CN115845850A - Preparation of foam metal-based monolithic catalyst and application of foam metal-based monolithic catalyst in photo-thermal degradation of VOCs - Google Patents
Preparation of foam metal-based monolithic catalyst and application of foam metal-based monolithic catalyst in photo-thermal degradation of VOCs Download PDFInfo
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- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 7
- 239000002070 nanowire Substances 0.000 description 7
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
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- 125000004122 cyclic group Chemical group 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The invention provides a foam metal-based monolithic catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: step a, preparing oxidized foam metal; step b, preparing the MOF-loaded oxidized foam metal; and c, preparing the foam metal-based monolithic catalyst loaded with the MOF-derived metal oxide. The preparation method is simple, and the prepared catalyst is an integral catalyst, is easy to separate and recover, can be produced in a large scale and is beneficial to industrial application. The catalyst can be applied to photo-thermal degradation of VOCs.
Description
Technical Field
The invention belongs to the technical field of material preparation and gas environment pollution control, and particularly relates to a foam metal-based monolithic catalyst, and a preparation method and application thereof.
Background
With the rapid development of urbanization and industrialization, the demand of human beings for energy is continuously increased, so that the emission of VOCs is rapidly increased, the excessive emission of pollutants causes the air quality in many parts of the world to be greatly reduced, and the environmental pollution is increasingly serious. The photothermal catalytic reaction is an environment-friendly catalytic oxidation technology, which is a process of completely oxidizing volatile organic pollutants into carbon dioxide and water in the presence of a catalyst by taking clean sunlight as an energy source, and is considered as one of the most effective methods for eliminating VOCs. Compared with the traditional photocatalytic reaction, the photothermal catalysis can also utilize infrared light of an infrared waveband which cannot be absorbed by the traditional photocatalysis, the light of the infrared waveband accounts for 53% of the solar spectrum, the surface temperature of the catalyst is mainly increased, and when the surface temperature of the catalyst reaches the ignition temperature of the reaction, the catalyst can catalyze and degrade VOCs. However, the primary task in achieving this technology is to develop efficient, stable catalysts and feasibility for large-scale practical applications.
The conventional powder catalyst is difficult to be directly applied to industrial application due to the defects of difficult separation and the like, the conventional monolithic catalyst generally disperses the powder catalyst on a honeycomb carrier (such as cordierite), but the batch operation of the catalyst and the actual industrial process with complicated operation flow can face a plurality of challenges. For example, the heat conduction coefficient of the cordierite Dan Dide causes uneven temperature distribution in the pore channels of the monolithic catalyst, the adsorption capacity to water greatly reduces the surface active sites, active components easily fall off from the surface of the carrier, the problems of inactivation and regeneration of the catalyst are obvious, and a large amount of resources and cost waste and secondary environmental pollution are caused. In recent years, a novel catalyst using a foam metal as a carrier has been proposed, and the carrier has the advantages of a three-dimensional macroporous structure, a large specific surface area, good thermal conductivity, low economic cost, good flexibility and the like, and is expected to become one of the most promising monolithic catalyst carriers. However, such monolithic catalysts have not been used in photothermal catalysis. Therefore, further exploration is needed to develop monolithic photothermal catalysts that are efficient, stable, and amenable to large-scale production.
Disclosure of Invention
In order to improve the technical problems, the invention provides a foam metal-based monolithic catalyst, a preparation method and application thereof.
The invention provides a preparation method of a catalyst, which specifically comprises the following steps:
step a, preparing oxidized foam metal: calcining the foam metal to obtain oxidized foam metal, wherein the surface of the oxidized foam metal is coated with metal oxide;
step b, preparing the MOF-loaded oxidized foam metal: b, putting the oxidized foam metal obtained in the step a into an MOF precursor solution for reaction, and loading MOF on the surface of the oxidized foam metal through crystallization and aging to obtain the oxidized foam metal loaded with MOF;
step c, preparing a foamed metal-based monolithic catalyst loaded with MOF-derived metal oxides: and c, calcining the MOF-loaded oxidized foam metal in the step b in air to obtain the catalyst, and loading MOF-derived metal oxide on the catalyst in situ.
According to an embodiment of the present invention, the metal foam in step a is further pretreated to remove oil and/or oxides from the surface of the metal foam.
Preferably, the pretreatment is performed under ultrasonic conditions. Preferably, the oily soil is removed in an organic solvent and the oxide is removed in an inorganic acid. Illustratively, the foam metal is treated in acetone to degrease the surface and in dilute hydrochloric acid to remove surface oxides.
Preferably, the foamed metal may be selected from foamed metals known in the art, such as at least one selected from copper foam, iron foam, nickel iron foam, or the like.
According to an embodiment of the invention, in step b, the MOF precursor solution is formulated by: dissolving metal salt in a solvent to prepare a solution A, dissolving an organic ligand in the solvent to prepare a solution B, and mixing the A, B solutions to obtain the MOF precursor solution.
Preferably, the metal salt is selected from at least one of a metal nitrate, a metal chloride or a metal sulfate.
Preferably, the organic ligand is selected from at least one of dimethylimidazole, terephthalic acid or trimesic acid.
Preferably, the solvent is selected from at least one of water, methanol, ethanol or N, N-dimethylformamide.
Preferably, the molar ratio of the metal salt to the organic ligand is (1-2): (2-8).
Preferably, the concentration of the metal salt in the solution A is 0.05-0.2 mol/L.
Preferably, the concentration of the organic ligand in the B solution ranges from 0.2mol/L to 0.8mol/L.
According to an embodiment of the present invention, in step b, the reaction is specifically: stirring and then protecting from light for reaction.
Preferably, the stirring conditions are: 10-40 ℃ for 5-30 min.
Preferably, the reaction conditions are: the reaction temperature is 5-140 ℃, preferably 5-40 ℃; the reaction time is 6 to 48 hours, preferably 8 to 15 hours.
According to an embodiment of the invention, in step b, the MOF is selected from at least one of Co-ZIF-L, ZIF-67 or Ni-ZIF.
According to an embodiment of the present invention, in step a or c, the calcination is performed under an air atmosphere.
Preferably, the calcining conditions of step a are: 400-700 ℃ for 0.5-6 h.
Preferably, the calcining conditions of step c are: 350-600 ℃ for 3-6 h.
Preferably, the calcination is carried out in a heating device, for example in a tube furnace.
Preferably, the temperature rise rate of the calcination is 2 to 5 ℃/min.
The invention also provides a catalyst, which is obtained by the preparation method.
According to an embodiment of the invention, the catalyst comprises an oxidic foam metal support and a MOF-derived metal oxide; the MOF derived metal oxide is supported in situ on the oxidized foam metal support.
According to an embodiment of the invention, the catalyst is a monolithic catalyst.
According to an embodiment of the present invention, the oxidized metal foam support comprises a metal foam and a metal oxide coated on the surface thereof; the metal oxide on the surface is obtained by calcination. Preferably, the foam metal has the above definition.
According to an embodiment of the invention, the MOF derived metal oxide is selected from NiO, co 3 O 4 、TiO 2 Or CeO 2 At least one of (1).
The invention also provides application of the catalyst, such as application in photo-thermal degradation of VOCs.
According to an embodiment of the invention, the photothermal degradation comprises photothermal degradation of toluene.
Preferably, the photothermal degradation is performed under an air atmosphere.
The invention has the beneficial effects that:
(1) Compared with powder catalyst, the catalyst of the invention is monolithic catalyst, easy to separate and recycle, can be produced in large scale, and is beneficial to industrial application. The stable foam metal-based monolithic catalyst is applied to photo-thermal degradation of VOCs, has excellent catalytic activity, higher stability and good anti-water vapor capacity when being applied to photo-thermal reaction, solves the problem of particulate pollution caused by suspension of nanoparticles in the air in the application process, and provides a new visual angle for industrial application of photo-thermal catalysis.
(2) According to the invention, the metal oxide is obtained by directly calcining the foam metal, so that the surface of the foam metal is rougher, the specific surface area is increased, and the loading of MOF-derived metal oxide and the exposure of active sites are facilitated. The foam metal-based monolithic catalyst prepared by the invention has the advantage of large surface area, can expose more active sites, and has the advantages of better catalytic performance, high stability, high repeated utilization degree and convenient recovery.
(3) The foam metal-based monolithic catalyst disclosed by the invention is simple in preparation process, low in energy consumption in the preparation process, convenient for industrial production and capable of randomly changing the shape and area in the using process.
(4) The catalyst obtained by the method has the advantages of uniform distribution of active components, difficult falling, no need of additional binder and environmental protection.
Drawings
FIG. 1 shows Cu of example 1 x SEM image of O/CF.
FIG. 2 shows Co in example 1 3 O 4 /Cu x HRTEM image of O/CF
FIG. 3 shows Cu of example 1 x O/CF and Co 3 O 4 /Cu x XRD pattern of O/CF.
FIG. 4 shows Co in example 1 3 O 4 /Cu x O/CF and Co of comparative example 1 3 O 4 The illumination intensity of the/CF is 750mW/cm 2 Activity chart of catalytic oxidation of toluene having a concentration of 200ppm under irradiation of (1).
FIG. 5 shows Co of example 1 3 O 4 /Cu x The illumination intensity of O/CF is 750mW/cm 2 The cyclic stability of toluene having a catalytic oxidation concentration of 200ppm under irradiation of (1).
FIG. 6 NiO/Cu of example 2 x The illumination intensity of O/CF is 960mW/cm 2 Activity chart of catalytic oxidation of toluene having a concentration of 200ppm under irradiation of (1).
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
In the following examples, the copper skeleton is not completely oxidized into copper oxide during calcination and oxidation, and the innermost part of the copper skeleton is still copper; the part of the surface layer which is directly contacted with the air can form a copper oxide nanowire; and cuprous oxide is formed in the middle part of the copper skeleton due to insufficient oxygen. So that Cu x O means CuO and Cu 2 Mixture of O, x and calcination temperature, calcinationTime, etc., and the value range of x is 1-2.
Example 1
Co 3 O 4 /Cu x The preparation of the O/CF monolithic catalyst comprises the following steps:
a. pretreatment of the copper foam: cutting foamy copper into a circle with the diameter of 22mm, placing the round shape in a beaker, adding acetone to remove oil stains on the surface by ultrasonic waves, then removing oxides on the surface by ultrasonic waves in dilute hydrochloric acid, washing with deionized water, and drying for later use.
b. Placing the treated foamy copper into a tube furnace, calcining for 4h at 400 ℃ in air atmosphere to obtain the product with Cu grown on the surface x Copper foam (Cu) of O nanowire x O/CF)。
c. Measuring 10mL of deionized water, placing the deionized water in a beaker, adding 2mmol of cobalt nitrate, and carrying out ultrasonic treatment until the cobalt nitrate is completely dissolved for later use; measuring 10mL of water, putting the water in a beaker, adding 8mmol of dimethyl imidazole, adding an aqueous solution of cobalt nitrate after ultrasonic treatment is carried out until the dimethyl imidazole is completely dissolved, stirring the mixture at normal temperature for 20min, and then adding the Cu obtained in the step b x And O/CF, stirring for 5min at normal temperature, standing for 12h at 30 ℃ in a dark place, taking out after reaction, and drying to obtain the Co-ZIF-L-loaded copper oxide foam.
d. Putting the sample prepared in the step c into a tube furnace, and calcining for 3h at 350 ℃ in air atmosphere to obtain Co 3 O 4 /Cu x An O/CF monolithic catalyst.
FIG. 1 shows Cu prepared in step b of example 1 x SEM image of O/CF, it can be seen that dense Cu is formed on the surface of the copper foam x And (4) O nano wires. Cu x The growth of the O nanowire improves the surface roughness of the foam copper and enlarges the specific surface area, which is beneficial to the subsequent loading of active components.
FIG. 2 shows Co prepared in step d of example 1 3 O 4 /Cu x HRTEM image of O/CF, co can be seen 3 O 4 Wrapped in Cu x And (4) the periphery of the O nanowire.
FIG. 3 shows Cu prepared in steps b and d of example 1 x O/CF and Co 3 O 4 /Cu x XRD pattern of O/CF, it can be seen that the surface of the copper foam after calcination is loaded with copper oxideHowever, no cobalt oxide peak was observed in the XRD pattern after supporting the cobalt oxide, which indicates that the cobalt oxide was highly dispersed on the surface of the oxidized copper foam.
Comparative example 1
Co 3 O 4 Preparation of a/CF monolithic catalyst the procedure of example 1 is followed, except that the copper foam is not calcined as in step b, but is directly subjected to the Co preparation in step 3 3 O 4 a/CF monolithic catalyst.
Test example 1
Evaluation of catalyst:
co prepared in example 1 and comparative example 1 were separately added 3 O 4 /Cu x O/CF and Co 3 O 4 the/CF monolithic catalyst was placed in a stainless steel reactor with quartz glass, the internal diameter of the reactor being 25mm, and the catalytic activity of toluene was tested at different light intensities. Introducing a toluene mixed gas with the concentration of 200ppm into a reactor, and controlling the light intensity to be 750mW/cm 2 The conversion of toluene was measured under irradiation. FIG. 4 shows the results of the catalysts prepared in example 1 and comparative example 1 under the condition of illumination intensity of 750mW/cm 2 The activity of catalytic oxidation of toluene under irradiation of (2) can be seen from the figure 3 O 4 /Cu x The O/CF has good catalytic activity, the toluene conversion rate is more than 98 percent, and CO 2 The yield is 80%, and the product still has good stability after 5 cycles. Co prepared in comparative example 1 3 O 4 Co prepared in example 1 compared to CF catalyst 3 O 4 /Cu x The catalytic effect of the O/CF monolithic catalyst is obviously improved.
FIG. 5 shows Co prepared in example 1 3 O 4 /Cu x The illumination intensity of O/CF is 750mW/cm 2 The cyclic stability of toluene having a catalytic oxidation concentration of 200ppm under irradiation of (1) can be seen 3 O 4 /Cu x The O/CF monolithic catalyst has good stability.
Example 2
NiO/Cu x Preparation of an O/CF monolithic catalyst, comprising the steps of:
a. pretreatment of the copper foam: taking foamy copper, cutting into a circle with the diameter of 22mm, placing the round in a beaker, adding acetone to remove surface oil stains by ultrasonic, then removing surface oxides by ultrasonic washing in dilute hydrochloric acid, washing with deionized water, and drying for later use.
b. Placing the treated foamy copper into a tube furnace, calcining for 4h at 400 ℃ in air atmosphere to obtain the product with Cu grown on the surface x Copper foam (Cu) of O nanowire x O/CF)。
c. Measuring 10mL of water, placing the water in a beaker, adding 2mmol of nickel nitrate, and carrying out ultrasonic treatment until the nickel nitrate is completely dissolved for later use; measuring 10mL of water, placing the water in a beaker, adding 8mmol of dimethyl imidazole, adding the nickel nitrate aqueous solution after ultrasonic treatment is carried out until the dimethyl imidazole is completely dissolved, stirring the mixture at normal temperature for 20min, and then adding the Cu obtained in the step b x And stirring the O/CF solution for 12 hours at the temperature of 30 ℃, taking out the O/CF solution after reaction, and drying the O/CF solution to obtain the Ni-ZIF-loaded copper oxide foam.
d. Putting the sample prepared in the step c into a tube furnace, and calcining the sample for 3 hours at 350 ℃ in air atmosphere to obtain NiO/Cu x An O/CF monolithic catalyst.
Test example 2
Evaluation of catalyst: niO/Cu prepared in example 2 x The O/CF monolithic catalyst was placed in a stainless steel reactor with quartz glass, the inside diameter of the reactor was 25mm, and the catalytic activity of toluene was tested under different light intensities. Introducing a toluene mixed gas with the concentration of 200ppm into a reactor, and controlling the light intensity to be 960mW/cm 2 The conversion of toluene measured under irradiation of (2) is 95% or more, and CO is measured 2 The yield thereof was found to be 76%.
FIG. 5 NiO/Cu prepared in example 2 x The illumination intensity of O/CF is 960mW/cm 2 The activity of toluene having a catalytic oxidation concentration of 200ppm under irradiation of (3) was shown, and NiO/Cu was observed x The O/CF has good catalytic activity.
Example 3
Co 3 O 4 /Cu x Preparation of an O/CF monolithic catalyst, comprising the steps of:
a. pretreatment of the copper foam: taking foamy copper, cutting into a circle with the diameter of 22mm, placing the round in a beaker, adding acetone to remove surface oil stains by ultrasonic, then removing surface oxides by ultrasonic washing in dilute hydrochloric acid, washing with deionized water, and drying for later use.
b. Placing the treated foamy copper into a tube furnace, calcining for 4h at 500 ℃ in air atmosphere to obtain the product with Cu grown on the surface x Copper foam (Cu) of O nanowire x O/CF)。
c. Measuring 20mL of methanol, placing the methanol in a beaker, adding 2mmol of cobalt nitrate, and carrying out ultrasonic treatment until the cobalt nitrate is completely dissolved for later use; measuring 20mL of methanol, placing the methanol in a beaker, adding 8mmol of dimethyl imidazole, adding a cobalt nitrate solution after ultrasonic treatment is carried out until the dimethyl imidazole is completely dissolved, stirring the mixture at normal temperature for 20min, and then adding the Cu obtained in the step b x And O/CF, stirring for 5min at normal temperature, standing for 10h in a dark place, taking out after reaction, and drying to obtain the ZIF-67-loaded copper oxide foam.
d. Putting the sample prepared in the step c into a tube furnace, and calcining for 3h at 350 ℃ in air atmosphere to obtain Co 3 O 4 /Cu x An O/CF monolithic catalyst.
The above description is directed to exemplary embodiments of the present invention. However, the scope of protection of the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention should be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the catalyst is characterized by comprising the following steps:
step a, preparing oxidized foam metal: calcining the foam metal to obtain oxidized foam metal, wherein the surface of the oxidized foam metal is coated with metal oxide;
step b, preparing the MOF-loaded oxidized foam metal: b, putting the oxidized foam metal obtained in the step a into an MOF precursor solution for reaction, and loading MOF on the surface of the oxidized foam metal through crystallization and aging to obtain the oxidized foam metal loaded with MOF;
step c, preparing a foamed metal-based monolithic catalyst loaded with MOF-derived metal oxides: and c, calcining the MOF-loaded oxidized foam metal in the step b in air to obtain the catalyst, and loading MOF-derived metal oxide on the catalyst in situ.
2. The method of claim 1, wherein the metal foam in step a is further pretreated to remove oil and/or oxides from the surface of the metal foam.
Preferably, the pretreatment is performed under ultrasonic conditions. Preferably, the oily soil is removed in an organic solvent and the oxide is removed in an inorganic acid. Illustratively, the metal foam is treated in acetone to degrease the surface and in dilute hydrochloric acid to remove surface oxides.
Preferably, the foam metal is selected from at least one of copper foam, iron foam, nickel-iron foam, and the like.
3. A method according to claim 1 or 2, wherein in step b, the MOF precursor solution is prepared by: dissolving metal salt in a solvent to prepare a solution A, dissolving an organic ligand in the solvent to prepare a solution B, and mixing the A, B solutions to obtain the MOF precursor solution.
Preferably, the metal salt is selected from at least one of a metal nitrate, a metal chloride or a metal sulfate.
Preferably, the organic ligand is selected from at least one of dimethylimidazole, terephthalic acid or trimesic acid.
Preferably, the solvent is selected from at least one of water, methanol, ethanol or N, N-dimethylformamide.
Preferably, the molar ratio of the metal salt to the organic ligand is (1-2): (2-8).
Preferably, the concentration of the metal salt in the solution A is 0.05-0.2 mol/L.
Preferably, the concentration of the organic ligand in the B solution ranges from 0.2mol/L to 0.8mol/L.
4. The process according to any one of claims 1 to 3, wherein in step b, the reaction is in particular: stirring the mixture firstly and then keeping the mixture away from light for reaction.
Preferably, the stirring conditions are: 10-40 ℃ for 5-30 min.
Preferably, the reaction conditions are: the reaction temperature is 5-140 ℃, preferably 5-40 ℃; the reaction time is 6 to 48 hours, preferably 8 to 15 hours.
5. The process of any one of claims 1 to 4, wherein in step b, the MOF is selected from at least one of Co-ZIF-L, ZIF-67 or Ni-ZIF.
6. The method according to any one of claims 1 to 5, wherein in step a or c, the calcination is performed under an air atmosphere.
Preferably, the calcining conditions of step a are: 400-700 ℃ for 0.5-6 h.
Preferably, the calcining conditions of step c are: 350-600 ℃ for 3-6 h.
Preferably, the calcination is carried out in a heating device.
Preferably, the temperature rise rate of the calcination is 2 to 5 ℃/min.
7. A catalyst obtained by the production method according to any one of claims 1 to 6.
8. The catalyst of claim 7, wherein the catalyst comprises an oxidized foam metal support and a MOF-derived metal oxide; the MOF derived metal oxide is supported in situ on the oxidized foam metal support.
9. The catalyst of claim 7 or 8, wherein the catalyst is a monolith catalyst.
Preferably, the oxidized metal foam support comprises the metal foam of claim 2 and a metal oxide coated on the surface thereof; the metal oxide on the surface is obtained by calcination.
Preferably, the MOF-derived metal oxideSelected from NiO and Co 3 O 4 、TiO 2 Or CeO 2 At least one of (1).
10. Use of a catalyst according to any one of claims 7 to 9, for example in the photothermal degradation of VOCs.
Preferably, the photothermal degradation comprises photothermal degradation of toluene.
Preferably, the photothermal degradation is performed under an air atmosphere.
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