CN115178295B - One-step synthesis method and application of enamine covalent organic framework supported non-noble metal monoatomic catalyst - Google Patents
One-step synthesis method and application of enamine covalent organic framework supported non-noble metal monoatomic catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 34
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 31
- 150000002081 enamines Chemical class 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000006352 cycloaddition reaction Methods 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 8
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- MNBSXKSWDLYJHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3,5-triol Chemical compound CC1=C(O)C(C)=C(O)C(C)=C1O MNBSXKSWDLYJHN-UHFFFAOYSA-N 0.000 claims description 4
- -1 oxalyl diamine Chemical class 0.000 claims description 4
- QGNJPFLIBOTDKU-UHFFFAOYSA-N 2,5-diaminobenzene-1,3-disulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=C(N)C(S(O)(=O)=O)=C1 QGNJPFLIBOTDKU-UHFFFAOYSA-N 0.000 claims description 3
- VOPSFYWMOIKYEM-UHFFFAOYSA-N 2,5-diaminobenzene-1,4-disulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=C(N)C=C1S(O)(=O)=O VOPSFYWMOIKYEM-UHFFFAOYSA-N 0.000 claims description 3
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 claims description 3
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- REJHVSOVQBJEBF-UHFFFAOYSA-N DSD-acid Natural products OS(=O)(=O)C1=CC(N)=CC=C1C=CC1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- UXOSWMZHKZFJHD-UHFFFAOYSA-N anthracene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC3=CC(N)=CC=C3C=C21 UXOSWMZHKZFJHD-UHFFFAOYSA-N 0.000 claims description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 3
- XOGODJOZAUTXDH-UHFFFAOYSA-M (N-methylanilino)methanesulfonate Chemical compound CN(CS([O-])(=O)=O)c1ccccc1 XOGODJOZAUTXDH-UHFFFAOYSA-M 0.000 claims description 2
- 125000001240 enamine group Chemical group 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006722 reduction reaction Methods 0.000 abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002135 nanosheet Substances 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006362 organocatalysis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910001509 metal bromide Inorganic materials 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 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
- 238000004458 analytical method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a one-step synthesis method of an enamine covalent organic framework supported non-noble metal monoatomic catalyst and application thereof in the field of energy catalysis. Ball milling the corresponding monomer and non-noble metal salt in a planetary ball mill, washing and vacuum drying to obtain enamine covalent organic framework supported non-noble metal single-atom catalyst X-TPPA (X=Fe, co, ni, cu, zn and other non-noble metals). The prepared X-TPPA has the morphology of a nano sheet with thinner thickness, and the loaded metal is highly and uniformly distributed. The enamine covalent organic framework supported non-noble metal monoatomic catalyst has a simple preparation method, can be synthesized in a large scale, has high potential industrial application value in the field of energy catalysis, and can be used for electrocatalytic water decomposition, oxygen reduction reaction, carbon dioxide reduction reaction and various organic catalytic reactions.
Description
Technical Field
The invention relates to the fields of nano material preparation and energy catalysis, in particular to synthesis of a non-noble metal monoatomic catalyst supported by enamine covalent organic frameworks and application of the catalyst as CO 2 And the use of epoxide cycloaddition catalysts.
Background
The nano material has ultrahigh specific surface area and obvious size effect, can provide sufficient surface reaction active sites for catalytic reaction, and is beneficial to the adsorption of reactants and the desorption of intermediate products and end products in the reaction process, so that the nano material is widely applied to the catalytic fields of thermocatalysis, electrocatalytic, photocatalysis, photoelectrocatalysis and the like. Covalent organic frameworks have been the hot spot of current basic and application research due to the advantages of high specific surface area, excellent water and heat resistance, good chemical stability, well-defined and controllable pore size, synergistic effect of multifunctional groups, and the like. Since the 21 st century, most covalent organic frameworks are synthesized by using organic solvents such as mesitylene, dioxane and n-butanol as raw materials, and the method has relatively high cost, severe synthesis conditions (such as long reaction time, and need of vacuum or nitrogen protection for synthesis), and needs to add some toxic and harmful reagents in the process of synthesizing polymers, thus being not environment-friendly. In addition, the synthesized covalent organic frameworks often have fewer active sites, which limits the use in new energy fields such as catalysis, adsorption, and the like. The single-atom catalyst has a 100% atomic utilization rate, a unique catalytic effect, uniform active site structure and ultrahigh catalytic activity caused by low coordination number, and is a novel important research content in the catalytic field in recent years. Thermodynamically, monoatoms have high surface energy, which easily leads to atom agglomeration and catalyst instability. The conventional monoatomic synthesis method has the problems of high energy consumption, harsh conditions, complicated procedures, uncontrollable capacity, low load and the like, and seriously hinders the development of monoatomic catalysts.
In recent years, due to the development of various methods for synthesizing covalent organic frameworks, the covalent organic frameworks synthesized by a ball milling method have unique microstructures and have more active sites, and the development and research of covalent organic frameworks prepared by a ball milling method are receiving more and more attention. Compared with the traditional covalent organic framework preparation method, the method also has the advantages of solvent-free use, simple method, short synthesis time, reservation of the original special structure of the ligand, contribution to mass production and the like. Meanwhile, the metal active site is introduced in situ, so that the catalytic effect can be improved, meanwhile, the metal can be distributed in a single-atom form through the pore canal limiting effect of the covalent organic framework, and the atom utilization rate of the metal is greatly improved. Therefore, the covalent organic framework supported single-atom catalyst is synthesized in one step by a ball milling method through screening proper ligands by using a new technology and a new method, is green and pollution-free, saves time and labor, and has incomparable practical significance for promoting the industrial production in the field of energy catalysis.
Disclosure of Invention
The invention aims to provide a preparation method of a non-noble metal monoatomic catalyst supported by an enamine-based covalent organic framework and application of the non-noble metal monoatomic catalyst supported by the enamine-based covalent organic framework.
The invention provides a preparation method of a non-noble metal monoatomic catalyst supported by an enamine covalent organic framework, which comprises the following steps:
mixing 2,4, 6-trimethyl phloroglucinol, ligand containing amino and metal salt, ball milling, centrifugal washing and vacuum drying to obtain the non-noble metal monoatomic catalyst supported by the enamine covalent organic framework.
Further, the amine group-containing ligand may be 4,4' -diaminostilbene-2, 2' -disulfonic acid, p-phenylenediamine ortho-sulfonate, 4' -diaminodiphenylamine-2 ' -sulfonic acid, 2, 5-diamino-1, 3-benzenedisulfonic acid, 2, 5-diamino-1, 4-benzenedisulfonic acid, 2' -disulfonic acid benzidine, p-phenylenediamine, biphenyldiamine, oxalyl diamine, or anthracene-2, 6-diamine.
Further, the metal salt may be a metal nitrate, a metal acetate, a metal sulfate, a metal chloride or a metal bromide.
Further, the metal may be any non-noble metal such as Fe, co, ni, cu or Zn.
Further, the rotation speed of the ball milling can be 100-500 rmp/min, and the ball milling time can be 0.5-12 h.
The enamine covalent organic framework supported non-noble metal monoatomic catalyst prepared by the method is a nano-sheet with a thinner morphology, and the metal is highly uniformly distributed.
The invention also provides the application of the enamine covalent organic framework supported non-noble metal monoatomic catalyst prepared by the method in the field of energy catalysis, including the application in catalyzing CO 2 Cycloaddition, water decomposition, oxygen reduction (ORR), carbon dioxide reduction (CO) 2 RR) and various organocatalytic reactions.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the non-noble metal monoatomic catalyst supported by the enamine covalent organic framework is synthesized for the first time through a one-step method;
(2) The morphology of the non-noble metal monoatomic catalyst supported by the enamine covalent organic framework is a thinner nano-sheet;
(3) The metal heights of the non-noble metal monoatomic catalyst supported by the enamine covalent organic framework are uniformly distributed;
(4) The preparation method is simple, time-saving, environment-friendly and capable of being prepared in a large amount;
(5) The enamine-based covalent organic framework-supported non-noble metal monoatomic catalyst of the invention shows excellent CO 2 Cycloaddition catalytic Properties, e.g., co-TPPA prepared at 1 atm CO 2 Sample catalyzed CO at 80℃with 5% TBAB and no additional solvent use 2 And epichlorohydrin cycloaddition at 2.5 and h up to 97.3% conversion with TOF values up to 2571 and 2571 h -1 ；
(6) The non-noble metal monoatomic catalyst supported by the enamine-based covalent organic framework of the invention has excellent stability, for example, the prepared Co-TPPA can be circularly catalyzed for 10 times under the conditions of normal pressure, 80 ℃ and 5% TBAB without using additional solvent, and the catalytic performance is not obviously reduced;
(7) The non-noble metal monoatomic catalyst supported by the enamine covalent organic framework has high potential application value in the field of energy catalysis, and can be used for HER, OER, ORR, CO 2 RR and various organocatalytic reactions.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of Co-TPPA in an embodiment of the invention.
FIG. 2 is a transmission electron microscope image of Co-TPPA in an embodiment of the invention.
FIG. 3 is a transmission electron microscope image of Co-TPPA in an embodiment of the invention.
FIG. 4 is an EDS-Mapping energy spectrum of Co-TPPA in an embodiment of the invention.
FIG. 5 is a chart showing the infrared absorption spectrum of Co-TPPA in the example of the present invention.
FIG. 6 is a Raman spectrum of Co-TPPA in an embodiment of the invention.
FIG. 7 is a graph of the X-ray photoelectron spectrum of Co-TPPA in an embodiment of the invention.
FIG. 8 shows the present inventionCo-TPPA 77K N in examples 2 Adsorption-desorption isotherm plot.
FIG. 9 is a schematic diagram of Co-TPPA 273K CO according to an embodiment of the present invention 2 Adsorption-desorption isotherm plot.
FIG. 10 shows the Co-TPPA catalyst for CO in an embodiment of the invention 2 And TOF and TON values of epichlorohydrin cycloaddition over time.
FIG. 11 shows the Co-TPPA catalyst for CO in an embodiment of the invention 2 And nuclear magnetic hydrogen spectrogram of cycloaddition conversion rate of epoxy chloropropane.
FIG. 12 is a schematic illustration of the Co-TPPA catalyzed CO in an embodiment of the invention 2 And cycloaddition of epichlorohydrin.
Detailed Description
The invention provides a one-step synthesis method of an enamine group covalent organic framework supported non-noble metal monoatomic catalyst, which comprises the following steps: mixing and ball milling 2,4, 6-trimethyl phloroglucinol, ligand containing amino and metal salt, centrifuging and vacuum drying to obtain enamine covalent organic framework supported non-noble metal monoatomic catalyst X-TPPA, wherein X can be Fe, co, ni, cu, zn and other non-noble metals.
Wherein the ligand containing amine group comprises 4,4' -diaminostilbene-2, 2' -disulfonic acid, o-p-phenylenediamine sulfonate, 4' -diaminodiphenylamine-2 ' -sulfonic acid, 2, 5-diamino-1, 3-benzene disulfonic acid, 2, 5-diamino-1, 4-benzene disulfonic acid, 2' -disulfonic acid benzidine, p-phenylenediamine, biphenyl diamine, oxalyl diamine, anthracene-2, 6-diamine, etc. The ball milling speed is 100-500 rmp/min, and the ball milling time is 0.5-12 h. The metal salt species comprises a metal nitrate, a metal acetate, a metal sulfate, a metal chloride or a metal bromide.
Synthetic X-TPPA is used as a catalyst, e.g. for catalyzing CO 2 And epoxides form cyclic carbonates with excellent catalytic properties.
In order to more clearly illustrate the objects, features and advantages of the present invention, some specific embodiments are described below. In the following description, numerous specific details are set forth, however, the invention may be practiced in other ways than as described herein, and thus the invention is not limited to the specific embodiments disclosed below.
Example 1 preparation of Co-TPPA
And (3) placing p-phenylenediamine, 2,4, 6-trimethyl phloroglucinol and cobalt bromide into a ball milling tank, wherein the rotating speed is controlled to be 100-500 rmp/min, and the ball milling time is 6 h. Then the mixture was washed three times with ethanol, deionized water and N, N-dimethylformamide by centrifugation. After centrifugation, the mixture was dried in a vacuum drying oven for 24. 24 h to obtain a sample Co-TPPA. The X-ray diffraction diagram of the Co-TPPA sample is shown in figure 1; scanning electron microscopy is shown in figure 2; transmission electron microscopy images are shown in figure 3; EDS-Mapping energy spectrum is shown in figure 4; the infrared absorption spectrum is shown in FIG. 5; the raman spectrum is shown in fig. 6; the X-ray photoelectron spectrum is shown in figure 7;77 K nitrogen adsorption-desorption isotherm diagram is shown in figure 8;273 KCO (KCO) 2 Adsorption-desorption isotherms are shown in figure 9.
Example 2 Co-TPPA catalytic CO2 and epichlorohydrin cycloaddition Performance test
Co-TPPA obtained in example 1 catalyzes CO 2 And epichlorohydrin cycloaddition Performance test was at 1 atm CO 2 Tested at 80 ℃, 5% TBAB, without additional solvent. The resulting product was analyzed by nuclear magnetic resonance hydrogen spectroscopy. The time-dependent plot of TOF and TON values shown in FIG. 10 was obtained by sampling analysis at 10, 30, 60, 90, 120, 150 min respectively, TON values were calculated as moles converted/moles active site, TOF values were calculated as moles converted/(moles active site time). In the figure, co-TPPA is known to be CO at 1 atm 2 Catalytic CO at 80℃with 5% TBAB and without additional solvent use 2 And epichlorohydrin can reach a maximum TOF value of 2571 and 2571 h -1 At the same time TON value is 695. Co-TPPA catalyzed CO as shown in FIG. 11 2 Nuclear magnetic hydrogen spectrogram of conversion rate of cycloaddition of epoxy chloropropane, and can be used for catalyzing CO under the condition of Co-TPPA 2 And the conversion of epichlorohydrin was 97.3%. After 10 times of Co-TPPA recycle catalysis, the performance is only reduced by 2.5%, which shows that the Co-TPPA has good stability.
The invention synthesizes enamine covalent with one-step method for the first timeThe non-noble metal monoatomic catalyst supported by the organic framework can be prepared in large batch by a simple ball milling and drying method, and the enamine covalent organic framework supported non-noble metal monoatomic catalyst with thinner dimension and uniformly distributed metal height can be prepared by the enamine covalent organic framework supported non-noble metal monoatomic catalyst, and the enamine covalent organic framework supported non-noble metal monoatomic catalyst has the advantages of simple preparation method, lower cost, suitability for large batch synthesis, high potential industrial application value in the field of energy catalysis and capability of being used for CO 2 Is added to the reaction mixture by cycloaddition, electrocatalytic water splitting reaction, oxygen Reduction Reaction (ORR), carbon dioxide reduction reaction (CO 2 RR) and various organocatalytic reactions.
In the form of CO 2 For example, CO is fixed by chemical reaction due to the huge influence of greenhouse effect caused by carbon dioxide on the global ecological environment 2 The generation of more valuable chemicals has wide application prospects, wherein CO 2 Is one of the most dominant methods. CO 2 Cycloaddition of (C) involves epoxide ring opening, activating CO 2 ，CO 2 The key steps of insertion, ring closure and the like are that the introduction of a catalyst is needed to increase the reactivity and the reaction efficiency. At present with respect to CO 2 Most of the conditions are still high temperature and high pressure, the use of organic solvents. However, the energy consumption and high cost caused by high temperature and high pressure are great challenges for industrial application, and the use of organic solvents also causes increased difficulty in separation after the reaction is completed and pollution to the environment. Co-TPPA has excellent CO 2 Cycloaddition catalytic performance, simple and quick preparation, greenness, easy realization of catalytic conditions and even great potential for industrial application.
Claims (2)
1. Non-noble metal monoatomic catalyst supported by enamine covalent organic framework and used for catalyzing CO 2 The application in cycloaddition is characterized in that the non-noble metal monoatomic catalyst supported by enamine group covalent organic frameworks comprises the following preparation steps:
mixing 2,4, 6-trimethyl phloroglucinol, ligand containing amino and metal salt, ball milling, centrifugal washing and vacuum drying to obtain the non-noble metal monoatomic catalyst supported by the enamine covalent organic framework;
wherein the ligand containing amine groups is 4,4' -diaminostilbene-2, 2' -disulfonic acid, o-p-phenylenediamine sulfonate, 4' -diaminodiphenylamine-2 ' -sulfonic acid, 2, 5-diamino-1, 3-benzene disulfonic acid, 2, 5-diamino-1, 4-benzene disulfonic acid, 2' -disulfonic acid benzidine, p-phenylenediamine, biphenyl diamine, oxalyl diamine or anthracene-2, 6-diamine; the metal salt is nitrate metal salt, acetate metal salt, sulfate metal salt, chloride metal salt or bromide metal salt; the metal is Fe, co, ni, cu or Zn.
2. The use according to claim 1, characterized in that: the rotation speed of the ball milling is 100-500 rmp/min, and the ball milling time is 0.5-12 h.
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