CN108258218B - Preparation method and application of carbon-point-doped titanium carbide hydrogel composite material - Google Patents
Preparation method and application of carbon-point-doped titanium carbide hydrogel composite material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a carbon-point-doped titanium carbide hydrogel composite material. To Ti3C2Colloidal solution of Tx MXenes adding nitric acid to make Ti3C2Tx MXenes surface nitration, adding carbon quantum dot to fix the carbon quantum dot to Ti3C2Tx MXenes at the surface and between the sheets to obtain cQDs/Ti3C2Tx precursor material to cQDs/Ti3C2And adding 1-hexadecyl-3-methylimidazole halide into the Tx precursor material, and preparing the three-dimensional conductive hydrogel composite material by using a hydrothermal synthesis method, namely the carbon-point-doped titanium carbide hydrogel composite material. Not only can improve the electric conductivity, thereby can prevent piling up of lamella and obtain great interlamellar spacing moreover, be favorable to improving proton transmission ability.
Description
Technical Field
The invention relates to a preparation method and application of a carbon-point-doped titanium carbide hydrogel composite material.
Background
The fuel cell is an environment-friendly power generation device, has higher power generation efficiency than other cells, and can also convert chemical energy into electric energy. The direct methanol fuel cell belongs to a proton exchange membrane cell, which can directly use methanol without first reforming. At the anode, methanol is oxidized to form H2O、CO2And electrons, similar to a standard proton exchange membrane cell, with protons passing through the membrane, and O2In the cathode reaction, electrons are discharged from the anode through the cathode (through an external circuit). The Direct Methanol Fuel Cell (DMFC) has the advantages of small mass, easy transportation and storage, small occupied space, more energy released by combustion and the like, and has bright development prospect in personal and social life. However, the conventional DMFC has various problems, such as usabilityThe energy and manufacturing cost are not enough to meet the current demand. Too low activity of the anode catalyst and methanol crossover are the largest two of these problems. The outstanding problem is that the catalytic activity of the anode is relatively low, because a large amount of noble metal is used, which makes the manufacturing and use costs of the DMFC high. Therefore, there is a need to improve the use efficiency of the noble metal-based catalyst and to improve the catalytic activity of the noble metal-based anode catalyst.
Over the past few decades, metal Nanoparticles (NPs) have been extensively studied due to their interesting properties and their promise for various applications in fields such as energy conversion, storage, sensing, chemical production and catalysis. However, small metal nanoparticles are generally thermodynamically unstable and tend to aggregate into larger particles due to their high surface energy. To prevent aggregation of the metal nanoparticles, a great deal of work has been devoted to enhancing the size effect of the metal nanoparticles of the porous support (e.g., zeolites, mesoporous aluminosilicates and other porous inorganic or organic materials), the interaction between the metal nanoparticles and the support. In this regard, an emerging two-dimensional titanium carbide (MXenes) has attracted increasing attention.
MXenes, which are two-dimensional (2D) metal carbides or carbonitrides, can be prepared by selective removal of an atomically thin aluminum layer from a ternary transition metal carbide (MAX phase) structure, has proven to be a candidate for electrode materials for lithium ion batteries, sodium ion hybrid capacitors, and supercapacitors, with volumetric capacitance exceeding that of most carbon materials. In addition, MXenes has been considered as one of the highly efficient electrode materials because the flexible interlayer space and the large gap space can accommodate more ions of high charge/discharge rate, advantageously exhibiting good rate and frequency response capability. However, the layered structure of MXenes is easily stacked during long-term storage resulting in smaller layer spacing, resulting in reduced proton transport capability.
Disclosure of Invention
In order to solve the defects of the prior art, one of the purposes of the invention is to provide a preparation method of a carbon-point-doped titanium carbide hydrogel composite material, and the prepared carbon-point-doped titanium carbide hydrogel composite material not only can improve the electric conductivity, but also can prevent the stacking of sheet layers so as to obtain larger interlayer spacing, and is beneficial to improving the proton transmission capability.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a process for preparing the carbon dot doped Ti-carbide hydrogel composite material3C2Colloidal solution of Tx MXenes adding nitric acid to make Ti3C2Tx MXenes surface nitration, adding carbon quantum dots (cQDs) to fix the carbon quantum dots to Ti3C2Tx MXenes at the surface and between the sheets to obtain cQDs/Ti3C2Tx precursor material to cQDs/Ti3C2And adding 1-hexadecyl-3-methylimidazole halide into the Tx precursor material, and preparing the three-dimensional conductive hydrogel composite material by using a hydrothermal synthesis method, namely the carbon-point-doped titanium carbide hydrogel composite material.
The invention firstly prepares the titanium carbide hydrogel composite material with the three-dimensional structure by adopting a hydrothermal synthesis method through 1-hexadecyl-3-methylimidazole halide, and the titanium carbide hydrogel composite material is compared with the existing Ti with the two-dimensional structure3C2Compared with Tx, the conductive capacity is high, the stacking of the sheets can be prevented from obtaining larger interlayer distance, and the proton transmission capacity can be improved.
The invention also aims to provide the carbon-point-doped titanium carbide hydrogel composite material prepared by the preparation method.
The invention also aims to provide a catalyst, which takes the carbon-point-doped titanium carbide hydrogel composite material as a carrier to load noble Metal Nano Particles (MNPs). The noble Metal Nanoparticles (MNPs) are one or more of palladium nanoparticles, platinum nanoparticles, ruthenium nanoparticles and the like.
The carbon-point-doped titanium carbide hydrogel composite material prepared by the invention can wrap noble metal nano particles, the obtained conductive MXenes hydrogel composite material catalyst well keeps the shape of network gel, and the noble Metal Nano Particles (MNPs) are uniformly wrapped in an MXenes layer, so that the conductive MXenes hydrogel composite material catalyst has excellent properties in the reaction of catalyzing methanol oxidation.
The fourth purpose of the invention is to provide a preparation method of the catalyst, the carbon-point-doped titanium carbide hydrogel composite material is dispersed in a salt solution, and a reducing agent is added to reduce noble metal ions in the salt solution to obtain MNPs/cQDs/Ti3C2Tx is the catalyst, wherein the salt solution contains one or more of palladium, platinum and ruthenium.
The fifth purpose of the invention is to provide an application of the catalyst in methanol catalytic oxidation.
The invention has the beneficial effects that:
1. the invention firstly prepares the titanium carbide hydrogel composite material with the three-dimensional structure by adopting a hydrothermal synthesis method through 1-hexadecyl-3-methylimidazole halide, and the titanium carbide hydrogel composite material is compared with the existing Ti with the two-dimensional structure3C2Compared with Tx, the conductive capacity is high, the stacking of the sheets can be prevented from obtaining larger interlayer distance, and the proton transmission capacity can be improved.
2. The carbon-point-doped titanium carbide hydrogel composite material prepared by the invention can wrap noble metal nano particles, the obtained conductive MXenes hydrogel composite material catalyst well keeps the shape of network gel, and the noble metal nano particles are uniformly wrapped in an MXenes layer and show excellent properties in the reaction of catalyzing methanol oxidation.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a flow diagram of a catalyst prepared in example 1;
fig. 2 is a TEM image of fully layered MXenes prepared in example 1;
FIG. 3 is a cyclic voltammogram of the catalyst prepared in example 1;
FIG. 4 is a time-current test curve for the catalyst prepared in example 1;
fig. 5 is a graph showing the absorption and desorption curves of hydrogen of the catalyst prepared in example 1.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The hydrothermal synthesis method described herein refers to a chemical reaction performed in a sealed pressure vessel under high temperature and high pressure conditions using water as a solvent. The high temperature in the hydrothermal synthesis refers to the temperature of 100-1000 ℃, and the high pressure refers to the pressure of 1 MPa-1 GPa.
The noble metals described in this application are palladium, platinum, ruthenium.
As described in the background art, in the prior art, the defect that the MXenes lamellar structure is easy to stack in the long-term storage process, so that the interlayer spacing is reduced, and the proton transport capability is reduced exists.
In one exemplary embodiment of the present application, a method for preparing a carbon-point-doped titanium carbide hydrogel composite material is provided, which is prepared by adding titanium carbide and titanium oxide to Ti3C2Colloidal solution of Tx MXenes adding nitric acid to make Ti3C2Tx MXenes surface nitration, adding carbon quantum dot to fix the carbon quantum dot to Ti3C2Tx MXenes at the surface and between the sheets to obtain cQDs/Ti3C2Tx precursor material to cQDs/Ti3C2Adding 1-hexadecyl-3-methylimidazole into Tx precursor materialThe oxazole halide is used for preparing a three-dimensional conductive hydrogel composite material by a hydrothermal synthesis method, namely the carbon-point-doped titanium carbide hydrogel composite material.
The titanium carbide hydrogel composite material with the three-dimensional structure is prepared for the first time by adopting a hydrothermal synthesis method through 1-hexadecyl-3-methylimidazole halide and the existing Ti with the two-dimensional structure3C2Compared with Tx, the conductive capacity is high, the stacking of the sheets can be prevented from obtaining larger interlayer distance, and the proton transmission capacity can be improved.
In order to improve the performance of the carbon-point-doped titanium carbide hydrogel composite material, the Ti is preferably selected3C2The preparation method of the colloid solution of Tx MXenes comprises etching off Ti with hydrofluoric acid3AlC2Heating aluminum in the solution to a certain temperature, stirring, adding water for washing, and performing ultrasonic treatment to obtain Ti3C2Tx MXenes。
Further preferably, the Ti3C2The specific preparation method of the Tx MXenes colloidal solution is that Ti is etched in hydrofluoric acid at 4-10 DEG C3AlC2An aluminum layer in the MAX phase is stirred for 10-15 min at 40-50 ℃ for 22-26 hours to synthesize Ti3C2Then adding the obtained Ti3C2Washing with distilled water, adding 150-200 mL of water, and carrying out ultrasonic treatment for 10-15 hours to obtain the completely layered composite material hydrosol Ti3C2Tx MXenes. Ti treated by the method3AlC2Thinner, thereby further improving the performance of the material.
Preferably, the reaction temperature of the hydrothermal synthesis method is 190-210 ℃, and the reaction time is 22-26 h. Under the condition, 1-hexadecyl-3-methylimidazole halide and Ti can be promoted3C2Activation energy of the surface termination group Tx reaction in Tx to form cQDs/Ti3C2Tx hydrogel.
In another embodiment of the present application, there is provided a carbon dot-doped titanium carbide hydrogel composite prepared by the above preparation method.
In a third embodiment of the present application, there is provided a catalyst having the above-described carbon dot-doped titanium carbide hydrogel composite as a carrier supporting noble Metal Nanoparticles (MNPs). The noble Metal Nanoparticles (MNPs) are one or more of palladium nanoparticles, platinum nanoparticles, ruthenium nanoparticles and the like.
The carbon-point-doped titanium carbide hydrogel composite material prepared by the method can wrap the noble metal nanoparticles, the obtained conductive MXenes hydrogel composite material catalyst well keeps the shape of network gel, and the noble metal nanoparticles are uniformly wrapped in the MXenes layer, so that the conductive MXenes hydrogel composite material catalyst has excellent properties in the reaction of catalyzing methanol oxidation.
In a fourth embodiment of the present application, a method for preparing the catalyst is provided, in which the carbon-doped titanium carbide hydrogel composite material is dispersed in a salt solution, and a reducing agent is added to reduce noble metal ions in the salt solution to obtain MNPs/cQDs/Ti3C2Tx is the catalyst, wherein the salt solution contains one or more of palladium, platinum and ruthenium.
Preferably, before adding the reducing agent, the pH of the salt solution after adding the carbon-point-doped titanium carbide hydrogel composite material is adjusted to 7.0-8.0.
Preferably, when trisodium citrate is used as the reducing agent, the temperature of the reduction reaction is 110 +/-5 ℃; when NaBH is used as the reducing agent, the reaction temperature is room temperature. The room temperature is 15 ~ 25 ℃.
Preferably, when the salt solution is a glycol solution of chloroplatinic acid, the reducing agent is trisodium citrate, and the temperature of the reduction reaction is 110 +/-5 ℃. The reaction time is 3-4 h.
Preferably, when the salt solution is an aqueous solution of sodium chloropalladate or a mixed aqueous solution of chloroplatinic acid and ruthenium chloride, and the reducing agent is NaBH, the reaction temperature is room temperature. The reaction time is 30-40 min.
In a fifth embodiment of the present application, there is provided a use of the above catalyst in catalytic oxidation of methanol.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific examples and comparative examples.
The reagents used in the examples were: titanium aluminum carbide (Ti)3AlC2) Hydrofluoric acid (HF), chloroplatinic acid (H)2PtCI6·6H2O), sodium chloropalladate (Na)2PdCl4) Ruthenium chloride (RuCl)3·3H2O), sodium hydroxide (NaOH), absolute ethanol, ethylene glycol, commercial catalyst Pt/C (20% by mass, Johnson Matthey corporation) was used as a cathode catalyst, 1-hexadecyl-3-methylimidazole halide, and the solid polymer electrolyte membrane was a Nafion membrane.
Example 1
Ti3C2Preparation of TxMXenes hydrosol
By selectively etching 1g of Ti in 10mL of hydrofluoric acid (AR (Hu test) at 4 ≥ 40.0%) at 4 ℃3AlC2(Nihao micro-nano technology of Changchun city, Ltd.) MAX phase Ti3AlC2The Al layer in the solution is stirred for 24 hours at 45 ℃ to synthesize Ti3C2. Then the suspension of the obtained material was washed with distilled water, centrifuged at 3500rpm for 5 minutes, the supernatant was decanted and dried under vacuum at 35 ℃ for 18 hours, 0.3g of the solid material was dispersed in 150mL of distilled water and sonicated for 10 hours to obtain a fully layered composite material hydrosol Ti (shown in TEM image of MXenes in FIG. 2)3C2Tx MXenes。
cQDs/Ti3C2Preparation of Tx hydrosol composite material
Prepared Ti3C2Colloidal solution of Tx MXenes with 10mL of 1mol-1And mixing nitric acid and performing ultrasonic treatment for 5 hours to perform surface nitration treatment. By nitrating Ti3C2Colloidal solution of Tx MXenes with carbon quantum dots (cQDs, prepared by known sonication method: about 0.29g of charcoal particles were taken and 5mol of charcoal particles were added-150mL of nitric acid solution (obtained by placing in an ultrasonic instrument and performing ultrasonic treatment (power 250w, frequency 50kHz) for 24 hours), mixing and ultrasonic treatment for 24 hours to form covalent bonds, and then fixing the cQDs to the Ti3C2Adjusting pH of TxMXenes on and between sheets with sodium hydroxide, adjusting pH to neutrality, centrifuging at 12000rpm for 5min, washing with distilled water, and vacuum washing at 35 deg.CAir-drying to obtain cQDs/Ti3C2Tx hydrosol composite.
cQDs/Ti3C2Preparation of Tx hydrogel composites
0.1g of synthesized cQDs/Ti was taken3C2Tx precursor material, 0.25g of 1-hexadecyl-3-methylimidazole halide is dispersed in 15mL of distilled water, and three-dimensional (3D) conductive hydrogel composite material cQDs/Ti is prepared by a hydrothermal method3C2Tx. Reacting in a reaction kettle at 200 ℃ for 25 hours, and providing high temperature to react the 1-hexadecyl-3-methylimidazole halide with Ti3C2Activation energy of the surface termination group Tx reaction in Tx to form cQDs/Ti3C2Tx hydrogel.
Preparation of the catalyst
Pt NPs/cQDs/Ti3C2Preparation of Tx hydrogel composites
1g of cQDs/Ti3C2The Tx sample is ultrasonically dispersed in 1mL of 0.0242M ethylene glycol solution of chloroplatinic acid, 198mL of distilled water is added, the pH value is adjusted to 7.0 by using a sodium hydroxide solution, 7mL of trisodium citrate solution with the mass fraction of 1 percent is added, the mixture is refluxed for three hours at 110 ℃, and the MXenes hydrogel composite material Pt NPs/cQDs/Ti with the noble metal nano particles loaded in the layer is prepared after cooling and washing3C2Tx. The complete preparation process is shown in figure 1.
Electrochemical characterization
The chemical performance characterization of the catalyst was mainly performed by Cyclic Voltammetry (CV) and time-current curve testing (I-T) by the electrochemical workstation.
The glassy carbon electrode (diameter 3mm) before testing was treated as follows: firstly, 0.3 mu m of alumina powder is used for grinding and polishing to obtain a mirror-surface smooth surface, then absolute ethyl alcohol and deionized water are used for ultrasonic washing in sequence, and then nitrogen airflow is used for blow-drying for standby. Then preparing a working electrode: 1mg of the above-synthesized catalyst material Pt NPs/cQDs/Ti3C2Respectively dispersing Tx and hydrogel composite materials in 2mL of water, uniformly dispersing the materials by ultrasound, dripping 6 mu L of the materials on the surface of a dried glassy carbon electrode, standing at room temperature for airing, and then dripping6 mu L of Nafion water solution with the mass fraction of 0.5 percent is placed on the surface of the electrode and is dried in the air at room temperature to be tested. An electrochemical workstation (CHI 660e) is used as a test instrument, a three-electrode system is used for testing, a working electrode is a glassy carbon electrode coated with a catalyst material, a counter electrode is a platinum wire electrode, a reference electrode is a Saturated Calomel Electrode (SCE), and electrocatalysis tests are carried out on 0.5M NaOH and 0.5M CH3OH in mixed aqueous solution, and nitrogen was introduced into the solution to remove oxygen before testing.
The results are shown in FIGS. 3 to 4, and FIG. 3 shows Pt NPs reduced in the same manner, and two-dimensional MXenes composite material Pt NPs/Ti loaded with Pt NPs3C2And Pt NPs/cQDs/Ti loaded with Pt NPs in the MXenes hydrogel composite material layer doped with carbon dots3C2Tx three catalysts at 0.5M NaOH +0.5M CH3Cyclic voltammogram in OH solution. The current density of the three catalysts for the catalytic oxidation of the methanol in the figure is 173.5mA mg-1 Pt、368.9mAmg-1 Pt、697.8mAmg-1 Pt。Pt NPs/cQDs/Ti3C2The current density of the catalytic oxidation of the methanol by Tx is higher than that of Pt NPs/Ti3C2And Pt NPs are increased. This result is consistent with the trend of higher catalyst activity with greater porosity.
FIG. 4 shows three catalyst portions in 0.5M NaOH +0.5M CH3Time-current test curve in OH solution, which is a visual illustration of Pt NPs/cQDs/Ti in different three catalyst samples3C2The Tx catalyst always maintained the maximum current density, indicating that the catalyst Pt NPs/cQDs/Ti3C2Tx has good activity and stability, and the catalyst has optimal performance.
FIG. 5 is a plot of cyclic voltammetry measurements of three catalysts in 0.5M NaOH solution, visually illustrating Pt NPs/cQDs/Ti in different catalyst samples3C2The Tx catalyst has the largest specific surface area of electrochemical activity, which shows that the catalyst Pt NPs/cQDs/Ti3C2Tx has good activity, and cQDs/Ti can be found3C2Tx hydrogel composites do enableImproving the proton transmission capability and being beneficial to the optimal performance of the Pt-based catalyst.
Example 2
The preparation method is the same as example 1, except that:
Pd NPs/cQDs/Ti3C2preparation of Tx hydrogel composites
1g of cQDs/Ti3C2The Tx sample is ultrasonically dispersed in 5mL of 0.0001M sodium chloropalladate aqueous solution, the pH value of the mixture is adjusted to 7.00 by sodium hydroxide, 2mL of NaBH reducing agent with the mass fraction of 1 percent is added, the mixture is stirred for set time of 30min, and the MXenes composite material Pd NPs/cQDs/Ti loaded with the noble metal nano particles in the layer is prepared after washing3C2Tx。
Example 3
The preparation method is the same as example 1, except that:
PtRu NPs/cQDs/Ti3C2preparation of Tx hydrogel composites
1g of cQDs/Ti3C2The Tx sample is ultrasonically dispersed in 5mL of 0.0001M mixed aqueous solution of chloroplatinic acid and ruthenium chloride, the pH value of the mixture is adjusted to 7.0 by sodium hydroxide, 2mL of NaBH reducing agent with the mass fraction of 1% is added, the mixture is stirred for 40min, and the MXenes hydrogel composite material PtRu NPs/cQDs/Ti with the noble metal nano particles PtNP and Ru NPs loaded in the layer is prepared after washing3C2Tx。
The characterization results of examples 2 to 3 were the same as those of example 1.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (11)
1. A preparation method of a carbon-point-doped titanium carbide hydrogel composite material is characterized in that Ti is added3C2Colloidal solution of Tx MXenes adding nitric acid to make Ti3C2Tx MXenes surface nitration, adding carbon quantum dot to fix the carbon quantum dot to Ti3C2Tx MXenes at the surface and between the sheets to obtain cQDs/Ti3C2Tx precursor material to cQDs/Ti3C2Adding 1-hexadecyl-3-methylimidazole halide into the Tx precursor material, and preparing a three-dimensional conductive hydrogel composite material by a hydrothermal synthesis method, namely the carbon-point-doped titanium carbide hydrogel composite material;
the reaction temperature of the hydrothermal synthesis method is 190-210 ℃, and the reaction time is 22-26 h.
2. The method according to claim 1, wherein the Ti is a titanium-based compound3C2The preparation method of the colloid solution of Tx MXenes comprises etching off Ti with hydrofluoric acid3AlC2Heating aluminum in the solution to a certain temperature, stirring, adding water for washing, and performing ultrasonic treatment to obtain Ti3C2Tx MXenes。
3. The method according to claim 2, wherein the Ti is a titanium-based compound3C2The specific preparation method of the Tx MXenes colloidal solution is that Ti is etched in hydrofluoric acid at 4-10 DEG C3AlC2An aluminum layer in the MAX phase is stirred for 10-15 min at 40-50 ℃ for 22-26 hours to synthesize Ti3C2Then adding the obtained Ti3C2Washing with distilled water, and carrying out ultrasonic treatment for 15-20 hours to obtain the completely layered composite material hydrosol Ti3C2Tx MXenes。
4. A carbon dot-doped titanium carbide hydrogel composite material prepared by the preparation method of any one of claims 1 to 3.
5. A catalyst, characterized in that the carbon dot-doped titanium carbide hydrogel composite material according to claim 4 is used as a carrier to support noble metal nanoparticles.
6. A method for preparing the catalyst of claim 5, wherein the carbon-point-doped titanium carbide hydrogel composite of claim 4 is dispersed in a salt solution, and a reducing agent is added to reduce noble metal ions in the salt solution to obtain cQDs/Ti3C2The Tx/M nano-particles are catalysts, wherein the salt solution contains one or more of palladium, platinum and ruthenium.
7. The method according to claim 6, wherein the pH of the salt solution to which the carbon-point-doped titanium carbide hydrogel composite is added is adjusted to 7.0 to 8.0 before the reducing agent is added.
8. The preparation method as claimed in claim 6, wherein when trisodium citrate is used as the reducing agent, the temperature of the reduction reaction is 110 +/-5 ℃; when NaBH is used as the reducing agent, the reaction temperature is room temperature.
9. The method according to claim 6, wherein the salt solution is a glycol solution of chloroplatinic acid, the reducing agent is trisodium citrate, and the temperature of the reduction reaction is 110 ± 5 ℃.
10. The method according to claim 6, wherein the salt solution is an aqueous solution of sodium chloropalladate or a mixed aqueous solution of chloroplatinic acid and ruthenium chloride, the reducing agent is NaBH, the reaction temperature is room temperature, and the reaction time is 30-40 min.
11. Use of the catalyst of claim 5 in the catalytic oxidation of methanol.
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