CN100351013C - CdS/Ti-MCM-41 loaded platinum photo catalyst and its preparation method - Google Patents
CdS/Ti-MCM-41 loaded platinum photo catalyst and its preparation method Download PDFInfo
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Abstract
The present invention discloses a novel CdS/Ti-MCM-41 loaded platinum composite catalyst and a preparation method thereof. Firstly, CTAB is used as a template agent; a hydrothermal method is used for synthesizing CTAB/Ti-MCM-41; the CTAB/Ti-MCM-41 obtains Ti-MCM-41 exchanged by Cd<2+> under the boiling point of carbinol by an ion exchange method; the Ti-MCM-41 is vulcanized in a hydrogen sulphide atmosphere for obtaining CdS/Ti-MCM-41 of a mesopore substrate; finally, platinum is loaded by a light reduction method. The hydrogen producing rate and the light corrosion resistance capability of a catalyst prepared by the preparation method in a light catalytic reaction are much stronger than those of cadmium sulfide prepared by a traditional coprecipitation method; the hydrogen producing rate achieves 890 mu mol. H<-1>. g<CdS><-1>; quantum efficiency achieves 2.6% in 420 nm; the light energy conversion efficiency of a visible light all band region achieves 0.62%. An obtained product has the advantages of high activity and good stability, and is favourable for popularization.
Description
Technical field
The present invention relates to the Hydrogen Energy preparation field, the clean technology of preparing of photocatalysis that relates to Hydrogen Energy, be to be the photocatalysis Decomposition hydrogen producing technology of raw material with water under the simulated solar visible light illumination condition, particularly a kind of compound in CdS/Ti-MCM-41 loaded platinum photo catalyst and preparation method thereof of pore matrix.
Background technology
Conventional primary energy is under-supply, liquid fuel is short, the fossil energy utilization causes severe contamination, CO
2Reduce discharging pressure and outlying district, rural area and made China face multiple pressure, impel people to have to seek new clean alternative energy source with energy problem etc.Strengthen the fundamental research that renewable energy conversion is utilized energetically, the regenerative resource high-quality of development high efficiency, low cost transforms with scale utilizes technology, become China energy science and technology field from now on ten or twenty year urgent task the most.China has very abundant regenerative resource resource, and potentiality to be exploited is huge, from long term growth, can satisfy the demand of national sustainable development to energy resources fully.Yet because most regenerative resource energy densities are low, dispersed strong, unstable, discontinuous, in time, season and weather and change and make us still lack the effective means that high efficiency, low cost utilizes regenerative resource on a large scale so far.
Hydrogen is desirable secondary energy sources, has the energy density height, and advantages such as can storing, can transport, be pollution-free is renewable energy conversion a Hydrogen Energy, is the desirable approach that solves above-mentioned difficulties.Along with 21 century is the fast development that the various Hydrogen Energies of representative are utilized technology with the fuel cell, following China will rise significantly to the demand of hydrogen, and the regenerative resource scale hydrogen producing technology of development high efficiency, low cost has important social, economic benefit.International community is always in " the hydrogen economy " that promotes to form sustainable development energetically.The key factor that Hydrogen Energy economy forms is to obtain cheap hydrogen energy source.And utilize the hydrogen manufacturing of solar energy photocatalytic decomposition water scale is the current and even following new and high technology that is hopeful most to accomplish scale production and obtains honest and clean low hydrogen.
The principle of photocatalysis hydrogen production is: under the irradiation of certain energy light, catalyst be subjected to exciting produce electronics and the hole right.Electron transfer is reduced to hydrogen to catalyst surface with water, and the hole is consumed by the sacrifice agent of the suitable cheapness that is added in the system.The key that realizes the solar energy photocatalytic decomposition water is to seek the visible light-responded high activity and high stability photochemical catalyst with appropriate bandgap, both realized that visible light was according to a large amount of electronics and the right generation in hole down, realize simultaneously right effectively the separating and in time consumed by reactant in light induced electron and hole in the photocatalytic hydrogen production by water decomposition course of reaction again, this efficient to photochemical catalyst has crucial effects.Although the report of visible light-responded in a large number photochemical catalyst is arranged at present in the world, mostly active on the low side and less stable.
Cadmium sulfide is a kind of generally acknowledged photochemical catalyst with higher photocatalytic hydrogen production activity, once be widely studied in later 1980s, but since very easily photoetch feature limits its development and use.Work out have the high yield hydrogen activity, special construction and pattern or compound cadmium sulfide photochemical catalyst and preparation method thereof of strong anti-photoetch, be the direction that the insider made great efforts always.
The method of existing preparation cadmium sulfide mainly can be divided into following three classes:
1. adopt inorganic salts such as the cadmium nitrate and the preparation of vulcanized sodium (or logical hydrogen sulfide) coprecipitation of cadmium
The cadmium sulfide of this method preparation is without crossing high-temperature process, and degree of crystallinity is relatively poor, generally exists with a cube phase morphology; Because reactant adopts inorganic salts,, a large amount of impurity are arranged inevitably still in addition although product is cleaned.Therefore its photocatalytic activity also lower (referring to Chinese invention patent CN1317993A, CN85100250, CN1594674).
2. prepared by co-precipitation gained cadmium sulfide is carried out high-temperature heat treatment
Heat treated mode has two kinds usually.A kind of is that the high temperature direct heat is handled in air, and this can improve cadmium sulfide degree of crystallinity also can form a large amount of cadmium oxides simultaneously, generally adopts follow-up acid solution chemical attack to handle again and removes cadmium oxide.Another kind is a high-temperature heat treatment under nitrogen protection, avoids the formation of cadmium oxide, but the contrast experiment finds the cadmium sulfide of this method preparation; aerial less stable, surface are easily by selective oxidation (Journal of Photochemistry Photobiology A, 1995; 86,185).
3. the preparation of special construction and pattern cadmium sulfide
The cadmium sulfide of special construction and pattern such as nanometer rods, nanotube etc., though this class cadmium sulfide by big quantity research, but still is in laboratory level, the preparation method is loaded down with trivial details, the preservation condition harshness is at room temperature very easily assembled and is made its special construction and pattern disappear.Though realized that liquid phase method prepares hexagonal phase cadmium sulfide at low temperatures, degree of crystallinity is generally relatively poor (referring to Chinese patent CN1504825, CN1556028).
From above elaboration to prior art as can be known, the cadmium sulfide of traditional co-precipitation method preparation is many with lower cube the existing mutually of activity without high-temperature process the time, and degree of crystallinity is relatively poor, and may have a large amount of impurity; Though and through improving its degree of crystallinity after the high-temperature process, but also need loaded down with trivial details subsequent treatment to remove a large amount of accessory substances that heat treatment produces, be that aerial oxidation resistance is poor, cause the photoetch aggravation in photocatalysis hydrogen production process then.
Summary of the invention
Purpose of the present invention just provides CdS/Ti-MCM-41 platinum catalyst of a kind of middle pore matrix and preparation method thereof, promptly provide a kind of with middle pore matrix Ti-MCM-41 molecular sieve and cadmium sulfide is compound, carry CdS/Ti-MCM-41 NEW TYPE OF COMPOSITE photochemical catalyst of the middle pore matrix that has higher product hydrogen activity and high stability behind the platinum and preparation method thereof, it can greatly improve the efficient of cadmium sulfide CdS photochemical catalyst catalytic decomposition water hydrogen manufacturing.
CdS/Ti-MCM-41 loaded platinum photo catalyst of pore matrix and preparation method thereof is as follows among the present invention:
The catalyst that makes consists of the mesoporous molecular sieve Ti-MCM-41 that cadmium sulfide CdS that mass content is 5%-15%, platinum that mass content is 2%-5% and mass content are 80%-90%.
A kind of preparation method of CdS/Ti-MCM-41 platinum catalyst of compound middle pore matrix carries out according to the following steps:
1) in 20 ℃ of-60 ℃ of water-bath, 0.36g-1.08g NaOH NaOH and 1.82g-5.26g softex kw CTAB are dissolved in the 45mL-135mL deionized water, slowly splash into the positive tetraethyl orthosilicate TEOS of 8.21mL-24.63mL with pipette, speed with 300-800rpm stirs, and is beneficial to the TEOS hydrolysis; 0.5h-2h after be added dropwise to 0.25g-0.75g butyl titanate TBOT, continue stirring behind the 0.5h-2h solution is transferred to is equipped with in the teflon-lined water heating kettle and in 100 ℃ of-110 ℃ of crystallization 24h-72h, mixture constitutive molar ratio NaOH: CTAB: TEOS: TBOT: H
2O=12.2: 6.8: 54.4: 1: 3400; After water heating kettle is reduced to room temperature, solution is filtered, spend deionised water repeatedly and, obtain white former powder CTAB/Ti-MCM-41 in 70 ℃ of-100 ℃ of dryings;
2) the former powder CTAB/Ti-MCM-41 of 2g-5g white is calcined 5h-10h removed template method CTAB in 500 ℃ of-650 ℃ of air atmosphere and obtain mesoporous molecular sieve matrix Ti-MCM-41;
3) with 1.0g-2.5g cadmium acetate CdAc
2Be dissolved among the 80mL-200mL methyl alcohol MeOH, add the former powder of 0.8g-2.0g CTAB/Ti-MCM-41, low whipping speed is under the magnetic agitation of 150-450rpm, backflow 4h-10h under the methyl alcohol boiling point, to be cooled to room temperature, centrifugation, with methyl alcohol MeOH and deionized water washing, with 0.1M vulcanized sodium Na
2S solution detects to washing lotion does not have Cd
2+Exist, 70 ℃ of-100 ℃ of vacuum drying 5h-10h obtain Cd
2+The mesoporous molecular sieve Ti-MCM-41 of exchange;
4) with Cd
2+The mesoporous molecular sieve Ti-MCM-41 of exchange is in 25 ℃ of-300 ℃ of logical H of room temperature
2S vulcanizes 4h-10h, and vacuumizes 12h-24h, to remove the H of absorption
2S gas, the CdS/Ti-MCM-41 of pore matrix in obtaining;
5) CdS/Ti-MCM-41 of the middle pore matrix that will prepare is with photoreduction met hod load platinum, and the CdS/Ti-MCM-41 of pore matrix carries the platinum composite photo-catalyst in can obtaining.
It is described that to carry the concrete steps of platinum with photoreduction met hod as follows:
1) be to add 0.05g-0.2g CdS/Ti-MCM-41 in the 100mL-250mL reactor and 50mL-200mL contains the sodium sulfite Na of 2.4g-9.6g as sacrifice agent at volume
2SO
3The aqueous solution; And adding 2mL-8mL platinum content is the chloroplatinic acid H of 0.0005g/mL
2PtCl
66H
2The O aqueous solution;
2) logical nitrogen purges 10min-20min in the illumination forward reaction device, and temperature is a room temperature, and pressure is 2MPa-10MPa, with the oxygen in the system of removing;
3) electric fan of opening in the xenon lamp device keeps room temperature, opens magnetic stirring apparatus 300-500rpm;
4) open xenon lamp power supply, the 350W xenon lamp;
5) behind the photo-reduction 2h-6h, close xenon lamp.
The CdS/Ti-MCM-41 of pore matrix carries the platinum novel composite catalyst in of the present invention, its photocatalysis is produced hydrogen activity and is greatly improved, anti-photoetch ability all is improved in aerial anti-surface oxidation and the light-catalyzed reaction, far is better than the cadmium sulfide of conventional method preparation.The type Ti-MCM-41 matrix has six regular side's mesopore pore passage structures, has good confinement effect, therefore process ion-exchange and sulfidation CdS germination are in the mesopore duct of Ti-MCM-41 matrix, light induced electron can effectively be separated with the hole after carrying platinum, visible light photocatalysis decomposes the aquatic products hydrogen activity and is greatly improved, and the highest hydrogen-producing speed reaches 890 μ molh on this breadboard micro-reaction equipment
-1GCdS
-1, reach 2.6% in the quantum efficiency at 420nm place, the visible region light energy use efficiency is reached 0.62%.Active undamped through the check of long-time continuous reaction experiment.Therefore the CdS/Ti-MCM-41 of the prepared middle pore matrix of this method carries the platinum novel composite catalyst and has characteristics such as active height, good stability.
The CdS/Ti-MCM-41 of pore matrix carries the platinum novel composite catalyst in of the present invention, on the one hand, because the existence of middle pore matrix Ti-MCM-41 and platinum, make light induced electron pore matrix Ti-MCM-41 from cadmium sulfide is transferred to also further transfer to noble metal platinum, the hole then rests on cadmium sulfide, and light induced electron is in time separated with the hole; On the other hand, because the CdS/Ti-MCM-41 of pore matrix fully contacted with reactant during big specific area made, the light induced electron hole can be in time and reactant reaction, improved the product hydrogen activity of catalyst, also suppress simultaneously the reaction of photohole and cadmium sulfide, improved the anti-photooxidation ability of the CdS/Ti-MCM-41 of middle pore matrix.Therefore, the CdS/Ti-MCM-41 of middle pore matrix carries the performance that the platinum novel composite catalyst has good photocatalytic hydrogen production by water decomposition.
Description of drawings
Fig. 1 is the transmission electron microscope photo figure of the mesoporous molecular sieve matrix Ti-MCM-41 that synthesizes;
Fig. 2 is the low angle XRD figure of intermediate product in middle pore matrix and the whole synthetic catalyst process thereof, and abscissa is represented scanning angle, and ordinate is represented signal strength signal intensity;
(a) is the low angle XRD curve of mesoporous molecular sieve matrix Ti-MCM-41 among Fig. 2;
(b) is through Cd among Fig. 2
2+The low angle XRD curve of the Ti-MCM-41 of exchange;
(c) is the low angle XRD curve of the CdS/Ti-MCM-41 composite catalyst of pore matrix in the end product among Fig. 2;
Fig. 3 be the CdS/Ti-MCM-41 composite catalyst of middle pore matrix with as the body of the reference ultraviolet-visible absorption spectroscopy figure of cadmium sulfide CdS mutually;
(a) is the ultraviolet-visible absorption spectroscopy curve of the CdS/Ti-MCM-41 of middle pore matrix among Fig. 3;
(b) is the ultraviolet-visible absorption spectroscopy curve as the body phase cadmium sulfide CdS of reference among Fig. 3;
Fig. 4 is the high angle XRD figure of the CdS/Ti-MCM-41 composite catalyst of pore matrix in the end product;
Fig. 5 is the visible light catalytic decomposition water experimental system figure that is used to verify product hydrogen activity of the present invention in the laboratory;
Fig. 6 be middle pore matrix the CdS/Ti-MCM-41 composite catalyst with as the body of reference substance mutually the photocatalysis of cadmium sulfide CdS produce hydrogen activity and characterize schematic diagram, abscissa is represented the time, ordinate is represented hydrogen output;
Fig. 7 is the ultraviolet-visible spectrogram that body phase CdS produces 7 hours front and back of hydrogen;
(a) produces the hydrogen ultraviolet-visible absorption spectroscopy curve of body phase cadmium sulfide CdS before among Fig. 7;
(b) produces the hydrogen ultraviolet-visible absorption spectroscopy curve of body phase cadmium sulfide CdS afterwards among Fig. 7.
Accompanying drawing is embodiments of the invention;
Below in conjunction with accompanying drawing content of the present invention is described in further detail.
The specific embodiment
Method compound with middle pore matrix Ti-MCM-41, the hydrogen sulfide sulfuration that the present invention adopts obtains producing the CdS/Ti-MCM-41 platinum catalyst of the middle pore matrix of hydrogen activity height and good stability, and concrete processing step is as follows:
Embodiment 1:
1) in 40 ℃ of water-baths, with 0.36g NaOH NaOH, 1.82g softex kw CTAB is dissolved in the 45mL deionized water, slowly splashes into the positive tetraethyl orthosilicate TEOS of 8.21mL with pipette, and the speed stirring with 800rpm is beneficial to the TEOS hydrolysis; 0.5h after be added dropwise to 0.25g butyl titanate TBOT, continue to stir behind the 1h solution is transferred to and be equipped with in the teflon-lined water heating kettle and in 100 ℃ of crystallization 72h.After water heating kettle is reduced to room temperature, solution is filtered, spend deionised water and dry repeatedly, obtain white former powder CTAB/Ti-MCM-41;
2) the former powder CTAB/Ti-MCM-41 of 2g white is calcined 10h removed template method CTAB in 500 ℃ of air atmosphere and obtain middle pore matrix Ti-MCM-41;
3) with 1.25g cadmium acetate CdAc
2Be dissolved among the 100mL methyl alcohol MeOH, add the former powder of 1.0gCTAB/Ti-MCM-41, low whipping speed is under the magnetic agitation of 450rpm, in methyl alcohol boiling point backflow 4h.To be cooled to room temperature, centrifugation with MeOH and deionized water washing, is used 0.1M Na
2S solution detects to washing lotion does not have Cd
2+Exist, 70 ℃ of vacuum drying 5h obtain Cd
2+The Ti-MCM-41 of exchange;
4) with Cd
2+The Ti-MCM-41 of exchange is in 25 ℃ of logical H
2S vulcanizes 6h, and vacuumizes 12h, to remove the H of absorption
2S gas, the CdS/Ti-MCM-41 of pore matrix in obtaining;
5) CdS/Ti-MCM-41 of the middle pore matrix that will prepare is with photoreduction met hod load platinum, and the CdS/Ti-MCM-41 of pore matrix carries the platinum composite photo-catalyst in can obtaining.The concrete Pt step of carrying is as follows:
1. be to add 0.2g CdS/Ti-MCM-41 in the 250mL reactor and 200mL contains the sodium sulfite Na of 9.6g as sacrifice agent at volume
2SO
3The aqueous solution; And the chloroplatinic acid H that to add an amount of 8mL platinum content be 0.0005g/mL
2PtCl
66H
2The O aqueous solution;
2. logical nitrogen purges 10min in the illumination forward reaction device, with the oxygen in the system of removing;
3. the electric fan of opening in the xenon lamp device keeps room temperature, opens magnetic stirring apparatus 300rpm;
4. open xenon lamp power supply, the 350W xenon lamp;
5. behind the photo-reduction 2h, close xenon lamp.
The CdS mass content is 8.7% in the catalyst, and the platinum mass content is 2%, Ti-MCM-41 mass content 89.3%.
Embodiment 2:
1) in 60 ℃ of water-baths, with 0.72g NaOH NaOH, 3.64g softex kw CTAB is dissolved in the 90mL deionized water, slowly splashes into the positive tetraethyl orthosilicate TEOS of 16.4mL with pipette, and the speed stirring with 500rpm is beneficial to the TEOS hydrolysis; Be added dropwise to 0.25g butyl titanate TBOT behind the 1h, continue stir behind the 1h solution is transferred to and be equipped with in the teflon-lined water heating kettle and in 100 ℃ of crystallization 72h.After water heating kettle is reduced to room temperature, solution is filtered, spend deionised water and dry repeatedly, obtain white former powder CTAB/Ti-MCM-41;
2) the former powder CTAB/Ti-MCM-41 of 2g white is calcined 5h removed template method CTAB in 500 ℃ of air atmosphere and obtain middle pore matrix Ti-MCM-41;
3) with 1.25g cadmium acetate CdAc
2Be dissolved among the 100mL methyl alcohol MeOH, add the former powder of 1.0gCTAB/Ti-MCM-41, low whipping speed is under the magnetic agitation of 250rpm, in methyl alcohol boiling point backflow 4h.To be cooled to room temperature, centrifugation with MeOH and deionized water washing, is used 0.1M Na
2S solution detects to washing lotion does not have Cd
2+Exist, 70 ℃ of vacuum drying 5h obtain Cd
2+The Ti-MCM-41 of exchange;
4) with Cd
2+The Ti-MCM-41 of exchange is in 70 ℃ of logical H
2S vulcanizes 6h, and vacuumizes 12h, to remove the H of absorption
2S gas, the CdS/Ti-MCM-41 of pore matrix in obtaining;
5) CdS/Ti-MCM-41 of the middle pore matrix that will prepare is with photoreduction met hod carried noble metal platinum, and the CdS/Ti-MCM-41 of pore matrix carries the platinum composite photo-catalyst in can obtaining.The concrete Pt step of carrying is as follows:
1. be to add 0.2g CdS/Ti-MCM-41 in the 250mL reactor and 200mL contains the sodium sulfite Na of 9.6g as sacrifice agent at volume
2SO
3The aqueous solution; And the chloroplatinic acid H that to add an amount of 16mL platinum content be 0.0005g/mL
2PtCl
66H
2The O aqueous solution;
2. logical nitrogen purges 10min in the illumination forward reaction device, with the oxygen in the system of removing;
3. the electric fan of opening in the xenon lamp device keeps room temperature, opens magnetic stirring apparatus 300rpm;
4. open xenon lamp power supply, the 350W xenon lamp;
5. behind the photo-reduction 6h, close xenon lamp.
The CdS mass content is 6.2% in the catalyst, and the platinum mass content is 3.8%, Ti-MCM-41 mass content 90%.
Embodiment 3:
1) in 40 ℃ of water-baths, with 0.72g NaOH NaOH, 3.64g softex kw CTAB is dissolved in the 90mL deionized water, slowly splashes into the positive tetraethyl orthosilicate TEOS of 16.4mL with pipette, and the speed stirring with 800rpm is beneficial to the TEOS hydrolysis; Be added dropwise to 0.25g butyl titanate TBOT behind the 1h, continue stir behind the 1h solution is transferred to and be equipped with in the teflon-lined water heating kettle and in 110 ℃ of crystallization 48h.After water heating kettle is reduced to room temperature, solution is filtered, spend deionised water and dry repeatedly, obtain white former powder CTAB/Ti-MCM-41;
2) the former powder CTAB/Ti-MCM-41 of 2g white is calcined 5h removed template method CTAB in 600 ℃ of air atmosphere and obtain middle pore matrix Ti-MCM-41;
3) with 2.5g cadmium acetate CdAc
2Be dissolved among the 200mL methyl alcohol MeOH, add the former powder of 2.0gCTAB/Ti-MCM-41, low whipping speed is under the magnetic agitation of 350rpm, in methyl alcohol boiling point backflow 6h.To be cooled to room temperature, centrifugation with MeOH and deionized water washing, is used 0.1M Na
2S solution detects to washing lotion does not have Cd
2+Exist, 100 ℃ of vacuum drying 10h obtain Cd
2+The Ti-MCM-41 of exchange;
4) with Cd
2+The Ti-MCM-41 of exchange is in 200 ℃ of logical H
2S vulcanizes 6h, and vacuumizes 12h, to remove the H of absorption
2S gas, the CdS/Ti-MCM-41 of pore matrix in obtaining;
5) CdS/Ti-MCM-41 of the middle pore matrix that will prepare is with photoreduction met hod carried noble metal platinum, and the CdS/Ti-MCM-41 of pore matrix carries the platinum composite photo-catalyst in can obtaining.The concrete Pt step of carrying is as follows:
1. be to add 0.05g CdS/Ti-MCM-41 in the 100mL reactor and 50mL contains the sodium sulfite Na of 2.4g as sacrifice agent at volume
2SO
3The aqueous solution; And the chloroplatinic acid H that to add an amount of 5mL platinum content be 0.0005g/mL
2PtCl
66H
2The O aqueous solution;
2. logical nitrogen purges 10min in the illumination forward reaction device, with the oxygen in the system of removing;
3. the electric fan of opening in the xenon lamp device keeps room temperature, opens magnetic stirring apparatus 350rpm;
4. open xenon lamp power supply, the 350W xenon lamp;
5. behind the photo-reduction 4h, close xenon lamp.
The CdS mass content is 7.3% in the catalyst, and the platinum mass content is 4.5%, Ti-MCM-41 mass content 88.2%.
Embodiment 4:
1) in 40 ℃ of water-baths, with 0.72g NaOH NaOH, 3.64g softex kw CTAB is dissolved in the 90mL deionized water, slowly splashes into the positive tetraethyl orthosilicate TEOS of 16.4mL with pipette, and the speed stirring with 600rpm is beneficial to the TEOS hydrolysis; 0.5h after be added dropwise to 0.25g butyl titanate TBOT, continue to stir behind the 2h solution is transferred to and be equipped with in the teflon-lined water heating kettle and in 100 ℃ of crystallization 24h.After water heating kettle is reduced to room temperature, solution is filtered, spend deionised water and dry repeatedly, obtain white former powder CTAB/Ti-MCM-41;
2) the former powder CTAB/Ti-MCM-41 of 5g white is calcined 8h removed template method CTAB in 650 ℃ of air atmosphere and obtain middle pore matrix Ti-MCM-41;
3) with 1.0g cadmium acetate CdAc
2Be dissolved among the 80mL methyl alcohol MeOH, add the former powder of 0.8gCTAB/Ti-MCM-41, low whipping speed is under the magnetic agitation of 250rpm, in methyl alcohol boiling point backflow 4h.To be cooled to room temperature, centrifugation with MeOH and deionized water washing, is used 0.1M Na
2S solution detects to washing lotion does not have Cd
2+Exist, 70 ℃ of vacuum drying 5h obtain Cd
2+The Ti-MCM-41 of exchange;
4) with Cd
2+The Ti-MCM-41 of exchange is in 300 ℃ of logical H
2S vulcanizes 2h, and vacuumizes 12h, to remove the H of absorption
2S gas, the CdS/Ti-MCM-41 of pore matrix in obtaining;
5) CdS/Ti-MCM-41 of the middle pore matrix that will prepare is with photoreduction met hod carried noble metal platinum, and the CdS/Ti-MCM-41 of pore matrix carries the platinum composite photo-catalyst in can obtaining.The concrete Pt step of carrying is as follows:
1. be to add 0.05g CdS/Ti-MCM-41 in the 100mL reactor and 100mL contains the sodium sulfite Na of 2.5g as sacrifice agent at volume
2SO
3The aqueous solution; And the chloroplatinic acid H that to add an amount of 6mL platinum content be 0.0005g/mL
2PtCl
66H
2The O aqueous solution;
2. logical nitrogen purges 15min in the illumination forward reaction device, with the oxygen in the system of removing;
3. the electric fan of opening in the xenon lamp device keeps room temperature, opens magnetic stirring apparatus 300rpm;
4. open xenon lamp power supply, the 350W xenon lamp;
5. behind the photo-reduction 2h, close xenon lamp.
The CdS mass content is 9.1% in the catalyst, and the platinum mass content is 5%, Ti-MCM-41 mass content 85.9%.
Embodiment 5:
1) in 20 ℃ of water-baths, 0.36g NaOH NaOH and 1.82g softex kw CTAB are dissolved in the 45mL deionized water, slowly splash into the positive tetraethyl orthosilicate TEOS of 8.21mL with pipette, the speed stirring with 400rpm is beneficial to the TEOS hydrolysis; 0.5h after be added dropwise to 0.25g butyl titanate TBOT, continue stirring behind the 0.5h solution is transferred to is equipped with in the teflon-lined water heating kettle and in 100 ℃ of crystallization 24h, after water heating kettle is reduced to room temperature, solution is filtered, spend deionised water repeatedly and, obtain white former powder CTAB/Ti-MCM-41 in 70 ℃ of dryings;
2) the former powder CTAB/Ti-MCM-41 of 2g white is calcined 5h removed template method CTAB in 500 ℃ of air atmosphere and obtain mesoporous molecular sieve matrix Ti-MCM-41;
3) with 1.0g cadmium acetate CdAc
2Be dissolved among the 80mL methyl alcohol MeOH, add the former powder of 0.8gCTAB/Ti-MCM-41, low whipping speed is under the magnetic agitation of 150rpm, and backflow 4h under the methyl alcohol boiling point is to be cooled to room temperature, and centrifugation is with methyl alcohol MeOH and deionized water washing, with 0.1M vulcanized sodium Na
2S solution detects to washing lotion does not have Cd
2+Exist, 70 ℃ of vacuum drying 5h obtain Cd
2+The mesoporous molecular sieve Ti-MCM-41 of exchange;
4) with Cd
2+The mesoporous molecular sieve Ti-MCM-41 of exchange is in 25 ℃ of logical H of room temperature
2S vulcanizes 4h, and vacuumizes 12h, to remove the H of absorption
2S gas, the CdS/Ti-MCM-41 of pore matrix in obtaining;
5) CdS/Ti-MCM-41 of the middle pore matrix that will prepare is with photoreduction met hod load platinum, and the CdS/Ti-MCM-41 of pore matrix carries the platinum composite photo-catalyst in can obtaining.The concrete Pt step of carrying is as follows:
1) be to add 0.05g CdS/Ti-MCM-41 in the 100mL reactor and 50mL contains the sodium sulfite Na of 2.4g as sacrifice agent at volume
2SO
3The aqueous solution; And adding 2mL platinum content is the chloroplatinic acid H of 0.0005g/mL
2PtCl
66H
2The O aqueous solution;
2) logical nitrogen purges 10min-20min in the illumination forward reaction device, and temperature is a room temperature, and pressure is 2MPa-10MPa, with the oxygen in the system of removing;
3) electric fan of opening in the xenon lamp device keeps room temperature, opens magnetic stirring apparatus 300-500rpm;
4) open xenon lamp power supply, the 350W xenon lamp;
5) behind the photo-reduction 2h, close xenon lamp.
The CdS mass content is 9.7% in the catalyst, and the platinum mass content is 2.2%, Ti-MCM-41 mass content 88.1%.
Embodiment 6:
1) in 60 ℃ of water-bath, 1.08g NaOH NaOH and 5.26g softex kw CTAB are dissolved in the 135mL deionized water, slowly splash into the positive tetraethyl orthosilicate TEOS of 24.63mL with pipette, the speed stirring with 800rpm is beneficial to the TEOS hydrolysis; Be added dropwise to 0.75g butyl titanate TBOT behind the 2h, continue stirring behind the 2h solution is transferred to is equipped with in the teflon-lined water heating kettle and in 110 ℃ of crystallization 72h, after water heating kettle is reduced to room temperature, solution is filtered, spend deionised water repeatedly and, obtain white former powder CTAB/Ti-MCM-41 in 100 ℃ of dryings;
2) the former powder CTAB/Ti-MCM-41 of 5g white is calcined 10h removed template method CTAB in 650 ℃ of air atmosphere and obtain mesoporous molecular sieve matrix Ti-MCM-41;
3) with 2.5g cadmium acetate CdAc
2Be dissolved among the 200mL methyl alcohol MeOH, add the former powder of 2.0gCTAB/Ti-MCM-41, low whipping speed is under the magnetic agitation of 450rpm, and backflow 10h under the methyl alcohol boiling point is to be cooled to room temperature, and centrifugation is with methyl alcohol MeOH and deionized water washing, with 0.1M vulcanized sodium Na
2S solution detects to washing lotion does not have Cd
2+Exist, 100 ℃ of vacuum drying 10h obtain Cd
2+The mesoporous molecular sieve Ti-MCM-41 of exchange;
4) with Cd
2+The mesoporous molecular sieve Ti-MCM-41 of exchange is in 300 ℃ of logical H of room temperature
2S vulcanizes 10h, and vacuumizes 24h, to remove the H of absorption
2S gas, the CdS/Ti-MCM-41 of pore matrix in obtaining;
5) CdS/Ti-MCM-41 of the middle pore matrix that will prepare is with photoreduction met hod load platinum, and the CdS/Ti-MCM-41 of pore matrix carries the platinum composite photo-catalyst in can obtaining.The concrete Pt step of carrying is as follows:
1) be to add 0.2g CdS/Ti-MCM-41 in the 250mL reactor and 200mL contains the sodium sulfite Na of 9.6g as sacrifice agent at volume
2SO
3The aqueous solution; And adding 20mL platinum content is the chloroplatinic acid H of 0.0005g/mL
2PtCl
66H
2The O aqueous solution;
2) logical nitrogen purges 20min in the illumination forward reaction device, with the oxygen in the system of removing;
3) electric fan of opening in the xenon lamp device keeps room temperature, opens magnetic stirring apparatus 500rpm;
4) open xenon lamp power supply, the 350W xenon lamp;
5) behind the photo-reduction 6h, close xenon lamp.
The CdS mass content is 6.4% in the catalyst, and the platinum mass content is 4.8%, Ti-MCM-41 mass content 88.8%.
The generation of hydrogen sulfide gas can add the 250g ferrous sulfide in kipp gas generator, with constant flow pump to wherein slowly adding the 3mol/L dilute sulfuric acid, promptly produce hydrogen sulfide gas and hydrogen sulfide gas is fed in the tube furnace, hydrogen sulfide tail gas is that the sodium hydroxide solution of 2mol/L is handled with concentration.
Fig. 1 provides the images of transmissive electron microscope of synthetic substrate, has clearly reflected the mesopore pore passage structure of matrix Ti-MCM-41 among the figure, and the aperture is about 3nm, can limit the growth of sulfuration every CdS effectively, and its particle diameter is controlled in the 3nm.
Fig. 2 (a) and (b), (c) are the low angle XRD figure of intermediate product in middle pore matrix and the whole synthetic catalyst process thereof.Can clearly see the characteristic diffraction peak of matrix (100), (110) and (200) crystal face from Fig. 2 (a), prove that synthetic substrate has six regular side's mesopore pore passage structures, this transmission electron microscope photo with Fig. 1 matrix Ti-MCM-41 is consistent.The intensity of (100) diffraction maximum has obviously than Fig. 2 (a) and weakens among Fig. 2 (b) and 2 (c), but the diffraction maximum of (100) crystal face shows as the strongest diffraction maximum, shows Cd
2+The Ti-MCM-41 of exchange and the mesopore pore passage structure of end product CdS/Ti-MCM-41 still exist.But compare with Fig. 2 (a), the diffraction maximum of (110) and (200) crystal face among Fig. 2 (b) and 2 (c) disappears, and this is attributable to Cd
2+With the CdS nano-particles filled part duct of Ti-MCM-41, reduced the order of central hole structure.
The CdS/Ti-MCM-41 of the middle pore matrix that Fig. 3 provides and the body ultraviolet-visible spectrogram demonstration of cadmium sulfide CdS mutually, the ABSORPTION EDGE of the CdS/Ti-MCM-41 of middle pore matrix is positioned at the 480nm place, with respect to the ABSORPTION EDGE 600nm blue shift of body phase cadmium sulfide CdS about 120nm, show the CdS particle that successfully grows nano-scale in having the Ti-MCM-41 mesopore duct of confinement effect, its energy gap has had tangible increase.According to λ
Onset-2R relation, the CdS particle diameter among the CdS/Ti-MCM-41 of middle pore matrix is no more than 3.0nm.
The CdS/Ti-MCM-41 that Fig. 4 has provided middle pore matrix is at 10-80 ° diffraction spectrogram.The diffraction maximum of 3 broads shows that CdS is a cube phase structure among the figure.According to the Scherrer equation, the particle diameter that calculates CdS is about 2.6nm, and this result is consistent with uv-vis spectra, is slightly less than the mesopore aperture of matrix Ti-MCM-41.
It below is the concrete confirmatory experiment that the present invention provides.
1. hydrogen performance evaluation is produced in photocatalysis
The test and validation experiment of all relevant visible light catalytic hydrogen production by water decomposition performances of the present invention is all finished in experimental system shown in Figure 5, Fig. 5 (a) and (b) experimental system mainly comprises following components: the Pyrex glass reactor, magnetic stirring apparatus, cut-off type optical filter (λ 〉=430nm, light transmittance 65%) and 350W xenon lamp device.350W xenon lamp device mainly comprises an xenon lamp control cabinet, a 350W xenon lamp, a reflective tile and a small electric fan.Because xenon lamp work the time can follow a large amount of heat to emit, to carry out air-cooledly so the rear portion has installed an electric fan additional, the temperature constant of practical measurement light-catalyzed reaction system is at 35 ± 5 ℃.
Experimental procedure:
1. be to add 0.2g CdS/Ti-MCM-41 in the 250mL reactor and 200mL contains the sodium sulfite Na of 9.6g as sacrifice agent at volume
2SO
3The aqueous solution; And the chloroplatinic acid H that to add an amount of 8mL platinum content be 0.0005g/mL
2PtCl
66H
2O;
2. logical nitrogen purges 10min-20min in the illumination forward reaction device, with the oxygen in the system of removing;
3. the electric fan of opening in the xenon lamp device keeps room temperature, opens magnetic stirring apparatus 300-500rpm;
4. open xenon lamp power supply, the 350W xenon lamp;
5. behind the photo-reduction 2h-6h, close xenon lamp.
5) reaction is every through one hour, gets 100 μ L gases and be expelled to and carry out gas composition and outer marking quantitative analysis (the SP-2100 type gas chromatograph that the BeiFen Instrument Techogy Co., Ltd., BeiJing City produces, TCD detector, 5A molecular sieve column) in the gas chromatograph in reactor.
6) behind the reaction 7h, vavuum pump carries out emptying to system, repeating step 2.
Fig. 6 produces the hydrogen result for the catalyst visible light catalytic, produces hydrogen condition: catalyst 0.2g, reactant liquor 200mL, light source 350W Xe lamp (λ 〉=430nm, light transmittance 65%) sacrifice agent: 9.6g Na
2SO
3
As seen from the figure, the CdS/Ti-MCM-41 of the prepared middle pore matrix of the present invention carries the platinum novel composite catalyst and produces the body phase cadmium sulfide CdS that hydrogen activity is higher than the traditional co-precipitation method preparation.The hydrogen-producing speed that the CdS/Ti-MCM-41 of the middle pore matrix of this method preparation carries the platinum novel composite catalyst can reach 890 μ molh
-1G
CdS -1, and produce hydrogen 35h activity continuously and do not see decay; As a comparison, the hydrogen-producing speed of body phase CdS only is 33 μ molh
-1G
CdS -1, and through after the product hydrogen of 7h, the color of body phase CdS has become dark-brown by initial redness, and serious photoetch has taken place, and the ultraviolet-visible spectrogram before and after its reaction has also proved this point, referring to Fig. 7.This catalyst that proves absolutely that method proposed by the invention prepares can separate light induced electron and hole efficiently, has improved the product hydrogen activity and the stability of CdS catalyst.
2. catalyst efficiency evaluation
Catalyst quantum efficient and light energy use efficiency computing formula are as follows:
The product hydrogen meter of light-catalyzed reaction is seen quantum efficiency and is calculated by following formula:
Energy conversion efficiency can be estimated with following formula:
Δ G in the formula (2)
P 0Expression produces the standard Gibbs free energy of the reaction of hydrogen, R
PBe the speed that produces standard conditions hydrogen, E
sBe incident intensity, A is the raying area.In the decomposition reaction of water, every generation a part hydrogen will shift two electronics, and the standard Gibbs that reacts when 298K can AG
H2 0=237kJ/mol.
The quantum efficiency of the photocatalysis hydrogen production of catalyst adopts single line light method to measure.The 350W xenon source installs the single line light that dominant wavelength is the logical type optical filter acquisition of band 420 ± 5nm of 420nm additional.(photoelectric instrument factory of Beijing Normal University produces, and model is: (λ: 400-1000nm) probe records add 350W xenon lamp behind the 420nm bandpass filter average to see through unit light intensity is W=3.52mW/cm the UV-B type) subsidiary FZ-A type to use the light intensity irradiatometer
2Because of effective irradiated area of reactor is A=π R
2=π * 2
2=12.56cm
2Can be regarded as on average by Q=WA is Q=4.42*10 through luminous energy
-2W.Adopt the logical type optical filter of 420nm band to do photocatalysis with the 350W xenon lamp and produce the hydrogen test, recording hydrogen-producing speed is 125.4 μ molh
-1G
CdS -1After installing the logical type optical filter of band additional, because of only having the photon of 420 ± 5nm scope, xenon source can see through, and light intensity greatly reduces, so hydrogen output produces hydrogen than all band light source that adopts the cut-off type optical filter to obtain λ 〉=430nm obvious decline is arranged.By formula (1) calculate CdS/Ti-MCM-41 to carry the platinum novel composite catalyst be 2.6% in the 420nm place sub-efficient of hydrogen output.For employed 350W xenon lamp, by formula (2) calculate Pt CdS-loaded/the Ti-MCM-41 photochemical catalyst is 0.62% at the visible light all band of λ 〉=430nm zone light energy use efficiency.
Claims (3)
1.CdS/Ti-MCM-41 loaded platinum photo catalyst is characterized in that, catalyst consists of the mesoporous molecular sieve Ti-MCM-41 that cadmium sulfide CdS that mass content is 5%-15%, platinum that mass content is 2%-5% and mass content are 80%-90%.
2, a kind of preparation method of CdS/Ti-MCM-41 platinum catalyst is characterized in that, carries out according to the following steps:
1) in 20 ℃ of-60 ℃ of water-bath, 0.36g-1.08g NaOH NaOH and 1.82g-5.26g softex kw CTAB are dissolved in the 45mL-135mL deionized water, slowly splash into the positive tetraethyl orthosilicate TEOS of 8.21mL-24.63mL with pipette, speed with 300-800rpm stirs, 0.5h-2h after be added dropwise to 0.25g-0.75g butyl titanate TBOT, continue stirring behind the 0.5h-2h solution is transferred to is equipped with in the teflon-lined water heating kettle and in 100 ℃ of-110 ℃ of crystallization 24h-72h, mixture constitutive molar ratio NaOH: CTAB: TEOS: TBOT: H
2O=12.2: 6.8: 54.4: 1: 3400; After water heating kettle is reduced to room temperature, solution is filtered, spend deionised water repeatedly and, obtain white former powder CTAB/Ti-MCM-41 in 70 ℃ of-100 ℃ of dryings;
2) with 1.0g-2.5g cadmium acetate CdAc
2Be dissolved among the 80mL-200mL methyl alcohol MeOH, add the former powder of 0.8g-2.0g CTAB/Ti-MCM-41, low whipping speed is under the magnetic agitation of 150rpm-450rpm, backflow 4h-10h under the methyl alcohol boiling point, to be cooled to room temperature, centrifugation is with methyl alcohol MeOH and deionized water washing, with 0.1M vulcanized sodium Na
2S solution detects to washing lotion does not have Cd
2+Exist, 70 ℃ of-100 ℃ of vacuum drying 5h-10h obtain Cd
2+The mesoporous molecular sieve Ti-MCM-41 of exchange;
3) with Cd
2+The mesoporous molecular sieve Ti-MCM-41 of exchange is in 25 ℃ of-300 ℃ of logical H of room temperature
2S vulcanizes 4h-10h, and vacuumizes 12h-24h, to remove the H of absorption
2S gas, the CdS/Ti-MCM-41 of pore matrix in obtaining;
4) CdS/Ti-MCM-41 of the middle pore matrix that will prepare is with photoreduction met hod load platinum, and the CdS/Ti-MCM-41 of pore matrix carries the platinum composite photo-catalyst in can obtaining.
3. preparation method according to claim 2 is characterized in that, described to carry the concrete steps of platinum with photoreduction met hod as follows:
1) be to add 0.05g-0.2g CdS/Ti-MCM-41 in the 100mL-250mL reactor and 50mL-200mL contains the sodium sulfite Na of 2.4g-9.6g as sacrifice agent at volume
2SO
3The aqueous solution; And adding 2mL-8mL platinum content is the chloroplatinic acid H of 0.0005g/mL
2PtCl
66H
2The O aqueous solution;
2) logical nitrogen purges 10min-20min in the illumination forward reaction device, and temperature is a room temperature, and pressure is 2MPa-10MPa, with the oxygen in the system of removing;
3) electric fan of opening in the xenon lamp device keeps room temperature, opens magnetic stirring apparatus 300-500rpm;
4) open xenon lamp power supply, the 350W xenon lamp;
5) behind the photo-reduction 2h-6h, close xenon lamp.
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| CN101708464B (en) * | 2009-12-10 | 2012-08-29 | 南京大学 | Cation resin matrix CdS-loaded composite material and preparation method thereof |
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| CN103889577B (en) * | 2011-10-21 | 2017-05-03 | 伊格提尔科技有限公司 | Methods of preparation and forming supported active metal catalysts and precursors |
| CN102814189A (en) * | 2012-09-13 | 2012-12-12 | 中国科学技术大学 | Preparation method and application of solid acid catalyst |
| RU2752496C1 (en) * | 2020-12-15 | 2021-07-28 | федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Composite mesoporous photocatalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000004993A1 (en) * | 1998-07-23 | 2000-02-03 | Korea Research Institute Of Chemical Technology | Photocatalyst for methane conversion, method for preparing the same and method for preparing low carbohydrates using the same |
| CN1310044A (en) * | 1998-09-09 | 2001-08-29 | 韩国化学研究所 | Cds photocatalyst for producing hydrogen, its producing process and process for producing hydrogen using the same catalyst |
| JP2001334148A (en) * | 2000-05-26 | 2001-12-04 | Kawasaki Heavy Ind Ltd | Material for holding photocatalytic function and method of holding photocatalytic function |
| CN1600416A (en) * | 2004-08-30 | 2005-03-30 | 中国科学院上海硅酸盐研究所 | Photocatalyst of nano titanium oxide modifed by cadmium selenide and preparation method |
| CN1692982A (en) * | 2005-03-02 | 2005-11-09 | 山东恒冠塑胶有限公司 | Nanometer catalyst for used under sunlight and its prepn. method |
-
2006
- 2006-02-27 CN CNB2006100418357A patent/CN100351013C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000004993A1 (en) * | 1998-07-23 | 2000-02-03 | Korea Research Institute Of Chemical Technology | Photocatalyst for methane conversion, method for preparing the same and method for preparing low carbohydrates using the same |
| CN1310044A (en) * | 1998-09-09 | 2001-08-29 | 韩国化学研究所 | Cds photocatalyst for producing hydrogen, its producing process and process for producing hydrogen using the same catalyst |
| JP2001334148A (en) * | 2000-05-26 | 2001-12-04 | Kawasaki Heavy Ind Ltd | Material for holding photocatalytic function and method of holding photocatalytic function |
| CN1600416A (en) * | 2004-08-30 | 2005-03-30 | 中国科学院上海硅酸盐研究所 | Photocatalyst of nano titanium oxide modifed by cadmium selenide and preparation method |
| CN1692982A (en) * | 2005-03-02 | 2005-11-09 | 山东恒冠塑胶有限公司 | Nanometer catalyst for used under sunlight and its prepn. method |
Non-Patent Citations (1)
| Title |
|---|
| M/Ti-MCM-41光催化剂的制备及产氢性能研究 沈少华，延卫，张耀君等.西安交通大学学报，第39卷第7期 2005 * |
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