TWI317301B - Photocatalyst for reduction of carbon dioxide to produce methanol and its process thereof - Google Patents

Description

1317301 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for preparing a medium supported by tetraoxide, and a method for carrying a light in the indium group oxide. The process of oxidizing and diverting (4) to form methanol in the process of oxidizing the catalyst to oxidize and oxidizing her catalyst is to separate the indium and the oxide of the group as the starting material, and the above two 働f, after grinding, in the _ to (10) (4) Slightly burn between 2 to 24 hours to obtain an indium oxide group, place the indium oxide group in a container, add an aqueous solution of nitric acid, and heat off the excess water after heating in a water bath. When the ratio between c and 1 is 1 to 1 G, the weight ratio of the oxidation/indium tetraoxide group is between 0.3% and 1%, and then hydrogen is used at 300 to 600. 〇: Restore! Up to 1 hour, then use oxygen to oxidize 1S for 5 hours to 15 °' to make the photocatalyst surface have both metallic nickel and oxidized bromine, wherein the indium tetraoxide button is "scale particle diameter, the particle diameter is in the micron to Between 3 microns, and it is crystalline. The present invention also includes a process for carrying out a disulfide reaction at room temperature to 8 Torr, wherein the carbon dioxide reduction process is carried out in a reactor using water and carbon dioxide as raw materials at a reaction temperature of from 1 Torr to 80 Å. (Between: the catalyst used is a catalyst of the indium group series, and the light source used is general sunlight or silk or material light. The method disclosed in the invention prepares a micro photocatalyst containing indium germanium, the particles thereof The diameter is fine in micron, the band gap is 27^, and the indium oxide group is present in the form of crystal brittle. This light touch has high activity for the reduction of visible carbon dioxide to methanol. [Prior Art] In sunlight or visible light Under the excitation, the semiconductor photocatalyst that converts carbon dioxide and water to sterol has been studied. Its towel contains oxygen scale, titanium dioxide, oxygen scale, sulfide, 1317301 gallium phosphide, carbon carbide, titanium-containing γ-type catalyst. Titanium-containing catalysts and copper-containing dioxide catalysts, etc., 'Inoue et al.'s paper Tao, vol. 277, p. 637, Year of the Owl] first revealed the use of oxidized cranes, titanium dioxide 'oxygen scales' Heterogeneous gallium and carbonized material semi-conducting county, each under the illumination of xenon lamps and mercury lamps, 'reducing carbon dioxide and water to methanol, formic acid, caps and trace amounts of methane, H. Yamasita et al. [Catal.Today, pp. 45 volumes, Pp. 221-227, 1998] discloses the preparation of titanium oxide-containing cerium-based media by ion exchange method, the loading capacity of titanium dioxide is uwt%, and the amount of methanol produced by high-counter lamps (wavelength greater than 280 Å) In order to use Tao... g Ikeue et al. [j. Phys. Chem", Vol. 1, pp. __8355, face-to-year] to reveal the preparation of heart-shaped (QH) ray by hydrothermal method, the light intensity is 265_m. 2_ shot, the amount of methanol produced is about 0.71μιηο11ι-νΐ-Ή; Tseng et al. [jc minus, vol. 221, pp. 432-44] the year of preparation of copper containing sol-gel method Titanium dioxide photocatalyst has a copper loading of 2%. Under the irradiation of poly(10)(4), the amount of methanol produced is about Θ 陶 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; The method of synthesizing the scales into methanol; the fine patent 626 lion miscellaneous copper, bismuth, the beginning and the lithium metal are each doped in the oxidized crane, the titanium oxide and the oxygen tilt can be used as the "construction" to form methanol and the light of the system _ The scale handle is a catalyst surface used for the production of methanol by the dioxic water and the formation of amethyst, method, mosquito and patent cap The method and method are different. The invention _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ At temperatures between 50 ° C and 'in the carbon dioxide broth of saturated carbon dioxide, methanol can be successfully produced. [Invention] The present invention is a kind of residual tetra-oxygen-free surface-form preparation green, and the species is carried on 13137301 indium. _ (4) The catalyst is activated by light to react carbon dioxide dissolved in water to form methanol under less than 8 〇〇c, wherein the nickel oxide/tetraoxide catalyst is prepared by using steel and (tetra) oxide as starting materials respectively. , both hook the above two substances, after grinding 'in _ to just. After calcining for 2 to Μ hours between c, an indium tetraoxide group is obtained, and the steel oxide group is placed in a container, and then the aqueous solution of Jujube is added, and the excess water is removed by heating in a water bath, and then When burning 1 to KH, the ratio of 'oxygen/tetraoxide' is between G 3 % and 丨%.

Then use hydrogen to fine to _T嶋i to the time, then use oxygen to reach. C 丨 丨 丨 5 5 5 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿The invention is also included at room temperature (d). q The carbon dioxide reduction reaction is carried out by the above-mentioned catalyst, and the second secret is the same as the catalyst. The catalyst used in the reaction of the raw material is between 1GS8G °C. The catalyst used is the catalyst of the indium bismuth series. The light source is either general sunlight or silk or light. This book also includes a method of generating methanol. When it is tied, it is produced by the sunlight or visible light or the light of each of the light. The indium and the oxides of the group are respectively the trioxide and the five secrets; the solution for generating the methanol reaction is mainly composed of the aqueous solution of hydrogencarbonate, and the pure non-salt solution is introduced to make the dioxins and the solution; The temperature at which the methanol is produced is between 8 and 8 cm.

The implementer ^-L oxime 2.7764 g (10 mmol X purchased from the company), grinding; weighing 4 g (10 mmol) (purchased from Aldrich), grinding; indium oxide The oxidized group was filled with 1317301 in σ, and the indium oxide and oxidation groups were placed in a container at HOG. The enamel was simmered for η hours, and cooled to room temperature to form InTa〇4 powder. The implementer weighed 2.7764 g (10 mmol) (purchased from the company) and grinded it; weighed cerium oxide 4. lion (1G millimolar) (purchased from Merck), ground; Indium oxide is mixed with the oxidation group to grind it, and the indium oxide and the oxidation group are placed in a container, calcined at 1 qing% for 12 hours, and cooled to a temperature of 1.05 g of the prepared indium lanthanum oxide. , placed in a container; weighed nitric acid recorded. 0123 grams 'dissolved in i.0500 ml of pure water, this is a nitrated aqueous solution; the acid nickel is reduced, the ground is dripped on her oxide, and touch Na; a water bath heating method, and timely stirring, to remove excess water on the indium button oxide; under the 35 () % under the simmering hour, the formation of 0.3 wt.% Ni0 / InTa04 powder. Embodiment 3: Φ Weigh 2.7764 g of indium oxide (10 mM X purchased from Merck), grind it; weigh 4.4189 g of yttrium oxide (10 mM X purchased from Merck), grind it; indium oxide Fully mixed with the oxidation group, ground; placed indium oxide and oxidation group in a container, simmered at 11 °c for 12 hours, cooled to room temperature; weighed the prepared oxide 丨.0·克, placed in the capacity; weighed 0.0204 grams of acid, dissolved in L0500 ml of pure water, this is the aqueous solution of the sulphuric acid; the aqueous solution of nitrate was dripped on the indium oxide and continued Mixing; using a water bath heating method, and timely smashing to remove excess water from the indium oxide; when it is burned for a while, 0.5 wt·% Ni0/InTa04 powder is formed. 1317301 Embodiment 4: Privately take indium oxide 2.7764 g (1G millimolar) (purchased from the company), grind it; weigh yttrium oxide λ Λ Λ / Λ ί ί Γ \ , , 4.4 丨 89 g (10 Miller X was purchased from Merck), ground; indium oxide mixed with cerium oxide

The solution is dropped onto the indium lanthanum oxide dropwise, and stirring is continued; using a water bath heating method, and ▼ timely win to remove excess water from the indium group oxide; simmer at 35 〇%] In hours, the l.Owt.% Ni0/InTa04 powder was produced. Embodiment 5: Weigh indium oxide 2. TO4 g (10 m moles from Merck material), grind it; weigh the oxidation group 4 gage 9 g (10 mmol) (purchased from Merck), grind; The oxidized sulphur is mixed with the oxidized group in a sufficient amount and ground; the indium oxide and cerium oxide are placed in a container, and calcined at 11 〇〇〇c for 12 hours, • cooled to room temperature; and the prepared indium bismuth oxide is weighed. 1. 〇5〇〇g, placed in a container; weigh 0.0123g of nickel nitrate, dissolved in 1.0500ml of pure water, this is a nitrate aqueous solution; nickel nitrate aqueous solution, drop by drop indium button oxide On, and continue to stir; use a water bath heating method, and timely stirring 'to remove the excess water from the indium vanadium oxide; after calcining at 350 ° C for 1 hour, it will produce 0.3 wt·% NiO / InTa〇 4 powder; then use hydrogen to reduce at 5 〇〇 0 C for 2 hours, and then oxidize with oxygen at 200 C for 1 hour to produce a metal Ni disk NiO on the surface of the photocatalyst, the composition of which can be NiO (0.3%) / InTa04R500-0200 Said. 11 1317301 Embodiment ϋ Weigh 2.7764 g of indium oxide (1G millimolar) (purchased from Merck), grind it; weigh 4.4189 g (1 〇 mmol) (purchased from the company) 'grinding'; Indium oxide is mixed with the oxidation group to be 'grinded'; indium oxide and antimony oxide are placed in a container, calcined at 11 ° C for 12 hours, cooled to room temperature, and the prepared oxide 丨 is weighed. (4) Q grams, placed in the container; weighed 4 grams of nitric acid recorded in lysium, dissolved in L0500 ml of pure water, this is the acid solution recorded; the aqueous solution of nitrate is dripped on her oxygen record, and the thief Na; the secret method plus _ way, and timely Na, to drive away excess water on the indium button oxide; at 35 () % 煆 煆 , , 即 , , 生成 生成 生成 生成 生成 生成 生成 生成 生成 生成 生成 生成 生成 生成 生成 生成 生成 生成 生成 0.5 生成 0.5 0.5 0.5 0.5 0.5 0.5 Then, using hydrogen gas to reduce at 5 Torr for 2 hours, and then using oxygen to oxidize under the core, when the metal catalyst is produced on the surface of the photocatalyst, the composition can be NiO (0.5%) / InTa04R500-0200 indicates. f Method 7 : Weigh 2.7764 g (10 mmol) of indium oxide (purchased from Merck), grind it; weigh 4.4189 g (10 mmol) (purchased from Merck) for grinding. Indium oxide and the oxidation group are mixed with S 'ground; the indium oxide and oxidation groups are placed in a container, calcined at 1100 〇C for 12 hours, cooled to room temperature; and the prepared indium bismuth oxide 1.0500 g is weighed. , placed in a container; weighed nitric acid recorded. 0409 grams of 'Shibuya in 1.0500 house liters of pure water' this is a nitrated aqueous solution; the nitrated water 'liquid' drops on the indium button oxide And continue to stir; use a water bath to heat the method, and timely mix 'to remove the excess water from the indium oxide; drive at 350 °C for 1 hour, that is, 1. Generate % Ni〇/InTa 〇4 powder; then reduced with hydrogen at 5 〇〇〇c for 2 hours, and then oxidized with oxygen at 200 ° C for 1 hour to produce metal N^NiOx. on the photocatalyst surface,

12 1317301 The composition can be expressed in NiO (1.0%) / InTa04R500-0200. Embodiment 8: The catalyst prepared in Embodiment 1 and 50 ml of a 0.2 M aqueous solution of hydrogencarbonate are placed in a reactor; the reaction system is first washed with carbon dioxide for 60 minutes to remove air in the system, and Saturate the carbon dioxide in an aqueous solution of potassium hydrogencarbonate to make the acid value of the aqueous solution reach 7; turn on the 500W _ sin lamp switch' at this time as the reaction start time (t=〇); the carbon dioxide gas continues to pass the reaction after the reaction starts. System, the liquid produced by the reaction is stored in the reaction system until the reaction time reaches 20 hours; after the reaction is completed, the light source supply is stopped and cooled to room temperature; the sample is loaded into the centrifuge to be centrifuged (Aotemont) HSIANGTAI) After centrifugation for 1 minute, the supernatant was taken out, and the product concentration was analyzed by a gas chromatograph analyzer (China Chromatography 8900). The chromatographic column was analyzed to be 3 m long and the diameter of 1/8 inch was not embroidered. The filler is a p〇rapak q molecular sieve of 6〇 to 8〇 mesh. The reaction results are as follows: time (hours) concentration (ppm) sterol production amount (micromol/gram catalyst) 20 2.365 21.112 Embodiment Q: The catalyst prepared in Embodiment 2 and the 5G milliliter rolling degree are G 2M The aqueous solution of potassium hydrogen hydride is placed in the reactor. • The carbon dioxide is rinsed in the reaction system for (9) minutes to remove the air in the system, and the carbon dioxide is saturated with the aqueous solution of Wei-hydrogen potassium solution to make the water _ 7; open 500W _ prime light switch, this time is set as the reaction start time (four)) carbon dioxide gas in the reaction

13 1317301 After continuous introduction into the reaction system, the liquid produced by the reaction is stored in the reaction system until the reaction time reaches 20 hours. After the reaction is completed, the light source is stopped and cooled to room temperature; the sample is placed in the centrifuge tube. Centrifuge (Utmon HSIANGTAI) for 1 minute, remove the supernatant, analyze the product concentration with a gas chromatograph analyzer (China Chromatography 8900), and analyze the column for 3 cm long. 1/8 inch of non-embroidered steel pipe, filled with p〇rapak q molecular sieve of 60 to 8 mesh. The reaction results are as follows: Time (hours) Concentration (ppm) Methanol production (micromol/gram catalyst) 20 2.259 20.167 Embodiment 10: The catalyst prepared in Embodiment 3 is at a concentration of 50 ml. v[The aqueous solution of potassium hydrogencarbonate is placed in the reactor, and the reaction system is backwashed with an emulsified stone for 60 minutes to remove the air in the system, and the dioxide is saturated in the aqueous solution of hydrogencarbonate to make the acid of the aqueous solution. The test value reaches 7; the 500W halogen lamp switch is turned on' at this time as the reaction start time (t=0); the carbon dioxide gas continues to pass into the reaction system after the reaction starts, and the liquid generated by the reaction is stored in the reaction system until the reaction The time is up to 20 hours; after the reaction is completed, the light source is stopped and cooled to room temperature; the sample is placed in a centrifuge tube, centrifuged for 1 minute with a centrifuge (Utmon HSIANGTAI), and the supernatant liquid is taken out to obtain a gas chromatography layer. The concentration of the product was analyzed by an analyzer (China Chromatography 8900). The chromatographic column was analyzed to be 3 m long, 1/8 inch diameter non-embroidered steel tube, and the filling was a Porapak Q molecular sieve of 60 to 80 mesh.

14 1317301 The reaction results are as follows: Time (hours) Concentration (ppm) Methanol production (micromol/gram catalyst) 20 2.677 23.900 Embodiment Ή : The catalyst prepared in Embodiment 4 is 50 liters in concentration. 2] V [the potassium hydrogen sulphate aqueous solution is placed in the reactor, the reaction system is first rinsed with two emulsified stones for 60 minutes to remove the air in the system, and an emulsified carbon is saturated in the aqueous solution of hydrogencarbonate, so that The acid value of the aqueous solution reaches 7; the 500W halogen lamp switch is turned on' at this time as the reaction start time (t=〇); the carbon dioxide gas continues to pass into the reaction system after the reaction starts, and the liquid generated by the reaction is stored in the reaction system. After the reaction time is up to 20 hours; after the reaction is completed, the lamp source supply is stopped and cooled to room temperature; the sample is placed in a centrifuge tube, centrifuged for 1 minute with a centrifuge (Utmon HSIANGTAI), and the supernatant liquid is taken out to the gas. The concentration of the product was analyzed by a phase chromatography analyzer (China Chromatography 8900). The chromatographic column was analyzed to be a 3 mm long, 1/8 inch diameter non-embroidered steel tube, and the filling was a Porapak Q molecular sieve of 60 to 8 mesh. The reaction results are as follows: Time (hours) Concentration (PPm) Methanol production (micromol/gram catalyst) 20 3.040 27.145 Embodiment 12: The catalyst prepared in Embodiment 5 and 50 ml of carbonic acid having a concentration of 0.2 M Potassium hydrogen solution

15 1317301

In the reactor; first flush the reaction system with carbon dioxide for 6G minutes to remove the air in the system, and make the carbon monoxide saturated in the aqueous solution of potassium hydrogen carbonate, so that the acidity of the aqueous solution reaches 7; open the 500W _ The reaction start time (t=G); the carbon dioxide gas continues to pass into the reaction system after the start of the reaction, and the liquid produced by the reaction is stored in the reaction system until the reaction time reaches 20 hours; after the reaction is completed, the lamp supply is stopped. And cooled to room temperature; the sample was placed in a centrifuge tube, centrifuged for 10 minutes in a centrifuge (Utmon HSIANGTAI), the supernatant was taken out, and the product concentration was analyzed by a gas chromatograph analyzer (China Chromatography). The column is 3 meters long, 1/8 inch diameter is not embroidered steel pipe, and the filling is p〇rapakq molecular sieve of 6〇 to 8〇 mesh. The reaction results are as follows: Time (hours) Concentration (ppm) Methanol production (micromol/gram catalyst)

Embodiment 13:

The medium prepared in Embodiment 6 and 5 liters of 2M aqueous solution of carbonic acid deficiency are placed in the reactor; the carbon dioxide is washed with carbon dioxide for 6 minutes to remove the secret air, and the carbon dioxide is saturated. Hydrogen potassium water and towel, so that the value of the aqueous solution is 7; open the 500W tooth light switch 'this time is set as the reaction start time (4)); carbon dioxide gas continues to be privately reactive after the reaction starts, and the counter-touch produces (4) bribes The reaction is assisted until the reaction time reaches 2G hours. 'After the reaction is completed, 'the lamp source is stopped, and cooled to room temperature; the sample is placed in a centrifuge tube'. Centrifuge (Utmon HSIANGTAI) for ω minutes, and the supernatant is removed. 16 1317301 The product concentration was analyzed by Gas Chromatography Analyzer (China Chromatography 8900). The chromatographic column was analyzed to be 3 m long, 1/8 inch diameter non-embroidered steel tube, and the filling was 60 to 80 mesh. p〇rapakQ molecular sieve. The reaction results are as follows: Time (hours) Concentration (ppm) The amount of sterol produced (micromolecule/gram catalyst) 20 2.867 25.601 Embodiment 14: The catalyst prepared in Embodiment 7 and the concentration of 50 ml are 〇, 2M The potassium bicarbonate aqueous solution is placed in the reactor; the reaction system is first flushed with carbon dioxide for 60 minutes to remove the air in the system, and the carbon dioxide is saturated in the aqueous potassium hydrogen sulphate solution to make the pH value of the aqueous solution reach 7; The 500W halogen lamp switch is set to the reaction start time (t=〇); the carbon dioxide gas continues to pass into the reaction system after the reaction starts, and the liquid generated by the reaction is stored in the reaction system until the reaction time reaches 20 hours; After completion, 'stop the light source supply and cool to room temperature; put the sample into the centrifuge tube, centrifuge with a centrifuge (Ottomon HSIANGTAI) for 1 minute, remove the supernatant, and use a gas chromatograph analyzer (Chinese chromatography) 8900) Analyze the product concentration. The chromatographic column was analyzed as a 3 m long '1/8 inch diameter non-embroidered steel tube, and the filling was a Pompak Q molecular sieve of 60 to 80 mesh. The reaction results are as follows: Time concentration Methanol production amount (hours) (ppm) (micromol/gram catalyst) 17 1317301 20 3.123 27.880 The reaction results of the above embodiments are shown in the following table; from these results, the catalyst of the present invention was confirmed at room temperature. Under, it can effectively produce sterols.

EXAMPLES Reaction time (hours) Methanol production (micromoles/hour•gram catalyst) 8 20 1.056 9 20 1.008 10 20 1.195 11 20 1.357 12 20 1.100 13 20 1.280 14 20 1.394

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Claims (1)

1317301 L X. Patent Application Range: L—a method for producing a nickel catalyst supported on indium lanthanum tetraoxide, which comprises starting an oxide of cerium; using an oxide of a button as a starting material; mixing the above two The substance 'grinds, from 900 to 1400. (: between 2 and 24 hours, get indium tetraoxide; put indium tin oxide in a container, add nickel nitrate aqueous solution, and remove excess water by water bath heating, at 300 to 500 °C Heat for 1 to 1 hour, so that the weight of nickel oxide is between 〇3 % and 1% of the total catalyst weight; then reduce it with hydrogen for 1 to 10 hours between 300 and 600 〇C, and then use oxygen or air. The oxidation is carried out at room temperature to 150 to 300 ° C for 1 to 5 hours. 2. The method of claim 1, wherein the weight ratio of nickel oxide is preferably between 0.5 and "%". a method for methanol, which comprises reacting with a nickel oxide/indium oxide group catalyst under irradiation of sunlight or visible light or ultraviolet light at a temperature of 1 Torr to 8 〇〇c to form methanol, which is characterized by indium tetraoxide. The button is a photocatalyst, and carbon dioxide is used as a reactant in a potassium hydrogencarbonate or sodium hydroxide aqueous solution, which is prepared by a. using an oxide of indium as a starting material; b. using a group of oxides as a starting material; c. Mixing the above two materials, grinding, and calcining between 9 (8) and just % for 2 to Μ hours, Indium oxide group; d. Nickel aqueous solution, and heated in a water bath for a few hours, so that the weight of nickel oxide is all placed in the container, then add nitric acid to drive away excess water, then heat at 350 °C 1 Between 0.3% and 1% of the weight of the catalyst; 19 1317301 e. Reduction with hydrogen at 500oC for 2 hours, then oxidation with oxygen for 2 hours between 2 °c f. Place the indium tetraoxide in the reactor, add potassium bicarbonate solution, and pass the dioxide The gas was allowed to saturate in an aqueous solution at 10 to 8 Torr for 1 hour. (: Irradiation between sunlight, visible light or ultraviolet light. 4. The method of claim 3, wherein the ratio of nickel is preferably between 0.5% and 1%. 20