CN104829651A - 一种锰酞菁衍生物及其合成方法和用途 - Google Patents
一种锰酞菁衍生物及其合成方法和用途 Download PDFInfo
- Publication number
- CN104829651A CN104829651A CN201510217851.6A CN201510217851A CN104829651A CN 104829651 A CN104829651 A CN 104829651A CN 201510217851 A CN201510217851 A CN 201510217851A CN 104829651 A CN104829651 A CN 104829651A
- Authority
- CN
- China
- Prior art keywords
- alpha
- electrolyte
- manganese
- phthalocyanine derivative
- catalyst
- 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.)
- Granted
Links
- 239000011572 manganese Substances 0.000 title claims abstract description 35
- -1 Manganese phthalocyanine derivative Chemical class 0.000 title claims abstract description 24
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 23
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003792 electrolyte Substances 0.000 claims abstract description 35
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 claims abstract description 30
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 16
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 16
- 239000011565 manganese chloride Substances 0.000 claims description 16
- 229940099607 manganese chloride Drugs 0.000 claims description 15
- 235000002867 manganese chloride Nutrition 0.000 claims description 15
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 230000000593 degrading effect Effects 0.000 claims description 5
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 16
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- 239000000460 chlorine Substances 0.000 abstract description 15
- 230000002829 reductive effect Effects 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract 2
- 230000003413 degradative effect Effects 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 206010039101 Rhinorrhoea Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 208000010753 nasal discharge Diseases 0.000 description 1
- 239000003993 organochlorine pesticide Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/11—Electrochemical processes, e.g. electrodialysis
- A62D3/115—Electrolytic degradation or conversion
-
- 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
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/04—Pesticides, e.g. insecticides, herbicides, fungicides or nematocides
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic substances containing halogen
-
- 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
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种锰酞菁衍生物及其合成方法和用途，该衍生物可用于电催化还原降解有机氯的催化剂，尤其可用于对滴滴涕(DDT)进行电化学催化还原降解的催化剂。所述方法是用设计合成的高溶解性的锰酞菁衍生物作为催化剂，利用电化学还原的方法降解滴滴涕。降解还原以铂金网分别为工作电极和辅助电极，饱和甘汞电极为参比电极，高溶解性的锰酞菁衍生物为催化剂，四丁基高氯酸铵(TBAP)为支持电解质，N,N-二甲基甲酰胺(DMF)为电解液，在一定的控制电位下短时间内对滴滴涕(DDT)进行电催化降解，转化率达到100％。该催化剂具有合成简单、降解速率快、转化率高等特点。
Description
技术领域
本发明涉及一种锰酞菁衍生物及其合成方法和用途，该衍生物可用于电化学还原降解有机氯的催化剂，尤其可用于对滴滴涕进行电化学催化还原降解的催化剂。
背景技术
有机氯农药是人们投放于环境中的使用量最大、毒性最广和污染最广泛的一类污染物，滴滴涕是其中的一种，也是列入《关于持久性有机污染物的斯德哥尔摩公约》中的12种持久性有机污染物之一。滴滴涕曾在20世纪60～80年代为我国大量生产和使用，于1992年被禁止使用，但在短期内难以消除由此引起的严重环境后果。
近年来，人们对有机氯污染物危害的认识日益加深，对有机氯污染物的处理研究也受到了更多的关注。目前针对滴滴涕(DDT)降解，采用的技术主要有微生物处理、化学催化等。
中国专利ZL201010158793.1公开了一种电化学还原降解滴滴涕(DDT)的方法，其特征在于：所述方法是以铂金网为工作电极和辅助电极，饱和甘汞电极为参比电极，卟啉类金属化合物为催化剂，四丁基高氯酸铵(TBAP)为支持电解质，N,N-二甲基甲酰胺(DMF)为电解液，电解滴滴涕，作为催化剂的卟啉类金属化合物，其结构为：
该专利涉及的可行的降解方法，应用于滴滴涕(DDT)降解时的速率却不够高，具体见对比例。
对比例1：
阴极电解槽中的电解液含有N-N二甲基甲酰胺(DMF)，支持电解质为四丁基高氯酸铵(TBAP)，每1L电解液(DMF)中含支持电解质为34.15g。
阳极电解槽中的电解液含有四苯基氯化锰卟啉[(TPP)Mn(III)Cl]、滴滴涕(DDT)，四丁基高氯酸铵、N-N二甲基甲酰胺(DMF)。每1L电解液中：[(TPP)Mn(III)Cl]0.49g、滴滴涕(DDT)3.76g、四丁基高氯酸铵34.15g。
施加电位在-1.60V(相对于饱和甘汞电极)，电解5小时。
移取1mL的阳极电解槽中的电解液，减压蒸馏除去DMF，用2mL环己烷或乙醚进行浸取，用气质联用(GC-MS)技术进行检测，降解率为82.8％。
对比例2：
阴极电解槽中的电解液含有N-N二甲基甲酰胺(DMF)，支持电解质为四丁基高氯酸铵(TBAP)，每1L电解液(DMF)中含支持电解质为34.15g。
阳极电解槽中的电解液含有四苯基氯化铁卟啉[(TPP)Fe(III)Cl]、滴滴涕(DDT)，四丁基高氯酸铵、N-N二甲基甲酰胺(DMF)。每1L电解液中：[(TPP)Fe(III)Cl]0.31g、滴滴涕(DDT)1.46g、四丁基高氯酸铵34.15g。
施加电位在-1.50V(相对于饱和甘汞电极)，电解3小时。
移取1mL的阳极电解槽中的电解液，减压蒸馏除去DMF，用2mL环己烷或乙醚进行浸取，用气质联用(GC-MS)技术进行检测，降解率为100％。
对比例的降解结果：
nL：电解时滴滴涕(DDT)的物质的量；np：电解时所用催化剂的物质的量。
目前技术方法普遍存在耗时长，单位处理量少、能耗大、设备成本大等一些缺点。
发明内容
针对现有技术中存在的不足，本发明提供了一种锰酞菁衍生物及其合成方法，可用作电催化降解滴滴涕的新型催化剂，具有合成简单和降解速率高的特点。
本发明是通过以下技术手段实现上述技术目的的。
一种锰酞菁衍生物，该衍生物为三价锰氯(α,α’-OC5H11)8-酞菁[Mn(III)Cl(α,α’-OC5H11)8-Pc]，结构通式为：
其中，
一种锰酞菁衍生物的合成方法，包括如下步骤：
在1,4-OC5H11-2,3-邻苯二氰中加入氯化锰，置于喹啉溶液中，160℃～200℃下，N2氛围中反应1～4h，经柱层析纯化可得到目标三价锰氯(α,α’-OC5H11)8-酞菁[Mn(III)Cl(α,α’-OC5H11)8-Pc]，产率大于80％，合成路径为：
一种锰酞菁衍生物的合成方法，包括如下步骤：
在1,4-OC5H11-2,3-邻苯二氰中加入氯化锰，置于喹啉溶液中，180℃下，N2氛围中反应2h，经柱层析纯化可得到目标三价锰氯(α,α’-OC5H11)8-酞菁[Mn(III)Cl(α,α’-OC5H11)8-Pc]，产率大于82.3％。
所述合成方法中，1,4-OC5H11-2,3-邻苯二氰和氯化锰物质的量之比为1:2。
所述锰酞菁衍生物作为电化学还原降解滴滴涕的催化剂。
所述锰酞菁衍生物作为电化学还原降解滴滴涕的催化剂时的使用方法，包括如下步骤：
(1)被电解的化合物为滴滴涕，以铂金网分别为工作电极和辅助电极，以饱和甘汞电极为参比电极；
(2)阴极电解槽中的电解液为N,N-二甲基甲酰胺DMF，电解液DMF中含有支持电解质四丁基高氯酸铵TBAP；
阳极电解槽中的电解液为N,N-二甲基甲酰胺DMF，电解液DMF中含有支持电解质四丁基高氯酸铵(TBAP)；电解液中还需加入三价锰氯(α,α’-OC5H11)8-酞菁[Mn(III)Cl(α,α’-OC5H11)8-Pc]作为催化剂，饱和甘汞电极和电解液用盐桥隔开，阴阳电解池之间采用陶瓷电解隔膜隔开；
(3)对电解液施加电压，电解。
所述锰酞菁衍生物作为电化学还原降解滴滴涕的催化剂，催化剂和滴滴涕物质的量之比为1：10。
上述步骤(3)中，所述施加的电压为-1.60～-2.00V，电解时间为1h。
上述步骤(2)中，所述阴极电解槽中每升电解液DMF中含有支持电解质四丁基高氯酸铵TBAP 34.15g；所述阳极电解槽中每升电解液DMF中含有支持电解质四丁基高氯酸铵TBAP 34.15g。
上述电解所得产物用气质联用仪(GC-MS)进行检测分析。
电解完成后，将阳极电解槽中的电解液减压蒸馏以回收DMF，再用两倍体积于电解液的环己烷或乙醚进行萃取，从萃取后的残渣中回收催化剂和支持电解质循环再利用。
本发明的有益效果为：
本发明提供的锰酞菁衍生物，合成方法简单，所得的三价锰氯(α,α’-OC5H11)8-酞菁[Mn(III)Cl(α,α’-OC5H11)8-Pc]可用于电化学还原降解滴滴涕的催化剂，该催化剂降解效率高，使用方法简单。
附图说明
图1为本发明的电解原理示意图；
具体实施方式
下面结合附图以及具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。
实施例：
阴极电解槽中的电解液含有N-N二甲基甲酰胺(DMF)，支持电解质为四丁基高氯酸铵，每1L电解液中含支持电解质为34.15g。
阳极电解槽中的电解液含有三价锰氯(α,α’-OC5H11)8-酞菁[Mn(III)Cl(α,α’-OC5H11)8-Pc]、滴滴涕，四丁基高氯酸铵、N-N二甲基甲酰胺。每1L电解液中：Mn(III)Cl(α,α’-OC5H11)8-Pc0.65g、滴滴涕1.78g、四丁基高氯酸铵34.15g。
分别施加电位在-1.60V，1.80V，2.00V(相对于饱和甘汞电极SCE)，电解1小时。
移取1mL的阳极电解槽中的电解液，减压蒸馏除去DMF，用2mL环己烷或乙醚进行浸取，用气质联用(GC-MS)技术进行检测，降解率为100％。
nL：电解时滴滴涕的物质的量；np：电解时所用催化剂的物质的量。
所述实施例为本发明的优选的实施方式，但本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员能够做出的任何显而易见的改进、替换或变型均属于本发明的保护范围。
Claims (9)
1.一种锰酞菁衍生物，其特征在于，该衍生物为三价锰氯(α,α’-OC5H11)8-酞菁[Mn(III)Cl(α,α’-OC5H11)8-Pc]，结构通式为：
其中，
2.如权利要求1所述的一种锰酞菁衍生物的合成方法，其特征在于，包括如下步骤：
在1,4-OC5H11-2,3-邻苯二氰中加入氯化锰，置于喹啉溶液中，160℃～200℃下，N2氛围中反应1～4h，经柱层析纯化可得到目标三价锰氯(α,α’-OC5H11)8-酞菁[Mn(III)Cl(α,α’-OC5H11)8-Pc]，产率大于80％，合成路径为：
3.如权利要求2所述的一种锰酞菁衍生物的合成方法，其特征在于，包括如下步骤：
在1,4-OC5H11-2,3-邻苯二氰中加入氯化锰，置于喹啉溶液中，180℃下，N2氛围中反应2h，经柱层析纯化可得到目标三价锰氯(α,α’-OC5H11)8-酞菁[Mn(III)Cl(α,α’-OC5H11)8-Pc]，产率大于82.3％。
4.如权利要求2或3所述的一种锰酞菁衍生物的合成方法，其特征在于，所述1,4-OC5H11-2,3-邻苯二氰和氯化锰物质的量之比为1:2。
5.如权利要求1所述的一种锰酞菁衍生物的用途，其特征在于，该化合物为电化学还原降解滴滴涕的催化剂。
6.如权利要求5所述的一种锰酞菁衍生物的用途，其特征在于，使用方法包括如下步骤：
(1)被电解的化合物为滴滴涕，以铂金网分别为工作电极和辅助电极，以饱和甘汞电极为参比电极；
(2)阴极电解槽中的电解液为N,N-二甲基甲酰胺DMF，电解液DMF中含有支持电解质四丁基高氯酸铵TBAP；
阳极电解槽中的电解液为N,N-二甲基甲酰胺DMF，电解液DMF中含有支持电解质四丁基高氯酸铵(TBAP)；电解液中还需加入三价锰氯(α,α’-OC5H11)8-酞菁[Mn(III)Cl(α,α’-OC5H11)8-Pc]作为催化剂，饱和甘汞电极和电解液用盐桥隔开，阴阳电解池之间采用陶瓷电解隔膜隔开；
(3)对电解液施加电压，电解。
7.如权利要求6所述的一种锰酞菁衍生物的用途，其特征在于，所述催化剂和滴滴涕物质的量之比为1：10。
8.如权利要求6所述的一种锰酞菁衍生物的用途，其特征在于，步骤(3)中，所述施加的电压为-1.60～-2.00V，电解时间为1h。
9.如权利要求6所述的一种锰酞菁衍生物的用途，其特征在于，步骤(2)中，所述阴极电解槽中每升电解液DMF中含有支持电解质四丁基高氯酸铵TBAP 34.15g；所述阳极电解槽中每升电解液DMF中含有支持电解质四丁基高氯酸铵TBAP 34.15g。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510217851.6A CN104829651B (zh) | 2015-04-30 | 2015-04-30 | 一种锰酞菁衍生物及其合成方法和用途 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510217851.6A CN104829651B (zh) | 2015-04-30 | 2015-04-30 | 一种锰酞菁衍生物及其合成方法和用途 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104829651A true CN104829651A (zh) | 2015-08-12 |
| CN104829651B CN104829651B (zh) | 2017-11-17 |
Family
ID=53807887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510217851.6A Expired - Fee Related CN104829651B (zh) | 2015-04-30 | 2015-04-30 | 一种锰酞菁衍生物及其合成方法和用途 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104829651B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107247081A (zh) * | 2017-04-26 | 2017-10-13 | 浙江理工大学 | 碳纳米管纤维负载金属酞菁制备电化学传感器 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5345032A (en) * | 1988-05-09 | 1994-09-06 | The Public Health Laboratory Service Board | Use of metal chelate complexes in dehalogenation |
| US7196240B2 (en) * | 2003-02-10 | 2007-03-27 | Ueda Textile Science Foundation | Method and equipment for making polychlorobiphenyl nontoxic |
| CN101810921A (zh) * | 2010-04-27 | 2010-08-25 | 江苏大学 | 一种电化学还原降解滴滴涕的方法 |
| CN103949033A (zh) * | 2014-04-18 | 2014-07-30 | 江苏大学 | 一种电化学催化还原降解六六六的方法 |
-
2015
- 2015-04-30 CN CN201510217851.6A patent/CN104829651B/zh not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5345032A (en) * | 1988-05-09 | 1994-09-06 | The Public Health Laboratory Service Board | Use of metal chelate complexes in dehalogenation |
| US7196240B2 (en) * | 2003-02-10 | 2007-03-27 | Ueda Textile Science Foundation | Method and equipment for making polychlorobiphenyl nontoxic |
| CN101810921A (zh) * | 2010-04-27 | 2010-08-25 | 江苏大学 | 一种电化学还原降解滴滴涕的方法 |
| CN103949033A (zh) * | 2014-04-18 | 2014-07-30 | 江苏大学 | 一种电化学催化还原降解六六六的方法 |
Non-Patent Citations (1)
| Title |
|---|
| 朱卫华等，: "卟啉锰电催化还原降解滴滴涕", 《江苏大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107247081A (zh) * | 2017-04-26 | 2017-10-13 | 浙江理工大学 | 碳纳米管纤维负载金属酞菁制备电化学传感器 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104829651B (zh) | 2017-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111286748B (zh) | 一种电化学合成咔唑类化合物的方法 | |
| Isse et al. | Electrocatalytic dechlorination of volatile organic compounds at a copper cathode. Part I: Polychloromethanes | |
| Li et al. | Aqueous electrocatalytic hydrogenation of furfural using a sacrificial anode | |
| Zhou et al. | Highly selective electrocatalytic reduction of carbon dioxide to carbon monoxide on silver electrode with aqueous ionic liquids | |
| Scialdone et al. | Electrochemical incineration of 1, 2-dichloroethane: Effect of the electrode material | |
| McGuire et al. | Electrochemical dechlorination of 4, 4′-(2, 2, 2-trichloroethane-1, 1-diyl) bis (chlorobenzene)(DDT) at silver cathodes | |
| EA201190253A1 (ru) | Установка и способ для восстановления твердого исходного сырья | |
| Huang et al. | Highly selective electrochemical hydrogenation of acetylene to ethylene at Ag and Cu cathodes | |
| Medeiros et al. | Electroreductive intramolecular cyclisation of bromoalkoxylated derivatives catalysed by nickel (I) tetramethylcyclam in “green” media | |
| Zhang et al. | Aqueous electrosynthesis of carbonyl compounds and the corresponding homoallylic alcohols in a divided cell | |
| CN104829651B (zh) | 一种锰酞菁衍生物及其合成方法和用途 | |
| CN111005033B (zh) | 一种西地那非中间体的电还原制备方法 | |
| CN103949033B (zh) | 一种电化学催化还原降解六六六的方法 | |
| Niu et al. | Electrocatalytic carboxylation of benzyl chloride at silver cathode in ionic liquid BMIMBF4 | |
| Wang et al. | Electrocarboxylation of haloacetophenones at silver electrode | |
| Liu et al. | Electrochemical oxidation of 1, 4-dichlorobenzene on platinum electrodes in acetonitrile-water solution: evidence for direct and indirect electrochemical oxidation pathways | |
| CN101810921B (zh) | 一种电化学还原降解滴滴涕的方法 | |
| WO2009071478A1 (de) | Verfahren zur reduktiven hydrodimerisierung von ungesättigten organischen verbindungen mittels einer diamantelektrode | |
| Ghobadi et al. | Excellent electrocatalytic activity of benzil for direct reduction of CO2 as well as indirect reduction of pyridine: A kinetic view of the electrocarboxylation process | |
| CN114134522A (zh) | 一种4,4′-联吡啶的电化学合成方法 | |
| Duñach et al. | Indirect electrochemical cyclization of bromoalkoxylated derivatives mediated by nickel (II) complex in environmental-friendly medium | |
| CN110656347B (zh) | 一种奥氮平中间体的电还原制备方法 | |
| Peverly et al. | Electrochemical reduction of 2, 4-dichloro-1-(4-chloro-2-methoxyphenoxy) benzene (methyl triclosan) at glassy carbon cathodes in dimethylformamide | |
| Lawin et al. | Reduction of organic compounds at lead cathodes and mediation by dimethylpyrrolidinium ion | |
| Dunach et al. | Electrochemical catalytic cyclization reactions using environmentally friendly methodologies |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| 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: 20171117 Termination date: 20180430 |