CN111732736B - Ni (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof - Google Patents
Ni (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111732736B CN111732736B CN202010629615.6A CN202010629615A CN111732736B CN 111732736 B CN111732736 B CN 111732736B CN 202010629615 A CN202010629615 A CN 202010629615A CN 111732736 B CN111732736 B CN 111732736B
- Authority
- CN
- China
- Prior art keywords
- organic framework
- metal organic
- salen ligand
- zinc
- crystal material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 41
- 239000003446 ligand Substances 0.000 title claims abstract description 37
- 239000013078 crystal Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 17
- -1 (R, R) -N, N' -bis (3-methyl-5-carboxysalicylidene) -1, 2-diphenylethylenediamine nickel Chemical compound 0.000 claims abstract description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZKOGUIGAVNCCKH-UHFFFAOYSA-N 4-phenyl-1,3-dioxolan-2-one Chemical compound O1C(=O)OCC1C1=CC=CC=C1 ZKOGUIGAVNCCKH-UHFFFAOYSA-N 0.000 claims abstract description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006555 catalytic reaction Methods 0.000 claims description 15
- 239000002178 crystalline material Substances 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tertiry butyl alcohol Natural products CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims 2
- KMZYFPGBXDCJKA-UHFFFAOYSA-N 1-iodo-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound IC12C(C=CC=C1)O2 KMZYFPGBXDCJKA-UHFFFAOYSA-N 0.000 claims 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims 1
- 239000005708 Sodium hypochlorite Substances 0.000 claims 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims 1
- 150000003751 zinc Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 10
- YBTRETBMVPGHNR-UHFFFAOYSA-N CC(C=C(C=C1C=C2C=CC=CC2C=CC2=CC=CC=C2)C(O)=O)=C1O Chemical group CC(C=C(C=C1C=C2C=CC=CC2C=CC2=CC=CC=C2)C(O)=O)=C1O YBTRETBMVPGHNR-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 241001233278 Scalopus aquaticus Species 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000013212 metal-organic material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000013336 microporous metal-organic framework Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000373 single-crystal X-ray diffraction data Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000010937 topological data analysis Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Ni (II) -Salen ligand metal organic framework crystal material and a preparation method and application thereof. The chemical formula of the material is as follows: { [ Zn ]4O(L)6]·DMF·H2O}nWherein L is a dicarboxylate dianion of (R, R) -N, N' -bis (3-methyl-5-carboxysalicylidene) -1, 2-diphenylethylenediamine nickel (II), and N is the degree of polymerization. The metal organic framework crystal material adopts a solvent thermal synthesis method, has simple operation, low cost and high yield, and is easy for large-scale industrial production. The prepared metal organic framework crystal material has higher thermal stability (400 ℃), and the BET specific surface area is 228m2(ii) in terms of/g. At 273K and 1atm for CO2Has an adsorption capacity of 18.8m3(iv) g. In the presence of an oxidant, styrene is catalyzed in a water phase to be selectively oxidized into benzaldehyde, the yield reaches 99%, the catalyst is recycled for five times, and the activity loss is small. In the presence of tetrabutylammonium bromide, styrene oxide and CO are catalyzed by 1atm and 50 ℃ without solvent2The reaction produces styrene carbonate with a yield of 91%, and the catalyst is recycled for five times and still keeps activity. This material is a good heterogeneous catalyst.
Description
Technical Field
The invention belongs to the field of preparation and application of MOFs new materials, and particularly relates to a preparation method of a metal organic framework taking (R, R) -N, N' -bis (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) as a ligand and application of the metal organic framework in the fields of gas adsorption and catalysis.
Background
Metal Organic Frameworks (MOFs) represent a class of hybrid organic-inorganic ordered network supramolecular materials, which are ordered network structures composed of organic bridging ligands and inorganic metal ions, including one-dimensional chain-like, two-dimensional layered and three-dimensional network structures. These materials consist of rigid multidentate bridging struts and metal nodes. High micropore volume, large pore size, and possibly high levels of metals that provide active sites are important features of such materials.
MOFs based on the metal Salen complex are usually prepared by a direct method, namely, the MOFs is constructed by directly using the metal complex as a connector and carrying out in-situ self-assembly on the metal complex and a metal node. As mentioned above, the metal Salen complex is a homogeneous catalyst which has excellent performance but is easy to pollute and waste, and is difficult to recycle. Thus, limiting its further application in the field of catalysis. The heterogeneous catalyst obtained by loading the mesoporous composite material is an effective means, and a metal organic framework is an excellent means by taking the heterogeneous catalyst as a basis, the MOFs is highly porous, has an ultrahigh specific surface area, and has stable physical/chemical properties, so that the MOFs is an ideal immobilized material, and the immobilized sites provided by the MOFs are far higher than other common materials, so that the immobilized capacity is stronger, and the MOFs are not easy to separate after being immobilized for multiple times and circularly used; specific active groups can be introduced into the framework to enhance the reaction capability and realize the series catalysis of multi-step reaction; and moreover, ligands can be modified to construct MOFs with specific structures so as to realize concerted catalysis. In summary, the abundant geometry of MOFs, the diversity of catalytic centers, and the tailorability give the catalyst more catalytic forms.
The heterogeneous catalyst synthesized by utilizing the MOFs preparation method immobilization strategy not only perfectly overcomes the problems of difficult recovery, instability and the like caused by the homogeneous catalyst, but also has more catalytic forms and frame structures, the application field is wider, the MOFs prepared based on the metal Salen complex gradually attracts the attention of researchers, and the related research is more and more intensive. The construction of MOFs requires the coordination self-assembly of an additional coordination point of a metal Salen complex with a metal ion or a metal cluster, and the current reports mainly focus on carboxylic acid type or pyridine type metal Salen ligands. As catalysts, such MOFs can be used to catalyze various types of reactions, such as: asymmetric silicon cyanation, photodegradation, and Diels-Alder reactions, etc. (Hu Y H, Liu C X, Wang J C, et al. organic Chemistry,2019,58(8): 4722-. For example, Jian-Fang Ma research group (Li J, Yang J, Li)u Y et al chemistry 2015,21(11):4413-4421) in 2015 Fe-Salen complex (III as organic ligand and Zn as transition metal respectively)2+、Cd2+In-situ self-assembly coordination is carried out to obtain two chiral MOFs (CMOF 1 and CMOF 2), researches find that the prepared crystal material can catalyze the degradation of 2-chlorophenol under the condition of visible light, and compared with a control homogeneous catalyst Fe-Salen complex (III), the CMOF 1 and CMOF 2 show higher catalytic activity, so that the complex not only benefits from the properties of high porosity and the like of the MOFs, but also increases the mutual contact between the catalyst and a degraded substance; the active metal center is combined with hydroxyl firstly under acidic condition and then reacts with hydrogen peroxide to obtain [ salen-Fe ]IIIOOH]And irradiating with visible light to obtain [ salen-Fe (V) ═ O]And. OH free radical, which is significantly greater than [ salen-Fe (V) ═ O]Is more reactive. The generated OH free radicals immediately react with degraded substances, thereby accelerating the reaction process and improving the catalytic efficiency.
Ying-Ying Liu research group (Wang H, Yang J, Liu Y, et al. Crystal Growth)&Design,2015,15(10):4986-4992) obtaining a porous trimetal organic framework, Fe, by in-situ self-assembly coordination of Salen complex precursor, barium chloride and sodium chloride3+Tetradentate with N, N, O, O to form a metal centre, carboxyl groups of Salen ligands with Ba2+And Na+Atoms are coordinated to generate a three-dimensional periodic network, so that a network crystal supramolecular catalyst with periodicity is obtained, and the first Fe-containing catalyst based on Schiff base ligandIIIThe research shows that the photocatalytic degradation activity of the 4-CP is higher than that of the 2-CP and the 3-CP, and the phenolic hydroxyl group is generally considered to be caused by the action of the phenolic hydroxyl group and can improve the electron density of para-position and ortho-position carbon atoms when the phenolic hydroxyl group is taken as an electron-donating group, so that the two positions are easily attacked by an electrophilic reagent, and the para-position is weaker, and the degradation activity is lower.
The dicarboxylic acid compound as an organic ligand has the characteristics of strong coordination capacity, various coordination modes, easy formation of hydrogen bonds and the like. The (R, R) -N, N' -bis (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) has two carboxyl coordination sites, can form various coordination modes with metal ions or metal clusters, and can obtain MOFs materials with various structures. In addition, (R, R) -N, N' -di (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) is coordinated with divalent nickel ions, and can be used as an active center to catalyze a plurality of organic reactions.
As can be seen from the literature, (R, R) -N, N' -bis (3-methyl-5-carboxysalicylidene) -1, 2-diphenylethylenediamine nickel (II) is a novel metal Salen ligand, and the ligand is coordinated with metal ions to form a metal organic framework material and has not been reported in the literature.
Disclosure of Invention
The invention aims to solve the first technical problem of providing a microporous metal organic framework crystal material with stable structure and higher specific surface area.
The second technical problem to be solved by the invention is to provide a preparation method of the metal organic framework crystal material, which is simple and easy to implement, low in cost, high in yield and easy for large-scale industrial production.
The third purpose of the invention is to provide the application of the metal organic framework crystal material in the fields of gas adsorption and catalysis.
The invention utilizes the characteristics that (R, R) -N, N' -di (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) has stronger coordination capability, multiple coordination modes, easy formation of hydrogen bond, aromatic ring accumulation effect and the like, and firstly uses the ligand and Zn2+Coordination forms a metal organic framework crystal material with novel structure. The material generally has porous holes and large specific surface area, and has good application prospect in the fields of catalysis, gas adsorption and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the Ni (II) -Salen ligand metal organic framework crystal material has the chemical formula { [ Zn ]4O(L)6]·DMF·H2O}nWherein L is a dicarboxylate dianion of (R, R) -N, N' -bis (3-methyl-5-carboxysalicylidene) -1, 2-diphenylethylenediamine nickel (II), and N is the degree of polymerization.
The crystal of the metal organic framework belongs to a monoclinic system, and the space group is I2.
The invention relates to a Ni (II) -Salen ligand metal organic framework crystal material and a preparation method and application thereof, which comprises the following steps:
(1) the divalent zinc salt compound, (R, R) -N, N' -bis (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) is dissolved in the solvent, evenly stirred and then added into a transparent high temperature resistant glass bottle with screw threads.
(2) Heating to raise the temperature, reacting the reactants at a certain temperature for a period of time, gradually reducing the temperature, cooling to room temperature, filtering, washing with DMF or DMA, and drying to obtain the metal organic framework crystal material.
The zinc salt compound is zinc nitrate salt, zinc chloride salt, zinc sulfate salt, zinc acetate salt and zinc perchlorate salt; the zinc ion has a valence of + 2;
the nickel ions are +2 valent;
the solvent DMF or DMA of the invention;
the molar ratio of the zinc salt compound to (R, R) -N, N' -bis (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) is 2: 0.8-2: 1, and the molar ratio of the zinc salt compound to the solvent is 1: 1000-1: 5000;
the reaction temperature of the invention is 80-100 ℃;
the reaction time is 1-120 hours;
the heating rate of the invention is 1-5 ℃/h.
The cooling rate of the invention is 1-10 ℃/h.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the metal organic framework crystal material synthesized by the invention has novel and unique structure.
(2) The invention adopts (R, R) -N, N' -di (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) and Zn2+The salt is used as raw material, the solvent thermal synthesis method is adopted, the method is simple and easy to implement, the cost is low, and the yield is highHigh efficiency and easy large-scale industrial production.
(3) The metal organic framework crystal material has a three-dimensional network structure, porosity and specific surface area (BET specific surface area of 228 m)2The temperature is 400 ℃ at 273K under 1atm2Has an adsorption capacity of 18.8cm3(ii) in terms of/g. In the presence of an oxidant, styrene is catalyzed in a water phase to be selectively oxidized into benzaldehyde, the yield reaches 99%, the catalyst is recycled for five times, and almost no activity loss exists. In addition, in the presence of tetrabutylammonium bromide, epoxystyrene and CO are catalyzed under the solvent-free reaction conditions of 1atm and 50 DEG C2The reaction produces styrene carbonate with a yield of 91%, and the catalyst is recycled for five times, and the activity of the catalyst is still maintained. The material has good application prospect in the fields of gas adsorption, catalysis and the like.
Drawings
FIG. 1 shows the molecular structure of Ni (II) -Salen (L) ligand of the metal-organic framework crystal material of the present invention. FIG. 2 shows the coordination mode of the crystal material Ni (II) -Salen (L) of the metal-organic framework of the present invention.
FIG. 3 is a diagram of a secondary structural unit of the metal organic framework crystalline material of the present invention.
FIG. 4 is a diagram of coordination cubic units of the metal-organic framework crystal material of the present invention.
FIG. 5 is a structural diagram of a dual interpenetrating topos of a metal organic framework crystalline material of the present invention.
FIG. 6 is an infrared spectrum of the metal organic framework crystal material of the present invention.
FIG. 7 is a thermogravimetric analysis of the metal-organic framework crystalline material of the present invention.
FIG. 8N at 77K for the MOM crystalline material of the present invention2Adsorption-desorption isotherm diagram. FIG. 9 shows that the crystalline material of the metal-organic framework of the present invention has CO at 273K2The attached drawing is shown.
FIG. 10 shows that the metal organic framework crystal material of the present invention catalyzes the oxidation of styrene to generate benzaldehyde1H NMR chart.
FIG. 11 shows that the metal organic framework crystal material of the present invention catalyzes the oxidation of styrene to generate benzaldehyde13C NMR chart.
FIG. 12 shows that the metal organic framework crystal material of the present invention catalyzes epoxystyrene and CO2To styrene carbonate1H NMR chart.
FIG. 13 shows that the metal organic framework crystal material of the present invention catalyzes epoxystyrene and CO2To styrene carbonate13C NMR chart.
Detailed Description
The Ni (II) -Salen ligand metal organic framework crystal material and the preparation method and the application thereof have the following synthesis steps and structural characterization:
dissolving a divalent zinc salt compound, (R, R) -N, N' -bis (3-methyl-5-carboxyl salicylidene) -1, 2-diphenyl ethylene diamine nickel (II) in a solvent, uniformly stirring, adding the mixture into a threaded high-temperature-resistant glass vial, heating to slowly raise the temperature, reacting the reactant at a certain temperature for a period of time, gradually reducing the temperature, cooling to room temperature, filtering, washing with the solvent, and drying to obtain { [ Zn ]4O(L)6]·DMF·H2O}nA crystalline material. Then measuring the single crystal structure of the compound by a Rigaku RAXIS-RAPID IPX-ray diffractometer, measuring the infrared spectrum of the compound by a Nicolet Nexus 470FTIR infrared spectrometer, testing the thermogravimetric/differential thermal analysis of a sample on a Q600 SDT thermogravimetric analyzer, testing the powder X-ray diffraction on a Bruker D8X-ray diffractometer, testing the C, H, N element analysis on a German Vario EL III element analyzer, testing the nitrogen adsorption isotherm on a Quantachrome AS-1MP instrument,1h NMR and13c NMR was measured on an Agilent DD2-400 NMR spectrometer.
The specific embodiment is as follows:
{[Zn4O(L)6]·DMF·H2O}nsynthesis and characterization of
Putting Ni (II) -Salen (L) ligand (10mg, 0.0169mmol, 1.0equiv) into a 10mL transparent high-temperature-resistant glass vial with threads, sequentially adding zinc nitrate hexahydrate (10mg, 0.0338mmol, 2.0equiv) and 2mL DMF, carrying out ultrasonic treatment for 2 minutes to dissolve the ligand, screwing a bottle cap after the ligand is completely dissolved, putting the bottle cap into an automatic program-controlled heating box, heating to 80 ℃ at the heating rate of 5 ℃/h, carrying out heat preservation for 3 days, and then cooling at the cooling rate of 5 ℃/hThe yield was reduced to room temperature, filtered to give brick-red crystals, washed with DMF and dried at room temperature to give 8.0mg, 80% yield (calculated as Ni-Salen). According to C198H162N14Ni6O42Zn8The theoretical value (%) of elemental analysis was calculated as: c, 55.49; n, 4.58; h, 3.81; experimental values: c, 55.38; n, 4.64; h, 3.86. IR (4000-400 cm)-1):3435(vs),3059(w),1660(vs),1610(vs),1400(vs),1323(m),1249(w),754(w),700(w)。
Single crystal X-ray diffraction data of the obtained compound were measured on a Rigaku RAXIS-RAPID IPX-ray diffractometer and collected at room temperature. The diffractometer uses CuKalpha rays with the wavelength ofWorking voltages and currents of 90kV and 50mA, collected in a ω -scan fashion for Lp factor correction, absorption correction using the CrystalClear program (Muller P., Herbst-Irmer R., Spek A.L., et al., International Union of Crystallographics Book Series, Oxford University Press: New York,2006, Chapter 7). Analyzing the structure by a direct method, then solving the coordinates of all non-hydrogen atoms by a difference Fourier method, obtaining organic hydrogen atoms by a theoretical hydrogenation method, and correcting the structure by a least square method. The calculation is completed by a SHELXTL program package (SHELdrick, G.M.: Crystal structure recovery with SHELXL. acta Crystalogger.2015, C71: 3-8.) on a microcomputer, and the structure of the compound is { [ Zn4O(L)6]·DMF·H2O}n. Table 1 shows the main crystallographic data of the metal-organic framework material.
TABLE 1
R1=Σ||Fo|-|Fc||/Σ|Fo|.wR2=[Σw(Fo2-Fc2)2/Σw(Fo2)2]1/2
FIG. 1 shows the molecular structure of the ligand Ni (II) -Salen (L). Single crystal derivatives of X-rayThe compounds were monoclinic, space group I2, as shown by the gamma ray study. Crystallographic data and structure refinement parameters are shown in table 1. Each asymmetric unit contains 6 Ni (II) -Salen ligands, 4 Zn (II) atoms, 1 coordinated water molecule and one coordinated DMF molecule. Each Zn atom is coordinated with 3 carboxyl groups, 3 carboxyl groups being derived from 3 different ligands. The secondary structural unit is a tetranuclear Zn-O octahedral structure [ Zn ]4O(CO2)6](FIG. 3). Since one Zn atom coordinates one water molecule and DMF molecule, this Zn atom is 6 coordinates and the remaining three Zn atoms are 4 coordinates, resulting in some distortion of the octahedral structure. Each secondary building block is linked to 6 ligands, both carboxyl groups of each Ni (II) -Salen ligand being represented by (kappa)1-κ1-μ2) The mode coordinates to two Zn atoms of the secondary building block (fig. 1). Topological analysis of the compound confirmed that linear ni (ii) -Salen maintained its di-connectivity, each secondary building block served as a six-link node, and that the ni (ii) -Salen ligand joined end-to-end with the secondary building blocks formed pcu lattices (fig. 4). Ni (II) -Salen is connected with secondary structural units to form a dual interpenetrating 3D network, and the topology of the networkThe symbol is (4)12.63) (FIG. 5).
FIG. 6 is an infrared spectrum of the metal organic framework, tested on a Nicolet Nexus 470FTIR infrared spectrometer using spectrally pure potassium bromide pellets, the sample and potassium bromide were dried under an ultraviolet lamp to remove water from the surface of the sample prior to testing, with a measurement range of 4000--1. From the infrared spectrogram, 3300-3600cm-1Is the absorption peak of the stretching vibration of the O-H bond of water. Due to the coordination of the ligand and the metal, the absorption peaks of some groups are changed. 3059cm-1Is an aromatic ring; 1660 vibrating with C ═ N expansion; 1610cm-1And 1400cm-1Each being a carboxyl groupsC ═ O and upsilonasVibration of 1323cm C ═ O-1The absorption peak is the skeletal oscillation of upsilon (C ═ C) in the aromatic ring of the ligand.
FIG. 7 shows the thermogravimetric/differential thermal analysis of the metal organic framework, which is performed on a Q600 SDT thermogravimetric analyzer, after zeroing, weighing 5-10 mg of sample, placing the sample into a ceramic dry pot for measurement, and performing measurement under a nitrogen atmosphere, wherein the heating rate is set to 10 ℃/min and the temperature is increased to 800 ℃. There are two distinct weight loss stages, weight loss of 17.6% between 30-400 ℃, corresponding to loss of 1 coordinated water molecule and 1 coordinated DMF molecule, and disordered solvent molecules in the pore channel; at 400-440 ℃, there was a sharp weight loss of 22.4%, the organic ligand began to decompose and the framework began to collapse. The weight loss was completed at 700 c and there was a total weight loss of about 51.7%.
FIG. 8 is a nitrogen adsorption isotherm of the metal organic framework, which is measured on a Quantachrome AS-1MP instrument, and before the measurement, the sample is activated in vacuum at 200 ℃ for 24h to remove the guest molecules in the pore channels of the sample. Using high purity N2(99.999%) 10 at 77K -61 measurement of N in the pressure range2The amount of adsorption was calculated and the BET specific surface area was calculated. The physical adsorption-desorption isotherm is a typical microporous adsorption isotherm (type I), and the BET specific surface area thereof is calculated to be 228m2/g。
FIG. 9 shows that the metal-organic framework is aligned to CO at 0.1-1atm and 273K2The adsorption quantity of the compound is measured on a Quantachrome AS-1MP instrument, and a sample is activated for 24 hours in vacuum at 200 ℃ before the test, so that guest molecules in the pore channels of the sample are removed. Using high purity CO2(99.998%). Experimental results on CO2The adsorption capacity of (2) was 18.8m3/g。
The step of catalyzing the selective oxidation reaction of styrene and hydrogen peroxide: styrene (2mmol), 2mL of water, hydrogen peroxide (3mmol) and { [ Zn ] were charged in a 10mL parallel eggplant-shaped bottle reactor, respectively4O(L)6]·DMF·H2O}n(0.025 mol%) and reacted at 60 deg.C for 15 hr, adding ethyl acetate 1.5mL after the reaction, centrifuging reaction solution and catalyst, extracting and separating for 4 times, mixing supernatant, concentrating, separating and purifying by silica gel column chromatography to obtain benzaldehyde (eluent is petroleum ether: ethyl acetate 25:1), passing through Agilent DD2-400 NMR instrument, CDCl3TMS was an internal standard for solvent, and the structures of the target products were characterized (fig. 10 and 11).
Cyclic catalytic experiments: after each catalytic reaction is finished, centrifugally separating the catalyst by a centrifugal machine, filtering, washing the catalyst by dichloromethane and acetone in sequence, heating and activating for 24 hours in vacuum at 150 ℃ to be used as the catalyst for the next circular catalysis. The product yield of 5-cycle catalysis is 99%, 97%, 95%, 94% and 92% in sequence.
Catalysis of epoxystyrene and CO2The ring expanding reaction step (2): in a 10mL parallel eggplant-shaped bottle reactor, epoxystyrene (10mmol), tetrabutylammonium bromide (0.025mmol) and { [ Zn ] were charged4O(L)6]·DMF·H2O}n(0.05 mol%) and a jacket containing CO at the top of the condenser tube2Placing the balloon in parallel with a gas for three times, reacting at 50 ℃ for 12 hours, adding 1.5mL of ethyl acetate into a reaction system after the reaction is finished, centrifugally separating the reaction solution and a catalyst, extracting and separating for 4 times, combining supernate, concentrating, separating and purifying by silica gel column chromatography to obtain a product, purifying by column chromatography (eluent is petroleum ether: ethyl acetate 12:1), and performing Agilent DD2-400 nuclear magnetic resonance spectroscopy, CDCl3TMS was an internal standard for solvent, and the structures of the target products were characterized (fig. 12 and 13).
Cyclic catalytic experiment: styrene oxide is used as a substrate for reaction, after each catalytic reaction is finished, a centrifugal machine centrifugally separates the catalyst, the catalyst is filtered, washed by dichloromethane and acetone in sequence, and heated and activated for 24 hours in vacuum at 150 ℃ to be used as the catalyst for the next circular catalysis. The product yield of 5-cycle catalysis is 91%, 90%, 88% and 85% in sequence.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the present invention without departing from the technical spirit of the present invention.
Claims (10)
1. A kind of Ni (C))-The preparation method of the Salen ligand metal organic framework crystal material is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: a divalent zinc salt compound, (b) aR, R)-N,N' -bis (3-methyl-5-carboxysalicylidene) -1, 2-diphenylethylenediamine nickel (II) ((III))) Dissolving in a solvent, stirring uniformly, and then adding into a transparent high-temperature-resistant glass vial with threads;
step two: slowly heating to 80-100 ℃ at a heating rate of 1-5 ℃/h, reacting for 1-120 hours, gradually reducing the temperature, cooling to room temperature at a cooling rate of 1-10 ℃/h, filtering, washing with a solvent, and drying to obtain a metal organic framework crystal material; the chemical formula is as follows:
{[Zn4O(L)6]·DMF·H2O}nwherein L is: (R, R)-N,N' -bis (3-methyl-5-carboxysalicylidene) -1, 2-diphenylethylenediamine nickel (II) ((III))) Abbreviation of dicarboxylate dianion of (a);
wherein the chemical structural formula of L is as follows:
in the above chemical formula:
and n is the degree of polymerization.
3. Ni (according to claim 1)) -a method for preparing a Salen ligand metal organic framework crystalline material, characterized in that: the zinc salt compound and (A) and (B)R, R)-N,N' -bis (3-methyl-5-carboxysalicylidene) -1, 2-diphenylethylenediamine nickel (N- (ll-butyl-N-ethyl-p-phenylenediamine)) The molar ratio of the zinc salt compound to the solvent is 2: 0.8-2: 1, and the molar ratio of the zinc salt compound to the solvent is 1: 1000-1: 5000.
9. A Ni (C) (prepared according to claim 1)) -the use of a Salen ligand metal organic framework crystalline material, characterized in that: the metal organic framework crystal material catalyzes epoxystyrene and CO in the presence of tetrabutylammonium bromide2The reaction produces styrene carbonate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010629615.6A CN111732736B (en) | 2020-07-03 | 2020-07-03 | Ni (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010629615.6A CN111732736B (en) | 2020-07-03 | 2020-07-03 | Ni (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111732736A CN111732736A (en) | 2020-10-02 |
CN111732736B true CN111732736B (en) | 2022-05-17 |
Family
ID=72652606
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010629615.6A Expired - Fee Related CN111732736B (en) | 2020-07-03 | 2020-07-03 | Ni (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111732736B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113292581B (en) * | 2021-05-12 | 2022-09-23 | 东南大学 | Novel coordination circular polarization luminescent crystalline compound and preparation method and application thereof |
CN115970761A (en) * | 2022-12-14 | 2023-04-18 | 中国五冶集团有限公司 | Synthesis method and test method of catalytic material of alumina reactor |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102153578A (en) * | 2011-02-28 | 2011-08-17 | 华南理工大学 | Rare-earth organic coordination polymer taking 4,4'-bipyridyl as template, and preparation method and application thereof |
CN102688776A (en) * | 2011-03-23 | 2012-09-26 | 中国科学院大连化学物理研究所 | Solid catalyst for hydration of epoxy compound to prepare diol and its application |
CN108129669A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of salen porous organic polymers and metal complex and application |
CN108568316A (en) * | 2018-04-27 | 2018-09-25 | 华南理工大学 | A kind of high stable zirconium base chiral catalyst and preparation method are applied with it |
CN109265703A (en) * | 2018-11-20 | 2019-01-25 | 东南大学 | It is a kind of three-dimensional containing zinc/copper chiral metal organic framework material and preparation method thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090005243A1 (en) * | 2007-04-23 | 2009-01-01 | Goddard William A | Doped metal organic frameworks for reversible H2 storage at ambient temperature |
-
2020
- 2020-07-03 CN CN202010629615.6A patent/CN111732736B/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102153578A (en) * | 2011-02-28 | 2011-08-17 | 华南理工大学 | Rare-earth organic coordination polymer taking 4,4'-bipyridyl as template, and preparation method and application thereof |
CN102688776A (en) * | 2011-03-23 | 2012-09-26 | 中国科学院大连化学物理研究所 | Solid catalyst for hydration of epoxy compound to prepare diol and its application |
CN108129669A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of salen porous organic polymers and metal complex and application |
CN108568316A (en) * | 2018-04-27 | 2018-09-25 | 华南理工大学 | A kind of high stable zirconium base chiral catalyst and preparation method are applied with it |
CN109265703A (en) * | 2018-11-20 | 2019-01-25 | 东南大学 | It is a kind of three-dimensional containing zinc/copper chiral metal organic framework material and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
"A chiral metal-organic framework for sequential asymmetric catalysis";Feijie Song et.al;《ChemComm》;20111231;第47卷(第29期);第8256-8258页 * |
Also Published As
Publication number | Publication date |
---|---|
CN111732736A (en) | 2020-10-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Hu et al. | Metal–organic frameworks with Lewis acidity: synthesis, characterization, and catalytic applications | |
Wu et al. | Copper (i) iodide cluster-based lanthanide organic frameworks: synthesis and application as efficient catalysts for carboxylative cyclization of propargyl alcohols with CO 2 under mild conditions | |
Peng et al. | Application of metal organic frameworks M (bdc)(ted) 0.5 (M= Co, Zn, Ni, Cu) in the oxidation of benzyl alcohol | |
Cheng et al. | New multifunctional 3D porous metal–organic framework with selective gas adsorption, efficient chemical fixation of CO 2 and dye adsorption | |
Li et al. | Microporous 2D indium metal–organic frameworks for selective CO 2 capture and their application in the catalytic CO 2-cycloaddition of epoxides | |
Shi et al. | A new three-dimensional metal–organic framework constructed from 9, 10-anthracene dibenzoate and Cd (ii) as a highly active heterogeneous catalyst for oxidation of alkylbenzenes | |
CN111732736B (en) | Ni (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof | |
Zhang et al. | The fixation of carbon dioxide with epoxides catalyzed by cation-exchanged metal-organic framework | |
CN112280052B (en) | Hierarchical pore ZIF-8 material and preparation method and application thereof | |
Wang et al. | Rational construction of an ssa-type of MOF through pre-organizing the ligand's conformation and its exceptional gas adsorption properties | |
Wang et al. | Triazine–polycarboxylic acid complexes: synthesis, structure and photocatalytic activity | |
Chen et al. | Introducing a flexible tetracarboxylic acid linker into functional coordination polymers: Synthesis, structural traits, and photocatalytic dye degradation | |
Gupta et al. | A robust and water-stable two-fold interpenetrated metal–organic framework containing both rigid tetrapodal carboxylate and rigid bifunctional nitrogen linkers exhibiting selective CO 2 capture | |
Du et al. | Polyoxometalate-induced ‘cage-within-cage’metal–organic frameworks with high efficiency towards CO 2 photoreduction | |
CN110075921A (en) | A kind of Ni (II) base crystalline-state catalyst and its preparation method and application | |
Yang et al. | An acid–base resistant paddle-wheel Cu (II) coordination polymer for visible-light-driven photodegradation of organic dyes | |
Lv et al. | Synthesis of titanium-oxo macrocyles and their catalytic properties for oxidative desulfurization | |
CN111690145B (en) | Pyridine type chiral Cu (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof | |
Leo et al. | A double basic Sr-amino containing MOF as a highly stable heterogeneous catalyst | |
Li et al. | Syntheses, structures and catalytic properties of Evans–Showell-type polyoxometalate-based 3D metal–organic complexes constructed from the semi-rigid bis (pyridylformyl) piperazine ligand and transition metals | |
Li et al. | An efficient and recyclable Cu@ UiO-67-BPY catalyst for the selective oxidation of alcohols and the epoxidation of olefins | |
CN108568316B (en) | High-stability zirconium-based chiral catalyst, preparation method and application thereof | |
CN110922420A (en) | 5-isonicotinamide pyridylisotitanium cadmium complex and preparation method and application thereof | |
CN111393663A (en) | Perylene bisimide base coordination polymer, preparation method and application thereof | |
Chen et al. | Two coordination polymers constructed from a multidentate carboxylic acid ligand with a tertiary amine serve as acid–base catalysts for the synthesis of chloropropene carbonate from CO 2 under atmospheric pressure |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for 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 |
Granted publication date: 20220517 |