CN105983410A - Heterogeneous compound photocatalyst and preparation method thereof - Google Patents
Heterogeneous compound photocatalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a heterogeneous compound photocatalyst and a preparation method thereof. The photocatalyst comprises a core, wherein the core is made from an n-type semiconductor material or a p-type semiconductor material; an intermediate layer, wherein the periphery of the core is coated with the intermediate layer, and the intermediate layer is made of reduced graphene oxide; and an outer layer, wherein the periphery of the intermediate layer is coated with the outer layer, and the outer layer is made of an n-type semiconductor material or a p-type semiconductor material different from the n-type semiconductor material or the p-type semiconductor material of the core in types. The heterogeneous compound photocatalyst has a p-r-n structure or an n-r-p structure, so radial separation of photon-generated carriers from the core to the outer layer is realized under the irradiation of lights in order to shorten the separation distance of the carriers. The reduced graphene oxide material positioned in the intermediate layer can accelerate transportation of electron hole pairs in order to inhibit compounding of the carriers, so separation of the carriers is promoted, thereby the photocatalysis efficiency is increased.
Description
Technical field
The present invention relates to light-catalyzed reaction field, in particular it relates to a kind of Heterogeneous Composite type photocatalyst and preparation method thereof.
Background technology
Photocatalysis is a kind of photochemical reaction in the presence of a catalyst, is the combination of photochemistry and catalyst.Photocatalytic hydrogen production by water decomposition is that the one that development in recent years is got up is energy-conservation, high effective green environmentally friendly new technique.But it is as the research and development of New function material, also facing a lot of limitation, as the highest in catalytic efficiency, catalysqt deactivation, secondary pollution, sunlight utilization rate are low etc..Based on this, developing and build heterojunction structure has become the important means of currently acquired novel high-performance catalysis material.
Photocatalytic semiconductor material can be divided into n-type semiconductor and p-type semiconductor according to carrier feature.Can prepare dissimilar composite photo-catalyst by compound for different types of semi-conducting material, main compound type has n-n type, p-p type and p-n junction.Wherein p-n heterojunction is not only able to the wave-length coverage by sensibilization extension wide band gap semiconducter, and can suppress Carrier recombination by built in field, increases substantially the photocatalysis performance of material, therefore enjoys domestic and international extensive concern.But, the built in field that p-n is formed, although the separation of photo-generated carrier can be realized, but the centrifugation of fixing built in field, can be along with the carrying out of photocatalytic process, electric field the two poles of the earth, p-n junction two ends Partial charge accumulates, and is gradually lowered separation of charge effect, thus inhibit the separation of electric charge, reduce photocatalysis performance.
But, along with the development of science and technology, the catalytic efficiency of existing photocatalyst has been unsatisfactory for application demand, develops and builds novel photocatalyst and have become as a new problem of research worker.
Summary of the invention
It is an object of the invention to provide a kind of Heterogeneous Composite type photocatalyst and preparation method thereof, to improve the photocatalysis efficiency of Heterogeneous Composite type photocatalyst.
To achieve these goals, one aspect of the present invention, it is provided that a kind of Heterogeneous Composite type photocatalyst, this photocatalyst includes:
Core, the material of core is n-type semiconductor or p-type semiconductor material；
Intermediate layer, is coated on the periphery of core, and the material in intermediate layer is redox graphene；
Outer layer, is coated on the periphery in intermediate layer, and the material of outer layer is n-type semiconductor different types of with core or p-type semiconductor material.
Meanwhile, in another aspect of the present invention, additionally providing the preparation method of a kind of Heterogeneous Composite type photocatalyst, this preparation method comprises the following steps:
Nanofiber or the nanotube of material I is prepared by electrostatic spinning process, standby as core material；Oxidation processes graphite prepares graphene oxide, standby as intermediate layer material；Under ultrasound condition, nanofiber or the nanotube of material I are contacted with graphene oxide mixing, is coated with graphene oxide in the nanofiber periphery of material I, obtains the first intermediate product；Under heating reducing condition, the graphene oxide in the first intermediate product that reduces forms redox graphene, obtains the second intermediate product；Second intermediate product is dispersed in material II source of dissolving, under the conditions of heating crystallize, at mix powder periphery co-crystal former matter II outer layer, obtains Heterogeneous Composite type photocatalyst；Wherein, material I is n-type semiconductor or p-type semiconductor material；Material II is n-type semiconductor different types of with material I or p-type semiconductor material, and material II source is the soluble-salt of material II.
Above-mentioned Heterogeneous Composite type photocatalyst provided by the present invention and preparation method thereof, by being formed at one layer of redox graphene (rGO of Surface coating of sandwich layer, it is abbreviated as r) intermediate layer, it is coated with one layer of outer layer again, form the Heterogeneous Composite type photocatalyst with p-r-n structure or n-r-p structure, this Heterogeneous Composite type photocatalyst is under the irradiation of light, and photo-generated carrier can realize, by the radial separation of core outer layers, this substantially reduces the separating distance of carrier.It is positioned at the redox graphene material in intermediate layer simultaneously, because having zero band gap, graphene layer introducing p-type quasiconductor can be passed through as by light induced electron, and realizing the long-acting centrifugation of carrier.The separation of electron hole pair is accelerated in photocatalytic process, the electronics produced will spread to n-type semiconductor direction, and the hole of generation will be spread to P-type semiconductor direction, being combined of suppression carrier, thus promote the separation of carrier, and then improve the catalytic efficiency of photocatalyst.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below.In the accompanying drawings:
Fig. 1 shows the structural representation according to the Heterogeneous Composite type photocatalyst in embodiment of the present invention；
Fig. 2 shows the radial section schematic diagram according to the Heterogeneous Composite type photocatalyst in embodiment of the present invention；
Fig. 3 shows the NiO-rGO-TiO of 1 preparation according to embodiments of the present invention2X-ray diffraction (XRD) collection of illustrative plates of Heterogeneous Composite type photocatalyst；
Fig. 4 shows the NiO-rGO-TiO of 1 preparation according to embodiments of the present invention2The Raman collection of illustrative plates of Heterogeneous Composite type photocatalyst；
Fig. 5 shows the NiO-rGO-TiO of 1 preparation according to embodiments of the present invention2Scanning electron microscope (SEM) photo of Heterogeneous Composite type photocatalyst；
Fig. 6 shows the NiO-rGO-TiO of 1 preparation according to embodiments of the present invention2Transmission electron microscope (TEM) photo of Heterogeneous Composite type photocatalyst；And
Fig. 7 shows the NiO-rGO-TiO of 1 preparation according to embodiments of the present invention2Heterogeneous Composite type photocatalyst is at 100mW/cm2The design sketch of lower photolysis water hydrogen.
Description of reference numerals
10 core 20 intermediate layers
30 outer layers
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
As background section is received, along with the development of science and technology, the catalytic efficiency of existing photocatalyst has been unsatisfactory for application demand.Developing and construct a kind of novel Heterogeneous Composite type photocatalyst in the present invention, as depicted in figs. 1 and 2, this photocatalyst includes: core 10, intermediate layer 20 and outer layer 30.Wherein the material of core 10 is n-type semiconductor or p-type semiconductor material.Intermediate layer 20 is coated on the periphery of core 10, and the material in intermediate layer 20 is redox graphene；Outer layer 30 is coated on the periphery in intermediate layer 20, and the material of outer layer 30 is n-type semiconductor different types of with core 10 or p-type semiconductor material.
Above-mentioned Heterogeneous Composite type photocatalyst provided by the present invention, by being formed at one layer of redox graphene (rGO of Surface coating of sandwich layer, it is abbreviated as r) intermediate layer 20, it is coated with one layer of outer layer 30 again, form the Heterogeneous Composite type photocatalyst with p-r-n structure or n-r-p structure, this Heterogeneous Composite type photocatalyst is under the irradiation of light, and photo-generated carrier can realize, by the radial separation of core 10 outer layers 30, this substantially reduces the separating distance of carrier.It is positioned at the redox graphene material in intermediate layer 20 simultaneously, because having zero band gap, graphene layer introducing p-type quasiconductor can be passed through as by light induced electron, and realizing the long-acting centrifugation of carrier.The transmission of electron hole pair can be accelerated in photocatalytic process, the electronics produced will spread to n-type semiconductor direction, the hole produced will be spread to p-type semiconductor direction, suppress the compound of carrier thus promotes the separation of carrier, and then improve the catalytic efficiency of photocatalyst.
Preferably, in the present invention above-mentioned Heterogeneous Composite type photocatalyst, core 10 is nanofiber or nanotube, and/or, outer layer 30 is nano wire or nano-particle
In the present invention above-mentioned Heterogeneous Composite type photocatalyst, particular/special requirement is not had for particle size, as long as being adapted to use demand.In the preferred embodiment of the present invention, in above-mentioned Heterogeneous Composite type photocatalyst, core 10 is diameter range 300 ± 100nm, the nanofiber of length 1-500 μm or nanotube.Intermediate layer 20 is the redox graphene material layer of thickness range 20 ± 10nm.Outer layer 30 is nano wire layer or the nano-particle layer of thickness range 150 ± 50nm.By the dimension limitation of Heterogeneous Composite type photocatalyst within the above range, may advantageously facilitate the sharp separation of photo-generated carrier, and then improve the catalytic efficiency of photocatalyst.It is further preferable that in above-mentioned Heterogeneous Composite type photocatalyst, the thickness range in intermediate layer 20 is 20 ± 5nm；Thickness range 150 ± the 25nm of outer layer 30.
In the present invention above-mentioned Heterogeneous Composite type photocatalyst for granule in the thickness of each layer do not have special requirement, but in order to optimize the effect of the redox graphene material as intermediate layer 20, in the preferred embodiment of the present invention, in above-mentioned Heterogeneous Composite type photocatalyst, the weight ratio in core 10 and intermediate layer 20 is 20:1-10:1, and the weight ratio of core 10 and the gross weight in intermediate layer 20 and outer layer 30 is 1:1-1:2.Being more highly preferred to the weight ratio in core 10 and intermediate layer 20 in above-mentioned Heterogeneous Composite type photocatalyst is 15:1-17:1.The gross weight in core 10 and intermediate layer 20 is 2:3-3:4 with the weight ratio of outer layer 30.
As long as in the present invention above-mentioned Heterogeneous Composite type photocatalyst for granule in the selection of layers of material based on n-r-p structure or p-r-n structure choice.Wherein it is possible to the n-type semiconductor used includes but not limited to TiO2、SrTiO3, ZnO, CdS, one or more in perovskite composite oxides and spinel complex oxide.The p-type semiconductor material that can use includes but not limited to NiO, Cu2S、Cu2O、Co3O4、Ag2O and Ag2One or more in S.
As long as forming n-r-p structure or p-r-n structure at the present invention above-mentioned Heterogeneous Composite type photocatalyst, it becomes possible to form the Heterogeneous Composite type photocatalyst higher than photocatalyst catalytic efficiency in prior art.In the preferred embodiment of the present invention, in above-mentioned Heterogeneous Composite type photocatalyst, core 10 is NiO, and intermediate layer 20 is redox graphene, and outer layer 30 is TiO2.Can be in conjunction with visible light catalytic effect excellent for NiO and TiO in this Heterogeneous Composite type photocatalyst2Excellent ultraviolet catalytic effect, and then can preferably improve the photocatalysis efficiency of Heterogeneous Composite type photocatalyst.
Above-mentioned Heterogeneous Composite type photocatalyst provided by the present invention, is referred to existing method of the prior art and is prepared.In the preferred embodiment of the present invention, the preparation method of a kind of above-mentioned Heterogeneous Composite type photocatalyst is provided, this preparation method comprises the following steps: prepared nanofiber or the nanotube of material I by electrostatic spinning process, as core 10 materials for later use；Oxidation processes graphite prepares graphene oxide, standby as intermediate layer material 20；Under ultrasound condition, nanofiber or the nanotube of material I are contacted with graphene oxide mixing, is coated with graphene oxide in the nanofiber periphery of material I, obtains the first intermediate product；Under heating reducing condition, the graphene oxide in the first intermediate product that reduces forms redox graphene, obtains the second intermediate product；Second intermediate product is dispersed in material II source of dissolving, under the conditions of heating crystallize, at mix powder periphery co-crystal former matter II outer layer 30, obtains Heterogeneous Composite type photocatalyst；Wherein, described material I is n-type semiconductor or p-type semiconductor material；Material II is n-type semiconductor different types of with material I or p-type semiconductor material, and material II source is the soluble-salt of material II.
The preparation method of above-mentioned Heterogeneous Composite type photocatalyst provided by the present invention, nanofiber or the nanotube of material I is prepared by electrostatic spinning process, while can producing nano-scale fiber powder, be conducive to the diameter of nanofiber prepared by controlling and length.By the way of ultrasonic agitation (stirring under i.e. at ultrasound condition), nanofiber and the graphene oxide of compounding substances I mixes, enable to graphene oxide and be fractured into the little granule of lamellar, make the little granule of this lamellar can be wrapped in the periphery of nanofiber of material I, and then redox graphene intermediate layer after reduction treatment, can be formed.Simultaneously by being joined by the mix powder including material I and redox graphene in the solution that material II source is dissolved, by the way of heating, at mix powder periphery co-crystal former matter II outer layer, and then form p-r-n structure or n-r-p structure.Said method provided by the present invention, combines compact, and easily operates, it is adaptable to large-scale industrial production while the Heterogeneous Composite each Rotating fields of type photocatalyst formed is clearly demarcated.
Below by the preparation method according to above-mentioned provided Heterogeneous Composite type photocatalyst, further illustrate the embodiment of each step.
(1) can be, commercially available prod about nanofiber or the nanotube of material I in the preparation method of above-mentioned Heterogeneous Composite type photocatalyst, it is also possible to be worked materials.
In the preferred embodiment of the present invention, the step of the nanofiber preparing material I above by electrostatic spinning process includes: being dissolved in the first solvent in material I source, stirring 3-12h obtains mixed solution A；Adding polyvinylpyrrolidone in mixed solution A, stirring 8-24h obtains mixed solution B；Mixed solution B is filled to syringe, syringe needle (0.6-1.0mm) is installed, under the conditions of voltage is 22kV, carries out electrostatic spinning, obtain nano wire；Sintering nano wire at 450-550 DEG C, obtain the nanofiber of material I, wherein, material I source is the soluble-salt of material I.
Simultaneously, in the above-mentioned methods, consumption for polyvinylpyrrolidone does not has particular/special requirement, and the consumption of preferably polyethylene ketopyrrolidine and the mass ratio of the first solvent are 1:10-1:20, and the consumption of particularly preferred polyvinylpyrrolidone and the mass ratio of the first solvent are 1:20.By both limited proportions within the range, the formation of beneficially nanofiber.
In the above-mentioned methods, particular/special requirement is not had for the first solvent, as long as material I can be dissolved and for volatile solution.The first solvent that can use the most in the present invention includes but does not include one or more in ethanol, acetic acid, methanol, isopropanol and N,N-dimethylformamide.
(2), the step of graphene oxide is prepared about oxidation processes graphite in the preparation method of above-mentioned Heterogeneous Composite type photocatalyst.
Can be commercially available prod at graphene oxide used in the present invention, it can also be worked materials, in the preferred embodiment of the present invention, the step that above-mentioned oxidation processes graphite prepares graphene oxide includes: is mixed with oxidisability strong acid by graphite, obtains mixture C；Mixture C is cooled to less than 0 DEG C, in mixture C, adds the first oxidant, stirring reaction 1-5h, obtain mixture D；Adding the second oxidant in mixed solution D, it is golden yellow for stirring to solution, and centrifugation obtains graphene oxide after drying.Preferably, in mixture C, the first oxidant is added with the speed of 0.01-0.1g/s.
In the above-mentioned methods, successively graphite is mixed with oxidisability strong acid, the first oxidant and the second oxidant, graphite is gradually aoxidized so that it is oxidation more complete, it is more beneficial for the little nanometer sheet of broken formation during subsequent ultrasonic stirs, to be attached to the periphery of the nanofiber of material I.
In the above-mentioned methods, the purpose using oxidisability strong acid is the graphite that preliminary oxidation processes.5-20 times that consumption (weight) is graphite weight of preferential oxidation strong acid.The oxidisability strong acid that preferably can use includes but not limited to one or more in concentrated sulphuric acid, nitric acid (concentration is 65wt.%-70wt.%) and permanganic acid ((pKa-2.5)).
In the above-mentioned methods, the purpose adding the first oxidant is for further graphite oxide.Preferably 5-10 times that consumption (weight) is graphite weight of this first oxidant.First preferably can used is oxidized to agent potassium permanganate, phosphorus pentoxide, one or more in potassium peroxydisulfate.
In the above-mentioned methods, the purpose adding the second oxidant is reoxidation graphite, makes the most complete of graphite oxidation.2-5 times that consumption (weight) is graphite weight of preferably second oxidant.The second oxidant that preferably can use is hydrogen peroxide.
Preferably, in order to reduce operational risk, before adding the second oxidant in mixed solution D, also include that the temperature controlling solution system is less than 55 DEG C, in mixture D, add diluent, to the pH value of solution step more than 0.01, preferably in mixture D, add diluent with the speed of 0.01-0.1g/s.
In the above-mentioned methods, the purpose adding diluent is to reduce the acidity of mixture D, to reduce operational hazards.The consumption of diluent is selected according to this purpose.In the preferred embodiment of the present invention, add diluent 5-10 times that consumption is mixture D weight, to obtain pH value of solution more than 0.01 mixed solution E.The diluent that can use in the present invention is preferably one or more in deionized water, purified water, ultra-pure water.
In the preferred embodiment of the present invention, before in the preparation method of above-mentioned Heterogeneous Composite type photocatalyst, oxidation processes graphite prepares the step of graphene oxide, also include the step that graphite is carried out pretreatment, the step of pretreatment includes: take oxidisability strong acid, adding surface conditioning agent in oxidisability strong acid, stirring and dissolving obtains preprocessing solution；Being added to preprocessing solution by graphite, 60-100 DEG C of isothermal holding 2-6h, cooling, after flushing, sucking filtration is dried to obtain the graphite of pretreatment.
In this approach, by the surface of graphite is carried out pretreatment, be conducive to improving the activity of graphite surface, and then be conducive to, in subsequent oxidation processes step, more preferably faster graphite being aoxidized, and then form graphene oxide.Preferably, in the step of above-mentioned pretreatment, it is possible to use surface conditioning agent include but not limited to one or more in potassium peroxydisulfate, phosphorus pentoxide, potassium permanganate, (weight) consumption that surface conditioning agent is preferably used is 0.5-2 times of graphite.Preferably, the consumption of described oxidisability strong acid is 5-20 times of described graphite weight, and described oxidisability strong acid is one or more in concentrated sulphuric acid, nitric acid and permanganic acid.
(3), the preparation method about above-mentioned Heterogeneous Composite type photocatalyst obtains the first intermediate product and the step of the second intermediate product.
In the preferred embodiment of the present invention, in said method, ultrasound condition is, in the first alcoholic solution, under the conditions of power is 100-800W, and ultrasonic agitation 0.5-3h；Heating reducing condition is: under the conditions of sealing and temperature are 120-180 DEG C, react 9-20h.
In a kind of detailed description of the invention of the present invention, the step obtaining the first intermediate product and the second intermediate product in said method includes: by the nanofiber dispersion of material I in the first alcoholic solution, obtain mixed solution；Graphite oxide is added mixed solution, under conditions of power is 100-800W, ultrasonic agitation 0.5-3h, obtain the first intermediate product；By the first intermediate product, seal under the conditions of being 120-180 DEG C with temperature, react 9-20h, obtain the second intermediate product.The most also including the step to the second purifying intermediate products, this step includes: the second intermediate product is cooled to room temperature, rinses to neutrality, and sucking filtration is dried to obtain the second intermediate product of purification.
In said method of the present invention, utilize the graphene oxide as intermediate layer material after oxidation, in the case of using ultrasonic agitation, the feature of the little granule of lamellar (graphene oxide) can be broken for, graphene oxide is distributed in the periphery of material I (n-type semiconductor or p-type semiconductor), and then after redox graphene, forms intermediate layer.
In the above-mentioned methods, the mesh using the first alcoholic solution is to generate redox graphene with graphene oxide generation reduction reaction.The first alcoholic solution that can use in the present invention includes but not limited to ethanol water (weight concentration is 20%-60%) and/or methanol aqueous solution (weight concentration is 20%-60%).
(4), about the step forming outer layer in the preparation method of above-mentioned Heterogeneous Composite type photocatalyst in the second intermediate product periphery crystallization.
In the preferred embodiment of the present invention, the mode being dispersed in by second intermediate product in material II source of dissolving includes: be dissolved in the second alcoholic solution in material II source, described second intermediate product, under conditions of power is 100-800W, ultrasonic agitation 0.5-2h is added after stirring mixing.In the preferred embodiment of the present invention, heating crystallize condition is: under the conditions of sealing and temperature are 160-200 DEG C, react 9-20h, is then annealed at 450-550 DEG C by product.
In a kind of detailed description of the invention of the present invention, the above-mentioned step at the second intermediate product periphery crystallization formation outer layer includes: being dissolved in the second alcoholic solution in material II source, stirring obtains mixed solution；Mix powder is added in mixed solution, under conditions of power is 100-800W, after ultrasonic agitation 0.5-2h under the conditions of sealing and temperature are 160-200 DEG C, react 9-20h, form outer layer with the crystallization in mix powder periphery, obtain Heterogeneous Composite type photocatalyst.
Preferably after the step obtaining above-mentioned Heterogeneous Composite type photocatalyst, also including purification step, this purification step includes being cooled to Heterogeneous Composite type photocatalyst room temperature, rinses to neutrality, and sucking filtration is dried to obtain the Heterogeneous Composite type photocatalyst of purification.
Before or after above-mentioned purification step, preferably also include annealing steps, the condition of this annealing steps is annealing 1-3h at 450-550 DEG C, be conducive to improving the crystallinity of Heterogeneous Composite type photocatalyst outer layer, the photocatalysis performance of the Heterogeneous Composite type photocatalyst prepared by optimization by annealing.
Said method provided by the present invention, utilizing material II source (soluble-salt of material II) is the feature with solubility, material II source is dissolved and forms solution, again the second intermediate product including material I and material II is joined in the solution of material II source, by the way of heating crystalline, at periphery forming material II outer layer of the second intermediate product.The method is easily controlled the thickness of outer layer, and can improve the purity of outer layer.
In the above-mentioned methods, the purpose using the second alcoholic solution is that the selection for this second alcoholic solution does not has particular/special requirement for dissolving material II source, as long as material II source can be dissolved.In the preferred embodiment of the present invention, preferably this second alcoholic solution is diethylene glycol aqueous solution (volume fraction is 50%-90%), or aqueous solution of propylene glycol (volume fraction is 50%-90%).
The beneficial effect of the preparation method of Heterogeneous Composite type photocatalyst of the present invention is further illustrated below with reference to specific embodiment.
One, embodiment 1 to 7 and comparative example 1
(1) embodiment 1
Preparation NiO-redox graphene (rGO)-TiO2(p-r-n) Heterogeneous Composite type photocatalyst
The preparation method of above-mentioned Heterogeneous Composite type photocatalyst comprises the steps:
(1) by 2.5g nickel acetate (C4H6O4Ni·4H2O) it is dissolved in the mixed solution of 15g ethanol and 4.5g acetic acid, after stirring 6h, adds 1g polyvinylpyrrolidone (PVP, Mw=1300000), continue stirring 12h.The syringe that the solution of 1ml is put into 5ml carries out electrostatic spinning, and using the syringe needle of diameter 0.8mm, catcher is 25cm with the distance of syringe needle.Voltage is 22kV.Finally product is placed at 500 DEG C calcining 2h, obtains the NiO nanofiber of a diameter of 300nm；
(2) by concentrated sulphuric acid (H2SO4) 50ml is placed in round-bottomed flask and is heated to 80 DEG C, is then sequentially added into 10g potassium peroxydisulfate and 10g phosphorus pentoxide (P2O5), stirring is until being completely dissolved.The graphite powder of 12g is joined in above-mentioned solution, and is maintained at 80 DEG C of 4h.Being cooled down by mixture, be washed with deionized, sucking filtration is dried to obtain the graphite of pretreatment.Then the graphite of pretreatment is put in the conical flask of 2L, add 460ml concentrated sulphuric acid, be cooled to 0 DEG C, then by 60g potassium permanganate (KMnO4) be slowly added in mixture, after stirring two hours, 1L deionized water is slowly added in flask, controls temperature and be less than 55 DEG C, after dilution, by the hydrogen peroxide (H of 50ml 30%2O2In), it is golden yellow for continuing stirring to solution, and centrifugation obtains graphene oxide after drying；
(3) weighing the NiO nanofiber powder 100mg that step (1) obtains, and be dispersed in the alcohol mixed solution of 50mL water and 25ml, gained mixed liquor is labeled as solution A；Add graphene oxide ultrasonic agitation (power the is 600W) 30min that 5mg step (2) obtains, make the graphene oxide crushing-type little granule of slabbing graphene oxide and be wrapped in NiO powder periphery, then solution is put in the reactor of 100ml, seal hydrothermal reaction kettle, put it in drying baker, hydrothermal temperature is made to control at 140 DEG C, response time is 12h, reduction aforementioned oxidation Graphene, reaction naturally cools to room temperature after terminating, products therefrom deionized water rinses repeatedly to neutrality, then sucking filtration, it is dried, obtain the NiO-rGO powder that thickness is 20nm of graphene oxide (rGO) layer；
(4) by 0.42g titanium potassium oxalate K2TiO(C2O4)2Being dissolved in the diethylene glycol of 5ml deionized water and 15ml, stir, gained solution is labeled as B (compared with prior art, it is not necessary to acid material)；It is subsequently adding the NiO-rGO powder of the 100mg that step (3) obtains, puts into after ultrasonic agitation (power is 100W) 1.5h is uniform in the reactor of 50ml.Then hydrothermal reaction kettle is sealed; put it in drying baker; hydrothermal temperature is made to control at 180 DEG C; response time is 9h, and reaction naturally cools to room temperature after terminating, and products therefrom deionized water rinses repeatedly to neutrality; then sucking filtration; it is dried, under argon shield, at 500 DEG C, makes annealing treatment 2h, obtain TiO2Layer thickness is the NiO-rGO-TiO of 100nm2Powder, i.e. prepares nickel oxide-redox graphene-titanium dioxide (p-r-n) nano-heterogeneous structure photocatalyst.
(2) NiO-rGO-TiO prepared by embodiment 12The structured testing of Heterogeneous Composite type photocatalyst:
(1) X-ray diffraction test
Test instrunment: Germany's Brooker D8X-x ray diffractometer x is analyzed.
Test result: as shown in Figure 3.Fig. 3 shows the NiO-rGO-TiO of 1 preparation according to embodiments of the present invention2X-ray diffraction (XRD) collection of illustrative plates of Heterogeneous Composite type photocatalyst, wherein ■ represents NiO, ● represent TiO2, as seen from Figure 3 the Heterogeneous Composite type photocatalyst prepared by embodiment 1 contains NiO and TiO simultaneously2, and NiO and TiO2It is evenly distributed.
(2) Raman spectrum test
Test instrunment: Renishaw Raman spectrometer is analyzed.
Test result: as shown in Figure 4.Fig. 4 shows the NiO-rGO-TiO of 1 preparation according to embodiments of the present invention2The Raman collection of illustrative plates of Heterogeneous Composite type photocatalyst, as seen from Figure 4 when drawing general frequency displacement dynamic more than 1000, it is at 1347cm-1And 1598cm-1Still there is peak, it can be seen that, there is redox graphene at the Heterogeneous Composite type photocatalyst prepared by the embodiment of the present invention 1, it can be seen that redox graphene is not washed off during intermediate reaction.
(3) microexamination
Optical viewer: HIT produces S4800 type scanning electron microscope and the Flied emission transmission electron microscope Tecnai G2 F20 of U.S. FEI production.
Observed result: as shown in Figure 5 and Figure 6.Fig. 5 shows the NiO-rGO-TiO of 1 preparation according to embodiments of the present invention2Scanning electron microscope (SEM) photo of Heterogeneous Composite type photocatalyst.Fig. 6 shows the NiO-rGO-TiO of 1 preparation according to embodiments of the present invention2Transmission electron microscope (TEM) photo of Heterogeneous Composite type photocatalyst.
From Fig. 5 and Fig. 6, embodiment 1 prepare Heterogeneous Composite type photocatalyst the NiO that kernel is rule of surface ((200)), intermediate layer is rGO, and outside is the TiO of surface imperfection2((105)), present invention p-r-n required for protection structure just.
(3) embodiment 2-7
Preparation NiO-rGO-TiO2((p-r-n) Heterogeneous Composite type photocatalyst, prepared NiO-rGO-TiO2((p-r-n) Heterogeneous Composite type photocatalyst is as shown in table 1 with the difference of embodiment 1, and preparation method is with reference to the method shown in embodiment 1.
The diameter of NiO core, length in the most prepared Heterogeneous Composite type photocatalyst, and rGO layer and TiO2The thickness of layer is obtained by control response parameter and material rate in preparation process, and is measured by transmission electron microscope (TEM) photo.
Table 1.
(4) comparative example 1-3
Comparative example 1: commercially available from the P25 nano-photocatalyst of Germany's goldschmidt chemical corporation.
Comparative example 2:NiO-rGO photocatalyst, preparation method is with reference to the embodiment of the present invention 1.
Comparative example 3:NiO photocatalyst, preparation method is with reference to the embodiment of the present invention 1.
(5) photocatalysis effect test.
Test instrunment: photocatalytic activity hydrogen generating system and gas chromatograph (GC-7900).
Method of testing: in photocatalyst joins the mixed solution of 70mL water and 30mL methanol in the embodiment of the present invention 1 to 7 and comparative example 1-3, at 100mW/cm2Simulated solar irradiation is hydrolyzed under irradiating.
Hydrogen-producing speed: generation gas is collected detection, calculates the amount of every gram of sample generation hourly hydrogen.
Test result (1): as shown in Figure 7:
In the figure 7, respectively illustrate the hydrogen-producing speed curve in 6h of the photocatalyst in the embodiment of the present invention 1 and comparative example 1-3.Use the NiO-rGO-TiO of embodiment 1 preparation as seen from Figure 72Heterogeneous Composite type photocatalyst, the hydrogen-producing speed in 6h is 0.3mmol/g/h, and it is far longer than the hydrogen-producing speed of NiO nanofiber and NiO-rGO nanofiber, and higher than business-like Degussa P25.
Test result (2): as shown in table 2.
Table 2.
As shown in table 2, at NiO core diameter between 250-350nm, rGO thickness between 15-25nm, TiO2Thickness NiO-rGO-TiO between 125-175nm2(photocatalytic activity of (p-r-n) Heterogeneous Composite type photocatalyst is higher, and hydrogen manufacturing effect is more preferable, is more than the twice of the Degussa P25 hydrogen manufacturing amount having been commercialized at present.
Two, embodiment 8-13
(1) NiO-rGO-TiO is prepared2((p-r-n) Heterogeneous Composite type photocatalyst, prepared NiO-rGO-TiO2((p-r-n) Heterogeneous Composite type photocatalyst is as shown in table 3 with the difference of embodiment 1, and preparation method is with reference to the method shown in embodiment 1.
In the most prepared Heterogeneous Composite type photocatalyst, the weight of each layer obtains by controlling the ratio of each raw material in preparation process, and by weighing, and the mode of calculated weight difference detects each layer weight.
Table 3.
| NiO core: rGO layer weight ratio | (NiO core+rGO layer): TiO2Layer weight ratio | |
| Embodiment 1 | 20:1 | 1:1 |
| Embodiment 8 | 18:1 | 1:1 |
| Embodiment 9 | 13:1 | 1:2 |
| Embodiment 10 | 10:1 | 2:3 |
| Embodiment 11 | 15:1 | 2:3 |
| Embodiment 12 | 17:1 | 3:4 |
| Embodiment 13 | 30:1 | 1:5 |
(2) photocatalysis effect test.
Method of testing: NiO-rGO-TiO prepared by embodiment 8-132Heterogeneous Composite type photocatalyst, joins in the mixed solution of 70mL water and 30mL methanol, at 100mW/cm2Simulated solar irradiation is hydrolyzed under irradiating.
Test result: as shown in table 4.
Table 4.
| Embodiment | 1 | 8 | 9 | 10 | 11 | 12 | 13 |
| Hydrogen-producing speed (mmol/g/h) | 0.3 | 0.28 | 0.29 | 0.3 | 0.32 | 0.33 | 0.15 |
As in table 4 data it can be seen that by optimizing the weight ratio of each layer in Heterogeneous Composite type photocatalyst so that NiO core: rGO layer weight ratio between 15:1-17:1, (NiO core+rGO layer): TiO2When layer weight ratio is between 2:3-3:4, NiO-rGO-TiO2(photocatalytic activity of (p-r-n) Heterogeneous Composite type photocatalyst is higher, and hydrogen manufacturing effect is more preferable.
Three, embodiment 14-17
(1) preparing different Heterogeneous Composite type photocatalysts, concrete Heterogeneous Composite type photocatalyst is as shown in table 5, and preparation method is with reference to the method shown in embodiment 1.
Table 5.
| P-r-n Heterogeneous Composite type photocatalyst | |
| Embodiment 1 | NiO-rGO-TiO2 |
| Embodiment 14 | Co3O4-rGO–TiO2 |
| Embodiment 15 | Ag2O-rGO-TiO2 |
| N-r-p Heterogeneous Composite type photocatalyst | |
| Embodiment 16 | TiO2-rGO-NiO |
| Embodiment 17 | TiO2-rGO-Ag2O |
(2) photocatalysis effect test.
Method of testing: p-r-n or n-r-p Heterogeneous Composite type photocatalyst embodiment 14-17 prepared, joins in the mixed solution of 70mL water and 30mL methanol, at 100mW/cm2Simulated solar irradiation is hydrolyzed under irradiating.
Test result: as shown in table 6.
Table 6.
| Embodiment | 1 | 14 | 15 | 16 | 17 |
| Hydrogen-producing speed (mmol/g/h) | 0.3 | 0.26 | 0.15 | 0.13 | 0.12 |
Be can be seen that by data in table 6, by adjusting p-type semiconductor material and n-type semiconductor, as long as forming the Heterogeneous Composite type photocatalyst of p-r-n or n-r-p structure, it is respectively provided with the hydrogen-producing speed of preferable photocatalytic water, close to the Degussa P25 even above having been commercialized at present.
Four, embodiment 18-20
(1) embodiment 18: preparation NiO-rGO-TiO2((p-r-n) Heterogeneous Composite type photocatalyst.
The preparation method of above-mentioned Heterogeneous Composite type photocatalyst is with reference to embodiment 1, and wherein difference is,
(2) 12g graphite is put in the conical flask of 2L, add 460ml concentrated sulphuric acid, be cooled to 0 DEG C, then by 60g potassium permanganate (KMnO4) be slowly added in mixing, after stirring two hours, 1L deionized water is slowly added in flask, controls temperature and be less than 50 DEG C, after dilution, by the hydrogen peroxide (H of 50ml 30%2O2In), it is golden yellow for continuing stirring to solution, and centrifugation obtains graphene oxide (not comprising the step that graphite carries out pretreatment) after drying.
(2) embodiment 19: preparation NiO-rGO-TiO2((p-r-n) Heterogeneous Composite type photocatalyst.
The preparation method of above-mentioned Heterogeneous Composite type photocatalyst comprises the steps:
(1) by 2.5g nickel acetate (C4H6O4Ni·4H2O) it is dissolved in the mixed solution of 15g ethanol and 4.5g acetic acid, after stirring 3h, adds 1g polyvinylpyrrolidone (PVP, Mw=1300000), continue stirring 8h.The syringe that the solution of 1ml is put into 5ml carries out electrostatic spinning, and using the syringe needle of diameter 0.8mm, catcher is 25cm with the distance of syringe needle.Voltage is 22kV.Finally product is placed at 450 DEG C calcining 3h, obtains NiO nanofiber；
(2) by concentrated sulphuric acid (H2SO4) 50ml is placed in round-bottomed flask and is heated to 60 DEG C, is then sequentially added into 10g potassium peroxydisulfate and 10g phosphorus pentoxide (P2O5), stirring is until being completely dissolved.The powdered graphite of 12g is joined in above-mentioned solution, and is maintained at 60 DEG C of 6h.Being cooled down by mixture, be washed with deionized, sucking filtration is dried to obtain the graphite of pretreatment.Then the graphite of pretreatment is put in the conical flask of 2L, add 460ml concentrated sulphuric acid, be cooled to-5 DEG C, then by 60g potassium permanganate (KMnO4) be slowly added in mixture, after stirring 5 hours, 1L deionized water is slowly added in flask, controls temperature and be less than 55 DEG C, after dilution, by the hydrogen peroxide (H of 50ml 30%2O2In), it is golden yellow for continuing stirring to solution, and centrifugation obtains graphene oxide after drying；
(3) weighing the NiO nanofiber powder 100mg that step (1) obtains, and be dispersed in the alcohol mixed solution of 50mL water and 25ml, gained mixed liquor is labeled as solution A；(sound intensity is 800W/m to graphene oxide ultrasonic agitation 60min that addition 10mg step (2) obtains2), make the graphene oxide crushing-type little granule of slabbing graphene oxide and be wrapped in NiO powder periphery, then solution being put in the reactor of 100ml, sealing hydrothermal reaction kettle, put it in drying baker, making hydrothermal temperature control at 180 DEG C, the response time is 9h, and reaction naturally cools to room temperature after terminating, products therefrom deionized water rinses repeatedly to neutrality, then sucking filtration, is dried, obtains the NiO-rGO powder that thickness is 30nm of rGO layer；
(4) by 0.7g titanium potassium oxalate K2TiO(C2O4)2Being dissolved in the diethylene glycol of 5ml deionized water and 15ml, stir, gained solution is labeled as B；It is subsequently adding the NiO-rGO powder of the 100mg that step (3) obtains, puts into after ultrasonic agitation (power is 800W) 0.5h in the reactor of 50ml.Then hydrothermal reaction kettle is sealed; put it in drying baker; hydrothermal temperature is made to control at 160 DEG C; response time is 15h, and reaction naturally cools to room temperature after terminating, and products therefrom deionized water rinses repeatedly to neutrality; then sucking filtration; it is dried, at argon shield and 500 DEG C, makes annealing treatment 1h, obtain TiO2Layer thickness is the NiO-rGO-TiO of 150nm2Powder, i.e. prepares nickel oxide-redox graphene-titanium dioxide (p-r-n) nano-heterogeneous structure photocatalyst.
(3) embodiment 20: preparation NiO-rGO-TiO2((p-r-n) Heterogeneous Composite type photocatalyst.
The preparation method of above-mentioned Heterogeneous Composite type photocatalyst comprises the steps:
(1) by 2.5g nickel acetate (C4H6O4Ni·4H2O) it is dissolved in the mixed solution of 15g ethanol and 4.5g acetic acid, after stirring 3h, adds 1g polyvinylpyrrolidone (PVP, Mw=1300000), continue stirring 24h.The syringe that the solution of 1ml is put into 5ml carries out electrostatic spinning, and using the syringe needle of diameter 0.8mm, catcher is 25cm with the distance of syringe needle.Voltage is 22kV.Finally product is placed at 550 DEG C calcining 1h, obtains NiO nanofiber；
(2) by concentrated sulphuric acid (H2SO4) 50ml is placed in round-bottomed flask and is heated to 100 DEG C, is then sequentially added into 10g potassium peroxydisulfate and 10g phosphorus pentoxide (P2O5), stirring is until being completely dissolved.The powdered graphite of 12g is joined in above-mentioned solution, and is maintained at 100 DEG C of 2h.Being cooled down by mixture, be washed with deionized, sucking filtration is dried to obtain the graphite of pretreatment.Then the graphite of pretreatment is put in the conical flask of 2L, add 460ml concentrated sulphuric acid, be cooled to 0 DEG C, then by 60g potassium permanganate (KMnO4) be slowly added in mixture, after stirring two hours, 1L deionized water is slowly added in flask, controls temperature and be less than 55 DEG C, after dilution, by the hydrogen peroxide (H of 50ml 30%2O2In), it is golden yellow for continuing stirring to solution, and centrifugation obtains graphene oxide after drying；
(3) weighing the NiO powder 100mg that step (1) obtains, and be dispersed in the alcohol mixed solution of 50mL water and 25ml, gained mixed liquor is labeled as solution A；(sound intensity is 100W/m to the graphene oxide ultrasonic agitation that addition 4mg step (2) obtains2) 180min, make the graphene oxide crushing-type little granule of slabbing graphene oxide and be wrapped in NiO powder periphery, then solution being put in the reactor of 100ml, sealing hydrothermal reaction kettle, put it in drying baker, making hydrothermal temperature control at 120 DEG C, the response time is 20h, and reaction naturally cools to room temperature after terminating, products therefrom deionized water rinses repeatedly to neutrality, then sucking filtration, is dried, obtains the NiO-rGO powder that thickness is 17nm of rGO layer；
(4) by 0.0.5g titanium potassium oxalate K2TiO(C2O4)2Being dissolved in the diethylene glycol of 5ml deionized water and 15ml, stir, gained solution is labeled as B；Being subsequently adding the NiO-rGO powder of the 100mg that step (3) obtains, (sound intensity is 100W/m to ultrasonic agitation2) put into after 2h in the reactor of 50ml.Then hydrothermal reaction kettle is sealed; put it in drying baker; hydrothermal temperature is made to control at 200 DEG C; response time is 12h, and reaction naturally cools to room temperature after terminating, and products therefrom deionized water rinses repeatedly to neutrality; then sucking filtration; it is dried, at argon shield and 500 DEG C, makes annealing treatment 1h, obtain TiO2Layer thickness is the NiO-rGO-TiO of 150nm2Powder, i.e. prepares nickel oxide-redox graphene-titanium dioxide (p-r-n) nano-heterogeneous structure photocatalyst.
(4) photocatalysis effect test.
Method of testing: NiO-rGO-TiO prepared by embodiment 18-202Heterogeneous Composite type photocatalyst, joins in the mixed solution of 70mL water and 30mL methanol, at 100mW/cm2Simulated solar irradiation is hydrolyzed under irradiating.
Test result: as shown in table 7.
Table 7.
| Embodiment | 1 | 18 | 19 | 20 |
| Hydrogen-producing speed (mmol/g/h) | 0.3 | 0.24 | 0.20 | 0.19 |
As shown in table 7, the amount difference by reactant can obtain the NiO-rGO-TiO of different ratio2P-r-n nano-heterogeneous structure photocatalyst, is respectively provided with the product hydrogen effect that comparison is excellent, and apparently higher than commercialization Degussa P25.
Five. embodiment 21:
Prepare titania nanotube-rGO-nickel oxide nanoparticle layer Heterogeneous Composite type photocatalyst:
(1) preparation method of above-mentioned Heterogeneous Composite type photocatalyst comprises the steps:
(1) by 6g ethanol, 3g acetylacetone,2,4-pentanedione, 4.95g butyl titanate, 19g acetic acid and the mixing of 10g mechanical pump oil, add 1g polyvinylpyrrolidone (PVP, mW=1300000) after stirring 6h, continue stirring 12h.The syringe that the above-mentioned solution of 1ml is put into 5ml carries out electrostatic spinning, and using the syringe needle of diameter 0.8mm, catcher is 25cm with the distance of syringe needle.Voltage is 22kV.Finally product is placed at 550 DEG C calcining 2h, obtains TiO2Nanotube；
(2) by concentrated sulphuric acid (H2SO4) 50ml is placed in round-bottomed flask and is heated to 80 DEG C, is then sequentially added into 10g potassium peroxydisulfate and 10g phosphorus pentoxide (P2O5), stirring is until being completely dissolved.The graphite powder of 12g is joined in above-mentioned solution, and is maintained at 80 DEG C of 4h.Being cooled down by mixture, be washed with deionized, sucking filtration is dried to obtain the graphite of pretreatment.Then the graphite of pretreatment is put in the conical flask of 2L, add 460ml concentrated sulphuric acid, be cooled to 0 DEG C, then by 60g potassium permanganate (KMnO4) be slowly added in mixture, after stirring two hours, 1L deionized water is slowly added in flask, controls temperature and be less than 55 DEG C, after dilution, by the hydrogen peroxide (H of 50ml 30%2O2In), it is golden yellow for continuing stirring to solution, and centrifugation obtains graphene oxide after drying；
(3) TiO that step (1) obtains is weighed2Nanotube powder 100mg, and be dispersed in the alcohol mixed solution of 50mL water and 25ml, gained mixed liquor is labeled as solution A；Add graphene oxide ultrasonic agitation (power the is 600W) 30min that 5mg step (2) obtains, make the graphene oxide crushing-type little granule of slabbing graphene oxide and be wrapped in TiO2Powder periphery, then solution is put in the reactor of 100ml, seal hydrothermal reaction kettle, put it in drying baker, hydrothermal temperature is made to control at 140 DEG C, response time is 12h, reduction aforementioned oxidation Graphene, and reaction naturally cools to room temperature after terminating, products therefrom deionized water rinses repeatedly to neutrality, then sucking filtration, is dried, obtains the TiO that thickness is 20nm of graphene oxide (rGO) layer2-rGO powder；
(4) by 0.388 gram of Ni (NO3)2·6H2In the 40ml distilled water of O.Then the TiO of 100mg2-rGO nanotube is distributed to Ni (NO3)2In solution, then soak 5 hours, to guarantee TiO2-rGO permeates with nickel nitrate solution.Subsequently, the sample soaked is collected carefully from solution, and is dried overnight in the baking oven of 110 DEG C, form nickel nitrate surface layer.Finally, at argon shield and 500 DEG C, process 2h, i.e. prepare titanium dioxide-Graphene-nickel oxide (n-r-p) nano-heterogeneous structure photocatalyst.
(2) photocatalysis effect test:
Method of testing is, TiO embodiment 21 prepared2-rGO-NiO Heterogeneous Composite type photocatalyst, joins in the mixed solution of 70mL water and 30mL methanol, at 100mW/cm2Simulated solar irradiation is hydrolyzed under irradiating.
Test result: as shown in table 8.
Table 8.
| Embodiment | 21 |
| Hydrogen-producing speed (mmol/g/h) | 0.26 |
Being understood by data in table 8 and find out, in the present invention, titania nanotube-rGO-nickel oxide nanoparticle layer Heterogeneous Composite type photocatalyst, has the hydrogen-producing speed of preferable photocatalytic water, hence it is evident that higher than the Degussa P25 having been commercialized at present.As can be seen here, Heterogeneous Composite type photocatalyst of the present invention, core configuration is not limited to as nanofiber, it is also possible to for nanotube, layer structure is also not necessarily limited to nano wire, can be nano-particle.It addition, tests prove that, core can be diameter range 300 ± 100nm in the present invention, the nanotube of length 1-500 μm, and outer layer can be the nano-particle layer of thickness range 150 ± 50nm.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can be carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in the case of reconcilable, can be combined by any suitable means, in order to avoid unnecessary repetition, various possible compound modes are illustrated by the present invention the most separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. a Heterogeneous Composite type photocatalyst, it is characterised in that described photocatalyst includes:
Core (10), the material of described core (10) is n-type semiconductor or p-type semiconductor material
Material；
Intermediate layer (20), is coated on the periphery of described core (10), the material of described intermediate layer (20)
Material is redox graphene；
Outer layer (30), is coated on the periphery of described intermediate layer (20), the material of described outer layer (30)
For with core (10) different types of n-type semiconductor or p-type semiconductor material.
Photocatalyst the most according to claim 1, wherein, described core (10) is Nanowire
Dimension or nanotube；
And/or, described outer layer (30) is nano wire or nano-particle.
Photocatalyst the most according to claim 2, wherein,
Described core (10) is diameter range 300 ± 100nm, the nanofiber of length 1-500 μm or
Person's nanotube；
Described intermediate layer (20) is the redox graphene material layer of thickness range 20 ± 10nm, excellent
Elect the redox graphene material layer of thickness range 20 ± 5nm as；
Described outer layer (30) is the nano wire layer of thickness range 150 ± 25nm, preferably thickness range
The nano wire layer of 150 ± 25nm or nano-particle layer.
4. according to the photocatalyst described in any one of claim 1-3, wherein,
The weight ratio of described core (10) and described intermediate layer (20) is 20:1-10:1, preferably 15:1-17:1；
The gross weight of described core (10) and intermediate layer (20) with the weight ratio of described outer layer (30) is
1:1-1:2, preferably 2:3-3:4.
5. according to the photocatalyst according to any one of claim 1-4, wherein,
Described n-type semiconductor is TiO2、SrTiO3, ZnO, CdS, perovskite composite oxides
With one or more in spinel complex oxide；
Described p-type semiconductor material is NiO, Cu2S、Cu2O、Co3O4、Ag2O and Ag2In S
One or more.
6. according to the photocatalyst according to any one of claim 1-5, wherein, described core (10)
For NiO, described intermediate layer (20) are redox graphene, and described outer layer (30) is TiO2。
7. the preparation method of a Heterogeneous Composite type photocatalyst, it is characterised in that described preparation method
Comprise the following steps:
Nanofiber or the nanotube of material I is prepared by electrostatic spinning process, standby as core material
With；
Oxidation processes graphite prepares graphene oxide, standby as intermediate layer material；
Under ultrasound condition, by the nanofiber of described material I or nanotube and graphene oxide mixing
Contact, to be coated with graphene oxide in the nanofiber periphery of described material I, obtains the first intermediate product；
Under heating reducing condition, the graphene oxide in described first intermediate product that reduces forms reduction-oxidation
Graphene, obtains the second intermediate product；
Described second intermediate product is dispersed in material II source of dissolving, under the conditions of heating crystallize,
Described mix powder periphery co-crystal former matter II outer layer, obtains described Heterogeneous Composite type photocatalyst；
Wherein, described material I is n-type semiconductor or p-type semiconductor material；Described material II is
N-type semiconductor different types of with material I or p-type semiconductor material, described material II source is thing
The soluble-salt of matter II.
Preparation method the most according to claim 7, wherein, described oxidation processes graphite prepares oxygen
Before the step of functionalized graphene, also include the step that described graphite is carried out pretreatment, the step of described pretreatment
Suddenly include:
Taking oxidisability strong acid, add surface conditioning agent in described oxidisability strong acid, stirring and dissolving obtains pre-
Process solution；
Described graphite is added to described preprocessing solution, 60-100 DEG C of isothermal holding 2-6h, cooling,
After flushing, sucking filtration is dried to obtain pretreated graphite；
Preferably, the one during described surface conditioning agent is potassium peroxydisulfate, phosphorus pentoxide, potassium permanganate
Or it is multiple；
Preferably, the consumption of described oxidisability strong acid is 5-20 times of described graphite weight, described oxidation
Property strong acid is one or more in concentrated sulphuric acid, nitric acid and permanganic acid.
Preparation method the most according to claim 7, wherein, described ultrasound condition is: first
In alcoholic solution, ultrasonic agitation 0.5-3h；Described heating reducing condition is: be 120-180 DEG C sealing with temperature
Under the conditions of, react 9-20h,
Preferably, described first alcoholic solution is the aqueous solution of ethanol and/or methanol.
Preparation method the most according to claim 7, wherein, by described second intermediate product dispersion
Mode in material II source dissolved includes:
Described material II source is dissolved in the second alcoholic solution, after stirring mixing, adds described second intermediate product,
Ultrasonic agitation 0.5-2h,
Preferably, described second alcoholic solution is diethylene glycol aqueous solution or aqueous solution of propylene glycol.
11. preparation methoies according to claim 7, wherein, described heating crystallize condition is:
Seal under the conditions of being 160-200 DEG C with temperature, react 9-20h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106629815A (en) * | 2016-12-26 | 2017-05-10 | 北京理工大学 | Semiconductor-based hetero-nanocrystal with hollow micro-reaction chamber structure, and preparation method thereof |
| CN108796532A (en) * | 2017-05-03 | 2018-11-13 | 天津大学 | Nickel oxide-cuprous oxide homojunction photocathode and preparation method thereof and the application in photocatalysis |
| CN108786806A (en) * | 2017-04-27 | 2018-11-13 | 北京纳米能源与系统研究所 | Photochemical catalyst and photocatalyst film and the preparation method and application thereof |
| CN113101947A (en) * | 2021-03-22 | 2021-07-13 | 华南理工大学 | Silver sulfide-reduced graphene oxide-titanium dioxide composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106629815A (en) * | 2016-12-26 | 2017-05-10 | 北京理工大学 | Semiconductor-based hetero-nanocrystal with hollow micro-reaction chamber structure, and preparation method thereof |
| CN108786806A (en) * | 2017-04-27 | 2018-11-13 | 北京纳米能源与系统研究所 | Photochemical catalyst and photocatalyst film and the preparation method and application thereof |
| CN108796532A (en) * | 2017-05-03 | 2018-11-13 | 天津大学 | Nickel oxide-cuprous oxide homojunction photocathode and preparation method thereof and the application in photocatalysis |
| CN113101947A (en) * | 2021-03-22 | 2021-07-13 | 华南理工大学 | Silver sulfide-reduced graphene oxide-titanium dioxide composite material and preparation method and application thereof |
| CN113101947B (en) * | 2021-03-22 | 2022-05-24 | 华南理工大学 | Silver sulfide-reduced graphene oxide-titanium dioxide composite material and preparation method and application thereof |
| CN115595689A (en) * | 2022-07-08 | 2023-01-13 | 苏州凯清碳中和科技有限公司（Cn） | Photocatalytic CO 2 Light guide fiber for preparing methanol and preparation method thereof |
| CN115595689B (en) * | 2022-07-08 | 2024-03-01 | 苏州凯清碳中和科技有限公司 | Photocatalytic CO 2 Optical fiber for preparing methanol and preparation method thereof |
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Application publication date: 20161005 |
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