CN111905771A - Preparation method of catalyst for modifying cuprous oxide with different crystal faces by selenium - Google Patents
Preparation method of catalyst for modifying cuprous oxide with different crystal faces by selenium Download PDFInfo
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- CN111905771A CN111905771A CN202010808847.8A CN202010808847A CN111905771A CN 111905771 A CN111905771 A CN 111905771A CN 202010808847 A CN202010808847 A CN 202010808847A CN 111905771 A CN111905771 A CN 111905771A
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- 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
- B01J27/057—Selenium or tellurium; Compounds thereof
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention discloses a preparation method of a catalyst for modifying cuprous oxide with different crystal faces by selenium, which comprises the following steps: weighing Cu2O and selenium powder are flatly paved at two ends of the magnetic boat, and then the magnetic boat is placed in a tube furnace for selenizing, thus obtaining the catalyst of the invention. The invention modifies selenium in Cu with different crystal faces2On O, the adsorption of Cu to OCHO is changed, and in addition, the side reaction is inhibited due to the doping of selenium, and finally, the Faraday efficiency of HCOOH is obviously improved. At the same time, pioneering study of Cu2The influence of selenization of different crystal planes of O on the Faraday efficiency of HCOOH, so that the crystal plane with the highest Faraday efficiency of HCOOH is obtained.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method of a catalyst for modifying cuprous oxide with different crystal faces by selenium.
Background
In recent years, the global face of an increasingly serious energy crisis due to the reduction of fossil energy, and further, it is widely considered that CO generated by combustion of fossil energy2Is the main cause of greenhouse effect. Therefore, new energy is developed to replace fossil energy and CO in the atmosphere is reduced2The content of (b) is currently a primary task. Research shows that under the action of catalyst, CO is produced2Can be converted into various reduction products, and therefore, research on the catalyst is hot. Among the numerous catalysts, the metal Cu is of great interest because Cu is the only one that can convert CO2Catalysts for reduction to various hydrocarbon products have problems of poor selectivity and reaction efficiency. Thus, improving the selectivity of the product is electrochemical reduction of CO2The first research task of (1). Among the numerous hydrocarbon products, formic acid is of great interest as a renewable clean energy source. However, the formic acid selectivity of Cu-based catalysts is too low to meet the needs of people. Therefore, it is an important research content to improve the selectivity of formic acid. Research shows that the Cu base modified by selenium can improve the yield of formic acid, and in addition, the influence of different crystal faces on formic acid selectivity is also reported, but the improvement effect is not obvious. Therefore, the invention creatively provides a method for modifying Cu with different crystal faces by selenium2O (hexahedron, octahedron) method for improving yield of formic acid, and effectively improves CO2Yield of formic acid produced by reduction.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst for modifying cuprous oxide with different crystal faces by selenium, wherein the selenium modification is carried out on different crystal faces, so that CO is improved2The selectivity of formic acid in the reduction process solves the problem of CO2The yield of formic acid is low in the reduction process.
The technical scheme of the invention is as follows: a preparation method of a catalyst for modifying cuprous oxide with different crystal faces by selenium comprises the following steps:
weighing Cu2O and selenium powder are flatly paved at two ends of the magnetic boat, and then the magnetic boat is placed in a tube furnace for selenizing, thus obtaining the catalyst of the invention.
The technical solution adopted by the invention is also characterized in that,
Cu2the mass ratio of the O to the selenium powder is 1: 1.5-3.
Cu2O may be hexahedron or octahedron.
The selenizing atmosphere in the selenizing process is Ar: h2The ratio of the carbon dioxide to the carbon dioxide is 9-12: 1, the temperature is 25-360 ℃, and the temperature rise reaction time is 90-100 min.
And introducing argon into the magnetic boat for 15-20 min before selenization.
The invention has the beneficial effects that: the preparation method can be used for treating Cu with different crystal faces2The selenium modification of O changes the adsorption of Cu to OCHO after the selenium is added, and in addition, the side reaction is inhibited due to the doping of the selenium, and finally, the Faraday efficiency of HCOOH is obviously improved. Meanwhile, the invention pioneers the research of Cu2The influence of selenization of different crystal planes of O on the Faraday efficiency of HCOOH, so that the crystal plane with the highest Faraday efficiency of HCOOH is obtained.
Drawings
FIG. 1 is a hexahedral Cu selenide in example 2 of the present invention2O and heat treating Cu at the same temperature2O catalyst in CO2A comparison graph of the faradaic efficiency of formic acid under different reduction potentials in the reduction process;
FIG. 2 shows selenized octahedral Cu in example 5 of the present invention2O and heat treating Cu at the same temperature2O catalyst in CO2Graph comparing faradaic efficiency for formic acid at different reduction potentials during reduction.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
A preparation method of a catalyst for modifying cuprous oxide with different crystal faces by selenium specifically comprises the following steps:
pre-prepared hexahedral Cu2O and selenium powder are flatly paved at two ends of the magnetic boat according to the proportion of 1 (1.5-3), then the magnetic boat is placed in a tube furnace for selenylation, and the selenylation atmosphere is Ar: h21 in the formula (9-12), due to the presence of H2Therefore, Ar gas is introduced for 15-20 min before selenization to exhaust the tube typeAir in the furnace, preventing explosion. And during selenizing, the temperature is 25-360 ℃, and the heating reaction time is 90-100 min, so that the catalyst disclosed by the invention is obtained.
A preparation method of a catalyst for modifying cuprous oxide with different crystal faces by selenium specifically comprises the following steps:
pre-prepared octahedral Cu2O and selenium powder are flatly paved at two ends of the magnetic boat according to the proportion of (1:1.5) -3, then the magnetic boat is placed in a tube furnace for selenizing, and the selenizing atmosphere is Ar: h21 in the formula (9-12), due to the presence of H2Therefore, Ar gas is introduced for 15-20 min before selenization so as to exhaust the air in the tube furnace and prevent explosion. And during selenizing, the temperature is 25-360 ℃, and the heating reaction time is 90-100 min, so that the catalyst disclosed by the invention is obtained.
Comparative example 1 hexahedral Cu2O heat treatment for preparing the catalyst:
pre-prepared hexahedral Cu2O is flatly laid in a magnetic boat and put into a tube furnace for heat treatment, and the treatment process is as follows: ar gas was introduced for 20min before the heat treatment to evacuate the air in the tube furnace to prevent explosion. The heat treatment atmosphere is Ar: h2The catalyst is obtained by heating at 360 ℃ for 100min, wherein the temperature is 12: 1.
Comparative example 2 octahedral Cu2O heat treatment for preparing the catalyst:
pre-prepared octahedral Cu2O is flatly laid in a magnetic boat and put into a tube furnace for heat treatment, and the treatment process is as follows: ar gas was introduced for 20min before the heat treatment to evacuate the air in the tube furnace to prevent explosion. The heat treatment atmosphere is Ar: h2The catalyst is obtained by heating at 360 ℃ for 100min, wherein the temperature is 12: 1.
Embodiment 1, a method for preparing a catalyst for modifying cuprous oxide with different crystal faces by selenium, specifically comprising the following steps:
pre-prepared hexahedral Cu2O and selenium powder are flatly paved at two ends of a magnetic boat according to the proportion of 1:1.5, then the magnetic boat is placed in a tube furnace for selenylation, and the selenylation atmosphere is Ar: h29:1, is prepared fromIn the presence of H2Therefore, argon gas is introduced for 15min before selenization to exhaust the air in the tube furnace, so as to prevent explosion. When the selenization is carried out, the temperature is 25 ℃, and the temperature-rising reaction time is 90min, thus obtaining the catalyst of the invention.
Embodiment 2, a method for preparing a catalyst for modifying cuprous oxide with different crystal faces by selenium, which comprises the following steps:
pre-prepared hexahedral Cu2O and selenium powder are flatly paved at two ends of a magnetic boat according to the proportion of 1:3, then the magnetic boat is placed in a tube furnace for selenylation, and the selenylation atmosphere is Ar: h212:1 due to the presence of H2Therefore, argon gas is introduced for 20min before selenization to exhaust the air in the tube furnace, so as to prevent explosion. During selenization, the temperature is 360 ℃, and the temperature-rising reaction time is 100min, thus obtaining the catalyst of the invention.
Embodiment 3, a method for preparing a catalyst for modifying cuprous oxide with different crystal faces by selenium, which comprises the following steps:
pre-prepared hexahedral Cu2O and selenium powder are flatly paved at two ends of a magnetic boat according to the proportion of 1:2, then the magnetic boat is placed in a tube furnace for selenylation, and the selenylation atmosphere is Ar: h210:1 due to the presence of H2Therefore, argon gas is introduced for 15min before selenization to exhaust the air in the tube furnace, so as to prevent explosion. During selenization, the temperature is 180 ℃, and the temperature rise reaction time is 95min, thus obtaining the catalyst of the invention.
Embodiment 4, a method for preparing a catalyst for modifying cuprous oxide with different crystal faces by selenium, which comprises the following steps:
pre-prepared octahedral Cu2O and selenium powder are flatly paved at two ends of a magnetic boat according to the proportion of 1:1.5, then the magnetic boat is placed in a tube furnace for selenylation, and the selenylation atmosphere is Ar: h29:1 due to the presence of H2Therefore, argon gas is introduced for 15min before selenization to exhaust the air in the tube furnace, so as to prevent explosion. When the selenization is carried out, the temperature is 50 ℃, and the temperature rise reaction time is 90min, thus obtaining the catalyst of the invention.
Embodiment 5, a method for preparing a catalyst for modifying cuprous oxide with different crystal faces by selenium, which comprises the following steps:
pre-prepared octahedral Cu2O and selenium powder are flatly paved at two ends of a magnetic boat according to the proportion of 1:3, then the magnetic boat is placed in a tube furnace for selenylation, and the selenylation atmosphere is Ar: h212:1 due to the presence of H2Therefore, argon gas is introduced for 20min before selenization to exhaust the air in the tube furnace, so as to prevent explosion. During selenization, the temperature is 360 ℃, and the temperature-rising reaction time is 100min, thus obtaining the catalyst of the invention.
Embodiment 6, a method for preparing a catalyst for modifying cuprous oxide with different crystal faces by selenium, which comprises the following steps:
pre-prepared octahedral Cu2O and selenium powder are flatly paved at two ends of a magnetic boat according to the proportion of 1:2, then the magnetic boat is placed in a tube furnace for selenylation, and the selenylation atmosphere is Ar: h210:1 due to the presence of H2Therefore, argon gas is introduced for 15min before selenization to exhaust the air in the tube furnace, so as to prevent explosion. During selenization, the temperature is 180 ℃, and the temperature rise reaction time is 95min, thus obtaining the catalyst of the invention.
Selenized hexahedral Cu prepared in example 2 of the present invention2O catalyst and selenized octahedral Cu prepared in example 52O catalyst, Heat treated Cu prepared in comparative examples 1 and 22O catalyst to CO2The research on the electrochemical reduction performance is carried out in a two-chamber three-electrode reaction device, and the detection of the reduction product HCOOH is realized by using a nuclear magnetic resonance spectrometer. Of these, comparative examples 1 and 2 are for the purpose of excluding the influence of heat treatment on the catalyst. FIG. 1 is a selenated hexahedral Cu prepared in example 2 of the present invention2O, Heat-treated hexahedral Cu prepared in comparative example 12Faradaic efficiency comparison of O versus HCOOH, as can be seen from fig. 1: comparative heat treated hexahedral Cu2O, selenized Cu2The hexahedron O is capable of producing significant FE of HCOOH at-0.85V reduction potential, up to 12%. FIG. 2 shows the selenized Cu prepared in example 5 of the present invention2O octahedron, Heat treated Cu prepared in comparative example 22Faraday efficiency of O octahedra versus HCOOH, shown in FIG. 2, compared to that of OoctahedraTreated octahedral Cu2O, selenized octahedron, reaches the maximum FE of HCOOH at 0.95V reduction potential, 9.2%. Comparing hexahedral and octahedral Cu2O, which shows that different crystal faces can obviously change the product selectivity after being selenized, and hexahedral Cu2O has the greatest faraday efficiency of HCOOH.
The principle of the invention is as follows: the Cu with different crystal faces modified by selenium prepared by the invention2Compared with an undoped catalyst, the O catalyst changes the adsorption of Cu to OCHO after adding selenium, so that the Faraday efficiency of HCOOH is obviously improved, and CO2Side reactions during the reduction are also suppressed because of the selenium doping. In particular, the different crystal planes Cu are selected in a targeted manner2Selenization was performed on O to study the effect of selenium doping on HCOOH yield. Obtaining hexahedral Cu2O has the best HCOOH selectivity performance.
The invention provides a preparation method of a catalyst for modifying cuprous oxide with different crystal faces by selenium, which effectively improves CO2Formic acid yield in the reduction reaction. For CO2The improvement of the selectivity of formic acid in the reduction process is generally realized by the modes of morphology, oxidation state, addition of a second metal and the like, because the strategies can change the electronic structure of the reaction, thereby influencing the selectivity of formic acid. However, the faradaic efficiency of formic acid is still insufficient for human needs. Therefore, there is a need to develop a catalyst that can significantly improve the faradaic efficiency of formic acid. The invention pioneers the research on Cu with different crystal faces2Effect of O (hexahedral, octahedral) selenization on formic acid selectivity, of which hexahedral, octahedral are more suitable for CO2Reduction reaction, and research shows that selenium modification has certain promotion effect on the generation of formic acid. During the selenization reaction, the set selenization atmosphere is (9-12): 1, because hydrogen is a reducing atmosphere and can form H with selenium2Selenium, further and Cu2And O reacts, the concentration is different, and the reaction degree is different. The catalyst prepared by the method can obviously improve the selectivity of the formic acid product.
Claims (5)
1. A preparation method of a catalyst for modifying cuprous oxide with different crystal faces by selenium is characterized by comprising the following steps:
weighing Cu2O and selenium powder are flatly paved at two ends of the magnetic boat, and then the magnetic boat is placed in a tube furnace for selenizing, thus obtaining the catalyst of the invention.
2. The preparation method of the catalyst for modifying cuprous oxide with different crystal faces by selenium according to claim 1, wherein said Cu is2The mass ratio of the O to the selenium powder is 1: 1.5-3.
3. The preparation method of the catalyst for modifying cuprous oxide with different crystal faces by selenium according to claim 1, wherein said Cu is2O may be hexahedron or octahedron.
4. The preparation method of the catalyst for modifying cuprous oxide with different crystal faces by selenium according to claim 1, wherein the selenization atmosphere in the selenization process is Ar: h2The ratio of the carbon dioxide to the carbon dioxide is 9-12: 1, the temperature is 25-360 ℃, and the temperature rise reaction time is 90-100 min.
5. The preparation method of the catalyst for modifying cuprous oxide with different crystal faces by selenium according to claim 1, wherein argon is introduced into the magnetic boat for 15-20 min before selenization.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196982A (en) * | 2021-11-12 | 2022-03-18 | 西安理工大学 | For electrocatalysis of CO2Process for preparing reduced CuSe catalysts |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012197199A (en) * | 2011-03-22 | 2012-10-18 | Dowa Electronics Materials Co Ltd | Copper selenide particle powder, and method for producing the same |
| WO2013178035A1 (en) * | 2012-05-28 | 2013-12-05 | 广东先导稀材股份有限公司 | Cuprous selenide preparation method |
| US20140339072A1 (en) * | 2013-05-17 | 2014-11-20 | Sunpower Technologies Llc | Photocatalytic CO2 Reduction System |
| CN107308959A (en) * | 2017-07-18 | 2017-11-03 | 安徽师范大学 | Cu2‑xSe nanometer sheet array foams carbon/carbon-copper composite material, preparation method and application |
| CN107519899A (en) * | 2017-10-11 | 2017-12-29 | 陕西科技大学 | A kind of selenizing cobalt catalyst and its preparation method and application |
| WO2018119543A1 (en) * | 2016-12-29 | 2018-07-05 | Pontificia Universidad Catolica De Chile | Method for producing a cu2o/tio2 nanoparticle catalyst, and cu2o/tio2 nanoparticle catalyst |
| CN110280277A (en) * | 2019-07-17 | 2019-09-27 | 肇庆市华师大光电产业研究院 | A kind of carbon dioxide electrochemical reduction catalyst and preparation method thereof |
| CN110694649A (en) * | 2019-11-11 | 2020-01-17 | 南昌航空大学 | Preparation method of copper selenide/titanium dioxide loaded visible light photocatalyst composite material |
-
2020
- 2020-08-12 CN CN202010808847.8A patent/CN111905771B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012197199A (en) * | 2011-03-22 | 2012-10-18 | Dowa Electronics Materials Co Ltd | Copper selenide particle powder, and method for producing the same |
| WO2013178035A1 (en) * | 2012-05-28 | 2013-12-05 | 广东先导稀材股份有限公司 | Cuprous selenide preparation method |
| US20140339072A1 (en) * | 2013-05-17 | 2014-11-20 | Sunpower Technologies Llc | Photocatalytic CO2 Reduction System |
| WO2018119543A1 (en) * | 2016-12-29 | 2018-07-05 | Pontificia Universidad Catolica De Chile | Method for producing a cu2o/tio2 nanoparticle catalyst, and cu2o/tio2 nanoparticle catalyst |
| CN107308959A (en) * | 2017-07-18 | 2017-11-03 | 安徽师范大学 | Cu2‑xSe nanometer sheet array foams carbon/carbon-copper composite material, preparation method and application |
| CN107519899A (en) * | 2017-10-11 | 2017-12-29 | 陕西科技大学 | A kind of selenizing cobalt catalyst and its preparation method and application |
| CN110280277A (en) * | 2019-07-17 | 2019-09-27 | 肇庆市华师大光电产业研究院 | A kind of carbon dioxide electrochemical reduction catalyst and preparation method thereof |
| CN110694649A (en) * | 2019-11-11 | 2020-01-17 | 南昌航空大学 | Preparation method of copper selenide/titanium dioxide loaded visible light photocatalyst composite material |
Non-Patent Citations (1)
| Title |
|---|
| 刘苏莉: ""金属和金属硫属化合物纳米晶的可控合成及其电催化性能研究"", 《中国优秀博硕士学位论文全文数据库（博士） 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196982A (en) * | 2021-11-12 | 2022-03-18 | 西安理工大学 | For electrocatalysis of CO2Process for preparing reduced CuSe catalysts |
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