CN116651453A - Cu synthesized by thermal decomposition 2 O/Cu heterostructure nano material and preparation method and application thereof - Google Patents
Cu synthesized by thermal decomposition 2 O/Cu heterostructure nano material and preparation method and application thereof Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 28
- 238000005979 thermal decomposition reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 230000001699 photocatalysis Effects 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012691 Cu precursor Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229940116318 copper carbonate Drugs 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 5
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 5
- 239000011941 photocatalyst Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 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
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 2
- XNEQAVYOCNWYNZ-UHFFFAOYSA-L copper;dinitrite Chemical compound [Cu+2].[O-]N=O.[O-]N=O XNEQAVYOCNWYNZ-UHFFFAOYSA-L 0.000 claims description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000003334 potential effect Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 7
- 229940112669 cuprous oxide Drugs 0.000 description 7
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 biosensors Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- 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
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
Abstract
The invention discloses a Cu synthesized by thermal decomposition 2 O/Cu heterostructure nano material, preparation method and application thereof, and formation of the structure utilizes Kirkendall effect, and Cu is used 2 The O surface is reduced to Cu and the different diffusion rates of oxygen atoms inside and outside the particle lead to the final formation of the nano-heterostructure. The inventionThe method is simple to operate and low in cost, the synthesized oxide/metal nano heterostructure material can have the properties of oxide and metal simple substance, the metal nano structure capped by the oxide has multiple functions and synergistic effect, and can have the properties of two substances at the same time, and under the interaction of the two properties, the structure can be applied to the fields of catalysis, photonics and the like, so that the structure has more excellent effect. The performance of single metal or single oxide can be optimized, and the composite structure is expected to explore more potential properties and be applied to wider fields.
Description
Technical Field
The invention belongs to the field of nano metal and oxide synthesis thereof, and in particular relates to Cu synthesized by thermal decomposition 2 O/Cu heterostructure nano material, and preparation method and application thereof.
Background
Cuprous oxide (Cu) 2 O) is a stable copper oxide with a theoretical direct bandgap of 2.2eV, which has high activity and selectivity for many oxidation/reduction reactions, and is one of the most commonly used catalysts, since it behaves like a P-type semiconductor. In addition, it is also an important component in materials such as high temperature superconductors, biosensors, medicine, water-splitting and environmental pollutants. Copper (Cu) is a very important metal material, is an important material for industrial production due to good ductility, electrical conductivity and low cost, and can be used in the fields of electric conduction, heat conduction, catalysis, medicine, energy sources, mechanical manufacturing, national defense and the like. On the nanoscale, the material has macroscopic quantum tunneling effect, small-size effect, surface effect, gibbs-Thomson effect and the like, so that the nanomaterial can show more excellent performance than a block.
Currently synthesizing Cu 2 The O/Cu nano heterostructure method comprises a chemical reduction method, a magnetron sputtering method and the like, and the chemical reduction method has the advantages of various medicines, complex reaction process, long time consumption, complex magnetron sputtering equipment system and high price. The thermal decomposition method used in the invention has relatively simple raw materials, principles and processes, and can rapidly obtain the product by using the most basic chemical device.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the invention provides the Cu with low cost and simple operation 2 O/Cu heterologyThe structure nanometer material and the synthesis method thereof realize the property of oxide and metal simple substance simultaneously, and further optimize the performance of single metal or single oxide.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
cu synthesized by thermal decomposition 2 The method for O/Cu heterostructure nano material comprises the following steps:
(1) Mixing a copper precursor containing oxygen element with an organic solvent, and fully stirring at 25-80 ℃ to form a uniform suspension;
(2) Heating the suspension in the step (1) to 100-350 ℃ in an inert gas atmosphere, preserving heat for 5-360 min, cooling to room temperature, centrifuging, drying and grinding to obtain the finished product.
Specifically, in the step (1), the copper precursor containing oxygen is selected from any one or more than two of basic copper carbonate, basic copper acetate, basic copper nitrate, basic copper nitrite, anhydrous copper acetate, cuprous acetate, copper formate, copper hydroxide, copper oxalate and copper oxide; the organic solvent is selected from any one or more than two of alkene or alkyne containing more than 12 carbon atoms and isomer thereof, preferably octadecene, hexadecene or octadecene.
Specifically, in the step (1), a copper precursor containing oxygen element and an organic solvent are mixed according to a mass ratio of 1: (4-12), and magnetic stirring or mechanical stirring is adopted for mixing, wherein the stirring speed is 50-700 r/min, and the time is 10-30 min.
Preferably, in the step (2), the inert gas is nitrogen or argon.
Preferably, in the step (2), the centrifugal rotation speed is 6000-10000 r/min; the centrifugation time is 5-20 min; the detergent used for centrifugation is a mixture of n-hexane and ethanol, preferably in a volume ratio of 3:1.
Preferably, in the step (2), the drying temperature is 60-80 ℃ and the drying time is 30-120 min.
Further, cu prepared by the preparation method 2 O/Cu heterostructure nanomaterials are alsoWithin the scope of the present invention.
Furthermore, the invention also claims the Cu 2 O/Cu heterostructure nanomaterial for photocatalytic CO 2 Application of reduction.
Specifically, the present invention will be described in the above Cu 2 O/Cu heterostructure nanomaterial for photocatalytic CO 2 The method specifically comprises the following steps:
s1: cu is added with 2 Placing O/Cu heterostructure nano material in a reaction container, and performing dark adsorption for 6-24 hours in a vacuum state;
s2: introducing CO to be reduced into a reaction vessel 2 Injecting deionized water, and irradiating Cu in the step (1) with light source 2 O/Cu heterostructure nano material as photocatalyst for CO 2 The gas undergoes a photocatalytic reduction reaction.
Specifically, in step S2, the high purity CO 2 The concentration of (2) is 99.999%; the photocatalyst and CO 2 The mass ratio of (2) is 1: (0.5-2); the mass ratio of the photocatalyst to deionized water is 1: (0.5-2).
Specifically, in step S2, the light source is any one or more than two of a xenon lamp, an LED lamp, a mercury lamp, a UVC lamp, a metal halide lamp, and a solar simulator.
The beneficial effects are that:
(1) The invention synthesizes the cuprous oxide/copper nano heterostructure by a liquid-phase high-temperature thermal decomposition method, and the formation of the structure utilizes Kirkendall effect, because of Cu 2 The O surface is reduced to Cu and the different diffusion rates of oxygen atoms inside and outside the particle lead to the final formation of the nano-heterostructure. In the process of selecting raw materials, considering the components of the metal oxide to be reserved, copper salt which contains oxygen atoms and is easy to be thermally decomposed to generate copper oxide is used as a precursor, and an organic solvent which has weak reducibility and does not coordinate with copper ions is used as a reducer.
(2) The invention adopts a low-cost and simple-operation method to synthesize the oxide/metal nano heterostructure nanomaterial, the structure can simultaneously have the properties of oxide and metal simple substance, the metal nano structure which is covered by the oxide has multiple functions and synergistic effect, and can simultaneously have the properties of two substances, and under the interaction of the two properties, the structure can be applied to the fields of catalysis, photonics, and the like, and can generate more excellent effects. The performance of single metal or single oxide can be optimized, and the composite structure is expected to explore more potential properties and be applied to wider fields.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is a schematic flow chart of the thermal decomposition reaction of the present invention.
Figure 2 is an XRD of the product of example 1.
Fig. 3 is an SEM image of the product of example 1.
FIG. 4 is the particle size distribution of the product of example 1.
FIG. 5 is a TEM image of the product of example 1.
FIG. 6 is a schematic view of the photocatalytic effect in example 1.
Fig. 7 is XRD of the product of comparative example 1.
Detailed Description
The invention will be better understood from the following examples.
Example 1
The invention adopts Cu synthesized by thermal decomposition in the flow chart shown in figure 1 2 The O/Cu heterostructure nanomaterial specifically comprises the following steps:
(1) 10mmol of basic copper carbonate and 30ml of octadecene were mixed and placed in a four-necked flask, heated to 80℃under magnetic stirring (400 r/min) and kept at that temperature for 20min, and then the mixture was heated to 300℃under a nitrogen atmosphere (0.2L/min) and kept at that temperature for 1 hour and cooled to room temperature.
(2) Centrifuging the reacted solution with a 3:1 mixture of n-hexane and ethanol at 8000r/min for 5 min, repeating the operation until the supernatant is clear and transparent, and then placing the product at 80deg.CDrying in an oven for 30 minutes. XRD of the obtained product is shown in figure 2, the phase composition of the product is composed of cuprous oxide and copper, the diffraction peak of copper is strong, the cuprous oxide is weak, SEM results are shown in figure 3, the obtained product is spherical particles with uniform morphology, the particles are dispersed, no agglomeration phenomenon exists, the particle size distribution of the powder is shown in figure 4, and the average particle size is 40nm. As shown in the TEM results of FIG. 5, it can be clearly observed that the outer surface of the copper particles is coated with an amorphous oxide layer with a lattice spacing ofCorresponds to the cuprous oxide (111) crystal face.
(3) Taking 500mg of the synthesized Cu 2 O/Cu heterostructure nanomaterial placement at 15.4cm 3 In the photocatalysis device, the device is kept in a vacuum state, and high-purity CO is introduced after dark adsorption for 12 hours 2 Reaching atmospheric pressure, injecting 1ml deionized water into the device, performing photocatalytic reaction under irradiation of xenon lamp, and detecting CO/CH every 30min 4 Is contained in the composition. As shown in FIG. 6, the structure is used for photocatalytic CO 2 The reduction experiment shows 0.029588 mu mol (g. Min) -1 And 0.025034. Mu. Mol. With (g. Min) -1 CH of (2) 4 Release rate.
Example 2
(1) 10mmol of anhydrous copper acetate and 30ml of octadecene were placed in a four-necked flask, heated to 80℃under magnetic stirring (400 r/min) and kept at the temperature for 20min, and then the mixture was heated to 300℃under a nitrogen atmosphere (0.2L/min) and kept at that temperature for 1 hour and cooled to room temperature.
(2) The reacted solution was centrifuged using a 3:1 mixture of n-hexane and ethanol, at 8000r/min for 5 minutes, the operation was repeated until the supernatant was clear and transparent, and then the product was dried in an oven at 80℃for 30 minutes.
(3) Taking 500mg of the synthesized Cu 2 O/Cu heterostructure nanomaterial placement at 15.4cm 3 In the photocatalysis device, the device is kept in a vacuum state, and high-purity CO is introduced after dark adsorption for 12 hours 2 Reaching atmospheric pressure, 1ml ofDeionized water is injected into the device, photocatalytic reaction is carried out under the irradiation of a xenon lamp, and CO/CH is detected every 30min 4 Is contained in the composition. The structure is used for photocatalysis of CO 2 The reduction experiment shows 0.019557 mu mol (g. Min) -1 And 0.011126667. Mu. Mol. With (g. Min) -1 CH of (2) 4 Release rate.
Example 3
(1) 10mmol of copper oxide and 30ml of octadecene were mixed and placed in a four-necked flask, heated to 80℃under magnetic stirring (400 r/min) and kept at that temperature for 20min, and then the mixture was heated to 280℃under a nitrogen atmosphere (0.2L/min) and kept at that temperature for 1 hour and cooled to room temperature.
(2) The reacted solution was centrifuged using a 3:1 mixture of n-hexane and ethanol, centrifuged at 8000r/min for 5 minutes, the operation was repeated until the supernatant was clear and transparent, and the product was then dried in an oven at 80℃for 1 hour.
(3) Taking 500mg of the synthesized Cu 2 O/Cu heterostructure nanomaterial was placed at 15.4cm 3 In the photocatalysis device, the device is kept in a vacuum state, and high-purity CO is introduced after dark adsorption for 12 hours 2 Reaching atmospheric pressure, injecting 1ml deionized water into the device, performing photocatalytic reaction under irradiation of xenon lamp, and detecting CO/CH every 30min 4 Is contained in the composition. The structure is used for photocatalysis of CO 2 The reduction experiment shows 0.044229667 mu mol (g. Min) -1 And 0.124696333. Mu. Mol. With (g. Min) -1 CH of (2) 4 Release rate.
Comparative example 1
(1) 10mmol of basic copper carbonate and 30ml of octadecene were mixed and placed in a four-necked flask, heated to 80℃under magnetic stirring (400 r/min) and kept at that temperature for 20min, and then the mixture was heated to 200℃under a nitrogen atmosphere (0.2L/min) and kept at that temperature for 1 hour and cooled to room temperature.
(2) The reacted solution was centrifuged using a 3:1 mixture of n-hexane and ethanol, centrifuged at 8000r/min for 5 minutes, the operation was repeated until the supernatant was clear and transparent, and the product was then dried in an oven at 80℃for 1 hour. XRD of the resulting powder is shown in fig. 7. At this temperature, basic copper carbonate is gradually reduced to cuprous oxide, and no copper is formed, and the cuprous oxide/copper heterostructure cannot be synthesized.
The invention provides a Cu synthesized by thermal decomposition 2 The O/Cu heterostructure nanomaterial, the preparation method and the application thought and method thereof, and the method and the way for realizing the technical scheme are numerous, the above description is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made to those skilled in the art without departing from the principle of the invention, and the improvements and modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (10)
1. Cu synthesized by thermal decomposition 2 The method for O/Cu heterostructure nano material is characterized by comprising the following steps of:
(1) Mixing a copper precursor containing oxygen element with an organic solvent, and fully stirring at 25-80 ℃ to form a uniform suspension;
(2) Heating the suspension in the step (1) to 100-350 ℃ in an inert gas atmosphere, preserving heat for 5-360 min, cooling to room temperature, centrifuging, drying and grinding to obtain the finished product.
2. The Cu synthesized by thermal decomposition according to claim 1 2 The method of the O/Cu heterostructure nanomaterial is characterized in that in the step (1), the copper precursor containing oxygen is selected from any one or more than two of basic copper carbonate, basic copper acetate, basic copper nitrate, basic copper nitrite, anhydrous copper acetate, cuprous acetate, copper formate, copper hydroxide, copper oxalate and copper oxide; the organic solvent is selected from any one or more than two of alkene or alkyne containing more than 12 carbon atoms and isomer thereof.
3. The Cu synthesized by thermal decomposition according to claim 1 2 O/Cu heterostructure nano-scaleThe method of the material is characterized in that in the step (1), a copper precursor containing oxygen element and an organic solvent are mixed according to the mass ratio of 1: (4-12), and magnetic stirring or mechanical stirring is adopted for mixing, wherein the stirring speed is 50-700 r/min, and the time is 10-30 min.
4. The Cu synthesized by thermal decomposition according to claim 1 2 The method for preparing the O/Cu heterostructure nanomaterial is characterized in that in the step (2), the inert gas is nitrogen or argon.
5. The Cu synthesized by thermal decomposition according to claim 1 2 The method of O/Cu heterostructure nano material is characterized in that in the step (2), the centrifugal rotating speed is 6000-10000 r/min; the centrifugation time is 5-20 min; the detergent used for centrifugation is a mixture of n-hexane and ethanol.
6. The Cu synthesized by thermal decomposition according to claim 1 2 The method for preparing the O/Cu heterostructure nano material is characterized in that in the step (2), the drying temperature is 60-80 ℃, and the drying time is 30-120 min.
7. Cu obtained by the process according to any one of claims 1 to 6 2 O/Cu heterostructure nanomaterials.
8. The Cu of claim 7 2 O/Cu heterostructure nanomaterial for photocatalytic CO 2 Application of reduction.
9. The use according to claim 8, characterized by the steps of:
s1: cu is added with 2 Placing O/Cu heterostructure nano material in a reaction container, and performing dark adsorption for 6-24 hours in a vacuum state;
s2: introducing CO to be reduced into a reaction vessel 2 Injecting deionized water, and irradiating Cu in the step (1) with light source 2 O/Cu heterostructure nanomaterial as photocatalystChemical agent for CO 2 The gas undergoes a photocatalytic reduction reaction.
10. The use according to claim 9, wherein in step S2, the photocatalyst is combined with CO 2 The mass ratio of (2) is 1: (0.5-2); the mass ratio of the photocatalyst to deionized water is 1: (0.5-2); the light source is any one or more than two of a xenon lamp, an LED lamp, a mercury lamp, a UVC lamp, a metal halide lamp or a sunlight simulator.
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