WO2000004993A1 - Photocatalyseur pour la transformation du methane, procede de preparation de ce photocatalyseur et procede de preparation d'hydrates de carbone inferieurs a l'aide de celui-ci - Google Patents

Photocatalyseur pour la transformation du methane, procede de preparation de ce photocatalyseur et procede de preparation d'hydrates de carbone inferieurs a l'aide de celui-ci Download PDF

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Publication number
WO2000004993A1
WO2000004993A1 PCT/KR1998/000224 KR9800224W WO0004993A1 WO 2000004993 A1 WO2000004993 A1 WO 2000004993A1 KR 9800224 W KR9800224 W KR 9800224W WO 0004993 A1 WO0004993 A1 WO 0004993A1
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photocatalyst
methane
sintering process
hours
metal
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PCT/KR1998/000224
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English (en)
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Dae Chul Park
Sang Yoon Lim
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Korea Research Institute Of Chemical Technology
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Priority to PCT/KR1998/000224 priority Critical patent/WO2000004993A1/fr
Publication of WO2000004993A1 publication Critical patent/WO2000004993A1/fr

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    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/48—Silver or gold
    • C07C2523/50—Silver
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/04—Sulfides

Definitions

  • the present invention relates, in general, to a novel photocatalyst for methane conversion reaction and, more particularly, to a photoreaction in which low carbohydrates, such as ethylene, ethane and propane, can be efficiently and economically prepared from methane in the presence of a photocatalyst. Also, the present invention is concerned with a method for preparing the photocatalyst and with a method for preparing low carbohydrates using the photocatalyst.
  • Natural gas consists mainly of methane.
  • the structure of this compound is thermodynamically very stable so that it is not easily broken. Nonetheless, much effort is made to activate methane, that is, to break the bond between the constituents, carbon and hydrogens, with the aim of preparing various carbohydrates therefrom.
  • methane that is, to break the bond between the constituents, carbon and hydrogens
  • methanol, ethanol, formaldehyde, ethane, ethylene, propane and aromatic carbohydrates which are and will be used as indispensable chemical raw materials, may be prepared by activating methane. For this reason, various studies have actively made on the activation of methane, directed mainly to ethylene production.
  • the conventional coupling reaction has a significant problem of being effective only at a high temperature ranging from approximately 600 to 800 °C.
  • the facility and energy invested in producing the desired products through the conventional coupling reaction increase in cost relative to the high temperature required.
  • the high temperatures cause the production of a large quantity of pollution, such as carbon dioxide.
  • the products of the coupling reaction e.g. ethane and ethylene
  • the activity of the reaction catalyst used is usually restricted to 10 % or so and hence, the selectivity thereof is low, as well. Consequently, the conventional method has every reason to be improved.
  • ethylene is produced from petroleum refining fractions by a thermal cracking process, which also requires a temperature of 800 °C or higher as in the coupling reaction of methane, so that there is still a problem of high cost for the facility and energy.
  • the thermal cracking process is advantageous owing to its capability of large-scale production provided that petroleum is abundant and cost- competitive .
  • an object of the present invention to overcome the aforementioned problems and to provide a photocatalyst for converting methane, which is activated at ordinary temperature and atmospheric pressure by artificial light, such as uv light. It is another object of the present invention to provide a method for preparing low carbohydrates, such as ethylene, ethane, propane, etc, from methane at low costs without causing the production of pollution of the environment.
  • the present invention which resulted from the intensive and thorough research of the present inventors, is based on the finding that a precious metal, selected from Pd, Ir, Ru, Cd, Cu, Ag and Pt, can play a spectacular role as a photocatalytically active ingredient when it is impregnated in a support, selected from ZnS, CdS and Ti0 2 . Illumination of artificial light upon a homogeneous suspension of the photocatalyst and methane in water can generate low carbohydrates, such as ethane, ethylene and propane, without difficulty at 5-55 °C under a pressure of a vacuum to 5 atm. Accordingly, in an aspect of the present invention, there is provided a photocatalyst, represented by the following formula III:
  • M stands for a metal selected from the group consisting of Pd, Ir, Ru, Cd, Ag and Pt
  • S stands for a support selected from the group consisting of ZnS (Zn:S 1:1 molar ratio), CdS (Cd:S 1:1 molar ratio) and Ti0 2 (anatase type)
  • A represents the amount of the M impregnated, ranging from 0.50 to 3.50 weight % based on the total weight of the photocatalyst (M+A) .
  • a method for preparing a photocatalyst in which a solution of a metal (M) in water is added with a support in such a way that the amount of the metal ranges from 0.50 to 3.50 weight % based on the total weight of the metal and the support, stirred for 18-30 hours at 40-70 °C, dried for 20-28 hours at 80-200 °C and sintered at 250-550 °C.
  • M metal
  • a method for preparing low carbohydrates in which a suspension of the photocatalyst in water is added with a sufficient amount of methane with stirring, and irradiated with artificial light, such as uv light, at 5-55 °C under a pressure of a vacuum-5 at .
  • the present invention pertains to a photocatalyst which can efficiently convert methane into low carbohydrates.
  • the photocatalyst consists of an inorganic active ingredient and a support, in accordance with the present invention.
  • the inorganic active ingredient is selected from the group consisting of palladium, iridium, ruthenium, cadmium, copper, argentum and platinum.
  • the support it is selected from the group consisting of zinc sulfide, cadmium sulfide and titan dioxide.
  • zinc sulfide and cadmium sulfide are preferably comprised of a 1:1 molar ratio of Zn:S and Cd:S, respectively.
  • Preferable titan dioxide is an anatase type.
  • the most preferable in the support group is titan dioxide in light of the experiment data which showed that the ZnS, CdS and Ti0 2 photosupports have a methane conversion rate of 0.0053%, 0.0045% and 0.0120%, respectively.
  • the present invention also pertains to preparation of the photocatalyst.
  • a selected, active metal is mixed with a selected support in such a way that the metal is present at an amount of 0.50-3.50 weight % based on the total weight of the metal and the support.
  • the resulting mixture is stirred for 18-30 hours at 40-70 °C.
  • a sintering process one of the following routes may be taken:
  • Examples of the salts containing the photocatalytically active metals include CuCl 2 -2H 2 0, RuCl 3 -xH 2 0, AgN0 3 , PdCl 2 , IrCl 3 -xHCl-yH 2 0, CdCl 2 -2.5H 2 0 and H 2 PtCl 5 -xH 2 0.
  • the active metal M is preferably impregnated at an amount of approximately 0.50-3.50 weight % based on the total weight of the photocatalyst and most preferably at an amount of approximately 2.00 weight %.
  • the present invention also pertains to a photoreaction in the preparation of the photocatalyst.
  • a suspension of the photocatalyst in water is added with a sufficient amount of methane with stirring.
  • the resulting suspension is irradiated with artificial light, such as uv light, to produce ethane, ethylene and propane.
  • the photoreactor is maintained at a temperature of 5-55 °C and at a pressure of a vacuum to 5 atm and preferably at room temperature and ordinary pressure.
  • the title catalyst was prepared in a similar manner to that of Preparation Example I, except that a solution of 0.095 g of iridium chloride ( IrCl 3 'xHCl -yH 2 0) in 60 cc of water was added to 3.047 g of completely dried titan dioxide (anatase type) .
  • the title catalyst was prepared in a similar manner to that of Preparation Example I, except that a solution of 0.095 g of ruthenium chloride (RuCl 3 -xHCl) in 60 cc of water was added to 3.047 g of completely dried titan dioxide (anatase type) .
  • the title catalyst was prepared in a similar manner to that of Preparation Example I, except that a solution of 0.248 g of cadmium chloride (CdCl 2 ⁇ 2.5HC1) in 60 cc of water was added to 6.093 g of completely dried titan dioxide (anatase type) .
  • the title catalyst was prepared in a similar manner to that of Preparation Example I, except that a solution of 0.096 g of cadmium chloride (AgN0 ) in 60 cc of water was added to 3.047 g of completely dried titan dioxide (anatase type).
  • An artificial uv light source was installed in a reactor 500 cc in volume of a photoreaction system 805 cc in volume, to distribute the light sufficiently and uniformly in the reactor while heat was insulated by cooling water.
  • a reactor which could circulate its internal air, 500 cc of purified water and 1 g of each of the partially oxidized palladium, platinum, iridium, ruthenium, cadmium, copper and silver catalysts which were prepared via the sintering process A of Preparation Example I, were charged.
  • the atmosphere of the reaction system was substituted with methane by feeding for 30 min. Then, the air current inside the photoreaction system was isolated from the exterior and uv light was radiated at 25 °C under an ordinary pressure.
  • the products of the above photoreaction were quantitatively analyzed via gas chromatography (1/8 x 6'/st.st., chromosoph 102, FID, N 2 ) .
  • the compositions of the products were found to be dependent on the synthesized catalysts, and are given in Table I, below.
  • Rh/Ti0 2 photocatalyst was prepared in a similar manner to the sintering process A of Preparation Example I (partial oxidation at 500 °C without any air flow) , except for using a solution of 0.248 g of rhodium chloride (RhCl , ⁇ xH 2 0) , instead of palladium chloride, in 60 cc of water. Using 1 g of this partially oxidized photocatalyst, the procedure of Example I was repeated to produce products. The composition of the products is given in Table 1, below. Table 1 Products Converted from Methane by Partially Oxidized Catalysts
  • a cobalt photocatalyst was prepared in a similar manner to the sintering process B of Preparation Example I (oxidation at 500 °C with an air flow at 50 seem) , except for using a solution of 0.603 g of cobalt nitrate (Co (N0 3 ) 2 - 6H 2 0) , instead of palladium chloride, in 60 cc of water. Using 1 g of this completely oxidized cobalt catalyst, the procedure of Example I was repeated to produce products whose composition is given in Table 2, below.
  • a zinc catalyst was prepared in a similar manner to the sintering process C of Preparation Example I (sintering at 300 °C with an air flow at 50 seem, followed by reducing at 300 °C with a hydrogen flow of 50 seem) , except for using a solution of 0.555 g of zinc nitrate (Zn (N0 3 ) 2 ⁇ 6H 2 0) , instead of palladium chloride, in 60 cc of water. Using 1 g of this completely reduced zinc catalyst, the procedure of Example I was repeated to produce products whose composition is given in Table 3, below.
  • An iron catalyst was prepared in a similar manner to the sintering process C of Preparation Example I (sintering at 300 °C with an air flow at 50 seem, followed by reducing at 300 °C with a hydrogen flow of 50 seem) , except for using a solution of 0.883 g of ferric nitrate (Fe (N0 3 ) 3 ⁇ 9H 2 0) , instead of palladium chloride, in 60 cc of water. Using 1 g of this completely reduced zinc catalyst, the procedure of Example I was repeated to produce products whose composition is given in Table 3, below. Table 3 Products Converted from Methane by Completely Reduced Catalysts
  • the photocatalysts according to the present invention have an ability to photo-activate methane at efficiencies which had been not yet accomplished by conventional catalysts. Consequently, in the presence of the photocatalysts, methane can be converted into low carbohydrates, such as ethylene, ethane and propane, at low costs without causing the production of pollution of the environment .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un photocatalyseur dont la composition correspond à la formule (III) M(A)/T, et qui permet de transformer le méthane en hydrates de carbone inférieurs avec une grande efficacité et sans polluer l'environnement. M représente un métal choisi dans le groupe comprenant Pd, Ir, Ru, Cd, Ag et Pt, tandis que T représente un excipient choisi dans le groupe comprenant ZnS (pour un rapport molaire Zn : S de 1 : 1), CdS (pour un rapport molaire Cd : S de 1 : 1) et TiO2. A représente quant à lui la quantité de M imprégnée et varie de 0,50 à 3,50 % en poids par rapport au poids total du photocatalyseur (M+A). Un sel de métal, comprenant un métal ayant une action catalytique, est dissous dans de l'eau puis mélangé à l'excipient séché de sorte que le métal soit présent dans une quantité allant de 0,50 à 3,50 % en poids par rapport au poids total du métal et de l'excipient. La suspension est mélangée de manière homogène, complètement séchée puis frittée de manière à préparer le photocatalyseur. L'application d'une lumière artificielle sur une suspension homogène du photocatalyseur et de méthane dans l'eau permet de former des hydrates de carbone inférieurs tel que de l'éthane, de l'éthylène et du propane, ceci sans difficulté aucune, à des températures allant de 5 à 55° C et à une pression sous vide allant jusqu'à 5 atm.
PCT/KR1998/000224 1998-07-23 1998-07-23 Photocatalyseur pour la transformation du methane, procede de preparation de ce photocatalyseur et procede de preparation d'hydrates de carbone inferieurs a l'aide de celui-ci WO2000004993A1 (fr)

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PCT/KR1998/000224 WO2000004993A1 (fr) 1998-07-23 1998-07-23 Photocatalyseur pour la transformation du methane, procede de preparation de ce photocatalyseur et procede de preparation d'hydrates de carbone inferieurs a l'aide de celui-ci

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PCT/KR1998/000224 WO2000004993A1 (fr) 1998-07-23 1998-07-23 Photocatalyseur pour la transformation du methane, procede de preparation de ce photocatalyseur et procede de preparation d'hydrates de carbone inferieurs a l'aide de celui-ci

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Cited By (10)

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JP2004255243A (ja) * 2003-02-24 2004-09-16 Sundecor:Kk 光触媒の製造方法、光触媒および気体浄化装置
WO2005003035A2 (fr) * 2003-07-04 2005-01-13 Showa Denko K.K. Sol contenant du dioxyde de titane, film mince forme a partir de ce sol et processus de fabrication dudit sol
CN100351013C (zh) * 2006-02-27 2007-11-28 西安交通大学 CdS/Ti－MCM－41载铂光催化剂及制备方法
CN102872885A (zh) * 2012-10-18 2013-01-16 中国科学技术大学 一种可见光响应型光催化剂及其制备方法
CN111167492A (zh) * 2018-11-12 2020-05-19 中国科学院上海硅酸盐研究所 铜修饰氮化碳及其制备方法和光催化甲烷转化的应用
CN112517082A (zh) * 2021-01-18 2021-03-19 福州大学 一种有机金属化合物修饰无机半导体复合光催化剂及其制备方法和应用
CN114133313A (zh) * 2021-12-03 2022-03-04 中国科学技术大学 一种基于单原子催化剂进行甲烷无氧偶联制备乙烷的方法
CN114591130A (zh) * 2020-12-07 2022-06-07 中国科学院大连化学物理研究所 一种光催化甲烷水相偶联的方法
CN115397554A (zh) * 2020-04-01 2022-11-25 威纳特德国有限公司 基于ZnS的光催化活性颗粒材料、其制备方法及用途
CN116217332A (zh) * 2021-12-06 2023-06-06 中国科学院大连化学物理研究所 一种光催化甲烷脱氢偶联的方法

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EP0486951A2 (fr) * 1990-11-19 1992-05-27 Hughes Aircraft Company Méthode catalytique pour prévenir la formation de dépôts dans des cellules Raman à méthane
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WO2005003035A2 (fr) * 2003-07-04 2005-01-13 Showa Denko K.K. Sol contenant du dioxyde de titane, film mince forme a partir de ce sol et processus de fabrication dudit sol
WO2005003035A3 (fr) * 2003-07-04 2005-03-31 Showa Denko Kk Sol contenant du dioxyde de titane, film mince forme a partir de ce sol et processus de fabrication dudit sol
CN100351013C (zh) * 2006-02-27 2007-11-28 西安交通大学 CdS/Ti－MCM－41载铂光催化剂及制备方法
CN102872885A (zh) * 2012-10-18 2013-01-16 中国科学技术大学 一种可见光响应型光催化剂及其制备方法
CN102872885B (zh) * 2012-10-18 2014-11-26 中国科学技术大学 一种可见光响应型光催化剂及其制备方法
CN111167492A (zh) * 2018-11-12 2020-05-19 中国科学院上海硅酸盐研究所 铜修饰氮化碳及其制备方法和光催化甲烷转化的应用
CN111167492B (zh) * 2018-11-12 2022-12-13 中国科学院上海硅酸盐研究所 铜修饰氮化碳及其制备方法和光催化甲烷转化的应用
CN115397554A (zh) * 2020-04-01 2022-11-25 威纳特德国有限公司 基于ZnS的光催化活性颗粒材料、其制备方法及用途
CN114591130A (zh) * 2020-12-07 2022-06-07 中国科学院大连化学物理研究所 一种光催化甲烷水相偶联的方法
CN112517082A (zh) * 2021-01-18 2021-03-19 福州大学 一种有机金属化合物修饰无机半导体复合光催化剂及其制备方法和应用
CN112517082B (zh) * 2021-01-18 2022-04-12 福州大学 一种有机金属化合物修饰无机半导体复合光催化剂及其制备方法和应用
CN114133313A (zh) * 2021-12-03 2022-03-04 中国科学技术大学 一种基于单原子催化剂进行甲烷无氧偶联制备乙烷的方法
CN114133313B (zh) * 2021-12-03 2023-03-10 中国科学技术大学 一种基于单原子催化剂进行甲烷无氧偶联制备乙烷的方法
CN116217332A (zh) * 2021-12-06 2023-06-06 中国科学院大连化学物理研究所 一种光催化甲烷脱氢偶联的方法

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