CN115869952A - Catalyst for plastic degradation hydrogen production and preparation method and application thereof - Google Patents
Catalyst for plastic degradation hydrogen production and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for preparing hydrogen by degrading plastic and a preparation method and application thereof, and relates to the field of waste treatment. The method comprises the following steps: respectively preparing an alcoholic solution A containing alumina and an alcoholic solution B containing iron salt and alkali, mixing, carrying out solvothermal reaction, filtering, drying, calcining in an oxygen-containing gas atmosphere, quenching, filtering and washing to obtain the catalyst. The catalyst is an alumina/ferric oxide composite material which contains hydroxyl and oxygen defects and has a heterojunction structure, has a high specific surface area, is beneficial to exposing active sites on the surface of the catalyst in the degradation process of plastics, can generate active hydrogen in situ, optimizes hydrogenolysis and enables long-chain alkane to be chain-broken, has the cracking capacity of the alumina on polyethylene plastics, also considers the catalytic activity of an iron element in the aromatization reaction in the pyrolysis process of the plastics, simultaneously brings more Lewis acid sites due to the oxygen defect structure of the ferric oxide, and has high catalytic activity and low cost.
Description
Technical Field
The invention relates to the field of waste treatment, in particular to a catalyst for preparing hydrogen by degrading plastics and a preparation method and application thereof.
Background
Global plastic feedstock yields are expected to reach 11 billion tons in 2050 according to the united nations environmental planning agency (UNEP). The plastic is used as an important component in the field of carbon cycle, and the effective resource recycling of the plastic is beneficial to simultaneously realizing carbon and pollutant emission reduction.
So far, the most common methods for treating waste plastics are landfill, incineration, pyrolysis and the like, wherein the former two methods have low decomposition efficiency on plastics and easily cause great pressure on environmental resources; the pyrolysis technology can convert waste plastics into high-value-added energy sources such as fuel oil, hydrogen, solid fuel and the like, but the pyrolysis technology usually needs to use noble metal catalysts such as ruthenium, platinum and the like, so that the technology implementation cost is too high and the landing is difficult.
Disclosure of Invention
The invention provides a catalyst for plastic degradation hydrogen production, a preparation method and application thereof, and aims to provide a catalyst which is low in cost and high in catalytic activity for plastic degradation hydrogen production, wherein the catalyst has a heterojunction structure and contains defects of hydroxyl and oxygen.
In order to solve the technical problems, one of the objects of the present invention is to provide a method for preparing a catalyst for hydrogen production by plastic degradation, comprising the following steps:
(1) Respectively preparing an alcoholic solution A containing alumina and an alcoholic solution B containing ferric salt and alkali, pouring the alcoholic solution B into the alcoholic solution A which is continuously stirred for solvothermal reaction, filtering after the reaction, and drying in an oxygen-containing gas atmosphere to obtain an aluminum-and-iron-containing precursor;
(2) Calcining the precursors containing aluminum and iron in the atmosphere of oxygen-containing gas, quenching after the calcination, filtering and washing to obtain the catalyst containing the heterojunction structure, wherein the structure also contains hydroxyl and oxygen defects.
By adopting the scheme, the aluminum-iron-containing precursor is prepared by a solvothermal method, the aluminum oxide can be used for avoiding the generation of spinel type iron aluminate from a product, the aluminum oxide/iron oxide composite material which contains hydroxyl and oxygen defects and has a heterojunction structure is obtained after calcination and quenching, the specific surface area of the material is high, the exposure of active sites on the surface of a catalyst in the degradation process of catalytic plastics is facilitated, in the whole degradation reaction process of the catalytic plastics, hydrogen on the exposed hydroxyl of the aluminum oxide/iron oxide catalyst and carbon on a hydrocarbon form a molecular hydrogen bond in situ, the activation energy of dehydrogenation is reduced, the hydrogenolysis is optimized, and long-chain alkane is broken. The alumina and ferric oxide heterojunction structure has the cracking capability of alumina on polyethylene plastics, and also has the catalytic activity of iron element in aromatization reaction in the plastic pyrolysis process, and meanwhile, the oxygen defect structure of ferric oxide brings more Lewis acid sites, so that the surface acidity of the catalyst is further improved, and the gas components generated by plastic degradation catalysis are increased.
Preferably, in step (1), the molar ratio of the iron salt to the alumina is 1: (0.1-20).
Preferably, in step (1), the molar ratio of the iron salt to the alumina is 1: (0.4-4).
Preferably, in step (1), the iron salt is one or more of iron nitrate, iron sulfate, iron acetate, iron chloride or hydrates thereof.
Preferably, the particle size of the alumina is 10-50nm.
Preferably, in step (1), the alcohol in alcohol solution a and alcohol solution B is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and sec-butanol.
Preferably, in step (1), the base in the alcohol solution B is one or more of ammonia, ethylenediamine and triethylamine, and the pH of the alcohol solution B is adjusted to 10.5-12.5 by using the base.
By adopting the scheme, because the surface of the aluminum oxide has rich Lewis acid sites, the crystal phase of a catalyst product prepared without adding alkali is relatively complicated and unstable, and the catalyst product possibly contains oxide, oxyhydroxide, hydrate containing ferric salt and the like.
Preferably, in the step (1), the temperature of the solvothermal reaction is 60-120 ℃, and the reaction time is 15-30 h; the drying temperature is 50-120 ℃.
Preferably, in the step (2), the calcining temperature is 150-600 ℃, and the calcining time is 0.1-4 h.
Preferably, in the step (2), the calcining temperature is 300-500 ℃, and the calcining time is 1-3 h.
Preferably, in step (2), quenching is performed in an iron-containing aqueous solution, wherein the iron in the iron-containing aqueous solution is one or more of ferric nitrate, ferrous sulfate, ferric sulfate, ferrous acetate, ferric triacetate, ferrous chloride and ferric chloride.
By adopting the scheme, the quenching medium influences the quenching effect, and during quenching, compared with a pure aqueous solution, the ferric salt aqueous solution has higher cooling speed, can bring more oxygen defect structures to materials and improves the activity of the catalyst.
Preferably, the concentration of iron in the iron-containing aqueous solution is 0.01 mol to 1 mol.
Preferably, in the steps (1) and (2), the atmosphere containing oxygen is one or more of air, oxygen/nitrogen mixed gas in any proportion, and oxygen/inert gas mixed gas in any proportion.
By adopting the scheme, the iron-based precursor on the surface of the aluminum oxide can be completely converted into the ferric oxide active species after the solvothermal reaction in the oxygen-containing gas atmosphere, and the aluminum oxide/ferric oxide with the heterojunction structure can be formed as the product.
In order to solve the technical problems, the invention also provides a catalyst for preparing hydrogen by degrading plastics.
In order to solve the above technical problems, the present invention provides a catalyst for use in the field of degradation of plastics.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst is an alumina/ferric oxide composite material which contains hydroxyl and oxygen defects and has a heterojunction structure, has a high specific surface area, is beneficial to exposing active sites on the surface of the material in the degradation process of catalytic plastics, can generate active hydrogen in situ, optimizes hydrogenolysis and breaks long-chain alkane, has the cracking capacity of the alumina on polyethylene plastics, also considers the catalytic activity of iron element in aromatization reaction in the pyrolysis process of the plastics, brings more Lewis acid sites by the oxygen defect structure of the ferric oxide, further improves the surface acidity of the catalyst, and increases gas components generated by degradation catalysis of the plastics.
Drawings
FIG. 1: is a scanning electron microscope picture of the catalyst for preparing hydrogen by degrading plastics in the embodiment 3 of the invention with the resolution of 200 nm;
FIG. 2: is a scanning electron microscope picture of the catalyst for preparing hydrogen by degrading plastics in the embodiment 3 of the invention with the resolution of 50 nm;
FIG. 3; is a nitrogen isothermal adsorption and desorption curve diagram of the catalyst for preparing hydrogen by degrading plastics in embodiment 3 of the invention;
FIG. 4: is a Fourier transform infrared spectrogram of the catalyst for preparing hydrogen by degrading plastics in the embodiment 3 of the invention;
FIG. 5: is a Fourier transform infrared spectrogram of the catalyst for preparing hydrogen by degrading plastics in example 5 of the invention;
FIG. 6: is a Fourier transform infrared spectrogram of the catalyst for preparing hydrogen by degrading plastics in comparative example 1;
FIG. 7 is a schematic view of: is a high-resolution transmission electron microscope image of the catalyst for preparing hydrogen by degrading plastics in the embodiment 3 of the invention;
FIG. 8: is an XPS diagram of a catalyst for preparing hydrogen by degrading plastics in example 3 of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
A catalyst for preparing hydrogen by degrading plastic comprises the following preparation steps:
(1) Preparing aluminum-containing and iron-containing precursors: ultrasonically dispersing 5mmol of aluminum oxide with the particle size of 20 nm in 100 mL of absolute ethyl alcohol to form a dispersion liquid A, and transferring the dispersion liquid A into an oil bath kettle for stirring; ultrasonically dispersing 0.5 mmol of anhydrous ferric chloride in 100 mL of anhydrous ethanol, adding 2 mL of ammonia water (with the concentration of 28 wt%), continuously ultrasonically treating to obtain a solution B, adjusting the pH value of the alcohol solution B to be within the range of 10.5-12.5 by using the ammonia water, pouring the solution B into the dispersion liquid A which is continuously stirred to perform solvothermal reaction at the reaction temperature of 80 ℃ for 24 hours, performing reduced pressure filtration after the reaction is finished, and drying overnight in a forced air drying oven in the atmosphere of 105 ℃ to obtain an aluminum and iron containing precursor;
(2) Preparing a catalyst for preparing hydrogen by degrading plastic: putting the aluminum-iron containing precursor powder obtained in the step (1) into a corundum porcelain boat, transferring the porcelain boat into a muffle furnace, and carrying out air atmosphere at 50 ℃ for min -1 The temperature is raised to 350 ℃ at the speed, the mixture is subjected to heat preservation for 2 hours for calcination, and the mixture is immediately transferred into 0.3 mol ferric chloride aqueous solution for quenching after the reaction is finished, filtered and washed by deionized water, thus obtaining the catalyst for plastic degradation hydrogen production.
Example two
The preparation method of the catalyst for preparing hydrogen by degrading plastics comprises the steps, reagents used in the steps and process parameters of the method are the same as those in the first embodiment, except that in the step (1), the content of alumina is 2mmol.
EXAMPLE III
The preparation method of the catalyst for preparing hydrogen by degrading plastics comprises the steps, reagents used in the steps and process parameters of the catalyst are the same as those in the first embodiment, except that in the step (1), the content of alumina and anhydrous ferric chloride is 2mmol.
The characterization result shows that the morphology structure of the third embodiment is shown in fig. 1-2, and after the aluminum-and iron-containing precursor obtained through the solvothermal reaction is calcined and extracted, as shown in fig. 8, the binding energy is 530.4 eV and 531 eVPeaks at positions of 1 eV, 531.8eV, and 532.5 eV represent Fe-O bond, al-O bond, hydroxyl group, and oxygen deficient structure (oxygen vacancy), respectively, indicating that iron oxide particles having oxygen deficient structure are alternately grown on the alumina film substrate. And as shown in fig. 7, the crystal planes belonging to the aluminum oxide (220) and the iron oxide (110) can be obviously observed in the catalyst prepared in example 3, and a heterojunction structure is formed at the boundary of the two crystal planes, which indicates that the obtained aluminum oxide/iron oxide composite material has a heterojunction structure. As shown in the nitrogen isothermal adsorption and desorption curve test of FIG. 3, the specific surface area of the catalyst prepared in the third example is as high as 142.53 m 2 g -1 The exposure of active sites on the surface of the catalyst in the degradation process of the catalytic plastic is facilitated; fourier transform infrared spectroscopy in FIG. 4 shows that the catalyst of example three was qualitatively analyzed except at 560cm -1 Has Fe-O bonds and is at 552 cm -1 And at 821 cm -1 The catalyst contains Al-O bonds and a large amount of hydroxyl groups, and hydrogen in the hydroxyl group structure forms molecular hydrogen bonds with carbon atoms on hydrocarbon obtained by plastic pyrolysis products in situ, so that the activation energy of dehydrogenation is reduced, the hydrogenolysis in the degradation process of catalytic plastic is optimized, and the products obtain more hydrogen gas.
Example four
The preparation method of the catalyst for preparing hydrogen by degrading plastics comprises the steps, reagents used in the steps and process parameters of the catalyst are the same as those in the first embodiment, except that in the step (1), the content of alumina is 2mmol, and the content of anhydrous ferric chloride is 5mmol.
EXAMPLE five
The preparation method of the catalyst for preparing hydrogen by degrading plastics has the same steps, reagents used in the steps and process parameters as those in the embodiment, and the difference is that in the step (2), a 0.3M ferric chloride aqueous solution used for quenching is replaced by deionized water.
The characterization results are shown in FIG. 5, which is a Fourier transform infrared spectrum of 552 cm in the structure of the catalyst of this example -1 And at 821 cm -1 At 560cm and containing Al-O bonds -1 Containing Fe-O bonds andthe partially adsorbed water molecules also contain a large number of hydroxyl groups.
Comparative example 1
A catalyst for preparing hydrogen by degrading plastic comprises the following steps: placing 5mmol of alumina with particle size of 20 nm in corundum porcelain boat, transferring the porcelain boat to muffle furnace, and heating at 50 deg.C for min in air atmosphere -1 Heating to 350 ℃ at the rate of the temperature rise, and keeping the temperature for 2 hours for calcination to obtain the catalyst.
Comparative example one, in which no iron oxide component was added and thus no quenching step was required, was characterized as shown in the Fourier Infrared Spectroscopy results of FIG. 6, and the catalyst structure of comparative example one was only 552 cm after qualitative analysis -1 And 821 cm -1 The compound contains Al-O bonds, partially adsorbed water molecules, a large amount of hydroxyl groups and no Fe-O bonds.
Performance test
1. The generation device and the detection device for the rapid pyrolysis and degradation of the plastics are respectively a vertical micro-reactor (Rx-3050 TR, frontier laboratory, japan) and a gas chromatography separation and detection (8890, agilent, USA) combined system. The system adopts helium as carrier gas, and the flow rate is 156 mL min -1 The plastic was high density polyethylene powder, 100 μ g charged, and the catalyst was examples 1-5 or comparative example 1, with a charge of 2 mg. During reaction, the upper layer pyrolysis reaction temperature of the vertical microreactor is 600 ℃, and the lower layer catalysis temperature is 800 ℃. During detection, gas products of the reaction are separated by a chromatographic column (113-4362, agilent) and detected by a thermal conductivity detector, wherein the reference flow is 20 mL min -1 . The initial temperature of the column box of the gas chromatograph is 40 ℃ for 6 min -1 The temperature rise rate of (2) was increased to 280 ℃ and maintained for 6 min. The quantitative hydrogen production of the plastic degradation catalyst adopts an external standard method, and the hydrogen production of the catalytic degradation high-density polyethylene powder in different examples and comparative examples is shown in the following table 1.
TABLE 1-amount of hydrogen produced by catalytic degradation of catalysts in examples and comparative examples of the present application
| Detecting items | Hydrogen production (μ L) |
| Example one | 20.63 |
| Example two | 32.19 |
| EXAMPLE III | 78.04 |
| Example four | 39.39 |
| EXAMPLE five | 66.16 |
| Comparative example 1 | 3.14 |
The performance detection results of the embodiment 1 and the comparative example 1 in the table 1 show that the catalyst is an alumina/iron oxide composite material which contains hydroxyl and oxygen defects and has a heterojunction structure, has a high specific surface area, is beneficial to exposure of active sites on the surface of the catalyst in the degradation process of catalytic plastics, has the cracking capacity of alumina on polyethylene plastics, gives consideration to the catalytic activity of iron element in aromatization reaction in the pyrolysis process of plastics, brings more Lewis acid sites due to the oxygen defect structure of the iron oxide, and has a catalytic activity remarkably higher than that of the alumina in the comparative example 1.
The performance test results of examples 1 and 5 in table 1 show that, in the application, the aqueous solution containing iron is used as the quenching medium, and compared with a simple aqueous solution, the aqueous solution containing salt has a higher cooling rate, and meanwhile, more oxygen defect structures can be brought to the material, and the activity of the catalyst is improved.
In combination with the performance test results of examples 1-4 in table 1, it can be seen that the present application, which defines the mole ratio of iron oxide to aluminum oxide, can control the catalytic activity of the catalyst when the mole ratio of iron oxide to aluminum oxide is 1:1, the hydrogen production capacity of the catalyst reaches the highest.
The above-mentioned embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, and it should be understood that the above-mentioned embodiments are only examples of the present invention and are not intended to limit the scope of the present invention. It should be understood that any modifications, equivalents, improvements and the like, which come within the spirit and principle of the invention, may occur to those skilled in the art and are intended to be included within the scope of the invention.
Claims (10)
1. A preparation method of a catalyst for preparing hydrogen by degrading plastics is characterized by comprising the following steps:
(1) Respectively preparing an alcoholic solution A containing aluminum oxide and an alcoholic solution B containing iron salt and alkali, pouring the alcoholic solution B into the alcoholic solution A which is continuously stirred for solvothermal reaction, filtering after the reaction, and drying in an oxygen-containing gas atmosphere to obtain precursors containing aluminum and iron;
(2) Calcining the precursor containing aluminum and iron in an oxygen-containing gas atmosphere, quenching after the calcination, filtering and washing to obtain the catalyst containing the heterojunction structure, wherein the structure also contains hydroxyl and oxygen defects.
2. The preparation method of the catalyst for hydrogen production through plastic degradation according to claim 1, wherein in the step (1), the molar ratio of the iron salt to the aluminum oxide is 1: (0.1-20).
3. The method for preparing the catalyst for hydrogen production through plastic degradation according to claim 1, wherein in the step (1), the iron salt is one or more of iron nitrate, iron sulfate, iron acetate, iron chloride or hydrates of the above substances.
4. The method for preparing the catalyst for hydrogen production through plastic degradation according to claim 1, wherein in the step (1), the alcohol in the alcohol solution A and the alcohol solution B is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and sec-butanol.
5. The method for preparing the catalyst for hydrogen production through plastic degradation according to claim 1, wherein in the step (1), the base in the alcohol solution B is one or more of ammonia, ethylenediamine and triethylamine, and the pH of the alcohol solution B is adjusted to 10.5-12.5 by using the base.
6. The preparation method of the catalyst for hydrogen production through plastic degradation according to claim 1, wherein in the step (1), the temperature of the solvothermal reaction is 60-120 ℃, the reaction time is 15-30 h, and the drying temperature is 50-120 ℃; in the step (2), the calcining temperature is 150-600 ℃, and the calcining time is 0.1-4 h.
7. The preparation method of the catalyst for hydrogen production through plastic degradation according to claim 1, wherein in the step (2), the quenching is performed in an iron-containing aqueous solution, wherein iron in the iron-containing aqueous solution is one or more of ferric nitrate, ferrous sulfate, ferric sulfate, ferrous acetate, ferric triacetate, ferrous chloride and ferric chloride, and the iron concentration in the iron-containing aqueous solution is 0.01 mol L -1 -1 mol L -1 。
8. The method for preparing the catalyst for hydrogen production through plastic degradation according to claim 1, wherein in the steps (1) and (2), the atmosphere containing oxygen is one or more of air, oxygen/nitrogen mixed gas in any proportion and oxygen/inert gas mixed gas in any proportion.
9. A catalyst obtained based on the method for preparing a catalyst for the production of hydrogen by degradation of plastics according to any one of claims 1 to 8.
10. Use of a catalyst according to claim 9 in the field of plastics degradation.
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Citations (4)
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| CN104588108A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst, and preparation method and application thereof |
| CN115072659A (en) * | 2022-07-19 | 2022-09-20 | 武汉新碳科技有限公司 | Method for preparing hydrogen by polyethylene plastic |
| CN115414937A (en) * | 2022-08-17 | 2022-12-02 | 华东理工大学 | Catalyst for preparing carbon nanotube by microwave catalytic pyrolysis of waste plastics and preparation method and application thereof |
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Patent Citations (4)
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|---|---|---|---|---|
| JP2000128664A (en) * | 1998-10-26 | 2000-05-09 | Showa Denko Kk | Outer wall material having photocatalytic function |
| CN104588108A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst, and preparation method and application thereof |
| CN115072659A (en) * | 2022-07-19 | 2022-09-20 | 武汉新碳科技有限公司 | Method for preparing hydrogen by polyethylene plastic |
| CN115414937A (en) * | 2022-08-17 | 2022-12-02 | 华东理工大学 | Catalyst for preparing carbon nanotube by microwave catalytic pyrolysis of waste plastics and preparation method and application thereof |
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