CN104607217A - Preparation method of copper silver phosphate with photodegradation function and photocatalytic application - Google Patents

Preparation method of copper silver phosphate with photodegradation function and photocatalytic application Download PDF

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CN104607217A
CN104607217A CN201510055123.XA CN201510055123A CN104607217A CN 104607217 A CN104607217 A CN 104607217A CN 201510055123 A CN201510055123 A CN 201510055123A CN 104607217 A CN104607217 A CN 104607217A
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silver
copper
solution
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马忠
谢洪德
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Suzhou Dejie Membrane Material Technology Co Ltd
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Suzhou Dejie Membrane Material Technology Co Ltd
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Abstract

The invention discloses a novel phosphate material with a photodegradation function, wherein a chemical formula of the novel photocatalyst material is Ag2Cu(PO3)4, and the novel phosphate material belongs to the field of inorganic photocatalytic materials, and is used for decomposing organic polymer compounds under the irradiation of ultraviolet light and near ultraviolet light; and the novel copper silver phosphate photocatalytic material can be prepared by adopting a high temperature solid phase method, a chemical solution method and a coprecipitation method; a preparation method of the novel copper silver phosphate photocatalytic material is simple, and the prepared material is uniform in granularity distribution and good in chemical stability, has a good photocatalytic effect, and can effectively degrade organic pollutants under the irradiation of the near ultraviolet light, thus being an ideal photocatalytic material. The preparation method disclosed by the invention is simple, the preparation conditions are mild, the energy consumption is low, the reaction time is short, industrialized production is easy to realize, and waste water and waste gas emissions do not exist, thereby being environmentally-friendly.

Description

A kind of preparation method and photocatalytic applications with the cupric phosphate silver of light degradation function
Technical field
The present invention relates to a kind of preparation method and application thereof of novel inorganic photocatalyst material, particularly for the photochemical catalyst Ag of degradable organic pollutant 2cu (PO 3) 4and preparation method thereof, belong to inorganic field of photocatalytic material.
Background technology
At present, the two large problems of facing mankind realizes sustainable development that is economic and society, and energy security, harmony and natural environment are the necessary conditions of social realization sustainable development.Solar energy has cheapness, the advantage such as clean, renewable, and therefore, efficient quick ground utilizes, conversion and to store solar energy be the target that people make great efforts.Photocatalitic Technique of Semiconductor just with the chemical conversion of solar energy be stored as core.By the crisis that the photocatalytic water technology that converts solar energy into Hydrogen Energy will be expected to thoroughly to solve the exhausted and greenhouse effects of fossil energy and brings; and photocatalytic degradation toxic organic pollutant and self-cleaning surface technology; by easily for we provide the living space of an environmental protection, therefore photocatalysis technology will become one of important means of coping with challenges.
In photocatalysis field, the material of most study is titanium dioxide (TiO 2).TiO 2be a kind of N-shaped oxide semiconductor, it mainly contains two kinds of crystalline forms: Detitanium-ore-type and rutile-type.It is generally acknowledged, Detitanium-ore-type has higher activity, and its valence band is about 3.2 electron-volts to the energy gap of conduction band.The band theory of its photocatalysis principle useful semiconductors is explained.With Metal Phase ratio, being with of semiconductor is discontinuous, between valence band (VB) and conduction band (CB), there is a forbidden band.When it be subject to photon energy be equal to or higher than the light irradiation of this energy gap time, the electronics (e in its valence band -) will be stimulated transits to conduction band, produces corresponding hole (h in valence band simultaneously +), define electron-hole pair.The electronics produced, hole are separated and move to particle surface under internal electric field effect.Photohole has very strong electronic capability, there is strong oxidizing property, the electronics in semiconductor grain surface adsorbed material or solvent can be captured, make the not light absorbing material of script oxidized, electron acceptor is then reduced by accepting the electronics on surface, completes light-catalyzed reaction process.
Although photocatalysis research has carried out the several years, new catalysis material is constantly reported, Chinese patent CN103464185A also reports silver pyrophosphate, tripolyphosphate silver and silver metaphosphate three kinds of photochemical catalysts, can at photocatalytic degradation organic compound under ultraviolet radiation.In addition the report of some phosphate photochemical catalysts is also had, the photochemical catalysts such as such as phosphoric acid tungsten, bismuth phosphate.On the basis of these reports, we have studied a kind of novel silver orthophosphate class photochemical catalyst Ag 2cu (PO 3) 4, find that this compounds has unique crystal structure and electronic structure, the photocatalysis performance of excellent ultraviolet light response, and there is no report at present.
Summary of the invention
Meaning of the present invention is to provide cupric phosphate silver photochemical catalyst that a kind of preparation method is simple, photocatalytic activity good, have a extensive future and preparation method thereof.
For reaching above object, the technical solution used in the present invention is:
A novel cupric phosphate silver catalysis material, its chemical formula is Ag 2cu (PO 3) 4, the sample thing of preparation is mutually pure, and particle size distribution is even.
A preparation method for Novel phosphoric acid copper silver catalysis material, adopts high temperature solid-state method, comprises the steps:
(1) with silver ion Ag +compound, copper ions Cu 2+compound, containing phosphonium ion P 5+compound be raw material, by general formula Ag 2cu (PO 3) 4the stoichiometric proportion of middle corresponding element takes each raw material, grinds and mixes;
(2) the mixture precalcining in air atmosphere step (1) obtained, precalcining temperature is 250 ~ 650 DEG C, and calcination time is 5 ~ 20 hours, naturally cools, grinds and mix;
(3) calcined in air atmosphere by the mixture that step (2) obtains, calcining heat is 650 ~ 1050 DEG C, and calcination time is 6 ~ 20 hours, naturally cools, and namely obtains Novel phosphoric acid copper silver catalysis material after grinding evenly.
Silver ion Ag described in above step +compound be silver oxide Ag 2o, silver nitrate AgNO 3with silver carbonate Ag 2cO 3in one; Described contains copper ion Cu 2+compound be cupric oxide CuO, copper carbonate CuCO 3, copper nitrate Cu (NO 3) 2with Kocide SD Cu (OH) 2in one or more combination; Described contains phosphonium ion P 5+compound be phosphorus pentoxide P 2o 5, ammonium dihydrogen phosphate (ADP) NH 4h 2pO 4, diammonium hydrogen phosphate (NH 4) 2hPO 4with phosphoric acid H 3pO 4in one.
Calcining heat described in step (2) is 300 ~ 650 DEG C, and calcination time is 6 ~ 19 hours; Calcining heat described in step (3) is 700 ~ 1000 DEG C, and calcination time is 7 ~ 19 hours.
The preparation method of another kind of cupric phosphate silver catalysis material, adopts chemical solution method, comprises the following steps:
(1) by chemical formula Ag 2cu (PO 3) 4in the stoichiometric proportion of each element, first take containing silver ion Ag +compound, be dissolved in appropriate dilute nitric acid solution, add thermal agitation, until dissolve completely, then add appropriate complexing agent, obtain solution A; Take containing copper ion Cu 2+compound, be dissolved in appropriate dilute nitric acid solution, add thermal agitation, until dissolve completely, then add appropriate complexing agent, obtain B solution; Take containing phosphonium ion P 5+compound, be dissolved in appropriate dilute nitric acid solution, add thermal agitation, until dissolve completely, obtain C solution.Finally, mixing A, B, C solution, stir and obtain mixed solution in 1-5 hour at 70-100 DEG C;
(2) placed in an oven by said mixture solution, temperature is 50 DEG C-100 DEG C, and the time is 12 hours, and ageing is also dried;
(3) after naturally cooling, take out presoma, calcine in air atmosphere, calcining heat is 600 ~ 1000 DEG C, and calcination time is 6 ~ 20 hours, and naturally after cooling, namely grinding evenly obtains the silver-colored catalysis material of cupric phosphate.
Silver ion Ag described in above step +compound be silver oxide Ag 2o, silver nitrate AgNO 3, silver carbonate Ag 2cO 3with silver sulfate Ag 2sO 4in one; Described contains copper ion Cu 2+compound be copper carbonate CuCO 3, cupric oxide CuO, copper sulphate CuSO 4with copper nitrate Cu (NO 3) 2in one; Described contains phosphonium ion P 5+compound be phosphorus pentoxide P 2o 5, ammonium dihydrogen phosphate (ADP) NH 4h 2pO 4, diammonium hydrogen phosphate (NH 4) 2hPO 4with phosphoric acid H 3pO 4in one; Described complexing agent is citric acid.
Calcining heat described in step (3) is 700 ~ 1000 DEG C, and calcination time is 6 ~ 19 hours.
The preparation method of the third cupric phosphate silver catalysis material, adopts coprecipitation, comprises the following steps:
(1) form soluble silver salt solution, described solution concentration is 2 mol/L;
(2) form soluble copper salting liquid, described solution concentration is 2 mol/L;
(3) form titanium pigment salting liquid, described solution concentration is 2 mol/L;
(4) forming volume fraction is the ammonia spirit of 30%;
(5) by chemical formula Ag 2cu (PO 3) 4the above-mentioned silver salt of proportioning, mantoquita and microcosmic salt solution, mix and blend, drips ammoniacal liquor to pH scope 9 ~ 10, and reaction precipitation thing, after separation, washing, drying, obtains presoma;
(6) by presoma at 600 ~ 1000 DEG C of temperature lower calcinations, calcination time is 7 ~ 20 hours, obtains a kind of cupric phosphate silver photocatalytic powder material.
Soluble silver salt described in above step can adopt silver oxide Ag 2o, silver nitrate AgNO 3, silver sulfate Ag 2sO 4with silver carbonate Ag 2cO 3in one, be dissolved in deionized water or dust technology and add thermal agitation gained; Described soluble copper salt can adopt copper carbonate CuCO 3, copper sulphate CuSO 4, copper nitrate Cu (NO 3) 2with the one in cupric oxide CuO, be dissolved in deionized water or dust technology and add thermal agitation gained; Described solubility microcosmic salt can adopt phosphorus pentoxide P 2o 5, ammonium dihydrogen phosphate (ADP) NH 4h 2pO 4, diammonium hydrogen phosphate (NH 4) 2hPO 4with phosphoric acid H 3pO 4in one, be dissolved in deionized water or dust technology and add thermal agitation gained.
Calcining heat described in step (6) is 650 ~ 1000 DEG C, and calcination time is 8 ~ 19 hours.
Novel cupric phosphate ag material of the present invention, preparation method is simple, photocatalytic activity good, have a extensive future, and can be used as excellent inorganic catalysis material.
Compared with prior art, technical solution of the present invention advantage is:
(1) Ag prepared 2cu (PO 3) 4the photocatalytic activity of photochemical catalyst is very good, within 240 minutes, the degradation rate of photocatalytic degradation methylene blue can reach 98%, can photocatalytic degradation methylene blue efficiently;
(2) Ag is prepared 2cu (PO 3) 4very extensively and it cheap, preparation method is simple simultaneously, and energy consumption is low, and cost is low for the raw material sources of photochemical catalyst.Obtained sample particle is tiny and be evenly distributed;
(3) the present invention discharges without waste gas and waste liquid, environmentally safe, Ag 2cu (PO 3) 4photochemical catalyst is a kind of eco-friendly inorganic catalysis material.
Accompanying drawing explanation
The Ag of Fig. 1 obtained by the embodiment of the present invention 1 2cu (PO 3) 4the X-ray powder diffraction pattern of sample;
The Ag of Fig. 2 obtained by the embodiment of the present invention 1 2cu (PO 3) 4the diffuse reflection collection of illustrative plates of sample;
The Ag of Fig. 3 obtained by the embodiment of the present invention 1 2cu (PO 3) 4the SEM figure of sample;
The Ag of Fig. 4 obtained by the embodiment of the present invention 1 2cu (PO 3) 4the sample EDS energy spectrogram of sample;
The Ag of Fig. 5 obtained by the embodiment of the present invention 1 2cu (PO 3) 4sample when illumination to the degradation curve of organic dyestuff methylene blue;
The Ag of Fig. 6 obtained by the embodiment of the present invention 1 2cu (PO 3) 4the kinetic curve figure of sample degradation methylene blue;
The Ag of Fig. 7 obtained by the embodiment of the present invention 4 2cu (PO 3) 4the X-ray powder diffraction pattern of sample;
The Ag of Fig. 8 obtained by the embodiment of the present invention 4 2cu (PO 3) 4the diffuse reflection collection of illustrative plates of sample;
The Ag of Fig. 9 obtained by the embodiment of the present invention 4 2cu (PO 3) 4the SEM figure of sample;
The Ag of Figure 10 obtained by the embodiment of the present invention 4 2cu (PO 3) 4the sample EDS energy spectrogram of sample;
The Ag of Figure 11 obtained by the embodiment of the present invention 4 2cu (PO 3) 4sample when illumination to the degradation curve of organic dyestuff methylene blue;
The Ag of Figure 12 obtained by the embodiment of the present invention 1 2cu (PO 3) 4the kinetic curve figure of sample degradation methylene blue.
Detailed description of the invention
Below in conjunction with drawings and Examples, technical solution of the present invention is further described.
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 particle diameter can be diminished by pulverizing means such as ball mills.
3, photocatalytic degradation methylene blue activity rating adopts self-control photocatalytic reaction device, illuminator is 500 watts of cylindrical shape xenon lamps, the cylindrical light catalytic reaction instrument that reactive tank uses pyrex to make, illuminator is inserted in reactive tank, and passing into condensed water cooling, during reaction, temperature is room temperature.Catalyst amount 100 milligrams, liquor capacity 250 milliliters, the concentration of methylene blue is 10 mg/litre.Catalyst is placed in reactant liquor, and catalysis time is set as 240 minutes, starts illumination after opening condensed water, within after illumination every 15 minutes, get a sample, centrifugal, get its supernatant, measure the absorbance of methylene blue solution with ultraviolet-visible spectrophotometer in wavelength 664-666 nanometers.According to Lambert-Beer's law, the absorbance of solution is directly proportional to concentration, therefore concentration can be replaced to calculate clearance, as the clearance of methylene blue solution by absorbance.Computing formula: degradation rate=(1-C/C 0) × 100%=(1-A/A 0) × 100%, wherein C 0, C is respectively concentration before and after photocatalytic degradation, A 0, A be respectively degraded before and after absorbance.
Embodiment 1:
According to chemical formula Ag 2cu (PO 3) 4, take silver oxide Ag respectively 2o:1.74 gram, cupric oxide CuO:0.6 gram, ammonium dihydrogen phosphate (ADP) NH 4h 2pO 4: 2.88 grams, add in agate mortar appropriate acetone mixed grinding evenly after, in air atmosphere, carry out precalcining, calcine 6 hours at 300 DEG C, finally with after stove cooling, take out sample; By the raw material of precalcining that obtains again in mortar with the abundant mixed grinding of identical method evenly after, again calcine in air atmosphere, calcine 7 hours at 700 DEG C, after cooling, grinding obtains cupric phosphate silver Ag 2cu (PO 3) 4catalyst.
See accompanying drawing 1, it is the X-ray powder diffraction pattern by sample prepared by the present embodiment technical scheme, and XRD test result shows, prepared cupric phosphate silver Ag 2cu (PO 3) 4degree of crystallinity is better, is monophase materials;
See accompanying drawing 2, it is the diffuse reflection spectrum by sample prepared by the present embodiment technical scheme, and as can be seen from the figure, this sample has the strongest absorption at 297 nano wave length light places;
See accompanying drawing 3, it is the SEM(SEM by sample prepared by the present embodiment technical scheme) collection of illustrative plates, as can be seen from the figure, gained sample particle is uniformly dispersed, and its average grain diameter is 10.42 microns;
See accompanying drawing 4, be the EDS energy spectrogram by sample prepared by the present embodiment technical scheme, containing Ag, Cu, P, O element in the sample as can be seen from the figure prepared.
See accompanying drawing 5, it be by sample prepared by the present embodiment technical scheme under UV Light to the degradation curve of organic dyestuff methylene blue.As can be seen from the figure, the degradation rate of this sample photocatalytic degradation methylene blue reaches 80% in 240 minutes, and the cupric phosphate silver Ag prepared is described 2cu (PO 3) 4material has good photocatalytic activity.
See accompanying drawing 6, it is the kinetic curve figure by sample degradation methylene blue prepared by the present embodiment technical scheme, and as can be seen from the figure, the apparent kinetics speed constant of this sample photocatalytic degradation methylene blue is 0.00598 minute -1.
Embodiment 2:
According to chemical formula Ag 2cu (PO 3) 4, take silver nitrate AgNO respectively 3: 1.70 grams, copper carbonate: 1.105 grams, phosphorus pentoxide P 2o 5: 1.18 grams, add in agate mortar appropriate acetone mixed grinding evenly after, in air atmosphere, carry out precalcining, calcine 10 hours at 450 DEG C, after stove cooling, take out sample; The raw material of precalcining is again even with the abundant mixed grinding of identical method, and again calcine in air atmosphere, calcine 10 hours at 800 DEG C, after cooling, grinding obtains cupric phosphate silver Ag 2cu (PO 3) 4catalyst.
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, EDS collection of illustrative plates, similar to embodiment 1 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 3:
According to chemical formula Ag 2cu (PO 3) 4, take silver carbonate Ag respectively 2cO 3: 2.76 grams, copper nitrate Cu (NO 3) 2: 1.877 grams, phosphoric acid H 3pO 4: 1.63 grams, add in agate mortar appropriate acetone mixed grinding evenly after, precalcining is carried out in air atmosphere, 550 DEG C of calcinings 14 hours, after stove cooling, take out sample the raw material of precalcining is again even with the abundant mixed grinding of identical method, again calcine in air atmosphere, calcine 14 hours at 900 DEG C, cooling grinding obtains cupric phosphate silver Ag 2cu (PO 3) 4catalyst.
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, EDS collection of illustrative plates, similar to embodiment 1 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 4:
According to chemical formula Ag 2cu (PO 3) 4, take silver nitrate AgNO respectively 3: 1.70 grams, Kocide SD Cu (OH) 2: 0.4875 gram, diammonium hydrogen phosphate (NH 4) 2hPO 4: 2.20 grams, add in agate mortar appropriate acetone mixed grinding evenly after, precalcining is carried out in air atmosphere, 650 DEG C of calcinings 19 hours, after stove cooling, take out sample the raw material of precalcining is again even with the abundant mixed grinding of identical method, again calcine in air atmosphere, calcine 19 hours at 1000 DEG C, cooling grinding obtains cupric phosphate silver Ag 2cu (PO 3) 4catalyst.
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, EDS collection of illustrative plates, similar to embodiment 1 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 5:
According to chemical formula Ag 2cu (PO 3) 4, take silver nitrate AgNO respectively 3: 1.70 grams, copper sulphate CuSO 45H 2o:1.25 gram, phosphoric acid H 3pO 4: 1.63 grams, to add respectively in deionized water and to add appropriate citric acid, after magnetic agitation a period of time, obtaining A, B, C solution respectively, by three kinds of solution mixing, continuing to stir a period of time.The mixed solution obtained the most at last is placed in baking oven, and design temperature is 80 DEG C, dries after 12 hours, naturally cools, and take out presoma, calcine in air atmosphere, calcining heat is 700 DEG C, and calcination time is 6 hours, and namely cooling grinding obtains cupric phosphate silver Ag 2cu (PO 3) 4catalyst.
See accompanying drawing 7, it is the X-ray powder diffraction pattern by sample prepared by the present embodiment technical scheme, and XRD test result shows, prepared cupric phosphate silver Ag 2cu (PO 3) 4also be monophase materials, degree of crystallinity is very good;
See accompanying drawing 8, it is the diffuse reflection spectrum by sample prepared by the present embodiment technical scheme, and as can be seen from the figure, this sample has the strongest absorption at 280 nano wave length light places;
See accompanying drawing 9, it is the SEM(SEM by sample prepared by the present embodiment technical scheme) collection of illustrative plates, as can be seen from the figure, gained sample particle is uniformly dispersed, and granularity is less, and its average grain diameter is 0.09 micron;
See accompanying drawing 10, be the EDS energy spectrogram by sample prepared by the present embodiment technical scheme, same containing Ag, Cu, P, O element in the sample as can be seen from the figure prepared.
See accompanying drawing 11, it is by the degradation curve of sample prepared by the present embodiment technical scheme to organic dyestuff methylene blue under the different UV Light time.As can be seen from the figure, the degradation rate of this sample photocatalytic degradation methylene blue can reach 98% in 240 minutes, and the cupric phosphate silver Ag prepared is described 2cu (PO 3) 4material has extraordinary photocatalytic activity.
See accompanying drawing 12, it is the kinetic curve figure by sample degradation methylene blue prepared by the present embodiment technical scheme, and as can be seen from the figure, the apparent kinetics speed constant of this sample photocatalytic degradation methylene blue is 0.01128 minute -1.
Embodiment 6:
According to chemical formula Ag 2cu (PO 3) 4, take silver sulfate Ag respectively 2sO 4: 1.56 grams, copper nitrate Cu (NO 3) 2: 0.9381 gram, phosphorus pentoxide P 2o 5: 1.18 grams, to add respectively in deionized water and to add appropriate citric acid, after magnetic agitation a period of time, obtaining A, B, C solution respectively, mixing, continuing to stir a period of time.Placed in baking oven by the mixed solution obtained, design temperature is 80 DEG C, dries 10 hours, and naturally after cooling, take out presoma, calcine in air atmosphere, calcining heat is 800 DEG C, and calcination time is 10 hours, and namely cooling grinding obtains cupric phosphate silver Ag 2cu (PO 3) 4catalyst.
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, EDS collection of illustrative plates, similar to embodiment 5 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 7:
According to chemical formula Ag 2cu (PO 3) 4, take silver carbonate Ag respectively 2cO 3: 1.38 grams, cupric oxide CuO:0.4014 gram, ammonium dihydrogen phosphate (ADP) NH 4h 2pO 4: 1.92 grams, to add respectively in deionized water and to add appropriate citric acid, after magnetic agitation a period of time, obtaining A, B, C solution respectively, mixing, continuing to stir a period of time.Placed in baking oven by the mixed solution obtained, design temperature is 80 DEG C, dries 12h, and naturally after cooling, take out presoma, calcine in air atmosphere, calcining heat is 900 DEG C, and calcination time is 15 hours, and namely cooling grinding obtains cupric phosphate silver Ag 2cu (PO 3) 4catalyst.
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, EDS collection of illustrative plates, similar to embodiment 5 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 8:
According to chemical formula Ag 2cu (PO 3) 4, take Ag respectively 2o:1.74 gram, copper carbonate CuCO 3: 3.76 grams, diammonium hydrogen phosphate (NH 4) 2hPO 4: 3.30 grams, to add respectively in deionized water and to add appropriate citric acid, after magnetic agitation a period of time, obtaining A, B, C solution respectively, mixing, continuing to stir a period of time.Placed in baking oven by the mixed solution obtained, design temperature is 80 DEG C, dries 12 hours, and naturally after cooling, take out presoma, calcine in air atmosphere, calcining heat is 1000 DEG C, and calcination time is 19 hours, and namely cooling grinding obtains cupric phosphate silver Ag 2cu (PO 3) 4catalyst.
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, EDS collection of illustrative plates, similar to embodiment 5 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 9:
According to chemical formula Ag 2cu (PO 3) 4, take silver oxide Ag 2o:1.16 gram, configuration concentration is the silver salt solution of 2 mol/L, takes copper nitrate Cu (NO 3) 2: 0.94 gram, configuration concentration is the copper salt solution of 2 mol/L, takes phosphoric acid H 3pO 4: 1.63 grams, configuration concentration is the microcosmic salt solution of 2 mol/L, mixing three kinds of solution & stir, is the ammonia spirit of 30% to mixed solution and dripping volume fraction, stops when pH is about 9 ~ 10, stir, after deionized water and ethanol washing, put into baking oven oven dry and obtain presoma, select air atmosphere, by above-mentioned presoma 650 DEG C of temperature lower calcinations 8 hours, namely cooling grinding obtains cupric phosphate silver Ag 2cu (PO 3) 4catalyst.
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, EDS collection of illustrative plates, similar to embodiment 5 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 10:
According to chemical formula Ag 2cu (PO 3) 4, take silver nitrate AgNO 3: 2.04 grams, configuration concentration is the silver salt solution of 2 mol/L, takes copper carbonate CuCO 3: 1.321 grams, configuration concentration is the copper salt solution of 2 mol/L, takes phosphorus pentoxide P 2o 5: 1.42 grams, configuration concentration is the microcosmic salt solution of 2 mol/L, mixing three kinds of solution & stir, is the ammonia spirit of 30% to mixed solution and dripping volume fraction, stops when pH is about 9 ~ 10, stir, after sediment deionized water and ethanol washing, put into baking oven oven dry and obtain presoma, select air atmosphere, by above-mentioned presoma 750 DEG C of temperature lower calcinations 12 hours, namely cooling grinding obtains cupric phosphate silver Ag 2cu (PO 3) 4catalyst.
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, EDS collection of illustrative plates, similar to embodiment 5 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 11:
According to chemical formula Ag 2cu (PO 3) 4, take silver sulfate Ag 2sO 4: 1.34 grams, configuration concentration is the silver salt solution of 2 mol/L, takes CuSO 4: 0.802 gram, configuration concentration is the copper salt solution of 2 mol/L, takes ammonium dihydrogen phosphate (ADP) NH 4h 2pO 4: 1.64 grams, configuration concentration is the microcosmic salt solution of 2 mol/L, mixing three kinds of solution & stir, is the ammonia spirit of 30% to mixed solution and dripping volume fraction, stops when pH is about 9 ~ 10, stir, after sediment deionized water and ethanol washing, put into baking oven oven dry and obtain presoma, select air atmosphere, by above-mentioned presoma 850 DEG C of temperature lower calcinations 16 hours, namely cooling grinding obtains cupric phosphate silver Ag 2cu (PO 3) 4catalyst.
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, EDS collection of illustrative plates, similar to embodiment 5 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 12:
According to chemical formula Ag 2cu (PO 3) 4, take silver carbonate Ag 2cO 3: 2.76 grams, configuration concentration is the silver salt solution of 2 mol/L, takes cupric oxide CuO:0.803 gram, and configuration concentration is the copper salt solution of 2 mol/L, takes diammonium hydrogen phosphate (NH 4) 2hPO 4: 3.31 grams, configuration concentration is the microcosmic salt solution of 2 mol/L, mixing three kinds of solution & stir, is the ammonia spirit of 30% to mixed solution and dripping volume fraction, stops when pH is about 9 ~ 10, stir, after sediment deionized water and ethanol washing, put into baking oven oven dry and obtain presoma, select air atmosphere, by above-mentioned presoma 1000 DEG C of temperature lower calcinations 19 hours, namely cooling grinding obtains cupric phosphate silver Ag 2cu (PO 3) 4catalyst.
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, EDS collection of illustrative plates, similar to embodiment 5 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.

Claims (11)

1. a novel cupric phosphate silver catalysis material, is characterized in that: its chemical formula is Ag 2cu (PO 3) 4.
2. Novel phosphoric acid copper silver catalysis material according to claim 1, is characterized in that: the sample thing of preparation is mutually pure, and particle size distribution is even.
3. a preparation method for Novel phosphoric acid copper silver catalysis material as claimed in claim 1, adopts high temperature solid-state method, it is characterized in that comprising the steps:
(1) with silver ion Ag +compound, copper ions Cu 2+compound, containing phosphonium ion P 5+compound be raw material, by general formula Ag 2cu (PO 3) 4the stoichiometric proportion of middle corresponding element takes each raw material, grinds and mixes;
(2) the mixture precalcining in air atmosphere step (1) obtained, precalcining temperature is 250 ~ 650 DEG C, and calcination time is 5 ~ 20 hours, naturally cools, grinds and mix;
(3) calcined in air atmosphere by the mixture that step (2) obtains, calcining heat is 650 ~ 1050 DEG C, and calcination time is 6 ~ 20 hours, naturally cools, and namely obtains Novel phosphoric acid copper silver catalysis material after grinding evenly.
4. the preparation method of a kind of novel cupric phosphate silver catalysis material according to claim 3, is characterized in that: described silver ion Ag +compound be silver oxide Ag 2o, silver nitrate AgNO 3with silver carbonate Ag 2cO 3in one or more combination; Described contains copper ion Cu 2+compound be cupric oxide CuO, copper carbonate CuCO 3, copper nitrate Cu (NO 3) 2with Kocide SD Cu (OH) 2in one or more combination; Described contains phosphonium ion P 5+compound be phosphorus pentoxide P 2o 5, ammonium dihydrogen phosphate (ADP) NH 4h 2pO 4, diammonium hydrogen phosphate (NH 4) 2hPO 4with phosphoric acid H 3pO 4in one or more combination.
5. the preparation method of a kind of novel cupric phosphate silver catalysis material according to claim 3, it is characterized in that: the calcining heat described in step (2) is 300 ~ 650 DEG C, calcination time is 6 ~ 19 hours; Calcining heat described in step (3) is 700 ~ 1000 DEG C, and calcination time is 7 ~ 19 hours.
6. a preparation method for cupric phosphate silver catalysis material as claimed in claim 1, adopts chemical solution method, it is characterized in that comprising the following steps:
(1) by chemical formula Ag 2cu (PO 3) 4in the stoichiometric proportion of each element, first take containing silver ion Ag +compound, be dissolved in appropriate dilute nitric acid solution, add thermal agitation, until dissolve completely, then add appropriate complexing agent, obtain solution A; Take containing copper ion Cu 2+compound, be dissolved in appropriate dilute nitric acid solution, add thermal agitation, until dissolve completely, then add appropriate complexing agent, obtain B solution; Take containing phosphonium ion P 5+compound, be dissolved in appropriate dilute nitric acid solution, add thermal agitation, until dissolve completely, obtain C solution;
Finally, mixing A, B, C solution, stir and obtain mixed solution in 1-5 hour at 70-100 DEG C;
(2) placed in an oven by said mixture solution, temperature is 50 DEG C-100 DEG C, and the time is 12 hours, and ageing is also dried;
(3) after naturally cooling, take out presoma, calcine in air atmosphere, calcining heat is 600 ~ 1000 DEG C, and calcination time is 6 ~ 20 hours, and naturally after cooling, namely grinding evenly obtains the silver-colored catalysis material of cupric phosphate.
7. the preparation method of a kind of novel cupric phosphate silver catalysis material according to claim 6, is characterized in that: described silver ion Ag +compound be silver oxide Ag 2o, silver nitrate AgNO 3, silver carbonate Ag 2cO 3with silver sulfate Ag 2sO 4in one or more combination; Described contains copper ion Cu 2+compound be copper carbonate CuCO 3, cupric oxide CuO, copper sulphate CuSO 4with copper nitrate Cu (NO 3) 2in one or more combination; Described contains phosphonium ion P 5+compound be phosphorus pentoxide P 2o 5, ammonium dihydrogen phosphate (ADP) NH 4h 2pO 4, diammonium hydrogen phosphate (NH 4) 2hPO 4with phosphoric acid H 3pO 4in one or more combination; Described complexing agent is citric acid.
8. the preparation method of a kind of novel cupric phosphate silver catalysis material according to claim 6, it is characterized in that: the calcining heat described in step (3) is 700 ~ 1000 DEG C, calcination time is 6 ~ 19 hours.
9. a preparation method for cupric phosphate silver catalysis material as claimed in claim 1, adopts coprecipitation, it is characterized in that comprising the following steps:
(1) form soluble silver salt solution, described solution concentration is 2 mol/L;
(2) form soluble copper salting liquid, described solution concentration is 2 mol/L;
(3) form titanium pigment salting liquid, described solution concentration is 2 mol/L;
(4) forming volume fraction is the ammonia spirit of 30%;
(5) by chemical formula Ag 2cu (PO 3) 4the above-mentioned silver salt of proportioning, mantoquita and microcosmic salt solution, mix and blend, drips ammoniacal liquor to pH scope 9 ~ 10, and reaction precipitation thing, after separation, washing, drying, obtains presoma;
(6) by presoma at 600 ~ 1000 DEG C of temperature lower calcinations, calcination time is 7 ~ 20 hours, obtains a kind of cupric phosphate silver photocatalytic powder material.
10. the preparation method of a kind of novel cupric phosphate silver catalysis material according to claim 9, is characterized in that: described soluble silver salt can adopt silver oxide Ag 2o, silver nitrate AgNO 3, silver sulfate Ag 2sO 4with silver carbonate Ag 2cO 3in one or more combination, be dissolved in deionized water or dust technology and add thermal agitation gained; Described soluble copper salt can adopt copper carbonate CuCO 3, copper sulphate CuSO 4, copper nitrate Cu (NO 3) 2one or more combinations with in cupric oxide CuO, are dissolved in deionized water or dust technology and add thermal agitation gained; Described solubility microcosmic salt can adopt phosphorus pentoxide P 2o 5, ammonium dihydrogen phosphate (ADP) NH 4h 2pO 4, diammonium hydrogen phosphate (NH 4) 2hPO 4with phosphoric acid H 3pO 4in one or more combination, be dissolved in deionized water or dust technology and add thermal agitation gained.
The preparation method of 11. a kind of novel cupric phosphate silver catalysis materials according to claim 9, it is characterized in that: the calcining heat described in step (6) is 650 ~ 1000 DEG C, calcination time is 8 ~ 19 hours.
CN201510055123.XA 2015-02-03 2015-02-03 Preparation method of copper silver phosphate with photodegradation function and photocatalytic application Pending CN104607217A (en)

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