CN110980789A - Copper-based two-dimensional sheet cerium oxide nanomaterial and synthesis method and application thereof - Google Patents
Copper-based two-dimensional sheet cerium oxide nanomaterial and synthesis method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of preparation of two-dimensional flaky cerium oxide nano materials, and discloses a copper-based two-dimensional flaky cerium oxide nano material as well as a synthesis method and application thereof, wherein the method comprises the following steps: adding the nano particles into hydrogen peroxide, soaking and stirring, adding ammonia water to corrode the surface, adding a cerium nitrate solution, continuing stirring, and adjusting the pH value of the mixed solution to be within the range of 9-11; washing the precipitate with water, centrifuging, and drying to obtain copper-based two-dimensional sheet cerium oxide nanomaterial. The cerium oxide material synthesized by the invention has a two-dimensional sheet structure, grows on the surface of copper nanoparticles, and has excellent potential application values of water gas conversion, VOC waste gas catalytic treatment, solid oxide fuel cells, industrial carbon dioxide catalytic reduction and the like. No surfactant is added in the synthesis process, so that the subsequent treatment processes of organic solvent washing, high-temperature calcination and the like in the material preparation process can be omitted, the energy consumption is reduced, and the pollution is reduced.
Description
Technical Field
The invention belongs to the field of preparation of two-dimensional sheet cerium oxide nano materials, relates to a copper-based two-dimensional sheet cerium oxide nano material and a synthesis method and application thereof, and particularly relates to a synthesis method for growing a two-dimensional sheet cerium oxide nano material on the surface of copper nanoparticles, which can be used for CO2Hydrogenation catalysis application.
Background
The nano cerium oxide has strong oxygen exchange capacity and oxygen storage capacity and is widely applied to the fields of petrochemical industry, automobile exhaust purification, mechanical polishing and the like. In recent years, with the development and research on the performance of cerium oxide, the great difference of the activities of CO oxidation and water gas shift reactions represented by the difference of oxygen vacancy concentration and charge difference of different crystal faces of cerium oxide is found, and in order to synthesize the cerium oxide with special crystal faces, the synthesis conditions are controlled by adding a surfactant and an anion regulator to obtain cerium oxide nano materials with different morphologies, such as spheres, rods, flower bundles, fibers, cubes, octahedrons, sheets and the like. Cerium oxide nano materials with various shapes are widely applied to reactions such as alkane dehydrogenation, methane coupling, methane reforming and the like. Research shows that the two-dimensional cerium oxide nanosheet has high catalytic reaction activity due to the existence of a large number of oxygen defects, high specific surface area and more active sites. Therefore, how to synthesize the sheet-like cerium oxide has become one of the research hotspots in the nanometer field in recent years.
In the prior art, a precipitation method and a template method are mainly adopted to synthesize the two-dimensional sheet cerium oxide. The two-dimensional flaky cerium oxide synthesized by the precipitation method has strong operability and wide application, and is mainly prepared by hydrothermal synthesis after precipitation, centrifugal washing, drying and calcining. Such as by adding surfactants, organic solvents, and the like. More specifically, CN201910047436.9 proposes adding a nonionic surfactant and alcohol amine as raw materials to perform a water bath cyclic heating precipitation reaction to obtain a sheet-like cerium oxide nano-material; CN 103922385A proposes a hydrothermal reaction for 48h at 120-160 ℃ with ethylenediamine as a precipitant, and calcining at 400 ℃ to obtain hexagonal nano flaky cerium oxide; CN 101962203A proposes that a surfactant is not added for carrying out high-temperature long-time hydrothermal reaction, but the morphology of the obtained cerium oxide material is not controllable. CN201610352324.0 proposes a sheet-like ceria catalyst obtained by a high-temperature hydrothermal reaction using ammonium sulfate and sodium sulfite as modifiers. And the other method is to synthesize two-dimensional sheet cerium oxide by a template method, wherein CN200510085508.7 proposes that an oxide is used as a substrate, glucose, acrylamide or metal organic compounds are added to the substrate to perform hydrothermal synthesis for 10-72 h at the high temperature of 90-220 ℃, and then the composite material is calcined at the high temperature of 600 ℃ to obtain flower-shaped cerium oxide, wherein the cerium oxide has a sheet structure.
However, the above prior art solution still has the following drawbacks or shortcomings: firstly, the method is complex, the preparation period is long, the hydrothermal reaction needs high temperature, and the energy consumption is high; secondly, they usually need to use alcohol amine and surfactant, but these surfactants are difficult to remove at a later stage and are easy to cause secondary pollution. Therefore, further research and improvement on the synthesis method are needed to better meet the requirements of multiple technologies such as green, high efficiency and the like.
Disclosure of Invention
Aiming at the defects or improvement requirements in the prior art, the invention provides a synthesis method of a copper-based two-dimensional sheet cerium oxide nano material, which aims to introduce hydrogen peroxide copper oxide nano particles, then form an alkali concentration gradient with a certain concentration on the surfaces of the copper nano particles by means of ammonia water etching, guide cerium salt to be aggregated, precipitated and aged on the surfaces of the copper nano particles after adding cerium salt, and obtain the two-dimensional sheet cerium oxide by centrifugal drying, so that the two-dimensional sheet cerium oxide nano material is wrapped on the surfaces of the copper nano particles under the condition of no need of a surfactant and an organic solvent, and the two-dimensional sheet cerium oxide nano material has the advantages of high overall reaction rate, low cost, convenient operation and control, environmental friendliness, excellent VOC removal, carbon dioxide reduction and other application values.
To achieve the above objects, according to one aspect of the present invention, there is provided a method of nano copper-based two-dimensional plate-shaped cerium oxide, comprising the steps of:
(i) dispersing 70-80 nm copper nanoparticles in hydrogen peroxide, stirring at 20-25 ℃ to form a surface oxide layer on the surfaces of the copper nanoparticles;
(ii) adding ammonia water into the solution generated in the step (i), keeping the solution at room temperature for a certain time for reaction, and quickly corroding the oxide layer on the surface of the copper nanoparticles by means of the corrosion effect of the ammonia water to obtain a blue solution; meanwhile, the ammonia water forms a concentration gradient on the surface of the copper nano-particles due to the reaction of the ammonia water and the oxide layer;
(iii) and (3) adding a cerium nitrate solution into the blue solution generated in the step (ii), adjusting the pH value of the mixed solution to be within the range of 9-11, rapidly generating a two-dimensional sheet cerium oxide nano material on the surface of the copper nano particles by means of the concentration gradient guidance of ammonia water under the condition of not adding a surfactant, and then washing with deionized water and centrifuging to obtain the copper-based two-dimensional sheet cerium oxide nano material.
Further, in the step (i), the concentration of the hydrogen peroxide solution in percentage by mass is 10% -20%, the addition amount of the copper nanoparticles is 0.1-0.5 g, the amount of the hydrogen peroxide solution is 2-10 ml, and the soaking time is 10-30 min.
Further, in the step (ii), the mass percent concentration of the selected ammonia water solution is 9-10%, the adding amount of ammonia water is 10-20 ml, and the stirring is carried out for 0.5-4 h.
Further, in the step (iii), the mass percentage concentration of the selected cerous nitrate solution is 30-40%, the addition amount is 2-5 ml, and the stirring is carried out for 10-30 min.
Further, the ammonia water is added in the step (ii) and then stirred at a stirring speed of 400 to 600 rpm.
Further, in the step (iii), the centrifugal treatment adopts a rotating speed of 3000 rpm-8000 rpm, the drying temperature is 80-100 ℃, and the drying time is 12 h-24 h.
According to another aspect of the invention, the copper-based two-dimensional sheet cerium oxide nanomaterial prepared by the method disclosed by any one of the preceding claims is also provided.
According to another aspect of the invention, the application of the nano copper-based two-dimensional flaky cerium oxide nano material in water gas conversion, VOC waste gas catalytic treatment, solid oxide fuel cells or industrial carbon dioxide catalysis is also provided.
In general, compared with the prior art, the above technical solution contemplated by the present invention can obtain the following beneficial effects:
(1) the invention introduces hydrogen peroxide copper oxide nanoparticles, then forms an alkali concentration gradient with a certain concentration on the surface of copper by means of ammonia water etching, stabilizes the pH value of a mixed solution within the range of 9-11 by the combined action of added cerium salt and ammonia water, so that the stable precipitation and aging of cerium ions are realized to obtain a synthesis route of two-dimensional sheet cerium oxide2And (4) hydrogenation to synthesize the methanol.
(2) The mass percentage concentration of hydrogen peroxide is 10-20%, the mass percentage concentration of copper nanoparticles is 0.1-0.5 g, the amount of hydrogen peroxide solution is 2-10 ml, and the soaking time is 10-30 min, so that the surface of the copper nanoparticles can be completely wrapped with an oxide layer, the growth of two-dimensional flaky cerium oxide on the surface of the copper nanoparticles can be guided, and the problem that the two-dimensional flaky cerium oxide is difficult to aggregate and integrate due to excessive consumption of the copper nanoparticles can be avoided.
(3) The mass percent concentration of the ammonia water solution is 9-10%, the adding amount of the ammonia water is 10-20 ml, and the stirring is carried out for 0.5-4 h, so that the better copper surface etching degree can be obtained, and a concentration gradient is fully formed on the surface of the copper nano-particles, thereby being beneficial to guiding the growth and the full wrapping of the two-dimensional sheet cerium oxide on the surface of the copper nano-particles in the follow-up process. If the ammonia content is too low or the stirring time is too short, the surface of the copper nanoparticles is easily wrapped incompletely after the cerium oxide is subsequently added, and if the ammonia content is too high or the stirring time is too long, the obtained cerium oxide nanoparticles are mainly granular rather than two-dimensional flaky easily after the cerium oxide is subsequently added.
(4) The cerous nitrate solution with the mass percentage concentration of 30-40 percent is added in an amount of 2-5 ml, and the mixture is stirred for 10-30 min, so that the surface of the copper nano-particles can be fully coated. The cerium nitrate salt solution has too high concentration, too much amount or too long stirring time, which can cause that the obtained cerium oxide nano material is not easy to form on the surface of the copper nano particle and even directly dispersed in the solution; and if the concentration of the cerous nitrate solution is too low, the amount of the cerous nitrate solution is too small or the stirring time is too short, the surface of the copper nano-particles is not easy to be completely wrapped.
(5) The stirring speed is 400 rpm-600 rpm after the ammonia water is added, which is beneficial to quickly forming a proper concentration gradient on the surface of the copper nano-particles and is convenient for forming two-dimensional sheet cerium oxide.
(6) The centrifugal treatment rotating speed is 3000 rpm-8000 rpm, the drying temperature is 80-100 ℃, and the drying time is 12 h-24 h, so that the copper-based two-dimensional sheet cerium oxide nano material with good surface coating quality and complete appearance can be more easily obtained.
(7) In the scheme of using the traditional copper nanoparticles alone or in a conventional mixed manner with other catalysts, the surfaces of the copper nanoparticles are completely exposed, and the copper nanoparticles are easy to contact with each other as the reaction proceeds to generate agglomeration and deactivation. Therefore, the method has the advantages of simple process and easy forming in addition to the advantages of growing the two-dimensional sheet cerium oxide nano material by taking the copper nanoparticles as the matrix, and can prevent the copper nanoparticles from directly contacting with each other in a mode of wrapping the two-dimensional sheet cerium oxide on the surfaces of the copper nanoparticles, thereby greatly reducing the occurrence of agglomeration and inactivation of the copper nanoparticle catalyst, not only the appearance of the obtained two-dimensional sheet cerium oxide is easy to control, but also the service life of the whole nano material can be greatly prolonged.
(8) The cerium oxide material synthesized by the invention has a two-dimensional sheet structure and grows on the surface of copper nanoparticles, so that the copper-based two-dimensional sheet cerium oxide nanomaterial with excellent performance is obtained, and the copper-based two-dimensional sheet cerium oxide nanomaterial has potential application values of water gas conversion, VOC (volatile organic compound) waste gas catalytic treatment, solid oxide fuel cells, industrial carbon dioxide catalytic reduction and the like. No surfactant is added in the synthesis process, so that the subsequent treatment processes of organic solvent washing, high-temperature calcination and the like in the material preparation process can be omitted, the energy consumption is reduced, and the pollution is reduced.
Drawings
FIG. 1 is a schematic flow chart of a method for synthesizing a nano copper-based two-dimensional sheet cerium oxide nano material constructed according to the present invention;
FIG. 2 is an XRD spectrum of a nano-copper-based two-dimensional plate-shaped cerium oxide nano-material obtained in example 1 according to the present invention;
fig. 3 is a SEM image of 1um scale showing a copper nano copper-based two-dimensional flaky cerium oxide nanomaterial product obtained according to example 1 of the present invention, by way of illustrative example;
FIG. 4 is a SEM image on a scale of 200nm showing a copper nano-copper based two-dimensional flaky cerium oxide nanomaterial product obtained in example 1 according to the present invention, as an illustrative example;
FIG. 5 is a SEM image on a scale of 200nm showing a copper nano-copper based two-dimensional flaky cerium oxide nanomaterial product obtained in example 5 according to the present invention, by way of illustrative example;
fig. 6 is a BET spectrum of the nano copper-based two-dimensional plate-shaped cerium oxide nanomaterial obtained in example 1 based on the present invention.
Fig. 7 is a BJH pore size distribution spectrum of the nano copper-based two-dimensional sheet cerium oxide nanomaterial obtained in example 1 based on the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Fig. 1 is a schematic flow chart of a method for synthesizing a copper-based two-dimensional sheet-shaped cerium oxide nanomaterial constructed according to the present invention, and as shown in fig. 1, the present invention provides a method for synthesizing a copper-based two-dimensional sheet-shaped cerium oxide nanomaterial. This will be explained in detail below.
First, a Cu nanoparticle surface oxidation step is performed.
Dispersing nano Cu particles (70nm-80nm) purchased from Aladdin medicines into hydrogen peroxide deionized water, and then centrifugally stirring at the temperature of 20-25 ℃. In the operation step, the hydrogen peroxide solution is preferably in a mass percentage concentration of 10-20%, the adding amount of the nano copper powder is 0.1-0.5 g, the amount of the hydrogen peroxide solution is 2-10 ml, and the soaking time is 10-30 min.
It is noted that according to the invention, the dispersion degree of Cu in hydrogen peroxide can be influenced by the addition amount difference of the nano copper powder; meanwhile, Cu nano materials can be oxidized by different concentrations of hydrogen peroxide, and the intensity of different oxidation processes can be obtained in a further given optimization range. Accordingly, according to a preferred embodiment of the present invention, the soaking time is controlled to be 10min to 30min in order to control the oxidation degree of Cu.
Next, a processing step of Cu surface etching is performed.
Adding ammonia water into the solution generated in the step (i), keeping the solution for a certain time for room temperature reaction, quickly corroding the surface copper oxide by means of the corrosion action of the ammonia water, and simultaneously forming a concentration gradient on the surface of copper by the ammonia water;
in the step (ii), the selected ammonia water solution preferably has a mass percentage of 9% -10% so as to carry out the corrosion rate of the surface copper oxide, the adding amount of the ammonia water is preferably 10 ml-20 ml, the etching amount of the copper oxide and the pH value of the solution after the late cerium salt is added are controlled, the stirring time is preferably 0.5 h-4 h, and the etching amount of Cu is controlled.
And finally, a step of producing the two-dimensional sheet cerium oxide nano material.
And (3) adding the blue solution generated in the step (ii) into a cerium nitrate solution, rapidly generating a two-dimensional sheet cerium oxide nano material under the condition of not adding a surfactant, and then carrying out washing with ionized water and centrifugal drying treatment to obtain the two-dimensional sheet cerium oxide nano material grown on the surface of the copper nano particles. In step (iii), the percentage of the selected cerium nitrate salt solution is preferably 30-40%, the addition amount is 2-5 ml, and the stirring is carried out for 10-30 min.
Generally, add through the copper nanoparticle and carry out surface oxidation in hydrogen peroxide solution, surface etching is carried out through aqueous ammonia again, adjust etching time and can control the etching degree, add the cerium salt solution, form cerium hydroxide sediment with the help of the aqueous ammonia concentration on copper nanoparticle surface, through certain ageing time, then with the help of proper temperature stoving treatment, need not surfactant active, two-dimentional slice cerium oxide nano-material is prepared on copper nanoparticle surface under the condition of organic solvent, and whole reaction rate is high, with low costs, the process is convenient for control, it is green pollution-free, possess excellent VOC and get rid of, application value such as carbon dioxide reduction
Fig. 1 is a schematic flow chart of a synthetic method for growing a two-dimensional sheet cerium oxide nano material on the surface of a copper nanoparticle constructed according to the present invention, and as shown in fig. 1, the present invention provides a synthetic method for a copper-based two-dimensional sheet cerium oxide nano material. This will be explained in detail below.
(i) First, a Cu nanoparticle surface oxidation step is performed.
Dispersing nano Cu particles (the particle diameter is 70nm-80nm) purchased from Aladdin medicines into hydrogen peroxide deionized water, and then centrifugally stirring at the temperature of 20-25 ℃. In the operation step, the hydrogen peroxide solution is preferably selected to have a mass percentage concentration of 10-20%, the adding amount of the nano copper powder is 0.1-0.5 g, the amount of the hydrogen peroxide solution is 2-10 ml, and the soaking time is 10-30 min.
It is noted that according to the invention, the dispersion degree of Cu in hydrogen peroxide can be influenced by the addition amount difference of the nano copper powder; meanwhile, Cu nano materials can be oxidized by different concentrations of hydrogen peroxide, and the intensity of different oxidation processes can be obtained in a further given optimization range. Correspondingly, according to a preferred embodiment of the present invention, the soaking time is controlled to be 10min to 30min, so as to control the oxidation degree of Cu, which is beneficial to subsequently obtain a final product with better surface appearance and coating quality.
(ii) Next, a processing step of Cu surface etching is performed.
Adding ammonia water into the solution generated in the step (i), keeping the solution for a certain time for room temperature reaction, quickly corroding the surface copper oxide by means of the corrosion action of the ammonia water, and simultaneously forming a concentration gradient on the surface of copper by the ammonia water;
in the step (ii), the percentage of the selected ammonia water solution is preferably 9% -10%, so that the corrosion rate of the surface copper oxide is facilitated, the adding amount of ammonia water is preferably 10 ml-20 ml, the etching amount of the copper oxide and the pH value of the solution after the cerium salt is added later are favorably controlled, and the stirring time is preferably 0.5-4 h, so that the etching amount of Cu is controlled.
(iii) And finally, a step of producing the two-dimensional sheet cerium oxide nano material.
And (3) adding the blue solution generated in the step (ii) into a cerium nitrate solution, rapidly generating a two-dimensional sheet cerium oxide nano material under the condition of not adding a surfactant, and then carrying out washing with deionized water and centrifugal drying treatment to obtain the copper-based two-dimensional sheet cerium oxide nano material. In step (iii), the percentage of the selected cerium nitrate salt solution is preferably 30-40%, the addition amount is 2-5 ml, and the stirring is carried out for 10-30 min.
The present invention will be explained in more detail below by means of a plurality of examples.
Example 1
Dispersing 0.3g of nano copper powder in 4ml of hydrogen peroxide with the percentage content of 15%, soaking for 10min, adding 10ml of 10% ammonia water, uniformly stirring in a beaker at the speed of 400rpm for 2h, wherein the mixed solution can be light blue due to the reaction of an oxide layer and the ammonia water, dripping 2ml of 30% cerium nitrate into the mixed solution to obtain gray precipitate, stirring at the speed of 400rpm, aging for 20min, collecting a precipitate sample, washing with deionized water, centrifuging at 6000rpm, repeatedly washing and centrifuging for 5 times, and drying in an oven at the temperature of 80 ℃ for 24h to obtain the nano copper-based two-dimensional sheet cerium oxide nano material.
Example 2
Dispersing 0.2g of nano copper powder in 4ml of hydrogen peroxide with the percentage content of 15%, soaking for 10min, adding 10ml of 10% ammonia water, uniformly stirring in a beaker at the speed of 400rpm for 1h, enabling the mixed solution to be light blue, dropwise adding 2ml of 30% cerium nitrate into the mixed solution to obtain gray precipitate, stirring at the speed of 400rpm, aging for 20min, collecting a sample, washing with deionized water, centrifuging at 8000rpm, repeatedly washing and centrifuging for 4 times, and drying in an oven at the temperature of 90 ℃ for 18h to obtain the nano copper-based two-dimensional sheet cerium oxide nano material.
Example 3
Dispersing 0.3g of nano copper powder in 4ml of hydrogen peroxide with the percentage content of 15%, soaking for 15min, adding 10% ammonia water in 10ml, uniformly stirring in a beaker at the speed of 400rpm for 30min, enabling the mixed solution to be light blue, dropwise adding 2ml of 30% cerium nitrate into the mixed solution to obtain gray precipitate, stirring at the speed of 400rpm, aging for 20min, collecting a sample, washing with deionized water, centrifuging at 7000rpm, repeatedly washing and centrifuging for 5 times, and drying in an oven at 100 ℃ for 12h to obtain the nano copper-based two-dimensional sheet cerium oxide nanomaterial.
Example 4
Dispersing 0.5g of nano copper powder in 4ml of hydrogen peroxide with the percentage content of 10%, soaking for 10min, adding 10ml of 10% ammonia water, uniformly stirring in a beaker at the speed of 500rpm for 4h, enabling the mixed solution to be light blue, dropwise adding 2ml of 30% cerium nitrate into the mixed solution to obtain gray precipitate, stirring at the speed of 400rpm, aging for 20min, collecting a sample, washing with deionized water, centrifuging at the speed of 5000rpm, repeatedly washing and centrifuging for 6 times, and drying in an oven at the temperature of 95 ℃ for 15h to obtain the nano copper-based two-dimensional sheet cerium oxide nanomaterial.
Example 5 (comparative example)
Dispersing 0.3g of nano copper powder in 4ml of hydrogen peroxide with the percentage content of 15%, soaking for 10min, adding 10ml of 10% ammonia water, uniformly stirring in a beaker at the speed of 400rpm for 8h, enabling the mixed solution to be light blue, dropwise adding 2ml of 30% cerium nitrate into the mixed solution to obtain gray precipitate, stirring at the speed of 400rpm, aging for 20min, collecting a sample, washing with deionized water, centrifuging at the speed of 6000rpm, repeatedly washing and centrifuging for 5 times, and drying in an oven at the temperature of 80 ℃ for 24h to obtain the nano copper-based two-dimensional sheet cerium oxide nanomaterial.
Example 6
Dispersing 0.3g of nano copper powder in 4ml of hydrogen peroxide with the percentage content of 20%, soaking for 30min, adding 10ml of 9% ammonia water, uniformly stirring in a beaker at the speed of 400rpm for 1h, enabling the mixed solution to be light blue, dropwise adding 2ml of 30% cerium nitrate into the mixed solution to obtain gray precipitate, stirring at the speed of 400rpm, aging for 20min, collecting a sample, washing with deionized water, centrifuging at the speed of 6000rpm, repeatedly washing and centrifuging for 5 times, and drying in an oven at the temperature of 80 ℃ for 24h to obtain the nano copper-based two-dimensional sheet cerium oxide nanomaterial.
Example 7 (comparative example)
Dispersing 0.9g of nano copper powder in 10ml of hydrogen peroxide with the percentage content of 15%, soaking for 10min, adding 10ml of 10% ammonia water, uniformly stirring in a beaker at the speed of 400rpm for 20min, enabling the mixed solution to be light blue, dropwise adding 2ml of 30% cerium nitrate into the mixed solution to obtain gray precipitate, stirring at the speed of 400rpm, aging for 20min, collecting a sample, washing with deionized water, centrifuging at the speed of 6000rpm, repeatedly washing and centrifuging for 5 times, and drying in an oven at the temperature of 80 ℃ for 24h to obtain the nano copper-based two-dimensional sheet cerium oxide nanomaterial.
Example 8
Dispersing 0.3g of nano copper powder in 4ml of hydrogen peroxide with the percentage content of 15%, soaking for 10min, adding 15ml of 10% ammonia water, uniformly stirring in a beaker at the speed of 400rpm for 20min, enabling the mixed solution to be light blue, dropwise adding 5ml of cerium nitrate with the mass fraction of 40% into the mixed solution to obtain gray precipitate, stirring at the speed of 400rpm, aging for 30min, collecting a sample, washing with deionized water, centrifuging at 6000rpm, repeatedly washing and centrifuging for 5 times, and drying in an oven at the temperature of 80 ℃ for 24h to obtain the nano copper-based two-dimensional sheet cerium oxide nanomaterial.
Example 9
Dispersing 0.3g of nano copper powder in 4ml of hydrogen peroxide with the percentage content of 15%, soaking for 10min, adding 20ml of 9% ammonia water, uniformly stirring in a beaker at the speed of 400rpm for 30min, enabling the mixed solution to be light blue, dropwise adding 2ml of 30% cerium nitrate into the mixed solution to obtain gray precipitate, stirring at the speed of 400rpm, aging for 25min, collecting a sample, washing with deionized water, centrifuging at 8000rpm, repeatedly washing and centrifuging for 4 times, and drying in an oven at the temperature of 90 ℃ for 24h to obtain the nano copper-based two-dimensional sheet cerium oxide nano material.
Referring to fig. 2, fig. 6 and fig. 7, based on XRD spectrogram, BET spectrogram and pore size distribution spectrogram of the nano copper-based two-dimensional sheet cerium oxide nano material product obtained in example 1 of the present invention, it can be obtained from the XRD spectrogram of fig. 2 that the sample obtained by the preparation method is cerium oxide material, the obtained sample has Cu nano substrate, and it can be obtained from the BET spectrogram of fig. 6 and the pore size distribution spectrogram of fig. 7 that the cerium oxide nano material prepared by the present invention belongs to mesoporous material.
In addition, taking the copper-based two-dimensional sheet cerium oxide nanomaterial obtained in example 1 as an example, SEM images on the scale of 1um and 200nm are exemplarily shown in fig. 3 and 4, respectively. As shown in the figure 3 and figure 4, it can be seen that the two-dimensional sheet cerium oxide grows on the surface of the copper nanoparticle, the two-dimensional sheet cerium oxide material growing on the surface of the copper nanoparticle is distributed relatively uniformly, and the surface of the Cu nanoparticle is not exposed and no single cerium oxide nanosheet exists in a large range. Examples 5 and 7 are comparative examples, and the cerium oxide nanomaterial grown on the surface of the copper nanoparticles obtained in example 5 is taken as an example, and SEM images thereof on a 200nm scale are exemplarily shown in fig. 5. As shown in fig. 5, it can be seen that the two-dimensional sheet cerium oxide is less, and on the surface of the nano-copper particle, the cerium oxide material is mostly in a particle state and is distributed relatively uniformly. In example 7, the Cu nanoparticles cannot be coated by the cerium oxide nanosheets, and the Cu catalyst is prone to agglomeration and deactivation in the catalytic hydrogenation reaction.
In conclusion, the surface of Cu is oxidized by introducing hydrogen peroxide, and then the Cu surface is etched by ammonia water, and the two-dimensional sheet cerium oxide grows on the surface of the Cu nano particle after adding cerium salt, so that the two-dimensional sheet cerium oxide nano material growing on the surface of the obtained copper nano particle is coated with the sheet cerium oxide on the copper surface, and isolated cerium oxide nano sheets do not appear. In addition, high-temperature calcination and high-temperature long-time hydrothermal treatment are not needed in the whole preparation process, so that the energy consumption is reduced, the operation is simple, and the control is easy.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A method for synthesizing a nano copper-based two-dimensional sheet cerium oxide nano material is characterized by comprising the following steps:
(i) dispersing 70-80 nm copper nanoparticles in hydrogen peroxide, stirring at 20-25 ℃ to form a surface oxide layer on the surfaces of the copper nanoparticles;
(ii) adding ammonia water into the solution generated in the step (i), keeping the solution at room temperature for a certain time for reaction, and quickly corroding the oxide layer on the surface of the copper nanoparticles by means of the corrosion effect of the ammonia water to obtain a blue solution; meanwhile, the ammonia water forms a concentration gradient on the surface of the copper nano-particles due to the reaction of the ammonia water and the oxide layer;
(iii) and (3) adding a cerium nitrate solution into the blue solution generated in the step (ii), adjusting the pH value of the mixed solution to be within the range of 9-11, rapidly generating a precursor of the two-dimensional sheet cerium oxide nano material on the surface of the copper nano particles by means of the concentration gradient guidance of ammonia water under the condition of not adding a surfactant, and then carrying out washing, centrifugation and drying treatment by using deionized water to obtain the copper-based two-dimensional sheet cerium oxide nano material.
2. The method for synthesizing copper-based two-dimensional sheet cerium oxide nanomaterial according to claim 1, wherein in step (i), the concentration of hydrogen peroxide is 10-20% by mass, the amount of copper nanoparticles added is 0.1-0.5 g, the amount of hydrogen peroxide solution is 2-10 ml, and the soaking time is 10-30 min.
3. The method for synthesizing the nano copper-based two-dimensional sheet cerium oxide nanomaterial according to claim 1, wherein in the step (ii), the mass percentage concentration of the selected ammonia aqueous solution is 9% -10%, the adding amount of ammonia water is 10 ml-20 ml, and the stirring is carried out for 0.5 h-4 h.
4. The method for synthesizing copper-based two-dimensional sheet-shaped nano cerium oxide material according to claim 1, wherein in the step (iii), the cerium nitrate salt solution is used with a mass percentage concentration of 30-40%, and the addition amount is 2-5 ml, and the mixture is stirred for 10-30 min.
5. The method for synthesizing a copper-based nano-sized two-dimensional sheet-shaped cerium oxide nanomaterial according to any one of claims 1 to 4, wherein the ammonia water is added in the step (ii) and then the mixture is stirred at a stirring speed of 400rpm to 600 rpm.
6. The method for synthesizing a nano copper-based two-dimensional sheet cerium oxide nanomaterial according to claim 5, wherein in the step (iii), the centrifugal treatment adopts a rotating speed of 3000rpm to 8000rpm, the drying temperature is 80 ℃ to 100 ℃, and the drying time is 12h to 24 h.
7. The copper-based two-dimensional sheet cerium oxide nanomaterial prepared by the synthesis method according to any one of claims 1 to 6.
8. The use of the copper-based nano-sized two-dimensional plate-shaped cerium oxide nanomaterial as claimed in claim 7 in water gas shift, VOC exhaust gas catalytic treatment, solid oxide fuel cell or industrial carbon dioxide catalysis.
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