CN116920914A - Bimetal supported porous carbon nanofiber catalyst and preparation method and application thereof - Google Patents
Bimetal supported porous carbon nanofiber catalyst and preparation method and application thereof Download PDFInfo
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- CN116920914A CN116920914A CN202311167810.1A CN202311167810A CN116920914A CN 116920914 A CN116920914 A CN 116920914A CN 202311167810 A CN202311167810 A CN 202311167810A CN 116920914 A CN116920914 A CN 116920914A
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- porous carbon
- carbon nanofiber
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 239000002133 porous carbon nanofiber Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 41
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 32
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 26
- 239000002121 nanofiber Substances 0.000 claims description 24
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 24
- 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 claims description 24
- 150000003751 zinc Chemical class 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 15
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 14
- 238000010041 electrostatic spinning Methods 0.000 claims description 14
- 238000011065 in-situ storage Methods 0.000 claims description 14
- 238000006352 cycloaddition reaction Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229920005594 polymer fiber Polymers 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000002924 oxiranes Chemical class 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001523 electrospinning Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
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- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000012423 maintenance Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000010949 copper Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 150000005676 cyclic carbonates Chemical class 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- -1 transition metal salt Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 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
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of photo-thermal catalysis, and discloses a supported bimetal porous carbon nanofiber catalyst, a preparation method and application thereof. Compared with the conventional method, the preparation and maintenance process of the porous carbon nanofiber is simpler to operate and higher in repeatability; the preparation process of the bimetallic material and the introduction of the adsorption method can not only increase the metal sites of the catalyst, but also treat heavy metal pollutants in water. The porous carbon nanofiber supported bimetallic catalyst prepared by the method effectively avoids the problems of agglomeration of metal sites, secondary pollution and the like of the catalyst, and has good circulation stability and catalytic activity; meanwhile, the preparation process also recovers heavy metal pollutants. Provides a certain feasibility strategy for improving the performance of the catalyst and utilizing the materials in multiple fields, and has good application prospect in the field of photo-thermal catalysis.
Description
Technical Field
The invention relates to the technical field of photo-thermal catalysis, in particular to a supported bimetal porous carbon nanofiber catalyst, a preparation method and application thereof.
Background
The massive use of fossil fuels to CO 2 Is considered to be a major cause of greenhouse effect. Thereby causing a series of environmental problems such as land desertification, glacier ablation, extreme weather, etc. In CO 2 Among the numerous methods of emission abatement, CO 2 The method is converted into cyclic carbonate with high added value, so that CO can be reduced 2 The cyclic carbonate has the characteristics of high dipole moment, high dielectric constant and the like, and is widely applied to the aspects of electrolyte of lithium batteries, medical synthesis intermediates, precursors for synthesizing organic compounds and the like. Thus, CO 2 Cycloaddition reaction to CO 2 The important direction of synthesis of organic compounds is also the main method of synthesis of cyclic carbonates.
Currently, the theory of Lewis Acid (LA) sites catalyzing this reaction is widely accepted, generally involving ring opening of the epoxide substrate, CO 2 Is inserted into the reactor, and the internal cyclization reaction is performed in three steps. However, most of the catalysts are required to be carried out under the condition of high temperature and high pressure, and the direct heating mode usually causes secondary consumption of energy. When the catalyst exhibits excellent photo-thermal properties, the CO can be driven by light energy 2 The kinetics of the cycloaddition reaction.
In recent years, CO has been converted using light energy or other renewable energy sources 2 Conversion to chemicals with high added value has become a trend. Light energy is favored by researchers compared to other forms of clean energy because it is more convenient to use and less likely to be usedFurther energy consumption is required. Therefore, CO is driven by light energy 2 Is converted into cyclic carbonate, and has high industrial value and scientific significance. Mono-metallic ZIF-8 derived carbon material is used for driving force to CO by utilizing light 2 When cycloaddition reaction is catalyzed, the defects of insufficient LA active site and low catalytic efficiency still exist.
Disclosure of Invention
The invention aims to provide a supported bimetal porous carbon nanofiber catalyst, a preparation method and application thereof, and aims to solve the problem that in the prior art, a single metal ZIF-8 derived carbon material is used for driving CO by utilizing light as driving force 2 When cycloaddition reaction is catalyzed, the technical problems of insufficient LA active site and low catalytic efficiency exist.
The invention provides a preparation method of a supported bimetal porous carbon nanofiber catalyst, which comprises the following steps:
step 1, preparing a nano polymer fiber containing zinc salt by adopting an electrostatic spinning method;
step 2, placing the nano polymer fiber in a methanol solution of 2-methylimidazole for in-situ growth to obtain a ZIF-8 loaded composite nano fiber;
step 3, absorbing heavy metal ions in the heavy metal ion aqueous solution by utilizing the composite nanofiber to obtain the bimetal composite nanofiber;
and 4, pre-oxidizing and carbonizing the bimetal composite nanofiber to obtain the catalyst.
Further, in step 1, preparing the nano polymer fiber containing zinc salt specifically includes:
dissolving polyacrylonitrile and zinc salt in an organic solvent, and mixing to obtain a stable and uniform electrostatic spinning precursor solution;
and forming the nano polymer fiber containing zinc salt through internal doping spinning by utilizing the electrostatic spinning precursor solution.
Wherein the mass ratio of zinc element in zinc salt to polyacrylonitrile is (0.5-2.5): 1.
Further, in step 1, the electrospinning method employs the following parameters: the high voltage between the anode and the cathode is 14kV, and the distance between the anode and the cathode copper plate is 19cm.
Further, in the in-situ growth process of the step 2, the molar ratio of the 2-methylimidazole to zinc ions in the zinc salt is (2-6): 1.
Further, in the step 3, the heavy metal ions are copper ions, the concentration of the copper ion aqueous solution is 20-140mg/L, the pH of the copper ion aqueous solution is 2-6.5, the adsorption temperature is 25-55 ℃, and the adsorption time is 0.5-5h.
Further, in the step 4, the whole carbonization process is carried out under the inert gas environment, the heating rate is 1-10 ℃/min, the catalyst is obtained after the catalyst stays for 0.5-5h at 100-250 ℃ and stays for 0.5-5h at 300-900 ℃.
The invention also provides a supported bimetal porous carbon nanofiber catalyst which is prepared by the preparation method.
The invention also provides application of the supported bimetal porous carbon nanofiber catalyst for photo-thermal catalysis of CO 2 Cycloaddition reaction with epoxide.
Further, the epoxide is at least one of styrene oxide, epichlorohydrin, bromopropane oxide, propylene oxide and butylene oxide.
Further, the cycloaddition reaction conditions are: CO 2 The pressure is 0.5-15MPa, and the reaction time is 5-10h.
Compared with the prior art, the invention has the beneficial effects that:
(1) The nano polymer fiber can fix metal on the fiber through internal doping spinning to prevent falling, and plays a role in limiting the domain, controlling the diameter of ZIF-8 particles and uniformly dispersing, and avoiding agglomeration of metal zinc.
(2) The catalyst of the invention combines internal doping spinning and in-situ growth in the preparation process, thereby ensuring the uniform loading of ZIF-8 on the fiber; and ZIF-8 is grown in situ, and compared with methods such as post-loading, hydrothermal, microwave heating and the like, the method has simple operation flow; meanwhile, the alkaline 2-methylimidazole solution etches part of PAN fibers, so that Zn (II) is exposed, and the exposed Zn (II) is used as a catalyst active site, so that the reaction efficiency can be improved.
(3) According to the invention, by adsorbing the loaded copper ions, the metal sites are increased, the agglomeration of metal copper is avoided, heavy metal pollutants in water are treated, and the bimetallic material has better catalytic activity than single metal.
(4) In the carbonization process, the catalyst can maintain good morphological characteristics by low-temperature pretreatment, and the PAN structure is damaged by high-temperature carbonization to obtain a carbon-based carrier; meanwhile, the whole process is in a nitrogen anoxic atmosphere, so that Zn (II) is not oxidized in the process, zn-N bonds are formed, active sites can be provided for the reaction, and the catalytic activity is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a catalyst preparation flow.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the catalyst of example 1.
FIG. 3 is a Transmission (TEM) image and elemental distribution diagram of the catalyst of example 1.
Fig. 4 is an X-ray diffraction (XRD) pattern of the catalyst of example 1.
FIG. 5 is an X-ray photoelectron spectroscopy (XPS) chart of the catalyst of example 1.
FIG. 6 is a graph of the analysis of the catalytic performance test of the catalyst of example 1.
FIG. 7 is a graph showing the catalytic performance of example 1 and comparative examples 1 and 2.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown.
The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention.
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The porous carbon nanofiber can expose metal sites, provide more reaction sites, increase the dispersibility of the catalyst, reduce mass transfer resistance by a special structure and improve reaction efficiency; the nanofiber has an ultrahigh length-diameter ratio and high catalytic and separation efficiency; the carbon-based material has better stability and provides conditions for recycling the catalyst; meanwhile, the carbon-based carrier is used as a good photo-thermal conversion material, so that the possibility of photo-thermal conversion is provided.
Based on the above, the embodiment of the invention provides a preparation method of a supported bimetal porous carbon nanofiber catalyst, and compared with other methods, when a bimetal material is obtained specifically, the preparation method provided by the invention has water stability and porosity by utilizing ZIF-8, and has a wide application prospect in the field of removing heavy metal ions in water by an adsorption method. The adsorption method is utilized to adsorb other metal ions from the aqueous solution, and the carbon material with double metals can be obtained after high-temperature pyrolysis. Not only can recycle heavy metal pollutants in water, but also can increase metal sites of ZIF-8 derived carbon materials, and improves catalytic performance. Meanwhile, the adsorption sites ZIF-8 are uniformly distributed on the surface of the fiber, so that heavy metal ions are uniformly dispersed on the surface of the fiber. The bimetallic material has higher photo-thermal conversion efficiency when being used as an active site, and promotes the photo-thermal conversion efficiency.
As shown in fig. 1, the preparation method provided by the invention mainly comprises the following steps:
step 1, preparing a nano polymer fiber containing zinc salt by adopting an electrostatic spinning method;
specifically, an electrostatic spinning method comprises the steps of firstly preparing an electrostatic spinning precursor solution, dissolving polyacrylonitrile and zinc salt in an organic solvent, and mixing to obtain a stable and uniform electrostatic spinning precursor solution; and then forming the nano polymer fiber containing zinc salt through internal doping spinning by utilizing the electrostatic spinning precursor solution.
Wherein, the zinc salt can be acetate, such as zinc acetate;
the organic solvent is an organic solvent capable of dissolving transition metal salt, such as N, N-Dimethylformamide (DMF) or dimethyl sulfoxide (DMSO);
when preparing the precursor solution, the mass ratio of zinc element and polyacrylonitrile in zinc salt is controlled to be (0.5-2.5): 1, the heating and stirring temperature and time of the precursor solution are not particularly limited, and the precursor solution can be ensured to obtain stable and uniform solution, and the temperature can be 40-80 ℃ and the time can be 4-8 hours as an example. It is also possible to prepare a stable and uniform mixed solution, such as a uniform gum solution, by stirring. As an example, there is no requirement for the rotor, and there is no particular limitation on the rotation speed and stirring time of the rotor, so long as a stable and uniform mixed solution is ensured. As an example, the rotational speed may be 100 to 1000r/min, e.g., 200 to 500r/min, and the stirring time may be 2 to 24 hours, e.g., 10 to 24 hours.
The electrospinning method can be carried out by packaging a prepared electrospinning precursor solution by a self-made tip glass tube, and as an example, the electrospinning method adopts the following parameters: the high voltage between the anode and the cathode is 14kV, and the receiving distance is 19cm.
Step 2, placing the nano polymer fiber in a methanol solution of 2-methylimidazole for in-situ growth to obtain a ZIF-8 loaded composite nano fiber;
in the step, compared with the direct feeding ZIF-8 powder, DMF and polyacrylonitrile for reaction, the in-situ growth in the invention can enable an alkaline 2-methylimidazole solution to etch part of PAN fibers, enable Zn (II) to be exposed, enable the exposed Zn (II) to serve as a catalyst active site, and improve the reaction efficiency.
Specifically, the molar ratio of zinc element and 2-methylimidazole in zinc salt is 1: (1-6).
The temperature and time of in-situ growth are not particularly limited, and the ZIF-8 in-situ growth is ensured to be supported on the nanofiber, and as an example, the ZIF-8 in-situ growth is carried out for 24 hours at room temperature.
Step 3, absorbing heavy metal ions in the heavy metal ion aqueous solution by utilizing the composite nanofiber to obtain the bimetal composite nanofiber;
here, the heavy metal ions may be copper ions, hexavalent chromium ions, trivalent aluminum ions, variable valence cerium ions, etc., and in the present invention, through literature research, copper is found to be a typical heavy metal, and its compound causes serious pollution in the environment, and has endangered human survival and development; at the same time can be used as LA locus to effectively catalyze CO 2 Cycloaddition reaction. The ZIF-8 adsorbs Cu (II) ions not only as active sites, but also can recycle Cu (II) ions in wastewater, thereby reducing the pollution of heavy metal Cu (II) to water. Thus, the heavy metal ion is set as copper ion.
Further, the adsorption temperature, time, and initial concentration of the solution are not particularly required, and as an example, the concentration of the copper ion aqueous solution is 20 to 140mg/L, the pH of the copper ion aqueous solution is 2 to 6.5, the adsorption temperature is 25 to 55 ℃, and the adsorption time is 0.5 to 5 hours.
And 4, carbonizing the bimetal composite nanofiber to obtain the catalyst.
Specifically, the carbonization comprises a low-temperature pretreatment stage and a high-temperature carbonization stage, wherein the whole process is performed in an inert gas environment, such as nitrogen, helium and argon or a mixed atmosphere of two or more of the nitrogen, the helium and the argon, the heating rate is 1-10 ℃/min, the low-temperature pretreatment stage is that the catalyst is kept at 100-250 ℃ for 0.5-5h, and the high-temperature carbonization stage is that the catalyst is obtained after the catalyst is kept at 300-900 ℃ for 0.5-5h.
The catalyst can keep better morphological characteristics by the early low-temperature pretreatment, and the nanofiber can be stabilized by selecting to stay for a certain time at one temperature point or a plurality of temperature points and keeping the total stay time between 0.5 and 5 hours in the range of heating to 100-250 ℃; high-temperature carbonization causes the PAN structure to be damaged, and a carbon-based carrier is obtained; meanwhile, the whole process is in a nitrogen anoxic atmosphere, so that Zn (II) is not oxidized in the process, zn-N bonds are formed, active sites can be provided for the reaction, and the catalytic activity is improved, wherein nitrogen sources in the Zn-N bonds come from dimethyl imidazole ligands of ZIF-8, and therefore, nitrogen can be replaced by inert gases such as helium, argon and the like.
The preparation method also comprises the step of carrying out suction filtration and washing on the intermediate product (namely the product obtained in the step 2 and the step 3).
The supported bimetal porous carbon nanofiber catalyst prepared by the method is porous carbon nanofiber loaded with zinc and copper, has no magnetism, two metals have no agglomeration phenomenon, the metal zinc exists in a Zn-N bond form, zn-N sites in the catalyst are uniformly distributed in the porous carbon nanofiber, the metal zinc loading amount is 6-15 wt%, the metal copper exists in a cuprous oxide and elemental copper form, and the two metals are uniformly distributed on the surface of the fiber.
The invention also discloses the application of the supported bimetal porous carbon nanofiber catalyst in photo-thermal CO catalysis 2 The cycloaddition reaction with epoxide.
Preferably, the reaction substrate is an epoxide such as at least one of styrene oxide, bromopropane oxide, epichlorohydrin, propylene oxide, ethylene oxide, and the like. A bromopropane substrate is preferred. By way of example, the epoxide is one or more of epibromohydrin, epichlorohydrin. The cycloaddition reaction conditions are as follows: CO 2 The pressure is 0.5-15MPa, and the reaction time is 5-10h.
The invention will be described in detail by way of example, and some reagents and apparatus used in the examples are as follows:
polyacrylonitrile Kunshan Yi Plastic Co., ltd
N, N-dimethylformamide AR,99% of Phoenix Ship chemical reagent technology Co., ltd
Zinc acetate AR,99% national medicine group chemical Co., ltd
2-methylimidazole AR,99% Beijing enokic technologies Co., ltd
Epichlorohydrin AR,99% Beijing enokic science and technology Co., ltd
Epoxybromopropane AR,99% Beijing enoKai technologies Co., ltd
Styrene oxide AR,99% Beijing enokic technologies Co., ltd
Ethylene oxide AR,99% Beijing enokia technology Co., ltd
Propylene oxide AR,99% Beijing enokia technology Co.Ltd
Tetrabutylammonium bromide AR,99% Beijing enokic technologies Co., ltd
Absolute ethanol AR,99% national pharmaceutical Congress chemical Co., ltd
Ethyl acetate AR,99% national pharmaceutical chemicals limited
Copper nitrate AR,99% national pharmaceutical Congress chemical reagent Co., ltd, electronic balance BSA224S, beijing Sidoricos instruments Co., ltd
Multipoint magnetic stirrer CJB-S-5D Henan Aibot technology development Co., ltd
High-voltage direct-current power supply DW-P503-1ACCC Tianjin city Dong Wen Gao power supply factory
Electrothermal blowing drying oven DHG-9053A Shanghai-Heng scientific instruments Co., ltd
Circulating water pump SHB-B95 Zhengzhou great wall Co., ltd
High low temperature tube electric furnace SK-G06143 Tianjin middle ring experiment electric furnace Co.Ltd
High temperature high pressure reactor 50mL Beijing Zhongzhui Jinjin Limited
300W xenon lamp CEL-HXF300 Beijing Zhongzhujin Yuan Limited
Custom-made photocatalytic reactor, 50mL Beijing Zhongzhui Zhuanjinyuan Co., ltd
Constant temperature heating magnetic stirrer DF-101S Henan Cheng Hua instrument Co., ltd
Scanning electron microscope PhenomPro Feina scientific instruments Co
Transmission electron microscope JEM-2010 JEOL Co
SmartLab9kW Rigaku Co., ltd., japan, X-ray diffractometer
X-ray photoelectron spectroscopy EscaLab-250Xi U.S. Thermo-Fisher Co
Fourier transform infrared instrument Nexus670 Nicolete Co., USA
UV-3600 Shimadzu corporation, a diffuse reflectance spectrophotometer for ultraviolet-visible light
ICPOES730Agilent for inductively coupled plasma atomic emission spectrometer
Gas chromatograph GC7920-7E2A Beijing Zhongzhui Jinjin Source Co., ltd
Photocatalytic Activity evaluation System CEL-PAEM-D6 Beijing Zhongzhujin Yuan Limited
Gas chromatograph GC-2010Plus Shimadzu Corp
GC-MS5975C Agilent technologies Co.Ltd
Air bath oscillator HZQ-C Harbin City east-Linked electronics development Co., ltd
The method is a conventional method unless otherwise specified. The starting materials are available from published commercial sources unless otherwise specified.
Example 1
And preparing the Zn (II)/PAN composite nanofiber by adopting an electrostatic spinning method. A10 wt% PAN/DMF solution was prepared, 2.0000g of PAN was accurately weighed and dissolved in 18.0000g of DMF, and the mixture was stirred at room temperature for 12 hours to obtain a PAN/MDF solution, which was then oil-bathed at 80℃for 6 hours. 2.1900g of zinc acetate was dissolved in 4.0000g of DMF and stirred for 12h to give a Zn (II)/DMF solution. 10.0000g of PAN/DMF solution and 4.0000g of Zn (II)/DMF solution were mixed by stirring and then stirred at room temperature for 12 hours to obtain a homogeneous solution by thoroughly mixing the two. And (3) carrying out electrostatic spinning on the spinning solution to obtain a Zn (II) -doped nanofiber membrane Zn (II)/PAN, wherein in the electrostatic spinning process, the voltage is 14kV, and the distance between the orifice of a spinning tube and a receiving plate is 19cm.
And preparing the ZIF-8-loaded PAN nanofiber membrane by adopting an in-situ growth method. 0.1000g of nanofiber membrane Zn (II)/PAN is placed in a methanol solution (30 mL) of 2-methylimidazole (0.1236 g), and in-situ growth is carried out for 24h at room temperature, so that a ZIF-8-loaded PAN nanofiber membrane ZIF-8/PAN is obtained.
Cu -x -preparation of ZIF-8/PAN composite nanofibers. Cu (II) ions are loaded on ZIF-8/PAN nanofiber by utilizing the adsorption characteristic of ZIF-8 and are marked as Cu -x ZIF-8/PAN (x is the initial concentration of Cu (II) ion solution).
And (3) placing the ZIF-8/PAN composite nanofiber in a porcelain boat, and carbonizing at a high temperature in a nitrogen atmosphere in the whole process. Heating at a speed of 2 ℃/min, respectively staying at 100 ℃ and 250 ℃ for 1h, and staying at 700 ℃ for 1h after heating to obtain the target product.
The left graph in fig. 2 shows the appearance of the bimetal nanofiber, the granular matters are loaded on the surface, the space structure is good, and the average diameter of the fiber is 800nm; the right image is an enlarged detail morphology image, particles are uniformly distributed on the fiber, and no agglomeration phenomenon exists.
Fig. 3 is a transmission image of the carbonized catalyst, wherein the carbon fiber carrier has a porous structure, elements such as Zn, cu and the like are uniformly distributed, the dispersibility is good, and the agglomeration phenomenon is avoided.
Fig. 4 shows that the catalyst had both cuprous oxide and elemental copper present after carbonization, and the crystallinity was good.
FIG. 5 shows that Zn-N bonds are present in the catalyst after carbonization.
Comparative example 1
The preparation of the single metal supported catalyst differs from example 1 in that the adsorbed copper solution concentration is 0.
Comparative example 2
The preparation process of the bimetallic catalyst without porous structure is different from that of the embodiment 1 in that zinc salt and copper salt are added into spinning solution simultaneously in the spinning process, and in-situ growth and adsorption processes are avoided.
Application example 1
By catalysing CO under illumination 2 And cycloaddition reaction of Epibromohydrin (EBH) the catalytic performance of the composite catalyst was tested, and the catalytic reaction was carried out in a reaction vessel with quartz window. 60 mu L of EBH and 3mL of DMF are weighed into a reaction kettle, and 30mg of catalyst and 32mg (0.1 mmol) of tetrabutylammonium bromide (TBAB) are weighed as cocatalysts. Sealing the gas outlet of the reaction kettle, and introducing CO from the gas inlet 2 The gas reaches a certain pressure, then the gas inlet is closed to open the gas outlet, and CO is carried out 2 Filling and discharging for three times to ensure that the air in the kettle is completely replaced, and finally CO 2 The gas pressure was maintained at 1bar. After the reaction is finished for 10 hours, the reaction kettle is cooled to room temperature, and the reaction liquid is extracted by using a mixed system of deionized water and ethyl acetate. Finally taking supernatant, and carrying out qualitative analysis by using a gas chromatograph-mass spectrometer to determineThe components in the reaction solution were determined, and the conversion was quantitatively calculated by a gas chromatograph.
Comparative example 1 and comparative example 2 and example 1 were tested for catalytic performance, respectively.
As shown in FIG. 6, the cyclic effect of the catalyst in catalyzing the cycloaddition reaction of carbon dioxide and epoxide under the condition of illumination and the substrate expansion data are shown, and as can be seen from the graph, the conversion rate of the epoxide substrate is maintained above 90% after the cyclic use for a plurality of times, and the selectivity is not changed obviously. The catalyst has good cycle stability and substrate universality.
As shown in fig. 7, the substrate conversion was 74.2% using the catalyst of example 1; with the monometal catalyst of comparative example 1, the conversion of epoxy substrate was 32%; the conversion of the epoxy substrate was 24.5% using the catalyst of comparative example 2, which was a non-porous structure. The supported bimetallic porous carbon fiber catalyst has high catalytic activity.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The preparation method of the supported bimetal porous carbon nanofiber catalyst is characterized by comprising the following steps of:
step 1, preparing a nano polymer fiber containing zinc salt by adopting an electrostatic spinning method;
step 2, placing the nano polymer fiber in a methanol solution of 2-methylimidazole for in-situ growth to obtain a ZIF-8 loaded composite nano fiber;
step 3, absorbing heavy metal ions in the heavy metal ion aqueous solution by utilizing the composite nanofiber to obtain the bimetal composite nanofiber;
and 4, carbonizing the bimetal composite nanofiber to obtain the catalyst.
2. The method for preparing a supported bimetal porous carbon nanofiber catalyst according to claim 1, wherein in step 1, preparing a nano polymer fiber containing zinc salt specifically comprises:
dissolving polyacrylonitrile and zinc salt in an organic solvent, and mixing to obtain a stable and uniform electrostatic spinning precursor solution;
forming nano polymer fibers containing zinc salt through internal doping spinning by utilizing electrostatic spinning precursor solution;
wherein the mass ratio of zinc element in zinc salt to polyacrylonitrile is (0.5-2.5): 1.
3. The method for preparing a supported bimetal porous carbon nanofiber catalyst according to claim 1, wherein in step 1, the electrospinning method uses the following parameters: the high voltage between the anode and the cathode is 14kV, and the distance between the anode and the cathode copper plate is 19cm.
4. The method for preparing the supported bimetal porous carbon nanofiber catalyst according to claim 1, wherein the molar ratio of 2-methylimidazole to zinc ions in zinc salt is (2-6): 1 in the in-situ growth process of step 2.
5. The method for preparing the supported bimetal porous carbon nanofiber catalyst according to claim 1, wherein in the step 3, copper ions are selected, the concentration of a copper ion aqueous solution is 20-140mg/L, the pH of the copper ion aqueous solution is 2-6.5, the adsorption temperature is 25-55 ℃, and the adsorption time is 0.5-5h.
6. The method for preparing the supported bimetal porous carbon nanofiber catalyst according to claim 1, wherein in the step 4, the whole carbonization process is performed under an inert gas environment, the heating rate is 1-10 ℃/min, the catalyst is obtained after the catalyst stays for 0.5-5h at 100-250 ℃, and the catalyst stays for 0.5-5h at 300-900 ℃.
7. A supported bimetallic porous carbon nanofiber catalyst prepared by the preparation method of any one of claims 1 to 6.
8. The use of a supported bimetallic porous carbon nanofiber catalyst according to claim 7 for photo-thermal catalysis of CO 2 Cycloaddition reaction with epoxide.
9. The use according to claim 8, wherein the epoxide is at least one of styrene oxide, epichlorohydrin, bromopropane oxide, propylene oxide, butylene oxide.
10. The use according to claim 8, wherein the cycloaddition reaction conditions are: CO 2 The pressure is 0.5-15MPa, and the reaction time is 5-10h.
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| CN113540478A (en) * | 2021-07-12 | 2021-10-22 | 南京工业大学 | Porous carbon-based nanofiber film material loaded by metal single atom and metal derivative thereof, and preparation method and application thereof |
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| US20150143806A1 (en) * | 2012-11-15 | 2015-05-28 | Kevin Lee Friesth | Quintuple-Effect Generation Multi-Cycle Hybrid Renewable Energy System with Integrated Energy Provisioning, Storage Facilities and Amalgamated Control System Cross-Reference to Related Applications |
| CN113540478A (en) * | 2021-07-12 | 2021-10-22 | 南京工业大学 | Porous carbon-based nanofiber film material loaded by metal single atom and metal derivative thereof, and preparation method and application thereof |
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