CN105457645A - Photocatalyst Li2CuGeO4 with visible light response function and preparing method thereof - Google Patents

Photocatalyst Li2CuGeO4 with visible light response function and preparing method thereof Download PDF

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Publication number
CN105457645A
CN105457645A CN201510954461.7A CN201510954461A CN105457645A CN 105457645 A CN105457645 A CN 105457645A CN 201510954461 A CN201510954461 A CN 201510954461A CN 105457645 A CN105457645 A CN 105457645A
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photocatalyst
visible light
cugeo
photochemical catalyst
powder
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方维双
唐莹
李洁
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Guilin University of Technology
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Guilin University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/835Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/17Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20Organic substances
    • A62D2101/26Organic substances containing nitrogen or phosphorus
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20Organic substances
    • A62D2101/28Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts

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Abstract

The invention discloses a wideband efficient photocatalyst Li2CuGeO4 with the visible light response function and a preparing method thereof. The chemical composition formula of the photocatalyst is Li2CuGeO4. The invention further discloses the preparing method for the material. The obtained photocatalyst has the advantages of being wide in spectrum response range, high in light conversion efficiency, good in stability and the like. Under radiation of visible light, the photocatalyst has a function of decomposing harmful chemical substances and organic biomass and an antibacterial function; in addition, the preparing method is simple, low in resultant temperature and cost, and suitable for industrial production and application.

Description

Visible light-responded photocatalyst Li 2cuGeO 4and preparation method thereof
Technical field
The present invention relates to a kind of visible light-responded photocatalyst Li 2cuGeO 4and preparation method thereof, belong to inorganic field of photocatalytic material.
Background technology
Along with socioeconomic development, people more and more pay close attention to for the energy and ecological environment, solve energy shortage and problem of environmental pollution be realize sustainable development, improve people's living standard and safeguard national security in the urgent need to.
From phase late 1970s, there has been proposed and to utilize in photochemical catalyst decomposition water and the organic matter such as agricultural chemicals in air and odorant, and scribble the application example such as self-cleaning of the surface of solids of photochemical catalyst.The principle of light-catalyzed reaction is that photochemical catalyst is after absorbing the photon higher than its band-gap energy, generate hole and electronics, these holes and electronics carry out oxidation reaction and reduction reaction respectively, reach the object of decomposing harmful chemical, organic-biological matter and sterilization.Photochemical catalyst has many kinds, and wherein most representative is titanium dioxide (TiO 2), titanium dioxide has been utilized to decompose organic matters such as the agricultural chemicals in water and in air and odorants, but the band gap of titanium dioxide is 3.2eV, only under the ultraviolet irradiation shorter than 400nm, just activity can be shown, can only at indoor or the local work having uviol lamp, almost can not utilize visible ray, this limits the use of titanium dioxide optical catalyst greatly.
Consider the practicality of photochemical catalyst in decomposing harmful substances, utilize sunshine to be indispensable as light source.Irradiate maximum to sunshine medium wavelength intensity of visible ray near 500nm on earth's surface, wavelength is the energy of the visible region of 400nm ~ 750nm is approximately 43% of sunshine gross energy, so in order to efficient utilization, the R and D of bismuth series photocatalyst have achieved a series of great achievement, and bismuthous compound is as BiVO 4, Bi 2moO 6, Bi 2mo 2o 9, Bi 2mo 3o 12and Bi 2wO 4be in the news and there is good absorption under visible light.A series of niobium (tantalum) hydrochlorate photochemical catalyst is widely studied owing to having higher photocatalytic activity.Such as, niobate photocatalyst Pb 3nb 4o 13, BiNbO 4and Bi 2mNbO 7(M=Al, Ga, In, Y, rare earth element and Fe) etc. with niobium potassium compound oxide photocatalyst as KNbO 3, KNb 3o 8, K 4nb 6o 17and K 6nb 10.6o 30deng all, there is good photocatalysis performance, but its intrinsic photocatalytic effect is very weak or do not have activity in visible-range.
Although photocatalysis research has carried out the several years, the current exploration to visible light-responded photochemical catalyst is the summary of experience drawn by great many of experiments with exploitation major part, in theory also cannot from the crystal structure of compound, composition, the physicochemical properties such as molecular weight are predicted its photocatalysis performance, therefore at present report to have visible light-responded photochemical catalyst kind still very limited, and it is low to there is light conversion efficiency, synthesis difficulty, poor stability and the problem such as spectral response range is narrow, research and develop that new preparation method is simple and to have the visible light-responded high efficiency photocatalyst of wideband be that this area scientific and technical personnel thirst for solving always but are difficult to the difficult problem that succeeds all the time, which greatly limits extensive use and the development of photochemical catalyst.We are to consisting of Li 2cuGeO 4, Li 2znGeO 4and Li 2mgGeO 4sample carried out Photocatalytic Performance Study.Found that Li 2cuGeO 4band gap width is 2.53eV, has excellent visible light-responded photocatalysis performance; Li 2znGeO 4and Li 2mgGeO 4for insulator, under ultraviolet irradiation, also do not show activity.
Summary of the invention
The object of this invention is to provide and a kind of there is visible light-responded photocatalyst Li 2cuGeO 4and preparation method thereof.
The chemical constitution formula with visible light-responded photochemical catalyst that the present invention relates to is: Li 2cuGeO 4.
Preparation method's concrete steps of above-mentioned visible light-responded photochemical catalyst are:
(1) by 99.9% analytically pure chemical raw material Li 2cO 3, CuO and GeO 2powder press Li 2cuGeO 4composition weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 700 ~ 750 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and average diameter of particles is diminished, lower than 2 μm, namely obtain Li 2cuGeO 4powder.
Advantage of the present invention: Li 2cuGeO 4the visible light-responded wide frequency range of photochemical catalyst, the high and good stability of light conversion efficiency, has the effect of decomposing harmful chemical, organic-biological matter and sterilization under visible light illumination; Preparation method is simple in addition, synthesis temperature is low, and cost is low, is applicable to industrial production and application.
Detailed description of the invention
To be specifically described the present invention below:
1, in order to obtain the composite oxides used in the present invention, first use solid-phase synthesis to prepare powder, namely using as the various oxide of raw material or carbonate according to the metering of target constitutional chemistry than mixing, then to synthesize in air atmosphere at ambient pressure.
2, in order to effectively utilize light, the size of the photochemical catalyst in the present invention is preferably in micron level, or even nano particle, and specific area is larger.With oxide powder prepared by solid-phase synthesis, its particle is comparatively large and surface area is less, but can pulverize means by ball mill makes particle diameter diminish.
3, photocatalysis experiment of the present invention is using methyl orange as simulation organic pollution, and its concentration is 20mg/L; Photocatalyst Li 2cuGeO 4addition be 1g/L; Light source uses the xenon lamp of 300W, the vessel that reactive tank uses pyrex to make, and obtains the light that wavelength is greater than 420nm, then irradiate photochemical catalyst by wave filter; Catalysis time is set as 60 minutes.
Embodiment 1:
(1) pure chemistry raw material Li will be analyzed 2cO 3, CuO and GeO 2powder press Li 2cuGeO 4composition weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 700 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and average diameter of particles is diminished, lower than 2 μm, namely obtain Li 2cuGeO 4powder.
Prepared photochemical catalyst, under being greater than the radiation of visible light of 420nm, reaches 97.3% to methyl orange clearance in 60 minutes at wavelength.
Embodiment 2:
(1) pure chemistry raw material Li will be analyzed 2cO 3, CuO and GeO 2powder press Li 2cuGeO 4composition weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 725 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and average diameter of particles is diminished, lower than 2 μm, namely obtain Li 2cuGeO 4powder.
Prepared photochemical catalyst, under being greater than the radiation of visible light of 420nm, reaches 98.5% to methyl orange clearance in 60 minutes at wavelength.
Embodiment 3:
(1) pure chemistry raw material Li will be analyzed 2cO 3, CuO and GeO 2powder press Li 2cuGeO 4composition weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 750 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and average diameter of particles is diminished, lower than 2 μm, namely obtain Li 2cuGeO 4powder.
Prepared photochemical catalyst, be greater than the radiation of visible light of 420nm at wavelength under, 60min reaches 98.3% to methyl orange clearance.
The present invention is never limited to above embodiment.Bound, the interval value of each temperature can realize the present invention, do not enumerate embodiment at this.
The made photocatalyst powder of above inventive embodiments can be carried on multiple matrix surface.Matrix can be glass, pottery, active carbon or quartz sand etc., and photochemical catalyst can be carried on matrix surface in the form of a film.

Claims (1)

1. a visible light-responded photochemical catalyst, is characterized in that the chemical constitution formula of described photochemical catalyst is Li 2cuGeO 4;
Preparation method's concrete steps of described photochemical catalyst are:
(1) pure chemistry raw material Li will be analyzed 2cO 3, CuO and GeO 2powder press Li 2cuGeO 4composition weigh batching;
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves;
(3) powder step (2) mixed 700 ~ 750 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and makes average diameter of particles lower than 2 μm, namely obtain Li 2cuGeO 4powder.
CN201510954461.7A 2015-12-20 2015-12-20 Photocatalyst Li2CuGeO4 with visible light response function and preparing method thereof Pending CN105457645A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106179371A (en) * 2016-07-19 2016-12-07 桂林理工大学 Visible light-responded photocatalyst Li2caCuGeO5and preparation method thereof
CN106215944A (en) * 2016-07-19 2016-12-14 桂林理工大学 Visible light-responded photocatalyst Li2cuSn2o6and preparation method thereof
CN106268744A (en) * 2016-07-24 2017-01-04 桂林理工大学 Visible light-responded photocatalyst Li In3si2o9and preparation method thereof
CN106268840A (en) * 2016-07-19 2017-01-04 桂林理工大学 Visible light-responded photocatalyst Li2baCuGe2o7and preparation method thereof
WO2017119410A1 (en) * 2016-01-05 2017-07-13 国立研究開発法人産業技術総合研究所 Lithium-copper composite oxide

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104383936A (en) * 2014-11-12 2015-03-04 桂林理工大学 Photocatalyst Li2Cu2Ge2O7 with visible light response and preparation method thereof
CN104437503A (en) * 2014-11-15 2015-03-25 桂林理工大学 Visible-light response photocatalyst Li2Cu2Si4O11 and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104383936A (en) * 2014-11-12 2015-03-04 桂林理工大学 Photocatalyst Li2Cu2Ge2O7 with visible light response and preparation method thereof
CN104437503A (en) * 2014-11-15 2015-03-25 桂林理工大学 Visible-light response photocatalyst Li2Cu2Si4O11 and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017119410A1 (en) * 2016-01-05 2017-07-13 国立研究開発法人産業技術総合研究所 Lithium-copper composite oxide
JPWO2017119410A1 (en) * 2016-01-05 2018-10-25 国立研究開発法人産業技術総合研究所 Lithium copper complex oxide
CN106179371A (en) * 2016-07-19 2016-12-07 桂林理工大学 Visible light-responded photocatalyst Li2caCuGeO5and preparation method thereof
CN106215944A (en) * 2016-07-19 2016-12-14 桂林理工大学 Visible light-responded photocatalyst Li2cuSn2o6and preparation method thereof
CN106268840A (en) * 2016-07-19 2017-01-04 桂林理工大学 Visible light-responded photocatalyst Li2baCuGe2o7and preparation method thereof
CN106268744A (en) * 2016-07-24 2017-01-04 桂林理工大学 Visible light-responded photocatalyst Li In3si2o9and preparation method thereof

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