CN105621474A - Hyperbranched graded cuprous oxide nanomateiral and preparation method and application thereof - Google Patents
Hyperbranched graded cuprous oxide nanomateiral and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a hyperbranched graded cuprous oxide nanomateiral. The preparation method comprises the following steps that a sodium hydroxide solution and a copper sulfate solution are mixed and stirred to be uniform to obtain a mixed solution; the mixed solution is added into a conical bottle, the conical bottle is put into an oil bath to be heated, the height of the liquid level of the oil bath needs to be higher than that of the mixed solution in the conical bottle, and uniform-velocity stirring is kept in the heating process; when the temperature of the mixed solution system reaches a hydrothermal reaction temperature, ethidene diamine and hydrazine hydrate are quickly injected into the conical bottle, and then reacting is performed at the hydrothermal reaction temperature until copper nanowire products are obtained; the copper nanowire products are washed, enriched and then put into a closed container filled with wet air to be oxidized, and then the hyperbranched graded cuprous oxide nanomateiral is obtained. The preparation method is simple and mild, short in cycle and low in energy consumption, the nanowire synthesis temperature and the subsequent oxidizing temperature do not exceed 80 DEG C, and the prepared cuprous oxide nanomateiral can achieve the excellent effect of photocatalytically splitting water into hydrogen.
Description
Technical field
The invention belongs to technical field of nano material, it is specifically related to a kind of over-expense classification cuprous nano material, and the preparation method and application of this over-expense classification cuprous nano material.
Background technology
Red copper oxide is the excellent p-type semiconductor material that a class is applicable to photoelectrochemistry hydrogen manufacturing, and its direct band gap is 2.2eV (at the bottom of conduction band-top of valence band :-0.28��1.92eV), is wherein defeated by H at the bottom of conduction band2O/H2Current potential (0V), and top of valence band is just in H2O/O2Electropotential (1.23eV), well meets the primary condition of normal-temperature light catalytic hydrolysis, and theoretical light current density is-14.7mAcm when AM1.5 simulated solar irradiation light intensity-2, sun power-hydrogen energy conversion efficiency reaches as high as 18%. But limiting its photoelectric transformation efficiency in actual applications topmost is that intrinsic carrier (positive and negative electric charge) moves distance much smaller than the incident degree of depth (10 ��m) of (only 20-100nm) light in cuprous oxide crystal because have two: one, and this can cause exciton just to occur compound to cause the waste of incident photon before being diffused into interface; Two is that the catalytic stability caused due to self photoetch phenomenon is poor.
Three-dimensional over-expense structure based on one-dimensional nano line, it is possible to well address these problems, the towering tree that its form is similar in nature virgin forest, construct with the extension branch being attached on trunk by nano wire trunk. Classification racemosus structure can not only effectively stop to occur between nano wire to flocculate and reunite, more can significantly improve specific surface area and porosity, strengthen the capture ability of incident beam and reactive material, promote high efficiency separation and the transmission of photogenerated charge, opto-electronic conversion and catalytic process provide more abundant reactive behavior position. Simultaneously, by the reasonable arrangement in three dimensions of the simple nanostructure of low-dimensional, the complex construction formed not only has the function of single nanostructure, synergistic effect can also be produced by the permutation and combination between them, while making full use of the finite space, the structural advantage of maximumization nano-material self.
Along with the development of nano material preparation technology, this kind of new multistage three-dimensional structure is widely used in constructing metal, semiconductor material, and is applied to energy storage, conversion, photochemical catalysis hydrolytic hydrogen production, the popular domain such as sensor and ultracapacitor. But, the three-dimensional high energy consumption technique substeps such as nano thread structure many employings chemical vapour deposition technique of overspending are produced at present, not only complex synthetic route, and often to be used noble metal catalyst in reacting, seriously limit suitability for industrialized production and the large-scale application of this unique texture. Therefore, the preparation in a mild condition of three-dimensional over-expense structure, still also exists a large amount of technological gap.
Summary of the invention
Based on above-mentioned technical problem, the present invention provides a kind of over-expense classification cuprous nano material, and the preparation method and application of this over-expense classification cuprous nano material.
The technology used in the present invention solution is:
A kind of over-expense classification cuprous nano material, comprises nano cuprous oxide wire matrix and the thorn-like cuprous nano sheet along nano cuprous oxide wire matrix axial array, and the direction of growth of thorn-like cuprous nano sheet is vertical with nano cuprous oxide wire matrix.
The preparation method of above-mentioned over-expense classification cuprous nano material, comprises the following steps:
Sodium hydroxide solution is mixed with copper-bath and stirs evenly by a, obtains mixing solutions;
The mixing solutions that step a is obtained by b adds in Erlenmeyer flask, is then placed in oil bath heating, and the liquid level of oil bath not had the height of mixing solutions in Erlenmeyer flask, keeps at the uniform velocity stirring in heat-processed;
When c solution system temperature to be mixed reaches hydrothermal temperature, being rapidly in Erlenmeyer flask and inject quadrol and hydrazine hydrate, reacting under this hydrothermal temperature afterwards, until obtaining copper nano-wire product;
The copper nano-wire product that step c is obtained by d, after washing, enrichment, is placed in the encloses container internal oxidition of full wet air, takes out after being oxidized, and namely obtains over-expense classification cuprous nano material.
In step a: the concentration of described sodium hydroxide solution is preferably 8��9 mol/L; The concentration of copper-bath is preferably 0.2��0.3 mol/L; The mol ratio of sodium hydroxide and copper sulfate is preferably 29��32: 1, more preferably 31:1.
In step b: stir magnetic agitation or the mechanical stirring mode of preferably adopting.
In step c: copper sulfate is preferably 0.08��0.10 with the ratio of quadrol amount of substance; Copper sulfate is preferably 0.55��0.8 with the ratio of hydrazine hydrate amount of substance.
In step c: described hydrothermal temperature is preferably 80 degrees Celsius, the hydro-thermal reaction time is preferably 1 hour.
In steps d: described washing process preferably adopts second alcohol and water respectively to wash three times, described washing, enriching step can adopt takes out filter and centrifugation apparatus.
In steps d: described oxidizing temperature is preferably 60��70 degrees Celsius; Oxidization time is preferably 5��6 hours.
In steps d: described oxidation humidity preferably controls in 65%��70% scope.
Above-mentioned over-expense classification cuprous nano material tool has been widely used, can be used as non-enzymatic sensor electrode material, photolysis water hydrogen gas material and photocatalysis degradation organic contaminant material, it is possible to be applied in the fields such as lithium ion battery energy storage, leakage of oil absorption, oily water separation.
The Advantageous Effects of the present invention is:
Gained of the present invention over-expense classification cuprous nano material catalytic performance is remarkable. The performance of semi-conductor catalysis has close associating with its structure with electronic conduction characteristic, and both to be the size by material itself, degree of crystallinity and surface properties in essence determine. In hyperbranched nano thread structure prepared by the present invention, it is covered with the burr thorn-like nanometer sheet structure that nano wire trunk is surperficial and end is sharp-pointed and can arrest more charged particle in limited space, promote the reactive material concentration around material surface, simultaneously, the branch tip with good crystallinity also promotes the sharp separation of photohole and electronics, accelerates the water splitting of water body. Coordinate the use of carried noble metal promotor, it is also possible to the effective generation suppressing material self photoetch, strengthen charge separation efficiency further. Photolysis water hydrogen experimental result shows, over-expense classifying nano Red copper oxide material light catalysis hydrolysis hydrogen generation efficiency be 263.8 micromoles/hour, far away higher than commercial cuprous oxide powder and contrast nanotube sample hydrogen generation efficiency (such as nano cuprous oxide wire structure: 89.7 micromoles/hour; Cuprous oxide nano particle: 12.9 micromoles/hour). Due to the barrier effect of the space steric effect of hyperbranched nanowire epitaxy branch, its nano wire trunk can be maintained a certain distance each other, not easily reunite, effectively avoid and extend, with the reaction times, the generation that specific surface area reduces this problem, thus overspending classification cuprous nano material within the investigation phase of 45 hours and showed higher stability, there is not obvious decay in its hydrogen generation efficiency.
The over-expense classification cuprous nano material preparation method convenient and efficient that the present invention proposes, by adopting Hydrothermal Synthesis and low temperature and moisture atmospheric oxidation process, can produce a large amount of target product within the short period of time (6 hours), and product rate is higher than 95%. This preparation method avoids High Temperature High Pressure severe condition in traditional chemical gas-phase deposition, just can carry out under lower than the atmospheric pressure environment of 100 degrees Celsius. Meanwhile, the method in process of production tail gas main component be nitrogen, surrounding environment can not be polluted. In addition, air in wet environment and moisture, reduce the potential barrier of copper nano-wire (100) crystal face, promoter action is served to triggering the epitaxy along<002>radial (being perpendicular to nano wire axially), effectively prevent the use of the noble metal catalyst inducing epitaxy in traditional technology, save production cost greatly. Products obtained therefrom purity height, size is even, product favorable reproducibility.
Over-expense classification cuprous nano material tool prepared by the present invention has been widely used, can be used as non-enzymatic sensor electrode material, photolysis water hydrogen gas material and photocatalysis degradation organic contaminant material, it is possible to be applied in the fields such as lithium ion battery energy storage, leakage of oil absorption, oily water separation.
Accompanying drawing explanation
Fig. 1 is that scanning electronic microscope (SEM) characterizes display the present invention's oxidising process in wet air under mild conditions, and CuNWs refers to for copper nano-wire, Cu2ONS-NWs refers to generation over-expense classification cuprous nano material.
Fig. 2 is high resolution scanning electron microscope (SEM) photo of over-expense classification cuprous nano material.
The X-ray diffraction (XRD) that Fig. 3 is the over-expense classification cuprous nano material that the present invention obtains characterizes spectrogram.
Fig. 4 is X-ray photoelectron spectroscopic analysis. Wherein, Fig. 4 a illustrates XPS spectrum peak entirely, and Fig. 4 b illustrates that Cu2p composes peak, and Fig. 4 c illustrates that O1s composes peak.
The high power transmission electron microscope TEM that Fig. 5 is over-expense classification cuprous nano material characterizes. Wherein, Fig. 5 a illustrates hyperbranched nano wire TEM photo, Fig. 5 b illustrates the high power TEM photo of region a and corresponding SAED spot, Fig. 5 c illustrates the HRTEM photo of region b, Fig. 5 d illustrates that the partial enlargement in broken box region is observed, Fig. 5 e illustrates the amplification observation in square region in Fig. 5 b, and Fig. 5 f illustrates the HRTEM photo of region d and region e and the FFT (fourier transformation diffraction spot) of correspondence thereof.
Fig. 6 extends the comparison diagram of changing conditions in time for over-expense classification cuprous nano material and with reference to sample (nano cuprous oxide wire, cuprous oxide nano particle) hydrogen generation efficiency under UV, visible light optical radiation.
Embodiment
Preparation process complexity is there is (in chemical vapour deposition technique for existing being applied in new energy field over-expense classification nanostructure synthesis technique, polystep reaction, the use of temperature programming and the external of all kinds of carrier gas add equipment complexity), energy consumption big reaction conditionss such as (require) High Temperature High Pressure, cost height (use of noble metal catalyst), the shortcomings such as non-ambient close friend (HUMAN HEALTH is had infringement by organometallic compound reaction after product), it is gentleer that the present invention provides one, safety, less energy-consumption, cheap and easy preparation method. the method take copper nano-wire as template, and under adopting low temperature and moisture air atmosphere method for oxidation can realize cold condition, preparation has the three-dimensional nano cuprous oxide wire overspending point level structure. by introducing hyperbranched nano thread structure, this cuprous nano material can provide more interface to promote photoabsorption area, reduces carrier mobility scope simultaneously, reduces the recombination probability in electronics-hole, thus can obtain excellent photolysis water hydrogen effect. and, the preparation method that the present invention proposes is simply gentle, and the cycle is short, and energy consumption is low, and nano wire synthesis temperature and subsequent oxidation temperature are no more than 80 degrees Celsius. also can adopt in the preparation process of laboratory to regulate the tubular oven of temperature and humidity as airtight well-oxygenated environment, in actual production process, production can be scaled up according to particular case, solve the problem that existing new energy materials limits its industrial application due to large-scale production difficulty.
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
(1) 85 gram of sodium hydroxide is dissolved in 250 ml deionized water, mixes with the copper-bath (0.044 grams per milliliter) of 10 milliliters and stirs 30 minutes, obtain mixing solutions after cooling slightly.
(2) filling Erlenmeyer flask heating in 80 degrees Celsius of oil (water) are bathed of above-mentioned homogeneous mixture solotion, the liquid level of oil bath not had the height of mixing solutions in Erlenmeyer flask, and maintain magneton rotating speed in Erlenmeyer flask is 500 revs/min simultaneously.
(3) when solution system temperature to be mixed reaches 80 degrees Celsius, it may also be useful to the syringe that range is 5 milliliters adds rapidly 2.14 milliliters of quadrols, then the injection being 1 milliliter with another range adds 0.18mL hydrazine hydrate. Continue heating 1 hour afterwards again, obtain the nano wire product of copper redness.
(4) above-mentioned products obtained therefrom second alcohol and water respectively washs three times, copper nano-wire product good for washing enrichment is placed in the airtight plastic box that length, width and height are 20 cm x 10 cm x 10 centimetres of full wet airs (humidity is 65-70%), put into 60 degrees Celsius of baking oven ageings to take out for 300 minutes, namely obtain over-expense classification cuprous nano material.
Fig. 1 illustrates that scanning electronic microscope (SEM) characterizes display oxidising process in wet air under mild conditions, as can be seen from Figure, the smooth exposed surface of One-Dimensional Pure copper nano-wire that hydrothermal method is produced becomes coarse owing to growing two grades of branched structures, and specific surface area significantly increases.
Fig. 2 is high resolution scanning electron microscope (SEM) photo of over-expense classification cuprous nano material. SEM photograph display nano wire trunk diameter is about 110 nanometers, and length is less than 5 microns, and the bottom surface of nanometer sheet is firmly attached on nano wire trunk, and width is 20 nanometers, and substrate is not about 15-40 nanometer not etc. to distance between two tips, and its thickness is 3-5 nanometer. These nanometer sheet make nanowire surface become abnormal rough, significantly improve specific surface area on the basis of original structure.
Fig. 3 is that powder x-ray diffraction (XRD) characterizes spectrogram. This spectrogram shows that product crystal structure is consistent with the standard card (JCPDF78-2076) of ruby copper, its characteristic diffraction peak corresponds respectively to cubic phase oxygenization cuprous (110), (111), (200), (220) and (311) crystal face, it was demonstrated that the chemical group of hyperbranched nano wire becomes Red copper oxide.
Fig. 4 is X-ray photoelectron spectroscopic analysis. Showing Cu2p3/2 combination in figure can be 932.3eV, and does not occur obvious satellite characteristic peak between Cu2p3/2 and Cu2p1/2, eliminates the possibility that divalence Cu ion exists. In addition, the characteristic peak of O1s is positioned at 528.5eV, with Red copper oxide lattice oxygen position consistency, does not find in addition significantly to take on peak, and thus provable sample surfaces composition is Red copper oxide.
Fig. 5 is high power transmission electron microscope (TEM) analysis chart. The lattice fringe showing two grades of thorn-like nanometer sheet in figure extends from the lattice fringe of nano wire trunk, and do not see obvious lattice distortion, demonstrating nanometer sheet and nano wire has identical crystalline structure, the over-expense nanowires body that both generate is an equal crystalline phase composition.
Embodiment 2
(1) it is that the sodium hydroxide solution of 8.5 mol/L mixes with the copper-bath (0.276 mol/L) of 50 milliliters and stirs 30 minutes by 1.25 liters of concentration.
(2) container filling above-mentioned homogeneous mixture solotion is placed in 80 degrees Celsius of oil (water) bath heating, and the liquid level of oil bath not had the height of mixing solutions in container, and maintain magneton rotating speed in container is 500 revs/min simultaneously.
(3) when solution system temperature to be mixed reaches 80 degrees Celsius, it may also be useful to the syringe that range is 20 milliliters adds rapidly 10.7 milliliters of quadrols, then the injection being 1 milliliter with another range adds 0.9mL hydrazine hydrate. Maintain 80 degrees Celsius afterwards and continue heating 1 hour, obtain copper nano-wire product.
(4) above-mentioned products obtained therefrom second alcohol and water respectively washs three times, subsequently copper nano-wire product good for washing enrichment is placed in the tubular oven of adjustable temperature and humidity, according to 5 degrees celsius/minute temperature programmings to 60 degree Celsius, and to continue to lead to into humidity be the water vapour of 70%, moisture flow velocity is 30sccm, and ageing obtains over-expense classification cuprous nano material after 5 hours.
Showing product through XRD analysis result is Red copper oxide. In typical case's SEM result and embodiment 1, Fig. 1 result is similar, prepares circulation ratio good after proving to scale up.
Over-expense classification cuprous nano material tool prepared by the present invention has been widely used, can be used as non-enzymatic sensor electrode material, photolysis water hydrogen gas material and photocatalysis degradation organic contaminant material, it is possible to be applied in the fields such as lithium ion battery energy storage, leakage of oil absorption, oily water separation. Below the application of product of the present invention in photolysis water hydrogen is described:
(1) 0.1g gained is overspend stirring in 250 milliliters of Pyrex round-bottomed flasks that the aqueous solution that classification cuprous nano material sample and 200mL contain 0.5 mol/L sodium sulphite and 0.5 mol/L S-WAT sacrifice agent seal at silica gel sealing plug even.
(2) milliliter platinum acid chloride solution (1 mg/ml) that adds 1 is slowly dripped subsequently with syringe and ultrasonic disperse 5 minutes.
(3) by the nitrogen bubble sweeping method emptying of the air in Prex bottle.
(4) the 300W xenon lamp being equipped with HOYA (�� > 420 nanometer) spectral filter is used to irradiate 30 minutes. Adopting ultraviolet-visible light to irradiate the light face of Prex bottle, in illumination process, magneton at the uniform velocity stirs with 500 revs/min, keeps catalyzer to be in suspended state in the solution always, and uses the constant temperature of reaction of cooling circulating water. Adopted microsyringe to extract above flask every 1 hour in reaction process change that 100 microliter are expelled in gas-chromatography to detect hydrogen output.
(5) for ensureing the impact that hydrogen-producing speed does not constantly increase by system pressure, every 5 hours by emptying for the hydrogen in system, re-start hydrogen output detection, so repeatedly carry out investigating the work-ing life of catalyzer.
Fig. 6 overspends classification cuprous nano material to extend comparing of changing conditions in time with comparative sample (nano wire and nanoparticle catalyst) hydrogen generation efficiency under UV, visible light optical radiation under same experimental conditions. As can be seen from Figure, overspend classifying nano Red copper oxide material under same experimental conditions to compare with nanoparticle catalyst with nano wire, ultraviolet-visible hydrolytic hydrogen production efficiency is more superior, per hour producing hydrogen 263.8 micromole, in 45 h cycle processes, there is not obvious reduction in photocatalytic activity.
Claims (10)
1. an over-expense classification cuprous nano material, it is characterized in that: comprising nano cuprous oxide wire matrix and the thorn-like cuprous nano sheet along nano cuprous oxide wire matrix axial array, the direction of growth of thorn-like cuprous nano sheet is vertical with nano cuprous oxide wire matrix.
2. overspend the preparation method of classification cuprous nano material for one kind, it is characterised in that comprise the following steps:
Sodium hydroxide solution is mixed with copper-bath and stirs evenly by a, obtains mixing solutions;
The mixing solutions that step a is obtained by b adds in Erlenmeyer flask, is then placed in oil bath heating, and the liquid level of oil bath not had the height of mixing solutions in Erlenmeyer flask, keeps at the uniform velocity stirring in heat-processed;
When c solution system temperature to be mixed reaches hydrothermal temperature, being rapidly in Erlenmeyer flask and inject quadrol and hydrazine hydrate, reacting under this hydrothermal temperature afterwards, until obtaining copper nano-wire product;
The copper nano-wire product that step c is obtained by d, after washing, enrichment, is placed in the encloses container internal oxidition of full wet air, takes out after being oxidized, and namely obtains over-expense classification cuprous nano material.
3. a kind of preparation method overspending classification cuprous nano material according to claim 2, it is characterised in that, in step a: the concentration of described sodium hydroxide solution is 8��9 mol/L; The concentration of copper-bath is 0.2��0.3 mol/L; The mol ratio of sodium hydroxide and copper sulfate is 29��32.
4. a kind of preparation method overspending classification cuprous nano material according to claim 2, it is characterised in that, in step b: stir and adopt magnetic agitation or mechanical stirring mode.
5. a kind of preparation method overspending classification cuprous nano material according to claim 2, it is characterised in that, in step c: copper sulfate is 0.08��0.10 with the ratio of quadrol amount of substance; Copper sulfate is 0.55��0.8 with the ratio of hydrazine hydrate amount of substance.
6. a kind of preparation method overspending classification cuprous nano material according to claim 2, it is characterised in that, in step c: described hydrothermal temperature is 80 degrees Celsius, the hydro-thermal reaction time is 1 hour.
7. a kind of preparation method overspending classification cuprous nano material according to claim 2, it is characterised in that, in steps d: described washing process adopts second alcohol and water respectively to wash three times, described washing, enriching step adopt takes out filter and centrifugation apparatus.
8. a kind of preparation method overspending classification cuprous nano material according to claim 2, it is characterised in that, in steps d: described oxidizing temperature is 60��70 degrees Celsius; Oxidization time is 5��6 hours.
9. a kind of preparation method overspending classification cuprous nano material according to claim 2, it is characterised in that, in steps d: described oxidation humid control is in 65%��70% scope.
10. over-expense classification cuprous nano material as described in claim 1-9 any claim is as non-enzymatic sensor electrode material, photolysis water hydrogen gas material, and photocatalysis degradation organic contaminant material, and it is applied in lithium ion battery energy storage, leakage of oil absorption, oily water separation field.
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| CN110357140B (en) * | 2019-03-18 | 2021-12-28 | 苏州东展羽绒服饰有限公司 | Superfine villous copper oxide nanowire, preparation method and application of superfine villous copper oxide nanowire to functional fabric |
| CN110668392A (en) * | 2019-10-10 | 2020-01-10 | 北京航空航天大学杭州创新研究院 | Enhanced heat dissipation Cu-Cu2O-core-shell nanowire array self-protection electrode and preparation method thereof |
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| WO2022050162A1 (en) * | 2020-09-03 | 2022-03-10 | 学校法人福岡工業大学 | Inorganic-nanosheet multilayer structure, inorganic-nanosheet liquid-crystal composition, method for producing inorganic-nanosheet multilayer structure, and method for producing inorganic-nanosheet liquid-crystal composition |
| CN112919525A (en) * | 2021-03-29 | 2021-06-08 | 蚌埠学院 | Preparation method of nano cuprous oxide |
| CN112919525B (en) * | 2021-03-29 | 2022-12-30 | 蚌埠学院 | Preparation method of nano cuprous oxide |
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