CN107983385A - A kind of nickel radical magnetic composite materials and its synthetic method and application - Google Patents
A kind of nickel radical magnetic composite materials and its synthetic method and application Download PDFInfo
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- CN107983385A CN107983385A CN201711214764.0A CN201711214764A CN107983385A CN 107983385 A CN107983385 A CN 107983385A CN 201711214764 A CN201711214764 A CN 201711214764A CN 107983385 A CN107983385 A CN 107983385A
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- nickel
- composite materials
- magnetic composite
- double
- benzene
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000010189 synthetic method Methods 0.000 title claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910001868 water Inorganic materials 0.000 claims abstract description 41
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000013110 organic ligand Substances 0.000 claims abstract description 12
- 239000011365 complex material Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000356 contaminant Substances 0.000 claims abstract description 5
- IALTXBACCYPMDZ-UHFFFAOYSA-N 4-methylidene-3h-pyridine Chemical class C=C1CC=NC=C1 IALTXBACCYPMDZ-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical class NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- -1 N, N'- Methylene Chemical group 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 239000003403 water pollutant Substances 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 239000004570 mortar (masonry) Substances 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- JGSLKNWXPRDWBA-UHFFFAOYSA-N 2-methylidene-1h-pyridine Chemical compound C=C1NC=CC=C1 JGSLKNWXPRDWBA-UHFFFAOYSA-N 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 13
- 239000000975 dye Substances 0.000 description 13
- 229960000907 methylthioninium chloride Drugs 0.000 description 13
- 238000010586 diagram Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002447 crystallographic data Methods 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000003639 trimesic acids Chemical class 0.000 description 3
- 239000001045 blue dye Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- AIDQCFHFXWPAFG-UHFFFAOYSA-N n-formylformamide Chemical compound O=CNC=O AIDQCFHFXWPAFG-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZCIHETYSZWUSQG-UHFFFAOYSA-N 3-methylidenepyrrole Chemical class C=C1C=CN=C1 ZCIHETYSZWUSQG-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000002023 wood Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/33—Electric or magnetic 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
A kind of nickel radical magnetic composite materials and its synthetic method and application, by NiCl2·6H2O, double (4 methylene pyridine) the benzene Isosorbide-5-Nitrae diformamides of N, N' and trimesic acid, add deionized water, the hydro-thermal reaction in autoclave, generation organic ligand nickel complex [Ni3(4‑bmbpd)3(BTC)2(H2O)4]·4H2O；By nickel complex, after being ground using agate mortar, disperse in ethanol, with ball mill grinding, centrifuge out crystallite state nickel complex material, be positioned in the tube furnace under nitrogen protection, calcining, obtains nickel radical magnetic composite materials.The application of the nickel radical magnetic composite materials as photocatalytically degradating organic dye contaminant material.Advantage is：Catalysis Rate is fast, efficient, and can facilitate recycling, to the photocatalytic activity of methylenum careuleum organic pollution up to 96%, can be used as methylenum careuleum organic pollution photocatalytic degradation material.
Description
Technical field
The invention belongs to catalysis material synthesize field, the synthesis of more particularly to a kind of nickel radical magnetic N-C composite materials and its
Using.
Background technology
Dyeing waste water is the production waste water of printing and dyeing mill's discharge based on processing cotton, fiber crops, chemical fibre and its blending product.Print
It is larger to contaminate waste water water, per 1 ton of dyeing and printing process, 100~200 tons of textile water consumption, wherein 80~90% become waste water.In waste water
The dyestuff of loss accounts for the 15% of dyestuff yield, causes huge environmental pressure.In various dyestuffs, methylene blue can be used for
Fiber crops, silk fabric, the dyeing of paper and the coloring of bamboo and wood；It can also be used to manufacture ink and color lake and biology, the dye of bacterial organisms
Color etc..Due to the dyestuff water solubility preferably, turnover rate is high in the production and use process, easily into water body,
Skin, eyes to environment and human body etc. are respectively provided with larger damaging effect.Therefore, new feature degradable material is developed
Reducing or eliminate methylene blue dye hazards of pollutants has important practical significance.
By the catalytic action of some inorganic oxides or Metal-organic complex catalyst, methylene blue can be in purple
A degree of degraded is carried out under outer optical condition.But not only time-consuming for whole degradation process, degradation rate is low, and above-mentioned urges
Agent is required for separating from catalyst system and catalyzing in recycling.Due to being imitated to improve the catalysis of above-mentioned catalyst
Above-mentioned catalyst, is usually all made tiny powder body material by fruit, and therefore, the difficulty for separating recycling is larger.To practical application
Cause certain obstacle.
Therefore, it is fast to prepare a kind of Catalysis Rate, it is efficient, and the dyestuff photochemical catalyst of recycling can be facilitated to have ten
Divide important meaning.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of nickel radical magnetic composite materials and its synthetic method and application,
Effectively shorten the photocatalytic degradation time of methylene blue, rapid efficient is realized by magnetic absorption, so as to recycle, save
Energy consumption, reduces environmental pollution.
The present invention technical solution be：
A kind of nickel radical magnetic composite materials, expression formula are as follows：
Ni@ONC
Wherein, the C-material that ONC is a small amount of nitrogen, oxygen mixes；
Its specific synthesis step is as follows：
(1) synthesis based on organic ligand nickel complex
By NiCl2·6H2O, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformamides of N, N'- and trimesic acid, addition are gone
Ionized water；Ultrasound 5min~12min formation suspended mixture at room temperature, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae of the N, N'--
The molar ratio of diformamide and trimesic acid is 1:1~1:2, double (4- methylene pyridines) benzene-formyls of Isosorbide-5-Nitrae-two of the N, N'-
Amine and NiCl2·6H2The molar ratio of O is 1:1~1:3, the NaOH solution tune pH for being 0.1mol/L with concentration is 4.2~7.2, is fallen
Enter in autoclave and be warming up to 105 DEG C~145 DEG C with 10 DEG C/h heating rates, 48h~120h is kept the temperature under hydrothermal condition, with
The rate of temperature fall of 2.5 DEG C/h cools to room temperature and obtains green bulk crystals, is alternately cleaned 3 times~5 times with deionized water and ethanol,
Naturally dry at room temperature, obtains organic ligand nickel complex [Ni3(4-bmbpd)3(BTC)2(H2O)4]·4H2O；
Wherein, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformamides of 4-bmbpd N, N'-, BTC is trimesic acid；
(2) synthesis of nickel radical magnetic composite materials
Nickel complex [the Ni that step (1) is synthesized3(4-bmbpd)3(BTC)2(H2O)4]·4H2O weighs 4 grams, using agate
When Nao mortar grinders 2 are small~4 it is small when, be subsequently dispersed in 2 milliliters~4 milliliters of ethanol, with ball mill grinding 20 minutes~40
Minute, crystallite state nickel complex material is centrifuged out, when drying 24 is small at 70 DEG C；2 grams of nickel complexes are positioned over nitrogen
Protection under tube furnace in, be warming up to 800 DEG C with 5 DEG C/h heating rates, when constant temperature 4 is small~6 it is small when, with 2.5~10 DEG C/h's
Rate of temperature fall cools to room temperature and obtains nickel radical magnetic composite materials.
Further, the molar ratio of double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformamides of the N, N'- and deionized water is
1:2800~1:8300.
A kind of synthetic method of nickel radical magnetic composite materials, it is comprised the following steps that：
(1) synthesis based on organic ligand nickel complex
By NiCl2·6H2O, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformamides of N, N'- and trimesic acid, addition are gone
Ionized water；Ultrasound 5min~12min formation suspended mixture at room temperature, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae of the N, N'--
The molar ratio of diformamide and trimesic acid is 1:1~1:2, double (4- methylene pyridines) benzene-formyls of Isosorbide-5-Nitrae-two of the N, N'-
Amine and NiCl2·6H2The molar ratio of O is 1:1~1:3, the NaOH solution tune pH for being 0.1mol/L with concentration is 4.2~7.2, is fallen
Enter in autoclave and be warming up to 105 DEG C~145 DEG C with 10 DEG C/h heating rates, 48h~120h is kept the temperature under hydrothermal condition, with
The rate of temperature fall of 2.5 DEG C/h cools to room temperature and obtains green bulk crystals, is alternately cleaned 3 times~5 times with deionized water and ethanol,
Naturally dry at room temperature, obtains organic ligand nickel complex [Ni3(4-bmbpd)3(BTC)2(H2O)4]·4H2O；
Wherein, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformamides of 4-bmbpd N, N'-, BTC is trimesic acid；
(2) synthesis of nickel radical magnetic composite materials
Nickel complex [the Ni that step (1) is synthesized3(4-bmbpd)3(BTC)2(H2O)4]·4H2O weighs 4 grams, using agate
When Nao mortar grinders 2 are small~4 it is small when, be subsequently dispersed in 2 milliliters~4 milliliters of ethanol, with ball mill grinding 20 minutes~40
Minute, crystallite state nickel complex material is centrifuged out, when drying 24 is small at 70 DEG C；By 2 grams of crystallite state nickel complex materials
Be positioned over nitrogen protection under tube furnace in, be warming up to 800 DEG C with 5 DEG C/h heating rates, when constant temperature 4 is small~6 it is small when, with 2.5
The rate of temperature fall of~10 DEG C/h cools to room temperature and obtains nickel radical magnetic composite materials.
Further, the molar ratio of double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformamides of the N, N'- and deionized water is
1:2800~1:8300.
A kind of application of nickel radical magnetic composite materials as photocatalytically degradating organic dye contaminant material.
A kind of application of nickel radical magnetic composite materials as photocatalytically degradating organic dye contaminant material, its specific step
It is rapid as follows：
Ni@ONC composite materials are added in the aqueous solution containing water pollutant, are passing through 40min-60min ultraviolet light light
After irradiation, using magnet, by Ni@ONC composite catalyst adsorption recovery, to recycle.
The beneficial effects of the invention are as follows：
Catalysis Rate is fast, efficient, and can facilitate recycling, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformazans of N, N'-
Methylene group among the organic amine ligand of acid amides, not only increases the coordination flexibility of ligand, and is opened to constructing higher-dimension
Skeleton plays the role of Space Expanding；Equal benzene front three three provides multidirectional space fulcrum for constructing for higher-dimension co-ordinating backbone；
The good Space Expanding ability of above two ligand effectively hinders the polymerization of the nickel in high-temperature sintering process, is Ni-based cluster
Formation provides guarantee, while the formation for porous C material provides space；Double (4- methylene pyridines) benzene -1,4- two of N, N'-
The introducing of imino group in formyl amine ligand, N sources are provided for nickel radical magnetic composite materials, to improve nickel radical magnetic compound
The rapid photocatalytic effect of material provides possibility；The selected as composite materials of nickel source metal provide magnetic basis, so as to
In effective recycling after photocatalytically degradating organic dye pollutant and recycle.To methylenum careuleum organic pollution under 40 minutes
Photocatalytic activity up to 96%, can be as the quick of methylenum careuleum organic pollution and the photocatalysis that can conveniently recycle
Degradable material.
Brief description of the drawings
Fig. 1 is [Ni of the invention3(4-bmbpd)3(BTC)2(H2O)4]·4H2The XRD diffraction patterns of O；
Fig. 2 is [Ni of the invention3(4-bmbpd)3(BTC)2(H2O)4]·4H2The thermal analysis curue of O；
Fig. 3 is [Ni of the invention3(4-bmbpd)3(BTC)2(H2O)4]·4H2The infrared spectrogram of O；
Fig. 4 is [Ni of the invention3(4-bmbpd)3(BTC)2(H2O)4]·4H2The coordination context diagram of O；
Fig. 5 is [Ni of the invention3(4-bmbpd)3(BTC)2(H2O)4]·4H2The tomograph of O；
Fig. 6 is the double interpenetrating topology diagram of [2 (H2O) 4 of Ni3 (4-bmbpd) 3 (BTC)] 4H2O of the invention；
Fig. 7 is the XRD diffraction patterns of the Ni@ONC of the present invention；
Fig. 8 is the SEM surface topography maps of the Ni@ONC of the present invention；
Fig. 9 is under ultraviolet light, and under no catalysts conditions, aqueous solution of methylene blue photocatalytic degradation in 180min is purple
It is outer to absorb figure；
Figure 10 be under ultraviolet light, using under Ni@ONC catalysts conditions, aqueous solution of methylene blue light in 40min
Catalytic degradation UV absorption figure；
Figure 11 is that the degradation rate of methylenum careuleum changes over time figure；
Figure 12 is to recycle photocatalytic activity block diagrams of the Ni@ONC to methylenum careuleum；
Figure 13 is Ni@ONC composite catalysts recycling schematic diagram.
Embodiment
Embodiment 1
(1) [Ni is synthesized3(4-bmbpd)3(BTC)2(H2O)4]·4H2O, wherein, double (the 4- methylene of 4-bmbpd N, N'-
Pyridine) benzene-Isosorbide-5-Nitrae-diformamide, structural formula is：BTC is trimesic acid root
By 0.1mmol NiCl2·6H2Double (4- methylene pyridines) benzene -1,4- diformamides of O, 0.10mmol N, N'-,
0.1mmol trimesic acids and 5mL H2O is added sequentially in 25mL beakers, at room temperature ultrasound 5min, obtains the mixing that suspends
Thing, after reconciling the pH to 4.2 of suspended mixture with the NaOH solution of 0.1mol/L, is transferred in the autoclave of 25mL, with
The rate of heat addition of 10 DEG C/h is warming up to 105 DEG C, and 48h is kept the temperature under hydrothermal condition, and room is cooled the temperature to the rate of temperature fall of 2.5 DEG C/h
Temperature, obtains green bulk crystals, and with deionized water and ethanol alternately cleaning 3 times, naturally dry, obtains [Ni at room temperature3(4-
bmbpd)3(BTC)2(H2O)4]·4H2O, yield 35%, its XRD diffracting spectrum is as shown in Figure 1, its coordination context diagram such as Fig. 4
Shown, its tomograph such as Fig. 5, its double interpenetrating topology diagram is as shown in Figure 6；
(2) Ni@ONC magnetic composites are synthesized
Nickel complex [the Ni that step (1) is synthesized3(4-bmbpd)3(BTC)2(H2O)4]·4H2O weighs 4 grams, using agate
2 hours of Nao mortar grinders, it is subsequently dispersed in 2 milliliters of ethanol, with ball mill grinding 20 minutes, centrifuges out crystallite state
Nickel complex material, when drying 24 is small at 70 DEG C.2 grams of crystallite state nickel complex materials are positioned over the tubular type under nitrogen protection
In stove, 800 DEG C, when constant temperature 4 is small are warming up to 5 DEG C/h heating rates, with the rate of temperature fall of 10 DEG C/h cool to room temperature obtain it is black
The Ni-based magnetic composite material of color solid.
Embodiment 2
(1) [Ni is synthesized3(4-bmbpd)3(BTC)2(H2O)4]·4H2O, wherein, double (the 4- methylene of 4-bmbpd N, N'-
Pyridine) benzene-Isosorbide-5-Nitrae-diformamide, BTC is trimesic acid root
By 0.2mmol NiCl2·6H2Double (4- methylene pyridines) benzene -1,4- diformamides of O, 0.10mmol N, N'-,
0.15mmol trimesic acids and 12mL H2O is added sequentially in 25mL beakers, at room temperature ultrasound 8min, obtains suspending mixed
Compound, after reconciling the pH to 6.4 of suspended mixture with the NaOH solution of 0.1mol/L, is transferred in the autoclave of 25mL,
125 DEG C are warming up to the rate of heat addition of 10 DEG C/h, 96h is kept the temperature under hydrothermal condition, is dropped temperature with the rate of temperature fall of 2.5 DEG C/h
To room temperature, green bulk crystals are obtained, with deionized water and ethanol alternately cleaning 4 times, naturally dry, obtains [Ni at room temperature3(4-
bmbpd)3(BTC)2(H2O)4]·4H2O, yield 85%, its XRD diffracting spectrum is as shown in Figure 1, its coordination context diagram such as Fig. 4
Shown, its tomograph such as Fig. 5, its double interpenetrating topology diagram is as shown in Figure 6；
(2) Ni@ONC magnetic composites are synthesized
Nickel complex [the Ni that step (1) is synthesized3(4-bmbpd)3(BTC)2(H2O)4]·4H2O weighs 4 grams, using agate
3 hours of Nao mortar grinders, it is subsequently dispersed in 3 milliliters of ethanol, with ball mill grinding 30 minutes, centrifuges out crystallite state
Nickel complex material, when drying 24 is small at 70 DEG C.2 grams of crystallite state nickel complex materials are positioned over the tubular type under nitrogen protection
In stove, 800 DEG C, when constant temperature 5 is small are warming up to 5 DEG C/h heating rates, with the rate of temperature fall of 2.5 DEG C/h cool to room temperature obtain it is black
The Ni-based magnetic composite material of color solid.
Embodiment 3
(1) [Ni is synthesized3(4-bmbpd)3(BTC)2(H2O)4]·4H2O, wherein, double (the 4- methylene of 4-bmbpd N, N'-
Pyridine) benzene-Isosorbide-5-Nitrae-diformamide, BTC is trimesic acid root
By 0.3mmol NiCl2·6H2Double (4- methylene pyridines) benzene -1,4- diformamides of O, 0.10mmol N, N'-,
0.2mmol trimesic acids and 15mL H2O is added sequentially in 25mL beakers, at room temperature ultrasound 12min, obtains suspending mixed
Compound, after reconciling the pH to 7.2 of suspended mixture with the NaOH solution of 0.1mol/L, is transferred in the autoclave of 25mL,
145 DEG C are warming up to the rate of heat addition of 10 DEG C/h, 120h is kept the temperature under hydrothermal condition, is dropped temperature with the rate of temperature fall of 2.5 DEG C/h
To room temperature, green bulk crystals are obtained, with deionized water and ethanol alternately cleaning 5 times, naturally dry, obtains [Ni at room temperature3(4-
bmbpd)3(BTC)2(H2O)4]·4H2O, yield 45%, its XRD diffracting spectrum is as shown in Figure 1, its coordination context diagram such as Fig. 4
Shown, its tomograph such as Fig. 5, its double interpenetrating topology diagram is as shown in Figure 6；
(3) Ni@ONC magnetic composites are synthesized
By the nickel complex [Ni of step (1)3(4-bmbpd)3(BTC)2(H2O)4]·4H2O weighs 4 grams, is ground using agate
Alms bowl grinds 4 hours, is subsequently dispersed in 4 milliliters of ethanol, with ball mill grinding 40 minutes, centrifuges out crystallite state nickel and matches somebody with somebody
Compound material, when drying 24 is small at 70 DEG C, is taken 2 grams to be placed in the tube furnace under nitrogen protection, is heated up with 5 DEG C/h heating rates
To 800 DEG C, when constant temperature 6 is small, room temperature is cooled to the rate of temperature fall of 5 DEG C/h and obtains black solid nickel radical magnetic composite materials.
The characterization of the nickel complex of organic ligand based on 1~embodiment of the embodiment of the present invention 3
Powder diffraction characterizes [Ni3(4-bmbpd)3(BTC)2(H2O)4]·4H2O phase purity
Collected on Rigaku Ultima IV powder x-ray diffractions and complete powder diffraction data, operation electric current is
40mA, voltage 40kV.Using copper target X-ray.Scanning constant, it is 0.1mm to receive slit width.Density data collects and uses 2 θ/θ
Scan pattern, 5 ° to 50 ° of scanning range, sweep speed are 5 °/s, and span is 0.02 °/time.Data fitting uses Cerius2 journeys
Sequence, the conversion of mono-crystalline structures powder diffraction spectrum analog use Mercury 1.4.1.As shown in Figure 1, the nickel based on organic ligand coordinates
The powder x-ray diffraction spectrogram of thing and the XRD spectra of fitting coincide substantially, and it is pure phase to show complex.
Thermogravimetric characterizes [Ni3(4-bmbpd)3(BTC)2(H2O)4]·4H2O stability
Heat endurance is completed using PE-Pyris Diamond S-II thermal analyzers, 10 DEG C/min of the rate of heat addition, temperature model
Enclose 20 DEG C~850 DEG C.Fig. 2 shows that the crystallization water for the nickel complex that the present invention synthesizes loses temperature at 175~210 DEG C, is coordinated bone
Frame decomposition temperature scope is 355 DEG C~410 DEG C.It mainly happens is that the reduction of NiO after 500 DEG C.
[Ni3(4-bmbpd)3(BTC)2(H2O)4]·4H2O IR Characterizations
[Ni as shown in Figure 33(4-bmbpd)3(BTC)2(H2O)4]·4H2Exist in O and come from N, double (the 4- methylene pyrroles of N'-
Pyridine) the obvious characteristic absorption peak such as the carboxyl of benzene -1,4- diformamides and trimesic acid root, amide groups, pyridine radicals.
Crystal structure determination
The monocrystalline of suitable size is chosen with microscope, at room temperature using Bruker SMART APEX II diffractometer (graphite
Monochromator, Mo-Ka) collect diffraction data.Scan modeDiffraction data carries out absorption correction using SADABS programs.Number
Completed respectively using SAINT and SHELXTL programs according to reduction and structure elucidation.Least square method determines that whole non-hydrogen atoms are sat
Mark, and obtain hydrogen atom position with theoretical hydrogenation method.Refine is carried out to crystal structure using least square method.Fig. 4~Fig. 6 is shown
Go out in 1~embodiment of embodiment 3 the basic coordination situation and expansion structure of the nickel complex based on organic ligand synthesized.It is brilliant
The partial parameters of body point diffraction Data Collection and structure refinement are as shown in table 1：
Table 1
The thing of the nickel radical magnetic composite materials Ni@ONC of 1~embodiment of the embodiment of the present invention 3 mutually characterizes
As shown in fig. 7, the diffraction maximum appeared near 22 DEG C illustrates that the carbon in nickel radical magnetic composite materials is mainly stone
Black carbon form exists, and appears in 38 DEG C of later diffraction maximums and illustrates that the nickel in nickel radical magnetic composite materials is mainly nickel simple substance
Form exists, and there are a small amount of nickel oxide.
The pattern of nickel radical magnetic composite materials Ni@ONC
As shown in figure 8, it is irregular pattern that micrometer nickel compound pattern, which can be observed, by scanning electron microscope.
[the Ni synthesized to embodiment 23(4-bmbpd)3(BTC)2(H2O)4]·4H2O and Ni@ONC composite materials
Photocatalytic degradation methylenum careuleum performance test experiment comprises the following steps that：
It is 10.0mgL that the Ni@ONC composite materials of 50mg are added 150mL concentration–1Aqueous solution of methylene blue in as real
Group is tested, by the complex [Ni of 50mg3(4-bmbpd)3(BTC)2(H2O)4]·4H2It is 10.0mgL that O, which adds 150mL concentration,–1's
In aqueous solution of methylene blue as a control group, and the dye molecule aqueous solution of same volume is taken as a control group.Stirring test group and right
Suspended matter is obtained according to the dye molecule aqueous solution 30min of group, 125W high-pressure sodium lamps are used in mechanical agitation as ultraviolet light light
Source is irradiated.For control group methylenum careuleum, take out 5mL solution every 5min and be centrifuged；Obtain clarification upper solution
Carry out UV tests.After being penetrated by 180min UV Lights, in the case of no photochemical catalyst and using composition catalyst, on
Stating control group methylene blue dye molecule can not almost degrade only by illumination, as shown in Figure 9；There are Ni@ONC composite woods
In the case of material, quick significant reduction occurs for the characteristic absorption of the dye molecule of above-mentioned experimental group aqueous solution of methylene blue, shows this
Dye molecule has occurred and that rapid decomposition, as shown in Figure 10.After being penetrated by 40min UV Lights, methylenum careuleum resolution ratio can
Reach 96.37%.It is as shown in figure 11 that methylenum careuleum resolution ratio changes over time figure.
, can be effective by Ni@ONC composite catalysts across the reactor for containing aqueous solution of methylene blue using magnet
Absorption in reactor bottom, outwell the residual solution after catalysis methylenum careuleum, add new aqueous solution of methylene blue, after removing magnet,
Ni@ONC composite materials can be distributed in aqueous solution of methylene blue under stirring again, carry out catalytic degradation again, catalysis drop
Solution rate is up to 96.20%, and by 10 circulations, the resolution ratio of methylenum careuleum can reach 96.14%, illustrate that Ni@ONC composite materials are one
Kind is quick, can conveniently separate recycling and effective organic dyestuff decomposes photochemical catalyst steadily in the long term.During recycling, methylenum careuleum
Resolution ratio block diagram it is as shown in figure 12.Ni@ONC composite catalysts recycling schematic diagram is as shown in figure 13.
It these are only the specific embodiment of the present invention, be not intended to limit the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification within the spirit and principles of the invention, being made,
Equivalent substitution, improvement etc., should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of nickel radical magnetic composite materials, it is characterized in that：
Expression formula is as follows：Ni@ONC
Wherein, the C-material that ONC is nitrogen, oxygen mixes；
Its specific synthesis step is as follows：
(1) synthesis based on organic ligand nickel complex
By NiCl2·6H2O, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformamides of N, N'- and trimesic acid, add deionization
Water；Ultrasound 5min~12min forms suspended mixture, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformazans of the N, N'- at room temperature
The molar ratio of acid amides and trimesic acid is 1:1~1:2, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformamides of the N, N'- with
NiCl2·6H2The molar ratio of O is 1:1~1:3, the NaOH solution tune pH for being 0.1mol/L with concentration is 4.2~7.2, pours into height
With 10 DEG C/h heating rates be warming up to 105 DEG C~145 DEG C in pressure reaction kettle, 48h~120h kept the temperature under hydrothermal condition, with 2.5 DEG C/
The rate of temperature fall of h cools to room temperature and obtains green bulk crystals, replaces cleaning 3 times~5 times with deionized water and ethanol, at room temperature
Naturally dry, obtains organic ligand nickel complex [Ni3(4-bmbpd)3(BTC)2(H2O)4]·4H2O；
Wherein, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformamides of 4-bmbpd N, N'-, BTC is trimesic acid；
(2) synthesis of nickel radical magnetic composite materials
Nickel complex [the Ni that step (1) is synthesized3(4-bmbpd)3(BTC)2(H2O)4]·4H2O weighs 4 grams, is ground using agate
When alms bowl grinding 2 is small~4 it is small when, be subsequently dispersed in 2 milliliters~4 milliliters of ethanol, with ball mill grinding 20 minutes~40 minutes,
Crystallite state nickel complex material is centrifuged out, when drying 24 is small at 70 DEG C；2 grams of crystallite state nickel complex materials are positioned over
Nitrogen protection under tube furnace in, be warming up to 800 DEG C with 5 DEG C/h heating rates, when constant temperature 4 is small~6 it is small when, with 2.5~10 DEG C/
The rate of temperature fall of h cools to room temperature and obtains nickel radical magnetic composite materials.
2. the nickel radical magnetic composite materials according to power requires 1, it is characterized in that：The N, N'- are double (4- methylene pyridines)
The molar ratio of benzene -1,4- diformamides and deionized water is 1:2800~1:8300.
3. a kind of synthetic method of nickel radical magnetic composite materials, it is characterized in that：
Comprise the following steps that：
(1) synthesis based on organic ligand nickel complex
By NiCl2·6H2O, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformamides of N, N'- and trimesic acid, add deionization
Water；Ultrasound 5min~12min forms suspended mixture, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformazans of the N, N'- at room temperature
The molar ratio of acid amides and trimesic acid is 1:1~1:2, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformamides of the N, N'- with
NiCl2·6H2The molar ratio of O is 1:1~1:3, the NaOH solution tune pH for being 0.1mol/L with concentration is 4.2~7.2, pours into height
With 10 DEG C/h heating rates be warming up to 105 DEG C~145 DEG C in pressure reaction kettle, 48h~120h kept the temperature under hydrothermal condition, with 2.5 DEG C/
The rate of temperature fall of h cools to room temperature and obtains green bulk crystals, replaces cleaning 3 times~5 times with deionized water and ethanol, at room temperature
Naturally dry, obtains organic ligand nickel complex [Ni3(4-bmbpd)3(BTC)2(H2O)4]·4H2O；
Wherein, double (4- methylene pyridines) benzene-Isosorbide-5-Nitrae-diformamides of 4-bmbpd N, N'-, BTC is trimesic acid；
(2) synthesis of nickel radical magnetic composite materials
Nickel complex [the Ni that step (1) is synthesized3(4-bmbpd)3(BTC)2(H2O)4]·4H2O weighs 4 grams, is ground using agate
When alms bowl grinding 2 is small~4 it is small when, be subsequently dispersed in 2 milliliters~4 milliliters of ethanol, with ball mill grinding 20 minutes~40 minutes,
Crystallite state nickel complex material is centrifuged out, when drying 24 is small at 70 DEG C；2 grams of nickel complexes are positioned under nitrogen protection
Tube furnace in, be warming up to 800 DEG C with 5 DEG C/h heating rates, when constant temperature 4 is small~6 it is small when, with the cooling of 2.5~10 DEG C/h speed
Rate cools to room temperature and obtains nickel radical magnetic composite materials.
4. the synthetic method of nickel radical magnetic composite materials according to claim 3, it is characterized in that：Double (the 4- of the N, N'-
Methylene pyridine) molar ratio of benzene -1,4- diformamides and deionized water is 1:2800~1:8300.
5. a kind of nickel radical magnetic composite materials as claimed in claim 1 are as photocatalytically degradating organic dye contaminant material
Application.
6. nickel radical magnetic composite materials according to claim 5 are as photocatalytically degradating organic dye contaminant material
Using it is comprised the following steps that：
Ni@ONC composite materials are added in the aqueous solution containing water pollutant, are penetrated by 40min-60min UV Lights
Afterwards, using magnet, by Ni@ONC composite catalyst adsorption recovery, to recycle.
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|---|---|---|---|---|
| CN108948368A (en) * | 2018-07-24 | 2018-12-07 | 中国人民解放军国防科技大学 | Method for rapidly preparing nickel-based metal organic framework material |
| CN111545222A (en) * | 2020-05-14 | 2020-08-18 | 渤海大学 | Co9S8S, N codoped core-shell structure carbonized nanocomposite material and synthetic method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709182A (en) * | 2013-12-06 | 2014-04-09 | 渤海大学 | Transition metal compounds based on semi-rigid, synthetic method and applications |
| CN104370952A (en) * | 2014-10-22 | 2015-02-25 | 渤海大学 | Organic-ligand-based multifunctional zinc complexes and application thereof |
| CN106391122A (en) * | 2016-08-16 | 2017-02-15 | 渤海大学 | A synthetic method of a polypyrrole-functionalized cobalt complex composite material and applications of the material |
-
2017
- 2017-11-28 CN CN201711214764.0A patent/CN107983385B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709182A (en) * | 2013-12-06 | 2014-04-09 | 渤海大学 | Transition metal compounds based on semi-rigid, synthetic method and applications |
| CN104370952A (en) * | 2014-10-22 | 2015-02-25 | 渤海大学 | Organic-ligand-based multifunctional zinc complexes and application thereof |
| CN106391122A (en) * | 2016-08-16 | 2017-02-15 | 渤海大学 | A synthetic method of a polypyrrole-functionalized cobalt complex composite material and applications of the material |
Non-Patent Citations (1)
| Title |
|---|
| XIU-LI WANG 等: "Various Polycarboxylate-Directed Cd(II) Coordination Polymers Based on a Semirigid Bis-pyridyl-bis-amide Ligand: Construction and Fluorescent and Photocatalytic Properties", 《CRYST. GROWTH DES.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108948368A (en) * | 2018-07-24 | 2018-12-07 | 中国人民解放军国防科技大学 | Method for rapidly preparing nickel-based metal organic framework material |
| CN108948368B (en) * | 2018-07-24 | 2021-05-07 | 中国人民解放军国防科技大学 | Method for rapidly preparing nickel-based metal organic framework material |
| CN111545222A (en) * | 2020-05-14 | 2020-08-18 | 渤海大学 | Co9S8S, N codoped core-shell structure carbonized nanocomposite material and synthetic method and application thereof |
| CN111545222B (en) * | 2020-05-14 | 2022-09-27 | 渤海大学 | Co 9 S 8 S, N codoped core-shell structure carbonized nanocomposite material and synthetic method and application thereof |
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