CN114805232A - Tetraazamacrocyclic nickel complex and micro-nano material and application thereof - Google Patents
Tetraazamacrocyclic nickel complex and micro-nano material and application thereof Download PDFInfo
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- CN114805232A CN114805232A CN202210356030.0A CN202210356030A CN114805232A CN 114805232 A CN114805232 A CN 114805232A CN 202210356030 A CN202210356030 A CN 202210356030A CN 114805232 A CN114805232 A CN 114805232A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 39
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- ADMPDKCEHNHOSZ-UHFFFAOYSA-N 5,7,12,14-tetraethyl-5,12-dimethyl-1,4,8,11-tetrazacyclotetradeca-7,14-diene Chemical compound CCC1=NCCNC(C)(CC)CC(CC)=NCCNC(C)(CC)C1 ADMPDKCEHNHOSZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000033444 hydroxylation Effects 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 3
- 238000003786 synthesis reaction Methods 0.000 claims 3
- 239000012530 fluid Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 238000000227 grinding Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002262 Schiff base Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000004696 coordination complex Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 manganese, iron porphyrin complexes Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- DUGOZIWVEXMGBE-UHFFFAOYSA-N Methylphenidate Chemical compound C=1C=CC=CC=1C(C(=O)OC)C1CCCCN1 DUGOZIWVEXMGBE-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 229940060942 methylin Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2531/847—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention discloses a tetra-aza macrocyclic nickel complex, a micro-nano material and application thereof, and relates to the technical field of metal organic complexes, wherein the molecular formula of the tetra-aza macrocyclic nickel complex is C 20 H 40 C l2 N 4 NiO 8 The structural formula is as follows:
the micro-nano material is obtained by preparing the tetraazamacrocyclic nickel complex into nano particles by a method of grinding and ultrasonic assistance. The inventionThe synthesis method of the crystal of the tetra-aza Schiff base macrocyclic nickel (II) complex is simple and convenient to operate; the complex and the micro-nano material thereof are applied to catalyzing phenol hydroxylation reaction, have better catalytic activity, and have better catalytic activity compared with complex crystals, so that the complex micro-nano material has important significance for designing and exploring novel aza-macrocyclic complex catalysts and micro-nano materials thereof.
Description
Technical Field
The invention relates to the technical field of metal organic complexes, in particular to a tetraazamacrocyclic nickel complex, a micro-nano material and application thereof.
Background
Due to the shortage of resources and the improvement of the requirement on environmental protection, the development of processes of full utilization of organic raw materials, energy conservation, consumption reduction and environmental friendliness in the catalytic process is more and more generally concerned. The selection of the catalyst in the catalytic reaction process is directly related to the success or failure of the reaction.
The metal complex catalyst belongs to one of catalysts having high activity and selectivity under mild conditions. Haber et al studied the catalytic performance of the metal complex catalyst Co (II) -porphyrin on the oxidation reaction of styrene, with the conversion of styrene being 100%, the selectivity of benzaldehyde being 66.3%, and the selectivity of styrene oxide being 20.6%. Nickel, manganese, iron porphyrin complexes are one of the most important catalyst types in epoxidation reactions in which hydrogen peroxide is used as an oxygen source.
In recent years, research of micro-nano technology in various fields is developed rapidly, and micro-nano catalysts have small particle sizes and limited unit cells contained in each crystal grain, so that the micro-nano catalysts show some unique structural and performance characteristics.
Zeng et al reported gold nanoparticles Au 55 (PPh 3 ) 12 Cl 6 At O 2 Shows good catalytic activity in the reaction of oxidizing styrene. Friend et al concluded that gold nanoparticles exhibit good catalytic selectivity in styrene oxide reactions due to their excellent quantum size effect carrier effect.
Researches on improving the activity and stability of the catalyst by preparing novel metal complex materials become research hotspots in the field of catalysis. The invention aims to design a novel metal complex micro-nano material with good catalytic activity.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a tetraazamacrocyclic nickel complex, a micro-nano material and application thereof.
The molecular formula of the tetraazamacrocyclic nickel complex is C 20 H 40 C l2 N 4 NiO 8 The structural formula is shown as the formula (I):
preferably, the crystals of the tetraazamacrocyclic nickel complex are monoclinic, P2 (1)/n; unit cell parameters:
α＝90°；
β＝93.3450(14)°；
γ＝90°。
the invention also provides a synthesis method of the tetraazamacrocyclic nickel complex, which comprises the following steps: dissolving 5,7,12, 14-tetraethyl-7, 14-dimethyl-1, 4,8, 11-tetraazacyclotetradec-4, 11-diene in methylIn alcohol, adding Ni (ClO) 4 ) 2 ·6H 2 Dissolving O in ethanol; and mixing the two solutions, heating and stirring, transferring to an oven for heating reaction, and naturally cooling to room temperature to obtain light brown yellow tetragonal prism crystals.
Preferably, 5,7,12, 14-tetraethyl-7, 14-dimethyl-1, 4,8, 11-tetraazacyclotetradeca-4, 11-diene and Ni (ClO) 4 ) 2 ·6H 2 The molar ratio of O is 1: 1; the volume ratio of methanol to ethanol is 1: 1.
preferably, the reaction is carried out in an oven at 50 ℃ for 24 h.
The invention also provides application of the tetraazamacrocyclic nickel complex in catalyzing phenol hydroxylation.
The invention also provides a tetraazamacrocyclic nickel complex micro-nano material, which is prepared by grinding the tetraazamacrocyclic nickel complex, dispersing the tetraazamacrocyclic nickel complex into ethanol, performing ultrasonic treatment, centrifuging supernatant, and drying to obtain yellow powder.
The invention also provides application of the tetraazamacrocyclic nickel complex micro-nano material in phenol hydroxylation catalysis.
Has the advantages that: the invention provides a tetra-aza Schiff base macrocyclic nickel (II) complex crystal, and the synthesis method is simple and convenient to operate; the complex is prepared into a micro-nano material, and the micro-nano material is applied to catalyzing phenol hydroxylation reaction, so that the micro-nano material has better catalytic activity, and compared with a complex crystal, the micro-nano material of the complex has better catalytic activity, and the micro-nano material of the complex has important significance for designing and exploring a novel aza-macrocyclic complex catalyst and the micro-nano material thereof.
Drawings
FIG. 1 is a crystal structure diagram of a tetraazamacrocyclic nickel complex of the present invention;
FIG. 2 is a diagram of the molecular unit cell stacking arrangement of the tetraazamacrocyclic nickel complexes of the present invention;
FIG. 3 is an SEM image of the tetraazamacrocyclic nickel complex micro-nano material of the invention.
Detailed Description
The technical means of the present invention will be described in detail below with reference to specific examples.
Example 1
The synthesis method of the crystal material of the tetraazamacrocyclic nickel complex comprises the following steps: 1mmol of 5,7,12, 14-tetraethyl-7, 14-dimethyl-1, 4,8, 11-tetraazacyclotetradeca-4, 11-diene was dissolved in 25mL of methanol, and 1mmol of Ni (ClO) was added 4 ) 2 ·6H 2 Dissolving O in 25mL of ethanol; and then stirring and mixing the two solutions at 50 ℃, placing the mixture into a reaction kettle with a polytetrafluoroethylene lining, placing the mixture into an oven, reacting at 50 ℃, and naturally cooling to room temperature after 24 hours to obtain the light brown yellow square column-shaped tetraazamacrocyclic nickel complex crystal.
And (3) characterizing the crystal material of the tetraazamacrocyclic nickel complex prepared by the method.
Infrared analysis: primary IR (KBr) data v (N-H)3486, 3417cm -1 (vs)，ν(C＝N)1647cm -1 (vs)，ν(C1O 4 - )1137cm -1 ,624cm -1 (vs)。
Structural characterization: the crystallographic data, typical bond length and bond angle data of the crystal of the tetraazamacrocyclic nickel complex are respectively shown in tables 1-3, the structure of the crystal of the complex is analyzed, and the molecular structure diagram and the molecular unit cell stacking arrangement diagram of the crystal of the complex are respectively shown in FIG. 1 and FIG. 2.
TABLE 1 Crystal data for tetraazamacrocyclic nickel complexes
TABLE 2 bond length data typical of tetraazamacrocyclic nickel complex crystals
TABLE 3 bond angle data typical of tetraazamacrocyclic nickel complex crystals
Example 2
Synthesizing a tetraazamacrocyclic nickel complex micro-nano material: grinding 0.5g of the tetraazamacrocyclic nickel complex prepared in example 1 for 1h, adding 20mL of ethanol, performing ultrasonic treatment for 10 min, taking supernatant, centrifuging, and drying in air to obtain yellow micron powder.
SEM representation is carried out on the prepared tetraazamacrocyclic nickel complex micro-nano material, and the result is shown in figure 3.
The tetraazamacrocyclic nickel complex and the micro-nano material thereof are used for catalytic research on phenol hydroxylation.
The reaction sequence for the oxidation of phenol is as follows:
catalysis of tetraazamacrocyclic nickel complexes: weighing 20mg of tetraazamacrocyclic nickel complex, adding into a round-bottom flask, adding 0.2g of phenol, adding 30mL of mixed solvent of ethanol and water with the volume ratio of 1:1, heating to 50 ℃, and dropwise adding 6mmol of 30% H while stirring 2 O 2 The solution was stirred at 50 ℃ under reflux for 5 hours and cooled. The yield of the benzenediol was measured by a liquid chromatograph, and an ultraviolet detector (λ 277nm), conversion rate: 30.3 percent.
Catalysis of a tetraazamacrocyclic nickel complex micro-nano material: weighing 10mg of tetraazamacrocyclic nickel complex micro-nano material, adding the micro-nano material into a round-bottom flask, adding 0.1g of phenol, adding 15mL of mixed solvent of ethanol and water with the volume ratio of 1:1, heating to 50 ℃, and dropwise adding 3mmol of 30% H under stirring 2 O 2 The solution was stirred and refluxed at 50 ℃ for 5 hours, and then cooled. The yield of the dihydroxybenzene was measured by liquid chromatograph, uv detector (λ 277nm), conversion: 44.6 percent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A tetraazamacrocyclic nickel complex which is characterized in that the molecular formula is C 20 H 40 C l2 N 4 NiO 8 The structural formula is shown as the formula (I):
2. the tetraaza according to claim 1A macrocyclic nickel complex, characterized in that the crystal of the tetraazamacrocyclic nickel complex is monoclinic, P2 (1)/n; unit cell parameters:
α＝90°；
β＝93.3450(14)°；
γ＝90°。
3. a process for the synthesis of tetraazamacrocyclic nickel complexes as claimed in claim 1 or 2, characterized by the following steps: dissolving 5,7,12, 14-tetraethyl-7, 14-dimethyl-1, 4,8, 11-tetraazacyclotetradeca-4, 11-diene in methanol, and dissolving Ni (ClO) 4 ) 2 ·6H 2 Dissolving O in ethanol; and mixing the two solutions, heating and stirring, transferring to an oven for heating reaction, and naturally cooling to room temperature to obtain light brown yellow tetragonal prism crystals.
4. A process for the synthesis of tetraazamacrocyclic nickel complexes as claimed in claim 3, characterized in that 5,7,12, 14-tetraethyl-7, 14-dimethyl-1, 4,8, 11-tetraazacyclotetradeca-4, 11-diene and Ni (ClO) 4 ) 2 ·6H 2 The molar ratio of O is 1: 1; the volume ratio of the methanol to the ethanol is 1: 1.
5. a process for the synthesis of tetraazamacrocyclic nickel complexes according to claim 3, characterized in that the reaction is carried out in an oven at 50 ℃ for 24 h.
6. Use of a tetraazamacrocyclic nickel complex according to claim 1 or 2 for catalyzing the hydroxylation of phenol.
7. A tetraaza macrocyclic nickel complex micro-nano material is characterized in that the tetraaza macrocyclic nickel complex of claim 1 or 2 is ground and dispersed into ethanol, ultrasonic treatment is carried out, supernatant fluid is taken, centrifuged and dried, and yellow powder is obtained.
8. The application of the tetraazamacrocyclic nickel complex micro-nano material as claimed in claim 7 in the catalysis of phenol hydroxylation.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150142755A (en) * | 2014-06-11 | 2015-12-23 | 한국과학기술원 | Method for manufacturing metal or metal oxide having micro-nano sizes using ultra-wave and metal or metal oxide thereby |
| CN105854911A (en) * | 2016-06-23 | 2016-08-17 | 中国石油大学(华东) | Micron nickel phosphide electro-catalytic material used for hydrogen evolution/oxygen evolution double functions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150142755A (en) * | 2014-06-11 | 2015-12-23 | 한국과학기술원 | Method for manufacturing metal or metal oxide having micro-nano sizes using ultra-wave and metal or metal oxide thereby |
| CN105854911A (en) * | 2016-06-23 | 2016-08-17 | 中国石油大学(华东) | Micron nickel phosphide electro-catalytic material used for hydrogen evolution/oxygen evolution double functions |
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