CN111375411B - Monoatomic Cu/TiO 2 Method for preparing nano-wire - Google Patents
Monoatomic Cu/TiO 2 Method for preparing nano-wire Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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Abstract
The invention discloses a monoatomic Cu/TiO 2 A method for preparing nanowires comprising the steps of: (1) Solvothermal synthesis of rutile TiO with surface defect 2 A nanorod; (2) Method for synthesizing monoatomic Cu/TiO by dipping method 2 A nanowire. The invention adds copper nitrate into rutile type TiO 2 The specific form of copper is controlled by controlling the loading amount of copper by dipping and precipitating the nano-rods in alkaline solution, and particularly, monoatomic Cu/TiO can be obtained 2 The preparation method of the invention is simple and effective, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to monoatomic Cu/TiO 2 A method for preparing nanowires.
Background
Fossil energy-driven mechanical transportation is one of the main causes of environmental pollution problems worldwide, causing serious air pollution. The main pollutants emitted by automobiles are CO, hydrocarbons (HC) and NOx. Among them, CO is the most toxic gas for human and animal plants. The CO in the urban air pollution source is mainly from the emission of automobile exhaust, and the emission of the CO exceeds more than half of the air pollutants. The catalytic oxidation method is one of the main methods for treating CO, and has the advantages of low operation temperature, high removal efficiency and the like. The CO oxidation catalyst is mainly composed of precious metal elements such as platinum, rhodium, palladium and the like, but is expensive, poor in hydrothermal stability and prone to poisoning. Therefore, the development of the catalytic material with low cost, high catalytic activity, high thermal stability and high toxicity resistance is of great significance. Therefore, non-noble metal oxide catalysts have been the focus of research. However, the non-noble metal oxide catalyst still has not been commercially used for low-temperature CO catalytic oxidation, and the main challenge is that the activity and stability of the catalyst cannot meet the industrial requirements. Therefore, a new synthetic route is sought, and the development of a new non-noble metal catalyst with higher efficiency is a key problem faced by scientists.
The monatomic catalyst not only has complete atom utilization rate, but also has excellent and unique physical and chemical characteristics due to quantum size effect, unsaturated coordination environment, metal-carrier interaction and the like, so the monatomic catalyst is widely researched by people. The metal monatomic catalyst can be used for realizing high catalytic efficiency by taking each metal atom as an active site. Compared with the micro-nano metal catalyst, the metal monatomic catalyst has the effect of being one to ten and one to hundred. The successful construction of the monatomic catalytic system deepens the research of the catalytic field into a smaller scale range, not only can recognize complex heterogeneous catalytic reaction from atomic layer, but also has huge application potential in industrial catalysis due to the excellent catalytic performance.
Of course, the preparation of monatomic catalysts presents challenges. When the size of the metal particles is reduced to the size of a single atom, the sharply increased surface free energy of the metal particles causes that the single atom material is extremely easy to agglomerate during preparation and application, nanoclusters and nanoparticles are formed, deactivation of the catalyst and other phenomena can be caused, and therefore the single atom catalyst is easy to lose the effect of the single atom. This is the biggest challenge in preparing monatomic materials. The current methods for preparing monatomic materials include mass separation soft landing methods, coprecipitation methods, impregnation methods, atomic layer deposition methods, reverse Ostwald ripening methods, stepwise reduction methods, solid phase melting methods, and the like. However, due to the limitations of the preparation process and the challenges of monatomic stability, how to simply and efficiently prepare high-quality catalysts remains a challenge.
Disclosure of Invention
In view of the above-mentioned problems, it is an object of the present invention to provide a monoatomic Cu/TiO compound 2 A method for preparing nanowires. In another aspect of the invention, the invention also relates to the monoatomic Cu/TiO 2 Nanowires and applications thereof.
In order to solve the technical problem of the invention, the following technical scheme is adopted:
one aspect of the invention relates to a monoatomic Cu/TiO compound 2 The preparation method of the nanowire is characterized by comprising the following steps:
(1) Solvothermal synthesis of rutile TiO with surface defect 2 And (3) nano-rods: uses tetrabutyl titanate as a precursor of titanium, and generates rutile TiO with surface defects through hydrolysis reaction 2 A nanowire;
(2) Method for synthesizing monoatomic Cu/TiO by dipping method 2 Nanowire: in the impregnation method, cu (NO) 3 ) 2 In an amount of rutile type TiO having surface defects 2 The amount of the nanowire added is 0.9 mass% or less.
In a preferred embodiment of the present invention, the solvothermal synthesis of rutile TiO having surface defects 2 In the step of the nano-rod, toluene is used as a solvent. At the same temperature, the toluene as solvent can reach higher pressure than hydrothermal reaction, thereby being beneficial to TiO 2 Under solvothermal conditions, toluene not only acts as a medium, solvent, transfer pressure and mineralizer, but also acts as a chemical component to make rutile TiO 2 The nanowires generate surface defects.
In a preferred embodiment of the present invention, the solvothermal synthesis is carried out for 5 hours or more. The length of the nanowire can be regulated and controlled by controlling the solvothermal synthesis time, and the length of the nanowire is increased along with the extension of the reaction time.
In another preferred embodiment of the present invention, the impregnation method is to add copper nitrate to the rutile TiO with surface defects 2 The nano-wires are subjected to impregnation precipitation in an alkaline solution. Without wishing to be bound by theory, rutile TiO forms with surface defects during immersion in aqueous solutions having a pH above 10 2 The nano-wire can have negative charges on the surface, the copper ions with positive charges can be preferentially adsorbed to the surface of the carrier due to the physical adsorption and charge action, and the metal species can be coordinated with the groups on the surface through further heat treatment, so that a monoatomic structure is formed.
In a preferred embodiment of the present invention, cu (NO) 3 ) 2 In an amount of rutile type TiO having surface defects 2 The addition amount of the nano wire is between 0.1 and 0.5 percent by mass. If gold is present in solutionThe Cu ion component is too high, and when the concentration exceeds a certain concentration, redundant Cu ions can agglomerate on the surface of the carrier, so that metal clusters or particles are formed; if the Cu ion in the solution is too low, the loading of the monoatomic ion is correspondingly reduced, thereby affecting the catalytic application thereof.
In another aspect, the invention also relates to the monoatomic Cu/TiO prepared by the method 2 A nanowire. Preferably, part or all of the Cu exists in TiO in the form of Cu + 2 The surface of the nanowire is coated with Cu 2+ Conversion to Cu + The catalytic activity of the catalyst can be improved.
In a preferred embodiment of the present invention, the TiO is 2 The diameter of the nano-wire is between 5 and 10 nanometers, and the length of the nano-wire is more than 200 nm.
For the monoatomic Cu/TiO of the present invention 2 In the case of nanowires, it is preferably used for catalytic oxidation of CO.
Although the impregnation method is a method for preparing a catalyst commonly used in the art, the present invention is achieved by adding copper nitrate to rutile type TiO having surface defects 2 The specific form of the copper is controlled by controlling the loading amount of the copper by carrying out immersion precipitation in an alkaline solution of the nano wire, and particularly, the monoatomic Cu/TiO can be obtained 2 The preparation method of the invention is simple and effective, and is suitable for large-scale industrial production.
Drawings
FIG. 1 shows a monoatomic Cu/TiO compound prepared in example 1 2 Characterization results of nanowire catalysts, wherein a: cu/TiO 2 High angle annular dark field images (HAADF) of monatomic catalysts; b Cu/TiO 2 Scanning electron microscopy transmission imaging (STEM) of monatomic catalysts;
FIG. 2 shows Cu nanoparticles/TiO prepared in comparative example 1 2 Characterization results of nanowire catalysts, wherein a is Cu/TiO 2 A high angle annular dark field image (HAADF) of the nanoparticle catalyst; b Cu/TiO 2 Scanning electron microscopy transmission imaging (STEM) of nanoparticle catalysts;
FIG. 3 is an X-ray photoelectron spectrum (XPS) of the catalysts prepared in example 1 and comparative example 1;
FIG. 4 is Electron Paramagnetic Resonance (EPR) spectra of catalysts prepared in example 1 and comparative example 1;
FIG. 5 is an Arrhenius curve of the catalysts prepared in example 1 and comparative example 1;
fig. 6 is a reaction activity curve of CO catalytic oxidation of the catalysts prepared in example 1 and comparative example 1.
Detailed Description
In order to further illustrate the technical solution of the present invention, the above technical solution is described in detail below with specific examples, but the present invention is not limited to the following embodiments.
Example 1:
synthesis of rutile TiO with surface defect by solvothermal method 2 And (3) nano-rods:
50ml of toluene, 5ml of tetrabutyl titanate and 5ml of hydrochloric acid are added into a 100ml reaction kettle; putting the reaction kettle into an oven, and keeping the temperature at 150 ℃ for 10 hours; and carrying out centrifugal separation on the turbid liquid in the reaction kettle to obtain TiO 2 A powder of nanowires.
Synthesizing a monatomic catalyst by an impregnation method:
adding TiO into the mixture 2 Adding the powder into deionized water, stirring, adding ammonia water or sodium hydroxide into a beaker, adjusting pH to 10, and adding Cu (NO) 3 ) 2 Adding the solution into the turbid solution, stirring for 6h 3 ) 2 In an amount of TiO 2 And then dried at 70 ℃. Grinding the obtained powder into fine powder in agate mortar, and then air-drying at 10 deg.C for min -1 The temperature rise rate of (2) was subjected to heat treatment at 500 ℃ for 5 hours. Obtaining monoatomic Cu/TiO 2 A nanowire catalyst.
Comparative example 1:
Cu(NO 3 ) 2 in an amount of TiO 2 1% by mass of (A), the same other steps as in example 1 were repeated to obtain Cu nanoparticles/TiO 2 A nanowire catalyst.
The characterization results of the nanowires prepared in example 1 and comparative example 1 are shown in fig. 1 to 4. As can be seen from the characterization results of FIG. 1, tiO 2 The loading on the nanowire is a Cu monoatomic rather than a nanoparticle morphology. From the characterization results of FIG. 2, tiO 2 The nanowire is loaded with Cu nanoparticles. FIG. 3 is an X-ray photoelectron spectroscopy (XPS) of the catalysts of example 1 and comparative example 1; FIG. 4 is an Electron Paramagnetic Resonance (EPR) spectrum of the catalysts of example 1 and comparative example 1; the results in conjunction with fig. 3 and 4 show that the surface copper of the catalyst of example 1 exhibits a valence of + 1.
Example 2:
in order to further evaluate the catalytic activity of the catalyst of the present invention, the present invention was evaluated by a CO catalytic oxidation activity evaluation experiment.
Evaluation of catalytic combustion activity of carbon monoxide (CO) the test was carried out in a fixed bed reactor simulated by a quartz tube having a diameter of 8 mm. 50mg of catalyst (about 0.1mg of Cu active species) was loaded into a quartz tube, which was placed in a tube furnace and ramped from room temperature to 450 ℃. The reaction gas composition (volume fraction) was: 1% of CO,5% 2 ,94％N 2 The total flow is 50mL/min, and the mass space velocity is 43000 mL/(g.h). Finally, the components of the reaction tail gas are subjected to online CO analysis by a gas chromatograph of a type of Tyt GC-2030, and the calculation formula of the conversion rate is as follows:
CO conversion (%) = (area of inlet CO peak-area of outlet CO peak)/area of CO methane peak × 100%
Apparent activation energy calculation formula:
lnr＝-+lnA+aln[CO]+bln[O 2 ](ii) a Wherein Ea represents apparent activation energy; r represents the reaction rate;
on 2CO 2 →2CO 2 In the reaction, the reaction rate r is calculated by the formula:
wherein the conversion rate of CO is below 10 percent, the gas flow is 50ml/min,a is the specific surface area of the catalyst of 86m 2 /kg。
The test results are shown in fig. 5 and 6. As can be seen from FIGS. 5 and 6, the monoatomic Cu/TiO of the present invention is compared with comparative example 1 2 The nanowire catalyst has better CO catalytic oxidation activity.
The applicant states that the detailed embodiments of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed embodiments, that is, the present invention is not limited to the above embodiments, and it should be understood by those skilled in the art that any modification to the present invention, equivalent replacement and addition of the present invention, selection of specific modes, etc. fall within the protection scope and disclosure of the present invention.
Claims (10)
1. Monoatomic Cu/TiO 2 The preparation method of the nanowire is characterized by comprising the following steps:
(1) Synthesis of rutile TiO with surface defect by solvothermal method 2 And (3) nano-rods: uses tetrabutyl titanate as a precursor of titanium, and generates rutile type TiO with surface defects through hydrolysis reaction 2 A nanowire;
(2) Method for synthesizing monoatomic Cu/TiO by dipping method 2 Nanowire: in the impregnation method, cu (NO) 3 ) 2 In an amount of rutile type TiO having surface defects 2 The amount of the nanowire added is 0.9 mass% or less.
2. The method according to claim 1, wherein the rutile type TiO with surface defects is synthesized by solvothermal method 2 In the step of the nano-rod, toluene is used as a solvent.
3. The process according to claim 1, wherein the solvothermal synthesis is carried out for 5 hours or more.
4. The method of claim 1, wherein the impregnation method is carried out by adding copper nitrate to rutile TiO with surface defects 2 The nano-wires are subjected to dip precipitation in an alkaline solution.
5. The method of claim 1, cu (NO) 3 ) 2 In an amount of rutile type TiO having surface defects 2 The addition amount of the nano wire is between 0.1 and 0.5 percent by mass.
6. Monoatomic Cu/TiO produced by the production method according to any one of claims 1 to 5 2 A nanowire.
7. The monoatomic Cu/TiO according to claim 6 2 The part or all of the Cu exists in TiO in the form of Cu + 2 The surface of the nanowire.
8. The monoatomic Cu/TiO according to claim 6 2 Nanowire of said TiO 2 The diameter of the nano-wire is between 5 and 10 nanometers, and the length of the nano-wire is more than 200 nm.
9. The monatomic Cu/TiO of any of claims 6~8 2 The application of the nano-wire as a catalyst for catalytic oxidation.
10. Use according to claim 9, of the monoatomic Cu/TiO 2 The nanowires are used for catalytic oxidation of CO.
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| Controllable synthesis of brookite/anatase/rutile TiO2 nanocomposites and single-crystalline rutile nanorods array;Yulong Liao等;《J. Mater. Chem.》;20120312;第22卷;第7937-7944页 * |
| Effect of Ti3+ on TiO2-Supported Cu Catalysts Used for CO Oxidation;Ching S. Chen等;《Langmui》;20120608;第28卷;第9996-10006页 * |
| Single atom Cu(I) promoted mesoporous titanias for photocatalytic Methyl Orange depollution and H2 production;Rima Trofimovaite等;《Applied Catalysis B: Environmental》;20180322;第232卷;第501–511页 * |
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