氢反应、氧化反应、酯化反应、环化反应、裂化反应、烷基化反应、聚合反应、重排反应。其实例包括苯加氢制环乙烷、苯酚加氢制环乙醇、草酸二甲酯加氢制乙二醇、乙二腈加氢制乙二胺、硝基苯加氢制苯胺、甲苯加氢制苯、甲醛加氢制甲醇、糠醛加氢制糠醇、醋酸甲酯加氢制乙醇、丙酮加氢制丙醇、一氧化碳加氢制合成气、呋喃加氢制四氢呋喃、乙炔加氢制乙烯、喹啉加氢制四氢喹啉、萘加氢制十氢萘、丁炔二醇加氢制1,4-丁二醇、肉桂醛加氢制肉桂醇、硝基苯加氢制苯胺、硝基苯乙烯加氢制氨基苯乙烯、二硝基苯加氢制苯二胺、巴豆醛加氢制巴豆醇、二甲基二硫化物加氢制甲基硫醇、1,3丁二烯加氢制丁烯、β-二酮加氢制β-二醇、苯酚加氢制环己酮、苯乙酮加氢制苯乙醇、3-戊酮加氢制仲辛醇、乙酸乙酯加氢制乙醇、4-异丁基苯乙酮加氢制1-(4-异丁基苯基)乙醇、石油炼制中加氢脱硫、对二甲苯氧化制对苯二甲酸、甲苯氧化制苯甲醛、烃类氧化制含氧化合物、环己烷氧化制环己醇、环己烷氧化环己酮、草酸酯化制草酸二甲酯、冰醋酸与正丙醇制醋酸正丙酯、乙酸与异戊醇酯化制乙酸异戊酯、乙酸与正丁醇制乙酸丁酯、莰烯与乙酸制乙酸异龙脑酯、柠檬酸与正丁醇制柠檬酸正丁酯、烯烃环化反应、聚丙烯腈环化、二氯丙醇环化制环氧氯丙烷、正辛烷裂化制甲烷、四氢萘裂化开环、异丁烷与丙烯烷基化制烷基化油、苯与乙烯烷基化制乙苯、甲苯与丙烯烷基化制甲基异丙苯、间二甲苯异丁基化制二甲苯麝香、苯酚与异丁烯烷基化制叔丁基苯酚、二异丁烯烷基化制对辛基苯酚、乙烯聚合制聚乙烯、丙烯腈聚合制聚丙烯腈、苯乙烯聚合制聚苯乙烯、乙二胺与己二酸聚合制聚六甲基己二酰胺、对苯二甲酸二甲酯与乙二醇酯制聚对苯二甲酸二甲酯、环己酮肟重排制己内酰胺、苯乙烯重排制备苯乙醛、脱氢芳樟醛重排制柠檬醛、N,N’-二芳基肼重排制4,4’-二氨基联苯的一种或者多种。
本发明的共价有机框架耦合纳米金属催化剂所使用的反应器为本领域已知的反应器,其实例包括固定床、浆态床、移动床和流化床及其组合。
本发明的共价有机框架耦合纳米金属催化剂及其制备方法具有以下的有益效果:
(1)本发明的共价有机框架耦合纳米金属催化剂将共价有机框架材料与现有多相催化剂相结合,利用共价有机框架材料包裹于纳米金属催化剂表面,这能够极大降低共价有机框架材料的用量和成本。在传统廉价但成熟的催化剂载体上负载金属纳米颗粒,再在纳米颗粒上包裹高成本的COF。如此COF的用量相较于纯COF负载载体会极大的下降。真正实现共价有机框架材料在多相催化中的应用。
(2)本发明的共价有机框架耦合纳米金属催化剂可以通过控制外层COF孔道结构调控催化剂的孔径大小,比表面积进而影响催化反应扩散过程,调控反应活性和选择性大小。
(3)本发明的共价有机框架耦合纳米金属催化剂在现有催化剂表面形成一层保护层,阻止现有催化剂纳米颗粒的长大,延长催化稳定性。
(4)本发明的方法合成的催化剂在化学化工反应中展现出优异的催化性能,可提高催化剂的活性、选择性和稳定性,为解决当今连续化工反应生产中的核心问题催化剂,提供了一种新的解决方案,且其制备方法简单,生产成本低,对设备的要求不高,符合实际生产要求,有较大的应用前景。
附图说明
图1展示现有技术中纳米Cu在纯载体(SiO2)上——Cu/SiO2在加氢催化下反应300h后的纳米颗粒平均大小。Cu/SiO2_300h17.57nm,失活。
图2展示本发明的纳米Cu在载体(SiO2)上后耦合COF—Cu/SiO2@COF在加氢催化下反应300h后的纳米颗粒平均大小。Cu/SiO2@COF_300h 7.23nm仍具有催化活性。
图3a-3d展示了本发明的纳米Cu在载体(SiO2)上后耦合COF—Cu/SiO2@COF催化剂的sem EDS图。
图4a-4b展示了本发明的纳米Cu在规整球形载体(SiO2)上后耦合COF—Cu/SiO2@COF催化剂的TEM图。
图5展示了现有技术的纳米Cu/SiO2催化剂以及本发明的实施例II(2)制得的纳米Cu/SiO2@COF催化剂用于草酸二甲酯(DMO)加氢制备乙二醇(EG)的效果。其中实心符号(●、▲)代表包裹了COF的催化剂,空心符号(○、Δ)代表现有技术的Cu/SiO2催化剂,黑色线条及符号(●、○)代表DMO的转化率,红色线条及符号(▲、Δ)代表乙二醇的选择性。
图6展示了现有技术的纳米Pd/SiO2催化剂以及本发明的实施例I制得的纳米Pd/SiO2@COF催化剂用于丙酮加氢制备异丙醇的效果。其中实心符号●代表本发明的包裹了COF的催化剂的情况下丙酮的转化率,空心符号○代表现有技术的Pd/SiO2催化剂的情况下丙酮的转化率。
具体实施方式
通过下述实施例来说明本发明的具体实施方式,但这些实施例仅仅是示例性的,不应该解释为对本发明的限制。
实施例I:制备负载于无机载体的纳米金属催化剂
纳米金属催化剂的制备方法是现有技术中已知的,通常如下制备:
步骤一:将活性组分金属盐加入去离子水中溶解,然后加入无机载体,混合均匀,室温下通风处干燥过夜;
步骤二:将上述样品于60-120℃干燥2-24h;再于马弗炉中200-700℃焙烧2-20h;
步骤三:将步骤二获得的样品于氢气氛围中还原活化处理,条件是温度20-450℃,压力0.1-1.0MPa,以体积空速为100-3000h-1的氢气流还原0.1-24h,优选2-8h。
实施例II:制备共价有机框架耦合纳米金属催化剂;
实施例II.1:制备Pd@SiO2-COF催化剂
配制体积比为1:2的二氧六环和均三甲苯混合溶剂。将0.050mmol1,3,5-三(4-氨苯基)苯溶于5mL混合溶剂,溶解完全,混合均匀,获得溶液。将0.050mmol均三苯甲醛溶于5mL混合溶剂,溶解完全,混合均匀,获得溶液。混合上述两种溶液,加入44.2mg根据实施例I的方法制备的负载于二氧化硅的纳米钯催化剂。
均匀分散后加入0.0015mmol三氟甲基磺酸钪(Sc(OTf)3),室温下反应三天。反应结束后,抽滤,分别用20mL混合溶剂洗涤三次固体,取沉淀固体,真空干燥得到固体Pd@SiO2-COF。
固载于微反应器中,评价Pd@SiO2-COF催化碘苯和苯硼酸Suziki反应催化性能,催化剂连续运行2000h,碘苯的转化率为100%。
实施例II.2:制备Cu@SiO2-COF催化剂
配制体积比为1:2的二氧六环和均三甲苯混合溶剂。将0.050mmol1,3,5-三(4-氨苯基)苯溶于5mL混合溶剂,溶解完全,混合均匀,获得溶液。将0.050mmol均三苯甲醛溶于5mL混合溶剂,溶解完全,混合均匀,获得溶液。混合上述两种溶液,加入25.6mg根据实施例I的方法制备的负载于二氧化硅的纳米铜催化剂,均匀分散后加入0.0015mmol Sc(OTf)3,室温下反应三天。反应结束后,抽滤,分别用20mL混合溶剂洗涤三次固体,取沉淀固体,真空干燥得到固体Cu@SiO2-COF。
获得的产物可如下表征:
通过Cu/SiO2@COF中只有COF中含有N元素来证明。从附图3a-3d的sem EDS数据可以看出存在N元素,由于Cu/SiO2@COF中只有COF中含有N元素,证实COF的存在。
可替代地,通过采用规整的球形载体SiO2进行表征。利用与上述相同方式将Cu负载到SiO2表面,再用COF进行包裹。从图4a、图4b的TEM图可以看出,COF选择性地优先包裹纳米Cu颗粒。
还可以通过证明催化剂的催化效果增强。例如,附图5所示,催化剂对草酸二甲酯加氢制备乙二醇效果增强。
于固定床反应器中,评价Cu@SiO2-COF催化草酸二甲酯(DMO)加氢的催化性能,反应条件:200℃,2.0MPa,WLHSV=1.0h-1,H2/DMO=200。催化剂连续运行1000h,DMO转化率100%,乙二醇选择性99.9%。
从附图1-2以及附图5可以明显看出,采用本发明的催化剂转化率提高,用量少,选择性好,防止催化剂失活及奥氏熟化。
实施例II.3:制备Ag@活性炭-COF催化剂
将1mmol的3,3'-二硝基联苯胺溶于10ml的乙醇中,加入0.005mmol的4-硝基苯甲醛,溶解完全,混合均匀,获得溶液。将0.05mmol的2,4,6-三(4-醛基苯基)-1,3,5-三嗪溶于50ml的乙醇,加入10mmol的3-氯苯胺,溶解完全,混合均匀,获得溶液。混合上述两种溶液,加入3.8mg负载于活性炭的纳米银催化剂,均匀分散后加入0.01mmolSc(OTf)3,室温下反应三天。反应结束后,抽滤,分别用20mL如实施例2中所述的体积比为1:2的二氧六环和均三甲苯混合溶剂洗涤三次固体,取沉淀固体,真空干燥得到固体Ag@活性炭-COF。
于固定床反应器中,评价Ag@活性炭-COF催化苯乙炔基磷酸二乙酯氧化生成(2-苯乙基-2-氧代)-磷酸二乙酯的催化性能,催化剂连续运行500h,DMO转化率100%,(2-苯乙基-2-氧代)-磷酸二乙酯选择性99.2%。
实施例II.4:制备Pd@SBA-15-COF催化剂
将0.05mmol的三(4-氨基苯基)-1,3,5-三嗪溶于50ml的二氯苯,加入10mmol的2-萘甲醛,溶解完全,混合均匀,获得溶液。将1mmol的2,4,6-三(4-醛基苯基)-1,3,5-三嗪溶于10ml的二氯苯,加入0.005mmol的庚胺,溶解完全,混合均匀,获得溶液。混合上述两种溶液,加入50.8mg负载于SBA-15的纳米钯催化剂,均匀分散后加入0.5mg苯磺酸,室温下反应38h。反应结束后,抽滤,分别用20mL如实施例2中所述的体积比为1:2的二氧六环和均三甲苯混合溶剂洗涤三次固体,取沉淀固体,真空干燥得到固体Pd@SBA-15-COF。
于固定床反应器中,评价Pd@SBA-15-COF催化丙酮加氢的催化性能,催化剂连续运行1200h,丙酮转化率100%,异丙醇选择性99.3%。
实施例II.5:制备Pt@Al2O3-COF催化剂
配制体积比为1:2的二氧六环和均三甲苯混合溶剂。将0.2mmol的均苯三硼酸溶于50ml的乙腈中,加入12mmol的苯硼酸,溶解完全,混合均匀,获得溶液。将0.2mmol的均苯三硼酸溶于50ml的二氯苯,加入12mmol的苯硼酸,溶解完全,混合均匀,获得溶液。混合上述两种溶液,加入7.2mg负载于多孔氧化铝的纳米铂催化剂,均匀分散后加入1.4mmol的苯磺酸,80℃下反应两天。反应结束后,抽滤,分别用20mL混合溶剂洗涤三次固体,取沉淀固体,真空干燥得到固体Pt@Al2O3-COF。
于流化床中,评价Pt@Al2O3-COF催化苯甲醛于甲苯中的酯化催化性能,催化剂连续运行600h,苯甲醛转化率100%,酯化效率97.8%。
实施例II.6:制备Ru@C3N4-COF催化剂
将0.8mmol的5,10,15,20-四(4-氨基苯基)卟啉溶于10ml的四氢呋喃,加入0.08mmol的2-甲基苯甲醛,溶解完全,混合均匀,获得溶液。将0.8mmol的2,3-二甲氧基对苯二甲醛溶于0ml的四氢呋喃,加入0.08mmol的-甲基苯胺,溶解完全,混合均匀,获得溶液。混合上述两种溶液,加入225mg负载于多孔氮化碳的纳米钌催化剂,均匀分散后,加入0.8mmol的三氟乙酸,50℃下反应三天。反应结束后,抽滤,分别用20mL如实施例2中所述的体积比为1:2的二氧六环和均三甲苯混合溶剂洗涤三次固体,取沉淀固体,真空干燥得到固体Ru@C3N4-COF。
于固定床反应器中,评价Ru@C3N4-COF催化苯胺加氢的催化性能,催化剂连续运行1000h,苯胺转化率100%,环己胺选择性99.0%。
实施例II.7:制备Sn@Al2O3-COF催化剂
配制体积比为1:2的二氧六环和均三甲苯混合溶剂。将17.5mg(0.050mmol)1,3,5-三(4-氨苯基)苯溶于5mL混合溶剂,溶解完全,混合均匀,获得溶液。将8.1mg(0.050mmol)均三苯甲醛溶于5mL混合溶剂,溶解完全,混合均匀,获得溶液。混合上述两种溶液,加入78.6mg负载于多孔氧化铝的纳米锡催化剂中,均匀分散后,加入0.734mg(0.0015mmol)Sc(OTf)3,室温下反应三天。反应结束后,抽滤,分别用20mL混合溶剂洗涤三次固体,取沉淀固体,真空干燥温度得到固体Sn@Al2O3-COF。
于固定床反应器中,评价Sn@Al2O3-COF催化苯甲醛肟重排生成苯甲酰胺的催化性能,催化剂连续运行950h,苯甲酰胺产率达67%。
Claims (14)
1.一种制备共价有机框架材料耦合纳米金属催化剂的方法,其包括以下步骤:
1)利用沉淀、浸渍、超声和溶胶凝胶方法中的一种或多种,将纳米金属负载于无机载体上,得到负载于无机载体上的纳米金属;
2)将COF单体A和COF单体B溶解或分散在有机溶剂中,加入控制剂AP和控制剂BP,得到COF反应液,基于有机溶剂的体积计,所述单体A和单体B的浓度为0.001-100M,控制剂AP和控制剂BP的浓度为0-1000M且不为0;其中所述控制剂AP选自单醛类、单硼酸类、酚类、醇类和单腈类,和所述控制剂BP选自单胺类、单酰肼类、单硼酸类和单腈类;
3)将获自步骤1)的负载于无机载体上的纳米金属均匀分散到获自步骤2)的COF反应液中,加入COF催化剂,在0-200℃下反应耦合0.1-96h,得到共价有机框架耦合纳米金属材料分散液,基于反应液的体积计,所述负载于无机载体上的纳米金属的浓度为0.1-4000mg/mL,所述COF催化剂的浓度为0.001-100mM/mL,和
4)将获自步骤3)的共价有机框架耦合纳米金属材料分散液过滤,用有机溶剂洗涤沉淀,在20-180℃下,在氮气、氩气或氦气保护下,常压或真空干燥0.1-48h,得到共价有机框架材料耦合纳米金属催化剂。
2.根据权利要求1所述的方法,其特征在于,所述负载于无机载体上的纳米金属为单金属纳米颗粒或金属合金纳米颗粒。
3.根据权利要求1所述的方法,其特征在于,所述载体选自活性炭、二氧化硅、硅藻土、多孔氧化铝、ZSM-5、SAPO-34、SAPO-11、MCM-41、SSZ-13、TM-5、TNU-9、SBA-15、多孔氮化碳和多孔碳化硅中的一种或多种。
4.根据权利要求1所述的方法,其特征在于,所述载体选自分子筛。
5.根据权利要求1-4任一项所述的方法,其特征在于,COF单体A选自1,4-苯二胺、2,5-二甲基-1,4-苯二胺、四甲基对苯二胺、联苯胺、3,3',5,5'-四甲基联苯-4,4'-二胺、3,3'-二硝基联苯胺、4,4'-二氨基三连苯、4,4'-二氨基二苯乙烯、对二氨基偶氮苯、2,6-蒽二胺、3,4-二氨基四氢呋喃、肼、1,2-环己二胺、1,2,4,5-二(二酰肼)苯、1,3,5-三(4-氨苯基)苯、2,4,6-三(4-氨基苯基)-1,3,5-三嗪、三聚氰胺、5,10,15,20-四(4-氨基苯基)卟啉、1,2,4,5-苯四胺、六氨基苯、1,6-二氨基芘、2,3,6,7,10,11-六氨基三亚苯、1,4-苯二硼酸、均苯三硼酸、1,4-苯二硼酸二频哪酯、4,7-双硼酸-2,1,3-苯并噻二唑、4,7-双(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)-2,1,3-苯并噻二唑、2,7-双硼酸芘、2,7-双(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)芘、4,4'-联苯基二硼酸、4,4'-联苯二硼酸二频哪醇酯、5,10,15,20-四(4-硼酸基苯基)卟啉、对苯二腈、2,6-蒽二腈、对苯二甲酰肼、2,5-二甲氧基对苯二甲酰肼、2,5-二乙氧基对苯二甲酰肼、及其组合。
6.根据权利要求5所述的方法,其特征在于,COF单体A选自1,4-苯二胺、1,3,5-三(4-氨苯基)苯、2,4,6-三(4-氨基苯基)-1,3,5-三嗪、5,10,15,20-四(4-氨基苯基)卟啉、1,4-苯二硼酸、均苯三硼酸、5,10,15,20-四(4-硼酸基苯基)卟啉和对苯二甲酰肼中的一种或多种。
7.根据权利要求1-4任一项所述的方法,其特征在于,COF单体B选自对苯二甲醛、联苯二甲醛、2,5-二羟基对苯二甲醛、2,5-二甲氧基对苯二甲醛、2,3-二羟基对苯二甲醛、2,3-二甲氧基对苯二甲醛、2,5-二炔氧基对苯二甲醛、乙二醛、均苯三甲醛、2,4,6-三羟基均苯三甲醛、1,3,5-三(4-醛基苯基)苯、2,4,6-三(4-醛基苯基)-1,3,5-三嗪、环己六酮、1,4-苯二硼酸、均苯三硼酸、1,4-苯二硼酸二频哪酯、4,7-双硼酸-2,1,3-苯并噻二唑、4,7-双(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)-2,1,3-苯并噻二唑、2,7-双硼酸芘、2,7-双(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)芘、4,4'-联苯基二硼酸、4,4'-联苯二硼酸二频哪醇酯、5,10,15,20-四(4-硼酸基苯基)卟啉、1,2,4,5-苯四酚、3,6-二甲基-1,2,4,5-苯四酚、3,6-二乙基-苯四酚、3,6-二丙基-1,2,4,5-苯四酚、2,3,6,7-萘四酚、2,3,6,7-蒽四酚、3,6,7,10,11-六羟基三亚苯、对苯二腈、2,6-蒽二腈、及其组合。
8.根据权利要求7所述的方法,其特征在于,COF单体B选自对苯二甲醛、联苯二甲醛、2,4,6-三羟基均苯三甲醛、1,2,4,5-苯四酚、3,6,7,10,11-六羟基三亚苯、1,4-苯二硼酸和均苯三硼酸中的一种或多种。
9.根据权利要求1-4任一项所述的方法,其特征在于,控制剂AP选自苯甲醛、2-氯苯甲醛、3-氯苯甲醛、4-氯苯甲醛、2-硝基苯甲醛、3-硝基苯甲醛、4-硝基苯甲醛、2-甲基苯甲醛、3-甲基苯甲醛、4-甲基苯甲醛、4-叔丁基苯甲醛、4-氟苯甲醛、1-萘甲醛、2-萘甲醛、甲醛、乙醛、丙醛、丁醛、戊醛、己醛、庚醛、辛醛、苯硼酸、4-叔丁基苯硼酸、正丙基硼酸、环己基硼酸、邻苯二酚、2,3-二羟基萘、乙二醇、2,3-二甲基-2,3-丁二醇、1,2-环己二醇、苯腈、萘腈、乙腈和环己腈中的一种或多种。
10.根据权利要求1-4任一项所述的方法,其特征在于,控制剂BP选自苯胺、2-氯苯胺、3-氯苯胺、4-氯苯胺、1,3-苯并噻唑-5-胺、2-硝基苯胺、3-硝基苯胺、4-硝基苯胺、2-甲基苯胺、3-甲基苯胺、4-甲基苯胺、4-叔丁基苯胺、4-氟苯胺、1-萘胺、2-萘胺、甲胺、乙胺、丙胺、丁胺、戊胺、己胺、庚胺、辛胺、环己胺、苯硼酸、4-叔丁基苯硼酸、正丙基硼酸、环己基硼酸、2,3-二羟基萘、乙二醇、2,3-二甲基-2,3-丁二醇、1,2-环己二醇、苯腈、萘腈、乙腈、环己腈、苯甲酰肼、4-氯苯甲酰肼、3-吡啶甲酰肼、甲酸酰肼、乙酸酰肼、丙酸酰肼和环己甲酰肼中的一种或多种。
11.根据权利要求1-4任一项所述的方法,其特征在于,COF催化剂选自甲酸、乙酸、三氟乙酸、苯磺酸、甲基苯磺酸、三氟甲磺酸钪、三氟甲磺酸铕、三氟甲磺酸铟、三氟甲磺酸镱、三氟甲磺酸钇、三氟甲磺酸锌中的一种或多种。
12.通过权利要求1-11任一项所述的方法获得的共价有机框架材料耦合纳米金属催化剂。
13.权利要求12所述的共价有机框架材料耦合纳米金属催化剂用于催化合成的用途,其特征在于,所述催化合成选自加氢反应、氧化反应、酯化反应、环化反应、裂化反应、烷基化反应、聚合反应和重排反应中的一种或多种。
14.根据权利要求13所述的用途,其特征在于,可应用的反应器选自固定床、浆态床、移动床、流化床、微反应器中的一种或多种。
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