CN1762583A - Method for preparing photocatalyst capable of responding to visible light - Google Patents

Method for preparing photocatalyst capable of responding to visible light Download PDF

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CN1762583A
CN1762583A CN 200510029314 CN200510029314A CN1762583A CN 1762583 A CN1762583 A CN 1762583A CN 200510029314 CN200510029314 CN 200510029314 CN 200510029314 A CN200510029314 A CN 200510029314A CN 1762583 A CN1762583 A CN 1762583A
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photochemical catalyst
visible light
load
preparation
ruo
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田蒙奎
上官文峰
袁坚
陈铭夏
施建伟
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Abstract

The photocatalyst in nanometer field has tungsten bronze structure as K4Ce2M10O30, wherein, M is Ta or Nb. The preparation method comprises: mixing salt contained K and oxides contained Ce, Ta or Nb by stoichiometric ratio, obtaining the product after high-temperature solid-phase reacting for more than 1h with firing temperature as 800-1450Deg. This catalyst has absorption capacity to visible light under 580-690nm, degrades pollutant efficiently, and photolyze water for hydrogen.

Description

The preparation method of the photochemical catalyst of energy responding to visible light
Technical field
That the present invention relates to is a kind of preparation method of field of nanometer technology, particularly a kind of preparation method of photochemical catalyst of energy responding to visible light.
Background technology
Photocatalysis is a kind of emerging depollution of environment and energy conversion technology.Photochemical catalyst oxidation or reduction effectively is adsorbed on its lip-deep pernicious gas molecule, and kill bacteria suppresses virus, harmful organic substance, bacterium etc. can be converted into innocuous substances such as water and carbon dioxide, and without any secondary pollution.Simultaneously, utilize photocatalysis technology can carry out photolysis water hydrogen, solar energy directly is converted to Hydrogen Energy.Typical case's representative as practical photochemical catalyst is a titanium dioxide.Titanium dioxide has the ultraviolet ray that can absorb 400nm or following wavelength, and forms free electron and electron hole.Therefore, in case free electron that produces and hole arrive the surface of particle, produce various free radicals such as OH with chemical combination such as oxygen or water, the material that is adsorbed on the oxidation Decomposition surface.This is the basic principle that photocatalysis is used for the depollution of environment.Photochemical catalyst also can be used for photolysis water hydrogen, and this is because formed free electron of optical excitation and hole have extremely strong reduction and oxidability, water directly can be resolved into hydrogen and oxygen.Therefore,, be expected to utilize sunshine, directly from various water, obtain the energy---the Hydrogen Energy of cleaning the most, solve from now on global energy and environmental problem along with the development of photocatalysis technology.Extensively and effectively utilizing of photocatalysis technology depended on the efficient of light-catalyzed reaction.Improving the photochemical catalyst performance is the key that improves photocatalysis efficiency.Can improve the activity of photochemical catalyst by following approach.(1) catalysis material nanometer and increasing specific surface area; (2) improve degree of crystallinity, reduce lattice defect; (3) modulation forbidden band structure improves absorption and utilization to visible light.In above method, approach (3) seems, and technology space is maximum and application prospect is the most extensive, therefore extremely people's attention and research in recent years.
Through the literature search of prior art is found, Chinese patent application number is 03140525.8, and name is called: nitrogenous optically catalytic TiO 2 film and preparation method thereof, this patent disclosure a kind of at O 2/ N 2In the reacting gas, adopt magnetically controlled sputter method to prepare nitrogenous optically catalytic TiO 2 film.The magnetically controlled sputter method unit scale is big, price is high, is not suitable for the preparation and the doping vario-property of nano-powder material simultaneously.Utilize NH 3Same TiO 2Reaction also can be synthesized the titanium dioxide optical catalyst of nitrating, but NH 3Danger and contaminative are big.In addition, remain limited, have some synthetic metal oxynitride photochemical catalyst of report that visible light is had good response characteristic in recent years owing to improve the absorption and the utilization of titanium dioxide by nitrogen-doping method to visible light.But, no matter be nitrogen-doped titanium dioxide or metal oxynitride, all have unstability, nitrogen will be overflowed under higher temperature or some condition, thereby loses the responding ability to visible light.
Summary of the invention
The object of the invention is to overcome the deficiency of above technical problem, has proposed a kind of preparation method of photochemical catalyst of energy responding to visible light.Make its photochemical catalyst of preparing have absorbability to the following visible light of 580-690nm, can be under visible light effectively degradation of contaminant and photolysis water hydrogen.
The present invention is achieved by the following technical solutions, and photochemical catalyst of the present invention is a kind of compound K with tungsten bronze structure 4Ce 2M 10O 30, M=Ta, Nb, wherein the stoichiometric proportion of element K, Ce, Ta or Nb, O is 4: 2: 10: 30, prepare by adopting solid reaction process, method is as follows:
To contain the salt and the oxide that contains Ce, Ta or Nb of K, press K: Ce: Ta or Nb=4: 2: 10 stoichiometric proportion prescription forms through high temperature solid state reaction after mixing.Described high temperature solid state reaction parameter is: firing temperature is 800-1450 ℃, and the solid phase reaction time is more than 1 hour.When firing temperature was lower than 800 ℃, solid phase reaction was difficult to carry out; When firing temperature is higher than 1450 ℃, the solid particulate matter sintering, specific area obviously descends, and photocatalytic activity reduces.
For the minimizing that prevents that K from causing because of high temperature distillation volatilization, preferably introduce surpass stoichiometric proportion 0.1～0.5 contain the K material, remaining K can remove by washing after the pyroreaction.
The salt of described K is any one in potassium chloride, potash, the potassium nitrate.
The described Ce of containing compound is any one in cerium oxide, cerium chloride, cerous carbonate, the cerous nitrate.
The described Ta of containing compound is a tantalum oxide.
The described Nb of containing compound is a niobium oxide.
The present invention by carrying method with Pt or RuO 2Or NiO xBe carried on K 4Ce 2M 10O 30(photocatalytic activity is further improved on M=Ta, Nb) surface.Concrete grammar is as follows:
The load of Pt can realize by following two kinds of methods: (1) is with K 4Ce 2M 10O 30(M=Ta, Nb) powder impregnation is in chloroplatinic acid (H 2PtCl 6) in the aqueous solution, in whipping process, utilize ultra violet lamp, make the Pt reduction, and load on K 4Ce 2M 10O 30(M=Ta is Nb) on the powder; (2) with K 4Ce 2M 10O 30(M=Ta, Nb) powder impregnation is in chloroplatinic acid (H 2PtCl 6) in the aqueous solution,, form the K of Pt load by heating evaporation, drying and calcining 4Ce 2M 10O 30(M=Ta, Nb) photochemical catalyst.
RuO 2Load can realize by the following method: with K 4Ce 2M 10O 30(M=Ta, Nb) powder impregnation is in ruthenic chloride (RuCl 3) in the aqueous solution,, form RuO by heating evaporation, drying and calcining 2The K of load 4Ce 2M 10O 30(M=Ta, Nb) photochemical catalyst.
Pt and RuO 2Common carrying method be: earlier by above method load RuO 2After, again by above method supporting Pt.
NiO xLoad can realize by the following method: with K 4Ce 2M 10O 30(M=Ta, Nb) powder impregnation is in nickel nitrate (Ni (NO 3) 2) in the aqueous solution,, form NiO by heating evaporation, drying and calcining xLoad with K 4Ce 2M 10O 30(M=Ta, Nb) photochemical catalyst.
The load capacity of above-described loaded optic catalyst is controlled at following scope: Pt:0.1-0.5wt%, RuO 2: 0.5-3.0wt%, NiO x: 0.1-3.0wt%.
The energy that the sun discharged reaches earth surface in 1 year total amount is 5.5 * 10 26J, by the present whole mankind 1 year 10,000 times of consumption energy summation.The low-density of solar energy and unstability thereof have limited its application, particularly are converted into the direct utilization of electric energy.Water and sunlight can claim it is inexhaustible material.The hydrogen that obtains from water as the form of having got back to water again after the energy use, is a kind of sustainable completely development and utilization.Utilize photocatalysis technology solar energy directly can be converted to chemical energy-Hydrogen Energy.Can photodissociation water practicability depend on energy conversion efficiency the most at last.The photochemical catalyst great majority that can be used for photodissociation water that people found and developed up to now only can absorb the ultraviolet ray of its wavelength less than 400nm.And ultraviolet ray only accounts for about 3% in sunshine.So photochemical catalyst provided by the present invention can absorb visible light, can greatly utilize sunshine, realize efficient photolysis water hydrogen, have positive meaning to solving the following energy and environmental problem.
In addition, aspect the depollution of environment, the photochemical catalyst that can absorb visible light provided by the present invention can be widely used in the surfaces such as indoor and outdoor body of wall of various buildings, can utilize natural daylight to purify pollutant in the atmosphere effectively, purify waste water, improve environmental quality, will bring great social benefit and economic benefit.
The specific embodiment
Content in conjunction with the inventive method provides following examples:
Embodiment 1:
1, potash, cerous nitrate and tantalum oxide is soluble in water by 1.1: 1: 2.5 mol ratio, heating edge is stirred to the moisture evaporate to dryness in electric heating agitator top, the mixture 110 ℃ of abundant oven dry in baking oven that obtain are placed on fully grinding in the agate mortar, earlier at 800 ℃ of following pre-burning 5h, grind afterwards at 1100 ℃ of high temperature sintering 12h, washing is dried after removing unnecessary potash, obtains needed K 4Ce 2Ta 10O 30
2, with 0.1g K 4Ce 2Ta 10O 30Photochemical catalyst is scattered in 20ml water and 20ml Na respectively 2SO 3(0.2M) solution places photo catalysis reactor, and directly external static was shone 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is done quantitative analysis with the gas chromatograph that has the thermal conductance detector.Under this condition at pure water and 0.2M Na 2SO 3K in the solution 4Ce 2Ta 10O 30Hydrogen-producing speed be respectively 55.4 μ mol/gh and 724.3 μ mol/gh; With behind the following wave spectrum of optical filter elimination 420nm, its hydrogen output is respectively 2.7 μ mol/gh and 31.6 μ mol/gh under the same terms in the above-mentioned photocatalytic reaction device.
Embodiment 2:
1, potash, cerous nitrate and niobium oxide is soluble in water by 1.2: 1: 2.5 mol ratio, heating edge is stirred to the moisture evaporate to dryness in electric heating agitator top, the mixture abundant oven dry in baking oven that obtains is placed on fully grinding in the agate mortar, afterwards at 1450 ℃ of high temperature sintering 1h, washing is dried after removing unnecessary potash, obtains needed K 4Ce 2Nb 10O 30
2, be target contaminant with the rhodamine B, under the room temperature in the photocatalytic reaction device with optical filter elimination 420nm following wave spectrum, light-catalyzed reaction after 2 hours this material the degradation rate of rhodamine B is reached about 40%.
Embodiment 3:
1, potassium chloride, cerous nitrate and tantalum oxide is soluble in water by 2.1: 1: 2.5 mol ratio, heating edge is stirred to the moisture evaporate to dryness in electric heating agitator top, the mixture that obtains is fully dried the back as for fully grinding in the agate mortar in baking oven, earlier at 800 ℃ of following pre-burning 5h, grind afterwards at 1200 ℃ of high temperature sintering 5h, washing is dried after removing unnecessary potash, obtains needed K 4Ce 2Ta 10O 30
2, take by weighing 5g K 4Ce 2Ta 10O 30Powder impregnation is in 7ml chloroplatinic acid (H 2PtCl 6) in the aqueous solution (0.0038M),, form the K of Pt load by heating evaporation, drying and calcining 4Ce 2Ta 10O 30Photochemical catalyst, the amount of the Pt of institute's load is 0.1wt%.
3, the photochemical catalyst 0.1g after the Pt load is scattered in 20ml water or 20ml Na 2SO 3(0.2M) solution places photo catalysis reactor, and directly external static was shone 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is done quantitative analysis with the gas chromatograph that has the thermal conductance detector.This condition is at pure water and 0.2M Na 2SO 3In the solution, K 4Ce 2Ta 10O 30Hydrogen-producing speed be respectively 423.8 μ mol/gh and 602.3 μ mol/gh; With behind the following wave spectrum of optical filter elimination 420nm, its hydrogen output is respectively 33.7 μ mol/gh and 56.3 μ mol/gh under the same terms in the above-mentioned photocatalytic reaction device.
Embodiment 4:
1, potassium nitrate, cerous nitrate and niobium oxide is soluble in water by 2.2: 1: 2.5 mol ratio, heating edge is stirred to the moisture evaporate to dryness in electric heating agitator top, the mixture abundant oven dry in baking oven that obtains is placed on fully grinding in the agate mortar, earlier at 800 ℃ of following pre-burning 5h, grind afterwards at 1100 ℃ of high temperature sintering 12h, washing is dried after removing unnecessary potash, obtains needed K 4Ce 2Nb 10O 30
2, take by weighing 0.1g K 4Ce 2Nb 10O 30Powder impregnated in 20ml chloroplatinic acid (H respectively 2PtCl 6) (0.00013M) and 20ml Na in the aqueous solution 2SO 3(0.2M) solution places photo catalysis reactor, and wherein the load capacity of Pt is 0.5wt%.The above-mentioned photo catalysis reactor direct external static under the 300W xenon lamp that fills solution was shone 4 hours, and the gas that light-catalyzed reaction produces is done quantitative analysis with the gas chromatograph that has the thermal conductance detector.This condition is at pure water and 0.2M Na 2SO 3In the solution, K 4Ce 2Nb 10O 30Hydrogen-producing speed be respectively 85.7 μ mol/gh and 461.1 μ mol/gh; With behind the following wave spectrum of optical filter elimination 420nm, its hydrogen output is respectively 5.0 μ mol/gh and 13.9 μ mol/gh under the same terms in the above-mentioned photocatalytic reaction device.
Embodiment 5:
1, potash, cerium oxide and tantalum oxide is soluble in water by 1.2: 1: 2.5 mol ratio, heating edge is stirred to the moisture evaporate to dryness in electric heating agitator top, the mixture abundant oven dry in baking oven that obtains is placed on fully grinding in the agate mortar, earlier at 800 ℃ of following pre-burning 5h, grind afterwards at 1000 ℃ of high temperature sintering 8h, washing is dried after removing unnecessary potash, obtains needed K 4Ce 2Ta 10O 30
2, with 0.5g K 4Ce 2Ta 10O 30Powder impregnation is in the ruthenic chloride (RuCl of 15ml 3) (0.005M) in the aqueous solution,,, form RuO at 500 ℃ of following sintering 2h by heating evaporation, drying 2The K of load 4Ce 2Ta 10O 30Photochemical catalyst, the RuO of institute's load 2Amount be 0.5wt%.
3, take by weighing RuO 2Catalyst 0.1g after the load is scattered in 20ml water and 20ml Na 2SO 3(0.2M) solution places photo catalysis reactor, and directly external static was shone 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is done quantitative analysis with the gas chromatograph that has the thermal conductance detector.This condition is at pure water and 0.2M Na 2SO 3In the solution, K 4Ce 2Ta 10O 30Hydrogen-producing speed be respectively 189.7 μ mol/gh and 1040.3 μ mol/gh, with behind the optical filter elimination 420nm following wave spectrum, its hydrogen output is respectively 2.6 μ mol/gh and 11.9 μ mol/gh under the same terms in the above-mentioned photocatalytic reaction device.
Embodiment 6:
1, potash, cerous carbonate and niobium oxide is soluble in water by 1.5: 1: 2.5 mol ratio, heating edge is stirred to the moisture evaporate to dryness in electric heating agitator top, the mixture abundant oven dry in baking oven that obtains is placed on fully grinding in the agate mortar, earlier at 800 ℃ of following pre-burning 5h, grind afterwards at 1100 ℃ of high temperature sintering 12h, washing is dried after removing unnecessary potash, obtains needed K 4Ce 2Nb 10O 30
2, with 0.1g K 4Ce 2Nb 10O 30Powder impregnation is in the ruthenic chloride (RuCl of 4.5ml 3) (0.005M) in the aqueous solution,,, form RuO at 500 ℃ of following sintering 2h by heating evaporation, drying 2Load with K 4Ce 2Nb 10O 30Photochemical catalyst, the RuO of institute's load 2Amount be 3.0wt%.
3, take by weighing RuO 2Catalyst 0.1g after the load is scattered in 20ml water and 20ml Na 2SO 3(0.2M) solution places photo catalysis reactor, and directly external static was shone 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is done quantitative analysis with the gas chromatograph that has the thermal conductance detector.This condition is at pure water and 0.2M Na 2SO 3In the solution, K 4Ce 2Nb 10O 30Hydrogen-producing speed be respectively 70.6 μ mol/gh and 672.3 μ mol/gh, with behind the optical filter elimination 420nm following wave spectrum, its hydrogen output is respectively 1.8 μ mol/gh and 2.7 μ mol/gh under the same terms in the above-mentioned photocatalytic reaction device.
Embodiment 7:
1, potash, cerium chloride and tantalum oxide is soluble in water by 1.2: 1: 2.5 mol ratio, heating edge is stirred to the moisture evaporate to dryness in electric heating agitator top, the mixture that obtains is fully dried the back as for fully grinding in the agate mortar in baking oven, earlier at 800 ℃ of following pre-burning 5h, grind afterwards at 1100 ℃ of high temperature sintering 12h, washing is dried after removing unnecessary potash, obtains needed K 4Ce 2Ta 10O 30
2, support RuO earlier by the method among the embodiment 3 2After, the method by embodiment 1 supports Pt again, obtains RuO 2The K that supports simultaneously with Pt 4Ce 2Ta 10O 30, wherein the loading of Pt is for being 0.3% of catalyst weight, RuO 2Loading be 2.5% of catalyst weight.
3, take by weighing and support RuO simultaneously 2Catalyst 0.1g with behind the Pt is scattered in 20ml water or 20mlNa 2SO 3(0.2M) solution places photo catalysis reactor, directly external static irradiation under the 300W xenon lamp _ hour, the gas that light-catalyzed reaction produces is done quantitative analysis with the gas chromatograph that has the thermal conductance detector.This condition is at pure water and 0.2M Na 2SO 3In the solution, K 4Ce 2Ta 10O 30Hydrogen-producing speed be respectively 497.7 μ mol/gh and 1474.7 μ mol/gh, with behind the optical filter elimination 420nm following wave spectrum, its hydrogen output is respectively 47.3 μ mol/gh and 74.1 μ mol/gh under the same terms in the above-mentioned photocatalytic reaction device.
Embodiment 8:
1, potash, cerous nitrate and niobium oxide is soluble in water by 1.1: 1: 2.5 mol ratio, heating edge is stirred to the moisture evaporate to dryness in electric heating agitator top, the mixture that obtains is fully dried the back as for fully grinding in the agate mortar in baking oven, earlier at 800 ℃ of following pre-burning 5h, grind afterwards at 1100 ℃ of high temperature sintering 12h, washing is dried after removing unnecessary potash, obtains needed K 4Ce 2Ta 10O 30
2, support RuO earlier by the method among the embodiment 3 2After, the method by embodiment 1 supports Pt again, obtains RuO 2The K that supports simultaneously with Pt 4Ce 2Nb 10O 30, wherein the loading of Pt is for being 0.2% of catalyst weight, RuO 2Loading be 2.0% of catalyst weight.
3, take by weighing and support RuO simultaneously 2With the catalyst 0.1g behind the Pt, be scattered in 20ml water and 20ml Na 2SO 3(0.2M) solution places photo catalysis reactor, and directly external static was shone 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is done quantitative analysis with the gas chromatograph that has the thermal conductance detector.This condition is at pure water and 0.2M Na 2SO 3In the solution, K 4Ce 2Nb 10O 30Hydrogen-producing speed be respectively 93.5 μ mol/gh and 1429.3 μ mol/gh, with behind the optical filter elimination 420nm following wave spectrum, its hydrogen output is respectively 5.6 μ mol/gh and 16.1 μ mol/gh under the same terms in the above-mentioned photocatalytic reaction device.
Embodiment 9:
1, potash, cerium oxide and tantalum oxide is soluble in water by 1.5: 1: 2.5 mol ratio, heating edge is stirred to the moisture evaporate to dryness in electric heating agitator top, the mixture that obtains is fully dried the back as for fully grinding in the agate mortar in baking oven, at 950 ℃ of high temperature sintering 16h, washing is dried after removing unnecessary potash, obtains needed K 4Ce 2Ta 10O 30
2, with 2g K 4Ce 2Ta 10O 30Powder impregnation is in 6.37ml Ni (NO 3) 2(0.125M) in the solution, fully stir behind the evaporating off water at 350 ℃ of sintering 1 hour in air, afterwards at H 2500 ℃ of reductase 12s hour in the atmosphere reoxidize 1 hour in 200 ℃ at last in air, the amount of the NiO that is supported is 3.0wt%.
3, take by weighing the catalyst 0.1g that supports behind the NiO, be scattered in 20ml water and 20ml Na 2SO 3(0.2M) solution places photo catalysis reactor, and directly external static was shone 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is done quantitative analysis with the gas chromatograph that has the thermal conductance detector.This condition is at pure water and 0.2M Na 2SO 3In the solution, K 4Ce 2Ta 10O 30Hydrogen-producing speed be respectively 220.9 μ mol/gh and 1191.4 μ mol/gh, with behind the optical filter elimination 420nm following wave spectrum, its hydrogen output is respectively 24.2 μ mol/gh and 186.1 μ mol/gh under the same terms in the above-mentioned photocatalytic reaction device.
Embodiment 10:
1, potash, cerium oxide and niobium oxide is soluble in water by 1.4: 1: 2.5 mol ratio, heating edge is stirred to the moisture evaporate to dryness in electric heating agitator top, the mixture that obtains is fully dried the back as for fully grinding in the agate mortar in baking oven, earlier at 800 ℃ of following pre-burning 5h, grind afterwards at 1100 ℃ of high temperature sintering 12h, washing is dried after removing unnecessary potash, obtains needed K 4Ce 2Nb 10O 30
2, with 4.0g K 4Ce 2Ta 10O 30Powder impregnation is in 5.35ml Ni (NO 3) 2(0.01M) in the solution, fully stir behind the evaporating off water at 350 ℃ of sintering 1 hour in air, afterwards at H 2500 ℃ of reductase 12s hour in the atmosphere reoxidize 1 hour in 200 ℃ at last in air, the amount of the NiO that is supported is 0.1wt%.
3, take by weighing the catalyst 0.1g that supports behind the NiO, be scattered in 20ml water or 20ml Na 2SO 3(0.2M) solution places photo catalysis reactor, and directly external static was shone 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is done quantitative analysis with the gas chromatograph that has the thermal conductance detector.This condition is at pure water and 0.2M Na 2SO 3In the solution, K 4Ce 2Nb 10O 30Hydrogen-producing speed be respectively 48.8 μ mol/gh and 1595.8 μ mol/gh, with behind the optical filter elimination 420nm following wave spectrum, its hydrogen output is respectively 4.3 μ mol/gh and 25.8 μ mol/gh under the same terms in the above-mentioned photocatalytic reaction device.
Embodiment 11:
1, potash, cerium oxide and tantalum oxide is soluble in water by 1.5: 1: 2.5 mol ratio, heating edge is stirred to the moisture evaporate to dryness in electric heating agitator top, the mixture that obtains is fully dried the back as for fully grinding in the agate mortar in baking oven, at 950 ℃ of high temperature sintering 16h, washing is dried after removing unnecessary potash, obtains needed K 4Ce 2Ta 10O 30
2, with 2g K 4Ce 2Ta 10O 30Powder impregnation is in 6.37ml Ni (NO 3) 2(0.042M) in the solution, fully stir behind the evaporating off water at 350 ℃ of sintering 1 hour in air, afterwards at H 2500 ℃ of reductase 12s hour in the atmosphere reoxidize 1 hour in 200 ℃ at last in air, the amount of the NiO that is supported is 1.0wt%.
3, take by weighing the catalyst 0.1g that supports behind the NiO, be scattered in 20ml water and 20ml Na 2SO 3(0.2M) solution places photo catalysis reactor, and directly external static was shone 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is done quantitative analysis with the gas chromatograph that has the thermal conductance detector.This condition is at pure water and 0.2M Na 2SO 3In the solution, K 4Ce 2Ta 10O 30Hydrogen-producing speed be respectively 154.6 μ mol/gh and 880.4 μ mol/gh, with behind the optical filter elimination 420nm following wave spectrum, its hydrogen output is distinguished 38.7 μ mol/gh and 236.1 μ mol/gh under the same terms in the above-mentioned photocatalytic reaction device.

Claims (10)

1, a kind of preparation method of photochemical catalyst of energy responding to visible light is characterized in that described photochemical catalyst is a kind of compound K with tungsten bronze structure 4Ce 2M 10O 30M=Ta, Nb, wherein the stoichiometric proportion of element K, Ce, Ta or Nb, O is 4: 2: 10: 30, prepare by adopting solid reaction process, and method is as follows: the salt and the oxide that contains Ce, Ta or Nb that will contain K, in K: Ce: Ta or Nb=4: after 2: 10 ratio prescription mixes, form through high temperature solid state reaction, described high temperature solid state reaction parameter is: firing temperature is 800-1450 ℃, and the solid phase reaction time is more than 1 hour.
2, the preparation method of the photochemical catalyst of energy responding to visible light according to claim 1 is characterized in that, by Pt or RuO 2Or the single load of NiOx or Pt and RuO 2Common load, further improve photocatalytic activity, the load capacity of loaded optic catalyst is controlled at following scope: Pt:0.1-0.5wt%, RuO 2: 0.5-3.0wt%, NiO x: 0.1-3.0wt%.
3, the preparation method of photochemical catalyst that can responding to visible light according to claim 2 is characterized in that, the method for supporting Pt is any in following two kinds:
(1) with K 4Ce 2M 10O 30Powder impregnation is in chloroplatinic acid H 2PtCl 6In the aqueous solution, in whipping process, utilize ultra violet lamp to make the Pt reduction, and load on K 4Ce 2M 10O 30On the powder;
(2) with K 4Ce 2M 10O 30Powder impregnation is in chloroplatinic acid H 2PtCl 6In the aqueous solution,, form the K of Pt load by heating evaporation, drying and calcining 4Ce 2M 10O 30Photochemical catalyst.
4, the preparation method of the photochemical catalyst of energy responding to visible light according to claim 2 is characterized in that load RuO 2Method specific as follows:
With K 4Ce 2M 10O 30Powder impregnation is in ruthenic chloride RuCl 3In the aqueous solution,, form RuO by heating evaporation, drying and calcining 2The K of load 4Ce 2M 10O 30Photochemical catalyst.
5, according to the preparation method of claim 2 or 3 or 4 described photochemical catalysts that can responding to visible light, it is characterized in that Pt and RuO 2Common carrying method be:
Elder generation is load RuO according to the method described above 2After, supporting Pt according to the method described above forms RuO again 2K with the common load of Pt 4Ce 2M 10O 30Photochemical catalyst.
6, the preparation method of the photochemical catalyst of energy responding to visible light according to claim 2 is characterized in that the method for load NiOx is specific as follows:
With K 4Ce 2M 10O 30(M=Ta, Nb) powder impregnation is in nitric acid nickel (NO 3) 2In the aqueous solution,, form NiO by heating evaporation, drying and calcining xThe K of load 4Ce 2M 10O 30Photochemical catalyst.
7, the preparation method of the photochemical catalyst of energy responding to visible light according to claim 1 is characterized in that the salt of described K is any one in potassium chloride, potash, the potassium nitrate.
8, the preparation method of the photochemical catalyst of energy responding to visible light according to claim 1 is characterized in that the described Ce of containing compound is any one in cerium oxide, cerium chloride, cerous carbonate, the cerous nitrate.
9, the preparation method of the photochemical catalyst of energy responding to visible light according to claim 1 is characterized in that the described Ta of containing compound is a tantalum oxide.
10, the preparation method of the photochemical catalyst of energy responding to visible light according to claim 1 is characterized in that the described Nb of containing compound is a niobium oxide.
CN 200510029314 2005-09-01 2005-09-01 Method for preparing photocatalyst capable of responding to visible light Pending CN1762583A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103691435A (en) * 2013-12-21 2014-04-02 海安县吉程机械有限公司 Preparation method of nano platinum particle supported mesoporous cerium dioxide photocatalyst
CN108786924A (en) * 2018-07-06 2018-11-13 哈尔滨理工大学 A kind of Ni (OH)2The preparation method of/TpPa-2 materials

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103691435A (en) * 2013-12-21 2014-04-02 海安县吉程机械有限公司 Preparation method of nano platinum particle supported mesoporous cerium dioxide photocatalyst
CN108786924A (en) * 2018-07-06 2018-11-13 哈尔滨理工大学 A kind of Ni (OH)2The preparation method of/TpPa-2 materials
CN108786924B (en) * 2018-07-06 2021-02-02 哈尔滨理工大学 A kind of Ni (OH)2Preparation method of/TpPa-2 material and hydrogen production by photolysis of water

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