CN112337455A - Preparation method of noble metal loaded two-dimensional nanosheet photocatalyst - Google Patents

Preparation method of noble metal loaded two-dimensional nanosheet photocatalyst Download PDF

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CN112337455A
CN112337455A CN202011252129.3A CN202011252129A CN112337455A CN 112337455 A CN112337455 A CN 112337455A CN 202011252129 A CN202011252129 A CN 202011252129A CN 112337455 A CN112337455 A CN 112337455A
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noble metal
organic solvent
dimensional
reaction
carbon dioxide
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李菊英
张月超
钱正芳
丁腾达
钱毅光
高小中
程亚楠
黄晓桐
潘伟杰
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Shenzhen University
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Shenzhen University
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Abstract

The invention discloses a preparation method of a noble metal loaded two-dimensional nanosheet photocatalyst, and relates to the technical field of photocatalysts. The method comprises the steps of stripping the two-dimensional nano material by using supercritical carbon dioxide carrying a first organic solvent, then introducing a second organic solvent and noble metal salt, contacting the noble metal salt and the stripped two-dimensional nano material in a supercritical state of the second organic solvent to react, and obtaining the target composite catalyst after the reaction is finished. The method utilizes the characteristics of strong diffusion, high expansion and organic matter carrying of the supercritical carbon dioxide to realize the rapid stripping of the target material to obtain the ultrathin nano material; and the high-dispersion noble metal supported catalyst is obtained by utilizing the outstanding dispersibility and reducibility of the supercritical organic matter. The method has the advantages of wide application range, simple operation process, recoverable carbon dioxide and organic solvent, low process cost and reduced environmental pollution risk.

Description

Preparation method of noble metal loaded two-dimensional nanosheet photocatalyst
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a preparation method of a noble metal loaded two-dimensional nanosheet photocatalyst.
Background
The noble metal comprises eight elements of gold, silver, platinum, palladium, ruthenium, rhodium, iridium and osmium, has excellent physical and chemical properties, high electrical conductivity, thermal conductivity and stability, and unique electrical and optical properties, and is widely applied to the fields of chemical industry, medicines, pesticides, environmental protection, energy, electronics and the like. The noble metal d is not filled with electron orbits, the surface of the noble metal d is easy to absorb reactants, an intermediate active compound is convenient to form, and the noble metal d has high catalytic activity, high temperature resistance, oxidation resistance, corrosion resistance and other characteristics. Researchers are working on reducing the amount of noble metal used to achieve high efficiency and stable catalytic performance. The preparation process of the supported catalyst is to coat the components with catalytic activity on a substrate with stronger mechanical strength. The supported catalyst solves the problems of poor mechanical strength, easy pulverization, difficult recovery and the like of some catalysts, can better disperse catalytic active components and prevent the catalytic active components from agglomerating, reduces the using amount of the active components, and further reduces the cost.
Chinese patent CN111659414A discloses a method for preparing a nano-composite noble metal catalyst with activated carbon as a carrier, which takes the activated carbon as the carrier, metal oxide as a modification auxiliary agent and Pd and Pt as active components, and is prepared by the steps of auxiliary agent loading, roasting, active component loading, aging, calcining, hydrogen reduction and the like, and the steps are complicated and the preparation period is long; chinese patent CN111097407A discloses a supported nano Pt/Al2O3Dissolving chloroplatinic acid and triethylamine in propylene carbonate, and stirring and reducing under hydrogen pressure to prepare Pt nano sol; mixing Al2O3Directly dipping the obtained Pt nano sol into the obtained Pt nano sol, stirring and adsorbing, standing and drying, and roasting to obtain the Pt/Al2O3Catalyst, control ofThe preparation steps are more; chinese patent CN111215115A discloses preparation of two-dimensional titanium carbide/two-dimensional graphite phase carbon nitride nanosheet heterojunction and photocatalytic reduction of CO2The application comprises the steps of dispersing titanium carbide aluminum powder in hydrofluoric acid for etching to remove an aluminum layer, filtering, washing and drying to obtain titanium carbide powder, then dispersing the titanium carbide powder into a urea solution, carrying out ultrasonic treatment in an ice water bath, drying the mixed solution to obtain a titanium carbide-urea precursor, and adding the titanium carbide-urea precursor into N2Roasting in the atmosphere to obtain a product, and has the advantages of long preparation period, multiple operation steps and lower efficiency of preparing the nano-sheets by ultrasonic stripping.
Disclosure of Invention
The technical problem to be solved by the invention is some defects mentioned in the background technology, and the invention provides a method for preparing a noble metal loaded two-dimensional nanosheet photocatalyst by combining supercritical carbon dioxide and supercritical organic matter.
In order to solve the above problems, the present invention proposes the following technical solutions:
a preparation method of a noble metal loaded two-dimensional nanosheet photocatalyst specifically comprises the following steps:
(1) placing the two-dimensional nano material and a first organic solvent in a high-temperature high-pressure reaction kettle I, then introducing carbon dioxide, heating and pressurizing to a supercritical state, and carrying out contact reaction for 0.5-6 h to obtain the stripped ultrathin nano material; wherein the temperature of the carbon dioxide in a supercritical state is 33-88 ℃, and the pressure is 7.5-26.5 MPa;
(2) adding a second organic solvent and noble metal salt into the reaction kettle I in the step (1), heating and pressurizing to a supercritical state of the second organic solvent, reacting the noble metal salt with the ultrathin nanometer material for 25-120 min, stopping the reaction, and cooling to obtain the noble metal loaded two-dimensional nanosheet photocatalyst; wherein the mass ratio of the noble metal elements contained in the noble metal salt to the ultrathin nanometer material is 1: (10-100).
The further technical scheme is that the two-dimensional nano material is selected from graphene, layered metal hydroxide, layered metal oxide, transition metal carbon/nitride, graphite phase nitrogen carbide, boron nitride, boron carbon nitride, layered sulfide, transition metal double halide or a mixture thereof.
The further technical scheme is that the first organic solvent is selected from alcohols, amines, ethers, lipids, aromatic hydrocarbons, sulfoxides or a mixture thereof.
The further technical scheme is that the first organic solvent is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, dimethyl sulfoxide or a mixture thereof.
The further technical proposal is that the second organic solvent is selected from methanol or ethanol.
The further technical scheme is that when the second organic solvent is methanol, the temperature of the supercritical state of the methanol is 240-285 ℃, and the pressure is 8.2-14.5 Mpa.
The further technical scheme is that when the second organic solvent is selected from ethanol, the temperature of the ethanol in a supercritical state is 245-285 ℃, and the pressure is 6.5-14.5 MPa.
The further technical scheme is that the noble metal salt is selected from chloroauric acid, sodium tetrachloroaurate, potassium tetrachloroaurate, platinum tetrachloride, chloroplatinic acid, sodium chloroplatinate, silver nitrate, silver sulfate, silver acetate, palladium dichloride, potassium tetrachloropalladate, sodium tetrachloropalladate, potassium hexachloropalladate, sodium hexachloropalladate, ruthenium trichloride, ammonium chlororuthenate, ruthenium nitrosyl nitrate or a mixture thereof.
The further technical scheme is that the step (1) further comprises the operation of recovering carbon dioxide and the first organic solvent after the reaction is finished.
The further technical scheme is that the step (2) further comprises the operation of recovering the second organic solvent after the reaction is finished.
The principle of the invention is as follows:
the material is rapidly stripped by utilizing the excellent fluidity and expansibility of the supercritical carbon dioxide and the characteristic of dissolving an organic solvent; the supported catalyst with high dispersion is prepared by utilizing the outstanding reducibility and dispersibility of the supercritical organic solvent.
Compared with the prior art, the invention can achieve the following technical effects:
the invention realizes the stripping of two-dimensional nano materials and the high dispersion of noble metal simple substances by utilizing the high expansion and strong diffusion of supercritical carbon dioxide and the capability of carrying organic matters and the strong dispersion and reduction capability of supercritical organic matters.
According to the preparation method of the noble metal loaded two-dimensional nanosheet photocatalyst, the supercritical carbon dioxide is used for dissolving and carrying the stripping agent, so that the two-dimensional nanomaterial can be quickly obtained, the reaction time is short, and the preparation process is simple; the carbon dioxide and the organic stripping agent can be recovered, so that the process cost is reduced; the preparation process of the two-dimensional nanosheet and the supported catalyst is completed in sequence in a closed space, and the purity of the product is high; after the preparation process is finished, the pressure can be directly released, the solid-liquid-gas separation is realized, the recovery is convenient, the product does not need to be dried, and the final residual solid in the kettle is the target composite photocatalyst.
Detailed Description
The technical solutions in the examples will be clearly and completely described below. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. 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.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention. As used in the description of embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
In the embodiment of the present invention, the photocatalytic ability is determined by the efficiency of catalyzing and degrading organic substances under the same conditions, methyl orange is used as a model compound, and the reaction conditions are as follows: under visible light (lambda is more than 420nm), the using amount of the catalyst is 1g/L, the concentration of methyl orange is 10ppm, and the treatment time is 30 min.
Example 1: a preparation method of a noble metal loaded two-dimensional nanosheet photocatalyst comprises the following specific steps:
(1) placing graphene and ethanol in a high-temperature high-pressure reaction kettle I, then introducing carbon dioxide, heating and pressurizing to a supercritical state, after contact reaction for 6 hours, terminating the reaction, releasing pressure and air, and leaving the stripped ultrathin nano graphene in the kettle, wherein the temperature of the carbon dioxide in the supercritical state is 33 ℃, and the pressure is 23.5 MPa;
(2) adding methanol and chloroauric acid (the mass ratio of gold element to ultrathin nano graphene is 1:100) into the reaction kettle I in the step (1), then heating and pressurizing to a supercritical state (285 ℃ and 8.2MPa) of methanol, after 100min of reaction, stopping the reaction, releasing pressure and air, cooling the reaction kettle to a proper temperature, disassembling the reaction kettle, obtaining the ultrathin nano graphene and gold composite catalyst, wherein the efficiency of photocatalytic degradation of methyl orange is 98.5%.
Example 2: a preparation method of a noble metal loaded two-dimensional nanosheet photocatalyst comprises the following specific steps:
(1) placing the layered metal hydroxide and methanol in a high-temperature high-pressure reaction kettle I, then introducing carbon dioxide, heating and pressurizing to a supercritical state, after contact reaction for 4 hours, terminating the reaction, releasing pressure and air, and leaving the stripped ultrathin nanometer metal hydroxide in the kettle, wherein the temperature of the carbon dioxide in the supercritical state is 55 ℃ and the pressure is 20 MPa;
(2) adding ethanol and silver nitrate (the mass ratio of silver element to ultrathin nano metal hydroxide is 1:10) into the reaction kettle I in the step (1), then heating and pressurizing to the supercritical state (245 ℃ and 6.5MPa) of the ethanol, reacting for 120min, stopping the reaction, relieving pressure and releasing air, cooling the reaction kettle to a proper temperature, disassembling the reaction kettle to obtain the catalyst compounded by the ultrathin nano metal hydroxide and the silver, wherein the efficiency of degrading methyl orange by photocatalysis is 96.7%.
Example 3: a preparation method of a noble metal loaded two-dimensional nanosheet photocatalyst comprises the following specific steps:
(1) putting the transition metal carbide and dimethyl sulfoxide into a high-temperature high-pressure reaction kettle I, introducing carbon dioxide, heating and pressurizing to a supercritical state, after contact reaction for 0.5h, terminating the reaction, releasing pressure and air, and leaving the stripped ultrathin nanometer transition metal carbide in the kettle, wherein the temperature of the carbon dioxide in the supercritical state is 88 ℃ and the pressure is 15 MPa;
(2) adding methanol and chloroplatinic acid (the mass ratio of platinum element to ultrathin nanometer transition metal carbide is 1:20) into the reaction kettle I in the step (1), then heating and pressurizing to a supercritical state of methanol (240 ℃, 10.5MPa), reacting for 80min, stopping the reaction, relieving pressure and releasing air, cooling the reaction kettle to a proper temperature, disassembling the reaction kettle, obtaining the catalyst compounded by the ultrathin nanometer transition metal carbide and platinum, wherein the efficiency of photocatalytic degradation of methyl orange is 97.3%.
Example 4: a preparation method of a noble metal loaded two-dimensional nanosheet photocatalyst comprises the following specific steps:
(1) putting transition metal nitride and n-butyl alcohol into a high-temperature high-pressure reaction kettle I, then introducing carbon dioxide, heating and pressurizing to a supercritical state, after 2h of contact reaction, terminating the reaction, relieving pressure and releasing air, and leaving the stripped ultrathin nanometer transition metal nitride in the kettle, wherein the temperature of the carbon dioxide in the supercritical state is 70 ℃ and the pressure is 7.5 MPa;
(2) adding ethanol and ruthenium trichloride (the mass ratio of ruthenium element to the ultrathin nanometer transition metal nitride is 1:50) into a reaction kettle I in the step (1), then heating and pressurizing to a supercritical state (285 ℃ and 14.5MPa) of ethanol, reacting for 40min, stopping the reaction, relieving pressure and releasing air, cooling the reaction kettle to a proper temperature, disassembling the reaction kettle, and obtaining the ultrathin nanometer transition metal nitride and ruthenium composite catalyst, wherein the efficiency of photocatalytic degradation of methyl orange is 95.8%.
Example 5: a preparation method of a noble metal loaded two-dimensional nanosheet photocatalyst comprises the following specific steps:
(1) placing graphite phase nitrogen carbide and isopropanol in a high-temperature high-pressure reaction kettle I, then introducing carbon dioxide, heating and pressurizing to a supercritical state, after contact reaction for 1.5h, terminating the reaction, releasing pressure and air, and leaving the stripped ultrathin nano graphite phase nitrogen carbide in the kettle, wherein the temperature of the carbon dioxide in the supercritical state is 45 ℃ and the pressure is 26.5 MPa;
(2) adding methanol and sodium chloroplatinate (the mass ratio of platinum element to ultrathin nano graphite phase carbonized nitrogen is 1:90) into the reaction kettle I in the step (1), then heating and pressurizing to a supercritical state of methanol (270 ℃, 10.5MPa), reacting for 60min, stopping the reaction, relieving pressure and releasing air, cooling the reaction kettle to a proper temperature, disassembling the reaction kettle, obtaining the ultrathin nano graphite phase carbonized nitrogen and ruthenium composite catalyst, wherein the efficiency of photocatalytic degradation of methyl orange is 98.4%.
Example 6: a preparation method of a noble metal loaded two-dimensional nanosheet photocatalyst comprises the following specific steps:
(1) placing boron nitride and n-propanol in a high-temperature high-pressure reaction kettle I, then introducing carbon dioxide, heating and pressurizing to a supercritical state, after contact reaction for 3 hours, terminating the reaction, relieving pressure and releasing air, and leaving the stripped ultrathin nanometer boron nitride in the kettle, wherein the temperature of the carbon dioxide in the supercritical state is 65 ℃ and the pressure is 12.5 MPa;
(2) adding ethanol and silver acetate (the mass ratio of silver element to ultrathin nanometer boron nitride is 1:80) into the reaction kettle I in the step (1), then heating and pressurizing to the supercritical state of ethanol (265 ℃, 12MPa), reacting for 25min, stopping the reaction, relieving pressure and releasing air, cooling the reaction kettle to a proper temperature, disassembling the reaction kettle to obtain the catalyst compounded by the ultrathin nanometer boron nitride and the silver, wherein the efficiency of photocatalytic degradation of methyl orange is 96.8%.
Example 7: a preparation method of a noble metal loaded two-dimensional nanosheet photocatalyst comprises the following specific steps:
(1) placing the layered sulfide and dimethyl sulfoxide into a high-temperature high-pressure reaction kettle I, then introducing carbon dioxide, heating and pressurizing to a supercritical state, after contact reaction for 1h, terminating the reaction, relieving pressure and releasing air, and leaving the stripped ultrathin nano layered sulfide in the kettle, wherein the temperature of the carbon dioxide in the supercritical state is 45 ℃ and the pressure is 10 MPa;
(2) adding methanol and sodium ruthenium chlorohydrate (the mass ratio of the ruthenium element to the ultrathin nano layered sulfide is 1:60) into the reaction kettle I in the step (1), then heating and pressurizing to a supercritical state (255 ℃ and 13MPa) of methanol, reacting for 40min, stopping the reaction, relieving pressure and releasing air, cooling the reaction kettle to a proper temperature, disassembling the reaction kettle to obtain the catalyst compounded by the ultrathin nano layered sulfide and ruthenium, wherein the efficiency of photocatalytic degradation of methyl orange is 97.1%.
Example 8: a preparation method of a noble metal loaded two-dimensional nanosheet photocatalyst comprises the following specific steps:
(1) putting transition metal halide and isopropanol into a high-temperature high-pressure reaction kettle I, then introducing carbon dioxide, heating and pressurizing to a supercritical state, after contact reaction for 5 hours, terminating the reaction, releasing pressure and air, and leaving stripped ultrathin nanometer transition metal halide in the kettle, wherein the temperature of the carbon dioxide in the supercritical state is 66 ℃ and the pressure is 18 MPa;
(2) adding ethanol and sodium tetrachloroaurate (the mass ratio of gold element to the ultrathin nanometer transition metal halide is 1:30) into a reaction kettle I in the step (1), then heating and pressurizing to a supercritical state (268 ℃ and 9MPa) of the ethanol, reacting for 30min, stopping the reaction, relieving pressure and air, cooling the reaction kettle to a proper temperature, disassembling the reaction kettle to obtain the ultrathin nanometer transition metal halide and gold composite catalyst, wherein the efficiency of photocatalytic degradation of methyl orange is 98.3%.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. A preparation method of a noble metal loaded two-dimensional nanosheet photocatalyst is characterized by comprising the following steps:
(1) placing the two-dimensional nano material and a first organic solvent in a high-temperature high-pressure reaction kettle I, then introducing carbon dioxide, heating and pressurizing to a supercritical state, and carrying out contact reaction for 0.5-6 h to obtain the stripped ultrathin nano material; wherein the temperature of the carbon dioxide in a supercritical state is 33-88 ℃, and the pressure is 7.5-26.5 MPa;
(2) adding a second organic solvent and noble metal salt into the reaction kettle I in the step (1), heating and pressurizing to a supercritical state of the second organic solvent, reacting the noble metal salt with the ultrathin nanometer material for 25-120 min, stopping the reaction, and cooling to obtain the noble metal loaded two-dimensional nanosheet photocatalyst; wherein the mass ratio of the noble metal elements contained in the noble metal salt to the ultrathin nanometer material is 1: (10-100).
2. The method of preparing a noble metal-supported two-dimensional nanosheet photocatalyst of claim 1, wherein the two-dimensional nanomaterial is selected from graphene, layered metal hydroxide, layered metal oxide, transition metal carbo/nitride, graphite phase nitrogen carbide, boron nitride, boron carbon nitride, layered sulfide, transition metal double halide, or a mixture thereof.
3. The method for preparing the noble metal supported two-dimensional nanosheet photocatalyst of claim 1, wherein the first organic solvent is selected from the group consisting of alcohols, amines, ethers, lipids, aromatic hydrocarbons, sulfoxides, and mixtures thereof.
4. The method of preparing a noble metal-supported two-dimensional nanosheet photocatalyst of claim 3, wherein the first organic solvent is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, dimethyl sulfoxide, or a mixture thereof.
5. The method of preparing a noble metal-supported two-dimensional nanoplatelet photocatalyst as recited in claim 1, wherein said second organic solvent is selected from the group consisting of methanol and ethanol.
6. The method for preparing the noble metal supported two-dimensional nanosheet photocatalyst of claim 5, wherein the second organic solvent is selected from methanol at a supercritical temperature of 240 to 285 ℃ and a pressure of 8.2 to 14.5 MPa.
7. The method for preparing the noble metal supported two-dimensional nanosheet photocatalyst of claim 5, wherein the second organic solvent is selected from ethanol at a supercritical temperature of 245-285 ℃ and a supercritical pressure of 6.5-14.5 MPa.
8. The method of claim 1, wherein the noble metal salt is selected from chloroauric acid, sodium tetrachloroaurate, potassium tetrachloroaurate, platinum tetrachloride, chloroplatinic acid, sodium chloroplatinate, silver nitrate, silver sulfate, silver acetate, palladium dichloride, potassium tetrachloropalladate, sodium tetrachloropalladate, potassium hexachloropalladate, sodium hexachloropalladate, ruthenium trichloride, ammonium chlororuthenate, ruthenium nitroacetonate or a mixture thereof.
9. The method for preparing a noble metal supported two-dimensional nanosheet photocatalyst as recited in claim 1, wherein step (1) further comprises recovering the carbon dioxide and the first organic solvent after the reaction is completed.
10. The method for preparing a noble metal supported two-dimensional nanosheet photocatalyst as recited in claim 1, wherein the step (2) further comprises recovering the second organic solvent after the reaction is completed.
CN202011252129.3A 2020-11-11 2020-11-11 Preparation method of noble metal loaded two-dimensional nanosheet photocatalyst Pending CN112337455A (en)

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