CN114733545A - Preparation method and application of water-oil amphiphilic tri-core-shell nano catalyst - Google Patents
Preparation method and application of water-oil amphiphilic tri-core-shell nano catalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011258 core-shell material Substances 0.000 title abstract description 29
- 239000011943 nanocatalyst Substances 0.000 title abstract description 7
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 31
- 239000010457 zeolite Substances 0.000 claims abstract description 31
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 150000001868 cobalt Chemical class 0.000 claims description 15
- 150000003751 zinc Chemical class 0.000 claims description 13
- 238000000197 pyrolysis Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 229910017052 cobalt Chemical group 0.000 abstract description 5
- 239000010941 cobalt Chemical group 0.000 abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 description 4
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 229910016507 CuCo Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229910003203 NH3BH3 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- -1 imidazole ester Chemical class 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000013173 zeolitic imidazolate framework-9 Substances 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- RYOLJRRNBRXUCN-UHFFFAOYSA-N 1h-pyrrole;hydrate Chemical compound O.C=1C=CNC=1 RYOLJRRNBRXUCN-UHFFFAOYSA-N 0.000 description 1
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N 3-Methyl-3-buten-2-one Chemical compound CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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- 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
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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- 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
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Abstract
A preparation method and application of a water-oil amphiphilic tri-core-shell nano catalyst. The invention uses bimetallic zeolite metal organic frame material as precursor, and dopes Cu by dipping method2+Ions are calcined by adopting a temperature programming method, so that the effective synthesis of various nitrogen-doped Cu @ Co @ graphite carbon core-shell materials is realized; the high-temperature calcination can generate a compact graphite carbon layer on the outer layer of the metal core-shell active site, thereby effectively improving the catalytic application of the catalystThe cycle stability; by utilizing the synergistic effect between copper and cobalt core-shell structures derived from the metal organic framework material and adjusting the proportion of nitrogen-doped species, the catalyst has water/oil amphipathy, and can realize high-efficiency organic catalysis in aqueous solution; the invention is suitable for various common metal organic framework material derivatives, and provides the application of the material in the aspect of high-selectivity hydrogenation of C ═ C bonds.
Description
Technical Field
The invention belongs to the technical field of nano materials, and relates to a preparation method and application of a water-oil amphiphilic tri-core-shell nano catalyst.
Background
The key to increasing the purity of fine chemicals to meet the requirements of industrial production is the increase in catalytic selectivity. Sp2Hydrogenation of hybrid unsaturated C ═ C bonds is widely used in the field of organic catalysis, but selective hydrogenation of C ═ C becomes complicated in the presence of competing groups such as carbonyl, nitro or nitrile; meanwhile, the use of a large amount of organic solvent causes environmental pollution. The realization of the selective hydrogenation of unsaturated C ═ C under green and mild conditions is a promising strategy, taking advantage of the synergistic effect between different metals in heterogeneous catalysts.
Chinese patent application CN114029081A discloses a bimetallic copper-cobalt-nitrogen-doped carbon material catalyst and a preparation method and application thereof, wherein the catalyst is a bimetallic copper-cobalt-nitrogen-doped carbon material derived from a zeolite-like imidazole ester framework Cu-Co-ZIF-9, and the chemical formula is Cu-Co/N-C. The preparation method comprises the following steps: dissolving the raw materials into a solvent by taking inorganic salt of copper, inorganic salt of cobalt, sodium formate and benzimidazole as raw materials and taking N, N-dimethylformamide as the solvent, uniformly stirring and crystallizing to obtain Cu-Co-ZIF-9, and calcining in a hydrogen-argon mixed atmosphere to obtain the bimetallic copper-cobalt nitrogen-nitrogen carbon material catalyst; the catalyst is applied to the reaction of preparing 2, 5-furandimethanol by hydrogenating 5-hydroxymethylfurfural, and has excellent catalytic performance. Although the catalyst has high catalytic activity and low production cost, the stability of the catalyst is not characterized, and related substances for enhancing the stability of the catalyst are not added.
Chinese patent application CN110876955A discloses a method for preparing a highly dispersed bimetallic catalyst with close active site atomic scale. The catalyst precursor is formed by packaging the copper-cobalt bimetallic polymer in the mesoporous silica pore channel, so that copper-cobalt species are anchored in the same polymer structure, close contact and close matching of atomic scales are realized, the high dispersion of the copper-cobalt bimetallic is guaranteed by utilizing the confinement effect of a regular mesoporous pore channel, the separation and agglomeration of the copper-cobalt bimetallic are inhibited, an excellent target product is obtained in the reaction of preparing low carbon alcohol from synthesis gas, the proportion of the low carbon alcohol in the total alcohol distribution reaches 64.4 percent by weight, and the catalytic performance is not obviously reduced within the reaction time of 200 hours. Although the catalyst has stronger stability, the catalytic activity is relatively low.
At present, unsaturated C ═ C hydrogenation is mostly realized in a large amount of organic solvents mutually soluble with substrates by adopting a Pd-based catalyst at high temperature and high pressure, and the method increases the operation complexity, economic cost and danger of hydrogenation to a certain extent. How to solve the selective hydrogenation of a plurality of unsaturated groups and exploring a selective hydrogenation catalyst which has high activity, high stability, economy, durability and easy dispersion is imperative.
Disclosure of Invention
The invention provides a preparation method and application of a water-oil amphiphilic tri-core-shell nano catalyst aiming at the problems in the prior art, the tri-core-shell nano catalyst provided by the invention not only realizes high-selectivity hydrogenation of C ═ C bonds in the presence of a plurality of unsaturated competitive groups, but also endows the catalyst with water/oil amphipathy, improves the high-efficiency catalytic performance of the catalyst on organic compounds in a water phase, and comprises high selectivity on products, environment-friendly solvent, simple and easy catalyst recovery and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
firstly, a preparation method of the catalyst is provided, which is characterized by comprising the following steps:
(1) mixing cobalt salt, zinc salt, ligand and methanol for reaction to obtain a bimetallic zeolite metal organic framework precursor;
(2) adding Cu into the bimetallic zeolite metal organic framework precursor obtained in the step (1)2+Obtaining a copper ion-bimetal zeolite metal organic framework precursor;
(3) and (3) pyrolyzing the copper ion-bimetal zeolite metal organic framework precursor obtained in the step (2) to obtain the Cu @ Co @ graphite carbon-nitrogen doped carbon matrix composite material.
Further, in the step (1), the cobalt salt is one or more of cobalt nitrate hexahydrate, cobalt chloride and cobalt acetate, the zinc salt is zinc nitrate hexahydrate, and the ligand is 2-methylimidazole.
Further, the preparation step of the bimetallic zeolite metal-organic framework precursor in the step (1) comprises the following steps: mixing and dissolving cobalt salt and zinc salt in methanol to obtain a solution A, dissolving ligand in methanol to obtain a solution B, adding the solution A into the solution B, and stirring for reaction to obtain the bimetallic zeolite metal organic framework material.
Furthermore, the concentration of cobalt salt and zinc salt in the solution A is 40-60g/L, the reaction temperature of the solution A and the solution B is 20-30 ℃, and the reaction time is 23-25 h.
Further, the ratio of the cobalt salt, the zinc salt, the ligand and the methanol solution is 140-1400mg:28-280mg:370-3700mg:8-80 mL.
Furthermore, the molar ratio of the cobalt salt to the zinc salt is 4-6: 0.5-1.5.
Further, the Cu in the step (2)2+Introducing into the cavity of a bimetallic zeolite metal-organic framework precursor by impregnation, the Cu2+One or more of copper nitrate, copper chloride and cuprous chloride, the bimetallic zeolite metal organic framework precursor and Cu2+The ratio of 450-550mg to 167-500 mu L.
Further, the pyrolysis in the step (3) is gradient temperature rise, and the gradient temperature rise program is set as follows: heating the copper ion-bimetal zeolite metal organic framework precursor at the temperature of 250-300 ℃ for 4-6h to promote Cu2+After reduction, continuing to heat at the temperature of 500 ℃ for 1.5-2.5H at 450-2And pyrolyzing the mixture in an Ar mixed atmosphere.
Further, the catalyst obtained by the preparation method.
Furthermore, the catalyst prepared by the preparation method is applied to the aspect of high-selectivity hydrogenation of C ═ C bonds.
Furthermore, the bimetal zeolite metal organic framework precursor is a porous material formed by coordination of cobalt and zinc bimetal and 2-methylimidazole, has rich nitrogen sources, can adjust the metal proportion, and can realize effective regulation and control of catalytic active sites.
Further, the bimetallic zeolite metal-organic framework precursor is prepared by a metal-organic framework material obtained by coordination of cobalt ions, zinc ions and 2-methylimidazole, and then cooling, cleaning and activating.
In some specific embodiments, a method for preparing a water/oil amphiphilic tri-core shell nano catalytic material comprises the following steps:
a. preparing a bimetallic zeolite metal organic framework precursor (BMZIF-5) in advance;
b. introducing Cu-containing into the bimetallic zeolite metal-organic framework precursor by impregnation2+The precursor of the bimetallic zeolite metal-organic framework is made to adsorb Cu2+Putting the BMZIF porous material into a cavity of the BMZIF porous material to obtain a copper ion/bimetal zeolite metal organic framework precursor;
c. placing the precursor in H2And directly pyrolyzing the mixture in a tubular furnace under Ar mixed atmosphere according to a preset program to obtain the multifunctional Cu @ Co @ graphite carbon-nitrogen doped carbon matrix composite material.
The preparation method of the precursor comprises placing BMZIF-5 in a small beaker, and slowly dripping Cu into the powdery precursor2+The salt solution is continuously stirred at a constant speed to ensure that Cu is contained2+Enriched within the bimetallic zeolite metal-organic framework precursor.
In some embodiments, when the metal organic framework material is BMZIF-5, the doping amount of the metal salt solution is 8.2 to 25.0 mg.
In some specific embodiments, the centrifugation conditions are: 10000-; the drying conditions are as follows: drying in a vacuum drying oven at 70-80 deg.C for 12-24 hr.
The metal organic framework used in the present invention may be a variety of common metal organic framework materials that are stable in water, acid or base solutions.
Compared with the prior art, the invention provides a water/oil amphiphilic tri-core-shell nano catalytic material capable of realizing high-selectivity hydrogenation of C-C bond, which has the following beneficial effects:
(1) the invention utilizes the porous adsorption effect of the metal organic framework material, and introduces metal ions into the metal organic framework material by adopting an impregnation method; greatly enriches heterogeneous catalysts derived from single metal organic framework materials;
(2) according to the invention, a temperature program is adjusted according to the reduction pyrolysis temperatures of different metals by using a temperature program strategy, so that the effective synthesis of different metal core-shell structures is realized;
(3) according to the invention, a compact graphite carbon layer can be generated on the outer layer of the metal core-shell active site by high-temperature calcination, so that the circulation stability of the catalyst in catalytic application is effectively improved;
(4) the invention utilizes the synergistic effect between the copper and cobalt core-shell structures derived from the metal organic framework material and adjusts the proportion of nitrogen-doped species, so that the catalyst has water/oil amphipathy and can realize high-efficiency organic catalysis in aqueous solution;
(5) the catalyst prepared by the invention can obviously improve NH3BH3Catalytic performance of dehydrogenation and highly selective tandem hydrogenation of unsaturated C ═ C.
Drawings
FIG. 1 is a scanning electron microscope photograph of the bimetallic zeolite organometallic framework material obtained in example 1, wherein a is a magnification of 500nm and b is a magnification of 200 nm;
FIG. 2 is the scanning microscope (a) and transmission microscope (b) pictures of the three core-shell nano-material obtained in example 1;
FIG. 3 is a powder X-ray diffraction characterization plot of the bimetallic zeolitic organometallic framework precursor and the tri-core shell nanomaterial obtained in example 1;
FIG. 4 is a graph of experimental simulated adsorption energy of theoretical models of different nitrogen species with styrene molecules and water molecules, respectively;
FIG. 5 is a graph of the yield of the water/oil amphiphilic tri-core shell nano material obtained in example 1 applied to an amino borane dehydrogenation reaction in an aqueous phase;
fig. 6 is a high-selectivity series hydrogenation reaction diagram of the water/oil amphiphilic tri-core-shell nanomaterial obtained in example 1 applied to unsaturated C ═ C in a water phase.
Detailed Description
It should be noted that the raw materials used in the present invention are all common commercial products, and the sources thereof are not particularly limited.
Example 1
The preparation method of the water/oil amphiphilic tri-core-shell nano-catalyst guided by the pyrolysis of the procedure of the embodiment is carried out according to the following steps:
a. preparing a bimetallic zeolite metal organic framework precursor (BMZIF-5):
fully dissolving cobalt nitrate hexahydrate and zinc nitrate hexahydrate in methanol according to the molar ratio of 5:1, quickly pouring into a methanol solution of 2-methylimidazole, and stirring at room temperature for 24 hours to obtain a bimetallic zeolite organic framework material; wherein the proportion of the cobalt salt, the zinc salt, the ligand and the methanol solution is 1400mg to 280mg to 3700mg to 80 mL;
b. centrifuging, washing and drying the metal organic framework precursor material, wherein the centrifuging conditions are as follows: 11000rpm, the washing solvent is methanol, and the drying conditions are as follows: drying the mixture for 12 hours at 75 ℃ in an oven;
c. synthetic metal ion @ metal organic framework material (Cu) guided by impregnation method2+@BMZIF-5)：
C, placing the bimetallic zeolite metal organic framework precursor treated in the step b into a small beaker, and slowly dripping Cu into the powdery precursor2+Stirring the solution of the copper alloy in the methanol solution at constant speed to ensure that the Cu is dissolved in the solution of the copper alloy2+Enrichment within a bimetallic zeolite-metal organic framework precursor;
d. c, drying the material prepared in the step c in vacuum to obtain a metal ion @ metal organic framework material (Cu)2+@BMZIF-5)；
e. A three-core-shell nano material with water/oil amphipathy guided by program pyrolysis;
the specific method comprises the following steps:
the metal ions prepared in the step d @ metal organic framework material (Cu)2+@ BMZIF-5) at H2Introducing air into a tubular furnace in Ar flowing atmosphere for 20min, setting a temperature rise program, and carrying out pyrolysis to obtain a water/oil amphiphilic tri-core-shell nano material;wherein the temperature raising procedure is specifically that the temperature is raised to 500 ℃ for 2h after the temperature is maintained at 250 ℃ for 5h, and finally the temperature is naturally lowered after the pyrolysis is carried out at 800 ℃ for 2 h.
f. And grinding the composite material to obtain the water/oil amphiphilic three-core-shell nano material.
From fig. 1, it can be seen that the precursor material obtained in this example is a uniformly dispersed polyhedral structure with a size of 200-300 nm.
The scanning microscope and transmission microscope observations of the three-core-shell nano-material obtained in this example show that, as shown in fig. 2, the three-core-shell nano-material obtained in this example is composed of a bright Cu @ Co inner core and a graphite carbon layer with a darker outer layer, and the size is 3-5 nm.
Powder X-ray diffraction characterization is performed on the bimetallic zeolite metal-organic framework precursor and the tri-core-shell nanomaterial obtained in this embodiment, and as can be seen from fig. 3, the tri-core-shell nanomaterial obtained in this embodiment simultaneously contains elemental copper and elemental cobalt.
The water/oil amphiphilicity of the three-core-shell nano-material obtained in the embodiment is researched, theoretical models of different nitrogen species are respectively subjected to simulated adsorption energy experiments with styrene molecules and water molecules, and as can be seen from fig. 4 and table 1, graphite nitrogen has relatively strong affinity for the styrene molecules based on van der waals force interaction; the intermolecular hydrogen bond formed by the lone pair electrons on the graphite nitrogen, the pyridine nitrogen and the pyrrole nitrogen and water is the main reason of hydrophilicity of the material.
TABLE 1
Aminoborane dehydrogenation reaction
The water/oil amphiphilic tri-core shell nano-material prepared according to the step of the embodiment 1 is applied to an amino borane dehydrogenation reaction. As can be seen from FIG. 5, the Cu @ Co @ graphitic carbon achieved the best activity, within about 3min, compared to single metal Co, Cu and CuCo alloy nanoparticlesAbout 100% of H is released2(68 mL); the stability of the catalyst can still maintain excellent catalytic efficiency after continuous 30-cycle experiments.
The method for preparing the Cu/N doped carbon substrate in FIG. 5: replacing BMZIF-5 in step a with ZIF-8 material, followed by metal ion @ metal organic framework material (Cu) prepared according to step d2+@ ZIF-8) at H2Ventilating a tubular furnace in a flowing Ar atmosphere for 20min, setting a temperature rise program, and performing pyrolysis to obtain a Cu/nitrogen-doped carbon matrix nano material; wherein the temperature raising procedure is specifically that the temperature is raised to 500 ℃ for 2h after the temperature is maintained at 250 ℃ for 5h, and finally the temperature is naturally lowered after the pyrolysis is carried out at 800 ℃ for 2 h.
The preparation method of the Co @ graphitic carbon/nitrogen-doped carbon matrix in fig. 5: directly placing the BMZIF-5 material obtained in the step b into H2Introducing air into a tubular furnace in an Ar flowing atmosphere for 20min, setting a temperature-raising program, and carrying out pyrolysis to obtain a Co @ graphite carbon/nitrogen-doped carbon matrix nano material; wherein the temperature raising procedure is specifically that the temperature is raised to 500 ℃ for 2h after the temperature is maintained at 250 ℃ for 5h, and finally the temperature is naturally lowered after the pyrolysis is carried out at 800 ℃ for 2 h.
The preparation method of the CuCo alloy @ graphitic carbon/nitrogen-doped carbon matrix in FIG. 5 comprises the following steps: the metal ion @ metal organic framework material (Cu) prepared in the step d2+@ BMZIF-5) at H2Introducing air in a tubular furnace in a flowing Ar atmosphere for 20min, setting a temperature rise program, and performing pyrolysis to obtain a CuCo alloy @ graphite carbon/nitrogen-doped carbon matrix nano material; wherein the temperature raising procedure is specifically that the temperature is kept at 500 ℃ for 2h, and then the mixture is pyrolyzed at 800 ℃ for 2h and then naturally cooled.
The preparation method of Cu @ Co/BMZIF-5 in FIG. 5 comprises the following steps: b, mixing the BMZIF-5 obtained in the step b with a certain amount of Cu2+/Co2+The precursor being added to the solution containing NH3BH3(30mg) in aqueous solution (20mL) and stirred at room temperature for 20min to give Cu @ Co/BMZIF-5 catalyst.
Wherein, in the preparation method of Cu @ Co/BMZIF-5, the copper salt can be one or more of cupric nitrate, cupric chloride and cuprous chloride; the cobalt salt can be one or more of cobalt nitrate, cobalt chloride and cobalt acetate; the amount of the copper salt is 8.2-25.0mg, and the amount of the cobalt salt is 140-1400 mg.
Wherein the catalytic reaction conditions are as follows: 30mg of amino borane is put into 20mL of water, 20mg of Cu @ Co @ graphite carbon/nitrogen doped carbon matrix is used as a catalyst, and the reaction is carried out at room temperature.
Highly selective tandem hydrogenation of C ═ C
The water/oil amphiphilic tri-core-shell nanomaterial prepared according to the step of example 1 is applied to a highly selective series hydrogenation reaction of unsaturated C ═ C in an aqueous phase (see fig. 6). As can be seen from table 2, different substrates can obtain C ═ C reduced products with high selectivity; wherein, for the ketene substances with high activity, the single C ═ C hydrogenation product can be obtained by controlling the reaction time. In short, the Cu @ Co @ graphitic carbon/nitrogen-doped carbon-based catalyst can achieve highly selective tandem hydrogenation of C ═ C in water under mild conditions.
TABLE 2
Wherein the above substrates used are respectively: ethyl cinnamate, methyl isobutenone.
Wherein the catalytic reaction conditions are as follows: 0.5mmol of substrate; 50mg of catalyst; the solvent is water; the reaction temperature was 50 ℃.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a catalyst is characterized by comprising the following steps:
(1) mixing cobalt salt, zinc salt, ligand and methanol for reaction to obtain a bimetallic zeolite metal organic framework precursor;
(2) adding Cu into the bimetallic zeolite metal organic framework precursor obtained in the step (1)2+Obtaining a copper ion-bimetal zeolite metal organic framework precursor;
(3) and (3) pyrolyzing the copper ion-bimetal zeolite metal organic framework precursor obtained in the step (2) to obtain the Cu @ Co @ graphite carbon-nitrogen doped carbon matrix composite material.
2. The preparation method according to claim 1, wherein in the step (1), the cobalt salt is one or more of cobalt nitrate hexahydrate, cobalt chloride and cobalt acetate, the zinc salt is zinc nitrate hexahydrate, and the ligand is 2-methylimidazole.
3. The method of claim 1, wherein the step of preparing the bimetallic zeolite-based metal-organic framework precursor in step (1) comprises: mixing and dissolving cobalt salt and zinc salt in methanol to obtain a solution A, dissolving ligand in methanol to obtain a solution B, adding the solution A into the solution B, and stirring for reaction to obtain the bimetallic zeolite metal organic framework material.
4. The method according to claim 3, wherein the concentrations of the cobalt salt and the zinc salt in the solution A are 40-60g/L, the reaction temperature of the solution A and the solution B is 20-30 ℃, and the reaction time is 23-25 h.
5. The preparation method as claimed in claim 1, wherein the ratio of the cobalt salt, the zinc salt, the ligand and the methanol solution is 140-1400mg:28-280mg:370-3700mg:8-80 mL.
6. The preparation method according to claim 1, wherein the molar ratio of the cobalt salt to the zinc salt is 4-6: 0.5-1.5.
7. The method according to claim 1, wherein the Cu in the step (2)2+Introducing into the cavity of a bimetallic zeolite metal-organic framework precursor by impregnation, the Cu2+One or more of cupric nitrate, cupric chloride and cuprous chloride, the bimetallic zeolite metal organic framework precursor and Cu2+The ratio of (1) is 450-550 mg-167-500 mu L.
8. The method according to claim 1, wherein the pyrolysis in the step (3) is a gradient temperature rise, and the gradient temperature rise program is configured as follows: heating the copper ion-bimetal zeolite metal organic framework precursor at the temperature of 250-300 ℃ for 4-6h to promote Cu2+After reduction, the Cu @ Co nano particles are continuously heated for 1.5 to 2.5 hours at the temperature of 500 ℃ of 450-2And pyrolyzing the mixture in an Ar mixed atmosphere.
9. A catalyst obtained by the production method according to any one of claims 1 to 8.
10. Use of a catalyst obtained by the process according to any one of claims 1 to 8 for the highly selective hydrogenation of C ═ C bonds.
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