CN113492004A - Method for efficiently manufacturing oxygen vacancy on surface of metal oxide catalyst - Google Patents
Method for efficiently manufacturing oxygen vacancy on surface of metal oxide catalyst Download PDFInfo
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- CN113492004A CN113492004A CN202010270029.7A CN202010270029A CN113492004A CN 113492004 A CN113492004 A CN 113492004A CN 202010270029 A CN202010270029 A CN 202010270029A CN 113492004 A CN113492004 A CN 113492004A
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- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
-
- B01J35/39—
-
- B01J35/50—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
Abstract
The invention discloses a method for efficiently manufacturing oxygen vacancies on the surface of a metal oxide catalyst, which comprises the steps of stirring the metal oxide catalyst in an acid solution with the concentration of 0.01-5M for a period of time at a certain temperature, separating and drying the metal oxide catalyst, and annealing the metal oxide catalyst at the temperature of 50-250 ℃ for 10 minutes-5 hours to obtain the metal oxide catalyst with the oxygen vacancies on the surface.
Description
Technical Field
The invention relates to a method for efficiently manufacturing a vacancy on the surface of a catalyst, in particular to a method for efficiently manufacturing an oxygen vacancy on the surface of a metal oxide catalyst, belonging to the technical field of environmental materials.
Background
With the development of modern industry, many environmental problems are increasingly prominent and need to be solved. Among them, the greenhouse effect caused by the greenhouse gas released by the combustion of a large amount of coal, oil and natural gas draws wide attention and attention of various countries. CO 22How to effectively capture, absorb and convert CO as one of the main greenhouse gases2To slow down and improve the greenhouse effect is one of the important directions of the current great research efforts. CO 22The catalytic conversion as a process for realizing carbon cycle, not only can reduce CO2While reducing CO to some extent2The total amount of emissions.
At present, CO2Photocatalytic reductants are mainly classified into metals and their oxides/sulfides, metal organic framework Materials (MOFs), and non-metallic semiconductor materials. Among them, metals and their oxides/sulfides are a very widely studied class of CO at present2A photocatalytic reducing agent. Due to the advantages of wide selection range, simple synthesis and the like, the method is favored by a large number of related researchers. But due to the defects of low specific surface area, few active sites and the like, the material is greatly influenced in CO2Development and application in the field of photocatalytic reduction.
The vacancies, as a crystal structure defect, can greatly affect the electronic structure and the energy band structure of the material, thereby having great influence on the catalytic activity. In the catalysis process, electrons and holes generated after the material is excited by light can preferentially jump to the intermediate energy level, so that the separation time of the electron and the hole is prolonged, the separation efficiency of the electron and the hole is improved, and further the CO of the material is improved2Photocatalytic activity. In addition, the existence of the vacancy can not only change the electronic structure and the energy band structure of the material, but also improve the CO pairing of the material2And change the CO of the material2Adsorption of structural models, thereby increasing CO2Catalytic performance of the photocatalytic reductant.
Disclosure of Invention
The invention aims to provide a method for efficiently manufacturing oxygen vacancies on the surface of metal oxide so as to improve the concentration of oxygen vacancies on the surface of the metal oxide and further improve photocatalytic CO2Reduction performance.
The invention discloses a method for efficiently manufacturing oxygen vacancies on the surface of a metal oxide, which comprises the steps of stirring a metal oxide catalyst in an acid solution with the concentration of 0.01-5M for a period of time at a certain temperature, separating and drying the metal oxide catalyst, and annealing the metal oxide catalyst at the temperature of 50-250 ℃ for 10 minutes-5 hours to obtain the metal oxide catalyst with the oxygen vacancies on the surface.
Preferably, the concentration of the acidic solution is 0.1-1M.
Preferably, the solute of the acidic solution is one or more of nitric acid, sulfuric acid, oxalic acid, boric acid, carbonic acid and hydrochloric acid.
Preferably, the solvent of the acidic solution is one or more of deionized water, ethylene glycol, isopropanol, ethanol and acetone.
Preferably, the temperature of the stirring treatment of the metal oxide catalyst in the acidic solution is below 50 ℃, and the stirring time is 10 minutes to 72 hours. In some embodiments, the temperature of the stirring treatment is preferably 10 to 30 ℃ and the time is preferably 10 to 48 hours. The optimal acid solution treatment temperature and acid solution treatment time can control the concentration of oxygen vacancies generated on the surface of the metal oxide catalyst within a certain range, do not damage the crystal structure of the metal oxidant, do not generate bulk oxygen vacancies, and improve the photocatalytic reduction of CO of the metal oxide catalyst2And (4) performance.
Preferably, the annealing atmosphere is one or more of nitrogen, argon, helium, hydrogen and ammonia.
Preferably, the separated and dried metal oxide catalyst is heated to the annealing temperature of 50-250 ℃ at a heating rate of 1-20 ℃/min to perform annealing treatment.
Preferably, the annealing temperature is 80-150 ℃, and the annealing time is 30 min-10 hour. The optimized annealing temperature and annealing time not only completely desorbs molecules adsorbed by oxygen vacancies generated on the surface of the metal oxide catalyst, but also avoids the formation of oxygen vacancies in the metal oxide, and reduces the photocatalytic reduction CO of the metal oxide catalyst to become a carrier recombination center2And (4) performance.
Preferably, the metal oxide catalyst comprises at least one of cerium dioxide, titanium dioxide, tungsten trioxide, manganese dioxide, zinc oxide.
Preferably, the separation mode is centrifugal separation.
The invention improves the existing metal oxide catalyst oxygen vacancy manufacturing technology and improves the photocatalysis CO of the metal oxide2The reduction performance has obvious effect and has the following characteristics:
(1) the method combining the solution method and the mild atmosphere heat treatment is low in cost and environment-friendly.
(2) The acid solution treatment concentration, time and temperature are controllable, and the oxygen vacancy concentration and the distribution of surface oxygen vacancies and bulk oxygen vacancies can be effectively controlled. Wherein the preferable acid solution concentration, treatment temperature and time may be such that oxygen vacancies are generated only on the surface of the metal oxide catalyst, and the concentration may be controlled within a suitable range; the optimized annealing temperature and annealing time not only completely desorbs molecules adsorbed by oxygen vacancies generated on the surface of the metal oxide catalyst, but also effectively avoids the situation that crystal lattices in the metal oxide generate thermal vibration in the annealing treatment to generate bulk oxygen vacancies, thereby avoiding the situation that the crystal lattices become carrier recombination centers to reduce the photocatalytic reduction CO of the metal oxide catalyst2And (4) performance.
(3) The oxygen vacancy concentration of the metal oxide is greatly increased, and CO is photocatalyzed2The reduction performance is greatly improved.
The catalyst containing oxygen vacancies prepared according to the method has not only a high oxygen vacancy concentration at the surface of the catalyst but also excellent photocatalytic CO2Reduction performance. Under the same evaluation conditions, the comprehensive effect of the method is superior to that of the currently reported similar preparation method.
Drawings
FIG. 1 is a TEM photograph of nano cerium oxide nanorods at different nano-scales after being treated in example 1;
FIG. 2 is a graph showing Electron Paramagnetic Resonance (EPR) data of nano-cerium oxide nanorods before and after the treatment in example 1;
FIG. 3 is a Raman spectrum of the nano-cerium oxide nanorods before and after the treatment in example 1;
FIG. 4 shows XPS-O1 s spectra of nano cerium oxide nanorods before and after treatment and after catalytic reaction in example 1;
FIG. 5 shows the nano cerium oxide nanorods photocatalytic CO before and after the treatment in example 12A CO yield map of the reduction product;
FIG. 6 is a photograph of the nano cerium oxide nanorod catalyst after being treated in example 2;
FIG. 7 is a photograph of the P25 catalyst after treatment in example 3;
FIG. 8 is a photograph of the nano cerium oxide nanorod catalyst after being treated in example 4;
FIG. 9 shows XPS Ce 3d spectra of nano cerium oxide nanorods before and after the treatment in comparative example 1;
FIG. 10 shows nano-cerium oxide nanorods photocatalytic CO before and after the treatment in comparative example 12A CO yield map of the reduction product;
FIG. 11 is XPS C1 s spectra of nano cerium oxide nanorods after treatment in comparative example 2;
in which CeO is present2Refers to untreated nano cerium oxide nanorods, CeO2-N2Means passing through N only2Annealing nano cerium oxide nano rod, 0.5-CeO2-100 refers to the nano cerium oxide nanorods, 0.5-CeO, treated in example 12100-after refers to the nano cerium oxide nano rod, CeO after the treatment and catalytic reaction of the example 12-100 refers to the nano cerium oxide nanorods treated by comparative example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The method for efficiently producing oxygen vacancies on the surface of the metal oxide catalyst of the present invention is a method of treating by an acidic solution method and annealing under mild heat treatment conditions. Both the acid treatment and the annealing treatment are aimed at creating oxygen vacancies in the metal oxide catalyst system. The acid treatment is more inclined to the surface, but the acid treatment is easy to change the crystal structure of the catalyst; while the annealing process also increases bulk oxygen vacancy concentration while creating surface oxygen vacancies. The method of the invention combines acid liquid treatment and annealing, enhances the separation efficiency of surface carriers and reduces the recombination probability of the bulk phase.
The following shows a specific technical solution as an example:
first, the metal oxide catalyst is subjected to a solution stirring treatment in an acidic solution of a certain concentration and at a certain temperature for a certain period of time in order to generate oxygen vacancies on the surface of the metal oxide catalyst. The preferable acid solution concentration, treatment temperature and time may be such that oxygen vacancies are generated only on the surface of the metal oxide catalyst, and the surface oxygen vacancy concentration may be controlled within a suitable range, without destroying the crystal structure of the metal oxidant, and without generating bulk oxygen vacancies. The concentration of the acidic solution is between 0.01M and 5M, preferably between 0.1 and 1M. The solute of the acidic solution includes but is not limited to one or more of nitric acid, sulfuric acid, oxalic acid, boric acid, carbonic acid and hydrochloric acid. The solvent of the acidic solution includes but is not limited to one or more of deionized water, ethylene glycol, isopropanol, ethanol and acetone. In some examples, the solution treatment is for a time period of between 10 minutes and 72 hours and the treatment temperature is between 0 ℃ and 50 ℃.
Then, the stirred solution is separated and dried to obtain a solution-treated metal oxide catalyst. The separation may be by centrifugation. As an example, the centrifugation speed may be 3000-.
And finally, keeping the separated and dried metal oxide catalyst at a certain temperature in a certain atmosphere at a certain heating rate for a certain period of time. The optimized annealing temperature and annealing time not only completely desorbs the molecules adsorbed by oxygen vacancies generated on the surface of the metal oxide catalyst, but also effectively avoids goldThe crystal lattice in the metal oxide generates thermal vibration in annealing treatment to generate bulk oxygen vacancy, thereby avoiding the phenomenon of being a carrier recombination center to reduce the photocatalytic reduction CO of the metal oxide catalyst2And (4) performance. The annealing atmosphere can be one or more of nitrogen, argon, helium, hydrogen and ammonia. In an alternative embodiment, the annealing temperature is between 50 ℃ and 250 ℃. Additionally, the annealing time may be between 10 minutes and 5 hours. In some embodiments, the ramp rate can be between 1 ℃/minute to 20 ℃/minute.
The invention improves the concentration of the surface oxygen vacancy of the catalyst and the ratio of the surface oxygen vacancy to the bulk oxygen vacancy by selecting a proper acidic solution for treatment and carrying out an annealing treatment at a mild atmosphere temperature, thereby improving the photocatalytic CO of the catalyst2Reduction performance. The catalyst after the treatment has a large amount of oxygen vacancies. These increased surface oxygen vacancies can broaden the conductivity of the metal oxide catalyst, the surface of the catalyst to CO2The adsorption capacity and the ultraviolet-visible light absorption capacity of the material promote the separation and migration of carriers; and the reduction of the oxygen vacancy of the metal oxide catalyst body is beneficial to reducing the recombination probability of the current carrier, thereby improving the separation rate and the utilization rate of the photo-generated electrons and further improving the photocatalytic performance of the metal oxide catalyst.
Example 1
Stirring the nano cerium oxide nanorod catalyst in 0.5M oxalic acid aqueous solution at 25 ℃ for 48h, centrifugally drying, and adding the catalyst in N2The temperature is raised to 100 ℃ at the speed of 10 ℃/min under the atmosphere and the temperature is kept for 60 minutes. The TEM picture of the treated nano cerium oxide nanorod is shown in the attached figure 1. As can be clearly seen from FIG. 1, the size of the oxygen vacancy-rich cerium oxide nanorod is 10-300nm, and the length-diameter ratio of the nanorod is 2-30 nm. The EPR data chart, the Raman spectrum and the XPS-Ce 3d spectrum of the treated nano cerium oxide nanorod are respectively shown in the attached figures 2, 3 and 4. As can be seen from the paramagnetic resonance spectrum (EPR) shown in FIG. 2, the prepared oxygen vacancy-rich cerium oxide nanorod is rich in a large number of oxygen vacancies. As can be seen from the Raman spectrum of FIG. 3, the cerium oxide after the acid solution and annealing treatment was 600cm-1Oxygen of (2)The Raman peak intensity of the vacancy is more obvious, which indicates that the prepared oxygen-rich vacancy cerium oxide nanorod is rich in a large number of oxygen vacancies. It can be seen from XPS O1 s spectrum (figure 4) that XPS peak of adsorbed oxygen on the surface of cerium oxide treated by acid solution and annealing becomes strong, and oxygen vacancy is kept stable after catalytic reaction, which shows that the prepared cerium oxide nanorod with oxygen-rich vacancy is rich in a large amount of oxygen vacancies and is kept stable in the catalytic reaction process.
Photocatalytic CO2The reduction performance test process comprises the following steps: weighing 50mg of the catalyst before and after treatment, dispersing the catalyst in absolute ethyl alcohol, uniformly dripping the catalyst on a 25 x 25mm glass sheet, drying the absolute ethyl alcohol, and placing the catalyst at the bottom of a photocatalytic reactor; confirming that the photocatalytic reactor is completely sealed, opening the inlet and outlet valves of the photocatalytic reactor, and introducing high-purity CO2Introducing gas into a washing bottle containing deionized water, introducing certain water vapor into the photocatalytic reactor in a bubbling manner, continuously purging for 30min, and removing air in the container to make CO containing water vapor2Filling the reactor; closing an inlet valve and an outlet valve of the photocatalytic reactor after purging is finished, and standing for 30min to wait for reactants on the surface of the catalyst to reach adsorption balance; the xenon lamp was turned on and the photocatalytic reaction was started. A1 mL sample of gas was injected into the gas chromatograph (FID detector) per hour for analysis using a gas-tight needle. In the catalytic reaction process, a cooling circulation device is utilized to control the temperature of a reaction container, and the temperature of cooling circulation water is kept at 15 ℃. Photocatalytic CO thereof2The reduction performance test result is shown in figure 5, and the treated nano cerium oxide nano-rods are used for photocatalytic reduction of CO2The yield of CO, a reaction product, was increased by a factor of about 12.5.
Example 2
Stirring the nano cerium oxide nanorod catalyst in 0.1M oxalic acid aqueous solution at 15 ℃ for 2h, centrifugally drying, heating the catalyst to 150 ℃ at 10 ℃/min in Ar atmosphere, and keeping the temperature for 30 min. The photo of the treated nano cerium oxide nanorod catalyst is shown in figure 6.
Example 3
A commercial titanium dioxide P25 catalyst is prepared through stirring the solution of 1M oxalic acid solution at 25 deg.C for 24 hr, centrifugal drying, and mixing with the solution of oxalic acid solutionN2The temperature is raised to 150 ℃ at the speed of 5 ℃/min under the atmosphere and the temperature is kept for 120 minutes. A photograph of the treated P25 catalyst is shown in FIG. 7.
Example 4
Stirring the nano cerium oxide nanorod catalyst in 1M oxalic acid aqueous solution at 25 ℃ for 72h, centrifugally drying, and adding the catalyst in N2The temperature is raised to 80 ℃ at the speed of 2 ℃/min under the atmosphere and the temperature is kept for 120 minutes. The photo of the treated nano cerium oxide nanorod catalyst is shown in figure 8.
Comparative example 1
The nano cerium oxide nanorod catalyst is directly added into N without being treated by acid liquor2The temperature is raised to 80 ℃ at the speed of 2 ℃/min under the atmosphere and the temperature is kept for 120 minutes. The XPS Ce 3d spectrum of the treated nano cerium oxide nanorod is shown in the attached figure 9. In comparative example 1, the peak strength of the directly annealed Ce 3d XPS is significantly lower than that of the cerium oxide subjected to the acid solution treatment and the annealing treatment, which indicates that the acid solution treatment can effectively increase the oxygen vacancy concentration on the surface of the metal oxide catalyst. Comparative example 1 photocatalytic CO of cerium oxide subjected to acid solution treatment and annealing treatment2Production of CO as a reduction product, and finding that CO is reduced by direct annealing of cerium oxide2The yield of CO, the reaction product, was increased by about 2-fold compared to the cerium oxide without any treatment (fig. 10), which is only 1/6 for the yield of CO, the cerium oxide after treatment in example 1.
Comparative example 2
The nano cerium oxide nano-rod catalyst is firstly treated by N without acid liquor2The temperature is raised to 80 ℃ at the speed of 2 ℃/min under the atmosphere and the temperature is kept for 120 minutes. Then stirring the solution in 0.5M oxalic acid water solution at 25 deg.C for 48h, and drying by centrifugation to obtain XPS C1 s spectrum of nano cerium oxide nanorod as shown in figure 11. Comparative example 1 cerium oxide annealed and then acid-treated has C1 s XPS peaks with CO at 290 and 288.4eV3 2-The catalyst surface has a large amount of adsorbed carbonic acid species which are stably adsorbed in the photocatalysis process and block surface oxygen vacancy from CO2Effective adsorption and catalytic conversion are carried out, and CO products detected in the photocatalytic reaction process are not all derived from CO2But mostly from the photodecomposition of small organic molecular impurities adsorbed on the catalyst surface.
Finally, it is necessary to mention that: the above embodiments are only used for further detailed description of the technical solutions of the present invention, and should not be understood as limiting the scope of the present invention, and the insubstantial modifications and adaptations made by those skilled in the art according to the above descriptions of the present invention are within the scope of the present invention.
Claims (10)
1. A method for efficiently manufacturing oxygen vacancies on the surface of a metal oxide catalyst is characterized in that the metal oxide catalyst is stirred for a period of time at a certain temperature in an acid solution with the concentration of 0.01-5M, and then is subjected to separation and drying, and the metal oxide catalyst is annealed for 10 minutes to 5 hours at the temperature of 50-250 ℃ to obtain the metal oxide catalyst with oxygen vacancies on the surface.
2. The method of claim 1, wherein the acidic solution has a concentration of 0.1 to 1M.
3. The method according to claim 1 or 2, wherein the solute of the acidic solution is one or more of nitric acid, sulfuric acid, oxalic acid, boric acid, carbonic acid, and hydrochloric acid.
4. The method according to any one of claims 1 to 3, wherein the solvent of the acidic solution is one or more of deionized water, ethylene glycol, isopropanol, ethanol, and acetone.
5. The method according to any one of claims 1 to 4, wherein the temperature of the stirring treatment of the metal oxide catalyst in the acidic solution is 50 ℃ or less, and the stirring time is 10 minutes to 72 hours.
6. The method according to any one of claims 1 to 5, wherein the annealing atmosphere is one or more of nitrogen, argon, helium, hydrogen, and ammonia.
7. The method according to any one of claims 1 to 6, wherein the separated and dried metal oxide catalyst is heated to the annealing temperature of 50 to 250 ℃ at a heating rate of 1 to 20 ℃/min to perform the annealing treatment.
8. The production method according to any one of claims 1 to 7, wherein the annealing temperature is 80 to 150 ℃ and the annealing time is 30 minutes to 10 hours.
9. The production method according to any one of claims 1 to 8, characterized in that the metal oxide catalyst includes at least one of cerium oxide, titanium dioxide, tungsten trioxide, manganese dioxide, zinc oxide.
10. The method according to any one of claims 1 to 9, wherein the separation means is centrifugation.
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