CN112642482B - Metal-anchored hollow covalent organic framework material and preparation method and catalytic application thereof - Google Patents
Metal-anchored hollow covalent organic framework material and preparation method and catalytic application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 29
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 230000003197 catalytic effect Effects 0.000 title abstract description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims abstract description 21
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 238000005530 etching Methods 0.000 claims abstract description 11
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 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 abstract description 8
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960001553 phloroglucinol Drugs 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004873 anchoring Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 238000004729 solvothermal method Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 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 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- WCYJXDMUQGVQQS-UHFFFAOYSA-N pyridine;ruthenium Chemical compound [Ru].C1=CC=NC=C1 WCYJXDMUQGVQQS-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
- 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
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- 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
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a preparation method of a metal ion anchored hollow covalent organic framework material and a photocatalytic application thereof, belonging to the technical field of material preparation and catalysis. Through a selective etching method, a ZIF-67 is used, p-phenylenediamine and trialdehyde phloroglucinol are subjected to catalytic reaction in an o-dichlorobenzene/n-butanol/pyrrolidine solution system to obtain an MOF/COF material with an egg yolk-eggshell structure, an internal metal organic framework is etched through acid washing, and metal ions are anchored on a covalent organic framework. The material of the invention has imine bonds and a unique hollow structure. The material is mild in preparation conditions, simple in preparation operation and microporous in structure, metal ions are anchored in a covalent organic framework through a selective etching method, good catalytic performance is shown, and the material has great application potential.
Description
Technical Field
The invention belongs to the technical field of material preparation and catalysis, and relates to a hollow covalent organic framework material, a synthesis method and a catalysis application thereof.
Background
With the development of the economic change, the energy and environmental problems become more serious, and the harm of the greenhouse effect becomes more prominent. The solar photocatalysis technology for converting carbon dioxide into valuable gas/liquid phase fuel has great application value and prospect, so that the content of carbon dioxide in the atmosphere can be reduced, and the requirement of renewable fuel can be partially met. Therefore, the conversion of carbon dioxide into carbon monoxide, methane, methanol, ethanol and other fuels under the photocatalytic condition has been greatly explored and studied. To date, photocatalytic reduction of carbon dioxide remains a challenge, as carbon dioxide is one of the most thermodynamically stable carbon compounds. The photocatalyst can obviously reduce the activation energy of the reaction of photocatalytic reduction of carbon dioxide, so the design and synthesis of the high-efficiency photocatalyst have great environmental and economic significance to China.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a metal anchoring hollow covalent organic framework material and a synthesis method and application thereof. The invention utilizes a selective etching method to prepare the yolk shell MOF/COF structure, and the metal anchoring hollow covalent organic framework material obtained by acid cleaning has better performance of photocatalytic reduction of carbon dioxide.
In order to achieve the purpose, the invention adopts the following technical scheme:
a yolk-eggshell structure (ZIF-67 @ TpPa) of metal organic framework/covalent organic framework is obtained by etching. The synthesis method of the metal ion anchored covalent organic framework material comprises the following steps:
the synthesis method specifically comprises the following steps:
(1) stirring ZIF-67, p-phenylenediamine and trialdehyde phloroglucinol for 12h at 50 ℃ to obtain ZIF-67@ Am-TpPa, then obtaining a dry solid at 50 ℃ and 70rpm through a rotary evaporator, adding the dry solid into an o-dichlorobenzene/n-butanol/pyrrolidine solution (volume ratio of 9:1:1, total volume of 1.65 mL) system, and reacting for 3 days at 120 ℃ to obtain egg yolk-eggshell ZIF-67@ TpPa; the mass ratio of ZIF-67 to p-phenylenediamine to trialdehyde phloroglucinol in the step (1) is 6.67: 3: 4.
(2) And (2) placing the yolk-eggshell ZIF-67@ TpPa prepared in the step (1) into a 10 mL glass bottle, adding dioxane and acetic acid, carrying out acid etching for 1 h, centrifuging with acetone to collect a product, and carrying out vacuum drying on the obtained powder to obtain the cobalt ion anchored hollow covalent organic framework material Co @ TpPa.
The metal-anchored hollow covalent organic framework material synthesized by the invention can be uniformly dispersed and recycled by anchoring metal ions in the covalent organic framework, and can be applied to photocatalytic carbon dioxide reduction.
The invention has the beneficial effects that:
1) according to the invention, through a selective etching method, ZIF-67 is used, p-phenylenediamine and trialdehyde phloroglucinol are subjected to catalytic reaction in an o-dichlorobenzene/n-butanol/pyrrolidine solution system to obtain an MOF/COF material with an egg yolk-eggshell structure, an internal metal organic framework is etched by acid washing, Co is anchored on a covalent organic framework, the synthetic yield is relatively high, the obtained material has a microporous structure, and the material has good catalytic performance and can be used for a photocatalytic reduction reaction.
2) The equipment and chemical reagents used in the synthesis method are easy to obtain, the process operation is simple and convenient, the process conditions are simple, the applicability is strong, the industrial application value is high, and the method is easy to popularize and utilize.
Drawings
FIG. 1 is a transmission image of Co @ TpPa;
FIG. 2 is an X-ray powder diffraction pattern of ZIF-67, ZIF-67@ TpPa, and Co @ TpPa;
FIG. 3 is a Fourier transform infrared spectrum of ZIF-67, ZIF-67@ TpPa, and Co @ TpPa;
FIG. 4 is a graph of carbon monoxide and hydrogen production versus reaction time for Co @ TpPa under photocatalytic conditions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood and understandable, the present invention is further described in detail with reference to the following embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention. In addition, the technical features mentioned in the embodiments of the present invention described below may be combined as long as they do not conflict with each other.
Example 1
A preparation method of a metal-anchored hollow covalent organic framework material comprises the following specific synthetic steps:
preparation of ZIF-67: respectively dissolving cobalt nitrate hexahydrate (582 mg, 2.0 mmol) and dimethylimidazole (769 mg, 8.0 mmol) in 50 mL of methanol solution, uniformly dispersing, stirring at the normal temperature of 500 rpm/min for 24 h, centrifuging with methanol to collect the product, and vacuum drying the obtained product at 60 ℃ overnight to obtain a purple product.
Preparation of egg yolk-eggshell ZIF-67@ TpPa: dissolving 16 mg of ZIF-67 and 7.2 mg of p-phenylenediamine in 11 mL of tetrahydrofuran solution, ultrasonically dispersing for 30 min, heating and stirring in a 50 ℃ oil bath for 30 min, dissolving 9.6 mg of trialdehyde phloroglucinol in 4 mL of tetrahydrofuran solution, dripping into a reaction system at the speed of 0.4 mL/min after uniform dispersion, continuously stirring for 12h, carrying out rotary evaporation to obtain an intermediate product, placing the intermediate product into a Pyrex tube (the volume is about 5 mL, the body length is 19 cm, the neck length is 1 cm), adding 1.35 mL of o-dichlorobenzene, 0.15 mL of n-butanol and 0.15 mL of pyrrolidine, then placing the Pyrex tube into a liquid nitrogen bath (-196 ℃) for quick freezing, carrying out vacuum-freezing-thawing (thawing by using normal-temperature water) for three times, and then carrying out flame sealing on the tube under the vacuum condition. After warming to room temperature, the pyrex tube was placed in an oven at 120 ℃ for 3 days and the product was collected by suction filtration with anhydrous acetone. Vacuum drying the obtained powder at 60 deg.C for 24 h to obtain egg yolk-eggshell ZIF-67@ TpPa.
Preparation of hollow Co @ TpPa: and (2) placing the yolk-eggshell ZIF-67@ TpPa prepared in the last step into a 10 mL glass bottle, adding 2 mL dioxane and 0.2 mL 3M acetic acid, carrying out acid etching for 1 h, centrifuging with acetone to collect a product, and carrying out vacuum drying on the obtained powder at 60 ℃ for 24 h to obtain the hollow Co @ TpPa.
Application example 1
The photocatalytic performance of the Co @ TpPa prepared by the invention comprises the following specific steps:
co @ TpPa (0.5 mg), ruthenium pyridine (6.5 mg) was added to a photocatalytic reactor containing 3 mL acetonitrile, 1mL water, and 1mL triethanolamine solvent. The reactor was evacuated and filled with carbon dioxide and cycled three times. Aliquots (0.2 mL) of gas were removed from the reactor at given time intervals by photocatalytic illumination with a xenon lamp light source. The gas components were analyzed by gas chromatography to obtain the carbon monoxide and hydrogen contents.
Fig. 1 shows that a Co @ TpPa material with a hollow structure is successfully prepared through a TEM image, and an ICP test shows that the content of element Co is 6.9%.
FIG. 2 shows disappearance of the ZIF-67 characteristic peak and appearance of the TpPa characteristic peak in Co @ TpPa by XRD, demonstrating that the ZIF-67 template has been completely removed and that the characteristic peak at 4.7 ℃ can demonstrate formation of TpPa.
FT-IR of FIG. 3 at 1258 cm-1The successful synthesis of TpPa is demonstrated by the appearance of characteristic peaks.
Fig. 4 shows that the material has good photocatalytic performance and can generate carbon monoxide and hydrogen under visible light conditions.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (4)
1. Use of a metal-anchored hollow covalent organic framework material, characterized in that: the metal-anchored hollow covalent organic framework material is used for preparing H by photocatalytic carbon dioxide reduction2And CO; the synthesis method of the metal-anchored hollow covalent organic framework material comprises the steps of anchoring metal ions in the covalent organic framework through a selective etching method; the synthesis method comprises the steps of carrying out catalytic reaction on ZIF-67, p-phenylenediamine and trialdehyde phloroglucinol in an o-dichlorobenzene/n-butanol/pyrrolidine solution system by using a selective etching method to obtain an MOF/COF material with an egg yolk-eggshell structure, etching an internal metal organic framework by acid washing, and anchoring metal ions on a covalent organic framework; the synthesis method specifically comprises the following steps:
stirring ZIF-67, p-phenylenediamine and trialdehyde phloroglucinol to react to obtain ZIF-67@ Am-TpPa, evaporating to dryness, adding the dried ZIF-67@ Am-TpPa into an o-dichlorobenzene/n-butanol/pyrrolidine solution system, and carrying out solvothermal reaction to obtain an egg yolk-eggshell ZIF-67@ TpPa;
placing the yolk-eggshell ZIF-67@ TpPa prepared in the step (1) into a 10 mL glass bottle, adding dioxane and acetic acid, carrying out acid etching for 1 h, centrifuging with acetone to collect a product, and carrying out vacuum drying on the obtained powder to obtain the metal anchored hollow covalent organic framework material;
the mass ratio of ZIF-67 to p-phenylenediamine to trialdehyde phloroglucinol in the step (1) is 6.67: 3: 4;
the stirring reaction in the step (1) is specifically stirring for 12 hours at 50 ℃;
the volume ratio of the o-dichlorobenzene/n-butanol/pyrrolidine solution in the step (1) is 9:1:1, and the total volume is 1.65 mL.
2. Use of the metal-anchored hollow covalent organic framework material according to claim 1, characterized in that: the step (1) of rotary evaporation drying specifically refers to obtaining a dry solid by a rotary evaporator at 50 ℃ and 70 rpm.
3. Use of the metal-anchored hollow covalent organic framework material according to claim 1, characterized in that: the solvent thermal reaction in the step (1) is specifically a reaction at 120 ℃ for 3 days.
4. Use of the metal-anchored hollow covalent organic framework material according to claim 1, characterized in that: and (3) the vacuum drying in the step (2) is vacuum drying at 60 ℃ for 24 h.
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| CN113842953A (en) * | 2021-10-11 | 2021-12-28 | 石家庄铁道大学 | NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst and preparation method thereof |
| CN115501915B (en) * | 2022-10-21 | 2023-10-27 | 江南大学 | Bimetal organic framework/covalent organic framework composite photocatalyst with core-shell structure and preparation method thereof |
| CN115646545B (en) * | 2022-12-03 | 2024-06-25 | 福州大学 | Preparation of bipyridine group-connected benzotrithiophene-based covalent organic photocatalytic material and photocatalytic full-decomposition water application thereof |
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| CN116078431B (en) * | 2022-12-13 | 2024-06-14 | 湘潭大学 | Au-based catalytic material based on hollow TTI-COF and application of Au-based catalytic material in catalyzing reduction of 4-nitrophenol |
| CN116621225B (en) * | 2023-07-12 | 2024-01-23 | 重庆上甲电子股份有限公司 | Flux and method for recovering manganese from perillaldehyde waste residues and application of flux and method for preparing trimanganese tetroxide for soft magnetism |
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