CN107936247A - 一种难溶盐与聚酰亚胺气凝胶复合光催化剂及其制备方法 - Google Patents
一种难溶盐与聚酰亚胺气凝胶复合光催化剂及其制备方法 Download PDFInfo
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- CN107936247A CN107936247A CN201711193341.5A CN201711193341A CN107936247A CN 107936247 A CN107936247 A CN 107936247A CN 201711193341 A CN201711193341 A CN 201711193341A CN 107936247 A CN107936247 A CN 107936247A
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- soluble salt
- halogen group
- preparation
- catalyst
- polyimide aerogels
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- 125000005843 halogen group Chemical group 0.000 claims description 57
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 37
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- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 2
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- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 4
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- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- QYYJDHYBOUCZGR-UHFFFAOYSA-N 6-(4-aminophenyl)cyclohexa-3,5-diene-1,1,3-triamine Chemical class NC1(N)CC(N)=CC=C1C1=CC=C(N)C=C1 QYYJDHYBOUCZGR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
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- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
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- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
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Abstract
本发明涉及一种难溶盐与聚酰亚胺气凝胶复合光催化剂及其制备方法。本发明针对目前有机‑无机复合光催化材料存在的复合均匀性和界面异质结调控等问题,采用多元化的分子设计将PI气凝胶材料与难溶盐复合在一起,使复合材料中无机纳米结构均匀分布在PI气凝胶中,二者通过异质结有效的结合在一起。通过本发明方法制备的PI/MX复合气凝胶催化剂既具有超高的比表面积、高效的吸附性、良好的稳定性、可回收性,还具有无机材料的独特性质,在重金属吸附、污染物降解等方面具有很好的应用潜力。
Description
技术领域
本发明属于有机无机复合材料制备领域,具体涉及一种难溶盐与聚酰亚胺气凝胶复合光催化剂及其制备方法。
背景技术
近几年有机-无机复合材料被广泛应用于光催化领域的各个方面,比如光催化降解有机污染物、光解水制氨、二氧化碳还原、选择性有机合成等。一般的有机-无机复合材料大部分集中在导电聚合物与TiO2、ZnO、Fe2O3、Cu2O等氧化物半导体上。如Deng等将聚吡咯和聚苯胺同时引入TiO2中合成了PPy-PANI/TiO2复合光催化材料,有效拓展了TiO2的可见光吸收范围,在可见光下能够高效分解对硝基苯酚(参见:Nanoscale,2013,5,8703)。一些金属-有机复合材料也表现出了很好的光催化性能,比如黄柏标课题组合成的Cu基卟啉MOF材料能将二氧化碳高效还原成甲醇(参见:Mater.Lett.,2016,164,640)。这些复合物中的有机相在光催化过程中性能较好,但此类粉末状材料大都难以回收利用,在实际应用过程中损耗较大。而气凝胶作为一种具有超低密度的固体物质,不仅方便回收利用,还具有对光催化效率影响极大的超高比表面积、吸附性和良好的稳定性,而且柔性的气凝胶还可制成器件用于工业化生产中。
目前聚酰亚胺(PI)气凝胶因超高的柔韧性和吸附性,作为气凝胶中的佼佼者,其性能在不断地被探索开发。PI聚合物作为一种新型光催化剂,由于较高的化学稳定性、成本低和丰富的储量,已经被报道可以光降解有机污染物,并且在可见光照射下,光分解水制氢,在光催化方面展现出极大的优势。如果将PI气凝胶作为有机-无机复合光催化材料的有机相,具有以下优点:(1)超高的比表面积能极大地提高活性位点的数量,良好的吸附性在光催化过程中大量吸附污染物于催化剂表面,对光催化效率的提高具有促进作用;(2)PI气凝胶良好的三维网络结构作为无机相的载体,可以更好的实现与无机相的均匀结合,有利于暴露无机相更多的活性位点,提高光催化效率;(3)PI气凝胶固体材料质轻、柔韧,有望设计合成应用于光催化方面的器件。
其实,有机-无机复合材料的性能不单单是依赖于各组分单体本身的特性,更大程度上是由有机相与无机相之间的界面结构和形貌所决定的。为了获得具有理想形貌、尺寸和界面性能的有机-无机纳米复合材料,人们尝试开发了许多合成方法,包括溶胶-凝胶法、自组装、插层法、共混法、原位聚合法等。PI有机-无机复合材料,极大的弥补了单组分的PI材料活性载流子寿命短、量子效率低、光能利用率差的问题,拓展了PI材料的应用范围。如专利CN 105709831 A,通过在磷酸银的制备过程中加入PI制备得到磷酸银/聚酰亚胺可见光复合光催化剂,此方法并不能实现磷酸银与聚酰亚胺的有效复合,二者之间无法形成异质结不利于光催化过程中电子的转移,而且粉末状材料不利于回收利用。Ma等通过一步热聚合方式制备了black-MoO3/PI复合材料,一步实现了有机-无机材料的复合,有利于二者界面之间形成异质结,发挥两种半导体之间的协同效应提高可见光利用率,但是这种将两种前驱体混合后一步制备核壳结构的方法无法调控两种材料的的均匀分布和有效接触,无法保证复合材料的均一性(参见:ACS Appl.Mater.Interfaces,2015,7,14628)。近期Ma等又通过原位生长将MoO3与PI复合在一起,此创新性的制备方法有利于将MoO3均匀分布在聚合物中,增强了二者之间的有效接触,进一步提高了复合材料之间的相互作用,但是单纯的原位生长法对于两种材料之间界面异质结的大小缺乏调控(参见:Sol.Energ.Mat.Sol.C.,2016,150,102)。
综上所述,现有技术中有机-无机复合光催化材料制备方法仍然存在很多问题,尤其是影响光催化性质的一些关键性问题仍未得到解决,主要包括:(1)如何设计实验实现有机-无机材料的有效复合,并保证复合材料各组分之间的分布均匀性;(2)如何实现各组分之间的有效接触和对异质结的调控;这些问题对光催化过程中电子的转移和光催化效率的提高至关重要。因此,亟需一种能够克服上述问题的有机-无机复合材料光催化及其制备方法。
发明内容
针对上述现有技术中有机-无机材料光催化剂的制备中有机-无机材料无法有效复合、复合材料各组分之间的分布不均匀、各组分之间无法有效接触和对异质结无法有效调控的问题,本发明旨在提供一种难溶盐与聚酰亚胺(PI)复合光催化剂及其制备方法,与现有技术相比,本发明能够使难溶盐均匀分布在PI气凝胶中,使二者之间以异质结紧密结合在一起,通过调节实验参数实现了对分布在聚酰亚胺中的无机难溶盐颗粒的尺寸调控。
本发明的目的之一是提供一种含有卤素基团X的聚酰亚胺气凝胶的制备方法。
本发明的目的之二是提供一种难溶盐与聚酰亚胺气凝胶复合光催化剂的制备方法。
本发明的目的之三是提供一种难溶盐与聚酰亚胺气凝胶复合光催化剂。
本发明的目的之四是提供上述难溶盐与聚酰亚胺气凝胶复合光催化剂及其制备方法的应用。
为实现上述发明目的,具体的,本发明公开了以下技术方案:
首先,本发明公开了一种含有卤素基团X的聚酰亚胺气凝胶的制备方法,所述方法包括如下步骤:
1)将中间体在催化剂条件下通过有机取代反应得到含有卤素基团X的单体;
2)将步骤1)中的含有卤素基团X的单体溶于有机溶剂中得到混合溶液,然后将二胺或者二酐加入上述混合溶液中搅拌溶解后,迅速加入交联剂,搅拌均匀后再依次加入醋酸酐和吡啶,经过化学酰亚胺化,得到含有卤素基团X的聚酰亚胺湿凝胶;
3)将步骤2)中得到的聚酰亚胺湿气凝胶在乙醇溶液中老化处理后,再利用乙醇超临界干燥法得到含有卤素基团X的聚酰亚胺气凝胶;
4)将步骤3)中制备的得到含有卤素基团X的聚酰亚胺气凝胶制成薄片,即得。
步骤1)中,所述中间体包括邻硝基氯苯,邻硝基溴苯,邻硝基碘苯。
步骤1)中,所述催化剂包括:NaOH/CH2O、N2H4、HCl/HBr/HI。
步骤1)中,所述中间体和催化剂的质量体积比(g/mL)为1~3:5。
步骤1)中,所述卤素基团X为:Cl、Br、I元素。
优选的,所述卤素基团X为Cl元素。
步骤2)中,所述有机溶剂包括N-甲基吡咯烷酮(NMP)。
步骤2)中,所述二胺或者二酐与有机溶剂的质量体积比为1~3:10~15。
步骤2)中,所述二胺包括:2,2-二氨基联苯胺(DMBZ),对苯二胺(PPDA)、4,4-二氨基二苯醚(ODA)。
步骤2)中,所述二酐包括:联苯四羧酸二酐(BPDA)、均苯四甲酸二酐(PMDA)、二苯醚四羧酸二酐(ODPA)。
步骤2)中,所述交联剂为1,3,5-三(4-氨基苯氧基)苯。
步骤2)中,所述交联剂与有机溶剂的体积比为1~3:5。
步骤2)中,所述醋酸酐、吡啶、有机溶剂的体积比为1:1:5~10。
步骤3)中,所述老化处理指:①将聚酰亚胺湿气凝胶胶凝老化3h后用50~75%N-甲基吡咯烷酮(NMP)的乙醇溶液浸泡18~24h;②用10~25%NMP的乙醇溶液浸泡①中湿气凝胶20~24h;③在乙醇溶液中将②中湿气凝胶老化24h即可。
步骤3)中,所述乙醇超临界干燥法指:在温度536~600K,压力6.6~10MPa,升温速度为80~100℃/min条件下进行乙醇超临界干燥。
步骤4)中,所述气凝胶薄片的厚度为1~5mm。
其次,本发明公开了一种难溶盐与聚酰亚胺气凝胶复合光催化剂的制备方法,所述方法包括如下步骤:
(1)以本发明制备的含有卤素基团X的聚酰亚胺湿气凝胶薄片为前驱体,将所述前驱体浸到可溶盐乙醇溶液,前驱体中的卤素基团X与可溶盐中的金属阳离子反应,得到含有难溶盐的聚酰亚胺复合气凝胶;
(2)利用乙醇超临界干燥法对步骤(1)得到的含有难溶盐的聚酰亚胺复合气凝胶进行处理,使聚酰亚胺与沉淀盐之间形成异质结,即得难溶盐与聚酰亚胺复合光催化剂。
步骤(1)中,所述可溶盐为:Pb(NO3)2,AgNO3,Hg(NO3)2。
步骤(1)中,所述前驱体与可溶盐乙醇溶液的质量体积比(g/mL)为:1~3:10。
步骤(1)中,所述可溶盐乙醇溶液中可溶盐的浓度为1~2mol/L。
步骤(1)中,所述反应时间为1~5min,反应在常温下进行。
步骤(2)中,所述乙醇超临界干燥的条件为:升温速度为80~120℃/min,保温温度为500~600K,保温时间为2~6h,压力为5~8MPa。
步骤(1)和(2)中,所述难溶盐为卤素基团X与上述硝酸盐中的金属阳离子Pb、Ag、Hg形成的难溶于水的无机盐,如AgCl、PbBr2、HgI2等。
再次,本发明公开了一种难溶盐与聚酰亚胺气凝胶复合光催化剂,该催化剂是由难溶盐与聚酰亚胺复合而成的光催化剂,所述难溶盐为卤素基团X与上述硝酸盐中的金属阳离子形成的难溶于水的无机盐。
最后,本发明公开了上述含有卤素基团X的聚酰亚胺气凝胶的制备方法、难溶盐与聚酰亚胺气凝胶复合光催化剂及其制备方法的应用,所述应用包括用于光催化降解有机污染物、光解水制氨、二氧化碳还原、选择性有机合成等。
本发明的特点在于:首先,本发明通过有机取代反应将卤素基团X引入到合成聚酰亚胺(PI)的二胺或者二酐单体中,通过酰亚胺化和超临界干燥法制备得到含有卤素基团X的PI气凝胶;本发明要首先引入卤素基团X,主要原因是:这些均匀分布在PI中的每一个卤素原子都像一个“抓手”,当Ag、Pb、Hg等金属阳离子与卤素原子接触时就会被这些“抓手”捕获,从而形成均匀分布在PI中的难溶性沉淀盐。然后,本发明将制备的含有卤素基团X的PI气凝胶切割成1-5mm厚度的薄片用以浸渍硝酸盐乙醇溶液,之所以采用这样的方法,主要原因是:利用难溶盐(MX)溶解度低的特点,可以使发生沉淀反应形成的无机难溶盐均匀附着在PI气凝胶中;尽管随着反应的进行MX会逐渐在气凝胶中聚集形成MX颗粒,但MX颗粒的大小受限于气凝胶的孔径大小,这样,本发明就可以通过调节PI气凝胶的孔尺寸进一步来调控MX颗粒的大小,实现对异质结的可控制备。最后,通过乙醇超临界处理,既维持了难溶盐与聚酰亚胺(PI/MX)复合气凝胶的结构和形貌,又可以通过乙醇超临界处理过程中的高温使PI与MX界面之间形成异质结,实现二者之间的有效复合,这种复合材料不仅光催化效率高而且性质极其稳定,银离子不易被光催化生成的光生电子还原成单质银,相比于磷酸银/聚酰亚胺复合光催化剂更适合工业化应用。需要说明的是:通过本发明方法制备的PI/MX复合气凝胶催化剂既具有超高的比表面积、高效的吸附性、良好的稳定性、可回收性,还具有无机材料的一些独特性质,如AgX等离子体催化剂具有高效的催化降解能力,AgX和PI复合之后能更好的发挥协同效应,使该材料在污水处理方面表现出多功能性、高效性和持久性。更重要的是,作为载体材料的PI气凝胶,质轻且柔性极好,所以在实际工业应用中,有望将此类材料制成器件一次性解决污水中的很多问题(物理吸附、化学降解、杀菌消毒),而且可循环重复利用,降低成本。
与现有技术相比,本发明取得了以下有益效果:
(1)本发明针对目前有机-无机复合光催化材料存在的复合均匀性和界面异质结调控等问题,采用多元化的分子设计将PI气凝胶材料与难溶盐复合在一起,使复合材料中无机纳米结构均匀分布在PI气凝胶中,二者通过异质结有效的结合在一起,使本发明制备的PI/MX复合气凝胶催化剂具有超高的比表面积和吸附性,在重金属吸附、污染物降解等方面具有很好的应用潜力。
(2)本发明制备的PI气凝胶的比表面积可达到400~600m2/g,孔径分布均匀,平均孔直径约为40~60nm,超高的比表面积不仅增加了暴露的光催化活性位点的数量,而且有利于吸附更多的污染物;均匀的孔径分布可以使复合的无机盐颗粒尺寸更加均一。
(3)本发明制备的PI气凝胶中的难溶盐颗粒尺寸均一,且均匀分布在PI气凝胶的孔径中,通过上述制备方法的设计和材料的选择,本发明很好地解决了现有技术中有机-无机材料光催化剂的制备中有机-无机材料无法有效复合、复合材料各组分之间的分布不均匀、各组分之间无法有效接触和对异质结无法有效调控的问题。
附图说明
图1是实施例1所得聚酰亚胺湿气凝胶的光学照片。
图2是实施例1所得聚酰亚胺气凝胶的比表面积和孔径分布曲线。
图3是实施例1所得PI/AgCl气凝胶的SEM照片。
具体实施方式
应该指出,以下详细说明都是例示性的,旨在对本申请提供进一步的说明。除非另有指明,本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是,这里所使用的术语仅是为了描述具体实施方式,而非意图限制根据本申请的示例性实施方式。如在这里所使用的,除非上下文另外明确指出,否则单数形式也意图包括复数形式,此外,还应当理解的是,当在本说明书中使用术语“包含”和/或“包括”时,其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
正如背景技术所介绍的,现有技术中,有机-无机材料光催化剂的制备中存在有机-无机材料无法有效复合、复合材料各组分之间的分布不均匀、各组分之间无法有效接触和对异质结无法有效调控的问题,为了解决上述问题,本发明提供一种难溶盐与聚酰亚胺复合光催化剂及其制备方法;下面结合具体的实施例,对本发明做进一步的说明。
实施例1:
1、含有卤素基团Cl的PI气凝胶的制备
(1)将53g邻硝基氯苯与160mL的催化剂NaOH、N2H4、HCl反应,得到3,3'-二氯-4,4'-二氨基联苯,作为含有卤素基团Cl的单体。
(2)将3.99g步骤(1)中得到的单体溶于50mLN-甲基吡咯烷酮中,搅拌溶解,得到混合溶液;然后将4.79g联苯四羧酸二酐加入到上述混合溶液中搅拌溶解,并迅速加入16mL0.02mol/L的1,3,5-三(4-氨基苯氧基)苯,搅拌均匀后再依次加入10.5mL醋酸酐和10.5mL吡啶,得到含氯的PI气凝胶。
(3)将步骤(2)中的PI气凝胶胶凝老化3h后用75%NMP的乙醇溶液浸泡24h,再用25%NMP的乙醇溶液浸泡24h,最后在乙醇溶液中老化24h,得到含有卤素基团Cl的PI湿凝胶。
(4)将步骤(3)中得到的湿凝胶在温度为536K,压力为6.6MPa,升温速度为100℃/min条件下进行乙醇超临界干燥,保温时间为5h,制得含有卤素基团Cl的PI气凝胶,并将上述气凝胶切割成2mm厚度的薄片待用。
2、PI/AgCl复合气凝胶的制备
将上述方法制备的1g含有卤素基团Cl的PI气凝胶薄片浸渍在30mL 1mol/L的AgNO3乙醇溶液中,2min后取出,得到PI/AgCl复合材料,然后将上述复合材料在升温速度为100℃/min,温度为536K,压力为6.6MPa、保温时间为5h下,进行乙醇超临界干燥,制得PI/AgCl复合气凝胶;所述乙醇超临界干燥的条件为:升温速度为80℃/min,保温温度为500K,保温时间为6h,压力为8MPa。
图1是本实施例制备的PI湿/气凝胶的光学照片;图2是本实施例制备的PI气凝胶的比表面积和孔径分布曲线;图3是PI/AgCl复合气凝胶的SEM图像,可以看出AgCl颗粒大小为40±5nm,尺寸比较均一,且均匀分布在PI气凝胶中,二者的均匀分布有利于在光催化过程中电子的有效传输,进而提供光催化效率。
实施例2
1、含有卤素基团Br的PI气凝胶的制备
(1)将50g邻硝基溴苯与150mL的催化剂CH2O、N2H4、HBr反应,得到3,3'-二溴-4,4'-二氨基联苯作为含有卤素基团Br的单体。
(2)将3.99g步骤(1)中得到的单体溶于50mLN-甲基吡咯烷酮(NMP)中,搅拌溶解,得到混合溶液;然后将5g均苯四甲酸二酐加入到上述混合溶液中搅拌溶解,并迅速加入10mL0.02mol/L的1,3,5-三(4-氨基苯氧基)苯,搅拌均匀后再依次加入10mL醋酸酐和10mL吡啶,得到含氯的PI气凝胶。
(3)将步骤(2)中的PI气凝胶胶凝老化3h后用75%NMP的乙醇溶液浸泡24h,再用25%NMP的乙醇溶液浸泡24h,最后在乙醇溶液中老化24h,得到含有卤素基团Br的PI湿凝胶。
(4)将步骤(3)中得到的湿凝胶在温度为600K,压力为10MPa,升温速度为80℃/min条件下进行乙醇超临界干燥,保温时间为5h,制得含有卤素基团Br的PI气凝胶,并将上述气凝胶切割成1mm厚度的薄片待用。
2、PI/AgBr复合气凝胶的制备
将上述方法制备的3g含有卤素基团Br的PI气凝胶薄片浸渍在10mL 2mol/L的AgNO3乙醇溶液中,1min后取出,得到PI/AgBr复合材料,然后将上述复合材料在升温速度为80℃/min,温度为500K,压力为5MPa、保温时间为5h下,进行乙醇超临界干燥,制得PI/AgBr复合气凝胶;所述乙醇超临界干燥的条件为:升温速度为120℃/min,保温温度为600K,保温时间为2h,压力为5MPa。
实施例3
1、含有卤素基团I的PI气凝胶的制备
(1)将50g邻硝基碘苯与250mL的催化剂NaOH、N2H4、HI反应,得到3,3'-二碘-4,4'-二氨基联苯,作为含有卤素基团I的单体。
(2)将3.99g步骤(1)中得到的单体溶于75mLN-甲基吡咯烷酮(NMP)中,搅拌溶解,得到混合溶液;然后将5g二苯醚四羧酸二酐加入到上述混合溶液中搅拌溶解,并迅速加入15mL 0.02mol/L的1,3,5-三(4-氨基苯氧基)苯,搅拌均匀后再依次加入7.5mL醋酸酐和7.5mL吡啶,得到含氯的PI气凝胶。
(3)将步骤(2)中的PI气凝胶胶凝老化3h后用50%NMP的乙醇溶液浸泡18h,再用10%NMP的乙醇溶液浸泡20h,最后在乙醇溶液中老化24h,得到含有卤素基团I的PI湿凝胶。
(4)将步骤(3)中得到的湿凝胶在温度为560K,压力为8MPa,升温速度为90℃/min条件下进行乙醇超临界干燥,保温时间为5h,制得含有Cl的PI气凝胶,并将上述气凝胶切割成5mm厚度的薄片待用。
2、PI/HgI2复合气凝胶的制备
将上述方法制备的3g含有卤素基团Br的PI气凝胶薄片浸渍在10mL 1mol/L的Hg(NO3)2乙醇溶液中,4min后取出,得到PI/PbI2复合材料,然后将上述复合材料在升温速度为80℃/min,温度为550K,压力为7MPa、保温时间为5h下,进行乙醇超临界干燥,制得PI/HgI2复合气凝胶;所述乙醇超临界干燥的条件为:升温速度为100℃/min,保温温度为550K,保温时间为4h,压力为6MPa。
实施例4
1、含有卤素基团I的PI气凝胶的制备
(1)将50g邻硝基碘苯与125mL的催化剂CH2O、N2H4、HI反应,得到3,3'-二碘-4,4'-二氨基联苯,作为含有卤素基团I的单体。
(2)将3.99g步骤(1)中得到的单体溶于75mLN-甲基吡咯烷酮(NMP)中,搅拌溶解,得到混合溶液;然后将22.5g 2,2-二氨基联苯胺加入到上述混合溶液中搅拌溶解,并迅速加入30mL 0.02mol/L的1,3,5-三(4-氨基苯氧基)苯,搅拌均匀后再依次加入9mL醋酸酐和9mL吡啶,得到含氯的PI气凝胶。
(3)将步骤(2)中的PI气凝胶胶凝老化3h后用60%NMP的乙醇溶液浸泡20h,再用15%NMP的乙醇溶液浸泡22h,最后在乙醇溶液中老化24h,得到含有卤素基团I的PI湿凝胶。
(4)将步骤(3)中得到的湿凝胶在温度为580K,压力为7MPa,升温速度为85℃/min条件下进行乙醇超临界干燥,保温时间为5h,制得含有Cl的PI气凝胶,并将上述气凝胶切割成3mm厚度的薄片待用。
2、PI/AgI复合气凝胶的制备
将上述方法制备的3g含有卤素基团Br的PI气凝胶薄片浸渍在10mL 1mol/L的AgNO3乙醇溶液中,4min后取出,得到PI/AgI复合材料,然后将上述复合材料在升温速度为80℃/min,温度为580K,压力为7MPa、保温时间为5h下,进行乙醇超临界干燥,制得PI/AgI复合气凝胶;所述乙醇超临界干燥的条件为:升温速度为110℃/min,保温温度为530K,保温时间为5h,压力为6MPa。
实施例5
1、含有卤素基团Br的PI气凝胶的制备
(1)将50g邻硝基溴苯与150mL的催化剂NaOH、N2H4、HBr反应,得到3,3'-二溴-4,4'-二氨基联苯作为含有卤素基团Br的单体。
(2)将3.99g步骤(1)中得到的单体溶于50mLN-甲基吡咯烷酮(NMP)中,搅拌溶解,得到混合溶液;然后将10g对苯二胺加入到上述混合溶液中搅拌溶解,并迅速加入10mL0.02mol/L的1,3,5-三(4-氨基苯氧基)苯,搅拌均匀后再依次加入12mL醋酸酐和10mL吡啶,得到含氯的PI气凝胶。
(3)将步骤(2)中的PI气凝胶胶凝老化3h后用75%NMP的乙醇溶液浸泡24h,再用25%NMP的乙醇溶液浸泡24h,最后在乙醇溶液中老化24h,得到含有卤素基团Br的PI湿凝胶。
(4)将步骤(3)中得到的湿凝胶在温度为600K,压力为10MPa,升温速度为80℃/min条件下进行乙醇超临界干燥,保温时间为5h,制得含有卤素基团Br的PI气凝胶,并将上述气凝胶切割成4mm厚度的薄片待用。
2、PI/PbBr2复合气凝胶的制备
将上述方法制备的3g含有卤素基团Br的PI气凝胶薄片浸渍在10mL 1.5mol/L的Pb(NO3)2乙醇溶液中,4min后取出,得到PI/PbBr2复合材料,然后将上述复合材料在升温速度为80℃/min,温度为580K,压力为7MPa、保温时间为5h下,进行乙醇超临界干燥,制得PI/PbBr2复合气凝胶;所述乙醇超临界干燥的条件为:升温速度为90℃/min,保温温度为580K,保温时间为3h,压力为7MPa。
以上所述仅为本申请的优选实施例而已,并不用于限制本申请,对于本领域的技术人员来说,本申请可以有各种更改和变化。凡在本申请的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本申请的保护范围之内。
Claims (10)
1.一种含有卤素基团X的聚酰亚胺气凝胶的制备方法,其特征在于:所述方法包括如下步骤:
1)将中间体在催化剂条件下通过有机取代反应得到含有卤素基团X的单体;
2)将步骤1)中的含有卤素基团X的单体溶于有机溶剂中得到混合溶液,然后将二胺或者二酐加入上述混合溶液中搅拌溶解后,迅速加入交联剂,搅拌均匀后再依次加入醋酸酐和吡啶,经过化学酰亚胺化,得到含有卤素基团X的聚酰亚胺湿凝胶;
3)将步骤2)中得到的聚酰亚胺湿气凝胶在乙醇溶液中老化处理后,再利用乙醇超临界干燥法得到含有卤素基团X的聚酰亚胺气凝胶;
4)将步骤3)中制备的得到含有卤素基团X的聚酰亚胺气凝胶制成薄片,即得。
2.如权利要求1所述的含有卤素基团X的聚酰亚胺气凝胶的制备方法,其特征在于:步骤1)中,所述中间体包括邻硝基氯苯,邻硝基溴苯,邻硝基碘苯;
所述催化剂包括:NaOH/CH2O、N2H4、HCl/HBr/HI;
所述中间体和催化剂的质量体积比(g/mL)为1~3:5;
所述卤素基团X为:Cl、Br、I元素。
3.如权利要求2所述的含有卤素基团X的聚酰亚胺气凝胶的制备方法,其特征在于:步骤2)中,所述交联剂为1,3,5-三(4-氨基苯氧基)苯;
所述有机溶剂包括N-甲基吡咯烷酮;
所述二胺为:2,2-二氨基联苯胺、对苯二胺、4,4-二氨基二苯醚;
所述二酐为:联苯四羧酸二酐、均苯四甲酸二酐、二苯醚四羧酸二酐。
4.如权利要求3所述的含有卤素基团X的聚酰亚胺气凝胶的制备方法,其特征在于:步骤2)中,所述二胺或者二酐与有机溶剂的质量体积比为1~3:10~15;
所述交联剂与有机溶剂的体积比为1~3:5;
所述醋酸酐、吡啶、有机溶剂的体积比为1:1:5~10。
5.如权利要求1-4任一项所述的含有卤素基团X的聚酰亚胺气凝胶的制备方法,其特征在于:步骤3)中,所述老化处理指:①将聚酰亚胺湿气凝胶胶凝老化3h后用50~75%N-甲基吡咯烷酮的乙醇溶液浸泡18~24h;②用10~25%NMP的乙醇溶液浸泡①中湿气凝胶20~24h;③在乙醇溶液中将②中湿气凝胶老化24h即可;
所述乙醇超临界干燥法指:在温度536~600K,压力6.6~10MPa,升温速度为80~100℃/min条件下进行乙醇超临界干燥。
6.一种难溶盐与聚酰亚胺气凝胶复合光催化剂的制备方法,其特征在于:所述方法包括如下步骤:
(1)以权利要求1中所述的方法制备的含有卤素基团X的聚酰亚胺湿气凝胶薄片为前驱体,将所述前驱体浸到可溶盐乙醇溶液,前驱体中的卤素基团X与可溶盐中的金属阳离子反应,得到含有难溶盐的聚酰亚胺复合气凝胶;
(2)利用乙醇超临界干燥法对步骤(1)得到的含有难溶盐的聚酰亚胺复合气凝胶进行处理,使聚酰亚胺与沉淀盐之间形成异质结,即得难溶盐与聚酰亚胺复合光催化剂。
7.如权利要求6所述一种难溶盐与聚酰亚胺气凝胶复合光催化剂的制备方法,其特征在于:步骤(1)中,所述前驱体的与可溶盐乙醇溶液的质量体积比(g/mL)为1~3:10;
所述可溶盐为:Pb(NO3)2,AgNO3,Hg(NO3)2;
所述可溶盐乙醇溶液中可溶盐的浓度为1-2mol/L;所述反应时间为1~5min,反应在常温下进行。
8.如权利要求6所述一种难溶盐与聚酰亚胺气凝胶复合光催化剂的制备方法,其特征在于:步骤(2)中,所述乙醇超临界干燥的条件为:升温速度为80~120℃/min,保温温度为500~600K,保温时间为2~6h,压力为5~8MPa。
9.如权利要求6所述一种难溶盐与聚酰亚胺气凝胶复合光催化剂的制备方法,其特征在于:所述步骤(1)和(2)中,难溶盐为卤素基团X与上述硝酸盐中的金属阳离子Pb、Ag、Hg形成的难溶于水的无机盐。
10.如权利要求1-4所述的含有卤素基团X的聚酰亚胺气凝胶的制备方法和/或如权利要求6-9所述的难溶盐与聚酰亚胺气凝胶复合光催化剂的制备方法在光催化降解有机污染物、光解水制氨、二氧化碳还原、选择性有机合成中的应用。
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CN109622043B (zh) * | 2018-12-18 | 2021-11-02 | 山东省科学院新材料研究所 | 一种PI/Ag气凝胶复合光催化材料及其制备方法和应用 |
JP2022516281A (ja) * | 2019-01-02 | 2022-02-25 | デリム カンパニー リミテッド | ポリアミド酸組成物の製造方法、ポリアミド酸組成物、これを用いたポリイミドフィルムの製造方法及びその製造方法によって製造されたポリイミドフィルム |
JP7317122B2 (ja) | 2019-01-02 | 2023-07-28 | デリム カンパニー リミテッド | ポリアミド酸組成物の製造方法、ポリアミド酸組成物、これを用いたポリイミドフィルムの製造方法及びその製造方法によって製造されたポリイミドフィルム |
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