CN110961105A - Graphene-hollow copper nanosphere composite material and preparation method and application thereof - Google Patents
Graphene-hollow copper nanosphere composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN110961105A CN110961105A CN201911178742.2A CN201911178742A CN110961105A CN 110961105 A CN110961105 A CN 110961105A CN 201911178742 A CN201911178742 A CN 201911178742A CN 110961105 A CN110961105 A CN 110961105A
- Authority
- CN
- China
- Prior art keywords
- graphene
- copper
- hollow copper
- composite material
- heating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000010949 copper Substances 0.000 title claims abstract description 161
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 158
- 239000002077 nanosphere Substances 0.000 title claims abstract description 121
- 239000002131 composite material Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 32
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 25
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- 150000001879 copper Chemical class 0.000 claims abstract description 11
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 11
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 44
- 239000002105 nanoparticle Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 4
- 239000011807 nanoball Substances 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 239000002114 nanocomposite Substances 0.000 abstract description 4
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 3
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 20
- 230000009467 reduction Effects 0.000 description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 17
- 238000003756 stirring Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000003344 environmental pollutant Substances 0.000 description 10
- 231100000719 pollutant Toxicity 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- 239000011805 ball Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a graphene-hollow copper nanosphere composite material and a preparation method and application thereof. The graphene-hollow copper nanosphere composite material is a composite material which uniformly loads hollow copper nanospheres on the surface of graphene, wherein the hollow copper nanospheres mainly comprise copper and cuprous oxide nanocomposite materials. The preparation method of the composite material comprises the following steps: 1) dispersing graphene oxide prepared by an improved Hummers method into a first part of ethylene glycol to form a solution A; 2) dissolving a copper salt in a second part of ethylene glycol to form a metal precursor solution B; 3) and mixing the solution A and the metal precursor solution B, and washing and drying a product obtained by heating through a controllable oxidation heating method to obtain the graphene-hollow copper nanosphere composite material. The composite material can be applied to the preparation of p-aminophenol by catalytic reduction hydrogenation of p-nitrophenol. Compared with the traditional copper-based catalyst, the material has a higher catalytic kinetic constant.
Description
Technical Field
The invention relates to a graphene-hollow copper nanosphere composite material and a preparation method and application thereof, and particularly relates to a graphene-hollow copper nanosphere composite material, a preparation method and application of the composite material in a pollutant p-nitrophenol hydrogenation reduction reaction.
Background
The water body pollution seriously threatens human health and is mainly caused by the nonstandard discharge of wastewater, waste materials and domestic sewage generated in the chemical production process. The p-nitrophenol is one of main pollutants discharged in petrochemical production, has good biochemical stability, is not easy to degrade, has no neglectable harm to water pollution and human health, and has the concentration of less than 10ng/L when being discharged according to the regulations of the American environmental protection Association. The treatment of p-nitrophenol is imminent.
Para-aminophenol is a common fine organic chemical intermediate, is mainly used in the fields of medicines, dyes, rubber antioxidants and the like, and has an indispensable position in human society. Therefore, the development of a novel material for the hydrogenation reduction of pollutant p-nitrophenol into fine organic chemical intermediate p-aminophenol has great development space.
Compared with the traditional bulk material, the nano material has large contact area with pollutants and better treatment efficiency due to the characteristics of large specific surface, small size effect, quantum tunneling effect and the like, so that the novel material designed based on the nano technology has a potentially excellent effect of treating the pollutants. Graphene is a polymer made of carbon atoms in sp2The novel two-dimensional nano material composed of the hybrid orbit has a special pi-bond structure. In addition, graphene has the characteristics of high thermal conductivity, high visible light transmittance, ultrahigh electron mobility and the like, and the characteristics are endowed by the grapheneIt has great potential in the fields of optics, electricity, mechanics and the like. By the oxidation stripping of the original graphite, graphene oxide with rich oxygen-containing functional groups, in which carbon atoms are hybridized in an sp3 form, can be obtained. The graphene and the graphene oxide have extremely high theoretical specific surface areas, are typical two-dimensional reinforced phases, and can be conjugated with metals, metal oxides, non-metals and biomacromolecules to construct a novel composite nano material.
The graphene nanocomposite shows unique physical and chemical properties of graphene on the basis of the original material. Graphene-based composites have thus far shown great potential for applications in a variety of areas, such as optoelectronic devices, supercapacitors, coating overlays, biosensors, and the like.
Furthermore, the overlap between the expansion orbital of graphene and the d-orbital of the transition metal may lead to strong metal-support interactions, which may modulate the electron density at the metal nanoparticle-graphene interface. In addition, the graphene realizes the synergistic promotion of a reaction mechanism by the advantages of large surface area and high adsorption capacity through adsorbing the substrate near the active site of the metal nanoparticle. Graphene-supported metal nanoparticle composites are therefore widely used as heterogeneous catalysts for a variety of organic reactions, including reduction, oxidation, and coupling, among other processes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a material capable of effectively catalyzing the hydrogenation reduction of p-nitrophenol to p-aminophenol.
In order to achieve the above object, the present invention provides a graphene-hollow copper nanosphere composite material, wherein the composite material is a composite material in which hollow copper nanospheres are uniformly loaded on a surface of graphene. The hollow copper nanospheres comprise elemental copper. In the graphene-hollow copper nanosphere composite material, preferably, the outer diameter of the hollow copper nanosphere is greater than 40nm and less than 500nm, and the spherical shell thickness of the hollow copper nanosphere is 10-30 nm.
In the graphene-hollow copper nanosphere composite material, preferably, the hollow copper nanospheres comprise copper nanoparticles and cuprous oxide nanoparticles; more preferably, the hollow copper nanospheres are compounded by copper nanoparticles, cuprous oxide nanoparticles and graphene oxide; further preferably, the hollow copper nanoball comprises 40-60% of carbon atoms, 20-35% of oxygen atoms and 20-40% of copper atoms, based on the total atomic number of the hollow copper nanoball. In a specific embodiment, the hollow copper nanosphere is composed of 39% of copper nanoparticles, 15% of cuprous oxide nanoparticles and 46% of graphene oxide based on the total mass of the hollow copper nanosphere.
The invention also provides a preparation method of the graphene-hollow copper nanosphere composite material, wherein the preparation method comprises the following steps:
(1) dispersing graphene oxide prepared by a modified Hummers method (Improved Hummers' method) into a first portion of ethylene glycol to form a solution A;
(2) dissolving a copper salt in a second part of ethylene glycol to form a metal precursor solution B;
(3) and mixing the solution A and the metal precursor solution B to obtain a mixed solution C, heating the mixed solution C (preferably by using a controllable oxidation heating method), and washing and drying a product obtained by heating to obtain the graphene-hollow copper nanosphere composite material.
In the above method for preparing a graphene-hollow copper nanosphere composite, preferably, in the step (2), the copper salt includes one or a combination of two or more of copper acetate, anhydrous copper sulfate, copper chloride, basic copper carbonate and copper nitrate; more preferably, the copper salt is copper acetate.
In the above preparation method of the graphene-hollow copper nanosphere composite material, preferably, in the step (2), the dosage ratio of the copper salt to the graphene oxide is 0.3-0.7mmol:30 mg; more preferably, the dosage ratio of the copper salt to the graphene oxide is 0.5mmol:30 mg.
In the preparation method of the graphene-hollow copper nanosphere composite material, preferably, in the step (1), the dosage ratio of the first part of ethylene glycol to the graphene oxide is 25-150mL:30 mg; more preferably, the dosage ratio of the first part of ethylene glycol to the graphene oxide is 75mL:30 mg.
In the preparation method of the graphene-hollow copper nanosphere composite material, in the step (2), the dosage ratio of the second part of ethylene glycol to the graphene oxide is 10-50mL:30 mg; more preferably, the amount ratio of the second part of ethylene glycol to the graphene oxide is 25mL to 30 mg.
In the above method for preparing the graphene-hollow copper nanosphere composite material, preferably, in step 3), the mixing is performed by stirring; more preferably, the stirring time is 30 to 90 minutes, and still more preferably, the stirring time is 60 minutes.
In the above method for preparing the graphene-hollow copper nanosphere composite material, preferably, in the step (3), the step of heating the mixed solution C includes the following steps: 1) heating the solution C under inert atmosphere or vacuum at 150-190 deg.C (preferably 170 deg.C) for 0.5-1h (preferably 0.5 h); 2) then heating under an oxidizing atmosphere, wherein the heating temperature is 150-190 ℃ (preferably 170 ℃), and the heating time is 0.5-2h (preferably 1.5 h); preferably, the heating mode in the step 1) and the step 2) is reflux heating. Wherein, the oxidizing atmosphere can be selected from air or oxygen atmosphere.
In one embodiment, in the step (3), the heating the mixed solution C includes the steps of: 1) heating the mixed solution C to a preset temperature, wherein the preset temperature is 150-190 ℃, and the preset temperature is preferably 170 ℃; 2) heating to a preset temperature, and then carrying out vacuum-pumping reflux heating for 0.5-1 hour, wherein the time for vacuum-pumping heating is preferably 0.5 hour; 3) then introducing an oxidizing atmosphere, preferably oxygen, and continuing to heat and reflux for 0.5-2 hours, wherein the oxidizing atmosphere is air or oxygen; the time of the heating reflux is preferably 1.5 hours.
In the above preparation method of the graphene-hollow copper nanosphere composite material, preferably, in the step (3), the mixing is performed by stirring; more preferably, the stirring time is 30 to 90 minutes, and still more preferably, the stirring time is 60 minutes.
In the above method for preparing a graphene-hollow copper nanosphere composite, preferably, in step (1), the graphene oxide is prepared by a preparation method comprising the following steps:
A. mixing graphite powder and potassium permanganate to obtain mixed powder, mixing concentrated sulfuric acid and concentrated phosphoric acid to obtain mixed acid, and adding the mixed powder into the mixed acid for heating reaction;
B. cooling the mixture reacted in the step A to room temperature, adding an ice-water mixture to obtain a mixed solution, and dropwise adding a hydrogen peroxide solution into the mixed solution until the mixed solution is bright yellow;
C. and C, washing and ultrasonically treating the solid product obtained in the step B, and drying to obtain the graphene oxide.
In the preparation method of the graphene oxide, the concentrated sulfuric acid is preferably concentrated sulfuric acid with a mass concentration of more than or equal to 85.0%; the concentrated phosphoric acid is preferably concentrated phosphoric acid with the mass concentration of more than or equal to 85.0 percent.
In the preparation method of the graphene oxide, the mass ratio of the graphite powder to the potassium permanganate is preferably 1: 6; the volume ratio of the concentrated sulfuric acid to the concentrated phosphoric acid is preferably 9: 1; the heating temperature is preferably 50 ℃, and the heating time is preferably 12 hours.
In the above graphene oxide preparation method, the concentration of the hydrogen peroxide is preferably 30%; the washing is preferably performed by hydrochloric acid washing and deionized water washing, the mass concentration of the hydrochloric acid is more preferably 30%, the number of times of hydrochloric acid washing is more than 3, and the number of times of deionized water washing is more than 3; the washing and the ultrasonic treatment are preferably carried out by using an ultrasonic cleaning machine, the ultrasonic treatment is carried out while the washing is carried out, the ultrasonic treatment is beneficial to realizing the stripping between layers of the graphene oxide, and a single-layer sheet is formed as far as possible; the drying is preferably carried out by means of freeze-drying.
In a specific embodiment of the above method for preparing graphene oxide, the mass ratio of the graphite powder to the potassium permanganate is preferably 1: 6; the volume ratio of the concentrated sulfuric acid to the concentrated phosphoric acid is preferably 9: 1; the dosage ratio of the graphite powder to the concentrated sulfuric acid is 1g:12 mL; the volume ratio of the ice-water mixture to the concentrated phosphoric acid is 10: 1.
In the above method for preparing the graphene-hollow copper nanosphere composite, preferably, in the step (3), the drying is vacuum drying.
In the preparation method of the graphene-hollow copper nanosphere composite material, preferably, in the step (3), the drying temperature is 60-100 ℃; more preferably, the temperature of the drying is 80 ℃.
In the above method for preparing the graphene-hollow copper nanosphere composite material, preferably, in the step (3), the drying time is 6 to 12 hours; more preferably, the drying time is 8 hours.
In the above method for preparing the graphene-hollow copper nanosphere composite material, preferably, in the step (3), the solvent used for washing is ethanol.
In the above method for preparing the graphene-hollow copper nanosphere composite material, preferably, in the step (3), the number of times of washing the ground is at least 3 times.
The preparation method of the graphene-hollow copper nanosphere composite material uses a controllable oxidation heating method to control the oxidation degree of the oxide by controlling the contact of the reactant and oxygen in the heating process, thereby realizing the acquisition of the 0-valent copper component
According to the preparation method of the graphene-hollow copper nanosphere composite material, the graphene oxide is used as a template to realize the attachment of the copper precursor, and the growth of the hollow copper nanospheres on the surface of the graphene is realized by using a controllable oxidation heating method. The hollow copper nanospheres are formed by compounding copper nanoparticles, cuprous oxide nanoparticles and graphene oxide. The invention also provides application of the graphene-hollow copper nanosphere composite material in preparation of p-aminophenol by reduction and hydrogenation of p-nitrophenol, wherein the graphene-hollow copper nanosphere composite material plays a catalytic role in the preparation of the p-aminophenol by reduction and hydrogenation of the p-nitrophenol.
In the above application, preferably, the reducing agent for preparing p-aminophenol by reductive hydrogenation of p-nitrophenol is sodium borohydride; more preferably, the amount ratio of p-nitrophenol to catalyst is 1mmol:50 mg.
The preparation method comprises the following steps of (1) preparing p-aminophenol by reducing and hydrogenating p-nitrophenol by using a graphene-hollow copper nanosphere composite material as a catalyst: adding 0.2mL of 1mmol/L p-nitrophenol solution into a reaction container, adding 2mL of deionized water, 0.5mL of 0.5mol/L sodium borohydride solution and 0.1mL of catalyst solution (aqueous solution of 5mg/50mL of graphene-hollow copper nanosphere composite material) to react to obtain p-aminophenol.
The hollow copper nanospheres in the graphene-hollow copper nanosphere composite material provided by the invention contain 0-valent copper, so that the efficient hydrogenation reduction of p-nitrophenol can be realized; particularly, in a better technical scheme, the hollow copper nanospheres are a composite system of metal and metal oxide, and are very beneficial to the catalytic components to play a synergistic effect to realize the efficient hydrogenation reduction of the nitrophenol. According to the preparation method of the graphene-hollow copper nanosphere composite material, the oxidation degree of copper element in a product is controlled by adopting a controllable oxidation heating method, so that the formation of the hollow copper nanosphere containing 0-valent copper and the graphene composite material is realized, and the formation difference of the hollow copper nanosphere containing 0-valent copper and cuprous oxide and the graphene composite material can be realized by adjusting when needed; in addition, the preparation method provided by the invention firstly prepares high-quality graphene oxide, and realizes the adhesion and growth of copper components by using the graphene oxide as a template, and finally forms the graphene-hollow copper nanosphere composite material through oxidation control in the process.
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
1. the invention provides a graphene-hollow copper nanosphere composite material based on copper nanoparticles, cuprous oxide nanoparticles and graphene oxide. The scheme realizes the regulation and control of the metal and metal oxide composite structure by a controllable oxidation heating method, and plays a synergistic role to realize high catalytic activity.
2. The graphene-hollow copper nanosphere composite material provided by the invention can effectively degrade pollutant p-nitrophenol; compared with the traditional copper-based catalyst, the graphene-loaded hollow copper ball has the advantages of large surface area, multiple active sites, rich pore channel structures and the like, the graphene can realize close adsorption with p-nitrophenol through pi-pi bonds, and the catalytic performance is promoted by the electron transfer cooperation between the graphene and the hollow copper ball.
3. Compared with the traditional copper-based catalyst, the graphene-hollow copper nanosphere composite material provided by the invention has a higher catalytic kinetic constant and better catalytic performance.
In a specific embodiment, the kinetic constant of the graphene-hollow copper nanosphere composite material p-nitrophenol provided by the invention is as high as 129000min-1g-1Complete conversion of the contaminants can be achieved within 210 seconds.
4. The preparation method provided by the invention is simple, has relatively low material cost and has better industrial application value
Drawings
Fig. 1A and 1B are transmission electron microscope images of the graphene-hollow copper nanosphere composite provided in example 1.
Fig. 2 is a scanning electron microscope image of the graphene-hollow copper nanosphere composite provided in example 1.
Fig. 3 is an X-ray crystal diffraction spectrum of the graphene-hollow copper nanosphere composite provided in example 1.
Fig. 4 is a uv-vis absorption spectrum diagram of the catalytic effect of the graphene-hollow copper nanosphere composite material provided in example 1.
FIG. 5 shows the catalytic effect ln of the graphene-hollow copper nanosphere composite material provided in example 1 (A)i/A0) Graph with time t.
Fig. 6A and 6B are a transmission electron microscope image and a scanning electron microscope image of a cross section of the graphene-hollow copper nanosphere composite provided in example 1, respectively.
Fig. 7 shows the result of inductively coupled plasma emission spectroscopy on the graphene-hollow copper nanosphere composite material provided in example 1.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a graphene-hollow copper nanosphere composite material, which is prepared by the following specific steps:
1) preparing graphene oxide by using an improved Hummers method, which specifically comprises the following steps:
A. mixing 0.75g of graphite powder and 4.5g of potassium permanganate to obtain mixed powder, mixing 90mL of concentrated sulfuric acid and 10mL of concentrated phosphoric acid, slowly adding the mixed powder into the mixed acid, stirring and heating in a water bath at 50 ℃ for 12 hours to react;
B. cooling the reacted mixture to room temperature, adding 100mL of ice-water mixture to obtain a mixed solution, dropwise adding a hydrogen peroxide solution with the mass concentration of 30% to the obtained mixed solution until the mixed solution is completely bright yellow, and stirring the mixed solution while dropwise adding hydrogen peroxide when the hydrogen peroxide solution is dropwise added;
C. and C, washing the solid product obtained in the step B with hydrochloric acid with the mass concentration of 30% for 3 times, washing with deionized water for 3 times, continuously performing ultrasonic treatment with an ultrasonic cleaning machine during washing to strip the layers of the graphene oxide as far as possible to form a single-layer sheet, and finally freeze-drying the washed product to obtain the graphene oxide.
2) 30mg of the graphene oxide powder prepared above was dispersed in 75mL of ethylene glycol to form a homogeneous solution a.
3) 0.5mmol of copper acetate is dissolved in 25mL of ethylene glycol to form a metal precursor mixed solution B.
4) And mixing the solution A and the metal precursor mixed solution B, stirring for 60 minutes to obtain a uniform suspension solution, carrying out reflux heating on the uniform suspension solution for 0.5 hour at 170 ℃ under a vacuum condition to carry out reaction, then introducing oxygen, and continuously carrying out reflux heating for 1.5 hours at 170 ℃. And naturally cooling the reacted product, washing the product for 3 times by using ethanol, and then drying the product for 8 hours in vacuum at the temperature of 80 ℃ to obtain the graphene-hollow copper nanosphere composite material.
The graphene-hollow copper nanosphere composite material provided in this example was subjected to electron microscope transmission, scanning and XRD detection, respectively. The electron microscope transmission and scanning images of the graphene-hollow copper nanosphere composite material provided in this embodiment are shown in fig. 1A-1B and fig. 2, and the outer diameter of the hollow copper nanosphere in the graphene-hollow copper nanosphere composite material is greater than 50nm and less than 400 nm; as shown in fig. 6A and 6B, the cross section of the graphene-hollow copper nanosphere composite material provided in this example is subjected to transmission and scanning by an electron microscope, and the thickness of the spherical shell of the hollow copper nanosphere in the graphene-hollow copper nanosphere composite material is 21.8 nm. An XRD spectrogram of the graphene-hollow copper nanosphere composite material provided in this embodiment is shown in fig. 3, and the hollow copper nanosphere of the graphene-hollow copper nanosphere composite material mainly comprises a copper and cuprous oxide nanocomposite material. The result of inductively coupled plasma emission spectroscopy analysis on the graphene-hollow copper nanosphere composite material provided in this example is shown in fig. 7, and it can be seen that the hollow copper nanosphere is composed of 46.1% of carbon atoms, 24.3% of oxygen atoms and 29.6% of copper atoms, based on 100% of total atomic number of the hollow copper nanosphere. As can be seen from fig. 3 and 7, the hollow copper nanospheres of the graphene-hollow copper nanosphere composite material are composed of a copper-cuprous oxide nanocomposite material and graphene oxide
Example 2
The embodiment provides a graphene-hollow copper nanosphere composite material, which is prepared by the following specific steps:
1) graphene oxide was prepared by the same modified Hummers method as in example 1, see step 1) of example 1.
2) And (3) dispersing 30mg of the graphene oxide powder in 60mL of ethylene glycol to form a uniform solution A.
3) 0.3mmol of copper acetate is dissolved in 30mL of ethylene glycol to form a metal precursor mixed solution B.
4) And mixing the solution A and the metal precursor mixed solution B, stirring for 60 minutes to obtain a uniform suspension solution, carrying out reflux heating on the uniform suspension solution for 0.5 hour at 150 ℃ under a vacuum condition to carry out reaction, then introducing air, and continuously carrying out reflux heating for 0.5 hour at 150 ℃. And naturally cooling the reacted product, washing the product for 3 times by using ethanol, and then drying the product for 8 hours in vacuum at the temperature of 80 ℃ to obtain the graphene-hollow copper nanosphere composite material.
The average outer diameter of the hollow copper nanospheres in the graphene-hollow copper nanosphere composite material prepared in this example is 80.15 nm.
Example 3
The embodiment provides a graphene-hollow copper nanosphere composite material, which is prepared by the following specific steps:
1 graphene oxide was prepared by the same modified Hummers method as in example 1, see step 1) of example 1.
2) 30mg of the graphene oxide powder is dispersed in 25mL of ethylene glycol to form a uniform solution A.
3) 0.7mmol of copper acetate was dissolved in 25mL of ethylene glycol to form a metal precursor mixed solution B.
4) And mixing the solution A and the metal precursor mixed solution B, stirring for 60 minutes to obtain a uniform suspension solution, carrying out reflux heating on the uniform suspension solution for 1 hour at 190 ℃ under a vacuum condition, then introducing oxygen, and continuously carrying out reflux heating for 2 hours at 190 ℃. And naturally cooling the reacted product, washing the product for 3 times by using ethanol, and then drying the product for 12 hours in vacuum at the temperature of 80 ℃ to obtain the graphene-hollow copper nanosphere composite material.
The average outer diameter of the hollow copper nanospheres in the graphene-hollow copper nanosphere composite material prepared in this example is 89.13 nm.
Example 4
The embodiment provides a graphene-hollow copper nanosphere composite material, which is prepared by the following specific steps:
1) graphene oxide was prepared by the same modified Hummers method as in example 1, see step 1) of example 1.
2) 30mg of the graphene oxide powder is dispersed in 75mL of ethylene glycol to form a uniform solution A.
3) 0.7mmol of copper acetate was dissolved in 10mL of ethylene glycol to form a metal precursor mixed solution B.
4) And mixing the solution A and the metal precursor mixed solution B, stirring for 60 minutes to obtain a uniform suspension solution, carrying out reflux heating on the uniform suspension solution for 1 hour at 160 ℃ under a vacuum condition, then introducing air, and continuously carrying out reflux heating for 1 hour at 160 ℃. And naturally cooling the reacted product, washing the product for 3 times by using ethanol, and then drying the product for 12 hours in vacuum at the temperature of 80 ℃ to obtain the graphene-hollow copper nanosphere composite material.
The average outer diameter of the hollow copper nanospheres in the graphene-hollow copper nanosphere composite material prepared in this example is 93.12 nm.
Example 5
The embodiment provides a graphene-hollow copper nanosphere composite material, which is prepared by the following specific steps:
1) graphene oxide was prepared by the same modified Hummers method as in example 1, see step 1) of example 1.
2) 30mg of the graphene oxide powder is dispersed in 100mL of ethylene glycol to form a uniform solution A.
3) 0.5mmol of copper acetate is dissolved in 25mL of ethylene glycol to form a metal precursor mixed solution B.
4) And mixing the solution A and the metal precursor mixed solution B, stirring for 60 minutes to obtain a uniform suspension solution, carrying out reflux heating on the uniform suspension solution for 0.5 hour at 160 ℃ under a vacuum condition for reaction, then introducing air, and continuously carrying out reflux heating for 2 hours at 160 ℃. And naturally cooling the reacted product, washing the product for 3 times by using ethanol, and then drying the product for 12 hours in vacuum at the temperature of 80 ℃ to obtain the graphene-hollow copper nanosphere composite material.
The average outer diameter of the hollow copper nanospheres in the graphene-hollow copper nanosphere composite material prepared in this example was 45.25 nm.
Performance testing
The catalytic performance of the graphene-hollow copper nanosphere composite material provided in the embodiments 1 to 5 on the hydrogenation reduction catalysis of pollutant p-nitrophenol is respectively tested, and the specific test process is as follows:
1) weighing a proper amount of the graphene-hollow copper nanosphere composite materials provided in the embodiments 1 to 5 in sequence, preparing the graphene-hollow copper nanosphere composite materials into 5mg/50mL aqueous solutions of the graphene-hollow copper nanosphere composite materials as catalyst solutions, and performing the following operations in sequence;
2) taking a base line by using deionized water, adding 0.2mL of prepared 1mmol/L p-nitrophenol solution into a cuvette, adding 2mL of deionized water and 0.5mL of 0.5mol/L sodium borohydride solution, then adding 0.1mL of deionized water, adjusting the detection wavelength band length of an ultraviolet-visible spectrophotometer to be 250-fold and 500nm for detection, and taking the detection result as initial data; adding 0.2mL of prepared 1mmol/L p-nitrophenol solution into a cuvette, adding 2mL of deionized water and 0.5mL of 0.5mol/L sodium borohydride solution, then adding 0.1mL of catalyst solution (the catalyst solution is 5mg/50mL of graphene-hollow copper nanosphere composite water solution), starting the reaction from the time of adding the catalyst, detecting once every 35 seconds by using an ultraviolet-visible spectrophotometer (adjusting the detection wavelength band length of the ultraviolet-visible spectrophotometer to 250-500nm before the experiment) and storing the data until the reaction is finished (namely, the initial peak at 400nm is gradually reduced to disappearance cutoff).
The contrast group is the catalytic performance of copper nanoparticles (the copper nanoparticles are prepared by adopting a liquid phase reduction method of polyhydric alcohol in the presence of CTAB and isopropanol, and the particle size of the copper nanoparticles is 2-50nm) for carrying out hydrogenation reduction catalysis on pollutant p-nitrophenol. The specific test procedure was the same as the experimental group except that the catalyst solution was an aqueous solution of copper nanoparticles (the copper nanoparticles having a particle diameter of 2-50nm, prepared by a liquid phase reduction method using a polyol in the presence of CTAB and isopropanol) at a concentration of 5mg/50 mL.
In the performance experiment, the graphene-hollow copper nanosphere composite material provided in example 1 is used for hydrogenation reduction catalysis of pollutant p-nitrophenol, and the measured ultraviolet-visible absorption spectrum diagram is shown in fig. 4, wherein the catalytic effect ln (a) is showni/A0) The relationship with time t is shown in FIG. 5 (A is absorbance, and the absorbance of p-nitrobenzene at the initial time is A0The absorbance of p-nitrobenzene at time i is Ai) The catalytic conversion of p-nitrophenol by the graphene-hollow copper nanosphere composite material provided in example 1 can be completed within 210 seconds, and the kinetic constant of the catalytic effect is calculated by the following formula:
wherein, C0Is the concentration of contaminant p-nitrophenol in the solution at the initial moment, CiConcentration of contaminant p-nitrophenol in the solution at time i, A0Absorbance of p-nitrobenzene at the initial time, AiThe absorbance of p-nitrobenzene at the moment i; k is a kinetic constant. The kinetic constant of the graphene-hollow copper nanosphere composite material for carrying out hydrogenation reduction catalysis on pollutant p-nitrophenol can reach 129000min at most-1g-1。
In the above performance test, the kinetic constants of the graphene-hollow copper nanosphere composite material provided in examples 1 to 5 and the conventional copper nanoparticles for catalytic conversion of p-nitrophenol are shown in table 1;
TABLE 1
| Catalyst and process for preparing same | Kinetic constant K (min) of catalytic effect-1g-1) |
| Example 1 | 129000 |
| Example 2 | 53000 |
| Example 3 | 48000 |
| Example 4 | 32000 |
| Example 5 | 73000 |
| Ordinary copper nanoparticles | 3700 |
The dynamic constant of the catalytic effect of the graphene-hollow copper nanosphere composite material provided in example 1 is up to 129000min-1g-1Copper nanoparticles (prepared by liquid phase reduction of polyhydric alcohol in the presence of CTAB and isopropanol, and having a particle diameter of 2-50nm) (3700 min)-1g-1) 35.1 times of; example 2 provides the graphene-hollow copper nanosphere composite material with the kinetic constant of catalytic effect as high as 53000min-1g-1Copper nanoparticles (prepared by liquid phase reduction of polyhydric alcohol in the presence of CTAB and isopropanol, and having a particle diameter of 2-50nm) (3700 min)-1g-1) 14.3 times of; example 3 provides a graphene-hollow copper nanosphere composite material with a kinetic constant of catalytic effect of 48000min-1g-1Copper nanoparticles (prepared by liquid phase reduction of polyhydric alcohol in the presence of CTAB and isopropanol, and having a particle diameter of 2-50nm) (3700 min)-1g-1) 13.0 times of; example 4 provides a graphene-hollow copper nanosphere composite material with a kinetic constant of catalytic effect as high as 32000min-1g-1Copper nanoparticles (copper nanoparticles prepared by liquid phase reduction of polyhydric alcohol in the presence of CTAB and isopropyl alcohol, the particle diameter of the copper nanoparticles being 2 to 50nm) (II)3700min-1g-1) 8.6 times of the total weight; example 5 provides a graphene-hollow copper nanosphere composite material with a kinetic constant of catalytic effect as high as 73000min-1g-1Copper nanoparticles (prepared by liquid phase reduction of polyhydric alcohol in the presence of CTAB and isopropanol, and having a particle diameter of 2-50nm) (3700 min)-1g-1) 19.7 times of. It can be seen that the graphene-hollow copper nanosphere composite materials provided in examples 1 to 5 have more excellent catalytic performance than conventional common copper-based catalysts (copper nanoparticles having a particle size of 2 to 50nm prepared in the presence of CTAB and isopropanol by a liquid phase reduction method using a polyol).
Claims (10)
1. A graphene-hollow copper nanosphere composite material is characterized in that a hollow copper nanosphere is uniformly loaded on the surface of graphene.
2. The graphene-hollow copper nanosphere composite of claim 1, wherein the outer diameter of the hollow copper nanospheres is greater than 40nm and less than 500nm and the spherical shell thickness of the hollow copper nanospheres is 10-30 nm.
3. The graphene-hollow copper nanosphere composite of claim 1 wherein the hollow copper nanospheres comprise copper nanoparticles, cuprous oxide nanoparticles; preferably, the hollow copper nanospheres are formed by compounding copper nanoparticles, cuprous oxide nanoparticles and graphene oxide; more preferably, the hollow copper nanoball comprises 40-60% of carbon atoms, 20-35% of oxygen atoms and 20-40% of copper atoms, based on 100% of the total atomic number of the hollow copper nanoball.
4. The preparation method of the graphene-hollow copper nanosphere composite of any of claims 1-3, wherein the preparation method comprises the steps of:
(1) dispersing graphene oxide prepared by an improved Hummers method into a first part of ethylene glycol to form a solution A;
(2) dissolving a copper salt in a second part of ethylene glycol to form a metal precursor solution B;
(3) and mixing the solution A and the metal precursor solution B to obtain a mixed solution C, heating the mixed solution C, washing and drying a product obtained by heating to obtain the graphene-hollow copper nanosphere composite material.
5. The production method according to claim 4,
the copper salt comprises one or the combination of more than two of copper acetate, anhydrous copper sulfate, copper chloride, basic copper carbonate and copper nitrate; preferably, the copper salt is copper acetate.
6. The production method according to claim 4,
the dosage ratio of the copper salt to the graphene oxide is 0.3-0.7mmol:30 mg; preferably, the dosage ratio of the copper salt to the graphene oxide is 0.5mmol:30 mg;
in the step (1), the dosage ratio of the first part of glycol to the graphene oxide is 25-150mL:30 mg; preferably, the dosage ratio of the ethylene glycol to the graphene oxide is 75mL:30 mg;
in the step (2), the dosage ratio of the second part of ethylene glycol to the graphene oxide is 10-50mL:30 mg; preferably, the dosage ratio of the second part of ethylene glycol to the graphene oxide is 25mL:30 mg.
7. The method according to claim 4, wherein the heating the mixed solution C in the step (3) comprises the steps of:
1) heating the solution C in an inert atmosphere or in a vacuum state at the temperature of 150 ℃ and 190 ℃ for 0.5-1 h;
2) then heating the mixture in an oxidizing atmosphere at the temperature of 150 ℃ and 190 ℃ for 0.5 to 2 hours;
preferably, the heating mode in the step 1) and the step 2) is reflux heating.
8. The production method according to claim 4, wherein, in the washing-drying method of step (3),
the drying temperature is 60-100 ℃; preferably, the temperature of the drying is 80 ℃;
the drying time is 6-12 h; preferably, the temperature of the drying is 8 h.
9. The preparation method according to claim 4, wherein the graphene oxide is prepared by a preparation method comprising the following steps:
A. mixing graphite powder and potassium permanganate to obtain mixed powder, mixing concentrated sulfuric acid and concentrated phosphoric acid to obtain mixed acid, and adding the mixed powder into the mixed acid for heating reaction;
B. cooling the mixture reacted in the step A to room temperature, adding an ice-water mixture to obtain a mixed solution, and dropwise adding a hydrogen peroxide solution into the mixed solution until the mixed solution is bright yellow;
C. washing and ultrasonically treating the solid product obtained in the step B, and drying to obtain the graphene oxide;
preferably, the concentrated sulfuric acid is concentrated sulfuric acid with the mass concentration of more than or equal to 85.0%, and the concentrated phosphoric acid is concentrated phosphoric acid with the mass concentration of more than or equal to 85.0%;
preferably, the mass ratio of the graphite powder to the potassium permanganate is 1: 6; the volume ratio of the concentrated sulfuric acid to the concentrated phosphoric acid is 9: 1;
preferably, the heating temperature is 50 ℃, and the heating time is 12 hours;
preferably, the mass concentration of the hydrogen peroxide is 30%;
preferably, the washing is performed by means of hydrochloric acid washing and deionized water washing.
10. The use of the graphene-hollow copper nanosphere composite of any of claims 1-3 in the preparation of p-aminophenol by the reductive hydrogenation of p-nitrophenol, wherein the graphene-hollow copper nanosphere composite is catalytic in the preparation of p-aminophenol by the reductive hydrogenation of p-nitrophenol;
preferably, the reducing agent for preparing the p-aminophenol by reducing and hydrogenating the p-nitrophenol is sodium borohydride; the dosage ratio of the p-nitrophenol to the catalyst is 1mmol:10-80 mg; more preferably, the dosage ratio of the p-nitrophenol to the catalyst is 1mmol:50 mg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911178742.2A CN110961105B (en) | 2019-11-27 | 2019-11-27 | Graphene-hollow copper nanosphere composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911178742.2A CN110961105B (en) | 2019-11-27 | 2019-11-27 | Graphene-hollow copper nanosphere composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110961105A true CN110961105A (en) | 2020-04-07 |
| CN110961105B CN110961105B (en) | 2021-05-28 |
Family
ID=70031857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911178742.2A Active CN110961105B (en) | 2019-11-27 | 2019-11-27 | Graphene-hollow copper nanosphere composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110961105B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112903761A (en) * | 2021-01-19 | 2021-06-04 | 重庆大学 | Molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350499A (en) * | 2011-09-28 | 2012-02-15 | 河北工业大学 | Cu/Cu2O core-shell composite microsphere and preparation method thereof |
| CN103387258A (en) * | 2013-08-07 | 2013-11-13 | 武汉理工大学 | Cuprous oxide nano hollow spheres as well as synthetic method and application method thereof |
| CN105565362A (en) * | 2015-12-21 | 2016-05-11 | 江苏大学 | Preparation method of reduced graphene oxide/cuprous oxide nano composite material |
-
2019
- 2019-11-27 CN CN201911178742.2A patent/CN110961105B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350499A (en) * | 2011-09-28 | 2012-02-15 | 河北工业大学 | Cu/Cu2O core-shell composite microsphere and preparation method thereof |
| CN103387258A (en) * | 2013-08-07 | 2013-11-13 | 武汉理工大学 | Cuprous oxide nano hollow spheres as well as synthetic method and application method thereof |
| CN105565362A (en) * | 2015-12-21 | 2016-05-11 | 江苏大学 | Preparation method of reduced graphene oxide/cuprous oxide nano composite material |
Non-Patent Citations (2)
| Title |
|---|
| XIAOYAN ZHOU ET AL: "Microwave-assisted synthesis of hollow CuO–Cu2O nanosphere/graphene composite as anode for lithium-ion battery", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| YUEHONG XIE ET AL: "Cu/Cu2O/rGO nanocomposites: solid-state self-reduction synthesis and catalytic activity for p-nitrophenol reduction", 《NEW J. CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112903761A (en) * | 2021-01-19 | 2021-06-04 | 重庆大学 | Molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110961105B (en) | 2021-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Guo et al. | Structure-controlled three-dimensional BiOI/MoS2 microspheres for boosting visible-light photocatalytic degradation of tetracycline | |
| Shen et al. | Built-in electric field induced CeO2/Ti3C2-MXene Schottky-junction for coupled photocatalytic tetracycline degradation and CO2 reduction | |
| Mou et al. | Ultrathin BiOCl/nitrogen-doped graphene quantum dots composites with strong adsorption and effective photocatalytic activity for the degradation of antibiotic ciprofloxacin | |
| Liang et al. | Highly dispersed bismuth oxide quantum dots/graphite carbon nitride nanosheets heterojunctions for visible light photocatalytic redox degradation of environmental pollutants | |
| Dong et al. | Self-assembled hollow sphere shaped Bi2WO6/RGO composites for efficient sunlight-driven photocatalytic degradation of organic pollutants | |
| Zhang et al. | Carbon layer derived carrier transport in Co/g-C3N4 nanosheet junctions for efficient H2O2 production and NO removal | |
| Wang et al. | Self-assembled BiOCl/Ti3C2Tx composites with efficient photo-induced charge separation activity for photocatalytic degradation of p-nitrophenol | |
| Xu et al. | Nitrogen-rich graphitic carbon nitride nanotubes for photocatalytic hydrogen evolution with simultaneous contaminant degradation | |
| Xu et al. | Amino-functionalized synthesis of MnO2-NH2-GO for catalytic ozonation of cephalexin | |
| Han et al. | The promoting role of different carbon allotropes cocatalysts for semiconductors in photocatalytic energy generation and pollutants degradation | |
| Smrithi et al. | Carbon dots decorated cadmium sulphide heterojunction-nanospheres for the enhanced visible light driven photocatalytic dye degradation and hydrogen generation | |
| Liu et al. | Facile preparation and characterization of anatase TiO2/nanocellulose composite for photocatalytic degradation of methyl orange | |
| Li et al. | Controlled preparation of MoS2/PbBiO2I hybrid microspheres with enhanced visible-light photocatalytic behaviour | |
| Maimaiti et al. | Photocatalytic synthesis of urea (CO2/N2/H2O) on coal-based carbon nanotubes with the Fe-core-supported Ti3+-TiO2 composite catalyst | |
| Zhang et al. | Synthesis of g-C3N4 microrods with superficial C, N dual vacancies for enhanced photocatalytic organic pollutant removal and H2O2 production | |
| Pei et al. | Enhancing visible-light degradation performance of g-C3N4 on organic pollutants by constructing heterojunctions via combining tubular g-C3N4 with Bi2O3 nanosheets | |
| Kannan et al. | Facile one-step synthesis of cerium oxide-carbon quantum dots/RGO nanohybrid catalyst and its enhanced photocatalytic activity | |
| CN101619177A (en) | Preparation method of nano-titanium dioxide coated nano-aluminium oxide | |
| Zhang et al. | Mo-doped carbon nitride homojunction to promote oxygen activation for enhanced photocatalytic performance | |
| Cao et al. | Cu nanoparticles decorating rGO nanohybrids as electrocatalyst toward CO2 reduction | |
| Zhang et al. | Cu 2 O/MoS 2 composites: a novel photocatalyst for photocatalytic degradation of organic dyes under visible light | |
| Han et al. | Construction of Ag/3D-reduced graphene oxide nanocomposite with advanced catalytic capacity for 4-nitrophenol and methylene blue | |
| Kuate et al. | Construction of 2D/3D black g-C3N4/BiOI S-scheme heterojunction for boosted photothermal-assisted photocatalytic tetracycline degradation in seawater | |
| Mohamed et al. | Dispersed Ag2O/Ag on CNT-graphene composite: an implication for magnificent photoreduction and energy storage applications | |
| CN110961105B (en) | Graphene-hollow copper nanosphere composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |