CN110038605B - AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2Application method of nano catalyst - Google Patents
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2Application method of nano catalyst Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 120
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 51
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- 239000011259 mixed solution Substances 0.000 claims abstract description 48
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- 238000003756 stirring Methods 0.000 claims abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 84
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 18
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 32
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 abstract description 32
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract description 32
- 238000005406 washing Methods 0.000 abstract description 31
- 238000002360 preparation method Methods 0.000 abstract description 28
- 229910003373 AgInS2 Inorganic materials 0.000 abstract description 27
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 7
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- AXYRIQGRDRIJFR-UHFFFAOYSA-K indium(3+);triacetate;hexahydrate Chemical compound O.O.O.O.O.O.[In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AXYRIQGRDRIJFR-UHFFFAOYSA-K 0.000 description 9
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- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2Preparation method of nano catalyst, taking Ti3AlC2Putting into hydrogen fluoride solution, stirring the mixed solution at room temperature, cleaning the mixed solution with deionized water, and drying under vacuum condition to obtain product a; putting the product a into deionized water, stirring uniformly, and sequentially adding AgNO3、In(OAC)3·6H2Stirring the L-cysteine and the Thioacetamide to obtain a product b of mixed salt solution, putting the product b into a stainless steel high-pressure reaction kettle, and heating to obtain a product c; washing the product c with deionized water or alcohol, and vacuum drying to obtain the desired AgInS2/Ti3C2And (3) a nano catalyst. The laminated structure of the catalyst increases the surface area, adsorbs and activates N2Enhanced capacity, benefit N2Reducing and synthesizing ammonia.
Description
Technical Field
The invention relates to AgInS2/Ti3C2Preparation and application method of nano catalyst, in particular to AgInS for synthesizing ammonia by photocatalytic nitrogen reduction2/Ti3C2Preparation of nano catalyst and its application method.
Background
Nitrogen (N) is the basis of all life and many industrial processes, the reduced form of nitrogen, especially the reduction to ammonia (NH), as early as the 20 th century3) Most of them are from microorganisms to N in the atmosphere2Until the German chemist Flritz-Harber invented the conversion of nitrogen and hydrogen in air into ammonia
The process was the first to produce ammonia on an industrial scale in 1913. This reaction process, which has a hundred years history, is still the main method for industrial synthesis of ammonia. Thus, the Haber-Bosch process is known as one of the most influential inventions in the 20 th century, but requires energy output that consumes about 1% to 2% of the world each year, with the major energy requirements coming from high reaction temperatures (700K) and pressures (100 atm). Furthermore, maintaining such reaction conditions requires a large amount of energy consumption and brings about many ecological problems (such as consumption of fossil energy, air pollution, water pollution, etc.). According to the regulations of the Paris climate Agreement and the Global climate Agreement, the chemical industry is looking for innovative ways to reduce greenhouse gas emissions associated with ammonia production. To address this need, a key goal of research in the field of modern nitrogen chemistry is to reduce fossil fuel usage by developing more efficient homogeneous or heterogeneous photo-catalytic techniques or by adjusting the enzymatic processes under natural nitrogen cycling.
At present, the novel low-energy-consumption green ammonia synthesis process mainly comprises an electrocatalysis method, a biocatalysis method, a thermocatalysis method, a plasma catalysis method, a photocatalysis method and the like. The electrocatalysis is mainly realized by adjusting external voltage through an external power supply to realize N2Reducing and synthesizing ammonia. The disadvantages are that: the external voltage needs to be accurately controlled, and meanwhile, a hydrogen evolution process can occur in the reaction process, and the hydrogen evolution reaction can rob electrons to greatly reduce the yield of the synthetic ammonia. A biocatalytic method: mainly realizes N by simulating the biological nitrogen fixation process and utilizing the action of biological enzyme2Reducing and synthesizing ammonia. The disadvantages are that: the biological reaction process is slow, and the reaction conditions need to be controlled to prevent the inactivation of the enzyme. And plasma catalysis: the material is electrified to form gaseous charged particles, so that the material has high electron supply capacity. The disadvantages are that: thermodynamic imbalance, instability, need of applying high voltage and certain voltage frequency, and reaction subject is N2And H2. Since 1977, Schrauzer et al (G.N.Schrauzer, T.D.Guth, J.Am.chem.Soc.99(1977) 7189-7193.) first passed through TiO2Under the irradiation of ultraviolet light, realize N2Reduction synthesis of ammoniaThe reaction opens the door of green synthesis of ammonia in a new era. Photocatalytic methods have attracted worldwide attention because of their high efficiency and cleanliness.
However, in the process of performing the photocatalytic method, a photocatalytic material is required, such as Xiong et al (reflecting Defect States in W)18O49Preparation of Mo-doped W by Mo Doping A Strength for Tuning N2 Activation times Solar-drive Nitrogen Fixation)18O49The nano-wire can realize photocatalytic synthesis of ammonia under the condition of all wave bands, but needs ultraviolet light and has low utilization rate of sunlight. Meanwhile, there is also a research on the photocatalytic synthesis of ammonia under visible light Conditions by using AuRu nano-alloy particles (Surface plasma annealing nickel oxidation in Pure Water through a discrete mechanical apparatus and mill Conditions), but the gold in the experiment is a precious metal and is not beneficial to practical application.
Disclosure of Invention
The invention aims to provide AgInS for synthesizing ammonia by photocatalytic nitrogen reduction2/Ti3C2Preparation of nano catalyst and its application method. The laminated structure of the catalyst increases the surface area, adsorbs and activates N2Enhanced capacity, benefit N2Reducing and synthesizing ammonia.
The technical scheme of the invention is as follows: AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2Preparation method of nano catalyst, the AgInS2/Ti3C2The nano catalyst consists of AgInS2And Ti3C2The preparation method comprises the following steps:
A、Ti3C2preparing ultrathin nanosheets: taking 1g of Ti3AlC2Putting the mixture into 20mL of hydrogen fluoride solution, stirring the mixture at room temperature for 45-52 h, then washing the mixture with deionized water until the pH value is more than or equal to 6, and drying the mixture for 18-30 h at 55-65 ℃ under a vacuum condition to obtain a product a;
B. preparation of mixed salt solution: putting 30-270 mg of a product into 40mL of deionized water, uniformly stirring, and sequentially adding17-34 mg AgNO3A certain amount of in (OAC)3·6H2And O, 100-200 mg of L-cysteine and 30-60 mg of Thioacetamide, and stirring to obtain a product b of a mixed salt solution, wherein the molar ratio of Ag to In is 1: 1;
C. and (3) crystallization: putting the product b in a stainless steel high-pressure reaction kettle, and heating for 3-7 h at 130-180 ℃ to obtain a product c;
D. washing: washing the product c with deionized water or alcohol for 4-5 times, and vacuum drying at 45-75 ℃ for 8-16 h to obtain the required AgInS2/Ti3C2And (3) a nano catalyst.
The AgInS applied to the photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2In the preparation method of the nano-catalyst, the volume ratio of water to hydrogen fluoride in the hydrogen fluoride solution in the step A is 2: 3.
the AgInS applied to the photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2In the preparation method of the nano catalyst, the deionized water washing or alcohol washing operation method in the step A and the step D is that deionized water or ethanol is added into the solution, and then the solution is placed into a centrifuge for centrifugal separation, and supernatant liquid is removed.
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2An application method of the nano catalyst comprises the step of weighing 15-25 mgAgInS2/Ti3C2And (3) putting the nano catalyst into a container, adding 100mL of water, introducing nitrogen into the container for aeration, stirring the container, then putting the mixed solution under a light source for irradiation, and collecting the generated gas to obtain the required synthetic ammonia.
The AgInS applied to the photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2In the application method of the nano-catalyst, 100mL of water also contains methanol, and the volume ratio of the methanol to the water is 1: 3 to 5.
The AgInS applied to the photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2In the application method of the nano catalyst, the nitrogen introduction amount is 15-25 ml/min, and the nitrogen purity is 90 percentThe above.
The AgInS applied to the photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2In the application method of the nano-catalyst, the illumination intensity of a light source is 8000-10000 lux.
The invention has the beneficial effects that: compared with the prior art, the AgInS of the invention2/Ti3C2The nano catalyst has increased surface area due to the layered structure of the material, and adsorbs and activates N2Enhanced capacity, benefit N2Reducing and synthesizing ammonia. In the process of synthesizing ammonia by reduction by the method, water and N can be obtained by using visible light and a catalyst only at normal temperature and normal pressure2Synthesis of NH3Greatly reduces the energy consumption and the cost, and simultaneously the reaction converts H2By H2And O substitution provides great convenience for transportation and storage of raw materials.
In the process of synthesizing ammonia by using the nano catalyst for reduction, sampling is carried out every other hour, and the concentration of the synthetic ammonia is detected by an indophenol blue spectrophotometry, wherein the yield of the composite nano material doped with 30 percent is about 38 mu mol/g at the most in the first hour, and the total yield in 5 hours can reach 90 mu mol/g.
Drawings
FIG. 1 is the AgInS prepared2/Ti3C2X-ray diffraction pattern (XRD) of the nanocatalyst, with the abscissa being twice the diffraction angle (degree) and the ordinate being the intensity of the diffraction peak (a.u.);
FIG. 2 is a prepared AgInS2/Ti3C2Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and energy spectroscopy (EDS) of the nanocatalysts.
FIG. 3 is a prepared AgInS2/Ti3C2Ultraviolet-visible light absorption spectroscopy (DRS) of the nanocatalyst;
FIG. 4 is a prepared AgInS2/Ti3C2X-ray photoelectron spectroscopy (XPS) of the nanocatalyst with binding energy (eV) on the abscissa and signal intensity (a.u.) on the ordinate;
FIG. 5 is a schematic representation of AgInS prepared2/Ti3C2The ammonia production efficiency of the nano catalyst;
FIG. 6 is a prepared AgInS2/Ti3C2Fluorescence spectrum (PL) of the nanocatalyst.
It can be seen from fig. 1 that the spinel phase AgInS corresponds to 2 θ ═ 24.9 °,26.6 °,28.3 ° and 44.5 °, respectively2Has four crystal faces (120), (002), (121) and (320), which completely correspond to standard cards (JCPDS:25-1328), and further, 2 θ is 8.5 °, 35.9 °, 41.7 ° and 60.4 ° respectively corresponding to Ti3C2Four crystal planes of (002), (008), (0010) and (110), which is in contrast to pure Ti3C2The XRD patterns of the two phases are consistent with Ti3C2Reduction in the amount of AgInS2The content increases, and the characteristic peaks at 35.9 ° and 41.7 ° 2 θ are gradually reduced, and the characteristic peaks at AgInS are gradually reduced2The characteristic peaks have the 2 theta of 24.9 degrees, 26.6 degrees and 28.3 degrees which are obviously increased. XRD result shows that AgInS is successfully prepared2/Ti3C2A composite nanomaterial.
In FIG. 2, 2a and 2b are Scanning Electron Micrographs (SEM), 2c are Transmission Electron Micrographs (TEM), and 2d are energy spectrum analysis (EDS). As can be seen in FIG. 2c, AgInS2/Ti3C2The composite nano material presents a layered structure, can increase the specific surface area of the material and promote N2Adsorption of molecules on the surface of the material, and AgInS as small particles on the surface2Nanoparticles, indicating that the two materials can be well combined to form a heterojunction, are shown in the EDS diagram of fig. 2d as the composition of the material, in which the F element is introduced during the etching process, but in negligible amounts.
FIG. 3 shows a graph of UV-vis DRS of materials with different doping ratios, from which it can be seen that the absorption boundary is near 800nm, which shows that the composite material shows strong absorption characteristics to visible light, and the doping ratio is 30% AgInS2/Ti3C2The peak of the composite nano material is widest, which indicates that the absorption of light is maximum, and Ti is doped3C2The utilization rate of light is improved, and the maximum light response effect is achieved.
FIG. 4 analysis of surface composition and chemical morphology of composite material by XPS, full spectrumResults show AgInS2/Ti3C2The material mainly comprises Ag, In, S, Ti, C and other elements, and the F element exists probably because residual F is left on the surface of the material during the etching process of the hydrogen fluoride solution.
FIG. 5 shows AgInS with different doping levels2/Ti3C2The yield of the synthesized ammonia under the illumination condition of the composite nano material varies with time, and as can be seen from the figure, the yield of the composite nano material with 30 percent of doping is maximum about 38 mu mol/g in the first hour, and the total yield of the composite nano material with 5 hours can reach 90 mu mol/g
FIG. 6 shows AgInS with different doping levels2/Ti3C2The fluorescence spectrogram of the composite nano material is used for researching the separation, transfer and recombination conditions of photo-generated electrons and holes on the surface of the material, the strength of a characteristic peak of the fluorescence spectrum represents the separation efficiency of the photo-generated electrons and the holes on the surface of the material, and the smaller the fluorescence intensity is, the result shows that-And h+The lower the recombination rate of (a). The composite nano material with 30 percent of doping in the composite material has the weakest characteristic peak and the e of the surface-And h+The separation efficiency is highest, and the photocatalytic performance is higher.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not to be construed as limiting the invention.
Example 1 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2The preparation method of the nano catalyst comprises the following steps:
A、Ti3C2preparing ultrathin nanosheets: weighing 1g of Ti3AlC2Mixing in 20mL hydrogen fluoride solution to attack Ti3AlC2Wherein the volume ratio of water to hydrogen fluoride in the hydrogen fluoride solution is 2: 3, stirring the mixed solution at room temperature for 48 hours, then cleaning the mixed solution by using deionized water until the pH value is more than or equal to 6, wherein the deionized water cleaning process comprises the steps of adding deionized water into the mixed solution, then placing the mixed solution into a centrifugal machine for centrifugal separation, and removing the deionized water after separationAnd removing the supernatant. Repeating the steps until the pH value of the solution is more than or equal to 6. Then drying the mixture for 24 hours at the temperature of 60 ℃ under vacuum to obtain a product a, namely Ti3C2A precursor of the nanosheet.
B. Preparation of mixed salt solution: putting 270mg of product a into 40mL of deionized water, uniformly stirring, and sequentially adding 17mg of AgNO330mg of in (OAC)3·6H2O (indium acetate hexahydrate), 100mg of L-cysteine and 30mg of Thioacetamide were stirred to obtain a product b of a mixed salt solution. Wherein the molar ratio of Ag to In is 1: 1. l-cysteine is mainly used as a binder for adsorbing Ag ions, and Thioacetamide is mainly used for providing sulfur.
C. And (3) crystallization: placing the product b in a stainless steel high-pressure reaction kettle, and heating at 150 ℃ for 5h to obtain a product c;
D. washing: and adding deionized water or ethanol into the product c, placing the product c into a centrifugal machine for centrifugal separation, removing supernate after separation, and repeating the steps for 4-5 times. Vacuum drying the separated substance at 60 deg.C for 12h to obtain the desired AgInS2/Ti3C2And (3) a nano catalyst.
This example gives a 10 wt% AgInS2/Ti3C2。
Example 2 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2The preparation method of the nano catalyst comprises the following steps:
A、Ti3C2preparing ultrathin nanosheets: weighing 1g of Ti3AlC2Mixing in 20mL hydrogen fluoride solution to attack Ti3AlC2Wherein the volume ratio of water to hydrogen fluoride in the hydrogen fluoride solution is 2: and 3, stirring the mixed solution at room temperature for 48 hours, then washing the mixed solution by using deionized water until the pH value is more than or equal to 6, wherein the deionized water washing process comprises the steps of adding deionized water into the mixed solution, then placing the mixed solution into a centrifugal machine for centrifugal separation, and removing supernatant after separation. Repeating the steps until the pH value of the solution is more than or equal to 6. Then drying at 60 deg.C under vacuum for 24 hr to obtain product aTi3C2A precursor of the nanosheet.
B. Preparation of mixed salt solution: 120mg of product a is put into 40mL of deionized water to be uniformly stirred, and 17mg of AgNO is sequentially added330mg of in (OAC)3·6H2O (indium acetate hexahydrate), 100mg of L-cysteine and 30mg of Thioacetamide were stirred to obtain a product b of a mixed salt solution. Wherein the molar ratio of Ag to In is 1: 1. l-cysteine is mainly used as a binder for adsorbing Ag ions, and Thioacetamide is mainly used for providing sulfur.
C. And (3) crystallization: placing the product b in a stainless steel high-pressure reaction kettle, and heating at 150 ℃ for 5h to obtain a product c;
D. washing: and adding deionized water or ethanol into the product c, placing the product c into a centrifugal machine for centrifugal separation, removing supernate after separation, and repeating the steps for 4-5 times. Vacuum drying the separated substance at 60 deg.C for 12h to obtain the desired AgInS2/Ti3C2And (3) a nano catalyst.
This example gives 20 wt% AgInS2/Ti3C2。
Example 3 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2The preparation method of the nano catalyst comprises the following steps:
A、Ti3C2preparing ultrathin nanosheets: weighing 1g of Ti3AlC2Mixing in 20mL hydrogen fluoride solution to attack Ti3AlC2Wherein the volume ratio of water to hydrogen fluoride in the hydrogen fluoride solution is 2: and 3, stirring the mixed solution at room temperature for 48 hours, then washing the mixed solution by using deionized water until the pH value is more than or equal to 6, wherein the deionized water washing process comprises the steps of adding deionized water into the mixed solution, then placing the mixed solution into a centrifugal machine for centrifugal separation, and removing supernatant after separation. Repeating the steps until the pH value of the solution is more than or equal to 6. Then drying the mixture for 24 hours at the temperature of 60 ℃ under vacuum to obtain a product a, namely Ti3C2A precursor of the nanosheet.
B. Preparation of mixed salt solutionPreparing: 70mg of a product is put into 40mL of deionized water to be uniformly stirred, and 34mg of AgNO is sequentially added360mg of in (OAC)3·6H2O (indium acetate hexahydrate), 200mg of L-cysteine and 60mg of Thioacetamide were stirred to obtain a product b of a mixed salt solution. Wherein the molar ratio of Ag to In is 1: 1. l-cysteine is mainly used as a binder for adsorbing Ag ions, and Thioacetamide is mainly used for providing sulfur.
C. And (3) crystallization: placing the product b in a stainless steel high-pressure reaction kettle, and heating at 150 ℃ for 5h to obtain a product c;
D. washing: and adding deionized water or ethanol into the product c, placing the product c into a centrifugal machine for centrifugal separation, removing supernate after separation, and repeating the steps for 4-5 times. Vacuum drying the separated substance at 60 deg.C for 12h to obtain the desired AgInS2/Ti3C2And (3) a nano catalyst.
This example produced 30 wt% AgInS2/Ti3C2。
Example 4 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2The preparation method of the nano catalyst comprises the following steps:
A、Ti3C2preparing ultrathin nanosheets: weighing 1g of Ti3AlC2Mixing in 20mL hydrogen fluoride solution to attack Ti3AlC2Wherein the volume ratio of water to hydrogen fluoride in the hydrogen fluoride solution is 2: and 3, stirring the mixed solution at room temperature for 48 hours, then washing the mixed solution by using deionized water until the pH value is more than or equal to 6, wherein the deionized water washing process comprises the steps of adding deionized water into the mixed solution, then placing the mixed solution into a centrifugal machine for centrifugal separation, and removing supernatant after separation. Repeating the steps until the pH value of the solution is more than or equal to 6. Then drying the mixture for 24 hours at the temperature of 60 ℃ under vacuum to obtain a product a, namely Ti3C2A precursor of the nanosheet.
B. Preparation of mixed salt solution: 45mg of a product is put into 40mL of deionized water and stirred evenly, and 34mg of AgNO is added in turn360mg of in (OAC)3·6H2O (indium acetate hexahydrate), 200mg of L-cysteine and 60mg of Thioacetamide were stirred to obtain a product b of a mixed salt solution. Wherein the molar ratio of Ag to In is 1: 1. l-cysteine is mainly used as a binder for adsorbing Ag ions, and Thioacetamide is mainly used for providing sulfur.
C. And (3) crystallization: placing the product b in a stainless steel high-pressure reaction kettle, and heating at 150 ℃ for 5h to obtain a product c;
D. washing: and adding deionized water or ethanol into the product c, placing the product c into a centrifugal machine for centrifugal separation, removing supernate after separation, and repeating the steps for 4-5 times. Vacuum drying the separated substance at 60 deg.C for 12h to obtain the desired AgInS2/Ti3C2And (3) a nano catalyst.
This example produced 40 wt% AgInS2/Ti3C2。
Example 5 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2The preparation method of the nano catalyst comprises the following steps:
A、Ti3C2preparing ultrathin nanosheets: weighing 1g of Ti3AlC2Mixing in 20mL hydrogen fluoride solution to attack Ti3AlC2Wherein the volume ratio of water to hydrogen fluoride in the hydrogen fluoride solution is 2: and 3, stirring the mixed solution at room temperature for 48 hours, then washing the mixed solution by using deionized water until the pH value is more than or equal to 6, wherein the deionized water washing process comprises the steps of adding deionized water into the mixed solution, then placing the mixed solution into a centrifugal machine for centrifugal separation, and removing supernatant after separation. Repeating the steps until the pH value of the solution is more than or equal to 6. Then drying the mixture for 24 hours at the temperature of 60 ℃ under vacuum to obtain a product a, namely Ti3C2A precursor of the nanosheet.
B. Preparation of mixed salt solution: 30mg of the product a is put into 40mL of deionized water to be uniformly stirred, and 34mg of AgNO is sequentially added360mg of in (OAC)3·6H2O (indium acetate hexahydrate), 200mg of L-cysteine and 60mg of Thioacetamide were stirred to obtain a mixtureAnd (c) mixing with a salt solution b. Wherein the molar ratio of Ag to In is 1: 1. l-cysteine is mainly used as a binder for adsorbing Ag ions, and Thioacetamide is mainly used for providing sulfur.
C. And (3) crystallization: placing the product b in a stainless steel high-pressure reaction kettle, and heating at 150 ℃ for 5h to obtain a product c;
D. washing: and adding deionized water or ethanol into the product c, placing the product c into a centrifugal machine for centrifugal separation, removing supernate after separation, and repeating the steps for 4-5 times. Vacuum drying the separated substance at 60 deg.C for 12h to obtain the desired AgInS2/Ti3C2And (3) a nano catalyst.
This example produced 50 wt% AgInS2/Ti3C2。
Example 6 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2The preparation method of the nano catalyst comprises the following steps:
A、Ti3C2preparing ultrathin nanosheets: weighing 1g of Ti3AlC2Mixing in 20mL hydrogen fluoride solution to attack Ti3AlC2Wherein the volume ratio of water to hydrogen fluoride in the hydrogen fluoride solution is 2: and 3, stirring the mixed solution at room temperature for 45 hours, then washing the mixed solution by using deionized water until the pH value is more than or equal to 6, wherein the deionized water washing process comprises the steps of adding deionized water into the mixed solution, then placing the mixed solution into a centrifugal machine for centrifugal separation, and removing supernatant after separation. Repeating the steps until the pH value of the solution is more than or equal to 6. Then drying for 30h at 55 ℃ under vacuum condition to obtain a product a, namely Ti3C2A precursor of the nanosheet.
B. Preparation of mixed salt solution: 150mg of product a is put into 40mL of deionized water to be uniformly stirred, and 25mg of AgNO is sequentially added344mg of in (OAC)3·6H2O (indium acetate hexahydrate), 150mg of L-cysteine and 45mg of Thioacetamide were stirred to obtain a product b of a mixed salt solution. Wherein the molar ratio of Ag to In is 1: 1. the L-cysteine is mainly used as a bonding agent for adsorbing Ag ionsWhile Thioacetamide is primarily used to provide elemental sulfur.
C. And (3) crystallization: placing the product b in a stainless steel high-pressure reaction kettle, and heating at 130 ℃ for 7h to obtain a product c;
D. washing: and adding deionized water or ethanol into the product c, placing the product c into a centrifugal machine for centrifugal separation, removing supernate after separation, and repeating the steps for 4-5 times. Vacuum drying the separated substance at 45 deg.C for 16h to obtain the desired AgInS2/Ti3C2And (3) a nano catalyst.
Example 7 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2The preparation method of the nano catalyst comprises the following steps:
A、Ti3C2preparing ultrathin nanosheets: weighing 1g of Ti3AlC2Mixing in 20mL hydrogen fluoride solution to attack Ti3AlC2Wherein the volume ratio of water to hydrogen fluoride in the hydrogen fluoride solution is 2: and 3, stirring the mixed solution at room temperature for 52 hours, then washing the mixed solution by using deionized water until the pH value is more than or equal to 6, wherein the deionized water washing process comprises the steps of adding deionized water into the mixed solution, then placing the mixed solution into a centrifugal machine for centrifugal separation, and removing supernatant after separation. Repeating the steps until the pH value of the solution is more than or equal to 6. Then drying for 18h at 65 ℃ under vacuum condition to obtain a product a, namely Ti3C2A precursor of the nanosheet.
B. Preparation of mixed salt solution: 150mg of product a is put into 40mL of deionized water to be uniformly stirred, and 25mg of AgNO is sequentially added344mg of in (OAC)3·6H2O (indium acetate hexahydrate), 150mg of L-cysteine and 45mg of Thioacetamide were stirred to obtain a product b of a mixed salt solution. Wherein the molar ratio of Ag to In is 1: 1. l-cysteine is mainly used as a binder for adsorbing Ag ions, and Thioacetamide is mainly used for providing sulfur.
C. And (3) crystallization: putting the product b in a stainless steel high-pressure reaction kettle, and heating at 180 ℃ for 3h to obtain a product c;
D. washing: to obtainAnd adding deionized water or ethanol into the product c, putting the product c into a centrifugal machine for centrifugal separation, removing supernate after separation, and repeating the step for 4-5 times. Vacuum drying the separated substance at 75 deg.C for 8h to obtain the desired AgInS2/Ti3C2And (3) a nano catalyst.
Example 8 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2The preparation method of the nano catalyst comprises the following steps:
A、Ti3C2preparing ultrathin nanosheets: weighing 1g of Ti3AlC2Mixing in 20mL hydrogen fluoride solution to attack Ti3AlC2Wherein the volume ratio of water to hydrogen fluoride in the hydrogen fluoride solution is 2: and 3, stirring the mixed solution at room temperature for 45 hours, then washing the mixed solution by using deionized water until the pH value is more than or equal to 6, wherein the deionized water washing process comprises the steps of adding deionized water into the mixed solution, then placing the mixed solution into a centrifugal machine for centrifugal separation, and removing supernatant after separation. Repeating the steps until the pH value of the solution is more than or equal to 6. Then drying for 30h at 55 ℃ under vacuum condition to obtain a product a, namely Ti3C2A precursor of the nanosheet.
B. Preparation of mixed salt solution: 100mg of a product is put into 40mL of deionized water to be uniformly stirred, and 30mg of AgNO is sequentially added353mg of in (OAC)3·6H2O (indium acetate hexahydrate), 165mg of L-cysteine and 50mg of Thioacetamide were stirred to obtain a product b of a mixed salt solution. Wherein the molar ratio of Ag to In is 1: 1. l-cysteine is mainly used as a binder for adsorbing Ag ions, and Thioacetamide is mainly used for providing sulfur.
C. And (3) crystallization: placing the product b in a stainless steel high-pressure reaction kettle, and heating at 130 ℃ for 7h to obtain a product c;
D. washing: and adding deionized water or ethanol into the product c, placing the product c into a centrifugal machine for centrifugal separation, removing supernate after separation, and repeating the steps for 4-5 times. Vacuum drying the separated substance at 45 deg.C for 16h to obtain the desired AgInS2/Ti3C2And (3) a nano catalyst.
Example 9 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2The preparation method of the nano catalyst comprises the following steps:
A、Ti3C2preparing ultrathin nanosheets: weighing 1g of Ti3AlC2Mixing in 20mL hydrogen fluoride solution to attack Ti3AlC2Wherein the volume ratio of water to hydrogen fluoride in the hydrogen fluoride solution is 2: and 3, stirring the mixed solution at room temperature for 52 hours, then washing the mixed solution by using deionized water until the pH value is more than or equal to 6, wherein the deionized water washing process comprises the steps of adding deionized water into the mixed solution, then placing the mixed solution into a centrifugal machine for centrifugal separation, and removing supernatant after separation. Repeating the steps until the pH value of the solution is more than or equal to 6. Then drying for 18h at 65 ℃ under vacuum condition to obtain a product a, namely Ti3C2A precursor of the nanosheet.
B. Preparation of mixed salt solution: 100mg of a product is put into 40mL of deionized water to be uniformly stirred, and 30mg of AgNO is sequentially added353mg of in (OAC)3·6H2O (indium acetate hexahydrate), 165mg of L-cysteine and 50mg of Thioacetamide were stirred to obtain a product b of a mixed salt solution. Wherein the molar ratio of Ag to In is 1: 1. l-cysteine is mainly used as a binder for adsorbing Ag ions, and Thioacetamide is mainly used for providing sulfur.
C. And (3) crystallization: putting the product b in a stainless steel high-pressure reaction kettle, and heating at 180 ℃ for 3h to obtain a product c;
D. washing: and adding deionized water or ethanol into the product c, placing the product c into a centrifugal machine for centrifugal separation, removing supernate after separation, and repeating the steps for 4-5 times. Vacuum drying the separated substance at 75 deg.C for 8h to obtain the desired AgInS2/Ti3C2And (3) a nano catalyst.
Example 10 of the present invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2Application method of nano catalyst, weighing 15mgAgInS2/Ti3C2And (3) putting the nano catalyst into a container, adding 100mL of water, introducing nitrogen into the container for aeration, stirring the container, then putting the mixed solution under a light source for irradiation, and collecting the generated gas to obtain the required synthetic ammonia.
The 100mL water also contains methanol, and the volume ratio of the methanol to the water is 1: 3, adding methanol mainly for removing the cavity in the solution.
The nitrogen gas introduction amount is 15ml/min, and the nitrogen gas purity is more than 90%.
The light intensity of the light source is 8000 lux.
Example 11 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2Application method of nano catalyst, weighing 25mgAgInS2/Ti3C2And (3) putting the nano catalyst into a container, adding 100mL of water, introducing nitrogen into the container for aeration, stirring the container, then putting the mixed solution under a light source for irradiation, and collecting the generated gas to obtain the required synthetic ammonia.
The 100mL water also contains methanol, and the volume ratio of the methanol to the water is 1: methanol was added mainly to remove the cavities from the solution.
The nitrogen gas introduction amount is 25ml/min, and the nitrogen gas purity is more than 90%.
The light intensity of the light source was 10000 lux.
Example 12 of the present invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2Application method of nano catalyst, weighing 20mgAgInS2/Ti3C2And (3) putting the nano catalyst into a container, adding 100mL of water, introducing nitrogen into the container for aeration, stirring the container, then putting the mixed solution under a light source for irradiation, and collecting the generated gas to obtain the required synthetic ammonia.
The 100mL water also contains methanol, and the volume ratio of the methanol to the water is 1: methanol was added mainly to remove the cavities from the solution.
The nitrogen gas introduction amount is 20ml/min, and the nitrogen gas purity is more than 90%.
The light source had an illumination intensity of 8880 lux.
Example 13 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2Application method of nano catalyst, weighing 18mgAgInS2/Ti3C2And (3) putting the nano catalyst into a container, adding 100mL of water, introducing nitrogen into the container for aeration, stirring the container, then putting the mixed solution under a light source for irradiation, and collecting the generated gas to obtain the required synthetic ammonia.
The 100mL water also contains methanol, and the volume ratio of the methanol to the water is 1: methanol was added mainly to remove the cavities from the solution.
The nitrogen gas introduction amount is 18ml/min, and the nitrogen gas purity is more than 90%.
The light intensity of the light source is 8500 lux.
Example 14 of the present invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2Application method of nano catalyst, 22mgAgInS is weighed2/Ti3C2And (3) putting the nano catalyst into a container, adding 100mL of water, introducing nitrogen into the container for aeration, stirring the container, then putting the mixed solution under a light source for irradiation, and collecting the generated gas to obtain the required synthetic ammonia.
The 100mL water also contains methanol, and the volume ratio of the methanol to the water is 1: 3.5, methanol is added mainly to remove the cavities in the solution.
The nitrogen gas introduction amount is 22ml/min, and the nitrogen gas purity is more than 90%.
The light intensity of the light source was 9500 lux.
Example 15 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2Application method of nano catalyst, weighing 15mgAgInS2/Ti3C2And (3) putting the nano catalyst into a container, adding 100mL of water, introducing nitrogen into the container for aeration, stirring the container, then putting the mixed solution under a light source for irradiation, and collecting the generated gas to obtain the required synthetic ammonia.
The 100mL water also contains methanol, and the volume ratio of the methanol to the water is 1: 3, adding methanol mainly for removing the cavity in the solution.
The nitrogen gas introduction amount is 15ml/min, and the nitrogen gas purity is more than 90%.
The light intensity of the light source was 10000 lux.
Example 16 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2Application method of nano catalyst, weighing 15mgAgInS2/Ti3C2And (3) putting the nano catalyst into a container, adding 100mL of water, introducing nitrogen into the container for aeration, stirring the container, then putting the mixed solution under a light source for irradiation, and collecting the generated gas to obtain the required synthetic ammonia.
The 100mL water also contains methanol, and the volume ratio of the methanol to the water is 1: methanol was added mainly to remove the cavities from the solution.
The nitrogen gas introduction amount is 15ml/min, and the nitrogen gas purity is more than 90%.
The light intensity of the light source was 10000 lux.
Example 17 of the invention:
AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2Application method of nano catalyst, weighing 25mgAgInS2/Ti3C2And (3) putting the nano catalyst into a container, adding 100mL of water, introducing nitrogen into the container for aeration, stirring the container, then putting the mixed solution under a light source for irradiation, and collecting the generated gas to obtain the required synthetic ammonia.
The 100mL water also contains methanol, and the volume ratio of the methanol to the water is 1: 3, adding methanol mainly for removing the cavity in the solution.
The nitrogen gas introduction amount is 25ml/min, and the nitrogen gas purity is more than 90%.
The light intensity of the light source is 8000 lux.
Claims (4)
1. AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2The application method of the nano catalyst is characterized in that: weighing 15-25 mgAgInS2/Ti3C2And (3) putting the nano catalyst into a container, adding 100mL of water, introducing nitrogen into the container for aeration, stirring the container, then putting the mixed solution under a light source for irradiation, and collecting the generated gas to obtain the required synthetic ammonia.
2. The AgInS applied to photocatalytic nitrogen reduction ammonia synthesis according to claim 12/Ti3C2The application method of the nano catalyst is characterized in that: the 100mL water also contains methanol, and the volume ratio of the methanol to the water is 1: 3 to 5.
3. The AgInS applied to photocatalytic nitrogen reduction ammonia synthesis according to claim 12/Ti3C2The application method of the nano catalyst is characterized in that: the nitrogen gas introduction amount is 15-25 ml/min, and the nitrogen gas purity is more than 90%.
4. The AgInS applied to photocatalytic nitrogen reduction ammonia synthesis according to claim 12/Ti3C2The application method of the nano catalyst is characterized in that: the illumination intensity of the light source is 8000-10000 lux.
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