CN115155651A - Platinum-based metal catalyst, and preparation method and application thereof - Google Patents

Platinum-based metal catalyst, and preparation method and application thereof Download PDF

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CN115155651A
CN115155651A CN202210944063.7A CN202210944063A CN115155651A CN 115155651 A CN115155651 A CN 115155651A CN 202210944063 A CN202210944063 A CN 202210944063A CN 115155651 A CN115155651 A CN 115155651A
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platinum
catalyst
manganese
metal
carrier
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CN115155651B (en
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杨艳辉
万晓月
戴翼虎
周春梅
张怡
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Hangzhou Fruit And Vegetable Fresh Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/157—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6562—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

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  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Wood Science & Technology (AREA)
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  • Polymers & Plastics (AREA)
  • Catalysts (AREA)
  • Storage Of Fruits Or Vegetables (AREA)

Abstract

The invention discloses a platinum-based metal catalyst and a preparation method and application thereof, wherein the catalyst takes a non-metallic oxide as a carrier and loads metal platinum and manganese; wherein the content of the metal platinum is 0.05 to 1.00 weight percent, and the content of the metal manganese is 0.1 to 1.0 weight percent; the preparation method comprises the following steps: (1) Adding chloroplatinic acid or chloroplatinic acid salt and manganese salt into water to prepare a solution, uniformly dispersing, adding the prepared solution into a non-metallic oxide carrier, grinding and vacuum drying; wherein the volume of the water is the saturated adsorption water volume of the carrier; (2) Reducing the product of the step (1) for 2-4 hours at 250-450 ℃ in a mixed atmosphere of hydrogen and inert gas to obtain the platinum-based metal catalyst; manganese is introduced into the platinum-based catalyst, and the ethylene can be catalytically decomposed at room temperature under the synergistic action of the platinum and the manganese; the catalyst is applied to the room-temperature preservation of fruits and vegetables, the preservative does not contact fruits, and the catalyst is safe and healthy, harmless to the environment, recyclable and good in preservation effect.

Description

Platinum-based metal catalyst and preparation method and application thereof
Technical Field
The invention relates to a metal catalyst, a preparation method and application thereof, in particular to a platinum-based metal catalyst, and a preparation method and application thereof.
Background
As a big agricultural country, the fruit and vegetable industry in China has strong supply capacity, and the fruit and vegetable yield is the first in the world at present. Most fruits and vegetables spontaneously release trace ethylene, which is an important reason for over-ripening or aging of fruits to cause rottenness and deterioration of fruits. In the United states 40% of crops such as fruit cannot be eaten due to rot problems, and over-fast ripening is one of the main reasons. In China, the rotten fruits of the Guangdong province due to the ethylene problem account for 30 percent of the total rotten fruits. The quantity of Chinese fruits and vegetables is very huge, the fruit yield reaches trillion, the annual vegetable yield is 8000 billion yuan, the single fruit sales volume in the electric commerce industry exceeds 1500 billion, and the fresh keeping has far influence on fruit growers and agricultural enterprises. The fruits and vegetables affected by ethylene are wide in variety and mainly comprise: carrot, banana, pear, passion fruit, peach, apple, plum, apricot, mango, kiwi, papaya, fig, avocado, cherry, guava and the like.
Aiming at removing trace ethylene in fruit transportation and prolonging the shelf life of fruits, three major technical methods, namely a biological method, a physical method and a chemical method, are developed at present. Wherein, the chemical method is to decompose ethylene by using a chemical reagent or a catalytic reaction, thereby playing a role in protecting fruits. A typical chemical method is potassium permanganate (KMnO) 4 ) And ozone (O) 3 ) And (4) oxidizing to remove ethylene. But KMnO 4 High toxicity, deterioration after ethylene is removed by oxidation; o is 3 Requires special equipment, and has the effects of self-interaction with some fruits to influence the quality of the fruits and has photochemical toxicity. Thus limiting KMnO 4 And O 3 And (5) popularization and application.
Another broad class of chemical processes utilizes a solid catalytic preservative and atmospheric oxygen to decompose ethylene oxide. In recent years, the method has attracted extensive attention at home and abroad due to the characteristics of no direct contact with fruits, no chemical toxicity, convenient use, lasting effect and the like. The early catalytic antistaling agent is mainly made of oxides such as manganese oxide and copper oxide, and auxiliary agents such as calcium, potassium and sulfur. These catalytic preservatives are relatively inexpensive to manufacture, but are not low in manganese and low in activity, and must function at temperatures of 120 ℃ or higher, and therefore require the assistance of a heating system. Therefore, the development of catalytic antistaling agent for removing ethylene at low temperature is the current research trend. Hao et al found that cobalt oxide loaded nanogold particles were able to remove ethylene at room temperature. But the gold loading was higher (4%) and the cost was higher. The carbon-modified titanium dioxide is used as a catalytic preservative for photocatalytic decomposition of ethylene, and can decompose ethylene at room temperature under the irradiation of ultraviolet light. The limitation of this method is the need to build a uv catalytic reaction unit. The platinum-based catalytic preservative prepared by the initial impregnation method is used for introducing 50ppm of ethylene at the temperature of 25 ℃, and the removal rate of the ethylene can reach 100 percent; in practical application scenarios, however, the lower the ethylene concentration, the more active platinum catalytic sites are needed; and the contained carbon monoxide poisons the platinum active site.
In the ethylene elimination technology for fruit preservation, a multiphase platinum-based method for removing ethylene by catalysis (low-temperature catalytic oxidation method) has more obvious advantages, but the fruit and vegetable preservation can not be realized under the condition of room temperature (10-25 ℃) and in actual scenes (low ethylene concentration, gases containing carbon monoxide, carbon dioxide and the like).
Disclosure of Invention
The purpose of the invention is as follows: the first object of the present invention is to provide a platinum-based metal catalyst that can catalytically remove ethylene at room temperature; a second object of the present invention is to provide a method for preparing the platinum-based catalyst; the third purpose of the invention is to provide the application of the platinum-based catalyst in fruit preservation.
The technical scheme is as follows: the platinum-based metal catalyst takes a non-metallic oxide as a carrier, and loads metal platinum and manganese; wherein the content of the metal platinum is 0.05 to 1.00 weight percent, and the content of the metal manganese is 0.1 to 1.0 weight percent.
The fruit fresh-keeping not only involves the catalytic oxidation of ethylene with ripening acceleration function, but also involves the catalytic oxidation of carbon monoxide and the like in the air during actual application, but also involves the activation of C-H, C-O and C-C. Both the Pt catalytic oxidation of ethylene and CO are active, but the amount/duration of catalytic carbon monoxide poisons the Pt active sites. The improved catalyst provides a new lattice oxygen catalytic active site for decomposing carbon monoxide by introducing manganese, prevents Pt poisoning and improves catalytic activity.
The particle size of the platinum nano-particles is 1-2 nm. The platinum nanoparticles are small, and can improve the catalytic active sites of Pt on the surface.
Preferably, the non-metal oxide is silica, alumina-silica, activated carbon or molecular sieve having a large specific surface area.
The preparation method of the catalyst comprises the following steps:
(1) Adding chloroplatinic acid or chloroplatinic acid salt and manganese salt into water to prepare a solution, uniformly dispersing, adding the prepared solution into a non-metallic oxide carrier, grinding and vacuum drying; wherein the volume of the water is the saturated adsorption water volume of the carrier;
(2) And (2) reducing the product obtained in the step (1) for 2 to 4 hours at the temperature of between 250 and 450 ℃ in the atmosphere of hydrogen and inert gas to obtain the platinum-based metal catalyst.
In the step (1), the solution is dispersed uniformly by ultrasonic dispersion, and the platinum and the manganese can be dispersed uniformly by grinding.
In the step (2), pt in chloroplatinic acid or chloroplatinic acid salt is reduced in a hydrogen atmosphere 4+ Is mostly reduced into Pt 0+ After decomposition of manganese salt, mnO is x 。
Preferably, the atmosphere containing hydrogen is a mixture of hydrogen and nitrogen, wherein the hydrogen is 5-20%, and the balance is nitrogen.
Preferably, the manganese salt is manganous nitrate, manganese chloride or manganese acetate.
Preferably, the chloroplatinate is H 2 PtCl 6 ·6H 2 O or Na 2 PtCl 6 ·6H 2 O。
The temperature of the vacuum drying is 25-50 ℃, and the time is 4-10 hours.
The catalyst of the invention is applied to fruit and vegetable fresh-keeping.
Has the beneficial effects that: compared with the prior art, the invention has the following remarkable advantages: (1) Manganese is introduced into the platinum-based catalyst, and the platinum and the manganese have synergistic effect, so that the catalyst has high catalytic activity and can catalytically decompose ethylene at room temperature; (2) The preparation method does not relate to the use of organic matters such as glycol or aromatic compounds, and is simple; (3) The catalyst is applied to the room-temperature preservation of fruits and vegetables, the preservative does not contact fruits, and the catalyst is safe and healthy, harmless to the environment, recyclable and good in preservation effect.
Drawings
FIG. 1 is a TEM image of a platinum-based catalyst prepared in example 1;
FIG. 2 is a Raman characterization plot of bananas of example 4;
FIG. 3 is a Raman characterization chart of the crystal pears of example 6.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
The platinum-based metal catalyst takes molecular sieve ZSM-5 as a carrier, and loads metal platinum and manganese; wherein the content of metal platinum is 0.45wt%, and the content of metal manganese is 0.32wt%.
The preparation method comprises the following steps:
(1) Adding 13.2mg of chloroplatinic acid hexahydrate and 16.3mg of manganese nitrate tetrahydrate into 0.2g of water to prepare a solution, performing ultrasonic dispersion, adding 1.1g of ZSM-5 carrier into the prepared solution, grinding, and performing vacuum drying at 25 ℃ for 10 hours;
(2) 10% the product of the step (1) in 10vol% 2 -90vol％N 2 Reducing for 3 hours at 300 ℃ in the atmosphere to obtain the platinum-based metal catalyst.
The synthesized platinum-based catalyst was characterized by TEM, and as a result, as shown in fig. 1, the average particle diameter of Pt nanoparticles was about 1.65nm.
Example 2
The platinum-based metal catalyst takes active carbon as a carrier and loads metal platinum and manganese; wherein the content of metal platinum is 0.80wt%, and the content of metal manganese is 0.90wt%.
The preparation method comprises the following steps:
(1) Adding 25.8mg of sodium chloroplatinate hexahydrate and 45.0mg of manganese acetate tetrahydrate into 0.8g of water to prepare a solution, performing ultrasonic dispersion, adding 1.1g of activated carbon carrier into the prepared solution, grinding, and performing vacuum drying at 50 ℃ for 4 hours;
(2) 10vol% of the product of step (1) 2 -90vol％N 2 Reducing for 4 hours at 250 ℃ in the atmosphere to obtain the platinum-based metal catalyst.
Example 3
The platinum-based metal catalyst takes titanium oxide as a carrier, and loads metal platinum and manganese; wherein the content of metal platinum is 0.10wt%, and the content of metal manganese is 0.20wt%.
The preparation method comprises the following steps:
(1) Adding 3.2mg of sodium chloroplatinate hexahydrate and 10.1mg of manganese acetate tetrahydrate into 0.85g of water to prepare a solution, performing ultrasonic dispersion, adding 1.1g of titanium oxide carrier into the prepared solution, grinding, and performing vacuum drying at 25 ℃ for 10 hours;
(2) 10% the product of the step (1) in 10vol% 2 -90vol％N 2 Reducing for 2 hours at 450 ℃ in the atmosphere to obtain the platinum-based metal catalyst.
Comparative example 1
On the basis of example 1, the metal manganese was replaced by an equivalent mass of platinum.
Applications of the invention
The platinum-based metal catalyst is applied to fruit and vegetable fresh-keeping.
The test method comprises the following steps:
(1) Filling 1g of catalyst into a non-woven fabric freshness protection package, and sticking the freshness protection package on a storage box cover made of polypropylene (PP);
(2) Fruits and vegetables with fruit stalks, no insect pest, no collision damage and basically consistent peel color are selected and respectively put into a storage box containing platinum-based catalyst and a storage box without platinum-based catalyst, the storage box is covered with a storage box cover for storage at room temperature, observation, inspection and recording are carried out at regular intervals, the fresh-keeping rate is calculated, and the calculation formula of the fresh-keeping rate is as follows:
Figure BDA0003784301010000041
example 4
4kg of bananas with basically consistent peel color and no collision damage are prepared, 2kg of bananas are respectively placed in a storage box containing the platinum-based catalyst prepared in example 1 and a storage box without the platinum-based catalyst, and the bananas are placed at room temperature for 8 days for observation.
The results of Raman characterization of bananas in the storage boxes containing and without the platinum-based catalyst are shown in fig. 2, the bananas in the storage boxes without the platinum-based catalyst had collapsed cells (fig. 2, b) and the bananas containing the platinum-based catalyst had filled cells (fig. 2, a).
The preservation rate of bananas in the storage box containing the platinum-based catalyst is 100%, and the preservation rate of bananas in the storage box without the platinum-based catalyst is 40%, namely under the same condition, the platinum-based catalyst can effectively prolong the preservation period of bananas.
Comparative example 2
On the basis of example 4, the platinum-based catalyst was changed to the catalyst synthesized in comparative example 1, and the other conditions were not changed.
The experiment result shows that the fresh-keeping rate is 70%. The preservation rate decreases, and the result shows that the synergistic effect of the platinum and the manganese is better than that of the platinum catalyst.
Example 5
2kg of passion fruit with basically consistent peel color and no collision damage is prepared, 1kg of the passion fruit is placed in the storage box containing the platinum-based catalyst prepared in the example 1 and the storage box without the platinum-based catalyst respectively, and the passion fruit is placed at room temperature for 16 days for observation.
The preservation rate of bananas in the storage box containing the platinum-based catalyst is 60%, and the preservation rate of bananas in the storage box without the platinum-based catalyst is 30%, namely under the same condition, the platinum-based catalyst can effectively prolong the preservation period of passion fruit.
Example 6
10kg of crystal pears with basically consistent peel color and no collision damage are prepared, 5kg of the storage box containing the platinum-based catalyst prepared in example 2 and 5kg of the storage box without the platinum-based catalyst are respectively placed in the storage box, and the storage box is placed at room temperature for 76 days for observation.
The results of Raman characterization of crystal pears in the storage cases containing and not containing the platinum-based catalyst are shown in fig. 2, wherein the cell walls of the crystal pears in the storage cases not containing the platinum-based catalyst are collapsed (fig. 3, b), and the crystal pears containing the platinum-based catalyst are full (fig. 3, a).
The preservation rate of bananas in the storage box containing the platinum-based catalyst is 83%, and the preservation rate of bananas in the storage box without the platinum-based catalyst is 16%, namely under the same condition, the platinum-based catalyst can effectively prolong the preservation period of crystal pears.
Example 7
4kg of carrots which have basically consistent peel color and are not damaged by collision are prepared, 2kg of the carrots are respectively placed in a storage box containing the platinum-based catalyst prepared in the embodiment 2 and a storage box without the platinum-based catalyst, and the carrots are placed at room temperature for 5 days for observation.
50% of carrots in the storage box containing the platinum-based catalyst are rotted, and 100% of carrots in the storage box without the platinum-based catalyst are rotted, namely under the same condition, the platinum-based catalyst can effectively prolong the fresh-keeping period of carrots.
Example 8
8kg of peaches with basically consistent peel color and no collision damage are prepared, 4kg of peaches are respectively placed in the storage box containing the platinum-based catalyst prepared in the example 2 and the storage box without the platinum-based catalyst, and the peaches are placed at room temperature for 14 days for observation.
The fresh fruit rate of the peaches in the storage box containing the platinum-based catalyst is 50%, and the peaches in the storage box without the platinum-based catalyst are 100% rotten, namely under the same condition, the platinum-based catalyst can effectively prolong the fresh-keeping period of the peaches.

Claims (8)

1. A platinum-based metal catalyst is characterized in that a non-metal oxide is used as a carrier to load metal platinum and manganese; wherein the content of the metal platinum is 0.05 to 1.00 weight percent, and the content of the metal manganese is 0.1 to 1.0 weight percent.
2. The catalyst according to claim 1, wherein the platinum nanoparticles have a particle size of 1 to 2nm.
3. The catalyst of claim 1, wherein the non-metal oxide is silica, alumina-silica, activated carbon, or molecular sieve.
4. A method for preparing the catalyst of claim 1, comprising the steps of:
(1) Adding chloroplatinic acid or chloroplatinic acid salt and manganese salt into water to prepare a solution, uniformly dispersing, adding the prepared solution into a non-metallic oxide carrier, grinding and vacuum drying; wherein the volume of the water is the saturated adsorption water volume of the carrier;
(2) And (2) reducing the product obtained in the step (1) for 2 to 4 hours at the temperature of between 250 and 450 ℃ in the atmosphere of hydrogen and inert gas to obtain the platinum-based metal catalyst.
5. The method for preparing the catalyst according to claim 4, wherein the manganese salt is manganous nitrate, manganous chloride or manganous acetate.
6. The method of claim 4, wherein the chloroplatinate is H 2 PtCl 6 Or Na 2 PtCl 6 ·6H 2 O。
7. The method for preparing the catalyst according to claim 4, wherein the temperature of the vacuum drying is 25 to 50 ℃ and the time is 4 to 10 hours.
8. Use of the catalyst of any one of claims 1 to 3 in the preservation of fruits and vegetables.
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CN101284774A (en) * 2008-05-23 2008-10-15 浙江大学 Process for preparing glyceric acid by one-step of direct catalytic oxidation with oxygen
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KR20120077637A (en) * 2010-12-30 2012-07-10 주식회사 효성 Preparation of the catalysts platinum system
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CN111266119A (en) * 2020-02-25 2020-06-12 南京工业大学 α -unsaturated aldehyde ketone selective hydrogenation platinum-based catalyst, and preparation method and application thereof
CN112604686A (en) * 2020-11-20 2021-04-06 珠海格力电器股份有限公司 Normal-temperature formaldehyde removal catalyst, and preparation method and application thereof
KR102283644B1 (en) * 2020-07-03 2021-07-30 서울시립대학교 산학협력단 Zeolite based bimetallic catalyst for ozone-catalytic oxidation of volatile organic compounds and oxidation method of volatile organic compounds using the same
CN113731479A (en) * 2021-09-28 2021-12-03 无锡威孚环保催化剂有限公司 HCHO catalyst capable of efficiently and rapidly degrading at room temperature and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1270840A (en) * 2000-04-21 2000-10-25 宜兴市联通净化材料有限公司 Preserving deodorizer and its maufacture and preserving and deodorizing refrigerator
CN101284774A (en) * 2008-05-23 2008-10-15 浙江大学 Process for preparing glyceric acid by one-step of direct catalytic oxidation with oxygen
CN101992101A (en) * 2009-08-31 2011-03-30 中国石油化工股份有限公司上海石油化工研究院 Precious metal catalyst
KR20120077637A (en) * 2010-12-30 2012-07-10 주식회사 효성 Preparation of the catalysts platinum system
CN102649555A (en) * 2011-02-25 2012-08-29 中国石油化工股份有限公司 Method for oxydehydrogenating gas material containing carbon monoxide
CN106040236A (en) * 2016-06-22 2016-10-26 安庆市天虹新型材料科技有限公司 Preparation method of nano catalyst for degrading methanal
CN111266119A (en) * 2020-02-25 2020-06-12 南京工业大学 α -unsaturated aldehyde ketone selective hydrogenation platinum-based catalyst, and preparation method and application thereof
KR102283644B1 (en) * 2020-07-03 2021-07-30 서울시립대학교 산학협력단 Zeolite based bimetallic catalyst for ozone-catalytic oxidation of volatile organic compounds and oxidation method of volatile organic compounds using the same
CN112604686A (en) * 2020-11-20 2021-04-06 珠海格力电器股份有限公司 Normal-temperature formaldehyde removal catalyst, and preparation method and application thereof
CN113731479A (en) * 2021-09-28 2021-12-03 无锡威孚环保催化剂有限公司 HCHO catalyst capable of efficiently and rapidly degrading at room temperature and preparation method thereof

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