CN101664676A - Preparation method of composite metal oxide/carbon nanotube type visible light catalyst - Google Patents
Preparation method of composite metal oxide/carbon nanotube type visible light catalyst Download PDFInfo
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- CN101664676A CN101664676A CN200910092440A CN200910092440A CN101664676A CN 101664676 A CN101664676 A CN 101664676A CN 200910092440 A CN200910092440 A CN 200910092440A CN 200910092440 A CN200910092440 A CN 200910092440A CN 101664676 A CN101664676 A CN 101664676A
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Abstract
The invention relates to a preparation method of a composite metal oxide/carbon nanotube type visible light catalyst, belonging to the technical field of composite metal oxide preparation. According to the characteristics of the structure designability and the laminate composition adjustability of the layered double hydroxide, firstly introducing a certain quantity of Mg<2+>, Zn<2+>, Al<3+>, Cr<2+>, In<3+> and Ga<3+> ions into a laminate, performing in-situ compounding with a surface-modified carbon nanotube to obtain a layered double hydroxide/carbon nanotube hybrid composite precursor and baking the precursor at high temperature to obtain the composite metal oxide/carbon nanotube type visible light catalyst with novel structure and highly dispersed active components. The catalyst shows favorable visible light degradation activity after being applied to a visible light degradation reaction of organic dye methyl orange and methylene blue.
Description
Technical field
The invention belongs to the composite metal oxide preparing technical field, be particularly related to a kind of preparation method of composite metal oxide/carbon nanotube type visible light catalyst, prepare composite metal oxide/carbon nanotube type visible light catalyst by layered double hydroxide/carbon nano-tube hybridization composite precursor, this catalyst is mainly used in the reaction of visible light degradating organic dye.
Technical background
In recent years, along with industry and economic construction growing, environmental pollution and energy shortage also become country and the social problem of paying close attention to gradually.People wish to prepare a kind of novel photocatalysis material, it is had concurrently can utilize clean energy resource (solar energy) to solve some environmental pollution (as water pollution etc.) two aspect advantages.TiO
2As a kind of environmental type photochemical catalyst, it is active and stable to have a higher light degradation, once be considered to be a kind of have better prospect catalysis material.But in actual light catalytic degradation process, because TiO
2Its energy gap (3.2eV) broad, and cause electricity conversion lower makes it can only utilize ultraviolet light in the sunshine (account for solar energy 4%); And simple TiO
2As photochemical catalyst the time, there is pair natural daylight utilization rate not high, solution inactivation in solution, catalyst is difficult to shortcomings such as recovery.And, can make TiO now by the method for metal or nonmetal doping
2The photochemical catalyst energy gap of class reduces, and allows its optical absorption edge cause UV district move to visible region, improves the utilization ratio of photochemical catalyst to sunshine.Though TiO
2The class photochemical catalyst can change TiO by the doping of different metals or nonmetalloid
2Energy gap, but be not clearly, and the TiO after mixing to the change of its energy gap
2The stability of photochemical catalyst is not high.Comparatively speaking, it is reported that some is by the perovskite of solid phase reaction preparation and the metal oxide such as the MIn of spinel-type
2O
4(M=Ca, Sr, Ba etc.) have the characteristic of utilizing the visible region in the natural daylight, and some organic dyestuff can be used to degrade.But the shortcoming of this type of photochemical catalyst is that its specific surface is lower, and the temperature of calcining during preparation is high and the time is long, and (1200 ℃, 12h), and the product crystalline phase of acquisition is impure etc.
CNT (CNTs) is because of having the double properties of metal and conductor, and in the light-catalyzed reaction process, derivation electronics that can be orderly reduces the load probability of hole～electronics, thereby improves photocatalytic activity.Again because the characteristic of high-ratio surface of CNT own and high dispersive, make it behind functional modification, can combine by some active force with some metal ion or oxide, reach the effect that improves active component and compound decentralization, and improve the specific area of compound and reduce the grain size of compound particle, thereby in some catalytic reaction, improve the catalytic activity of catalyst.
Layered double hydroxide (LDHs) is to be arranged in order and the crystal that forms along the third dimension by the laminate of two-dimensional, and its laminate main body constitutes by a certain proportion of divalence and the mutual high degree of dispersion of trivalent metal ion and with covalent bond.Most typical is to contain carbonate anion hydrotalcite [Mg
6Al
2(OH)
16CO
34H
2O], Mg during the hydrotalcite laminate is formed
2+, Al
3+Can be by the metal ion such as the Co of the close corresponding valence state of other ionic radius
2+, Zn
2+Deng divalent metal In
3+, Ga
3+, Cr
3+Replace Deng the part or all of isomorphous of trivalent metal cation, the interlayer carbonate anion also can be by inorganic and organic ion and complex anion replacement.In this layer structure, be equally distributed in a certain way in each small construction unit; And be positioned at the anion of interlayer owing to be subjected to the coordination, electronics transfer effect or the like of restriction, interlayer ion and laminate group in attraction, the repulsion between interlayer ion, the layer space of laminate electric charge and influence, it is also very even to distribute.Particularly for In
3+Oxide In
2O
3(or Ga
3+, Cr
3+Oxide) energy gap to be starkly lower than TiO
2(3.2eV) or ZnO (3.37eV), can utilize In
3+Oxide Deng trivalent metal ion has this characteristic of visible light catalysis activity, earlier this type of trivalent metal cation being carried out part or all of isomorphous replacement in LDHs enters between the laminate of LDHs, again the CNT of LDHs and finishing is carried out compound, by at N
2Roasting under the atmosphere uniform temperature condition can be prepared and had active component high degree of dispersion and the high composite metal oxide/carbon nano tube type visible light catalytic material of photocatalytic activity.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of composite metal oxide/carbon nanotube type visible light catalyst prepares composite metal oxide/carbon nanotube type visible light catalyst by layered double hydroxide/carbon nano-tube hybridization composite precursor.
The present invention has the advantages that according to layered double hydroxide structure designability and laminate are formed adjustable sex change, introduces a certain amount of Mg at laminate
2+, Zn
2+, Al
3+, Cr
2+, In
3+, Ga
3+Ion, by with the compound layered double hydroxide/carbon nano-tube hybridization composite precursor that obtains of the CNT original position of finishing, again this precursor is carried out composite metal oxide/carbon nanotube type visible light catalyst that high-temperature roasting obtains new structure.The catalyst of this unique texture has the active component high degree of dispersion, the metal oxide particle particle diameter is little by (5～20nm), can bring into play the advantage of photoelectricity conduction effect preferably between active component and CNT, make it in the reaction of visible light degradating organic dye methyl orange and methylene blue, show higher light degradation activity (92～98%).
This method for preparing catalyst is:
A. 1～2g CNT and 0.25～0.5g pyrene butyric acid are dissolved in the absolute ethyl alcohol of 50～100ml ultrasonic concussion 10～15min respectively; With the two mixing, ultrasonic again concussion 0.5～1h behind magnetic agitation 5～10min, gained solution carries out suction filtration with miillpore filter, and filter cake places 60～80 ℃ of vacuum drying 16～20h after spending absolute ethanol washing 3～5 times again.
B. with solubility divalent metal M
2+With trivalent metal M
3+Nitrate be dissolved in the deionized water, be mixed with mixing salt solution, described M
2+Can be Mg
2+Or Zn
2+In one or both; Described M
3+Can be Al
3+, In
3+, Ga
3+Or Cr
3+In one or more, wherein essential Ga
3+, In
3+Or Cr
3+In one or more; NaOH and sodium carbonate are dissolved in preparation mixed-alkali solution in the deionized water, and wherein the NaOH molar concentration is 0.34～1.44mol/L, and the sodium carbonate molar concentration is 0.14～0.6mol/L.
C. the mixing salt solution that configures among the CNT of modified in the steps A and the step B is mixed, mixed solution is transferred in the reactor of band stirring, at room temperature slowly drip mixed-alkali solution while stirring to mixed solution, make the pH that reaches titration end-point 9～10, after aqueous slkali to be mixed drips, it is 40～80 ℃ that temperature is risen to crystallization temperature by room temperature, crystallization time is 4～12h, reaction finishes the back suction filtration, be washed till cleaning solution neutrality with deionized water, use absolute ethanol washing again 3～5 times, at last filter cake is put into 60～80 ℃ of baking oven vacuum drying 12～16h, obtain layered double hydroxide/carbon nano-tube hybridization composite precursor.
D. the hybrid composite precursors that step C is prepared places atmosphere furnace, passes to N
2Atmosphere, flow velocity are 60～80ml/min, are warming up to 500～800 ℃ with the speed of 5～10 ℃/min, and insulation 3～5h naturally cools to room temperature then, obtains the visible light catalyst of composite metal oxide/carbon nano tube type.
M among the step B
2+Molar concentration be 0.21～0.9mol/L, M
3+Molar concentration be 0.07～0.3mol/L, keep M
2+With M
3+Mol ratio be 3: 1; The quality and the divalent metal M that add CNT among the step C
2+The mass ratio of nitrate is 0.08～0.25: 1.
The present invention has following remarkable result: (1) can prepare highly compound layered double hydroxide/carbon nano-tube hybridization composite precursor by compound with the CNT original position of finishing; (2) trivalent metal cation on the LDH laminate can form metal oxide and the spinel compound with visible light catalysis activity with bivalent cation in the hybrid composite material precursor in follow-up high-temperature roasting, their high degree of dispersion are on the surface of CNT, and formation has composite metal oxide/carbon nanotube type visible light catalyst that adhesion is strong, the composite oxides particle diameter is little; (3) composite metal oxide/carbon nanotube type visible light catalyst shows visible light degradation capability preferably to organic dyestuff methyl orange and methylene blue, has application promise in clinical practice aspect the water pollution processing.
The specific embodiment
Embodiment 1:
Take by weighing Mg (NO
3)
26H
2O, Al (NO
3)
39H
2O and In (NO
3)
34H
2O is dissolved in deionized water preparation mixing salt solution, and wherein the molar concentration of each metal ion species is respectively [Mg
2+]=0.21mol/L, [Al
3+]=0.035mol/L, [In
3+]=0.035mol/L.With deionized water preparation NaOH and Na
2CO
3Mixed-alkali solution, [NaOH]=0.34mol/L wherein, [Na
2CO
3]=0.14mol/L.Take by weighing CNT after 0.25g modifies again with after the 50ml mixing salt solution mixes, slowly be added drop-wise to mixed-alkali solution in the mixing salt solution, when the pH in the system reaches 9, stop to drip mixed ammonium/alkali solutions, 40 ℃ of water-baths, crystallization 6h filters, spend deionised water to cleaning solution and be neutral, vacuum drying 12h obtains MgAlIn～LDH/CNTs hybrid composite precursors; The composite precursor for preparing is placed atmosphere furnace, pass to N
2Atmosphere, gas flow rate are 60ml/min, are warming up to 800 ℃ with the speed of 5 ℃/min, and insulation 3h naturally cools to room temperature then, obtains composite metal oxide/carbon nanotube type visible light catalyst, and wherein the metal oxide particle particle diameter is 5nm.
Take by weighing the 0.05g catalyst and place and contain volume for 100ml concentration is the quartzy bottle of 50ppm methyl orange, utilize xenon lamp simulation radiation of visible light to carry out the visible light catalytic reaction, 3h afterreaction conversion ratio reaches 98.0%
Embodiment 2:
Take by weighing Mg (NO
3)
26H
2O, Al (NO
3)
39H
2O and Ga (NO
3)
39H
2O is dissolved in deionized water preparation mixing salt solution, and wherein the molar concentration of each metal ion species is respectively [Mg
2+]=0.6mol/L, [Al
3+]=0.1mol/L, [Ga
3+]=0.1mol/L.With deionized water preparation NaOH and Na
2CO
3Mixed-alkali solution, [NaOH]=0.72mol/L wherein, [Na
2CO
3]=0.4mol/L.Take by weighing again after 0.5g modifies CNT with after the 50ml mixing salt solution mixes, slowly be added drop-wise to mixed-alkali solution in the mixing salt solution, when the pH in the system reaches 9, stop to drip mixed ammonium/alkali solutions, in 60 ℃ of water-baths, crystallization 4h filters, spend deionised water to cleaning solution and be neutral, vacuum drying 12h obtains MgAlGa～LDH/CNTs hybrid composite precursors; The composite precursor for preparing is placed atmosphere furnace, pass to N
2Atmosphere, gas flow rate are 60ml/min, are warming up to 500 ℃ with the speed of 5 ℃/min, and insulation 3h naturally cools to room temperature then, obtains composite metal oxide/carbon nanotube type visible light catalyst, and wherein the metal oxide particle particle diameter is 15nm.
Take by weighing the 0.05g catalyst and place volume for 100ml concentration is the quartzy bottle of 50ppm methyl orange, utilize xenon lamp simulation radiation of visible light to carry out the visible light catalytic reaction, 3h afterreaction conversion ratio reaches 95.0%
Embodiment 3:
Take by weighing Zn (NO
3)
26H
2O, Al (NO
3)
39H
2O and In (NO
3)
34H
2O is dissolved in deionized water preparation mixing salt solution, and wherein the molar concentration of each metal ion species is respectively [Zn
2+]=0.3mol/L, [Al
3+]=0.05mol/L, [In
3+]=0.05mol/L.With deionized water preparation NaOH and Na
2CO
3Mixed-alkali solution, [NaOH]=0.48mol/L wherein, [Na
2CO
3]=0.2mol/L.Take by weighing again the 0.5g CNT with after the 50ml mixing salt solution mixes, slowly be added drop-wise to mixed-alkali solution in the mixing salt solution, when the pH in the system reaches 10, stop to drip mixed ammonium/alkali solutions, in 60 ℃ of water-baths, crystallization 8h filters, spend deionised water to cleaning solution and be neutral, vacuum drying 12h obtains ZnAlIn～LDH/CNTs hybrid composite precursors; The composite precursor of preparation is placed atmosphere furnace, pass to N
2Atmosphere, gas flow rate are 80ml/min, are warming up to 800 ℃ with the speed of 10 ℃/min, and insulation 4h naturally cools to room temperature then, obtains composite metal oxide/carbon nanotube type visible light catalyst, and wherein the metal oxide particle particle diameter is 10nm.
Take by weighing the 0.05g catalyst and place volume for 100ml concentration is the quartzy bottle of 50ppm methylene blue, utilize xenon lamp simulation radiation of visible light to carry out the visible light catalytic reaction, 3h afterreaction conversion ratio reaches 97.0%
Embodiment 4:
Take by weighing Zn (NO
3)
26H
2O, Al (NO
3)
39H
2O and Cr (NO
3)
39H
2O is dissolved in deionized water preparation mixing salt solution, and wherein the molar concentration of each metal ion species is respectively [Zn
2+]=0.9mol/L, [Al
3+]=0.15mol/L, [Cr
3+]=0.15mol/L.With deionized water preparation NaOH and Na
2CO
3Mixed-alkali solution, [NaOH]=1.44mol/L wherein, [Na
2CO
3]=0.6mol/L.Take by weighing again the 1.0g CNT with after the 50ml mixing salt solution mixes, slowly be added drop-wise to mixed-alkali solution in the mixing salt solution, when the pH in the system reaches 10, stop to drip mixed ammonium/alkali solutions, in 80 ℃ of water-baths, crystallization 12h filters, spend deionised water to cleaning solution and be neutral, vacuum drying 16h obtains ZnAlCr～LDH/CNTs hybrid composite precursors; The composite precursor of preparation is placed atmosphere furnace, pass to N
2Atmosphere, gas flow rate are 80ml/min, are warming up to 800 ℃ with the speed of 10 ℃/min, and insulation 5h naturally cools to room temperature then, obtains composite metal oxide/carbon nanotube type visible light catalyst, and wherein the metal oxide particle particle diameter is 20nm.
Take by weighing the 0.05g catalyst and place volume for 100ml concentration is the quartzy bottle of 50ppm methylene blue, utilize xenon lamp simulation radiation of visible light to carry out the visible light catalytic reaction, 3h afterreaction conversion ratio reaches 92.0%
Claims (2)
- The preparation method of 1 one kinds of composite metal oxide/carbon nanotube type visible light catalyst is characterized in that, preparation process is as follows:A. 1～2g CNT and 0.25～1g pyrene butyric acid are dissolved in the absolute ethyl alcohol of 50～100ml ultrasonic concussion 10～15min respectively; With the two mixing, ultrasonic again concussion 1～1.5h behind magnetic agitation 5～10min, gained solution carries out suction filtration with miillpore filter, and filter cake places 60～80 ℃ of vacuum drying 16～20h after spending absolute ethanol washing 3～5 times again;B. with solubility divalent metal M 2+With trivalent metal M 3+Nitrate be dissolved in the deionized water, be mixed with mixing salt solution, described M 2+Can be Mg 2+Or Zn 2+In one or both; Described M 3+Can be Al 3+, In 3+, Ga 3+Or Cr 3+In one or more, wherein essential Ga 3+, In 3+Or Cr 3+In one or more; NaOH and sodium carbonate are dissolved in preparation mixed-alkali solution in the deionized water, and wherein the NaOH molar concentration is 0.34～1.44mol/L, and the sodium carbonate molar concentration is 0.14～0.6mol/L;C. the mixing salt solution that configures among the CNT of modified in the steps A and the step B is mixed, mixed solution is transferred in the reactor of band stirring, at room temperature slowly drip mixed-alkali solution while stirring to mixed solution, make the pH that reaches titration end-point 9～10, after aqueous slkali to be mixed drips, it is 40～80 ℃ that temperature is risen to crystallization temperature by room temperature, crystallization time is 4～12h, reaction finishes the back suction filtration, be washed till cleaning solution neutrality with deionized water, use absolute ethanol washing again 3～5 times, at last filter cake is put into 60～80 ℃ of baking oven vacuum drying 12～16h, obtain layered double hydroxide/carbon nano-tube hybridization composite precursor;D. the hybrid composite precursors that step C is prepared places atmosphere furnace, passes to N 2Atmosphere, flow velocity are 60～80ml/min, are warming up to 500～800 ℃ with the speed of 5～10 ℃/min, and insulation 3～5h naturally cools to room temperature then, obtains the visible light catalyst of composite metal oxide/carbon nano tube type.
- 2, preparation method according to claim 1 is characterized in that M among the step B 2+Molar concentration be 0.21～0.9mol/L, M 3+Molar concentration be 0.07～0.3mol/L, keep M 2+With M 3+Mol ratio be 3: 1; The quality and the divalent metal M that add CNT among the step C 2+The mass ratio of nitrate is 0.08～0.25: 1.
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| CN103157457B (en) * | 2011-12-08 | 2014-11-05 | 北京化工大学 | Mg/Zn/In composite metal oxide photocatalyst, preparation method and applications thereof |
| CN103272596B (en) * | 2013-06-09 | 2016-05-18 | 太原理工大学 | A kind of preparation method of ternary hetero-junctions visible-light photocatalyst |
| CN103272596A (en) * | 2013-06-09 | 2013-09-04 | 太原理工大学 | Preparation method of ternary heterojunction visible light photocatalyst |
| CN104952636A (en) * | 2015-05-14 | 2015-09-30 | 北京化工大学 | Preparation method of nanocarbon/hydrotalcite array composite |
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| CN109999789A (en) * | 2019-05-20 | 2019-07-12 | 西北师范大学 | A kind of preparation and application of palygorskite/Zn-Mg-Cr ternary metal oxide composite photo-catalyst |
| CN111604015A (en) * | 2020-06-07 | 2020-09-01 | 宁夏大学 | Preparation method of shell-core structure composite material with metal compound coated by nano carbon material |
| CN111604015B (en) * | 2020-06-07 | 2022-02-22 | 宁夏大学 | Preparation method of shell-core structure composite material with metal compound coated by nano carbon material |
| CN116099522A (en) * | 2023-04-12 | 2023-05-12 | 中化学科学技术研究有限公司 | Polyester alcoholysis catalyst and preparation method thereof |
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