CN115178295A - One-step synthesis method and application of non-noble metal monoatomic catalyst supported by enamine covalent organic framework - Google Patents
One-step synthesis method and application of non-noble metal monoatomic catalyst supported by enamine covalent organic framework Download PDFInfo
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- CN115178295A CN115178295A CN202210503066.7A CN202210503066A CN115178295A CN 115178295 A CN115178295 A CN 115178295A CN 202210503066 A CN202210503066 A CN 202210503066A CN 115178295 A CN115178295 A CN 115178295A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 37
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 32
- 150000002081 enamines Chemical class 0.000 title claims abstract description 16
- 238000001308 synthesis method Methods 0.000 title abstract description 5
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- 238000006555 catalytic reaction Methods 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000001240 enamine group Chemical group 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 8
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- 150000003839 salts Chemical class 0.000 claims abstract description 7
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- 238000000354 decomposition reaction Methods 0.000 claims abstract description 4
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- 238000000034 method Methods 0.000 claims description 20
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- 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 7
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- 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
- VKURVCNKVWKGLX-UHFFFAOYSA-N 5-amino-2-(4-aminoanilino)benzenesulfonic acid Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1S(O)(=O)=O VKURVCNKVWKGLX-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
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- 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
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-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
- 229910001509 metal bromide Inorganic materials 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 3
- 229960001553 phloroglucinol Drugs 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- -1 oxalyl diamine Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000001228 spectrum 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
- 230000000694 effects Effects 0.000 description 3
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- 239000003960 organic solvent Substances 0.000 description 3
- 150000002924 oxiranes Chemical class 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
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 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
- 238000011109 contamination Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
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- 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
- 238000001000 micrograph Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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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
- 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
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- 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
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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
- 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
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Abstract
The invention discloses a one-step synthesis method of an enamine group covalent organic framework supported non-noble metal monatomic catalyst and application thereof in the field of energy catalysis. And (2) carrying out ball milling on corresponding monomers and non-noble metal salt in a planetary ball mill, washing and vacuum drying to obtain the non-noble metal monoatomic catalyst X-TPPA (X = Fe, co, ni, cu, zn and other arbitrary non-noble metals) supported by the enamine group covalent organic framework. The prepared X-TPPA is in a nanosheet shape with a relatively thin thickness, and the loaded metal is highly and uniformly distributed. The enamine-based covalent organic framework supported non-noble metal monatomic 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 field of nano material preparation and energy catalysis, in particular to synthesis of a non-noble metal monoatomic catalyst supported by an enamine-based covalent organic framework 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, is beneficial to the adsorption of reactants in the reaction process and the desorption of intermediate products and final products, and is widely applied to the catalytic fields of thermal catalysis, electrocatalysis, photocatalysis, photoelectrocatalysis and the like. The covalent organic framework has the advantages of high specific surface area, excellent water and heat resistance, good chemical stability, well-defined and controllable pore size, synergistic effect of multiple functional groups and the like, and is always a hot spot of current basic and application research. Since the 21 st century, most of the synthesis processes of covalent organic frameworks use organic solvents such as mesitylene, dioxane, n-butanol and the like as raw materials, so that the cost is relatively high, the synthesis conditions are harsh (for example, the reaction time is long, synthesis needs to be carried out under vacuum or nitrogen protection), and some toxic and harmful reagents need to be added in the process of synthesizing polymers, so that the method is not environment-friendly. In addition, the synthesized covalent organic framework has fewer active sites, so that the application of the covalent organic framework in the fields of new energy sources such as catalysis and adsorption is limited. The single-atom catalyst has 100% atom utilization rate, unique catalytic effect, uniform active site structure and ultrahigh catalytic activity caused by low coordination number, and becomes a novel important research content in the catalytic field in recent years. Thermodynamically, the monoatomic species has a high surface energy, easily causing atomic agglomeration and catalyst instability. The conventional monatomic synthesis method has the problems of high energy consumption, harsh conditions, complex procedures, uncontrollable capacity, low load capacity and the like, and the development of the monatomic catalyst is seriously hindered.
In recent years, due to the development of various methods for synthesizing covalent organic frameworks, which have unique microstructures and more active sites, the research for developing and using covalent organic frameworks prepared by the ball milling method has been receiving increasing attention. Compared with the traditional covalent organic framework preparation method, the method has the advantages of solvent-free use, simple method, short synthesis time, reservation of the original special structure of the ligand, contribution to large-scale production and the like. Meanwhile, the in-situ introduction of the metal active sites can not only increase the catalytic effect, but also enable the metal to be distributed in a single atom form through the pore confinement effect of the covalent organic framework, thereby greatly increasing the atom utilization rate of the metal. Therefore, the covalent organic framework supported monatomic catalyst is synthesized in one step by screening appropriate ligands through a new technology and a new method and using a ball milling method, is green and pollution-free, saves time and labor, and has incomparable practical significance for promoting industrial production in the field of energy catalysis.
Disclosure of Invention
The invention aims to provide a preparation method of a non-noble metal monatomic catalyst supported by an enamine group covalent organic framework and application of the non-noble metal monatomic catalyst supported by the enamine group covalent organic framework.
The invention provides a preparation method of a non-noble metal monatomic catalyst supported by an enamine group covalent organic framework, which comprises the following steps:
mixing 2,4,6-triacyl phloroglucinol, an amino-containing ligand and a metal salt, then carrying out ball milling, then carrying out centrifugal washing and vacuum drying to obtain the non-noble metal monatomic catalyst supported by the enamine base covalent organic framework.
Further, the ligand containing an amine group may be 4,4' -diaminostilbene-2,2 ' -disulfonic acid, o-sulfonic acid p-phenylenediamine, 4,4' -diaminodiphenylamine-2 ' -sulfonic acid, 2,5-diamino-1,3-benzenedisulfonic acid, 2,5-diamino-1,4-benzenedisulfonic acid, 2,2' -disulfonic acid benzidine, p-phenylenediamine, biphenyldiamine, oxalyldiamine, 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 to 500 rmp/min, and the ball milling time can be 0.5 to 12 hours.
The non-noble metal monatomic catalyst supported by the enamine covalent organic framework prepared by the method is a nanosheet with a thin appearance, and the metal height is uniformly distributed.
The invention also provides application of the enamine group covalent organic framework supported non-noble metal monoatomic catalyst prepared by the method in the field of energy catalysis, including application in catalyzing CO 2 Cycloaddition, water decomposition, oxygen Reduction Reaction (ORR), carbon dioxide reduction reaction (CO) 2 RR) and various organic catalytic reactions.
Compared with the prior art, the invention has the following beneficial effects:
(1) The non-noble metal monatomic catalyst supported by the enamine group covalent organic framework is synthesized by a one-step method for the first time;
(2) The non-noble metal monatomic catalyst supported by the enamine-based covalent organic framework has a relatively thin nanosheet shape;
(3) The metal of the non-noble metal monatomic catalyst supported by the enamine-based covalent organic framework is highly and uniformly distributed;
(4) The preparation method is simple, time-saving and environment-friendly, and can be used for mass preparation;
(5) The enamine group covalent organic framework supported non-noble metal monatomic catalyst of the invention shows excellent CO 2 Cycloaddition catalytic properties, e.g. Co-TPPA prepared at 1 atm CO 2 Samples catalyzed CO at 80 ℃, 5% TBAB and no additional solvent used 2 The conversion rate of cycloaddition of epichlorohydrin and epichlorohydrin in 2.5 h is as high as 97.3%, and the TOF value is as high as 2571 h -1 ；
(6) The non-noble metal monatomic catalyst supported by the enamine-based covalent organic framework has excellent stability, for example, the prepared Co-TPPA can be circularly catalyzed for 10 times under the conditions of normal pressure, 80 ℃, 5% TBAB and no additional solvent, and the catalytic performance is not obviously reduced;
(7) The non-noble metal monoatomic catalyst supported by the enamine group covalent organic framework has high potential application value in the field of energy catalysis, and can be used for HER, OER, ORR and CO 2 RR and various organic catalytic reactions.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of Co-TPPA in an example of the present invention.
FIG. 2 is a TEM image of Co-TPPA in the example of the present invention.
FIG. 3 is a TEM image of Co-TPPA in the example of the present invention.
FIG. 4 is an EDS-Mapping energy spectrum of Co-TPPA in the example of the present invention.
FIG. 5 is a diagram showing an infrared absorption spectrum of Co-TPPA in the example of the present invention.
FIG. 6 is a Raman spectrum of Co-TPPA in the example of the present invention.
FIG. 7 is an X-ray photoelectron spectrum of Co-TPPA in the example of the present invention.
FIG. 8 shows Co-TPPA 77K N in an example of the present invention 2 Adsorption-desorption isotherm diagram.
FIG. 9 shows a 273K CO Co-TPPA of an example of the present invention 2 Adsorption-desorption isotherm diagram.
FIG. 10 shows that Co-TPPA catalyzes CO in example of the present invention 2 And TOF and TON values of the cycloaddition of epichlorohydrin over time.
FIG. 11 shows that Co-TPPA catalyzes CO in example of the present invention 2 And nuclear magnetic hydrogen spectrum diagram of cycloaddition conversion rate of epoxy chloropropane.
FIG. 12 shows that Co-TPPA catalyzes CO in example of the present 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 monatomic catalyst, which comprises the following steps: mixing 2,4,6-triacyl phloroglucinol, an amino-containing ligand and a metal salt, ball-milling, centrifuging, and drying in vacuum to obtain the enamine group covalent organic framework supported non-noble metal monatomic catalyst X-TPPA, wherein X can be any non-noble metal such as Fe, co, ni, cu, zn and the like.
Wherein, the ligand containing amine groups comprises 4,4' -diaminostilbene-2,2 ' -disulfonic acid, o-sulfonic acid p-phenylenediamine, 4,4' -diaminodiphenylamine-2 ' -sulfonic acid, 2,5-diamino-1,3-benzene disulfonic acid, 2,5-diamino-1,4-benzene disulfonic acid, 2,2' -disulfonic acid benzidine, p-phenylenediamine, biphenyldiamine, oxalyl diamine, anthracene-2,6-diamine, and the like. The rotating speed of the ball milling is 100 to 500 rmp/min, and the ball milling time is 0.5 to 12 hours. The metal salt species includes a metal nitrate, a metal acetate, a metal sulfate, a metal chloride or a metal bromide.
Use of synthetic X-TPPA as catalyst, e.g. for catalyzing CO 2 And epoxide to generate cyclic carbonate, and has excellent catalytic performance.
In order that the objects, features and advantages of the invention may be more clearly illustrated, some specific embodiments are described below. In the following description, numerous specific details are set forth, however, the present invention may be practiced in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments disclosed below.
Example 1 preparation of Co-TPPA
P-phenylenediamine, 2,4,6-trimethylacylphloroglucinol and cobalt bromide are put into a ball milling tank, the rotating speed is controlled to be 100-500 rmp/min, and the ball milling time is 6 h. Then, the mixture was washed with ethanol, deionized water, and N, N-dimethylformamide by centrifugation three times. After the centrifugation is finished, the mixture is placed into a vacuum drying oven to be dried for 24 h, and the sample Co-TPPA is obtained. The X-ray diffraction pattern of the Co-TPPA sample is shown in figure 1; FIG. 2 shows a scanning electron microscope; FIG. 3 is a transmission electron microscope image; the EDS-Mapping energy spectrum is shown in figure 4; the infrared absorption spectrogram is shown in FIG. 5; the Raman spectrum is shown in FIG. 6; the X-ray photoelectron spectrum is shown in FIG. 7;77 The K nitrogen adsorption-desorption isotherm diagram is shown in FIG. 8;273 KCO 2 The adsorption-desorption isotherm is shown in figure 9.
Example 2 Co-TPPA catalyzed cycloaddition Performance testing of CO2 and epichlorohydrin
Co-TPPA from example 1 catalyzes CO 2 The cycloaddition performance of the epoxy chloropropane is measured to be CO at 1 atm 2 80 ℃, 5% TBAB and no additional solvent was used. The obtained product is detected and analyzed by nuclear magnetic resonance hydrogen spectrum. FIG. 10 shows graphs of TOF and TON values as a function of time obtained by sampling analysis at 10, 30, 60, 90, 120, and 150 min respectively, the TON value being calculated as moles converted/moles of active site, and the TOF value being calculated as moles convertedMoles/(moles active site time) are calculated. The CO of Co-TPPA at 1 atm is known 2 80 ℃, 5% TBAB and catalysis of CO without additional solvent use 2 The highest TOF value of the epichlorohydrin can reach 2571 h -1 While the TON value reaches 695. FIG. 11 shows Co-TPPA catalyzed CO 2 The nuclear magnetic hydrogen spectrum diagram of the conversion rate of cycloaddition with the epichlorohydrin shows that the Co-TPPA catalyzes CO under the condition 2 And the conversion of epichlorohydrin was 97.3%. After 10 times of circular catalysis of Co-TPPA shown in FIG. 12, the performance is only reduced by 2.5%, which shows that the Co-TPPA has good stability.
The non-noble metal monatomic catalyst supported by the enamine-based covalent organic framework can be synthesized by a one-step method for the first time, the non-noble metal monatomic catalyst supported by the enamine-based covalent organic framework with thin size and highly uniform metal distribution can be prepared in a large batch by a simple ball milling and drying method, the preparation method of the non-noble metal monatomic catalyst supported by the enamine-based covalent organic framework is simple, the cost is low, the catalyst is suitable for large-batch synthesis, has high potential industrial application value in the field of energy catalysis, and can be used for CO 2 Cycloaddition of (C), electrocatalytic water decomposition reaction, oxygen Reduction Reaction (ORR), carbon dioxide reduction reaction (CO) 2 RR) and various organic catalytic reactions.
With CO 2 For example, since greenhouse effect due to carbon dioxide exerts a great influence on the global ecological environment, CO is fixed by chemical reaction 2 The generation of more valuable chemicals, among which CO, has a wide application prospect 2 Cycloaddition of (b) is one of the most prominent methods. CO2 2 The cycloaddition of (A) includes epoxide ring opening, activating CO 2 ，CO 2 And key steps such as insertion and ring closure are carried out, and the introduction of a catalyst is required to increase the reaction activity and improve the reaction efficiency. Currently about CO 2 The most of the conditions are still high temperature and high pressure, and the use of organic solvents. However, energy consumption and high cost due to high temperature and high pressure are great challenges for industrial application, and the use of organic solvent also increases the difficulty of separation after the reaction is finished and causes environmental pollutionAnd (3) contamination. Co-TPPA has excellent CO 2 The cycloaddition catalyst has the advantages of simple, quick and green preparation, and the catalytic conditions are easy to reach, even has huge potential for industrial application.
Claims (8)
1. A preparation method of a non-noble metal monatomic catalyst supported by an enamine group covalent organic framework comprises the following steps:
mixing 2,4,6-triacyl phloroglucinol, an amino-containing ligand and a metal salt, then carrying out ball milling, then carrying out centrifugal washing and vacuum drying to obtain the non-noble metal monatomic catalyst supported by the enamine base covalent organic framework.
2. The method of claim 1, wherein: the ligand containing amino groups is 4,4' -diaminostilbene-2,2 ' -disulfonic acid, o-sulfonic acid p-phenylenediamine, 4,4' -diaminodiphenylamine-2 ' -sulfonic acid, 2,5-diamino-1,3-benzene disulfonic acid, 2,5-diamino-1,4-benzene disulfonic acid, 2,2' -disulfonic acid benzidine, p-phenylenediamine, biphenyldiamine, oxalyl diamine or anthracene-2,6-diamine.
3. The method of claim 1, wherein: the metal salt is a metal nitrate, a metal acetate, a metal sulfate, a metal chloride or a metal bromide.
4. The method of claim 3, wherein: the metal is Fe, co, ni, cu or Zn.
5. The method of claim 1, wherein: the rotation speed of the ball milling is 100 to 500 rmp/min, and the ball milling time is 0.5 to 12 hours.
6. An enamine-based covalent organic framework supported non-noble metal monatomic catalyst obtained according to the method of any one of claims 1~5.
7. The application of the enamine-based covalent organic framework supported non-noble metal monatomic catalyst according to claim 6 in the field of energy catalysis.
8. Use according to claim 7, characterized in that: the non-noble metal monoatomic catalyst supported by the enamine covalent organic framework is applied to catalyzing CO 2 Cycloaddition, water decomposition, oxygen Reduction Reaction (ORR) or carbon dioxide reduction reaction (CO) 2 RR）。
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