CN110721716A - Catalysis of CO2Selective hydrogenation to CH4And a process for preparing the same - Google Patents
Catalysis of CO2Selective hydrogenation to CH4And a process for preparing the same Download PDFInfo
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Abstract
The invention relates to a catalyst, in particular to a catalyst for catalyzing CO2Selective hydrogenation to CH4And a process for preparing the same. The preparation method comprises the following steps: dissolving tetrabutyl titanate in an ethanol solution, dropwise adding the solution into a urea-containing solution to obtain a mixed solution, evaporating the mixed solution, and calcining the evaporated mixed solution at 350-500 ℃ to obtain N-TiO2Dispersing in deionized water, adding chloroplatinic acid solution, stirring, evaporating, and purifying in H2Carrying out reduction reaction in gas at 300-400 ℃ for 2-4 h to obtain Pt/N-TiO2. The invention prepares Pt/N-TiO2Will be used as a catalyst in promoting CO2Hydrogenation to CH4The use of (1). The introduction of the N element improves the electron density of the surface of the Pt metal nano particle contacted with the N element, so that the Pt metal nano particle is opposite to CO2The adsorption of the intermediate product CO of the hydrogenation reaction is enhanced, which is beneficial to generating CH4Increase CH4While improving the stability of the catalyst.
Description
Technical Field
The invention relates to a catalyst, in particular to a catalyst for catalyzing selective hydrogenation of CO2 to generate CH4 and a preparation method thereof.
Background
Due to the use of fossil fuels such as coal, petroleum and natural gas, a great deal of CO is released2And the greenhouse gases cause global temperature rise, which leads to a series of environmental problems such as sea level rise, drought, frequent flood disasters and the like. Meanwhile, with the rapid development of economy and society in China, the demand of fossil energy is increasingly increased. With the increasing exhaustion of fossil energy, China must develop new energy substances to meet the increasing energy consumption demand and ecological environment requirement of people. Wherein CO is passed through2The hydrogenation reaction can lead CO to2Conversion to CO, CH4、CH3OH and other energy substances which can not only reduce CO in the atmosphere2The concentration of the (D) can be converted into a novel energy substance, and the (D) has important significance in relieving energy crisis and protecting environment. Wherein CH4As a fuel with a higher calorific value has been more and more introduced into the lives of people, CH is therefore4The preparation of (A) has important significance.
Pt/TiO2Is catalyzing CO2A catalyst commonly used in hydrogenation reactions has been studied in large quantities due to its high conversion efficiency. With Pt/TiO2CO for catalyst2Hydrogenation reactions, the hydrogenation products of which are predominantly CH4And CO. Due to CH4Has been increasingly concerned by researchers, and thus how to increase the CH content of the product4The selectivity of (a) is a problem which needs to be solved. Researchers have increased CH in products by various means4Selectivity of (2). Zhang et al reduce CO by increasing Pt loading2Activation energy of methanation, thereby increasing CH in the product4Selectivity of (2). Zhang et al by introducing La2O3To increase the basic sites of the catalyst while promoting PtStability of metal nanoparticles to increase CH in product4Selectivity of (2). However, these methods have some disadvantages such as complicated catalyst synthesis process, easy deactivation of the catalyst, etc., which greatly limit the wide application of these catalysts, and thus new methods and materials for increasing CO have been sought2CH in hydrogenation reaction product4The selectivity of (a) is very urgent.
Disclosure of Invention
Technical problem to be solved
To solve the above problems of the prior art, the present invention provides a pair CH4Catalytic CO with better selectivity and stability2Selective hydrogenation to CH4The catalyst of (4) and a process for preparing the same;
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
catalytic CO2Selective hydrogenation to CH4The method for preparing a catalyst of (1), which comprises the following steps carried out in this order:
s1 into N-TiO2
Dissolving tetrabutyl titanate in an ethanol solution, dropwise adding the solution into a urea-containing solution to obtain a mixed solution, stirring for 2-4 h, evaporating to obtain white powder, and calcining at 350-500 ℃ to obtain N-TiO2;
S2 preparation of Pt/N-TiO2
The obtained N-TiO is subjected to2Dispersing in deionized water, adding a chloroplatinic acid solution, stirring for 2-4 h, and evaporating to obtain gray powder; mixing the gray powder with H2Pt/N-TiO obtained by reduction reaction in gas at 300-400 ℃ for 2-4 h2Namely the catalyst.
Further, in step S1, the volume/weight ratio of the tetrabutyl titanate to the urea is: 1-5 ml: 40 mg; dissolving tetrabutyl titanate and ethanol according to the volume ratio of 1-5: 10; the urea content of the urea-comprising solution was 2 mg/ml.
Further, in step S1, tetrabutyl titanate is dissolved in the ethanol solution and then stirred for 20-40 min.
Further, in step S1, the evaporation temperature is 100 ℃, and the calcination time is 1-3 hours.
Further, in step S2, N-TiO2The concentration of the dispersion after dispersion in deionized water is 0.5-2 mg/ml; the concentration of the chloroplatinic acid solution is 0.01 mol/L; h2H in gas2And N2The volume ratio of the components is 1: 8-12.
The invention also provides a method for catalyzing CO according to any one of the schemes2Selective hydrogenation to CH4The Pt/N-TiO prepared by the method for preparing the catalyst2。
The present invention provides a Pt/N-TiO compound according to any of the above aspects2As catalyst in promoting CO2Hydrogenation to CH4The use of (1).
Specifically, 0.1 to 0.4 weight part of Pt/N-TiO2Fully mixing with 1-1.5 parts by weight of quartz sand, filling into a reaction device, and adding CO2/H2And filling the/Ar (3/12/85) mixed gas into the reaction system, and finishing the reaction after reacting for 3-10 h.
The invention firstly prepares the N-TiO by a sol-gel method2Then wet precipitation and H2Synthesizing Pt/N-TiO in the reduction process2A catalyst. N atoms may be incorporated into TiO2Thereby changing the TiO lattice2The physicochemical properties of (a). Wherein the electronegativity of N atom is weaker, the adsorption strength of the N atom to electrons on the surface of the Pt metal nano particle contacted with the N atom is reduced, and the electron density on the surface of the Pt metal nano particle is improved, and the carbon dioxide (CO) is generated2The adsorption of the intermediate product CO and the further hydrogenation reaction to generate CH are facilitated in the hydrogenation reaction4Thereby achieving the purpose of increasing CH in the product4The purpose of selectivity. Meanwhile, the introduction of N can strengthen the carrier N-TiO2The contact between the catalyst and Pt inhibits the agglomeration of Pt metal nano particles in the reaction process, thereby improving the stability of the catalyst. Therefore, the invention can better overcome Pt/TiO2Catalyst for catalyzing CO2CH in hydrogenation reaction product4Low selectivity and stable catalystPoor in performance, and constructing novel CO2The hydrogenation catalyst has important guiding significance.
(III) advantageous effects
The invention has the beneficial effects that:
1. the invention synthesizes Pt/N-TiO2The method is simple and easy to implement, good in repeatability, considerable in yield and wide in application prospect.
2. The invention introduces N element to improve the electron density of the surface of the Pt metal nano particle contacted with the N element, so that the N element can react with CO2The adsorption of the hydrogenation reaction intermediate product CO is enhanced, thereby being beneficial to further hydrogenating the intermediate product to generate CH4Increasing CH in the product4Selectivity of (2).
3. The invention is in relation to catalyzing CO2CH in hydrogenation reaction product4The conventional Pt/TiO with the defects of low selectivity, poor stability and the like2Catalyst, p-CH4Has stronger selectivity and stability.
Drawings
FIG. 1 shows Pt/N-TiO of the present invention2XRD contrast pattern with other substances;
FIG. 2 shows Pt/N-TiO of the present invention2H with other substances2-TPR curve versus graph;
FIG. 3 shows Pt/N-TiO of the present invention2Catalytic CO with other substances2Generating a comparison graph of CO;
FIG. 4 shows Pt/N-TiO of the present invention2Catalytic CO with other substances2Generating CH4A comparison graph of (A);
FIG. 5 shows Pt/TiO2In CO2In-situ infrared spectrograms of the hydrogenation reaction process at different temperatures;
FIG. 6 shows Pt/N-TiO2In CO2In-situ infrared spectrograms of the hydrogenation reaction process at different temperatures;
FIG. 7 shows Pt/TiO2In CO2CO and CH formation in each round of the cyclic reaction4A schematic of the amounts;
FIG. 8 shows Pt/N-TiO2In CO2CO and CH formation in each round of the cyclic reaction4A schematic of the amounts;
FIG. 9 shows Pt/TiO after recycle reaction2The particle size of Pt metal nanoparticles on the surface of the catalyst;
FIG. 10 shows Pt/N-TiO after the recycle reaction2The particle size of Pt metal nanoparticles on the surface of the catalyst.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
Catalytic CO2Selective hydrogenation to CH4The method for preparing a catalyst of (1), which comprises the following steps carried out in this order:
s1 into N-TiO2
Dissolving 5-25 ml of tetrabutyl titanate in 10-250 ml of ethanol solution, stirring for 20-40 min, dropwise adding the solution into 100ml of urea-containing solution with the urea content of 200mg, stirring for 2-4 h, evaporating at 100 ℃ to obtain white powder, and calcining at 350-500 ℃ for 1-3 h to obtain N-TiO2;
S2 preparation of Pt/N-TiO2
The obtained N-TiO is subjected to2Dispersing in deionized water to obtain a solution with the concentration of 0.5-2 mg/ml, adding 0.3-0.6 ml of 0.01mol/L chloroplatinic acid solution, stirring for 2-4 h, and evaporating to obtain gray powder; mixing the gray powder with H2And N2Carrying out reduction reaction in mixed gas with the volume ratio of 1: 8-12 at the temperature of 300-400 ℃ for 2-4 h to obtain Pt/N-TiO2I.e. to catalyze CO2Selective hydrogenation to CH4The catalyst of (1).
The invention also provides Pt/N-TiO prepared by the preparation method2。
The invention relates to Pt/N-TiO2Will be used as a catalyst in promoting CO2Hydrogenation to CH4The use of (1). 0.1 to 0.4 weight part of Pt/N-TiO2Fully mixing with 1-1.5 parts by weight of quartz sand, filling into a reaction device, and adding CO2/H2And filling the/Ar (3/12/85) mixed gas into the reaction system, and finishing the reaction after reacting for 3-10 h.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
Catalysis of CO2Selective hydrogenation to CH4The method for preparing the catalyst comprises the following steps:
s1 into N-TiO2
S11, dissolving 5ml of tetrabutyl titanate in 10ml of ethanol solution, dropwise adding the tetrabutyl titanate into 100ml of urea-containing solution with the urea content of 200mg after stirring for 20min, continuously stirring for 2h, and evaporating at 100 ℃ to obtain white powder; calcining the obtained white powder at 350 ℃ for 1h to obtain N-TiO2;
S2 preparation of Pt/N-TiO2: the obtained 100mgN-TiO2Dispersing in 100ml of deionized water, adding 0.3ml of 0.01mol/L chloroplatinic acid solution, stirring for 2 hours, and evaporating the solution to obtain gray powder; mixing the gray powder with H2And N2Reducing the mixed gas with the volume ratio of 1: 8-12 at 300 ℃ for 2h to obtain Pt/N-TiO2I.e. to catalyze CO2Selective hydrogenation to CH4The catalyst of (1).
Example 2
Catalysis of CO2Selective hydrogenation to CH4The catalyst of (1), comprising the steps of:
s1 into N-TiO2:
S11, dissolving 15ml of tetrabutyl titanate in 50 ethanol solution, dropwise adding the tetrabutyl titanate into 100ml of urea-containing solution with the urea content of 200mg after stirring for 30min, continuously stirring for 3h, and evaporating to obtain white powder; calcining the obtained white powder at 450 ℃ for 2h to obtain N-TiO2;
S2 preparation of Pt/N-TiO2: the obtained 100mgN-TiO2Dispersing in 100ml of deionized water, adding 0.5ml of 0.01mol/L chloroplatinic acid solution, stirring for 3 hours, and evaporating the solution to obtain gray powder; mixing the gray powder with H2And N2Reducing the mixed gas with the volume ratio of 1:10 at 350 ℃ for 3h to obtain Pt/N-TiO2I.e. to catalyze CO2Selective hydrogenation to CH4The catalyst of (1).
Example 3
Catalysis of CO2Selective hydrogenation to CH4The method for preparing the catalyst comprises the following steps:
s1 into N-TiO2
S11, dissolving 25ml of tetrabutyl titanate in 250ml of ethanol solution, dropwise adding the tetrabutyl titanate into 100ml of urea-containing solution with the urea content of 200mg after stirring for 40min, continuously stirring for 4h, and evaporating at 100 ℃ to obtain white powder; calcining the obtained white powder at 500 ℃ for 3h to obtain N-TiO2;
S2 preparation of Pt/N-TiO2: the obtained 200mgN-TiO2Dispersing in 100ml of deionized water, adding 0.6ml of 0.01mol/L chloroplatinic acid solution, stirring for 4 hours, and evaporating the solution to obtain gray powder; mixing the gray powder with H2And N2Reducing the Pt/N-TiO in mixed gas with the volume ratio of 1:12 for 4 hours at the temperature of 400 DEG C2I.e. to catalyze CO2Selective hydrogenation to CH4The catalyst of (1).
Example 4
Catalysis of CO2Selective hydrogenation to CH4The method for preparing the catalyst comprises the following steps:
s1 into N-TiO2
S11, dissolving 25ml of tetrabutyl titanate in 220ml of ethanol solution, dropwise adding the tetrabutyl titanate into 100ml of urea-containing solution with the urea content of 200mg after stirring for 22min, continuously stirring for 4h, and evaporating at 100 ℃ to obtain white powder; calcining the obtained white powder at 390 ℃ for 1h to obtain N-TiO2;
S2 preparation of Pt/N-TiO2: the obtained 50mgN-TiO2Dispersing in 100ml of deionized water, adding 0.5ml of 0.01mol/L chloroplatinic acid solution, stirring for 4 hours, and evaporating the solution to obtain gray powder; mixing the gray powder with H2And N2Reducing the Pt/N-TiO in mixed gas with the volume ratio of 1:11 for 2 hours at 380 DEG C2I.e. to catalyze CO2Selective hydrogenation to CH4The catalyst of (1).
Example 5
Catalysis of CO2Selective hydrogenation to CH4The process for the preparation of the catalyst of (1),which comprises the following steps:
s1 into N-TiO2
S11, dissolving 10ml of tetrabutyl titanate in 230ml of ethanol solution, dropwise adding the tetrabutyl titanate into 100ml of urea-containing solution with the urea content of 200mg after stirring for 35min, continuously stirring for 2h, and evaporating at 100 ℃ to obtain white powder; calcining the obtained white powder at 500 ℃ for 2h to obtain N-TiO2;
S2 preparation of Pt/N-TiO2: the obtained 130mgN-TiO2Dispersing in 100ml of deionized water, adding 0.4ml of 0.01mol/L chloroplatinic acid solution, stirring for 2 hours, and evaporating the solution to obtain gray powder; the Pt/N-TiO obtained by the way that gray powder is treated in mixed gas of H2 and N2 with the volume ratio of 1:12 at the temperature of 420 ℃ for 2 hours2I.e. to catalyze CO2Selective hydrogenation to CH4The catalyst of (1).
Example 6
Catalysis of CO2Selective hydrogenation to CH4The method for preparing the catalyst comprises the following steps:
s1 into N-TiO2
S1, dissolving 18ml of tetrabutyl titanate in 90ml of ethanol solution, dropwise adding the tetrabutyl titanate into 100ml of urea-containing solution with the urea content of 200mg after stirring for 38min, continuously stirring for 2.5h, and evaporating at 100 ℃ to obtain white powder; calcining the obtained white powder at 360 ℃ for 3h to obtain N-TiO2;
S2 preparation of Pt/N-TiO2: the obtained 130mgN-TiO2Dispersing in 100ml of deionized water, adding 0.4ml of 0.01mol/L chloroplatinic acid solution, stirring for 3 hours, and evaporating the solution to obtain gray powder; the gray powder is in H2And N2Reducing the Pt/N-TiO in mixed gas with the volume ratio of 1:9 at 310 ℃ for 4h to obtain the Pt/N-TiO2I.e. to catalyze CO2Selective hydrogenation to CH4The catalyst of (1).
Example 7
TiO prepared in example 12、N-TiO2、
Pt/N-TiO2And Pt/TiO2The powders were respectively tested to obtain the results shown in FIG. 1The XRD patterns are described; as can be seen from FIG. 1, the prepared Pt/N-TiO2XRD diffraction peak and TiO of powder2Are consistent, wherein diffraction peaks at 25.1,37.8,47.9,53.8,55.0,62.4,70.1 and 75.5 ° are attributed to anatase TiO2(JCPDS. No. 01-071-. Diffraction peaks at 30.6,42.3 and 68.9 degrees were assigned to brookite TiO2(JCPDS. No. 01-076-. However, no diffraction peak corresponding to the Pt species was found in the XRD pattern, which may be due to the low content of Pt.
Example 8
The Pt/N-TiO obtained in example 22And Pt/TiO2、TiO2、N-TiO2
The respective reduction temperatures were measured to obtain H shown in FIG. 22-TPR curve. Figure 2 results in that the reduction temperature of the Pt species increased from 105 ℃ to 109 ℃ with the introduction of N atoms, which indicates that the introduction of N atoms can enhance the contact between Pt and the support, thereby increasing the reduction temperature of the Pt species.
Example 9
Pt/N-TiO2Will act as a catalyst to promote CO2Hydrogenation to CH4The method comprises the following steps:
0.4 part by weight of Pt/N-TiO prepared in example 12Fully mixing with 1.1 weight part of quartz sand, filling into a reaction device, and adding CO2/H2the/Ar (3/12/85) mixed gas is filled into the reaction system, and the reaction is finished after 3 hours of reaction at 300 ℃. In the reaction process, detecting CO and CH by using Aglient7820 chromatography4The reaction activity was measured and samples were taken at intervals of 30 min. And mixing Pt/TiO2CO was carried out under the same conditions as above2Hydrogenation reaction, and separately determining CO and CH4To evaluate the respective reactivity, the results are shown in fig. 3 and 4.
As can be seen from FIGS. 3 and 4, the Pt/N-TiO compound is used2And Pt/TiO2CO for catalyst2The yield of CO in the products of the hydrogenation reaction is not basically different. But when Pt/N-TiO is used2When the catalyst is used, the product contains CH4Improved by 2.4 times, which indicates that introduction of N favors CH4The selectivity is improved. The CO yield gradually decreases with increasing reaction time, while CH4The yield of (2) was gradually increased, which also indicates that CO is CO2Intermediate products of the methanation process.
Example 10
Pt/N-TiO2Will act as a catalyst to promote CO2Hydrogenation to CH4The method comprises the following steps:
0.3 part by weight of Pt/N-TiO prepared in example 32And then the mixture is fully mixed with 1.2 parts by weight of quartz sand and then filled into an infrared reaction device. Respectively testing infrared absorption spectra at 50 deg.C, 100 deg.C, 150 deg.C, 170 deg.C, 190 deg.C, 200 deg.C, 210 deg.C, 220 deg.C, 230 deg.C, 240 deg.C and 250 deg.C, and respectively measuring the in-situ infrared spectra with Pt/TiO as shown in FIG. 62The reaction was performed under the same conditions as in the comparative experiment, and the results were measured as in-situ IR spectra shown in FIG. 5.
As can be seen from FIGS. 5 and 6, in Pt/TiO2On the surface of the catalyst, the infrared absorption peak corresponding to Pt-CO completely disappears at 230 ℃. In Pt/N-TiO2The disappearance temperature of the infrared absorption peak corresponding to Pt — CO increased to 250 ℃. This result shows that the introduction of N can enhance the CO to Pt metal nanoparticles2The adsorption strength of the hydrogenation intermediate product CO is favorable for further hydrogenation reaction of CO to generate CH4。
Example 11
Pt/N-TiO2Will act as a catalyst to promote CO2Hydrogenation to CH4The method comprises the following steps:
0.2 part by weight of Pt/N-TiO prepared in example 42Fully mixing with 1.2 parts by weight of quartz sand, filling into a reaction device, and adding CO2/H2the/Ar (3/12/85) mixed gas is filled into the reaction system and reacts for 5 hours at 350 ℃ to finish the reaction. In the reaction process, detecting CO and CH by using Aglient7820 chromatography4The reaction activity was measured and samples were taken at intervals of 30 min. After the reaction is finishedPt/N-TiO of2The above steps were repeated again to circulate the reaction 4 times, and the results of the respective measurements are shown in FIG. 8, and the TEM test was performed on the reacted catalyst, and the results of the test are shown in FIG. 10. Pt/TiO 22Catalyst in CO2A comparative experiment was carried out in the hydrogenation cycle. The measurement results are shown in FIGS. 7 and 9, respectively.
FIG. 7 shows Pt/TiO after 4 cycles of experiments2Catalysis of CO2The total conversion of the hydrogenation reaction was reduced by 39.2%. When Pt/N-TiO is used2In the case of a catalyst (as shown in FIG. 8), CO2The total conversion of the hydrogenation reaction is reduced by only 29.2%. TEM test is carried out on the catalyst after the cyclic reaction, and the result of particle size statistical analysis shows that Pt/TiO2The growth of Pt metal nanoparticles on the catalyst surface was 4.15nm (as shown in FIG. 9), while Pt/N-TiO2The surface Pt metal nanoparticles grew only to 3.45nm (as shown in fig. 10). The result shows that the introduction of N can inhibit the agglomeration of Pt metal nanoparticles on the surface of the catalyst, thereby improving the stability of the catalyst.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (6)
1. Catalytic CO2Selective hydrogenation to CH4The method for preparing the catalyst is characterized by comprising the following steps of:
s1 into N-TiO2
Dissolving tetrabutyl titanate in an ethanol solution, dropwise adding the solution into a urea-containing solution to obtain a mixed solution, stirring for 2-4 h, evaporating to obtain white powder, and calcining at 350-500 ℃ to obtain N-TiO2;
S2 preparation of Pt/N-TiO2
The obtained N-TiO is subjected to2Dispersing in deionized water, adding chlorineStirring the platinum acid solution for 2-4 h, and evaporating to obtain gray powder; mixing the gray powder with H2Pt/N-TiO obtained by reduction reaction in gas at 300-400 ℃ for 2-4 h2Namely the catalyst.
2. Catalytic CO according to claim 12Selective hydrogenation to CH4The method for preparing the catalyst of (1), which is characterized in that: in step S1, the tetrabutyl titanate and urea are in a volume/weight ratio of: 1-5 ml: 40 mg; dissolving tetrabutyl titanate and ethanol according to the volume ratio of 1-5: 10; the urea content of the urea-comprising solution was 2 mg/ml.
3. Catalytic CO according to claim 12Selective hydrogenation to CH4The method for preparing the catalyst of (1), which is characterized in that: in step S1, tetrabutyl titanate is dissolved in the ethanol solution and then stirred for 20-40 min.
4. Catalytic CO according to claim 12Selective hydrogenation to CH4The method for preparing the catalyst of (1), which is characterized in that: in the step S1, the evaporation temperature is 100 ℃, and the calcination time is 1-3 h.
5. Catalytic CO according to claim 12Selective hydrogenation to CH4The method for preparing the catalyst of (1), which is characterized in that: in step S2, N-TiO2The concentration of the solution after dissolving in deionized water is 0.5-2 mg/ml; the concentration of the chloroplatinic acid solution is 0.01 mol/L; h2H in gas2And N2The volume ratio of the components is 1: 8-12.
6. A catalytic CO according to any one of claims 1 to 52Selective hydrogenation to CH4The catalyst prepared by the method can obtain Pt/N-TiO2。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102211033A (en) * | 2011-04-15 | 2011-10-12 | 中国林业科学研究院林产化学工业研究所 | Method for preparing platinum and nitrogen codoped active carbon supported titanium dioxide photocatalyst |
US20140274669A1 (en) * | 2013-03-12 | 2014-09-18 | National Yunlin University Of Science & Technology | Catalytic Article and Method for Preparing the Same |
CN106807399A (en) * | 2017-02-27 | 2017-06-09 | 华中科技大学 | Selective deposition has the preparation method of the titanium deoxide catalyst of Mock gold particle |
CN108722464A (en) * | 2018-05-29 | 2018-11-02 | 福州大学 | It is a kind of using nitrogen-doped titanium dioxide as Pd triple effect low temperature catalysts of carrier and its preparation method and application |
-
2019
- 2019-09-25 CN CN201910908452.2A patent/CN110721716A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102211033A (en) * | 2011-04-15 | 2011-10-12 | 中国林业科学研究院林产化学工业研究所 | Method for preparing platinum and nitrogen codoped active carbon supported titanium dioxide photocatalyst |
US20140274669A1 (en) * | 2013-03-12 | 2014-09-18 | National Yunlin University Of Science & Technology | Catalytic Article and Method for Preparing the Same |
CN106807399A (en) * | 2017-02-27 | 2017-06-09 | 华中科技大学 | Selective deposition has the preparation method of the titanium deoxide catalyst of Mock gold particle |
CN108722464A (en) * | 2018-05-29 | 2018-11-02 | 福州大学 | It is a kind of using nitrogen-doped titanium dioxide as Pd triple effect low temperature catalysts of carrier and its preparation method and application |
Non-Patent Citations (3)
Title |
---|
CHEN XIAODONG ET AL: "Catalytic performance of the Pt/TiO2 catalysts in reverse water gas shift reaction: Controlled product selectivity and a mechanism study", 《CATALYSIS TODAY》 * |
郝瑞鹏等: "贵金属负载TiO_2对光催化还原CO_2选择性的影响", 《燃料化学学报》 * |
陈术清: "加热和光照条件下Ru/TiO2催化二氧化碳甲烷化研究", 《无机材料学报》 * |
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---|---|---|---|---|
CN114797918A (en) * | 2022-05-30 | 2022-07-29 | 安徽工业大学 | Titanium dioxide-based hydrogenation catalyst material and preparation method and application thereof |
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