CN112871210B - 一种有序介孔高分子多相光催化剂的制备方法 - Google Patents
一种有序介孔高分子多相光催化剂的制备方法 Download PDFInfo
- Publication number
- CN112871210B CN112871210B CN201911204938.4A CN201911204938A CN112871210B CN 112871210 B CN112871210 B CN 112871210B CN 201911204938 A CN201911204938 A CN 201911204938A CN 112871210 B CN112871210 B CN 112871210B
- Authority
- CN
- China
- Prior art keywords
- ordered mesoporous
- photocatalyst
- ethanol
- phenol
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- 229920000642 polymer Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 208000006930 Pseudomyxoma Peritonei Diseases 0.000 claims abstract description 20
- 229920000306 polymethylpentene Polymers 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 125000006617 triphenylamine group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 107
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229920001992 poloxamer 407 Polymers 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 125000003630 glycyl group Chemical class [H]N([H])C([H])([H])C(*)=O 0.000 claims 1
- 150000002475 indoles Chemical class 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 abstract description 10
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004471 Glycine Substances 0.000 abstract description 5
- -1 glycine ester Chemical class 0.000 abstract description 5
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 abstract description 5
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000002861 polymer material Substances 0.000 description 9
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000008098 formaldehyde solution Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种有序介孔高分子多相光催化剂的制备方法,包括下列步骤:(1)制备含三苯基胺官能团的高分子预聚体;(2)制备含有三苯基胺官能团的有序介孔高分子多相光催化剂。所述的高分子多相光催化剂TPA‑PMPs的BET比表面积在205~460m2/g之间,具有很好的二维六方有序介孔结构,催化剂载入量为0.55~1.20mmol/g。本发明提供的方法具有以下特点:(1)原料便宜易得、合成方法简便;(2)该多相催化剂具有很好的光催化活性,可用于催化甘氨酸酯与吲哚反应合成3,3’‑二吲哚基乙酸酯类化合物;(3)反应完成后催化剂可简便回收及循环使用。
Description
技术领域
本发明属于材料化学领域,特别涉及一种有序介孔高分子多相光催化剂的制备方法及其应用。
背景技术
自2008年以来,可见光催化逐渐引起研究者的广泛关注,并成为促进有机反应的重要手段。可见光催化具有反应条件温和、洁净以及环境友好等特性,因此其在化工中间体制备、药物合成等领域有着很好的应用前景。但是目前可见光催化反应往往需要添加钌、铱等贵金属配合物作为光催化剂。光催化剂价格昂贵且不能回收利用,这极大地限制了该类反应在工业中的应用。鉴于这一点,近年来也有研究者致力于将光催化剂引入有机或无机载体,得到多相化的光催化剂。尽管这些研究在一定程度上解决了光催化剂的回收利用问题,但是受载体及载入方式的限制,现有多相化的光催化剂普遍存在稳定性差、活性位点分布不均等缺点,所以催化效果往往明显差于均相光催化剂。
有序介孔高分子材料具有高度有序的孔道、大的比表面积以及易修饰等特性,因此其近年来成为多孔材料领域研究的热点。赵东元院士课题组以苯酚和甲醛为原料合成的FDU-15是一种易于大量合成、造价便宜的有序介孔高分子材料。我们设想,在合成FDU-15材料时,通过加入适量含有苯酚结构单元的光催化剂,即可得到具有光催化活性的有序介孔高分子材料。这样既可以利用材料中有序的介孔孔道,实现催化位点的均匀分布,又可以实现光催化剂的简便回收利用。但是迄今为止,还没有见到有关有序介孔高分子光催化剂的报道。
发明内容
本发明的目的在于提供一种有序介孔高分子多相光催化剂的制备方法,并将其用于催化甘氨酸酯与吲哚反应合成3,3’-二吲哚基乙酸酯类化合物。
本发明的目的可以通过以下技术方案得以实现。
一种有序介孔高分子多相光催化剂的制备方法,包括如下步骤:
1)在313~323K条件下,将三苯基胺、苯酚、20wt%的氢氧化钠水溶液以及37%甲醛水溶液搅拌均匀后,于343~348K温度下反应1~2h,得到含有三苯基胺结构的低聚物预聚体溶液,冷却至室温,用0.5~6.0mol/L HCl调节此预聚体溶液的pH至中性,减压蒸除水分,将残余物配成乙醇溶液备用。
2)将1.5~3.0g的三嵌段共聚物Pluronic F127溶于30~60g乙醇中得到澄清液,向其中加入一定量上述预聚体乙醇溶液,搅拌10~20min,装入培养皿中挥发除去乙醇;
3)将培养皿置于373~393K温度下固化24~35h后,得到树脂状固体;将此固体置于管式炉中,在惰性气体保护、618~628K加热条件下高温焙烧2~3h脱除模板剂,即可得到含三苯基胺官能团的有序介孔高分子多相光催化剂TPA-PMPs。
所述的三苯基胺:苯酚:甲醛:氢氧化钠=1:8:30:1~4:2:30:1(摩尔比)。
所述的预聚体乙醇溶液中乙醇的量为6.0~13.0g。
所述的苯酚、甲醛、三苯基胺和F127均为化学纯或者分析纯,所有水溶液均在去离子水中配制。
所述的高分子多相光催化剂TPA-PMPs的BET比表面积在205~460m2/g之间,具有很好的二维六方有序介孔结构,催化剂载入量为0.55~1.20mmol/g。
甘氨酸酯与吲哚反应合成3,3’-二吲哚基乙酸酯类化合物的反应方程式为:
在10mL圆底烧瓶中依次加入甘氨酸酯、吲哚、TPA-PMPs催化剂、柠檬酸和乙腈,在室温及可见光照射下反应,TLC监测反应结束后,加入少量NaOH水溶液淬灭反应,用乙酸乙酯萃取,减压蒸除溶剂,柱层析(石油醚:乙酸乙酯=4:1)纯化得到3,3’-二吲哚基乙酸酯类化合物。多相催化剂TPA-PMPs可通过离心的方式回收,用少量NaOH水溶液以及大量去离子水、乙醇洗涤数次,于323~333K下真空干燥,即可用于下一次催化循环。
上述光催化反应的产率为87%,这表明TPA-PMPs光催化材料具有很好的光催化活性。该光催化剂可重复使用5次而活性无明显下降。
TPA-PMPs光催化剂具有优异的催化活性及循环能力,主要归因于:
1、TPA-PMPs光催化剂具有规整有序的二维六方介孔结构、均匀的孔径分布、较大的比表面积。这些特点保证了光催化活性位点的均匀分布、底物与活性中心的充分接触。
2、TPA-PMPs光催化剂为功能化的A阶酚醛树脂进一步热固得到的介孔材料,具有酚醛树脂的性能,因此具有很好的机械强度,使用数次后,该介孔材料仍具有较为有序的介孔结构,从而保证了较好的光催化活性。
附图说明
附图用来提供对本发明的进一步理解,并且构成说明书的一部分,与本发明的实施例一起用于解释本发明,并不构成对本发明的限制。在附图中:
图1是本发明中有序介孔高分子多相光催化剂TPA-PMPs的粉末XRD图;
图2是本发明中有序介孔高分子多相光催化剂TPA-PMPs循环能力测试图。
具体实施方式
为了更好地说明有序介孔高分子多相光催化剂的制备过程,下面举出一些具体的制备过程及反应的应用实施例,但本发明并不局限于所列举的实例。
实施例1
在318K下,将0.52g二(4-苯酚)基苯基胺和1.51g苯酚加入0.40g 20wt%氢氧化钠水溶液中,在此温度下搅拌15min,再加入4.87g 37%甲醛水溶液,于345K下反应1.2h。冷却至室温,用3.0mol/L的HCl水溶液调节pH至中性,在320K下减压蒸除水。向残余液体中加入12.3g乙醇,搅拌均匀,静置、沉淀除去氯化钠,得到预聚体乙醇溶液。将3.0g F127溶于60.0g乙醇中,向其中加入14.0g预聚体乙醇溶液,室温搅拌15min后倒入培养皿中,挥发除去乙醇,然后将培养皿置于烘箱于393K下烘烤24h。将所得树脂状固体磨细后置于管式炉中,在氮气保护下,623K高温焙烧3h脱除模板剂,即可得到含三苯基胺的介孔高分子材料TPA-PMPs。
实施例2
在318K下,0.42g二(4-苯酚)基苯基胺、0.66g苯酚加入0.20g 20wt%氢氧化钠水溶液中搅拌10min,再加入2.43g 37%甲醛水溶液,于345K下反应1.0h。冷却至室温,用0.6mol/L HCl水溶液调节pH至中性,在320K下减压蒸除水。向残余液体中加入6.2g乙醇搅拌均匀,静置、沉淀除去氯化钠,得到预聚体乙醇溶液。将1.5g F127溶于30.0g乙醇中,加入7.0g预聚体乙醇溶液,室温搅拌10min后倒入培养皿中,挥发除去乙醇,然后将培养皿置于烘箱于383K下烘烤26h。将所得树脂状固体磨细后置于管式炉中,在氩气保护下,628K高温焙烧3h脱除模板剂,即可得到含三苯胺的介孔高分子材料TPA-PMPs。
实施例3
在315K下,0.55g二(4-苯酚)基苯基胺、0.56g苯酚加入0.20g 20wt%氢氧化钠水溶液中搅拌12min,再加入2.43g 37%甲醛水溶液,于345K下反应1.0h。冷却至室温,用0.6mol/L HCl水溶液调节pH至中性,在321K下减压蒸除水。向残余液体中加入7.2g乙醇搅拌均匀,静置、沉淀除去氯化钠,得到预聚体乙醇溶液。将2.0g F127溶于40.0g乙醇中,加入8.0g预聚体乙醇溶液,室温搅拌10min后倒入培养皿中,挥发除去乙醇,然后将培养皿置于烘箱于373K下烘烤28h。将所得树脂状固体磨细后置于管式炉中,在氩气保护下,620K高温焙烧3h脱除模板剂,即可得到含三苯胺的介孔高分子材料TPA-PMPs。
实施例4
在315K下,0.83g二(4-苯酚)基苯基胺、0.38g苯酚加入0.20g 20wt%氢氧化钠水溶液中搅拌10min,再加入2.43g 37%甲醛水溶液,于343K下反应1.5h。冷却至室温,用1.0mol/L HCl水溶液调节pH至中性,在318K下减压蒸除水。向残余液体中加入6.2g乙醇搅拌均匀,静置、沉淀除去氯化钠,得到预聚体乙醇溶液。将1.5g F127溶于30.0g乙醇中,加入7.0g预聚体乙醇溶液,室温搅拌10min后倒入培养皿中,挥发除去乙醇,然后将培养皿置于烘箱于375K下烘烤27h。将所得树脂状固体磨细后置于管式炉中,在氮气保护下,625K高温焙烧3h脱除模板剂,即可得到含三苯胺的介孔高分子材料TPA-PMPs。
实施例5
在318K下,1.11g二(4-苯酚)基苯基胺、0.19g苯酚加入0.20g 20wt%氢氧化钠水溶液中搅拌15min,再加入2.43g 37%甲醛水溶液,于345K下反应1.0h。冷却至室温,用1.5mol/L HCl水溶液调节pH至中性,在321K下减压蒸除水。向残余液体中加入6.7g乙醇搅拌均匀,静置、沉淀除去氯化钠,得到预聚体乙醇溶液。将1.5g F127溶于30.0g乙醇中,加入7.5g预聚体乙醇溶液,室温搅拌10min后倒入培养皿中,挥发除去乙醇,然后将培养皿置于烘箱于375K下烘烤30h。将所得树脂状固体磨细后置于管式炉中,在氮气保护下,628K高温焙烧2.5h脱除模板剂,即可得到含三苯胺的介孔高分子材料TPA-PMPs。
催化剂用途例
在10mL圆底烧瓶中依次加入甘氨酸酯(0.1mmol)、吲哚(0.21mmol)、TPA-PMPs催化剂(0.005mmol),柠檬酸(0.15mmol)和乙腈(2mL),在室温及蓝光照射下反应,TLC监测反应结束后,加入少量NaOH水溶液淬灭反应,用乙酸乙酯萃取,减压蒸除溶剂,柱层析(石油醚:乙酸乙酯=4:1))纯化得到3,3’-二吲哚基乙酸酯类化合物。
Claims (6)
1.一种有序介孔高分子多相光催化剂的制备方法,其特征在于:包括如下步骤:
1)在313~323K条件下,在将二(4-苯酚)基苯基胺、苯酚、20wt%的氢氧化钠水溶液以及37%甲醛水溶液搅拌均匀后,于343~348K下反应1~2h,得到含有三苯基胺结构的低聚物预聚体溶液,冷却至室温,用0.5~6.0mol/L HCl调节此预聚体溶液的pH至中性,减压蒸除水分,将残余物配成乙醇溶液备用;
2)将1.5~3.0g的三嵌段共聚物Pluronic F127溶于30~60g乙醇中得到澄清液,向其中加入一定量上述的预聚体乙醇溶液,搅拌10~20min,装入培养皿中挥发除去乙醇;
3)将培养皿置于373~393K温度下固化24~35h后,得到树脂状固体;将此固体置于管式炉中,在惰性气体保护、618~628K加热条件下高温焙烧2~3h脱除模板剂,即可得到含三苯基胺官能团的有序介孔高分子多相光催化剂TPA-PMPs。
2.根据权利要求1所述的一种有序介孔高分子多相光催化剂的制备方法,其特征在于:反应物的摩尔比为二(4-苯酚)基苯基胺:苯酚:甲醛:氢氧化钠=1:8:30:1~4:2:30:1。
3.根据权利要求1所述的一种有序介孔高分子多相光催化剂的制备方法,其特征在于:所述的预聚体-乙醇溶液中乙醇的用量为6.0~13.0g。
4.根据权利要求1所述的一种有序介孔高分子多相光催化剂的制备方法,其特征在于:所述的苯酚、甲醛、二(4-苯酚)基苯基胺和F127均为化学纯或者分析纯,所有水溶液均在去离子水中配置。
5.根据权利要求1所述的一种有序介孔高分子多相光催化剂的制备方法,其特征在于:所述的高分子多相光催化剂TPA-PMPs的BET比表面积在205~460m2/g之间,具有很好的二维六方有序介孔结构,催化剂载入量为0.55~1.20mmol/g。
6.根据权利要求1所述的一种有序介孔高分子多相光催化剂的制备方法,其特征在于:所述的有序介孔高分子多相光催化剂TPA-PMPs可用于催化甘氨酸酯与吲哚反应合成3,3’-二吲哚基乙酸酯类化合物。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911204938.4A CN112871210B (zh) | 2019-11-29 | 2019-11-29 | 一种有序介孔高分子多相光催化剂的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911204938.4A CN112871210B (zh) | 2019-11-29 | 2019-11-29 | 一种有序介孔高分子多相光催化剂的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112871210A CN112871210A (zh) | 2021-06-01 |
CN112871210B true CN112871210B (zh) | 2023-09-29 |
Family
ID=76038925
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911204938.4A Active CN112871210B (zh) | 2019-11-29 | 2019-11-29 | 一种有序介孔高分子多相光催化剂的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112871210B (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101455983A (zh) * | 2008-12-30 | 2009-06-17 | 上海师范大学 | 一种PPh2-有序介孔高分子-Pd(II)非均相催化剂的制备方法及其应用 |
CN103008013A (zh) * | 2012-12-31 | 2013-04-03 | 盐城师范学院 | 一种负载型磺酸金属酞菁光催化剂及其制备方法和应用 |
CN105536762A (zh) * | 2015-12-14 | 2016-05-04 | 江南大学 | 一种C/TiO介孔复合光催化剂及其制备方法 |
CN109092362A (zh) * | 2018-07-25 | 2018-12-28 | 大连理工大学 | 具有可见光催化芳杂环化合物三氟甲基化性能的三苯胺基金属有机配聚物的制备方法及应用 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2949076B1 (fr) * | 2009-08-17 | 2011-10-07 | Centre Nat Rech Scient | Compositions catalytique solides a base de materiaux organiques mesoporeux |
-
2019
- 2019-11-29 CN CN201911204938.4A patent/CN112871210B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101455983A (zh) * | 2008-12-30 | 2009-06-17 | 上海师范大学 | 一种PPh2-有序介孔高分子-Pd(II)非均相催化剂的制备方法及其应用 |
CN103008013A (zh) * | 2012-12-31 | 2013-04-03 | 盐城师范学院 | 一种负载型磺酸金属酞菁光催化剂及其制备方法和应用 |
CN105536762A (zh) * | 2015-12-14 | 2016-05-04 | 江南大学 | 一种C/TiO介孔复合光催化剂及其制备方法 |
CN109092362A (zh) * | 2018-07-25 | 2018-12-28 | 大连理工大学 | 具有可见光催化芳杂环化合物三氟甲基化性能的三苯胺基金属有机配聚物的制备方法及应用 |
Non-Patent Citations (2)
Title |
---|
Poly (triphenylamine)-decorated UIO-66-NH2 mesoporous architectures with enhanced photocatalytic activity for CO2 reduction and H2 evolution;Xiaojun Wang 等;Journal of CO2 Utilization;第51卷;第101654 * |
基于三苯胺和咔唑的联吡啶铱化合物的合成 及其在光催化水产氢中的应用研究;郑众 等;合成化学;第26卷(第1期);1-8 * |
Also Published As
Publication number | Publication date |
---|---|
CN112871210A (zh) | 2021-06-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101667222B1 (ko) | 카보닐화 반응에 의한 초산 제조용 Rh-C3N4 불균일 촉매 | |
CN103657643B (zh) | 一种制备纳米钯金属催化剂的方法 | |
CN109482235B (zh) | 一种n-掺杂介孔碳负载的金属纳米催化剂的制备方法及其应用 | |
CN105772091A (zh) | 一类用于co2还原的催化剂及其应用 | |
CN105693490B (zh) | 一种氧化制备2,3,5‑三甲基苯醌的方法 | |
CN103706395A (zh) | 一种纳米钌催化剂及应用 | |
CN114920908B (zh) | 含芴酮的有机共轭聚合物及其在α-酮酯合成中的应用 | |
CN111484533A (zh) | 手性螺环膦-氮-膦三齿配体及其铱催化剂的制备方法和应用 | |
CN114768877B (zh) | 一种纤维素负载Cu2O/TiO2催化材料及其应用于对苯醌甲基化物硼加成反应的方法 | |
US20170021342A1 (en) | Process for preparing catalyst loaded polyphenylene particles, the obtained polyphenylene particles and their use as catalysts | |
CN101805256A (zh) | 金/介孔碳催化剂在葡萄糖选择氧化制备葡萄糖酸反应中的应用 | |
CN113149865B (zh) | 一种用于催化合成α-氰基肉桂酸乙酯的有机碱性催化剂的制法和应用 | |
CN112871210B (zh) | 一种有序介孔高分子多相光催化剂的制备方法 | |
CN112076776B (zh) | 用于选择性光催化氧化醇生成酯的质子化氮化碳及其应用 | |
CN113333021A (zh) | 具有高催化活性的多孔聚合物负载钯催化剂及其在催化Suzuki-Miyaura反应中的应用 | |
CN109772419B (zh) | 在限域空间构筑氮化碳基超薄纳米片复合材料的制备方法 | |
CN114957207B (zh) | 一种水溶性光催化剂在光催化反应中的应用 | |
CN115772077B (zh) | 一种由阿拉伯糖醇催化转化制备手性d-甘油酸的方法 | |
CN113731469B (zh) | 一种用于催化氧化酯化反应的固体催化剂及其制备方法和应用 | |
KR101667223B1 (ko) | 카보닐화 반응에 의한 초산 제조용 Rh/WxC 불균일 촉매 | |
CN116083411B (zh) | 一种非均相光-酶偶联催化剂、制备方法及其应用 | |
CN114702384B (zh) | 酶解木质素基多级孔碳负载钼氧化物催化木质素醇解制备对羟基肉桂酸酯的方法 | |
CN104549208A (zh) | 一种合成碳酸二甲酯的催化剂及其制备方法和应用 | |
CN115926189B (zh) | 一种复合材料hkust-1@pq及其制备方法 | |
CN115260252B (zh) | 一种新型呸啶型配合物的合成方法及应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |