CN104557931B - N-吡啶基苝四甲酰二亚胺的制备及其光催化制氢性能 - Google Patents

N-吡啶基苝四甲酰二亚胺的制备及其光催化制氢性能 Download PDF

Info

Publication number
CN104557931B
CN104557931B CN201310509971.4A CN201310509971A CN104557931B CN 104557931 B CN104557931 B CN 104557931B CN 201310509971 A CN201310509971 A CN 201310509971A CN 104557931 B CN104557931 B CN 104557931B
Authority
CN
China
Prior art keywords
formula
compound
formyl
imide
pyridine radicals
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.)
Expired - Fee Related
Application number
CN201310509971.4A
Other languages
English (en)
Other versions
CN104557931A (zh
Inventor
李冬梅
田忠贞
崔书霞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Jinan
Original Assignee
University of Jinan
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Jinan filed Critical University of Jinan
Priority to CN201310509971.4A priority Critical patent/CN104557931B/zh
Publication of CN104557931A publication Critical patent/CN104557931A/zh
Application granted granted Critical
Publication of CN104557931B publication Critical patent/CN104557931B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

本发明涉及一类N‑吡啶基苝四甲酰二亚胺及其制备方法和应用。该化合物利用取代苝酐与4‑氨基吡啶在高温条件反应制备，工艺过程简单易行。将N‑吡啶基苝四甲酰二亚胺与丁二酮肟咕络合物结合，可作为用于太阳能可见光催化分解水制氢的光催化剂，N‑吡啶基苝四甲酰二亚胺吸收可见光，产生电子，通过配位键传导给金属钴，进而催化水的分解制氢。

Description

N-吡啶基苝四甲酰二亚胺的制备及其光催化制氢性能
技术领域
本发明属于N-吡啶基苝四甲酰二亚胺的制备及其在新能源领域的应用。具体涉及N-吡啶基苝四甲酰二亚胺的制备方法及其该材料作为光催化剂在太阳能可见光分解水制氢中的应用。
背景技术
进入二十世纪以来，人类的工业文明得以迅猛发展，由此引发的能源危机和环境污染成为亟待解决的的严重问题，利用和转换太阳能是解决世界范围内的能源危机和环境问题的一条重要途径。光解水制氢是太阳能光化学转换与储存的最好途径，因为氢燃烧后只生成水，不污染环境，是便于储存和运输的可再生能源;
然而新烟碱杀虫剂大量频繁的使用造成了较为严重的抗性问题，在一定程度上限制了该类化合物的应用；同时该类化合物对蜜蜂的毒性已日益引起人们的关注，都成为制约此类化合物发展的重要问题。并且新烟碱类杀虫剂主要对同翅目和鞘翅目害虫高效，其相对较窄的杀虫谱也限制了虫害防治方面的用药选择性;
因此，如何对有具高活性的硝基亚甲基化合物进行结构改造，以产生新的、更有效的杀虫剂，解决新烟碱类杀虫剂的抗性问题，扩大杀虫谱，使其应用于杀虫剂就成为本发明需要解决的技术问题。
发明内容
本发明目的在于提供一类N-吡啶基苝四甲酰二亚胺化合物及其制备方法;
本发明的另一个目是N-吡啶基苝四甲酰二亚胺作为光催化剂作用于太阳能可见光催化分解水制氢的应用;
本发明的目的通过以下技术方案来实现;
N-吡啶基苝四甲酰二亚胺，通式为（A）：
式中：
R为取代或未取代的苯基;
本发明化合物的制备方法:
本发明化合物的制备方法可以是本领域常用的制备方法，本发明提供了一种优选的通式(A)所述的化合物制备方法，包括方法：
将式(b)化合物和式(c)化合物反应，从而得到式(A)化合物；
所述反应温度为150-250℃，较佳地为200-250℃，更佳地为230℃;
所用的溶剂选自：喹啉或咪唑，优选喹啉。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数按重量计算;
实施例1.
1, 7-二(4-叔辛基酚氧基)-3,4,9,10-苝四酸酐的合成
向250 mL三口烧瓶中加入150 mL的DMF，然后加入4.01g的1,7-二溴苝酐、6.01 g的辛基酚和4.75 g的 CsCO3，在氩气保护下，加热回流反应。 TCL跟踪反应原料消失，5小时后反应完成，停止加热。冷却至室温，加入80 mL冰醋酸，室温下继续搅拌1个小时。所得溶液冷冻析出固体，抽滤并用冷的甲醇洗涤数次，干燥所得固体;
(2)POPPDA的合成
称取上述干燥后的固体0.48g置于100mL的三口烧瓶中，加入20mL干燥过的喹啉，然后加入0.19g4-氨基吡啶，0.07g醋酸锌，通入氩气，并及加热至回流反应20个小时，反应完成后，停止反应并冷却至室温，然后向其中加入100mL2N盐酸搅拌0.5个小时，搅拌完成后抽滤，用水和甲醇洗涤，放入干燥器干燥，即得粗品。利用硅胶柱层析提纯（V二氯甲烷:V甲醇=50:1），收集第二色带洗脱液，减压蒸干得暗红色产物，即为纯品;
化合物试验数据:
1H NMR(400 MHz, CDCl3): δ(ppm) 9.543 (d, J = 8.4 Hz, 2H, H-1, H-1′),8.784 (d, J = 5.2 Hz, 4H, PyH), 8.571 (d, J = 8.4 Hz, 2H, H-2, H-2′), 8.206(s, 2H, H-3), 7.469 (d, J = 8.8 Hz, 4H, PhH), 7.304 (d, J = 6.0 Hz, 4H, PyH),7.076 (d, J = 8.8 Hz, 4H, PyH), 1.764 (s, 4H, 2CH2), 1.404 (s, 12H, 4CH3),0.773 (s, 18H, 2C(CH3) 3). 13C NMR (400 MHz, CDCl3): δ(ppm) 29.72, 31.85,38.52, 57.09, 119.25, 121.61, 123.28, 124.40, 128.5, 129.06, 130.36, 133.68,142.89, 148.14, 150.89, 151.78, 155.95, 162.29. HRMS (EI+): calcd forC62H57N4O6, 952.4200; found, 952.4207。
实施例2.
丁二酮肟钴络合物[Co(DH)(DH2)Cl2]的合成：
在250mL三口烧瓶中加入25 g（0.105 mol）水合氯化钴，750 mL丙酮和24.5g（0.211 mol）丁二酮肟，混合物搅拌10min，过滤除去不溶物。所得母液过夜静置，析出绿色晶体，过滤，丙酮洗涤，干燥得产品28.5 g（76%）。
实施例3.
吡啶基丁二酮肟钴络合[(py)Co(DH)(DH2)Cl]的合成：
将实施例2中合成的丁二酮肟钴络合物（3.3g，0.009mol）悬浮在85mL氯仿溶剂中，向溶液中加入吡啶（1.8g）并振荡。反应5分钟后加入30mL水，强力搅拌2个小时，除去水层。氯仿层水洗3次，旋干大部分氯仿，加入95%的乙醇溶液，析出固体，使用二氯甲烷乙醇溶剂重结晶，得褐色晶体，产率60%。Anal. Calcd for C13ClCoH19N5O4: C, 38.9; H, 4.7; Co,14.6, Found: C, 38.8; H, 5.0; Co, 14.7。
实施例4.
分别称取牺牲剂1.25g的Na2S和0.25g的Na2SO3溶入盛有50mL蒸馏水的100mL光照一侧为平面的Prex玻璃平底反应瓶中。称取实施例1制备的N-吡啶基苝四甲酰二亚胺和实施例2中制备的丁二酮肟钴络合物0.1g加入反应瓶中；
将反应瓶放在磁力搅拌器上搅拌，将三通进样玻璃瓶塞插入反应瓶中，以氮灯作为模拟太阳光源，打开氛灯稳流电源，滤光片滤去<420 nm的紫外光，光源经滤光片滤光后照射至反应瓶侧面，检测可见光照射6h的复合催化剂的光催化分解水制氢活性。氢气的检测采用气相色谱仪装配的TCD检测器，TDX-01填充柱。太阳能可见光催化分解水产H2结果如表1所示；
表1: 太阳能可见光催化分解水产H2结果
光照时间(h) 1 2 3 5 5 6
H2 (mL/g ) 0.81 2.10 3.81 5.56 7.43 9.16
实施例5.
分别称取牺牲剂1.25g的Na2S和0.25g的Na2SO3溶入盛有50mL蒸馏水的100mL光照一侧为平面的Prex玻璃平底反应瓶中。称取实施例1制备的N-吡啶基苝四甲酰二亚胺和实施例3中制备的丁基丁二酮肟钴络合物0.1g加入反应瓶中；
将反应瓶放在磁力搅拌器上搅拌，将三通进样玻璃瓶塞插入反应瓶中，以氮灯作为模拟太阳光源，打开氛灯稳流电源，滤光片滤去<420 nm的紫外光，光源经滤光片滤光后照射至反应瓶侧面，检测可见光照射6h的复合催化剂的光催化分解水制氢活性。氢气的检测采用气相色谱仪装配的TCD检测器，TDX-01填充柱。太阳能可见光催化分解水产H2结果如表2所示；
表2: 太阳能可见光催化分解水产H2结果
光照时间(h) 1 2 3 5 5 6
H2 (mL/g ) 0.81 2.10 3.81 5.56 7.43 9.16
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (5)

1.具有式(A)所示结构的化合物：
式中：R为2,4,4-三甲基戊基取代的苯基。
2.一种权利要求1中所述式(A)化合物的制备方法，其特征在于：
将式(b)化合物和式(c)化合物反应，从而得到式(A)化合物；
上述各式中，R如权利要求1中所定义；
所述反应温度为150-250℃；
所用的溶剂选自喹啉或咪唑。
3.权利要求1中所述式(A)化合物作为光催化剂作用于太阳能可见光催化分解水制氢的应用。
4.如权利要求3所述的应用，其特征在于，采用氙灯作为模拟太阳能光源，采用滤光片滤掉紫外光，评价太阳能可见光催化分解水分解制氢产率。
5.如权利要求3所述的应用，包括下列步骤：
1)分别定量称取牺牲剂Na2S和Na2SO3溶入盛有50mL蒸馏水的100mL光照一侧为Prex玻璃的平底反应瓶中，称取适量的权利要求1中所述式(A)化合物加入至反应瓶中；
2)将反应瓶放在磁力搅拌器上，将三通进样玻璃瓶塞插入反应瓶中，打开氙灯稳流电源，用滤光片滤去<420nm的紫外光，光源透过滤光片后照射至反应瓶侧面；
3)采用气相色谱仪配备的TCD检测器，TDX-01填充柱对生成的气相产物进行检测，评价太阳能可见光催化分解水制氢产率。
CN201310509971.4A 2013-10-25 2013-10-25 N-吡啶基苝四甲酰二亚胺的制备及其光催化制氢性能 Expired - Fee Related CN104557931B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310509971.4A CN104557931B (zh) 2013-10-25 2013-10-25 N-吡啶基苝四甲酰二亚胺的制备及其光催化制氢性能

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310509971.4A CN104557931B (zh) 2013-10-25 2013-10-25 N-吡啶基苝四甲酰二亚胺的制备及其光催化制氢性能

Publications (2)

Publication Number Publication Date
CN104557931A CN104557931A (zh) 2015-04-29
CN104557931B true CN104557931B (zh) 2016-08-17

Family

ID=53075097

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310509971.4A Expired - Fee Related CN104557931B (zh) 2013-10-25 2013-10-25 N-吡啶基苝四甲酰二亚胺的制备及其光催化制氢性能

Country Status (1)

Country Link
CN (1) CN104557931B (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112354558A (zh) * 2020-10-22 2021-02-12 盐城工学院 一种PDINH@TiO2光催化剂及其制备方法和应用
CN112574237B (zh) * 2020-12-16 2022-06-17 河南盛鼎建设集团有限公司 一种g-C3N4/PTCDI-Br复合材料及其制备方法和应用
CN113600235B (zh) * 2021-07-06 2023-01-17 江苏大学 HCl介导法合成1DPDI/ZnFe2O4S型异质结磁性光催化剂的方法及其应用
CN115611915A (zh) * 2022-10-13 2023-01-17 上海理工大学 一种苝系金属化合物及其复合材料的制备方法与应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100340558C (zh) * 2005-10-17 2007-10-03 东南大学 N,n＇－二吡啶基－3,4,9,10－苝四甲酰二亚胺衍生物及其合成方法
EP2379647B1 (en) * 2008-12-17 2014-09-24 Clariant International Ltd. Dyes for polymer coloration, their preparation and their use
CN102574806B (zh) * 2009-10-29 2014-07-02 大日精化工业株式会社 苝四甲酰二亚胺衍生物
CN102091654B (zh) * 2010-11-19 2012-08-08 中国科学院化学研究所 膜状结构的有机半导体可见光光催化剂及其制法和应用

Also Published As

Publication number Publication date
CN104557931A (zh) 2015-04-29

Similar Documents

Publication Publication Date Title
CN104557931B (zh) N-吡啶基苝四甲酰二亚胺的制备及其光催化制氢性能
Jiang et al. Ionic liquid extraction and catalytic oxidative desulfurization of fuels using dialkylpiperidinium tetrachloroferrates catalysts
Yao et al. A CdII‐Based Metal‐Organic Framework with pcu Topology as Turn‐On Fluorescent Sensor for Al3+
Bezaatpour et al. Synthesis, characterization, and immobilization of nickel (II) tetradentate Schiff-base complexes on clay as heterogeneous catalysts for the oxidation of cyclooctene
Basappa Chidananda et al. Benzimidazolyl based Schiff base palladium complex in an ionic liquid: an effective combination for Suzuki coupling
Dayan et al. Palladium (II) complexes bearing bidentate pyridyl-sulfonamide ligands: Synthesis and catalytic applications
Song et al. Synthesis of β-oxopropylcarbamates in a recyclable AgBr/ionic liquid catalytic system: An efficient assembly of CO2 under ambient pressure
Chang et al. Lewis acid promoted dehydration of amides to nitriles catalyzed by [PSiP]‐pincer iron hydrides
Du et al. Zinc powder catalysed formylation and urealation of amines using CO2 as a C1 building block
Zou et al. Catalyst-free hierarchical reduction of CO2 with BH3N (C2H5) 3 for selective N-methylation and N-formylation of amines
Xu et al. Selective aerobic oxidation of sulfides to sulfoxides catalyzed by coenzyme NAD+ models
Lin et al. Selective reduction of carbonyl groups in the presence of low-valent titanium reagents
Zhang et al. Synthesis of isoflavones by room-temperature nickel-catalyzed cross-couplings of 3-iodo (bromo) chromones with arylzincs
CN104211723B (zh) 乙烯基硼化试剂的合成及应用
Nagashima et al. Catalytic Activity of Molecular Rhenium Sulfide Clusters [Re 6 S 8 (OH) 6− n (H 2 O) n](4− n)−(n= 0, 2, 4, 6) with Retention of the Octahedral Metal Frameworks: Dehydrogenation and Dehydration of 1, 4-Butanediol
CN106316935B (zh) 一种Abemaciclib中间体的制备方法
Barbasiewicz et al. Latent metathesis catalyst stabilized with NO2⋯ I interaction
Alakonda et al. Copper (I) catalysis: Synthesis of N, N′-diarylated and N-aryl, N′-formylated chiral C2-symmetric diamines
JP6109604B2 (ja) オクタヒドロビナフチル誘導体
Cibian et al. Facile synthesis of hydroxyformamidines by the N-oxidation of their corresponding formamidines
JP2018118925A (ja) 鉄錯体触媒を用いたカルボニル化合物のヒドロシリル化反応によるアルコキシシランの製造方法
Wang et al. Mechanistic aspects of the cycloaddition of CO 2 with propylene oxide using the trans-Ru (py) 4 Cl 2 catalyst
Lou et al. Synthesis and reactivity of tetraalkoxyl [60] fullerene epoxides, C60 (O)(OR) 4
CN105777815A (zh) 二价锇配合物及其制备方法和应用
Aloui et al. Synthesis and X‐Ray Analysis of a New [6] Helicene

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160817

Termination date: 20181025