CN105289578A - Metal oxide/carbon nanotube composite photocatalyst, and preparation method and application thereof - Google Patents
Metal oxide/carbon nanotube composite photocatalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of nanocomposite materials, and discloses a metal oxide/carbon nanotube composite photocatalyst, and a preparation method and an application thereof. The method comprises the following steps: 1, adding oxidized carbon nanotubes to deionized water, stirring, and carrying out ultrasonic treatment to obtain a colloidal solution; 2, adding a metal salt to the colloidal solution, stirring, carrying out ultrasonic treatment, adding an alkali solution in a dropwise manner, stopping the dropwise addition of the alkali solution when the pH value is 6.5-7, continuously stirring, ageing the obtained reaction solution, centrifuging, washing, drying, and grinding to obtain a precursor anionic clay/carbon nanotube composite material; and 3, placing the composite material in a tubular furnace, and carrying out heating and high temperature calcining to obtain the metal oxide/carbon nanotube composite photocatalyst. The composite photocatalyst prepared in the invention effectively combines the respective advantages of the metal oxide and the carbon nanotubes, improves the catalysis activity and stability of a catalyst, and also has the advantages of low cost of raw materials, and good electron conduction ability.
Description
Technical field
The invention belongs to field of nanocomposite materials, relate to a kind of nano composite photocatalytic material, particularly a kind of mixed-metal oxides/CNT composite photo-catalyst and preparation method thereof and application.
Background technology
In recent years, along with the development of the compound probability such as polycarbonate plastic, epoxy resin, bisphenol-A is discharged in water body environment in a large number as a kind of synthesis material, thus produces interference to the endogenous hormone function of the mankind and animal, causes metabolic dysfunction.Multiphase photocatalysis, as a kind of high-level oxidation technology, is a green technology in environment and new energy field extensive application prospect, and therefore, photocatalysis technology is often applied to processing on the organic wastewater containing this kind of incretion interferent.Zinc oxide (ZnO), as a kind of conventional semiconductors photochemical catalyst, because of its greater band gap, only can absorb the luminous energy of ultraviolet light wave band, and light induced electron easily and hole-recombination, and easily by photoetch, makes it be difficult to be used widely in practice.At present, be improve the photocatalytic activity of ZnO, and make it have response to visible ray, to the application of ZnO photocatalyst mainly concentrate on metal or nonmetal doping and by with other metal oxide, as TiO
2, CoO, LaMO
3, ZnCr
2o
4deng, build the aspects such as heterojunction structure.
To take anionic clay as presoma prepare mixed-metal oxides hetero-junctions through high-temperature calcination and be applied in photocatalysis field is one of study hotspot in recent years.Anionic clay ([MII1-xMIIIx (OH) 2] x+ [Am-x/mnH2O]), also houghite is claimed, be a class be the layered double-hydroxide that main body is formed by two or three metal hydroxides, there is larger specific surface and interlamellar spacing more flexibly.Metal cation on main body laminate can need to be designed to dissimilar stratified material according to function.In photocatalysis field, usually using elements such as Zn, Ti as main element, layered double-hydroxide is designed to the semi-conducting material with photocatalytic activity.By adulterating some transition metals (as Cr, Ni, Co etc.) i.e. energy gap of adjustable semiconductor, it is made to have good response at visible-range.Because metal cation is uniformly distributed on main body laminate, layered hydroxide, after high-temperature calcination, forms the hybrid metal metal oxide heterojunction structure that photocatalytic activity is higher, catalytic performance is more stable.Build the migration rate that heterojunction structure improves photo-generated carrier on the one hand effectively, add the site of photo-generated carrier compound on the other hand.
Summary of the invention
In order to overcome the shortcoming and defect of prior art, primary and foremost purpose of the present invention is the preparation method providing a kind of metal oxide/carbon nano-tube composite photo-catalyst.The present invention adopts a step method of formation to prepare presoma anionic clay/carbon nano tube compound material, then prepares metal oxide/carbon nano-tube compound light catalyst by vacuum high-temperature calcination method.Can be evenly dispersed in mixed-metal oxides by method CNT of the present invention.Prepared photochemical catalyst effectively in conjunction with metal oxide and CNT advantage separately, can improve catalytic activity and the stability of catalyst.
Another object of the present invention is to provide the metal oxide/carbon nano-tube prepared by above-mentioned preparation method composite photo-catalyst.
Another object of the present invention is the application providing above-mentioned metal oxide/carbon nano-tube composite photo-catalyst.Described composite photo-catalyst is containing the application in bisphenol-A field, mainly catalytic degradation bisphenol-A under the condition of visible ray.
Object of the present invention is achieved through the following technical solutions:
A preparation method for metal oxide/carbon nano-tube composite photo-catalyst, comprises the following steps:
(1) preparation of oxide/carbon nanometer tube colloidal solution: CNT is oxidized, obtains oxide/carbon nanometer tube; Again oxide/carbon nanometer tube is added in deionized water, stir, ultrasonic process, obtain the oxide/carbon nanometer tube colloidal solution disperseed;
(2) preparation of presoma anionic clay/carbon nano tube compound material:
(2-1) slaine is added in the oxide/carbon nanometer tube colloidal solution of step (1), stir, ultrasonic, obtain the mixed solution of oxide/carbon nanometer tube and metal ion;
(2-2) under the condition stirred, aqueous slkali is added drop-wise in the mixed solution of oxide/carbon nanometer tube and metal ion, generate flocculent deposit gradually, when the pH of reaction solution stops after 6.5 ~ 7 dripping aqueous slkali, continue stirring 1 ~ 2h, then by reactant liquor at 60 ~ 70 DEG C of burin-in process 12 ~ 36h, centrifugal, washing, dry, grinding, obtain presoma anionic clay/carbon nano tube compound material;
(3) preparation of mixed-metal oxides/carbon nano tube compound material: presoma anionic clay/carbon nano tube compound material is placed in tube furnace, heat up and carry out high-temperature calcination, obtaining mixed-metal oxides/carbon nano tube compound material and the metal oxide/carbon nano-tube composite photo-catalyst of powdery.
Described in step (1), mixing speed is 3000 ~ 4000rpm, and described mixing time is 24 ~ 48h; Described ultrasonic time is 6 ~ 8h, and described supersonic frequency is preferably 40 ~ 60kHZ.
Described in step (1), CNT is preferably multi-walled carbon nano-tubes, and outer tube diameter is less than 8nm, and interior caliber is 2-5nm, and pipe range is 0.5-2 μm.
The method for oxidation of CNT described in step (1) is mixed solution (the volume ratio 1:3 of red fuming nitric acid (RFNA) and concentrated sulfuric acid CNT being added red fuming nitric acid (RFNA) and the concentrated sulfuric acid, the mass fraction of red fuming nitric acid (RFNA) is 65 ~ 68%, the mass fraction of the concentrated sulfuric acid is 96 ~ 98%) at 100 DEG C reflux 4 ~ 5h, centrifugal, deionized water washing is to neutral, at 60 ~ 80 DEG C, dry 24 ~ 48h, obtains oxide/carbon nanometer tube; CNT is (1 ~ 2) g:(100 ~ 200 with the mass volume ratio of the mixed liquor of acid) mL; Described centrifugal speed is 3500 ~ 4500rpm, and centrifugation time is 5 ~ 10min.
In oxide/carbon nanometer tube colloidal solution described in step (1), oxide/carbon nanometer tube concentration is 1.187 ~ 11.94mg/mL.
Slaine described in step (2-1) is more than one in divalent metal salt or trivalent metal salt, is preferably the mixture of divalent metal salt and trivalent metal salt; In described divalent metal salt, metal ion is Zn
2+, in trivalent metal salt, metal ion is Cr
3+; Described divalent metal salt is preferably Zn (NO
3)
26H
2o, ZnCl
2or ZnSO
4h
2more than one in O, described trivalent metal salt is preferably Cr (NO
3)
39H
2o, CrCl
36H
2o or Cr
2(SO
4)
36H
2more than one in O; Described divalent metal salt is more preferably Zn (NO
3)
26H
2o, described trivalent metal salt is more preferably Cr (NO
3)
39H
2o.When slaine is the mixture of divalent metal salt and trivalent metal salt, Zn
2+with Cr
3+mol ratio be preferably (1 ~ 3): 1, more preferably, Zn
2+with Cr
3+mol ratio be 2:1.
In oxide/carbon nanometer tube described in step (2-1) and slaine, metallic element total mass ratio is: (0.025 ~ 0.27): 1; Described mixing time is 8 ~ 12h, and mixing speed is 3000 ~ 4000rpm; Described ultrasonic time is 3 ~ 5h, and supersonic frequency is 40 ~ 60kHZ;
Step (2-2) described aqueous slkali is NaOH and Na
2cO
3mixed ammonium/alkali solutions, its total alkali concn is 1.0 ~ 3.0mol/L, wherein [NaOH]=0.8 ~ 2.4mol/L, [Na
2cO
3]=0.2 ~ 0.6mol/L; Preferably, total alkali concn is 2.0mol/L, [NaOH]=1.6mol/L, [Na
2cO
3]=0.4mol/L.
The speed of step (2-2) described dropping is 0.5 ~ 1.5mL/min, and the speed preferably dripped is 1.0mL/min; The course of reaction of described generation flocculent deposit is carried out at ambient temperature; Described ageing time is preferably 12 ~ 24h; Described centrifugal rotating speed is 3500 ~ 4500rpm, and centrifugation time is 2 ~ 5min; Described washing refers to and adopts deionized water and absolute ethyl alcohol to carry out alternately washing, washing times 5 ~ 6 times; Described drying condition is in 60 ~ 80 DEG C of drying 24 ~ 48h; The described order number sieved is 200 orders.
Step (3) described calcining heat is 600 ~ 800 DEG C, and calcination time is 2 ~ 4h; Described heating rate is 5 DEG C/min.
The atmosphere of step (3) described calcining is vacuum atmosphere, nitrogen atmosphere or air atmosphere, is preferably vacuum atmosphere; The vacuum of described vacuum atmosphere is-0.2 ~-0.1MPa; The nitrogen flow of described nitrogen atmosphere is 1.0mL/min; The air mass flow of described air atmosphere is 1.0mL/min.
Described metal oxide/carbon nano-tube composite photo-catalyst is prepared by above-mentioned preparation method.
The application of described metal oxide/carbon nano-tube composite photo-catalyst in Photocatalytic Activity for Degradation Organic Pollutants In Water; Described organic matter is preferably the environmental hormones such as bisphenol-A.
Principle: the carbon atom in CNT is with sp
2be hybridized to master, there is certain bending in its network structure simultaneously, forms Space expanding, wherein form certain sp
3hybrid bond, the chemical bond that the carbon atom namely in CNT is formed has sp simultaneously
2and sp
3mixed hybridization state, these p tracks overlap each other thus large π key that height of formation delocalized outer at CNT lamella, and therefore electronics can move freely in carbon nanotube mesh structures, makes it have excellent electrical conductivity performance.The electric conductivity of CNT excellence shows that it can transmit light induced electron fast, and light induced electron is separated effectively with cavity energy, and can reduce light induced electron and photohole recombination rate.Therefore, CNT and metal-oxide semiconductor (MOS) compound can be utilized fully the electric conductivity of CNT excellence, the light induced electron that semiconductor surface is produced is separated effectively with cavity energy, thus make hole and electronics participate in redox reaction respectively, to improve the photocatalytic activity of semiconductor.In addition, take CNT as substrate, metal oxide is attached to the specific area that CNT greatly can improve composite, to increase liquid-solid contact area, thus improve the photocatalytic activity of catalyst.CNT is oxidized, make its surface band negative electricity, fully can be combined by electrostatic interaction with the metal cation of positively charged, prepare presoma anionic clay/carbon nano tube compound material by coprecipitation again, through high-temperature calcination mixed-metal oxides/CNT composite photo-catalyst.
Compared with prior art, advantage of the present invention is:
(1) by method of the present invention, CNT can be evenly dispersed in mixed-metal oxides, thus makes composite photo-catalyst can effectively in conjunction with metal oxide and CNT advantage separately; The heterojunction structure that mixed-metal oxides is formed is higher compared to the catalytic activity of single metal oxides; Adding of CNT can transporting electronics effectively, reduces the compound probability of light induced electron and photohole, improves the catalytic activity of catalyst;
(2) relative to precious metal doping, not only cost is lower to the present invention is based on the composite of CNT, and the ability of transporting electronics is also far above noble metal;
(3) the present invention adopts vacuum high-temperature to calcine, and relative to high-temperature calcination under inert atmosphere or air atmosphere condition, the mixed-metal oxides catalytic performance of generation is higher and more stable.
Accompanying drawing explanation
Fig. 1 is that the XRD of the mixed-metal oxides (MMO) that the mixed-metal oxides/carbon nano tube compound material (MMO-CNTs-0.131) of embodiment 3 preparation is prepared with embodiment 5 schemes;
Fig. 2 is the TEM figure of mixed-metal oxides/carbon mano-tube composite (MMO-CNTs-0.131) prepared by embodiment 3;
Fig. 3 is that the UV-vis of the mixed-metal oxides (MMO) that the mixed-metal oxides/carbon nano tube compound material (MMO-CNTs-0.131) of embodiment 3 preparation is prepared with embodiment 5 schemes;
Fig. 4 is the photocatalytic degradation effect figure of mixed-metal oxides (MMO) prepared by mixed-metal oxides/carbon nano tube compound material of preparing of embodiment 3,6,7 and embodiment 5.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
A preparation for mixed-metal oxides/CNT composite photo-catalyst, comprises the following steps:
(1) take 0.1781g oxide/carbon nanometer tube and be placed in 500mL beaker, add 150mL deionized water, with the rotating speed magnetic agitation 48h of 4000rpm, be placed in 50kHz ultrasonic washer again and process 8h, make oxide/carbon nanometer tube dispersed one-tenth black transparent colloid, obtain CNT colloidal solution; The mass ratio of described oxide/carbon nanometer tube and the middle metallic element gross mass of step (2) is [oxide/carbon nanometer tube o-MWCNTs]: [metallic element gross mass]=0.026:1;
(2) Zn (NO of 0.075mol (26.955g) is taken
3)
26H
2(15.005g) Cr (NO of O and 0.0375mol
3)
39H
2o (Zn
2+: Cr
3+mol ratio is 2:1), add in the CNT colloidal solution in step (1), with the rotating speed magnetic agitation 12h of 4000rpm, more ultrasonic process 4h (supersonic frequency is 50kHz), obtain the mixed solution of metal ion and oxide/carbon nanometer tube, be designated as solution A;
(3) 0.32mol (12.80g) NaOH and 0.08mol (8.48g) Na is taken
2cO
3, be placed in 300mL beaker, add deionized water, be stirred to solid and dissolve completely, obtain aqueous slkali, be designated as solution B, in solution B, two kinds of paper mill wastewater are respectively [NaOH]=1.6M, [Na
2cO
3]=0.4M;
(4) solution A is placed in Keep agitation on magnetic stirring apparatus (mixing speed is 4000rpm), then at ambient temperature, solution B is slowly instilled (rate of addition is 1.0mL/min) in solution A by constant pressure funnel, flocculent deposit is generated gradually in reaction solution, in time recording solution ph and be 6.5 ~ 7.0, reaction completes, obtain soliquid, again this soliquid is continued to stir 1h, put it into again in thermostat water bath, aging 24h at 65 DEG C; Be cooled to room temperature, with the centrifugal 3min of the rotating speed of 4000rpm, after removing supernatant, be precipitated thing, alternately wash this precipitation 5 times to its pH value close to 7.0 with deionized water and absolute ethyl alcohol, after each washing respectively in centrifuge with the centrifugal 3min of 4000rpm, remove supernatant; Product moves in vacuum drying chamber, 65 DEG C of vacuum drying 48h, crosses 200 mesh sieves, obtain powder sample and presoma anionic clay/carbon nano tube compound material, by this sample called after LDH-CNTs-0.026 after grinding 2h;
(5) quartz boat that the above-mentioned powder sample of 4.0g is placed in 30*25mm is got, put it in tube furnace, vacuumize and (before calcining, tube furnace is vacuumized 30min, vacuum is-0.2MPa, and controlling tube furnace in calcination process is vacuum environment), be warming up to 700 DEG C with the heating rate of 5 DEG C/min, insulation calcining 3h, naturally cool to room temperature, obtain mixed-metal oxides/carbon nano tube compound material, by its called after MMO-CNTs-0.026.
Embodiment 2
A preparation for mixed-metal oxides/carbon nano tube compound material, is characterized in that comprising the following steps:
(1) take 0.4456g oxide/carbon nanometer tube and be placed in 500mL beaker, add 150mL deionized water, with the rotating speed magnetic agitation 48h of 4000rpm, be placed in 50kHz ultrasonic washer again and process 8h, make oxide/carbon nanometer tube dispersed one-tenth black transparent colloid, obtain CNT colloidal solution; The mass ratio of described oxide/carbon nanometer tube and the middle metallic element gross mass of step (2) is [oxide/carbon nanometer tube o-MWCNTs]: [metallic element gross mass]=0.065:1;
(2) Zn (NO of 0.075mol (26.955g) is taken
3)
26H
2(15.005g) Cr (NO of O and 0.0375mol
3)
39H
2o (Zn
2+: Cr
3+mol ratio is 2:1), add in the CNT colloidal solution in step (1), with 4000rpm rotating speed magnetic agitation 12h, then 50kHz ultrasonic process 4h, obtain the mixed solution of metal ion and oxide/carbon nanometer tube, be designated as solution A;
(3) (8.48g) Na of NaOH and the 0.08mol of 0.32mol (12.80g) is taken
2cO
3, be placed in 300mL beaker, add deionized water, be stirred to solid and dissolve completely, obtain aqueous slkali, be designated as solution B, in solution B, two kinds of paper mill wastewater are respectively [NaOH]=1.6M, [Na
2cO
3]=0.4M;
(4) solution A is placed in Keep agitation on magnetic stirring apparatus (mixing speed is 4000rpm), then at ambient temperature, solution B is slowly instilled (rate of addition is 1.0mL/min) in solution A by constant pressure funnel, flocculent deposit is generated gradually in reaction solution, when recording solution ph and being 6.5 ~ 7.0, stop dripping aqueous slkali, obtain soliquid; Continue to stir 1h, again suspension is put into thermostat water bath, aging 24h at 65 DEG C, be cooled to room temperature, with the centrifugal 3min of 4000rpm rotating speed, after removing supernatant, be precipitated thing, alternately wash this precipitation 5 times to its pH value close to 7.0 with deionized water and absolute ethyl alcohol, after each washing respectively in centrifuge with the centrifugal 3min of 4000rpm, remove supernatant; Sediment is moved in vacuum drying chamber, 65 DEG C of vacuum drying 48h, cross 200 mesh sieves after grinding 2h, obtain powder sample and presoma anionic clay/carbon nano tube compound material, by this sample called after LDH-CNTs-0.065;
(5) quartz boat that the above-mentioned powder sample of 4.0g is placed in 30*25mm is got, put it in tube furnace, vacuumize and (before calcining, tube furnace is vacuumized 30min, vacuum is-0.2MPa, and controlling tube furnace in calcination process is vacuum environment), be warming up to 700 DEG C with the heating rate of 5 DEG C/min, insulation calcining 3h, naturally cool to room temperature, obtain mixed-metal oxides/carbon nano tube compound material, by its called after MMO-CNTs-0.065.
Embodiment 3
A preparation for mixed-metal oxides/carbon nano tube compound material, is characterized in that comprising the following steps:
(1) accurately take 0.898g oxide/carbon nanometer tube and be placed in 500mL beaker, add 150mL deionized water, with the rotating speed magnetic agitation 48h of 4000rpm, be placed in 50kHz ultrasonic washer again and process 8h, make oxide/carbon nanometer tube dispersed one-tenth black transparent colloid, obtain CNT colloidal solution; The mass ratio of described oxide/carbon nanometer tube and the middle metallic element gross mass of step (2) is [oxide/carbon nanometer tube o-MWCNTs]: [metallic element gross mass]=0.131:1;
(2) Zn (NO of 0.075mol (26.955g) is taken
3)
26H
2(15.005g) Cr (NO of O and 0.0375mol
3)
39H
2o (Zn
2+: Cr
3+mol ratio is 2:1), add in the CNT colloidal solution in step (1), with 4000rpm rotating speed magnetic agitation 12h, then 50kHz ultrasonic process 4h, obtain the mixed solution of metal ion and oxide/carbon nanometer tube, be designated as solution A;
(3) (8.48g) Na of NaOH and the 0.08mol of 0.32mol (12.80g) is taken
2cO
3, be placed in 300mL beaker, add deionized water, be stirred to solid and dissolve completely, obtain aqueous slkali, be designated as solution B, in solution B, two kinds of paper mill wastewater are respectively [NaOH]=1.6M, [Na
2cO
3]=0.4M;
(4) solution A is placed in Keep agitation on magnetic stirring apparatus (mixing speed is 4000rpm), then at ambient temperature, solution B is slowly instilled (rate of addition is 1.0mL/min) in solution A by constant pressure funnel, flocculent deposit is generated gradually in reaction solution, when recording solution ph and being 6.5 ~ 7.0, stop dripping aqueous slkali, obtain soliquid; Continue to stir 1h, again suspension is put into thermostat water bath, aging 24h at 65 DEG C, be cooled to room temperature, with the centrifugal 3min of 4000rpm rotating speed, after removing supernatant, be precipitated thing, alternately wash this precipitation 6 times to its pH value close to 7.0 with deionized water and absolute ethyl alcohol, after each washing respectively in centrifuge with the centrifugal 3min of 4000rpm, remove supernatant; Sediment moves in vacuum drying chamber, 65 DEG C of vacuum drying 48h, crosses 200 mesh sieves, obtain powder sample and presoma anionic clay/carbon nano tube compound material, by this sample called after LDH-CNTs-0.131 after grinding 2h;
(5) quartz boat that the above-mentioned powder sample of 4.0g is placed in 30*25mm is got, put it in tube furnace, vacuumize and (before calcining, tube furnace is vacuumized 30min, vacuum is-0.2MPa, and controlling tube furnace in calcination process is vacuum environment), be warming up to 700 DEG C with the heating rate of 5 DEG C/min, insulation calcining 3h, naturally cool to room temperature, obtain mixed-metal oxides/carbon nano tube compound material, by its called after MMO-CNTs-0.131.The X-ray diffraction (XRD) of described mixed-metal oxides/carbon nano tube compound material as shown in Figure 1; Its transmission electron microscope (TEM) as shown in Figure 2; Its ultraviolet-visible UV-vis DRS (UV-vis) as shown in Figure 3.
Embodiment 4
A preparation for mixed-metal oxides/carbon nano tube compound material, is characterized in that comprising the following steps:
(1) accurately take 1.789g oxide/carbon nanometer tube and be placed in 500mL beaker, add 150mL deionized water, with the rotating speed magnetic agitation 48h of 4000rpm, be placed in 50kHz ultrasonic washer again and process 8h, make oxide/carbon nanometer tube dispersed one-tenth black transparent colloid, obtain CNT colloidal solution; The mass ratio of described oxide/carbon nanometer tube and the middle metallic element gross mass of step (2) is [oxide/carbon nanometer tube o-MWCNTs]: [metallic element gross mass]=0.261:1;
(2) Zn (NO of 0.075mol (26.955g) is taken
3)
26H
2(15.005g) Cr (NO of O and 0.0375mol
3)
39H
2o (Zn
2+: Cr
3+mol ratio is 2:1), add in the CNT colloidal solution in step (1), with 4000rpm rotating speed magnetic agitation 12h, then 50kHz ultrasonic process 4h, obtain the mixed solution of metal ion and oxide/carbon nanometer tube, be designated as solution A;
(3) (8.48g) Na of NaOH and the 0.08mol of 0.32mol (12.80g) is taken
2cO
3, be placed in 300mL beaker, add deionized water, be stirred to solid and dissolve completely, obtain aqueous slkali, be designated as solution B, in solution B, two kinds of paper mill wastewater are respectively [NaOH]=1.6M, [Na
2cO
3]=0.4M;
(4) solution A is placed in Keep agitation on magnetic stirring apparatus (mixing speed is 4000rpm), then at ambient temperature, solution B is slowly instilled (rate of addition is 1.0mL/min) in solution A by constant pressure funnel, flocculent deposit is generated gradually in reaction solution, when recording solution ph and being 6.5 ~ 7.0, stop dripping aqueous slkali, obtain soliquid; Continue to stir 1h, again suspension is put into thermostat water bath, aging 24h at 65 DEG C, be cooled to room temperature, with the centrifugal 3min of 4000rpm rotating speed, after removing supernatant, be precipitated thing, alternately wash this precipitation 5 times to its pH value close to 7.0 with deionized water and absolute ethyl alcohol, after each washing respectively in centrifuge with the centrifugal 3min of 4000rpm, remove supernatant; Sediment is moved in vacuum drying chamber, 65 DEG C of vacuum drying 48h, cross 200 mesh sieves after grinding 2h, obtain powder sample and presoma anionic clay/carbon nano tube compound material, by this sample called after LDH-CNTs-0.261;
(5) quartz boat that the above-mentioned powder sample of 4.0g is placed in 30*25mm is got, put it in tube furnace, vacuumize and (before calcining, tube furnace is vacuumized 30min, vacuum is-0.2MPa, and controlling tube furnace in calcination process is vacuum environment), be warming up to 700 DEG C with the heating rate of 5 DEG C/min, insulation calcining 3h, naturally cool to room temperature, obtain mixed-metal oxides/carbon nano tube compound material, by its called after MMO-CNTs-0.261.
Embodiment 5
A kind of preparation of zinc chrome mixed-metal oxides (ZnCr-MMO), comprises the following steps:
(1) Zn (NO of 0.075mol (26.955g) is accurately taken
3)
26H
2cr (the NO of O and 0.0375mol (15.005g)
3)
39H
2o (mol ratio Zn
2+: Cr
3+=2:1), be placed in 500mL beaker, add 150mL deionized water, be stirred to solid and dissolve completely, obtain the blackish green mixed salt solution clarified, be designated as solution A;
(2) 0.32mol (12.80g) NaOH and 0.08mol (8.48g) Na is taken
2cO
3, by claiming reagent is placed in 300mL beaker, adding deionized water, being stirred to solid and dissolving completely, obtain aqueous slkali, be designated as solution B, in solution B, two kinds of paper mill wastewater are respectively [NaOH]=1.6M, [Na
2cO
3]=0.4M;
(3) solution A is placed in Keep agitation on magnetic stirring apparatus (mixing speed is 4000rpm), then at ambient temperature, solution B is slowly instilled (rate of addition is 1.0mL/min) in solution A by constant pressure funnel, the flocculent deposit of lilac is generated gradually in reaction solution, when recording solution ph and being 8.5 ~ 9.0, stop dripping aqueous slkali, obtain soliquid; Continued to stir 1h by this soliquid, then put it in thermostat water bath, at 65 DEG C, aging 24h, is cooled to room temperature, with the centrifugal 3min of 4000rpm, after removing supernatant, is precipitated; Alternately wash this precipitation 6 times to its pH value close to 7.0 with deionized water and absolute ethyl alcohol, after each washing respectively in centrifuge with the centrifugal 3min of 4000rpm, remove supernatant; Product moves in vacuum drying chamber, 65 DEG C of vacuum drying 48h, crosses 200 mesh sieves, obtain powder sample, by this sample called after ZnCr-LDH after grinding 2h;
(5) quartz boat that the above-mentioned powder sample of 4.0g is placed in 30*25mm is got, put it in tube furnace, vacuumize and (before calcining, tube furnace is vacuumized 30min, vacuum is-0.2MPa, controlling tube furnace in calcination process is vacuum environment), be then warming up to 700 DEG C with the heating rate of 5 DEG C/min, insulation calcining 3h, naturally cool to room temperature, obtain ZnO and ZnCr
2o
4mixed-metal oxides, by its called after ZnCr-MMO and MMO.X-ray diffraction (XRD) figure of described mixed-metal oxides as shown in Figure 1; Its ultraviolet-visible UV-vis DRS (UV-vis) curve as shown in Figure 3.
Embodiment 6
A preparation for mixed-metal oxides/carbon nano tube compound material, is characterized in that comprising the following steps:
(1) accurately take 0.898g oxide/carbon nanometer tube and be placed in 500mL beaker, add 150mL deionized water, with the rotating speed magnetic agitation 48h of 4000rpm, be placed in 50kHz ultrasonic washer again and process 8h, make oxide/carbon nanometer tube dispersed one-tenth black transparent colloid, obtain CNT colloidal solution; The mass ratio of described oxide/carbon nanometer tube and the middle metallic element gross mass of step (2) is [oxide/carbon nanometer tube o-MWCNTs]: [metallic element gross mass]=0.131:1;
(2) Zn (NO of 0.075mol (26.955g) is taken
3)
26H
2(15.005g) Cr (NO of O and 0.0375mol
3)
39H
2o (Zn
2+: Cr
3+mol ratio is 2:1), add in the CNT colloidal solution in step (1), with 4000rpm rotating speed magnetic agitation 12h, then 50kHz ultrasonic process 4h, obtain the mixed solution of metal ion and oxide/carbon nanometer tube, be designated as solution A;
(3) (8.48g) Na of NaOH and the 0.08mol of 0.32mol (12.80g) is taken
2cO
3, be placed in 300mL beaker, add deionized water, be stirred to solid and dissolve completely, obtain aqueous slkali, be designated as solution B, in solution B, two kinds of paper mill wastewater are respectively [NaOH]=1.6M, [Na
2cO
3]=0.4M;
(4) solution A is placed in Keep agitation on magnetic stirring apparatus (mixing speed is 4000rpm), then at ambient temperature, solution B is slowly instilled (rate of addition is 1.0mL/min) in solution A by constant pressure funnel, flocculent deposit is generated gradually in reaction solution, when recording solution ph and being 6.5 ~ 7.0, stop dripping aqueous slkali, obtain soliquid; Continue to stir 1h, again suspension is put into thermostat water bath, aging 24h at 65 DEG C, be cooled to room temperature, with the centrifugal 3min of 4000rpm rotating speed, after removing supernatant, be precipitated thing, alternately wash this precipitation 6 times to its pH value close to 7.0 with deionized water and absolute ethyl alcohol, after each washing respectively in centrifuge with the centrifugal 3min of 4000rpm, remove supernatant; Sediment is moved in vacuum drying chamber, 65 DEG C of vacuum drying 48h, cross 200 mesh sieves after grinding 2h, obtain powder sample and presoma anionic clay/carbon nano tube compound material, by this sample called after LDH-CNTs-0.131;
(5) quartz boat that the above-mentioned powder sample of 4.0g is placed in 30*25mm is got, put it in tube furnace, before calcining, tube furnace is filled with nitrogen 30min with deaeration, controlling nitrogen flow in tube furnace in calcination process is 1.0mL/min, then be warming up to 700 DEG C with the heating rate of 5 DEG C/min, insulation calcining 3h, naturally cools to room temperature, obtain mixed-metal oxides/carbon nano tube compound material, by its called after MMO-CNTs-0.131-N.
Embodiment 7
A preparation for mixed-metal oxides/carbon nano tube compound material, is characterized in that comprising the following steps:
(1) accurately take 0.898g oxide/carbon nanometer tube and be placed in 500mL beaker, add 150mL deionized water, with the rotating speed magnetic agitation 48h of 4000rpm, be placed in 50kHz ultrasonic washer again and process 8h, make oxide/carbon nanometer tube dispersed one-tenth black transparent colloid, obtain CNT colloidal solution; The mass ratio of described oxide/carbon nanometer tube and the middle metallic element gross mass of step (2) is [oxide/carbon nanometer tube o-MWCNTs]: [metallic element gross mass]=0.131:1;
(2) Zn (NO of 0.075mol (26.955g) is taken
3)
26H
2(15.005g) Cr (NO of O and 0.0375mol
3)
39H
2o (Zn
2+: Cr
3+mol ratio is 2:1), add in the CNT colloidal solution in step (1), with 4000rpm rotating speed magnetic agitation 12h, then 50kHz ultrasonic process 4h, obtain the mixed solution of metal ion and oxide/carbon nanometer tube, be designated as solution A;
(3) (8.48g) Na of NaOH and the 0.08mol of 0.32mol (12.80g) is taken
2cO
3, be placed in 300mL beaker, add deionized water, be stirred to solid and dissolve completely, obtain aqueous slkali, be designated as solution B, in solution B, two kinds of paper mill wastewater are respectively [NaOH]=1.6M, [Na
2cO
3]=0.4M;
(4) solution A is placed in Keep agitation on magnetic stirring apparatus (mixing speed is 4000rpm), then at ambient temperature, solution B is slowly instilled (rate of addition is 1.0mL/min) in solution A by constant pressure funnel, flocculent deposit is generated gradually in reaction solution, when recording solution ph and being 6.5 ~ 7.0, stop dripping aqueous slkali, obtain soliquid; Continue to stir 1h, again suspension is put into thermostat water bath, aging 24h at 65 DEG C, be cooled to room temperature, with the centrifugal 3min of 4000rpm rotating speed, after removing supernatant, be precipitated thing, alternately wash this precipitation 6 times to its pH value close to 7.0 with deionized water and absolute ethyl alcohol, after each washing respectively in centrifuge with the centrifugal 3min of 4000rpm, remove supernatant; Sediment is moved in vacuum drying chamber, 65 DEG C of vacuum drying 48h, cross 200 mesh sieves after grinding 2h, obtain powder sample and presoma anionic clay/carbon nano tube compound material, by this sample called after LDH-CNTs-0.131;
(5) quartz boat that the above-mentioned powder sample of 4.0g is placed in 30*25mm is got, put it in tube furnace, controlling tube furnace air flow amount in calcination process is 1.0mL/min, then 700 DEG C are warming up to the heating rate of 5 DEG C/min, insulation calcining 3h, naturally cool to room temperature, obtain mixed-metal oxides/carbon nano tube compound material, by its called after MMO-CNTs-0.131-A.
Embodiment 8 (Application Example)
The application of mixed-metal oxides/carbon nano tube compound material in Photocatalytic Activity for Degradation bisphenol-A, is characterized in that comprising the following steps:
(1) accurately take 0.01g bisphenol-A in 50mL beaker, add a small amount of water and make it dissolve, ultrasonic 2h, in 1L volumetric flask, be made into the bisphenol-A solution of 10ppm;
(2) ZnCr-MMO and MMO (embodiment 5) of 0.125g, MMO-CNTs-0.131 (embodiment 3), MMO-CNTs-0.131-N (embodiment 6), MMO-CNTs-0.131-A (embodiment 7) is accurately taken respectively in 250mL quartz reaction bottle, add 250mL bisphenol-A solution, reaction bulb is placed in constant speed on magnetic stirring apparatus to stir, lucifuge 30min makes bisphenol-A solution reach adsorption equilibrium on a catalyst;
(3) 300W xenon lamp is adopted to be simulated solar radiant, 200min is reacted under above-mentioned reaction unit is placed in illumination condition, interval 20min samples about 2mL, after 0.45 μm of filtering with microporous membrane, with high performance liquid chromatograph (L-2000, Hitachi) detect its concentration, determined wavelength is 276nm.Photocatalysis effect as shown in Figure 4.
As we know from the figure, mixed-metal oxides/carbon nano tube compound material is all improved significantly compared to mixed-metal oxides to the photocatalytic degradation efficiency of bisphenol-A and degradation rate, the light induced electron that in composite, the quick transporting metal oxide surface of CNT energy produces is described, thus effectively suppress the compound in light induced electron and hole, bisphenol-A is degraded in time.In addition, the composite photocatalysis performance that the composite calcined under vacuum condition is calcined under condition of nitrogen gas and air conditions has significantly improved.Moreover due to the high-specific surface area of CNT, in dark reaction process, composite demonstrates superpower adsorption effect, this has important practical significance for effective organic matter removed in water body.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for metal oxide/carbon nano-tube composite photo-catalyst, is characterized in that: comprise the following steps:
(1) preparation of oxide/carbon nanometer tube colloidal solution: CNT is oxidized, obtains oxide/carbon nanometer tube; Again oxide/carbon nanometer tube is added in deionized water, stir, ultrasonic process, obtain the oxide/carbon nanometer tube colloidal solution disperseed;
(2) preparation of presoma anionic clay/carbon nano tube compound material:
(2-1) slaine is added in the oxide/carbon nanometer tube colloidal solution of step (1), stir, ultrasonic, obtain the mixed solution of oxide/carbon nanometer tube and metal ion;
(2-2) under the condition stirred, aqueous slkali is added drop-wise in the mixed solution of oxide/carbon nanometer tube and metal ion, generate flocculent deposit gradually, when the pH of reaction solution stops after 6.5 ~ 7 dripping aqueous slkali, continue stirring 1 ~ 2h, then by reactant liquor at 60 ~ 70 DEG C of burin-in process 12 ~ 36h, centrifugal, washing, dry, grinding, obtain presoma anionic clay/carbon nano tube compound material;
(3) preparation of mixed-metal oxides/carbon nano tube compound material: presoma anionic clay/carbon nano tube compound material is placed in tube furnace, heat up and carry out high-temperature calcination, obtaining mixed-metal oxides/carbon nano tube compound material and metal oxide/carbon nano-tube composite photo-catalyst.
2. the preparation method of metal oxide/carbon nano-tube composite photo-catalyst according to claim 1, is characterized in that: slaine described in step (2-1) is more than one in divalent metal salt or trivalent metal salt; In oxide/carbon nanometer tube described in step (2-1) and slaine, metallic element total mass ratio is: (0.025 ~ 0.27): 1;
The atmosphere of step (3) described calcining is vacuum atmosphere, nitrogen atmosphere or air atmosphere.
3. the preparation method of metal oxide/carbon nano-tube composite photo-catalyst according to claim 2, is characterized in that: slaine described in step (2-1) is the mixture of divalent metal salt and trivalent metal salt; In described divalent metal salt, metal ion is Zn
2+, in trivalent metal salt, metal ion is Cr
3+, Zn
2+with Cr
3+mol ratio be (1 ~ 3): 1;
The atmosphere of step (3) described calcining is vacuum atmosphere, and the vacuum of described vacuum atmosphere is-0.2 ~-0.1MPa.
4. the preparation method of metal oxide/carbon nano-tube composite photo-catalyst according to claim 3, is characterized in that: described divalent metal salt is Zn (NO
3)
26H
2o, ZnCl
2or ZnSO
4h
2more than one in O, described trivalent metal salt is Cr (NO
3)
39H
2o, CrCl
36H
2o or Cr
2(SO
4)
36H
2more than one in O.
5. the preparation method of metal oxide/carbon nano-tube composite photo-catalyst according to claim 1, is characterized in that: described in step (2-2), aqueous slkali is NaOH and Na
2cO
3mixed ammonium/alkali solutions, its total alkali concn is 1.0 ~ 3.0mol/L, wherein [NaOH]=0.8 ~ 2.4mol/L, [Na
2cO
3]=0.2 ~ 0.6mol/L;
The speed of step (2-2) described dropping is 0.5 ~ 1.5mL/min; Described ageing time is 12 ~ 24h;
Step (3) described calcining heat is 600 ~ 800 DEG C, and calcination time is 2 ~ 4h; Described heating rate is 5 DEG C/min.
6. the preparation method of metal oxide/carbon nano-tube composite photo-catalyst according to claim 5, is characterized in that: described in step (2-2), total alkali concn of aqueous slkali is 2.0mol/L, [NaOH]=1.6mol/L, [Na
2cO
3]=0.4mol/L; The speed dripped described in step (2-2) is 1.0mL/min.
7. the preparation method of metal oxide/carbon nano-tube composite photo-catalyst according to claim 1, is characterized in that: in oxide/carbon nanometer tube colloidal solution described in step (1), oxide/carbon nanometer tube concentration is 1.187 ~ 11.94mg/mL;
Described in step (1), mixing speed is 3000 ~ 4000rpm, and described mixing time is 24 ~ 48h; Described ultrasonic time is 6 ~ 8h, and described supersonic frequency is 40 ~ 60kHz;
Described in step (2-1), mixing time is 8 ~ 12h, and mixing speed is 3000 ~ 4000rpm; Described ultrasonic time is 3 ~ 5h, and supersonic frequency is 40 ~ 60kHz;
The described centrifugal rotating speed of step (2-2) is 3500 ~ 4500rpm, and centrifugation time is 2 ~ 5min; Described washing refers to and adopts deionized water and absolute ethyl alcohol to carry out alternately washing, washing times 5 ~ 6 times; Described drying condition is in 60 ~ 80 DEG C of drying 24 ~ 48h.
8. the preparation method of metal oxide/carbon nano-tube composite photo-catalyst according to claim 1, it is characterized in that: the method for oxidation of CNT described in step (1) be CNT is added mass fraction be 65 ~ 68% red fuming nitric acid (RFNA) and mass fraction be in the mixed solution of the concentrated sulfuric acid of 96 ~ 98%, reflux 4 ~ 5h at 100 DEG C, centrifugal, deionized water washing is to neutral, at 60 ~ 80 DEG C, dry 24 ~ 48h, obtains oxide/carbon nanometer tube; The mass volume ratio of CNT and mixed solution is (1 ~ 2) g:(100 ~ 200) mL; The volume ratio 1:3 of red fuming nitric acid (RFNA) and the concentrated sulfuric acid.
9. the metal oxide/carbon nano-tube composite photo-catalyst prepared by method described in any one of claim 1 ~ 8.
10. the application of metal oxide/carbon nano-tube composite photo-catalyst in Photocatalytic Activity for Degradation Organic Pollutants In Water according to claim 9.
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| CN110350144A (en) * | 2018-04-03 | 2019-10-18 | 清华大学 | Battery electrode, the preparation method of battery electrode and hybrid energy-storing device |
| CN110342493A (en) * | 2018-04-03 | 2019-10-18 | 清华大学 | Transition metal oxide/carbon nano tube compound material and preparation method thereof |
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| CN112138646A (en) * | 2020-09-07 | 2020-12-29 | 淮阴工学院 | Preparation method of ZnO/CNTS nano photocatalytic composite material |
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