CN112221528B - Monoatomic catalyst, preparation method and application thereof - Google Patents
Monoatomic catalyst, preparation method and application thereof Download PDFInfo
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- 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
- B01J35/39—Photocatalytic properties
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
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- 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
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- 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
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Abstract
The invention discloses a monatomic catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: carrying out high-temperature polymerization reaction on an organic matter which is taken as a precursor and is rich in nitrogen and carbon to prepare a block carbon nitride material, and then carrying out stripping treatment to obtain a carbon nitride ultrathin nanosheet; carrying out hydrothermal reaction on a hydrothermal reaction system containing the carbon nitride ultrathin nanosheets, a transition metal source and a solvent to prepare a transition metal oxide/carbon nitride composite material; and calcining and etching the transition metal oxide/carbon nitride composite material to obtain the monatomic catalyst. The invention greatly improves the nitrogen fixation performance of the monatomic catalyst by loading the transition metal monatomic on the carbon nitride ultrathin nanosheet and further performing ammoniation treatment, and the ammonia production efficiency can reach 675 mu mol g ‑1 h ‑1 。
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a monatomic catalyst, and a preparation method and application thereof.
Background
Ammonia (NH) 3 ) Is an indispensable chemical substance in industrial and agricultural production and is a basic raw material for synthesizing common fiber and chemical fertilizer. Nitrogen (N) gas generation using iron-based catalyst 2 ) With hydrogen (H) 2 ) React to synthesize NH 3 Although discovered over a century ago, the Haber-Bosch process of (A) was still currently nitrogen fixation for the preparation of NH 3 The main industrial processes of (1). However, this process requires relatively high reaction conditions (over 673K and 100 bar), consumes more than 1% of the global energy supply, and also requires the conversion of fossil fuels to produce large quantities of hydrogen, which inevitably produces large quantities of greenhouse gases (CO) 2 ). Although the reaction conditions of the process have been improved to achieve the purposes of reducing energy consumption and improving efficiency in the past 100 years, another method for carrying out the ammonia synthesis reaction under normal temperature and mild environmental conditions is still urgently needed.
Semiconductor photocatalysis is a promising technology that can pass through under mild environmental conditionsN 2 Reduction for artificial NH 3 A method of photosynthesis. The semiconductor is excited by solar energy to generate electron-hole pairs, high-energy electrons in energy band and H generated by water decomposition + For N to 2 Fixed to NH 3 Is indispensable in the molecule. Although N is 2 The molecule has ultrahigh dissociation energy (941 kJ. Mol) -1 ) But when energetic electrons are transferred from the semiconductor conduction band to the surface-bonded N 2 The nonpolar triple bonds are weakened and activated when the molecules are in the opposite bond orbit. In this case N 2 In the photocatalytic reduction process of (2), the cleavage of the triple bond is usually the rate determining step, which is in parallel with N 2 The chemical adsorption of molecules on the active sites of the photocatalyst is closely related. A recent work by the team of professor Zhongke Daxiong Xiong Yujie indicated that in Mo-doped W 18 O 49 In the nanowires, the coordinatively unsaturated metal atom having an oxygen defect can be used as N 2 The sites of chemisorption and electron transfer of (a). Likewise, ti on titanium dioxide with oxygen deficiency 3+ Species were also shown to be N 2 The reduced active sites promote efficient conversion of light energy to chemical energy. However, other types of N 2 Activation sites have not been discovered, particularly those based on coordination environment regulation of charge transport active sites.
Since the first discovery in 2011, heterogeneous monatomic catalysts have generally been used as charge transfer centers for various catalytic reactions, and have attracted great attention in recent years. From the point of view of coordination chemistry, in monoatomic catalysts, the individual and isolated metal atoms immobilized on a support can be regarded as homogeneous catalysts. Compared with nanoclusters, nanoparticles and bulk catalysts, monatomic catalysts have higher activity and selectivity, determined by their unsaturated coordination and tunable electronic structure. Although the performance of monatomic species in electrocatalytic reactions (e.g., OER and ORR) has been widely reported, there has been limited work to demonstrate the feasibility of using monatomic catalysts in photocatalytic reactions, such as monatomic Pt or single-site Co as promoters to promote H 2 And for driving CO with visible light 2 Reduced monoatomic Co sites. However, in photocatalysisThe effective monatomic species in the nitrogen fixation process and their exact mechanism as a catalyst remain extremely limited.
Tungsten is a transition metal of group vib of the periodic table of the elements and is characterized by an electronic structure with open d and f shell layers. Notably, such non-3 d high valent metals can form a number of oxidation states, the most common of which is +6, and their coordination number can change from 6 to 4 during the structural change. As is common for carbide and nitride materials, e.g. W 2 C. WC and WN, etc., which have a platinum-like behavior for chemisorption of a substrate during catalysis. Compared with platinum, tungsten has the advantage that the electronic structure of the d-band can realize the design regulation of the density of central states (DOS) of the d-band by regulating the coordination number of carbon or nitrogen. Thus, when a single atom is used as the active center, the modulatable electronic structure may be directed toward an adsorbate (e.g., N) 2 ) The activation of (a) has an important contribution.
Disclosure of Invention
The invention mainly aims to provide a monatomic catalyst, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a monatomic catalyst, which comprises the following steps:
providing nitrogen and carbon rich organic as a precursor;
carrying out high-temperature polymerization reaction on the organic matter rich in nitrogen and carbon to prepare a block carbon nitride material, and then carrying out stripping treatment to obtain the carbon nitride ultrathin nanosheet (g-C) 3 N 4 Ultrathin nanosheets);
carrying out hydrothermal reaction on a hydrothermal reaction system containing the carbon nitride ultrathin nano-sheet, a transition metal source and a solvent to prepare a transition metal oxide/carbon nitride composite material (transition metal oxide/g-C) 3 N 4 Composite materials);
and calcining and etching the transition metal oxide/carbon nitride composite material to obtain the monatomic catalyst.
The embodiment of the invention also provides a monatomic catalyst prepared by the method, and the monatomic catalyst comprises carbon nitride ultrathin nanosheets and transition metal monatomic supported on the carbon nitride ultrathin nanosheets.
The embodiment of the invention also provides the application of the monatomic catalyst in photocatalytic reduction type reaction.
The embodiment of the invention also provides a photocatalytic nitrogen fixation reaction, which comprises the following steps:
providing the aforementioned monatomic catalyst;
and introducing nitrogen into a second mixed reaction system containing the monatomic catalyst and water, and reacting under the illumination condition.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method, the melamine is used as a precursor, the ultrathin CN nanosheet is prepared through high-temperature polymerization and liquid-phase stripping, and the transition metal source compound is further selected to provide transition metal atoms, so that the monatomic catalyst is prepared, has excellent nitrogen fixation performance, and particularly for the W monatomic catalyst, the nitrogen fixation performance of the W monatomic catalyst is greatly improved through regulating and controlling the coordination environment of the monatomic W. In the nitrogen fixation ammonia synthesis experiment, the efficiency of synthesizing ammonia by CN ultrathin nanosheets loaded with monatomic W reaches 180 mu mol g -1 h -1 About CN ultra-thin nanometer (56 mu mol g) -1 h -1 ) 3 times of the nitrogen-fixing performance of the WCN, and the nitrogen-fixing performance of the WCN is further improved by carrying out coordination control on the WCN through ammoniation, particularly the ammonia production efficiency of a WCN sample (WCN-500 ℃) after ammoniation treatment at 500 ℃ can reach 675 mu mol g -1 h -1 By the coordination control on the monoatomic W in the sample, the nitrogen fixation catalytic activity of the monoatomic W catalyst is greatly enhanced, and a new method is provided for preparation of the monoatomic photocatalytic material and improvement and mechanism exploration of the photocatalytic nitrogen fixation performance of the monoatomic W catalyst.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a graph of ammonia production efficiency of CN ultrathin nanosheets and WCN monatomic catalysts in examples 1-4 of the present invention under argon and nitrogen atmospheres respectively;
FIG. 2 shows NH of CN ultrathin nanosheets and WCN single-atom catalysts in examples 1 and 3 of the present invention after irradiation of Xe lamp for 1h 3 A synthetic efficiency map of (a);
FIG. 3 is a schematic view of a nitrogen fixation reaction apparatus in an exemplary embodiment of the present invention;
FIG. 4 is a graph showing ammonia production efficiency of catalysts WCN-450 and WCN-500 in argon and nitrogen atmosphere after ammoniation treatment at 450 ℃ and 500 ℃ respectively for CN ultrathin nanosheets in example 1, WCN monatomic catalyst in example 3 and WCN monatomic catalyst in example 3 in the invention.
Detailed Description
In view of the defects of the prior art, the present inventors have long studied and largely practiced to propose the technical solution of the present invention, which is mainly a monatomic catalyst prepared by a hydrothermal-calcination-etching three-step method, and will clearly and completely describe the technical solution of the present invention, it is obvious that the described embodiments are a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
An aspect of an embodiment of the present invention provides a method for preparing a monatomic catalyst, which includes:
providing nitrogen and carbon rich organic as a precursor;
carrying out high-temperature polymerization reaction on the organic matter rich in nitrogen and carbon to prepare a block carbon nitride material, and then carrying out stripping treatment to obtain the carbon nitride ultrathin nanosheet (g-C) 3 N 4 Ultrathin nanosheets);
carrying out hydrothermal reaction on a hydrothermal reaction system containing the carbon nitride ultrathin nano-sheet, a transition metal source and a solvent to prepare a transition metal oxide/carbon nitride composite material (transition metal oxide/g-C) 3 N 4 Composite materials);
and calcining and etching the transition metal oxide/carbon nitride composite material to obtain the monatomic catalyst.
In some more specific embodiments, the nitrogen and carbon rich organic includes any one or a combination of two or more of melamine, urea, and thiourea, without limitation.
Further, the thickness of the carbon nitride ultrathin nanosheet is 2.1-10 nm.
Further, the preparation method comprises the following steps: and carrying out polymerization reaction on the organic matter rich in nitrogen and carbon at 450-600 ℃ for 1-2h to prepare the bulk carbon nitride material.
Further, the peeling treatment includes a liquid phase ultrasonic peeling method.
In some more specific embodiments, the preparation method comprises: dissolving a transition metal source in a solvent to form a transition metal solution, mixing the transition metal solution with a dispersion liquid containing carbon nitride ultrathin nanosheets, adding an acid to form a hydrothermal reaction system, and carrying out hydrothermal reaction at 170-190 ℃ for 5-10 h to obtain the transition metal oxide/carbon nitride composite material, wherein the pH value of the hydrothermal reaction system is below 1.
Further, the acid includes hydrochloric acid or sulfuric acid, and is not limited thereto.
Further, the organic substance containing nitrogen and carbon includes any one or a combination of two or more of melamine, urea, and thiourea, and is not limited thereto.
Further, the transition metal source includes any one or a combination of two or more of a W source, a V source, a Cr source, a Mn source, an Fe source, a Co source, a Ni source, a Cu source, a Zn source, and a Mo source, and is preferably a W source.
Further, the molar ratio of the carbon nitride ultrathin nanosheet to the transition metal source is 2.
Further, the transition metal oxide/g-C 3 N 4 The transition metal oxide in the composite material includes any one or a combination of two or more of a W-based oxide, a V-based oxide, a Cr-based oxide, a Mn-based oxide, a Fe-based oxide, a Co-based oxide, a Ni-based oxide, a Cu-based oxide, a Zn-based oxide, and a Mo-based oxide, and is not limited thereto.
Further, the solvent includes water or ethanol, and is not limited thereto.
In some more specific embodiments, the preparation method comprises: under a protective atmosphere, for the transition metal oxide/g-C 3 N 4 Calcining the composite material at 400-600 ℃ for 2h, and then calcining the calcined transition metal oxide/g-C 3 N 4 The composite material is etched in an alkaline environment and/or an acidic environment for 2-12 h.
Further, the protective atmosphere includes an inert gas atmosphere and/or a nitrogen gas atmosphere, and is not limited thereto.
Further, the inert gas atmosphere includes an argon gas atmosphere, and is not limited thereto.
Further, a calcined transition metal oxide/g-C subjected to etching treatment in an alkaline environment 3 N 4 The composite material comprises W-based oxide/g-C 3 N 4 Composite material and/or Mo-based oxide/g-C 3 N 4 Composite materials, and is not limited thereto.
Further, the alkaline environment includes KOH and/or NaOH, and is not limited thereto.
Further, a calcined transition metal oxide/g-C subjected to etching treatment in an acidic environment 3 N 4 The composite material comprises V-based oxide/g-C 3 N 4 Composite material, cr-based oxide/g-C 3 N 4 Composite material, mn-based oxide/g-C 3 N 4 Composite material, fe-based oxide/g-C 3 N 4 Composite material, co-based oxide/g-C 3 N 4 Composite material, ni-based oxide/g-C 3 N 4 Composite material and Cu-based materialoxide/g-C 3 N 4 Composite material, zn-based oxide/g-C 3 N 4 Any one or a combination of two or more of the composite materials, and is not limited thereto.
Further, the acidic environment includes hydrochloric acid and/or sulfuric acid, and is not limited thereto.
In some more specific embodiments, the method for preparing the monatomic catalyst further comprises:
and in the ammonia atmosphere, carrying out ammoniation treatment on the material obtained after the etching treatment at the temperature of between 300 and 500 ℃ for 1 to 5 hours to obtain the monatomic catalyst.
Yet another aspect of an embodiment of the present invention provides a monatomic catalyst, including g-C, prepared by the foregoing method 3 N 4 Ultrathin nanosheet and g-C-supported nanosheet 3 N 4 Transition metal monoatomic on the ultrathin nanometer sheet.
Further, the transition metal monoatomic includes any one or a combination of two or more of W, V, cr, mn, fe, co, ni, cu, zn, and Mo, but is not limited thereto.
Furthermore, the content of the transition metal monoatomic in the monoatomic catalyst is 2-5 wt%.
In some more specific embodiments, the method of preparing the W monatomic catalyst specifically comprises: graphite phase carbon nitride (g-C) 3 N 4 Preparation of CN and CN (W/g-C) loaded by monoatomic W 3 N 4 WCN for short);
(1) Preparation of CN:
firstly, organic matter containing nitrogen and carbon is used for preparing blocky CN through high-temperature polycondensation, and then the CN ultrathin nanosheet is prepared by combining a liquid-phase ultrasonic stripping method;
(2) Preparation of WCN
Carrying out hydro-thermal treatment on the dispersion liquid of the tungsten salt and the CN ultrathin nanosheet to prepare a CN composite material loaded by tungsten oxide;
and calcining the tungsten oxide-loaded CN composite material, and then etching redundant tungsten oxide by concentrated alkali to only leave W atoms anchored with CN, thereby obtaining the WCN monatomic catalyst.
Further, the nitrogen-and carbon-containing organic substance includes any one or a combination of two or more of melamine, urea, and thiourea, and is not limited thereto.
Further, the method comprises: carrying out hydrothermal treatment on sodium tungstate and CN ultrathin nanosheets to obtain white precipitates according to a certain proportion at 180 ℃, annealing the white precipitates in a reduction atmosphere through a CVD furnace, finally soaking a sample in an alkaline solution to elute oxygen, and carrying out centrifugation, cleaning and drying treatment to obtain the WCN monatomic catalyst.
Further, the hydrothermal treatment is carried out under acidic conditions (pH is less than or equal to 1), and the acidic environment comprises HCl or H 2 SO 4 And is not limited thereto.
Further, the reaction temperature of the hydrothermal treatment is 180 ℃, and the reaction time is any one of 5h, 6h, 7h, 8h, 9h and 10 h.
Further, the temperature of the calcination treatment is any one of 400 ℃, 450 ℃, 500 ℃, 550 ℃ and 600 ℃.
Further, the calcination treatment was performed under a protective atmosphere for the purpose of enhancing the bonding strength between the CN substrate and the adjacent tungsten atoms.
Further, the protective atmosphere includes an inert gas atmosphere and/or a nitrogen gas atmosphere, and is not limited thereto.
Further, the etching treatment is performed in an alkaline environment, and the excess tungsten oxide particles can be etched through the etching treatment.
Further, the alkaline environment comprises NaOH or KOH.
Furthermore, the coordination control of the monatomic W in the WCN monatomic catalyst can be realized by performing high-temperature ammoniation treatment on the product after the concentrated alkali etching treatment.
Further, the temperature of the high-temperature amination treatment is any one of 300 ℃, 350 ℃, 400 ℃, 450 ℃ and 500 ℃.
Further, the time of the high-temperature ammoniation treatment is any one of 1h, 2h, 3h, 4h and 5 h.
In the present invention, from the viewpoint of coordination chemistry, in the monatomic catalyst, the single and isolated metal atoms immobilized on the carrier can be regarded as a homogeneous catalyst, and the monatomic catalyst has higher activity and selectivity as compared with nanoclusters, nanoparticles and bulk catalysts, which are determined by its unsaturated coordination and adjustable electronic structure. Tungsten is a transition metal of group vib of the periodic table of the elements and is characterized by an electronic structure with open d and f shell layers. It is noteworthy that such non-3 d high valent metals can form a number of oxidation states, the most common of which is +6, and that their coordination numbers can change from 6 to 4 during the structural change. As is common for carbide and nitride materials, e.g. W 2 C. WC and WN, etc., which have a platinum-like behavior for chemisorption of a substrate during catalysis. Compared with platinum, tungsten has the advantage that the d-band electronic structure can realize the design regulation of the d-band central state Density (DOS) by regulating the coordination number of carbon or nitrogen. Thus, when a single atom is used as the active center, the modulatable electronic structure may be directed toward an adsorbate (e.g., N) 2 ) The activation of (a) has an important contribution.
In some more specific embodiments, the photocatalytic nitrogen fixation reaction comprises (shown in schematic figure 3 of the nitrogen fixation reaction apparatus): for catalyst containing WCN single atom and saturated N 2 The aqueous solution system is illuminated, then ultraviolet spectrum test is carried out after the color development of the Neisseria reagent, and the corresponding ammonia concentration can be obtained, and then the related activity index of the monatomic photocatalysis nitrogen fixation is judged.
Another aspect of the embodiments of the present invention also provides a use of the aforementioned monatomic catalyst in a photocatalytic reduction reaction.
Further, the photocatalytic reduction reaction includes any one of a photocatalytic nitrogen fixation reaction, a photocatalytic hydrogen production reaction, and a photocatalytic carbon dioxide reaction, but is not limited thereto.
Another aspect of an embodiment of the present invention also provides a photocatalytic nitrogen fixation reaction, including:
providing the aforementioned monatomic catalyst;
and introducing nitrogen into a second mixed reaction system containing the monatomic catalyst and water, and reacting under the illumination condition.
In some more specific embodiments, the photocatalytic nitrogen fixation reaction further comprises: and after the second mixed reaction system finishes the reaction, carrying out Neisseria reagent color development treatment on the obtained solution, and testing through an ultraviolet spectrum to obtain the ammonia concentration of the obtained solution.
Further, the second mixed reaction system also comprises ethanol.
Further, the light source used in the lighting condition is an Xe lamp, and the lighting intensity is 26mW cm -2 。
Further, the light source is full spectrum light.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
A certain amount of melamine is weighed into a 30ml quartz crucible, and the crucible is placed in a muffle furnace at 2 ℃ for min -1 The temperature is raised to 550 ℃ at the temperature raising rate, and the temperature is kept for 2 hours to obtain a yellow block-shaped object; grinding and refining the yellow massive object, adding water, performing ultrasonic dispersion for 16 hours until the solution becomes milky white, performing suction filtration, drying and collecting to obtain a CN ultrathin nanosheet;
weighing 50mg of CN ultrathin nanosheets, placing the CN ultrathin nanosheets into a beaker, adding 40ml of deionized water and 10ml of absolute ethyl alcohol, ultrasonically dispersing the nanosheets in an ultrasonic cleaning machine for 2 hours, then transferring the nanosheets into a photocatalytic reaction container, sealing the reaction container, placing the reaction container on a magnetic stirrer to continuously stir the solution, connecting circulating water at two ends of the reactor, cooling the reactor by the aid of the circulating water, maintaining the temperature of the reactor at 20 ℃, and then adding 60ml of min into the reaction container -1 Is continuously fed with N with a purity of 99.9% 2 And after 1h, starting a 300W Xe lamp for illumination reaction, setting a light source as full spectrum light, and setting the irradiation intensity to be 26mW cm -2 Extracting 1ml of reaction solution by using a 5ml syringe every 15min in the whole reaction process, filtering out the catalyst, collecting the catalyst into a 1.5ml centrifuge tube, and finally detecting NH by using Nessler's reagent 3 And NH 4 + Yield of (2), NH in this example 3 The efficiency of the synthesis of (A) is shown in FIG. 1 as CN-N 2 Shown; FIG. 2 shows NH of CN ultrathin nanosheets irradiated by Xe lamp for 1h in the present example 3 The synthesis efficiency of (2).
Example 2
A certain amount of melamine is weighed into a 30ml quartz crucible, and the crucible is placed in a muffle furnace at 2 ℃ for min -1 The temperature is raised to 550 ℃ at the temperature raising rate, and the temperature is kept for 2 hours to obtain a yellow block-shaped object; grinding and refining the yellow massive object, adding water, performing ultrasonic dispersion for 16 hours until the solution becomes milky white, performing suction filtration, drying and collecting to obtain a CN ultrathin nanosheet;
weighing 50mg of CN ultrathin nanosheets, placing the CN ultrathin nanosheets into a beaker, adding 40ml of deionized water and 10ml of absolute ethyl alcohol, ultrasonically dispersing the nanosheets in an ultrasonic cleaning machine for 2 hours, then transferring the nanosheets into a photocatalytic reaction container, sealing the reaction container, placing the reaction container on a magnetic stirrer to continuously stir the solution, connecting two ends of the reactor with circulating water, cooling the reactor by the circulating water to maintain the temperature of the reactor at 20 ℃, and then placing the reactor into the reaction container at 60 ml/min -1 Ar with the purity of 99.9 percent is continuously introduced at the flow rate, after 1 hour, a 300W Xe lamp is turned on for illumination reaction, a light source is set to be full-spectrum light, and the irradiation intensity is 26mW cm -2 Extracting 1ml of reaction solution by using a 5ml syringe every 15min in the whole reaction process, filtering out the catalyst, collecting the catalyst into a 1.5ml centrifuge tube, and finally detecting NH by using Nessler's reagent 3 And NH 4 + Yield of (2), NH in this example 3 The efficiency of the synthesis of (A) is shown in FIG. 1 as CN-Ar.
Example 3
A certain amount of melamine was weighed into a 30ml quartz crucible and the crucible was placed in a muffle furnace at 2 ℃ min -1 The temperature rising rate of (2) is increased to 550 ℃, and the temperature is kept for 2 hours, thus obtaining yellowGrinding and refining the yellow blocky object, adding water, performing ultrasonic dispersion for 16 hours until the solution becomes milky white, performing suction filtration, drying and collecting to obtain CN ultrathin nanosheets;
0.23g of sodium tungstate (Na) 2 WO 4 ·2H 2 O) is dissolved in 30ml of deionized water, then CN ultrathin nanosheet (120 mg) is added, uniform stirring is carried out on a magnetic stirrer, 1mol/L hydrochloric acid is dropwise added to adjust the pH value of the solution to 1, ultrasonic stirring is carried out for 30min, then the solution is transferred to a polytetrafluoroethylene lining, the stainless steel lining is placed into a stainless steel reaction kettle to be screwed down, hydrothermal reaction is carried out in an oven at 180 ℃ for 10h, the product is washed by distilled water and dried, and yellowish-white precipitate (WO) is obtained 3 /g-C 3 N 4 ) The yellow-white color is precipitated (WO) 3 /g-C 3 N 4 ) Placing in a CVD tube furnace at 5 deg.C/min -1 Heating to 450 ℃, using Ar as protective gas to prevent oxidation, calcining at 450 ℃ for 2h, finally etching in 3mol/L KOH solution for 12h, and then centrifuging, cleaning and drying to obtain the WCN monatomic catalyst;
weighing 50mg WCN monatomic catalyst, placing the WCN monatomic catalyst in a beaker, adding 40ml of deionized water and 10ml of absolute ethyl alcohol, ultrasonically dispersing for 2 hours in an ultrasonic cleaning machine, then transferring the WCN monatomic catalyst into a photocatalytic reaction container, sealing the reaction container, placing the reaction container on a magnetic stirrer to continuously stir the solution, connecting two ends of the reactor with circulating water, cooling the reactor by the circulating water, maintaining the temperature at 20 ℃, and then adding the WCN monatomic catalyst into the reaction container at 60 ml/min -1 Is continuously fed with N with a purity of 99.9% 2 After 1h, a 300W Xe lamp is turned on to perform illumination reaction, a light source is set to be full spectrum light, and the irradiation intensity is 26mW cm -2 Extracting 1ml of reaction solution by using a 5ml syringe every 15min in the whole reaction process, filtering out the catalyst, collecting the catalyst into a 1.5ml centrifuge tube, and finally detecting NH by using Nessler's reagent 3 And NH 4 + The yield of (2) is calculated to obtain the synthetic ammonia efficiency of 180 mu mol g -1 h -1 NH in this example 3 The synthesis efficiency of (A) is as shown in WCN-N in FIG. 1 2 Shown; FIG. 2 shows NH of WCN monatomic catalyst after 1h Xe lamp irradiation in the present example 3 The synthesis efficiency of (2).
Example 4
A certain amount of melamine was weighed into a 30ml quartz crucible and the crucible was placed in a muffle furnace at 2 ℃ min -1 Heating to 550 ℃ at the heating rate, keeping the temperature for 2 hours to obtain a yellow block, grinding and refining the yellow block, adding water, ultrasonically dispersing for 16 hours until the solution becomes milky white, performing suction filtration, drying and collecting to obtain CN ultrathin nanosheets;
0.23g of sodium tungstate (Na) 2 WO 4 ·2H 2 O) is dissolved in 30ml of deionized water, then CN ultrathin nanosheet (120 mg) is added, uniform stirring is carried out on a magnetic stirrer, 1mol/L hydrochloric acid is dropwise added to adjust the pH value of the solution to 1, ultrasonic stirring is carried out for 30min, then the solution is transferred to a polytetrafluoroethylene lining, the stainless steel lining is placed into a stainless steel reaction kettle to be screwed down, hydrothermal reaction is carried out in an oven at 180 ℃ for 10h, the product is washed by distilled water and dried, and yellowish-white precipitate (WO) is obtained 3 /g-C 3 N 4 ) The yellowish white is precipitated (WO) 3 /g-C 3 N 4 ) Placing in a CVD tube furnace at 5 deg.C/min -1 Heating to 450 ℃, using Ar as protective gas to prevent oxidation, calcining at 450 ℃ for 2h, finally etching in 3mol/L KOH solution for 12h, and then centrifuging, cleaning and drying to obtain the WCN monatomic catalyst;
weighing 50mg WCN monatomic catalyst, placing in a beaker, adding 40ml of deionized water and 10ml of absolute ethyl alcohol, ultrasonically dispersing for 2 hours in an ultrasonic cleaning machine, then transferring into a photocatalytic reaction container, sealing the reaction container, placing on a magnetic stirrer to continuously stir the solution, connecting circulating water at two ends of the reactor, cooling at 20 ℃, and then adding 60 ml/min into the reaction container -1 Ar with the purity of 99.9 percent is continuously introduced at the flow rate, after 1 hour, a 300W Xe lamp is turned on for illumination reaction, a light source is set to be full spectrum light, and the irradiation intensity is 26mW cm -2 Extracting 1ml of reaction solution by using a 5ml syringe every 15min in the whole reaction process, filtering out the catalyst, collecting the catalyst into a 1.5ml centrifuge tube, and finally detecting NH by using Nessler's reagent 3 And NH 4 + Yield of (2), NH in this example 3 The synthesis efficiency of (A) is shown in WCN-Ar in FIG. 1.
And (3) performance characterization:
fig. 1 is the ammonia production efficiency under a nitrogen atmosphere of the CN ultrathin nanosheet in example 1, the ammonia production efficiency under an argon atmosphere of the CN ultrathin nanosheet in example 2, the ammonia production efficiency under a nitrogen atmosphere of the WCN monatomic catalyst in example 3, and the ammonia production efficiency under an argon atmosphere of the WCN monatomic catalyst in example 4, and it can be seen that even under xenon lamp irradiation, no observable ammonia was detected in an argon atmosphere, and significant ammonia generation was observed in a nitrogen atmosphere, indicating that NH was produced 3 Intrinsic imino and amino groups originating from the nitrogen atmosphere and from the light, but not from CN defects or edges;
FIG. 2 shows NH of CN ultrathin nanosheets and WCN monatomic catalysts in examples 1 and 3 of the present invention after irradiation with Xe lamp for 1h 3 The synthesis efficiency chart of (1) shows that the ammonia production efficiency of the WCN monatomic catalyst reaches 180 [ mu ] mol g after 1h of illumination -1 h -1 Approximately CN ultrathin nanosheet (56. Mu. Mol. G) -1 h -1 ) 3 times of the total weight of the composition.
FIG. 4 shows the ammonia generating efficiency of WCN-450 and WCN-500 catalysts subjected to ammoniation treatment at 450 ℃ and 500 ℃ respectively by the CN ultrathin nanosheets in example 1, the WCN monatomic catalyst in example 3 and the WCN monatomic catalyst in example 3 in the invention under argon and nitrogen atmosphere, and the ammonia generating efficiency can reach 675 mu mol g at most by the catalyst subjected to ammoniation treatment at 500 ℃ (WCN-500 ℃) -1 h -1 。
Example 5
A certain amount of melamine was weighed into a 30ml quartz crucible and the crucible was placed in a muffle furnace at 2 ℃ min -1 Heating to 450 ℃ at the heating rate, keeping the temperature for 2 hours to obtain a yellow block, grinding and refining the yellow block, adding water, ultrasonically dispersing for 16 hours until the solution becomes milky white, performing suction filtration, drying and collecting to obtain CN ultrathin nanosheets;
0.23g of sodium tungstate (Na) 2 WO 4 ·2H 2 O) deionization dissolved in 30mlAdding CN ultrathin nanosheet (120 mg) into the seawater, uniformly stirring the mixture on a magnetic stirrer, dropwise adding 1mol/L hydrochloric acid to adjust the pH value of the solution to be 1, ultrasonically stirring the solution for 30min, transferring the solution to a polytetrafluoroethylene lining, then putting the polytetrafluoroethylene lining into a stainless steel reaction kettle to be screwed, carrying out hydrothermal reaction in an oven at the temperature of 170 ℃ for 10h, cleaning the product with distilled water and drying the product to obtain a yellow-white precipitate (WO) 3 /g-C 3 N 4 ) The yellow-white color is precipitated (WO) 3 /g-C 3 N 4 ) Placing in a CVD tube furnace at 5 deg.C/min -1 Heating to 450 ℃, using Ar as protective gas to prevent oxidation, calcining at 400 ℃ for 2h, finally etching in 3mol/L KOH solution for 12h, and then centrifuging, cleaning and drying to obtain the WCN monatomic catalyst;
weighing 50mg WCN monatomic catalyst, placing in a beaker, adding 40ml of deionized water and 10ml of absolute ethyl alcohol, ultrasonically dispersing for 2 hours in an ultrasonic cleaning machine, then transferring into a photocatalytic reaction container, sealing the reaction container, placing on a magnetic stirrer to continuously stir the solution, connecting circulating water at two ends of the reactor, cooling at 20 ℃, and then adding 60 ml/min into the reaction container -1 Is continuously fed with N with a purity of 99.9% 2 After 1h, a 300W Xe lamp is turned on to perform illumination reaction, a light source is set to be full spectrum light, and the irradiation intensity is 26mW cm -2 Extracting 1ml of reaction solution by using a 5ml syringe every 15min in the whole reaction process, filtering out the catalyst, collecting the catalyst into a 1.5ml centrifuge tube, and finally detecting NH by using Nessler's reagent 3 And NH 4 + The yield of the fertilizer is high, and a good effect is achieved.
Example 6
A certain amount of melamine was weighed into a 30ml quartz crucible and the crucible was placed in a muffle furnace at 2 ℃ min -1 Heating to 500 ℃ at the heating rate, keeping the temperature for 1.5 hours to obtain a yellow block, grinding and refining the yellow block, adding water, ultrasonically dispersing for 16 hours until the solution becomes milky white, performing suction filtration, drying and collecting to obtain CN ultrathin nanosheets;
0.23g of sodium tungstate (Na) 2 WO 4 ·2H 2 O) is dissolved in 30ml of deionized water, then CN ultrathin nanosheets (120 mg) are added, uniform stirring is carried out on a magnetic stirrer, 1mol/L hydrochloric acid is dropwise added to adjust the pH value of the solution to be 1, ultrasonic stirring is carried out for 30min, then the solution is transferred to a polytetrafluoroethylene lining, the stainless steel lining is placed into a stainless steel reaction kettle to be screwed down, hydrothermal reaction is carried out for 5h in an oven at 190 ℃, products are washed by distilled water and dried, and yellowish white precipitates (WO) are obtained 3 /g-C 3 N 4 ) The yellowish white is precipitated (WO) 3 /g-C 3 N 4 ) Placing in a CVD tube furnace at 5 deg.C/min -1 Heating to 450 ℃, using Ar as protective gas to prevent oxidation, calcining at 600 ℃ for 2h, finally etching in 3mol/L KOH solution for 2h, and then centrifuging, cleaning and drying to obtain the WCN monatomic catalyst;
weighing 50mg WCN monatomic catalyst, placing the WCN monatomic catalyst in a beaker, adding 40ml of deionized water and 10ml of absolute ethyl alcohol, ultrasonically dispersing for 2 hours in an ultrasonic cleaning machine, then transferring the WCN monatomic catalyst into a photocatalytic reaction container, sealing the reaction container, placing the reaction container on a magnetic stirrer to continuously stir the solution, connecting two ends of the reactor with circulating water, cooling the reactor by the circulating water, maintaining the temperature at 20 ℃, and then adding the WCN monatomic catalyst into the reaction container at 60 ml/min -1 Is continuously fed with N with a purity of 99.9% 2 After 1h, a 300W Xe lamp is turned on to perform illumination reaction, a light source is set to be full spectrum light, and the irradiation intensity is 26mW cm -2 Extracting 1ml of reaction solution by using a 5ml syringe every 15min in the whole reaction process, filtering out the catalyst, collecting the catalyst into a 1.5ml centrifuge tube, and finally detecting NH by using Nessler's reagent 3 And NH 4 + The yield of the fertilizer also obtains good effect.
Example 7
A certain amount of melamine was weighed into a 30ml quartz crucible and the crucible was placed in a muffle furnace at 2 ℃ min -1 Heating to 600 ℃ at the heating rate, keeping the temperature for 1h to obtain a yellow block-shaped object, grinding and refining the yellow block-shaped object, adding water, performing ultrasonic dispersion for 16h until the solution becomes milky white, performing suction filtration, drying and collecting to obtain CN ultrathin nanosheets;
0.23g of sodium tungstate (Na) 2 WO 4 ·2H 2 O) is dissolved in 30ml of deionized water, then CN ultrathin nanosheets (120 mg) are added, uniform stirring is carried out on a magnetic stirrer, 1mol/L hydrochloric acid is dropwise added to adjust the pH value of the solution to be 1, ultrasonic stirring is carried out for 30min, then the solution is transferred to a polytetrafluoroethylene lining, the stainless steel lining is placed into a stainless steel reaction kettle to be screwed down, hydrothermal reaction is carried out in an oven for 10h under the condition of 180 ℃, products are washed by distilled water and dried, and yellowish white precipitates (WO) are obtained 3 /g-C 3 N 4 ) The yellow-white color is precipitated (WO) 3 /g-C 3 N 4 ) Placing in a CVD tube furnace at 5 deg.C/min -1 Heating to 450 ℃, using Ar as protective gas to prevent oxidation, calcining at 450 ℃ for 2h, finally etching in 3mol/L KOH solution for 12h, and then centrifuging, cleaning and drying to obtain the WCN monatomic catalyst;
weighing 50mg WCN monatomic catalyst, placing the WCN monatomic catalyst in a beaker, adding 40ml of deionized water and 10ml of absolute ethyl alcohol, ultrasonically dispersing for 2 hours in an ultrasonic cleaning machine, then transferring the WCN monatomic catalyst into a photocatalytic reaction container, sealing the reaction container, placing the reaction container on a magnetic stirrer to continuously stir the solution, connecting two ends of the reactor with circulating water, cooling the reactor by the circulating water, maintaining the temperature at 20 ℃, and then adding the WCN monatomic catalyst into the reaction container at 60 ml/min -1 Is continuously fed with N with a purity of 99.9% 2 After 1h, a 300W Xe lamp is turned on to perform illumination reaction, a light source is set to be full spectrum light, and the irradiation intensity is 26mW cm -2 Extracting 1ml of reaction solution by using a 5ml syringe every 15min in the whole reaction process, filtering out the catalyst, collecting the catalyst into a 1.5ml centrifuge tube, and finally detecting NH by using Nessler's reagent 3 And NH 4 + The yield of the fertilizer also obtains good effect.
Comparative example 1
Weighing a certain amount of melamine, placing the melamine into a 30ml quartz crucible, placing the crucible into a muffle furnace at 2 ℃ min -1 The temperature is raised to 550 ℃ at the temperature raising rate, and the temperature is kept for 2 hours to obtain a yellow block-shaped object;
0.23g of sodium tungstate (Na) 2 WO 4 ·2H 2 O) was dissolved in 30ml of deionized water, and then a yellow block (120 mg) was added,stirring at constant speed on a magnetic stirrer, dropwise adding 1mol/L hydrochloric acid to adjust the pH value of the solution to 1, ultrasonically stirring for 30min, transferring into a polytetrafluoroethylene lining, screwing in a stainless steel reaction kettle, performing hydrothermal reaction in an oven at 180 ℃ for 10h, cleaning the product with distilled water, and drying to obtain yellowish white precipitate (WO) 3 /g-C 3 N 4 ) The yellow-white color is precipitated (WO) 3 /g-C 3 N 4 ) Placing in a CVD tube furnace at 5 deg.C/min -1 Heating to 450 ℃, using Ar as protective gas to prevent oxidation, calcining at 450 ℃ for 2h, finally etching in 3mol/L KOH solution for 12h, and then centrifuging, cleaning and drying to obtain the WCN monatomic catalyst;
weighing 50mg WCN monatomic catalyst, placing the WCN monatomic catalyst in a beaker, adding 40ml of deionized water and 10ml of absolute ethyl alcohol, ultrasonically dispersing for 2 hours in an ultrasonic cleaning machine, then transferring the WCN monatomic catalyst into a photocatalytic reaction container, sealing the reaction container, placing the reaction container on a magnetic stirrer to continuously stir the solution, connecting two ends of the reactor with circulating water, cooling the reactor by the circulating water, maintaining the temperature at 20 ℃, and then adding the WCN monatomic catalyst into the reaction container at 60 ml/min -1 Ar with the purity of 99.9 percent is continuously introduced at the flow speed, after 1 hour, a 300W Xe lamp is turned on for illumination reaction, a light source is set to be full spectrum light, and the irradiation intensity is 26mW cm -2 Extracting 1ml of reaction solution by using a 5ml syringe every 15min in the whole reaction process, filtering out the catalyst, collecting the catalyst into a 1.5ml centrifuge tube, and finally detecting NH by using Nessler's reagent 3 And NH 4 + The calculated yield of (W/CN powder) for synthesizing ammonia reaches 46 mu mol g -1 h -1 Mainly, the specific surface area of the CN powder is relatively small, and the thickness of the CN powder is relatively large and the number of defects is small, so that the attachment sites of the monoatomic W that can be provided are relatively reduced, thereby affecting the nitrogen fixation efficiency.
Comparative example 2
Weighing a certain amount of melamine, placing the melamine into a 30ml quartz crucible, placing the crucible into a muffle furnace at 2 ℃ min -1 Heating to 550 ℃, keeping the temperature for 2 hours to obtain yellow block-shaped objects, then grinding and refining the yellow block-shaped objects, adding water, and ultrasonically dispersing for 16 hours until the temperature is up to 550 DEG CThe solution is changed into milky white, and is filtered, dried and collected to obtain CN ultrathin nanosheets;
0.23g of sodium tungstate (Na) 2 WO 4 ·2H 2 O) is dissolved in 30ml of deionized water, then CN ultrathin nanosheets (120 mg) are added, uniform stirring is carried out on a magnetic stirrer, 1mol/L hydrochloric acid is dropwise added to adjust the pH value of the solution to be 1, ultrasonic stirring is carried out for 30min, then the solution is transferred to a polytetrafluoroethylene lining, the stainless steel lining is placed into a stainless steel reaction kettle to be screwed down, hydrothermal reaction is carried out in an oven for 10h under the condition of 180 ℃, products are washed by distilled water and dried, and yellowish white precipitates (WO) are obtained 3 /g-C 3 N 4 )；
50mg of a yellowish white precipitate are Weighed (WO) 3 /g-C 3 N 4 ) Placing in a beaker, adding 40ml of deionized water and 10ml of absolute ethyl alcohol, ultrasonically dispersing for 2h in an ultrasonic cleaning machine, then transferring into a photocatalytic reaction container, sealing the reaction container, placing on a magnetic stirrer to continuously stir the solution, connecting circulating water at two ends of the reactor, cooling to maintain 20 ℃, and then adding into the reaction container at 60 ml/min -1 Ar with the purity of 99.9 percent is continuously introduced at the flow speed, after 1 hour, a 300W Xe lamp is turned on for illumination reaction, a light source is set to be full spectrum light, and the irradiation intensity is 26mW cm -2 Extracting 1ml of reaction solution by using a 5ml syringe every 15min in the whole reaction process, filtering out the catalyst, collecting the catalyst into a 1.5ml centrifuge tube, and finally detecting NH by using Nessler's reagent 3 And NH 4 + Calculated to yield (WO) 3 /CN) the efficiency of synthesizing ammonia reaches 51.3 mu mol g -1 h -1 Mainly due to the WO formed 3 Is a stable structure, has strong constraint on surrounding electrons, and is relative to a monoatomic W, WO 3 Redox requires a large potential to drive.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered illustrative in all respects and not restrictive, the scope of the invention being defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A method for preparing a monatomic catalyst, comprising:
providing nitrogen and carbon rich organic as a precursor;
carrying out polymerization reaction on the organic matter rich in nitrogen and carbon at 450-600 ℃ for 1-2h to prepare a block carbon nitride material, and then carrying out stripping treatment to obtain carbon nitride ultrathin nanosheets; wherein the thickness of the carbon nitride ultrathin nanosheet is 2.1-10 nm;
dissolving a transition metal source in a solvent to form a transition metal solution, mixing the transition metal solution with a dispersion liquid containing carbon nitride ultrathin nanosheets, adding acid to form a hydrothermal reaction system, and carrying out hydrothermal reaction at 170-190 ℃ for 5-10 hours to prepare a transition metal oxide/carbon nitride composite material, wherein the pH value of the hydrothermal reaction system is below 1, and the transition metal source is selected from any one or a combination of more than two of a W source, a V source, a Cr source, a Mn source, a Fe source, a Co source, a Ni source, a Cu source and a Zn source;
calcining the transition metal oxide/carbon nitride composite material at 400-600 ℃ for 2h under a protective atmosphere, and then etching the calcined transition metal oxide/carbon nitride composite material in an alkaline environment and/or an acidic environment for 2-12 h; then, in the atmosphere of ammonia gas, the material obtained after etching treatment is subject to ammoniation treatment for 1-5 h at 300-500 ℃ to obtain the monatomic catalyst.
2. The method of claim 1, wherein: the organic matter rich in nitrogen and carbon is selected from any one or the combination of more than two of melamine, urea and thiourea; the stripping treatment comprises a liquid phase ultrasonic stripping method.
3. The method of claim 1, wherein: the acid is selected from hydrochloric acid and/or sulfuric acid; the molar ratio of the carbon nitride ultrathin nanosheet to the transition metal source is 2: 1; the transition metal oxide in the transition metal oxide/carbon nitride composite material comprises any one or the combination of more than two of W-based oxide, V-based oxide, cr-based oxide, mn-based oxide, fe-based oxide, co-based oxide, ni-based oxide, cu-based oxide and Zn-based oxide; the solvent comprises water and/or ethanol.
4. The method of claim 1, wherein: the transition metal source is selected from a W source.
5. The production method according to claim 1, characterized in that: the protective atmosphere is selected from an inert gas atmosphere and/or a nitrogen atmosphere;
the transition metal oxide/carbon nitride composite material subjected to the calcination treatment and the etching treatment in the alkaline environment comprises a W-based oxide/carbon nitride composite material; the alkaline environment is selected from KOH and/or NaOH;
the transition metal oxide/carbon nitride composite material subjected to the etching treatment in the acidic environment is selected from any one or a combination of more than two of a V-based oxide/carbon nitride composite material, a Cr-based oxide/carbon nitride composite material, a Mn-based oxide/carbon nitride composite material, a Fe-based oxide/carbon nitride composite material, a Co-based oxide/carbon nitride composite material, a Ni-based oxide/carbon nitride composite material, a Cu-based oxide/carbon nitride composite material and a Zn-based oxide/carbon nitride composite material; the acidic environment comprises hydrochloric acid and/or sulfuric acid.
6. A monatomic catalyst produced by the method of any one of claims 1 to 5, which comprises ultra-thin carbon nitride nanosheets and a transition metal monatomic supported on the ultra-thin carbon nitride nanosheets; the transition metal single atom is selected from any one or the combination of more than two of W, V, cr, mn, fe, co, ni, cu and Zn; the content of transition metal single atom in the single atom catalyst is 2-5 wt%.
7. Use of the monatomic catalyst of claim 6 in a photocatalytic reduction reaction;
the photocatalytic reduction type reaction comprises any one of a photocatalytic nitrogen fixation reaction, a photocatalytic hydrogen production reaction and a photocatalytic carbon dioxide reaction.
8. A photocatalytic nitrogen fixation reaction is characterized by comprising:
providing the monatomic catalyst of claim 6;
introducing nitrogen into a second mixed reaction system containing the monatomic catalyst and water, and reacting under the illumination condition, wherein the light source used in the illumination condition is an Xe lamp, and the illumination intensity is 26 mW-cm -2 。
9. The photocatalytic nitrogen fixation reaction according to claim 8, further comprising: and after the second mixed reaction system finishes the reaction, carrying out Neisseria reagent color development treatment on the obtained solution, and testing through an ultraviolet spectrum to obtain the ammonia concentration of the obtained solution.
10. The photocatalytic nitrogen fixation reaction according to claim 8, characterized in that: the second mixed reaction system further comprises ethanol.
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