WO2003051512A1 - Photocatalyseur a film mince, son procede de production, procede de traitement du sulfure d'hydrogene utilisant le catalyseur optique a film mince et procede de production de l'hydrogene - Google Patents

Photocatalyseur a film mince, son procede de production, procede de traitement du sulfure d'hydrogene utilisant le catalyseur optique a film mince et procede de production de l'hydrogene Download PDF

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WO2003051512A1
WO2003051512A1 PCT/JP2002/013136 JP0213136W WO03051512A1 WO 2003051512 A1 WO2003051512 A1 WO 2003051512A1 JP 0213136 W JP0213136 W JP 0213136W WO 03051512 A1 WO03051512 A1 WO 03051512A1
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thin
hydrogen
compound semiconductor
film
sulfide
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PCT/JP2002/013136
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English (en)
Japanese (ja)
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Kazuyuki Tohji
Atsuo Kasuya
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Japan Science And Technology Corporation
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0495—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by dissociation of hydrogen sulfide into the elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a thin-film photocatalyst, a method for producing the same, and a method for treating hydrogen sulfide and a method for producing hydrogen using the thin-film photocatalyst.
  • the present invention can be used in the chemical industry where hydrogen and sulfur are required, the chemical industry where hydrogen sulfide generated in the desulfurization process and the like are treated, and the environmental protection field where odorous substances and air pollutants are removed.
  • the present invention relates to a thin-film photocatalyst, a method for producing the same, and a method for using the same. Background art
  • photocatalytic technology has begun to be put to practical use utilizing the properties that promote various chemical reactions, such as decomposition of environmental pollutants, odorous components, and various germs. Examples include antibacterial tiles used in hospital operating rooms, air purifiers and air conditioners, glass for lighting on highways, and so on. While these photocatalysts have been put to practical use by using their oxidation promoting ability, research has also been conducted to obtain hydrogen by applying a photocatalyst to water or the like, or to fix and reduce carbon by acting on carbon dioxide gas. ing.
  • Fig. 3 shows the currently used crude oil desulfurization process.
  • heavy naphtha is hydrorefined and all sulfur contained in crude oil is converted to hydrogen sulfide and recovered.
  • the hydrogen sulfide generated here is oxidized to recover sulfur through a process called the Claus method.
  • This Claus process is a process in which one-third of hydrogen sulfide is oxidized into sulfur dioxide, and the remaining hydrogen sulfide is reacted with the gas to form sulfur. That is, in the chemical formula, it is expressed as follows.
  • Hydrogen gas is used for the hydrogenation of heavy naphtha in the crude oil desulfurization process shown in Fig. 3.
  • One method of producing hydrogen gas is the method shown in Fig. 5.
  • the hydrogen gas production method shown in Fig. 5 called the cryogenic hydrogen purification method or nitrogen cleaning method, generates hydrogen from a hydrogen-rich gas, and is a crude gas generated from processes other than the aforementioned hydrocarbon cracking. Also applicable to
  • the raw material gas is compressed and washed with sodium hydroxide to remove gaseous carbonate, hydrogen sulfide and the like.
  • it is cooled by a low-temperature purified hydrogen gas in a heat exchanger, and methane and hydrocarbon gas of C4 or more are liquefied and removed.
  • methane and hydrocarbon gas of C4 or more are liquefied and removed.
  • carbon monoxide and nitrogen are discharged in a liquid form from the tower bottom by being raised from the tower bottom to the top and washed with liquefied nitrogen descending from the top, and purified and separated. Hydrogen is removed from the top of the tower.
  • any photocatalyst that works in almost the entire wavelength range of sunlight can effectively utilize solar energy.
  • the present invention has been made in view of the above-mentioned problems of the related art, and has as its object to provide a thin-film photocatalyst using a compound semiconductor capable of generating hydrogen from hydrogen sulfide, and a method for producing the same.
  • Another object of the present invention is to provide a method for treating hydrogen sulfide and a method for producing hydrogen, wherein hydrogen can be efficiently recovered from hydrogen sulfide using the thin-film photocatalyst. Disclosure of the invention
  • the thin-film photocatalyst of the present invention is characterized in that a layer made of a compound semiconductor is fixed on a substrate, and the compound semiconductor contains an oxygen atom.
  • the compound semiconductor is preferably a metal sulfide.
  • the manufacturing method is such that a substrate is immersed in a solution containing a chemical species to be a compound semiconductor raw material, and the compound semiconductor is deposited and fixed on the surface of the substrate by a chemical bath deposition method (CBD method). It is characterized by.
  • CBD method chemical bath deposition method
  • the compound semiconductor is preferably a group II-VI compound semiconductor, and more preferably a metal sulfide. Further, it is particularly desirable to use zinc sulfide or sulfided dome.
  • the photocatalyst in the form of a thin film on a substrate, the photocatalyst is more excellent in handleability than the particulate form, and can be used as a practical photocatalyst. Also, a photocatalyst with a large area can be produced with a small amount of catalyst.
  • the particles are fixed on the substrate without being dispersed in the solution like particles, the efficiency of converting the light energy by receiving irradiation light is improved by setting the irradiation angle to the optimum angle. Can be done.
  • the CBD method is a method in which a substrate is immersed in a solution containing a chemical species to be a precursor, and a heterogeneous reaction proceeds between the solution and the substrate surface to deposit a thin film on the substrate. It is.
  • This method does not require complicated equipment as shown in Fig. 6, and enables thin film preparation under relatively low temperature conditions.
  • a desired thin film can be obtained by controlling the solution composition, and a strong bond of chemical adsorption of the thin film to the substrate can be expected.
  • the nucleation reaction that precipitates a compound from solution in the CBD (chemi-cl bath-deposition) method is more heterogeneous than when new phase nuclei are formed in isolation in a homogeneous phase. It is known that the interface energy required for nucleation of a new phase is smaller when a part exists and nucleation occurs there (heterogeneous nucleation). Using this heterogeneous nucleation, some method
  • the CBD method in which the concentration of ions in the solution is reduced to below saturation and the deposition is caused selectively on the substrate, has the following advantages over other thin film deposition methods.
  • the equipment is simple, it can be deposited at a lower temperature (near room temperature) compared to the vapor deposition method, etc., it can be applied to large areas at low cost, and it can be adapted to various applications. That is, it can be deposited on a suitable base material.
  • a substrate made of silicon, glass, nickel, zinc, platinum, resin, or the like can be used as the substrate.
  • metals are desirable, and platinum is particularly desirable.
  • any other material can be used as long as the material can effectively precipitate and fix the photocatalyst material.
  • the thickness of the thin film is preferably 5 to 100 nm for ZnS, and preferably 200 to 50 O nm for CdS.
  • the thin film may be a single film composed of a single component or a single film composed of a plurality of components, and may be a single-layer film or a multilayer film. It is also possible to form a thin film in which the components are continuously changed in the thickness direction.
  • the composition of the thin film can be changed, for example, by changing the solvent for depositing the compound semiconductor on the base material.
  • solvent ZnS0 4, SC (NH 2) 2, NH 3, N 2 H 4, (NH 4) 2 S_ ⁇ 4 tends Z n S is precipitated With, ZnS_ ⁇ 4
  • SC (NH 2 ) 2 and NH 3 are used, Zn easily precipitates. Therefore, by precipitating using these two solutions while changing the ratio, a large amount of ZnO is deposited on the side of the substrate, and a large amount of ZnS is deposited on the side of the surface far from the substrate. Becomes possible.
  • the method for treating hydrogen sulfide using a thin-film photocatalyst of the present invention is characterized in that a thin-film photocatalyst having a layer made of a compound semiconductor immobilized on a substrate is immersed in a solution in which hydrogen sulfide is dissolved. And recovering sulfur.
  • a thin-film photocatalyst consisting of a compound semiconductor layer is particularly immersed in an alkaline solution in which hydrogen sulfide is dissolved. Can be recovered.
  • This method of treating hydrogen sulfide with a thin-film photocatalyst includes (1) a step of dissolving hydrogen sulfide in an alkaline solution, and (2) immersing the thin-film photocatalyst in a solution in which hydrogen sulfide is dissolved.
  • the reaction formula of each step is represented by the following formula.
  • the efficiency of hydrogen generation from aqueous solution by a thin-film photocatalyst is much higher than that of a particulate photocatalyst. This is because the photocatalyst is immobilized in the form of a thin film and has a large surface area due to the presence of appropriate irregularities on the surface of the thin film, and fine catalyst particles are immobilized on the substrate. This is probably because the efficiency of converting the energy into hydrogen generation by receiving irradiation light has been improved.
  • hydrogen is produced by immersing a thin-film photocatalyst having a layer made of a compound semiconductor on a substrate in a solution in which hydrogen sulfide is dissolved. It is characterized by doing.
  • This method for producing hydrogen is similar to the method for treating hydrogen sulfide described above, and the hydrogen produced at that time is recovered to produce hydrogen.
  • FIG. 1 is a graph showing the relationship between the light irradiation time and the amount of generated hydrogen when a thin film photocatalyst of a Zn compound according to the present invention is used,
  • FIG. 2 is a graph showing the relationship between the light irradiation time and the amount of generated hydrogen when using the Cd compound thin film photocatalyst according to the present invention
  • FIG. 3 is a diagram schematically showing a general crude oil desulfurization process
  • FIG. 4 is a diagram illustrating a conventional technology (Klaus method) of a method for treating hydrogen sulfide
  • FIG. 5 is a diagram illustrating a conventional technology (cryogenic hydrogen purification method or nitrogen cleaning method) of a hydrogen production method.
  • FIG. 6 is a schematic perspective view showing an apparatus for producing a thin-film photocatalyst by the CBD method.
  • FIG. 7 is a view schematically showing a hydrogen sulfide treatment system according to one embodiment of the present invention.
  • FIG. 8 is a diagram showing a TEM photograph of the cross-sectional shape of the ZnS thin film
  • FIG. 9 is a TEM-EDM photograph of the atomic distribution of Zn in FIG. 8
  • FIG. 10 is a TEM-EDM photograph of the atomic distribution of S in FIG. 8
  • FIG. FIG. 12 is a TEM-EDM photograph of the atomic distribution of Zn
  • FIG. 12 is a TEM photograph of the cross-sectional shape of the ZnS—CdS thin film
  • FIG. 13 is a TEM-EDM photograph of the atomic distribution of Zn in FIG.
  • FIG. 14 is a TEM-EDM photograph of the Cd atomic distribution in FIG. 12
  • FIG. 15 is a TEM-EDM photograph of the S atomic distribution in FIG. 12, and FIG. FIG.
  • FIG. 17 is a view showing a TEM-EDM photograph of the atomic distribution of 0 in 12, and FIG. 17 is a view showing an experimental apparatus for examining the activity of the thin film photocatalyst of the compound semiconductor according to the present invention.
  • a substrate is immersed in a solution containing a chemical species to be a raw material of a compound semiconductor, and the compound semiconductor is deposited and fixed on the surface of the substrate by a CBD method.
  • the CBD method is a method in which a thin film is selectively deposited on a substrate by immersing the substrate in a solution containing a chemical species to be a precursor and causing a heterogeneous reaction between the solution and the substrate surface. is there.
  • This method can be performed using an apparatus as shown in Fig. 6, does not require a complicated apparatus, and can produce a thin film at a relatively low temperature.
  • FIG. 6 is a schematic perspective view showing an apparatus for producing a thin-film photocatalyst by the CBD method.
  • 61 is a thermal stirrer
  • 62 is a reaction solution
  • 63 is a base material
  • 64 is a magnetic stirrer
  • 65 is a thread for hanging the base material.
  • the conditions for depositing a thin film by the CBD method require precise conditions, unlike the case where particles prepared separately in advance are attached to a substrate.
  • the conditions are considered below.
  • the condition that the product of ion concentration exceeds the solubility product, that is, the solubility product is K sp ,
  • activation treatment of the substrate surface is also effective for forming a thin film.
  • Methods for activating the substrate include etching and heating of the substrate with a strong acid or strong alkali, application of ultrasonic waves, and the like.
  • the formation of a good thin film in a solution reaction is realized by causing a heterogeneous reaction by using an active substrate in an unsaturated state where the solution is close to saturation.
  • the method for treating hydrogen sulfide according to the present invention includes recovering hydrogen and sulfur by immersing a thin-film photocatalyst having a layer made of a compound semiconductor on a substrate in a solution in which hydrogen sulfide is dissolved.
  • FIG. 7 schematically shows a processing system for explaining an embodiment of a method for processing hydrogen sulfide using a thin-film photocatalyst according to the present invention.
  • This processing system consists of a hydrogen sulfide dissolving tank 1 for dissolving hydrogen sulfide, a photocatalytic reaction tank 3 for recovering hydrogen gas from a solution in which hydrogen sulfide is dissolved, and a sulfur catalyst from the solution after hydrogen gas recovery.
  • 3136 It consists of a sulfur recovery tank 5 for recycling and recycling the solution after sulfur recovery to the hydrogen sulfide dissolution tank 1.
  • the hydrogen sulfide dissolving tank 1 contains an alkaline solution, into which hydrogen sulfide gas is introduced and dissolved.
  • Alkaline solutions only provide a site for dissolution and dissociation of hydrogen sulfide and a reaction, but do not alter themselves.
  • a description will be given using an example of an aqueous sodium hydroxide solution.
  • any aqueous solution that dissolves and dissociates hydrogen sulfide can be used.
  • the sodium sulfide solution is sent to the photocatalyst reactor 3 where the thin film photocatalyst according to the present invention is immersed and irradiated with light (visible light and / or ultraviolet light) from the light source 7 by the following formula. As shown in Fig. 7, hydrogen gas and polysulfide ions are generated, and hydrogen gas is recovered.
  • polysulfide ions are recovered as sulfur using the above disproportionation reaction.
  • the solution from which the sulfur is recovered returns to sodium hydroxide and is reused as a solution for dissolving hydrogen sulfide.
  • sulfur can be recovered in the same manner as in the Claus method by decomposing hydrogen sulfide using a thin-film photocatalyst, and hydrogen consumed in the desulfurization step Can be manufactured.
  • this method for treating hydrogen sulfide eliminates the need for energy, such as heating and coagulation, as in the Claus method, and does not involve sulfur dioxide, which is more dangerous than hydrogen sulfide. Are better.
  • the method for producing hydrogen according to the present invention is characterized in that hydrogen is produced by immersing a thin-film photocatalyst having a layer made of a compound semiconductor on a substrate in a solution in which hydrogen sulfide is dissolved. .
  • This embodiment is already included in a part of the method for treating hydrogen sulfide described above.
  • the generation mechanism when the above reagents are used is considered to be as follows.
  • Zn 2 + forms a complex with NH 3 .
  • OH_ forms a simple substance or Zn (OH) 2 and is adsorbed to the substrate, and causes a hydrolysis reaction of SC (NH 2 ) 2 .
  • S 2 produced by this reaction is considered as a thin film of ZnS is formed in conjunction with Z n (OH) 2.
  • the above reagents and their concentration conditions are such that the concentration of Zn 2+ that is present in the solution freely is reduced by using a complexing agent, and the concentration of OH is reduced by using a buffer.
  • the SC (NH 2 ) 2 whose ion concentration product is lower than the solubility product and the supply of S 2 + ions proceeds more slowly than sodium sulfide Na 2 S, enables It is thought that they are efficiently deposited on the top.
  • a soda-lime glass slide glass immersed in a 1 mo 1/1 sodium hydroxide NaOH aqueous solution for 12 hours was used as a base material.
  • Five kinds of reagents were added to 100 ml of water to a predetermined concentration, the substrate was immersed in this solution, heated at 85 ° C for 10 minutes with stirring, and then precipitated at room temperature for 6 hours. .
  • the heating of the solution aims at accelerating the reaction and activating the substrate. Further, the substrate was washed with water and then annealed at 200 ° C for 2 hours.
  • a buffer Anmoniumu sulfate (NH 4) 2 S0 4 ) may reduce the pH was increased by temperature Rise of the reaction bath, i.e., the pH of the bath is raised OH- increases, Z n It is considered that (OH) 2 can be prevented from precipitating in the bathtub.
  • the ZnS thin film could not be prepared using either NH 3 or N 2 H 4 alone, but could be prepared only by using both simultaneously.
  • the temperature dependence of thin film deposition it is judged that thin films are not deposited only by the room temperature process. At high temperature, the solution itself turned white, and it is considered that particles precipitated in the solution. Therefore, the temperature dependence of the deposition conditions is considered to be important.
  • the ZnO thin film was formed in the middle of the ZnS thin film formation mechanism, or by a change in conditions depending on the presence or absence of a reagent. This is considered to be the formation of Zn 2+ by complexation with NH 3 or N 2 H 4 and reaction with 0H—.
  • the reaction mechanism is as follows.
  • Zn (OH) 2 is first deposited by the above reaction process, and is converted to an oxide by annealing.
  • Table 1 summarizes the state of deposition of the thin film when the composition of the reaction solution is different. The unit is mo 1 Z 1. Table 1
  • Solubility product cd S is 5. 01 X 10- 28 [(mo 1 X 1) 2] and very small, by controlling the C d 2+ concentration in the solution is an important factor of the thin film control. Therefore, ammonia NH 3 was used as a complexing agent in order to keep the C d 2+ concentration in the solution below saturation.
  • cd 2+ ion generating species 3 CdS0 4 ⁇ 8H 2 As cd 2+ ion generating species 3 CdS0 4 ⁇ 8H 2 0, S 2 - Using Chio urea SC (NH 2) 2 as an ion generating species. NH 3 dissociates in water into ammonium ion NH 4 + and hydroxide ion OH—, which decomposes SC (NH 2 ) 2 to release S 2 .
  • CdS thin films were prepared and evaluated under several conditions using NH 3 concentration and heating rate as parameters.
  • the film thickness can be controlled by changing the NH 3 concentration. That, 100 m l using a measuring flask 3 CdS0 4 ⁇ 8H 2 0 and 0. 0 1 mo 1 Bruno 1, Chio urea SC (NH 2) 2 and 0. 0 lmo 1/1 and 25 wt.% Of NH 3 1.
  • Omo lZ l [Example 6] 1.2mo 1/1 [Example 7], 1.5mo 1/1 [Example 8], 1.8mo 1/1 [Example 9], 2
  • the solution was weighed to obtain Orno 1/1 (Example 10), and the solution was adjusted. That is, in each of Examples 6 to 10, the concentration of NH 3 is different.
  • the thin film obtained by this method has a light orange color, which is a characteristic color of CdS called force-dummy yellow, and suggests the presence of CdS. Therefore, as a result of phase identification by XRD, CdS, Cd ⁇ and Cd (OH) 2 were confirmed in Examples 6 to 8, CdS was confirmed in Example 9, and very small CdS was observed in Example 10. S was confirmed.
  • the precipitated particles of CdS can be changed by heating. That is, a nucleation reaction occurs on the substrate in response to a rise in temperature, and crystals grow around the nucleus. However, rapid temperature changes encourage more nuclei to form without waiting for crystal growth.
  • the precipitation amount increases as the heating rate decreases. From the observation, the temperature at which the equilibrium between NH 3 and Cd 2 + shifts and film formation starts is 50-60 ° C. The longer the time maintained in this temperature range, the more the crystal grows, It is thought to increase.
  • the thickness and the particle size of the CdS thin film can be controlled by the difference in the NH 3 concentration and the heating rate condition.
  • the element distribution of the cross section of the ZnS thin film formed by the above method was analyzed by transmission electron microscope ( ⁇ ⁇ ) and energy dispersive X-ray analysis (EDX).
  • the thin film was formed by performing deposition for 6 hours three times and then annealing. The outermost surface of the thin film sample was coated with tungsten.
  • FIG. 8 is a ⁇ ⁇ photograph showing the cross-sectional shape of the obtained ZnS thin film
  • FIG. 9 is a E-EDM photograph showing the atomic distribution of ⁇ in FIG. 8
  • FIG. 10 is an SDM photograph in FIG.
  • FIG. 11 is a TEM-EDM photograph showing the atomic distribution of
  • FIG. 11 is a TEM-EDM photograph showing the atomic distribution of 0 in FIG. From FIG. 11, it can be seen that this ZnS thin film contains oxygen atoms.
  • the element distribution of the cross section of the ZnS-CdS thin film formed by the above method was analyzed by transmission electron microscope (TEM) and energy dispersive X-ray analysis (EDX).
  • the thin film was prepared by depositing the CdS thin film three times for 2 to 3 hours on the ZnS thin film obtained by annealing after performing the deposition for 6 hours three times. Formed by annealing. The outermost surface of the thin film sample was coated with tungsten.
  • FIG. 12 is a T ⁇ photograph showing the cross-sectional shape of the obtained ZnS_CdS thin film
  • FIG. 13 is a photograph showing an atomic distribution of ⁇ in FIG. 12
  • FIG. 14 is a photograph.
  • Fig. 15 is a TEM-EDM photograph showing the atomic distribution of Cd in Fig. 12
  • Fig. 15 is a TEM-EDM photograph showing the atomic distribution of S in Fig. 12
  • Fig. 16 is a TEM showing the atomic distribution of O in Fig. 12.
  • this device has a photoreactor 11 made of quartz glass, a hydrogen quantification unit 13 for quantifying the generated hydrogen gas, and a pressure inside the device that increases due to the generation of hydrogen gas.
  • Solution reservoir 15 to prevent light, a 500 W mercury lamp (not shown) for light irradiation, a condenser lens 19 for condensing light 17, and a reflector 21 for irradiating light 17 to the photocatalyst.
  • the operation is as follows: First, the entire system is filled with an aqueous solution of sodium sulfide, the thin-film photocatalyst is settled at the bottom of the photoreaction vessel 11, the gas vent plug 23 is closed, and a 500 W mercury lamp is turned on from the bottom of the vessel 11 In the hydrogen determination section 13, the amount of hydrogen generated is measured at regular irradiation times.
  • the reflecting mirror 21 is for visible to ultraviolet light (Sigma Kogyo TFAH 100-15-0.3)
  • the 500 W mercury lamp is an ultra-high pressure mercury lamp of ⁇ COM BNMO-500 DI
  • the condenser lens is quartz. Was used.
  • the hydrogen generation experiment from aqueous solution using the thin film photocatalyst described above was performed by the CBD method.
  • Examples 1 ZnS3 ⁇ 4 film
  • Examples 2, 4, and 5 Z ⁇ thin film
  • particulate ZnO reference example
  • the experimental results were obtained with the irradiation time taken up to 300 minutes on the horizontal axis and the amount of hydrogen generated at that time taken up to 70 m1 on the vertical axis.
  • the amount of hydrogen generated is almost proportional to the irradiation time.
  • the vehicle was almost on a straight line, indicating that the deterioration of each sample was not so significant.
  • the amount of the Z ⁇ sample used is 50 to 10 Omg.
  • each thin film sample is less than 1 mg. Nevertheless, the thin-film samples produced 50-60% of the fine particles of 50-100 Omg in amount of hydrogen. This indicates that the method of using a thin film and fixing it on a substrate has a much higher photoreaction efficiency than that of particles.
  • the reason for the high efficiency when formed into a thin film is that the photocatalyst is immobilized in a thin film and has a large surface area due to the presence of appropriate irregularities on the surface of the thin film. This is probably because the immobilization on the material improved the efficiency of receiving irradiation light and converting its energy to hydrogen generation.
  • the amount of hydrogen generated per unit time of the ZnS thin film is slightly lower than that of Z ⁇ .
  • One of the causes is considered to be the difference in the surface area of the thin film.
  • Example 4 Among them, i.e. ZnS0 4, thin films prepared in NH 3, N 2 H 4 is to give the highest hydrogen generation amount. This is thought to be due to its crystal structure. However, in each case, the difference in the amount of generated hydrogen is very small, so it is difficult at this stage to determine which thin film generates the most hydrogen.
  • the thickness and grain size of the CdS thin film can be controlled by changing the NH 3 concentration and the heating rate conditions.
  • Light irradiation experiments were performed in Na 2 S solutions adjusted to 0.1 lmo 1/1 using the C d S thin film examples 6 to 10 prepared under various NH 3 concentration conditions, and the results in Fig. 2 were obtained. .
  • a highly active thin-film photocatalyst that is inexpensive and convenient to handle can be provided.
  • this thin-film photocatalyst processes hydrogen sulfide, an environmentally harmful substance, in a simple process without generating harmful substances such as sulfurous acid gas, and efficiently and inexpensively produces sulfur and hydrogen, which are useful for the entire industry. can do.
  • the method for treating hydrogen sulfide using this highly active photocatalyst is applied to the desulfurization step of crude oil and the like, and the method for producing hydrogen, the hydrogen generated by the treatment of hydrogen sulfide can be used again in the desulfurization step. Extremely useful chemicals ⁇ Recycling becomes possible.

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Abstract

L'invention porte sur un photocatalyseur à film mince d'un composé semi-conducteur et sur son procédé de production qui consiste à immerger une base (63) dans une solution (62) contenant une espèce chimique pour un matériau de composé semi-conducteur, et précipiter et immobiliser le composé semi-conducteur sur la surface de la base par dépôt dans un bain de produits chimiques. Au cours de ce procédé, on utilise sélectivement un agent complexant et un agent tampon, et on immerge une base dans une solution contenant une espèce chimique (telle que Zn) de façon à obtenir un précurseur tandis que se poursuit une réaction non uniforme entre la solution et la surface de la base, et un film mince est sélectivement précipité sur la base, ce qui permet d'obtenir un catalyseur optique à film mince tel que ZnS ou ZnO. Un photocatalyseur à film mince est ainsi utilisé pour produire le soufre et l'hydrogène par réaction sur du sulfure d'hydrogène, ce photocatalyseur étant d'une manipulation facile.
PCT/JP2002/013136 2001-12-19 2002-12-16 Photocatalyseur a film mince, son procede de production, procede de traitement du sulfure d'hydrogene utilisant le catalyseur optique a film mince et procede de production de l'hydrogene WO2003051512A1 (fr)

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CN100446855C (zh) * 2007-06-26 2008-12-31 福州大学 复合半导体光催化剂ZnO和ZnS的原位合成及其同步负载方法
WO2012089792A2 (fr) 2010-12-29 2012-07-05 Eni S.P.A. Cellule photoélectrolytique tandem pour la photo-oxydation de sulfures avec la production d'hydrogène

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