CN115837271A - Composite material catalyst and preparation and application thereof - Google Patents
Composite material catalyst and preparation and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 5
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- 238000001354 calcination Methods 0.000 claims description 31
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 22
- -1 methyl titanate Chemical compound 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 13
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention discloses a composite material catalyst and preparation and application thereof, belonging to the technical field of new materials and energy chemical industry. Compared with pure titanium dioxide, the titanium dioxide prepared by the methodNi and Zr co-doped TiO 2 The grain size is reduced, the electron diffusion freedom degree is improved, the spectral response range is enlarged, more oxygen vacancies can be introduced by the carbon coating action, and the photon-generated carrier transfer rate of the composite material is improved; the oxygen vacancy formed by carbon coating and the oxygen vacancy formed by Ni and Zr codoping can also generate a synergistic effect, which is beneficial to improving TiO together 2 Photocatalytic activity of (a); this application is to TiO 2 Catalytic reduction of CO 2 The field is effectively expanded, and the catalyst can be used for catalyzing and reducing CO by using a titanium-based catalyst 2 The application of the field provides a new idea.
Description
Technical Field
The invention belongs to the technical field of new materials and energy chemical industry, particularly relates to a composite material catalyst, and preparation and application thereof, and particularly relates to a Ni and Zr co-doped TiO x @ C composite catalyst, preparation method thereof and application thereof in CO 2 Application in the field of photocatalytic reduction.
Background
Driven by low-cost and renewable energy sources (such as solar energy or wind energy), the carbon dioxide is converted into chemical raw materials or liquid fuels with high added values, so that the global energy crisis can be effectively relieved, and the carbon cycle is promoted. In recent years, artificial photosynthesis has been used in CO 2 The fields of transformation and utilization are of great interest to those skilled in the art. Wherein the titanium dioxide photocatalysts CO 2 The transformation is a transformation treatment technology which is started in recent years, and the technology has the characteristics of no mass transfer limitation, capability of being operated at normal temperature, simple processing technology, stable characteristics and no toxicity. But due to TiO 2 Wide band gap (E) g = 3.o-3.2 eV), it is difficult for visible light with small photon energy to reach an excited state, so it can be excited only by ultraviolet light of 400nm or less. Thus pure TiO 2 Cannot fully utilize solar energy, has low photocatalytic reaction efficiency, and is suitable for TiO 2 The modification research is carried out to become the catalytic reduction of CO 2 The hot spot in the field, the purpose of modification is mainly to extend TiO 2 The response range to visible light improves the utilization efficiency of the sunlight.
Earlier researches show that the catalytic oxidation activity of titanium dioxide doped with metal ions can be improved to different degrees, such as Wangjie et al, mg and Zr codoped TiO 2 Photocatalytic reduction of CO 2 "in this paper, it is pointed out that when Mg and Zr are codoped, zr 4+ Substituted TiO 2 In crystal lattice Ti 4+ ，Mg 2+ Substituted TiO 2 In crystal lattice Ti 4+ Increase surface alkaline sites, with pure TiO 2 In contrast, mg/Zr-TiO 2 The forbidden band width is reduced, the Mg and the Zr have synergistic effect, the light absorption range is widened, and the TiO can be improved 2 Photocatalytic reduction of CO under visible and ultraviolet light 2 The performance of (c). It is noted that the TiO is simply doped by introducing metal ions 2 The modification may generate deep level recombination centers, which may reduce the photocatalytic efficiency, and the stability of the catalyst may be affected to some extent.
Therefore, it is necessary to deal with TiO 2 The modification work is further studied to further improve the moving speed of the photoacoustic current carrier, avoid the recombination of photon-generated electron-hole pairs and help to improve TiO 2 The light response range and the light catalytic activity are that the titanium-based catalyst is used for catalyzing and reducing CO 2 Applications in the art provide more meaningful references and guidance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a composite material catalyst and preparation and application thereof 2 Photocatalytic activity ofAnd (4) sex.
The technical scheme of the invention is as follows: a preparation method of a composite catalyst comprises the following steps:
1) Stirring and mixing a methyl titanate solution and a butyl acetate solution to obtain a mixed solution A;
2) Dissolving a certain amount of nickel salt and zirconium salt in a mixed solvent to form a mixed solution B;
3) Slowly adding the mixed solution A into the mixed solution B, stirring until a transparent and uniform colloidal solution is formed, aging, drying in a vacuum drying oven to obtain gel, grinding into gel particles, and calcining to obtain Ni/Zr-TiO 2 A powdered product;
4) The powdery Ni/Zr-TiO prepared in the step 3) is put into 2 Immersing into glucose solution, calcining in reducing atmosphere to obtain Ni/Zr codoped TiO x @ C composite catalyst.
Further, in the step 1), the volume ratio of the methyl titanate to the butyl acetate is 10-5, and the stirring time is 1-3 h.
Furthermore, in the step 3), after the mixed solution A and the mixed solution B are mixed, the molar ratio of Ni, zr and Ti is 0-2% to 0-4% to 1, and the doping amount of Ni and Zr is not 0.
Furthermore, in the step 3), the calcining temperature is 360-440 ℃, and the calcining time is 1-4 h.
Further, in the step 4), the calcining atmosphere is Ar/H 2 Or N 2 The calcination temperature is 380-420 ℃, and the calcination time is 1-3 h.
Further, in the step 4), the concentration of the glucose solution is 0.02-0.04 mol/L, ni/Zr-TiO 2 Soaking in glucose solution for 4-6 hr, and calcining.
Further, in the step 2), the mixed solvent is prepared by compounding methyl titanate, water and butyl acetate according to the volume ratio of 5.
Further, in the step 3), after the mixed solution A and the mixed solution B are mixed, the molar ratio of Ni, zr and Ti is 2%:2%:1.
The composite material catalyst prepared by the method is Ni and Zr co-doped TiO x A catalyst of the formula @ C,the composite material catalyst is applied to catalytic reduction of CO 2 When in the field, it catalyzes CO 2 The yield of the CO is higher than that of pure TiO 2 Ni and Zr codoped TiO not subjected to carbon coating treatment 2 And TiO doped with single metal Ni or single metal Zr x @C。
Compared with the prior art, the invention has the following advantages:
1. the application utilizes the mode of metal ion doping to improve TiO 2 Catalytic oxidation activity, and calcining grape sugar coating in reducing atmosphere to react with Ni/Zr-TiO 2 The particles are carbon coated, which is helpful in TiO coating 2 More oxygen vacancy introduced on the surface to produce TiO x Is more beneficial to the rapid movement of photo-generated carriers, reduces the reaction activation energy, and reduces CO 2 The catalytic reaction activity is further improved;
2. when Ni and Zr are codoped, zr 4+ Substitute for Ti 4+ To TiO 2 The crystal lattice gaps of (3) cause oxygen vacancies and more basic sites on the surface of the catalyst, so that part of oxygen can escape from the surface of the crystal lattice to capture photogenerated holes, and the doping of Zr enables TiO to 2 Has higher specific surface area and better heat resistance, is beneficial to the diffusion of free electrons from the center to the surface, and in addition, zr doping causes TiO 2 Lattice distortion forms a capture trap, and the photoacoustic charge carrier separation efficiency can be improved; and Ni 2+ Can be made into TiO 2 Distortion of crystal lattice, reduction of activation energy of reaction, CO 2 The catalytic reaction activity is improved; therefore, the Ni and Zr codoping can generate a synergistic effect, the recombination of photo-generated electron-hole pairs can be effectively avoided, and the TiO is improved 2 While enhancing the catalytic reaction performance of TiO 2 The glass transition temperature of (2);
3. under the irradiation of sunlight, the oxygen vacancy formed by carbon coating and the oxygen vacancy formed by Ni and Zr codoping produce synergistic effect, which is helpful for improving TiO together 2 The composite material catalyst prepared by the method is to TiO 2 Catalytic reduction of CO 2 The field is effectively expanded, and the catalyst can be used for catalyzing and reducing CO by using a titanium-based catalyst 2 Applications in the field provide efficient pointingGuiding a new thought;
4. the reaction reagent used in the method has the advantages of small environmental pollution, low energy requirement required by reaction, mild reaction conditions, uniform and fine catalyst particles prepared by a sol-gel method, and ensured safety and reliability of the whole preparation process.
Drawings
FIG. 1 shows that the photocatalytic materials prepared in example 1 and comparative examples 1 to 4 catalyze CO 2 Converting into a yield statistical chart of CO;
FIG. 2 is a TEM image of the composite photocatalytic material prepared in example 1;
fig. 3 is an XRD pattern of the photocatalytic materials prepared in example 1 and comparative example 1.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings, but not limited thereto, and any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be covered by the protection scope of the present invention.
Example 1: preparation of Zr and Ni co-doped TiOx @ C composite photocatalytic material
Mixing 10mL of methyl titanate and 5mL of butyl acetate, and stirring for 1 hour to obtain a mixed solution A; weighing a certain amount of Zr (NO) 3 ) 4 ·5H 2 O and Ni (NO) 3 ) 2 ·6H 2 Dissolving the two in a mixed solution of methyl titanate, water and butyl acetate (volume ratio of 5; slowly adding the mixed solution A into the mixed solution B, fully stirring for 1h until the mixed solution A becomes a transparent and uniform colloidal solution, wherein the molar ratio of Zr to Ni to Ti is 2% to 1; aging the sol at 50 ℃, then putting the sol into a vacuum drying oven, drying the sol at 120 ℃ to obtain gel, taking out the gel, and grinding the gel into particles; putting the gel particles into a muffle furnace, and calcining for 2h at 400 ℃ to obtain Ni/Zr-TiO 2 A powdered product; the resulting powdered product was then immersed in a 0.02mol/L glucose solution for 5H in Ar/H 2 Calcining for 2h at 400 ℃ under the atmosphere to obtain the final product.
Example 2: zr and Ni codopingTiO x Preparation of @ C composite photocatalytic material
Mixing 10mL of methyl titanate and 5mL of butyl acetate, and stirring for 2 hours to obtain a mixed solution A; weighing a certain amount of Zr (NO) 3 ) 4 ·5H 2 O and Ni (NO) 3 ) 2 ·6H 2 Dissolving the two in a mixed solution of methyl titanate, water and butyl acetate (volume ratio of 5; slowly adding the mixed solution A into the mixed solution B, wherein the molar ratio of Zr to Ni to Ti is 0.5% to 2% to 1, and fully stirring for 1h until the mixed solution A becomes a transparent and uniform colloidal solution; aging the sol at 50 ℃, then putting the sol into a vacuum drying oven, drying the sol at 120 ℃ to obtain gel, taking out the gel, and grinding the gel into particles; putting the gel particles into a muffle furnace, and calcining for 1h at the temperature of 420 ℃ to obtain Ni/Zr-TiO 2 A powdered product; the resulting powdered product was then immersed in a 0.02mol/L glucose solution for 5H in Ar/H 2 Calcining for 3h at 380 ℃ under the atmosphere to obtain the final product.
Example 3: zr and Ni co-doped TiO x Preparation of @ C composite photocatalytic material
Mixing 10mL of methyl titanate and 2mL of butyl acetate, and stirring for 3 hours to obtain a mixed solution A; weighing a certain amount of Zr (NO) 3 ) 4 ·5H 2 O and Ni (NO) 3 ) 2 ·6H 2 Dissolving the two in a mixed solution of methyl titanate, water and butyl acetate (volume ratio of 5; slowly adding the mixed solution A into the mixed solution B, fully stirring for 1h until the mixed solution A becomes a transparent and uniform colloidal solution, wherein the molar ratio of Zr to Ni to Ti is 4: 2: 1; aging the sol at 50 ℃, then putting the sol into a vacuum drying oven, drying the sol at 120 ℃ to obtain gel, taking out the gel, and grinding the gel into particles; putting the gel particles into a muffle furnace, and calcining for 4 hours at 360 ℃ to obtain Ni/Zr-TiO 2 A powdered product; the resulting powdered product was then immersed in a 0.02mol/L glucose solution for 5H in Ar/H 2 Calcining for 1h at 420 ℃ under the atmosphere to obtain the final product.
Example 4: zr and Ni co-doped TiO x Preparation of @ C composite photocatalytic material
10mL ofMixing methyl titanate and 5mL of butyl acetate, and stirring for 1 hour to obtain a mixed solution A; weighing a predetermined amount of Zr (NO) 3 ) 4 ·5H 2 O and Ni (NO) 3 ) 2 ·6H 2 Dissolving the two in a mixed solution of methyl titanate, water and butyl acetate (volume ratio of 5; slowly adding the mixed solution A into the mixed solution B, fully stirring for 1h until the mixed solution A becomes a transparent and uniform colloidal solution, wherein the molar ratio of Zr to Ni to Ti is 1: 1; aging the sol at 50 ℃, then putting the sol into a vacuum drying oven, drying the sol at 120 ℃ to obtain gel, taking out the gel and grinding the gel into particles; putting the gel particles into a muffle furnace, and calcining for 2.5h at 380 ℃ to obtain Ni/Zr-TiO 2 A powdered product; the resulting powdered product was then immersed in a 0.02mol/L glucose solution for 5h under N 2 Calcining for 1.5h at 420 ℃ under the atmosphere to obtain the final product.
Comparative example 1: ni-doped TiO x Preparation of @ C composite photocatalytic material
Mixing 10mL of methyl titanate and 4mL of butyl acetate, and stirring for 2 hours to obtain a mixed solution A; weighing a certain amount of Ni (NO) 3 ) 2 ·6H 2 Dissolving the compound in a mixed solution of methyl titanate, water and butyl acetate (volume ratio of 5; slowly adding the mixed solution A into the mixed solution B, fully stirring for 1h until the mixed solution A becomes a transparent and uniform colloidal solution, wherein the molar ratio of Ni to Ti is 2: 1; aging the sol at 50 ℃, then putting the sol into a vacuum drying oven, drying the sol at 120 ℃ to obtain gel, taking out the gel and grinding the gel into particles; putting the gel particles into a muffle furnace, and calcining for 1h at 440 ℃ to obtain Ni-TiO 2 A powdered product; the resulting powdered product was then immersed in a 0.02mol/L glucose solution for 5H in Ar/H 2 Calcining for 3h at 400 ℃ under the atmosphere to obtain the final product.
Comparative example 2: zr-doped TiO x Preparation of @ C composite photocatalytic material
Mixing 10mL of methyl titanate and 3mL of butyl acetate, and stirring for 1 hour to obtain a mixed solution A; weighing a certain amount of Zr (NO) 3 ) 4 ·5H 2 O, dissolving it in methyl titanate,Preparing a mixed solution B from a mixed solution of water and butyl acetate (volume ratio of 5; slowly adding the mixed solution A into the mixed solution B, fully stirring for 1h until the mixed solution A becomes a transparent and uniform colloidal solution, wherein the molar ratio of Zr to Ti is 2% to 1; aging the sol at 50 ℃, then putting the sol into a vacuum drying oven, drying the sol at 120 ℃ to obtain gel, taking out the gel, and grinding the gel into particles; putting the gel particles into a muffle furnace, and calcining for 1.5h at 410 ℃ to obtain Zr-TiO 2 A powdered product; the resulting powdered product was then immersed in a 0.02mol/L glucose solution for 5H in Ar/H 2 Calcining for 2h at 380 ℃ under the atmosphere to obtain the final product.
Comparative example 3: zr and Ni co-doped TiO 2 Preparation of composite photocatalytic material
Mixing 10mL of methyl titanate and 5mL of butyl acetate, and stirring for 3 hours to obtain a mixed solution A; weighing a certain amount of Zr (NO) 3 ) 4 ·5H 2 O and Ni (NO) 3 ) 2 ·6H 2 Dissolving the two in a mixed solution of methyl titanate, water and butyl acetate (volume ratio of 5; slowly adding the mixed solution A into the mixed solution B, fully stirring for 1h until the mixed solution A becomes a transparent and uniform colloidal solution, wherein the molar ratio of Zr to Ni to Ti is 2% to 1; aging the sol at 50 ℃, then putting the sol into a vacuum drying oven, drying the sol at 120 ℃ to obtain gel, taking out the gel, and grinding the gel into particles; putting the gel particles into a muffle furnace, and calcining for 4 hours at 370 ℃ to obtain Ni/Zr-TiO 2 A powdered product.
Comparative example 4: tiO 2 2 Preparation of photocatalytic Material
Mixing 10mL of methyl titanate and 5mL of butyl acetate, and stirring for 1 hour to obtain a mixed solution A; adding a mixed solution of methyl titanate, water and butyl acetate (volume ratio of 5; standing the sol at 50 deg.C for a period of time, then placing into a vacuum drying oven, drying at 110 deg.C to obtain gel, taking out, and grinding into granules; putting the gel particles into a muffle furnace, and calcining for 1.5h at 420 ℃ to obtain TiO 2 A powdered product.
Testing the photocatalytic performance:
0.1g of the photocatalytic materials prepared in examples 1 to 4 and comparative examples 1 to 4 were charged into a photocatalytic reaction system, respectively, and high purity CO was obtained 2 (99.999%) was introduced into a constant temperature water bath at a flow rate of 15mL/min to obtain a mixed gas containing 35% of water vapor, which was then introduced into a catalytic reactor. Ventilating for 20min, turning off the air outlet when adsorption saturation is reached, reducing the total flow to 10mL/min, stopping ventilation after 10min, then turning on the 300W xenon lamp light source, and turning off the light source after 10h of irradiation. 1mL of the gas was taken out from the reactor and quantitatively analyzed by a gas chromatograph equipped with a Flame Ionization Detector (FID).
From the catalytic results of the composite materials prepared in examples 1 to 4, it is known that Zr-doped TiO is present in different proportions x @ C catalysis of CO 2 The obtained CO yield is also obviously different when the molar ratio of Zr to Ti is 2%:1, the catalytic effect is best.
FIG. 1 shows that different photocatalytic materials prepared in example 1 and comparative examples 1-4 catalyze CO under UV irradiation 2 、CO 2 Statistical results of the yields of conversion to CO, it can be seen from FIG. 1 that CO is a Ni/Zr doped TiO 2 Composite photocatalytic CO 2 The main product of (1). Under the condition of UV radiation, ni/Zr codoped TiO x @ C composite catalyst (example 1) catalyzes CO 2 The amount of CO produced is significantly higher than that of TiO doped with single element Ni only x @ C (comparative example 1), tiO doped with only elemental Zr x @ C (comparative example 2) and pure TiO 2 (comparative example 4); from the conversion results of example 1 and comparative example 3, it can be seen that CO is present after carbon coating 2 The catalytic performance is obviously improved, and the carbon-coated catalyst can be coated on TiO 2 More oxygen vacancy introduced on the surface to produce TiO x Is more beneficial to the rapid movement of photo-generated carriers, reduces the reaction activation energy and further improves the CO 2 And (4) catalytic reaction activity.
As can be seen from FIG. 3, XRD patterns of the catalytic materials prepared in comparative example 1 and comparative example 1 show that TiO was doped with Zr 2 The crystallinity decreased, probably due to Zr 4+ Into TiO 2 Unit cell substituted for Ti 4+ Of TiO 2 2 The crystal lattice can be deformed to generate defectsAnd is concentrated on the surface of the material, resulting from the inhibition of crystal growth.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The preparation method of the composite material catalyst is characterized by comprising the following steps of:
1) Stirring and mixing a methyl titanate solution and a butyl acetate solution to obtain a mixed solution A;
2) Dissolving a certain amount of nickel salt and zirconium salt in a mixed solvent to form a mixed solution B;
3) Slowly adding the mixed solution A into the mixed solution B, stirring to form a transparent and uniform colloidal solution, aging, drying in a vacuum drying oven to obtain gel, grinding into gel particles, and calcining to obtain Ni/Zr-TiO 2 A powdered product;
4) The powdery Ni/Zr-TiO prepared in the step 3) is put into 2 Immersing into glucose solution, calcining in reducing atmosphere to obtain Ni/Zr codoped TiO x @ C composite catalyst.
2. The method for preparing the composite catalyst according to claim 1, wherein in the step 1), the volume ratio of the methyl titanate to the butyl acetate is 10-5, and the stirring time is 1-3 h.
3. The method of claim 1, wherein in step 3), after the mixture A and the mixture B are mixed, the molar ratio of Ni, zr and Ti is 0-2% to 0-4% to 1, and the amount of Ni and Zr is not 0.
4. The method for preparing a composite catalyst according to claim 1, wherein in the step 3), the calcination temperature is 360-440 ℃ and the calcination time is 1-4 h.
5. The method of claim 1, wherein in step 4), the calcination atmosphere is Ar/H 2 Or N 2 The calcination temperature is 380-420 ℃, and the calcination time is 1-3 h.
6. The method of claim 1, wherein in the step 4), the concentration of the glucose solution is 0.02-0.04 mol/L, and the concentration of Ni/Zr-TiO is 0.02-0.04 mol/L 2 Soaking in glucose solution for 4-6 hr, and calcining.
7. The preparation method of the composite catalyst according to claim 1, wherein in the step 2), the mixed solvent is prepared by mixing methyl titanate, water and butyl acetate according to a volume ratio of 5.
8. The method of claim 3, wherein in step 3), the mixture A and the mixture B are mixed in a molar ratio of Ni, zr and Ti of 2% to 1.
9. A composite catalyst prepared by the method according to any one of claims 1 to 8, wherein the composite catalyst is Ni and Zr co-doped TiO x @ C catalyst.
10. The use of a composite catalyst as claimed in claim 9 in the catalytic reduction of CO 2 The application is characterized in that the composite material catalyst catalyzes CO 2 The yield of the CO is higher than that of pure TiO 2 Ni and Zr codoped TiO not subjected to carbon coating treatment 2 And TiO doped with single metal Ni or single metal Zr x @C。
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