CN111569875A - Copper/porous carbon nanorod material, preparation method and application - Google Patents
Copper/porous carbon nanorod material, preparation method and application Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 73
- 239000010949 copper Substances 0.000 title claims abstract description 73
- 239000002073 nanorod Substances 0.000 title claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000013148 Cu-BTC MOF Substances 0.000 claims abstract description 20
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 16
- -1 amine compounds Chemical class 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- QPGJEXWQNJCCSN-UHFFFAOYSA-K [Cu+3].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 Chemical compound [Cu+3].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 QPGJEXWQNJCCSN-UHFFFAOYSA-K 0.000 claims abstract description 4
- 230000015556 catabolic process Effects 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000006731 degradation reaction Methods 0.000 claims abstract description 3
- 239000002105 nanoparticle Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 8
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 8
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000012621 metal-organic framework Substances 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000002131 composite material Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000593 degrading effect Effects 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 4
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 239000013084 copper-based metal-organic framework Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001338 self-assembly 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000009827 uniform distribution Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a copper/porous carbon nanorod material, a preparation method and application thereof. Firstly, dissolving trimesic acid and sodium hydroxide or potassium hydroxide in an aqueous solution, adding an aqueous solution of soluble metal copper salt, and stirring at normal temperature to prepare a copper trimesate (Cu-BTC) precursor; and calcining the Cu-BTC precursor in a protective atmosphere, and cooling to obtain the copper/porous carbon nanorod material. The preparation method abandons the means of organic solvent, high temperature, high pressure and the like required in the prior MOF preparation process, adopts a normal-temperature aqueous solution method for preparation, and has simple and easy preparation process and environmental protection. The prepared copper/porous carbon nano-rod material has excellent catalytic degradation effect on phenolic and amine compounds in wastewater.
Description
Technical Field
The invention belongs to the technical field of preparation of water treatment materials, and relates to a copper/porous carbon nanorod composite material, a preparation method and application.
Background
The waste water containing phenolic compounds and amine compounds is one of the industrial waste water with great harm and wide pollution range in the world today. If the waste water is not treated, the waste water can be directly discharged and irrigated to farmlands to pollute the atmosphere, water, soil and food. Therefore, phenolic and amine compounds are receiving more and more attention. Currently, many methods are used for phenolic compounds and amine compounds, such as adsorption, catalysis, membrane separation, extraction, precipitation, activated sludge, and biofilm methods. Among them, the sodium borohydride-assisted catalytic reduction method is considered to be a promising method due to its advantages of simplicity and rapidity. However, some conventional catalyst materials, such as noble metals like Au and Ag, are limited by price and catalytic performance, and cannot be practically applied. Therefore, we propose to prepare a copper/carbon nano rod material derived from a copper-based metal organic framework material for degrading phenolic compounds and amine compounds.
Metal Organic Frameworks (MOFs) are a class of crystalline porous materials with periodic network structures formed by the interconnection of inorganic metal centers (metal ions or metal clusters) and organic ligands through self-assembly. MOF materials, due to their stable structure, the presence of a large number of organic ligands and the uniform distribution of metal ions, have been used as templates by many researchers to synthesize derivative materials of different structures and components, including carbon materials, metal compounds, and metal compound carbon composites in general. MOF derived materials have now been widely used in the fields of energy storage and conversion such as lithium ion batteries, lithium sulfur batteries, supercapacitors and electrocatalysis, but there have been few reports in the field of wastewater treatment, particularly in applications for removing phenolic compounds from water. For example, Zhao et al and Niu et al use Cu-MOF prepared by solvothermal method as a precursor, and obtain the copper-based carbon composite material after calcination. The two copper-based carbon composites were found to be capable of catalyzing the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) (X.ZHao, Y.Tan, F.Wu, H.Niu, Z.Tang, Y.Cai, J.P.Giesy, Sci.TotalEnviron,2016,571, 380. 387; H.Niu, S.Liu, Y.Cai, F.Wu, X.ZHao, Micropo.Mesopo.Mater.,2016,2019,48-53) as catalysts. However, the preparation of these reported Cu-MOF precursors often requires the use of organic solvents, high temperatures, high pressures, and the like, is environmentally hazardous, and is not conducive to large-volume industrial production. In order to solve the problems, a cheap and easily obtained trimesic acid ligand is adopted to react with a metal copper salt in a water phase by a normal-temperature precipitation method to obtain a copper trimesate precursor.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming means such as organic solvent, high temperature, high pressure and the like required in most of the existing MOF preparation processes, and provides a novel copper/porous carbon nanorod material which is simple, convenient, efficient and used for degrading phenols and amines and a preparation method thereof.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the copper/porous carbon nanorod material is characterized by comprising copper nanoparticles and porous carbon nanorods, wherein the copper nanoparticles are distributed in a porous carbon nanorod matrix, the average length of the carbon nanorods is 200-1500nm, the average diameter of the carbon nanorods is 50-200nm, the average size of the copper nanoparticles is 20-80nm, and the specific surface area of the copper/porous carbon nanorod material is 50-200m2/g。
The preparation method of the copper/porous carbon nanorod material comprises the following steps:
(1) mixing trimesic acid (H)3BTC) and sodium hydroxide or potassium hydroxide are dissolved in the aqueous solution, the aqueous solution of soluble metal copper salt is added, the mixture is mixed and stirred at normal temperature, and then the precursor of copper trimesate (Cu-BTC) is obtained after centrifugal washing and drying;
(2) and (2) calcining the Cu-BTC precursor obtained in the step (1) in a protective atmosphere, and cooling to obtain the copper/porous carbon nanorod material.
Further, in the step (1), the amount ratio of the trimesic acid to the sodium hydroxide or potassium hydroxide is 1: 3; the concentration of the aqueous solution of the trimesic acid is 0.01-0.1 mol/L.
Further, in the step (1), the soluble metal copper salt is one or more of copper sulfate, copper acetate, copper nitrate and copper chloride.
Further, in the step (1), the concentration of the aqueous solution of the copper metal salt is 0.01-0.1 mol/L.
Further, in the step (1), the mixing and stirring time is 5 to 120 min. The drying condition is 70 ℃ and 12 h.
Further, in the step (2), the protective atmosphere is nitrogen or argon; the temperature rise rate of the calcination is 1-10 ℃/min, the calcination time is 1-24 hours, and the calcination temperature is 500-1000 ℃.
The copper/porous carbon nanorod material is applied to a catalyst for degrading phenolic or amine compounds.
Further, the phenolic or amine compound is p-nitrophenol, o-nitrophenol or p-nitroaniline.
Compared with the prior art, the invention has the advantages that:
(1) cheap ligand and metal salt are used as raw materials, so that the price is low.
(2) Most measures such as organic solvents, high temperature, high pressure and the like required in the MOF preparation process are abandoned, and the MOF is prepared by a normal-temperature water solution method, so that the preparation process is simple and environment-friendly.
(3) Can realize the mass preparation of the porous copper-carbon nano rods and has very high application prospect.
(4) The prepared copper-carbon nano rod material has excellent catalytic degradation performance on phenolic compounds and amine compounds which are difficult to degrade in wastewater treatment due to unique appearance and structural characteristics.
Drawings
FIG. 1 (a) is an SEM picture of a Cu-BTC precursor of example 1; (b) the XRD pattern of the Cu-BTC precursor prepared in example 1 was used.
FIG. 2 is an SEM photograph of the copper/carbon nanorods prepared in example 1.
FIG. 3 is a TEM spectrum of the copper/carbon nanorods prepared in example 1.
FIG. 4 is an XRD pattern of the copper/carbon nanorods prepared in example 1.
FIG. 5 is a nitrogen adsorption-desorption isotherm of the copper/carbon nanorods prepared in example 1.
In FIG. 6, (a), (b), and (c) are UV-vis spectra of the copper/carbon nanorods for catalytically degrading 4-NP, O-NP, and 4-NA, respectively, prepared in example 1.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1:
the preparation process of the copper/carbon nanorod material of the embodiment is as follows:
(1) dissolving 2mmol of trimesic acid and 6mmol of sodium hydroxide in 25mL of aqueous solution, and stirring at room temperature until the trimesic acid and the sodium hydroxide are completely dissolved; dissolving 3mmol of copper acetate in 25mL of deionized water, and continuously stirring at room temperature for a period of time until the copper acetate is completely dissolved to obtain a copper acetate aqueous solution; mixing the aqueous solution of trimesic acid and sodium hydroxide with the aqueous solution of copper acetate, and stirring at normal temperature for 5 min; centrifuging, and washing with deionized water or ethanol for 3 times; drying the precursor in a forced air drying oven at 60 ℃ for 12h to obtain a Cu-BTC precursor;
(2) and (2) heating the Cu-BTC precursor obtained in the step (1) to 800 ℃ at the speed of 5 ℃/min in a tube furnace in a nitrogen atmosphere, and calcining for 2 hours to obtain the copper/carbon nanorod material.
In the prepared copper/carbon nanorod material, copper nanoparticles are distributed in a porous carbon nanorod matrix, the average length of a carbon nanorod is 500nm, the average diameter of the carbon nanorod is 100nm, the average size of the copper nanoparticles is 26nm, and the specific surface area of the copper/porous carbon nanorod material is 103m2/g。
FIG. 1 is an SEM image and an XRD spectrum of the Cu-BTC precursor prepared in the present example, and it can be seen from FIG. 1 that the Cu-BTC nanorod is obtained. Fig. 2, fig. 3, fig. 4, and fig. 5 are SEM images, TEM images, XRD images, and nitrogen adsorption-desorption isotherms of the copper/carbon nanorod composite material prepared in this example, and it can be seen from the test results that the copper/carbon nanorod composite material is obtained after calcination, and the copper-carbon nanorod composite material maintains the nanorod morphology of the Cu-BTC precursor, and the copper nanoparticles are dispersed in the carbon nanorod matrix.
The method for catalytically degrading p-nitrophenol, o-nitrophenol and p-nitroaniline by using the copper/carbon nanorod material prepared in the embodiment comprises the following steps:
(1) respectively dissolving p-nitrophenol, o-nitrophenol and p-nitroaniline in deionized water, and respectively preparing 0.01mol/L aqueous solution of p-nitrophenol, o-nitrophenol and p-nitroaniline; dissolving sodium borohydride in water to prepare 0.1mol/L sodium borohydride aqueous solution; ultrasonically dispersing the copper/carbon nano rod composite material in water to prepare 2mg/mL copper/carbon nano rod material aqueous dispersion.
(2) To a standard quartz cuvette having an optical path of 1.0cm and a volume of 4mL, 2.5mL of an aqueous sodium borohydride solution and 25. mu.l of an aqueous solution of p-nitrophenol, o-nitrophenol or p-nitroaniline were sequentially added, followed by 10. mu.l of an aqueous dispersion of copper/carbon nanorod material. After adding the copper/carbon nano-rod material, measuring the ultraviolet visible absorption spectrum at intervals;
fig. 6 is a graph showing the ultraviolet-visible absorption spectrum of the copper/carbon nanorod material prepared in this example as a catalyst for degrading p-nitrophenol, o-nitrophenol, and p-nitroaniline. As can be seen from FIG. 6, after the copper-carbon nanorod catalyst prepared in this example is added, p-nitrophenol, o-nitrophenol and p-nitroaniline can be completely degraded.
Example 2:
the preparation process of the copper/carbon nanorod material of the embodiment is as follows:
(1) dissolving 2mmol of trimesic acid and 6mmol of sodium hydroxide in 25mL of aqueous solution, and stirring at room temperature until the trimesic acid and the sodium hydroxide are completely dissolved; dissolving 3mmol of copper sulfate in 25mL of deionized water, continuously stirring at room temperature for a period of time until the copper sulfate is completely dissolved, mixing trimesic acid and sodium hydroxide aqueous solution with copper sulfate aqueous solution, and stirring at normal temperature for 1.5 hours; centrifuging, and washing with deionized water or ethanol for 3 times; drying the precursor in a blast drying oven at 70 ℃ for 12h to obtain a Cu-BTC precursor;
(2) and (3) heating the obtained Cu-BTC precursor to 800 ℃ at the speed of 10 ℃/min in a tube furnace in the nitrogen atmosphere, and calcining for 1.5 hours to obtain the copper/carbon nanorod material.
In the copper/carbon nanorod material prepared in the embodiment, copper nanoparticles are distributed in the porous carbon nanorod matrix, the average length of the carbon nanorod is 1000nm, the average diameter of the carbon nanorod is 80nm, and the copper nanoparticles areThe average size of the particles is 20nm, and the specific surface area of the copper/porous carbon nanorod material is 65m2/g。
Example 3:
the preparation process of the copper/carbon nanorod composite material of the embodiment is as follows:
(1) dissolving 2mmol of trimesic acid and 6mmol of potassium hydroxide in 100mL of aqueous solution, and stirring at room temperature until the trimesic acid and the potassium hydroxide are completely dissolved; dissolving 3mmol of copper nitrate in 50mL of deionized water, and continuously stirring at room temperature for a period of time until the copper nitrate is completely dissolved; mixing trimesic acid, sodium hydroxide aqueous solution and copper nitrate aqueous solution, and stirring for 1.5 hours at normal temperature; centrifuging, and washing with deionized water or ethanol for 3 times; drying the precursor in a blast drying oven at 70 ℃ for 12h to obtain a Cu-BTC precursor;
(2) and (3) heating the obtained Cu-BTC precursor to 700 ℃ at the speed of 8 ℃/min in a tube furnace in the nitrogen atmosphere, and calcining for 3 hours to obtain the copper/carbon nanorod material.
In the copper/carbon nanorod composite material prepared in this example, copper nanoparticles are distributed in the porous carbon nanorod matrix, the average length of the carbon nanorods is 800nm, the average diameter is 70nm, the average size of the copper nanoparticles is 40nm, and the specific surface area of the copper/porous carbon nanorod material is 74m2/g。
Example 4:
the preparation process of the copper/carbon nanorod composite material of the embodiment is as follows:
(1) dissolving 4mmol of trimesic acid and 12mmol of potassium hydroxide in 50mL of aqueous solution, and stirring at room temperature until the trimesic acid and the potassium hydroxide are completely dissolved; dissolving 4mmol of copper chloride in 50mL of deionized water, and continuously stirring at room temperature for a period of time until the copper chloride is completely dissolved; mixing trimesic acid, sodium hydroxide aqueous solution and copper chloride aqueous solution, and stirring for 2 hours at normal temperature; centrifuging, and washing with deionized water or ethanol for 3 times; drying the precursor in a blast drying oven at 70 ℃ for 12h to obtain a Cu-BTC precursor;
(2) and (3) heating the obtained Cu-BTC precursor to 1000 ℃ at a speed of 4 ℃/min in a tube furnace in a nitrogen atmosphere, and calcining for 1 hour to obtain the copper/carbon nanorod material.
The true bookIn the copper/carbon nanorod composite material prepared in the example, copper nanoparticles are distributed in a porous carbon nanorod matrix, the average length of carbon nanorods is 1200nm, the average diameter is 80nm, the average size of the copper nanoparticles is 60nm, and the specific surface area of the copper/porous carbon nanorod material is 90m2/g。
Example 5:
the preparation process of the copper/carbon nanorod composite material of the embodiment is as follows:
(1) dissolving 4mmol of trimesic acid and 6mmol of sodium hydroxide in 50mL of aqueous solution, and stirring at room temperature until the trimesic acid and the sodium hydroxide are completely dissolved; dissolving 2mmol of copper nitrate and 2mmol of copper acetate in 50mL of deionized water, and continuously stirring at room temperature for a period of time until complete dissolution; mixing trimesic acid, sodium hydroxide aqueous solution and copper acetate aqueous solution, and stirring at normal temperature for 0.5 hour; centrifuging, and washing with deionized water or ethanol for 3 times; drying the precursor in a blast drying oven at 70 ℃ for 12h to obtain a Cu-BTC precursor;
(2) and (3) heating the obtained Cu-BTC precursor to 850 ℃ at 3 ℃/min in a tube furnace in a nitrogen atmosphere, and calcining for 2 hours to obtain the copper/carbon nanorod material.
In the copper/carbon nanorod composite material prepared in the embodiment, copper nanoparticles are distributed in the porous carbon nanorod matrix, the average length of the carbon nanorod is 800nm, the average diameter is 50nm, the average size of the copper nanoparticles is 25nm, and the specific surface area of the copper/porous carbon nanorod material is 80m2/g。
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (9)
1. The copper/porous carbon nanorod material is characterized by comprising copper nanoparticles and porous carbon nanorods, wherein the copper nanoparticles are distributed in a porous carbon nanorod matrix, the average length of the carbon nanorods is 200-1500nm, the average diameter of the carbon nanorods is 50-200nm, and the copper nanoparticles are flatThe average size is 20-80nm, and the specific surface area of the copper/porous carbon nanorod material is 50-200m2/g。
2. The method for preparing the copper/porous carbon nanorod material according to claim 1, comprising the following steps:
(1) mixing trimesic acid (H)3BTC) and sodium hydroxide or potassium hydroxide are dissolved in the aqueous solution, the aqueous solution of soluble metal copper salt is added, the mixture is mixed and stirred at normal temperature, and then the precursor of copper trimesate (Cu-BTC) is obtained after centrifugal washing and drying;
(2) and (2) calcining the precursor obtained in the step (1) in a protective atmosphere, and cooling to obtain the copper/porous carbon nanorod material.
3. The production method according to claim 2, wherein in the step (1), the mass ratio of the trimesic acid and the sodium hydroxide or potassium hydroxide is 1: 3; the concentration of the aqueous solution of the trimesic acid is 0.01-0.1 mol/L.
4. The method according to claim 2, wherein in the step (1), the soluble metal copper salt is one or more of copper sulfate, copper acetate, copper nitrate and copper chloride.
5. The method according to claim 2, wherein in the step (1), the concentration of the aqueous solution of the copper metal salt is 0.01 to 0.1 mol/L.
6. The production method according to claim 2, wherein in the step (1), the mixing stirring time is 5 to 120 min. The drying condition is 70 ℃ and 12 h.
7. The production method according to claim 2, wherein in the step (2), the protective atmosphere is nitrogen or argon; the temperature rise rate of the calcination is 1-10 ℃/min, the calcination time is 1-24 hours, and the calcination temperature is 500-1000 ℃.
8. The use of the copper/porous carbon nanorod material according to claim 1, characterized in that it is a catalyst for the degradation of phenolic or amine compounds.
9. The use of the copper/porous carbon nanorod material according to claim 8, wherein the phenolic or amine compound is p-nitrophenol, o-nitrophenol or p-nitroaniline.
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