CN114939405B - 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst, preparation method and nitrogen fixation application thereof - Google Patents

3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst, preparation method and nitrogen fixation application thereof Download PDF

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CN114939405B
CN114939405B CN202210687929.0A CN202210687929A CN114939405B CN 114939405 B CN114939405 B CN 114939405B CN 202210687929 A CN202210687929 A CN 202210687929A CN 114939405 B CN114939405 B CN 114939405B
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3dpcn
porous carbon
carbon nitride
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indium oxide
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CN114939405A (en
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孙婷
高平
张仕贤
王明
刘军
吴智仁
荣新山
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Changzhou Tianmei New Material Technology Engineering Research Institute Co ltd
Jiangsu University
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Jiangsu University
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract

The invention discloses a 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst, a preparation method thereof and nitrogen fixation application, and relates to the technical field of photocatalytic material synthesis. The invention firstly takes melamine and cyanuric acid as raw materials, prepares 3D porous carbon nitride by a supermolecular assembly method, then mixes the 3D porous carbon nitride with indium nitrate and ethylenediamine, prepares 3DPCN/In by solvothermal reaction 2 O 3 The composite catalyst is calcined to obtain 3D porous carbon nitride composite oxygen-enriched defect indium oxide 3DPCN/V O ‑In 2 O 3 A composite catalyst. The catalyst prepared by the invention has better photocatalytic nitrogen fixation and ammonia production performances, is simple to operate, has popularization effect on photocatalytic green synthesis of ammonia, and has the advantages of energy conservation and environmental protection.

Description

3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst, preparation method and nitrogen fixation application thereof
Technical Field
The invention relates to the technical field of photocatalytic material synthesis, in particular to a 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst, a preparation method and nitrogen fixation application thereof.
Background
Ammonia is one of the largest industrial synthetic chemicals in the world, and is widely applied in the fields of modern industry, agriculture and the like because of the advantages of high energy density, easy liquefaction, convenient transportation and the like.
Nitrogen (N) 2 ) Immobilization is one of the most important chemical processes in nature, and is indispensable to both human and the earth's ecosystem. At present, the Haber-Bosch method is mainly adopted for artificially fixing nitrogen, which uses nitrogen (N) in the presence of an iron-based catalyst 2 ) And hydrogen (H) 2 ) As a raw material, a reaction process carried out under a severe condition of high temperature and high pressure. The Haber-Bosch process consumes about 2% of the total energy in the world each year; meanwhile, the process discharges 3 hundred million tons of greenhouse gases each year, which causes huge environmental pollution.
In order to alleviate the problems of high energy consumption and great environmental pollution in the existing industrial ammonia synthesis process, the nitrogen can be driven to reduce the ammonia synthesis reaction by utilizing renewable resources (such as solar energy), and the method is one of hot spots and continuous pursuits of the industrial and academic industries worldwide. The photocatalytic nitrogen reduction ammonia synthesis technology has the advantages of cleanness, sustainability, mild reaction conditions and the like, is expected to solve the problems of high energy consumption, environmental pollution and the like caused by industrial ammonia synthesis, and brings hot attention to the industry and academia. Therefore, the development of the catalyst with high-efficiency photocatalytic nitrogen fixation activity realizes energy-saving and environment-friendly nitrogen fixation synthesis of ammonia, and has important research significance.
Graphite phase carbon nitride (g-C) 3 N 4 ) Has unique electronic structure and excellent chemical stability. However, the conventionally synthesized bulk g-C 3 N 4 The surface active interface is small in the photocatalysis reaction, the electron and the hole are easy to be combined and the N is opposite to the electron 2 The problem of weak adsorption of molecules, etc. Indium oxide (In) 2 O 3 ) Is an n-type semiconductor, and has a direct band gap of 3.6eV and an indirect band gap of 2.6eV. In (In) 2 O 3 Has two crystal phases, namely a cubic phase (C-In 2 O 3 ) And hexagonal phase (H-In) 2 O 3 ). Under general conditions, in 2 O 3 The crystal structure of cubic manganese ore (space group is Ia3, and the lattice contains 16 units) is easily crystallized. In (In) 2 O 3 Due to the remarkable chemical property and high electron conductionElectrical and optical transparency and a large forbidden bandwidth have attracted attention in recent years.
J.Inorg.chem.2009:903-909, reports the use of sea urchin-like H-In 2 O 3 Nano-structure degradation rhodamine B (RhB), experimental results show that sea urchin-shaped H-In 2 O 3 Can effectively degrade RhB and has photocatalytic efficiency ratio In 2 O 3 The nano square is high. Sea urchin-like H-In 2 O 3 The high photocatalytic efficiency is due to high surface oxygen vacancies, special morphology, and high specific surface area. But not with the carbon nitride material composite design and the Z-type photocatalytic system design, and not with the reduction nitrogen fixation study.
ACS Applied Materials&Interfaces,2019,11:27686-27696, report that by designing a Z-type photocatalytic structure, a reaction site with a strong redox capability can be reserved on the basis of inhibiting electron-hole recombination. The study teaches that the design of the electron transfer route can effectively improve photon utilization rate, but does not involve the regulation of the catalyst structure to N 2 Influence of molecular adsorption/activation properties.
J.Phys.chem.C,2010,114,6157-6162, the use of In by a modified co-precipitation method is reported 2 O 3 NaNbO in rod shape modified by nano particles 3 The component compound is found to be capable of improving photocatalytic methanol solution H under visible light 2 Generating efficiency and improving the efficiency of photolysis of water under ultraviolet light. The characterization result proves that the improvement of the photocatalytic activity is caused by the fact that the formation component compound can promote the transmission of photo-generated holes, so that the recombination of electron-hole pairs is inhibited. However, the study did not relate to the construction of oxygen-enriched defective photocatalysts and still did not relate to nitrogen fixation performance studies.
Disclosure of Invention
The invention aims to provide a 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst, a preparation method and nitrogen fixation application thereof, so as to solve the problems in the prior art, and the catalyst has better photocatalytic nitrogen fixation and ammonia production performance and has the advantage of simple preparation method.
In order to achieve the above object, the present invention provides the following solutions:
the invention provides a preparation method of a 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst, which comprises the following steps:
(1) Adding melamine and cyanuric acid into a solvent, and reacting under the protection of nitrogen to obtain 3D porous carbon nitride (3 DPCN);
(2) Mixing the 3D porous carbon nitride (3 DPCN) with indium nitrate In the presence of a solvent, adding ethylenediamine, performing solvothermal reaction on the obtained reaction system, cooling after the reaction is finished, collecting precipitate, drying, and performing heating treatment to obtain the 3DPCN/In 2 O 3 A composite catalyst;
(3) The 3DPCN/In 2 O 3 Calcining the composite catalyst to obtain the 3D porous carbon nitride composite oxygen-enriched defect indium oxide composite catalyst (3 DPCN/V) O -In 2 O 3 )。
Further, the molar ratio of the melamine to the cyanuric acid is 0.5:1-1.5:1. Preferably, the molar ratio is 1:1.
the solvent in the step (1) is methanol, ethanol, isopropanol or dimethyl sulfoxide. Dimethyl sulfoxide is preferred.
Further, the reaction process of the step (1) is supermolecule assembly, the reaction temperature is 400-600 ℃, and the reaction time is 1-5 h. Preferably, the reaction temperature is 550℃and the reaction time is 2 hours.
Further, the temperature rising rate in the reaction process of the step (1) is 5-15 ℃ min -1 . Preferably, the temperature rise rate is 15 ℃ min -1 。
Further, the hydrothermal reaction temperature in the step (2) is 120-220 ℃, and the reaction time is 1-24 h. Preferably, the hydrothermal reaction temperature is 180 ℃ and the reaction time is 16h.
Further, in the step (2), the mass ratio of the indium nitrate to the 3DPCN (3D porous carbon nitride) is 1:1-1:20.
Further, the drying temperature in the step (2) is 30-90 ℃, preferably 60 ℃; the temperature of the heating treatment is 400-600 ℃ and the time is 1-5 h; preferably, the temperature of the heat treatment is 500 ℃ and the time is 2 hours.
Further, the heating rate of the heating treatment in the step (2) is 2-8 ℃/min. Preferably 5 deg.c/min.
Further, in the step (2), the solvent is methanol, ethylene glycol or absolute ethanol. Preferably absolute ethanol.
Further, the volume ratio of the solvent to ethylenediamine in step (2) is 0.5: 1-2: 1. preferably 1:1.
further, the step (2) further comprises a step of stirring after adding ethylenediamine, wherein the stirring time is 10-30 min, preferably 15min.
Further, the temperature of the calcination treatment in the step (3) is 300-600 ℃, and the calcination time is 1-5 h. Preferably, the calcination treatment is carried out at a temperature of 500℃for a calcination time of 2 hours.
The temperature rising rate of the calcination treatment in the step (3) is 5-15 ℃/min, preferably 10 ℃/min.
The invention also provides the 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst prepared by the preparation method.
The invention further provides application of the catalyst in photocatalytic nitrogen fixation and ammonia production.
The photocatalytic nitrogen fixation ammonia production verification experiment of the invention is as follows:
under normal temperature and pressure, adding the prepared catalyst into 500mL of methanol aqueous solution, and performing ultrasonic treatment to ensure uniform dispersion of the catalyst. Under the illumination condition, nitrogen (N) is introduced into the dispersion liquid at a certain aeration rate 2 ) Sampling for a certain time, centrifuging, collecting the clear liquid, and measuring the ammonia production efficiency by adopting a Nahner reagent spectrophotometry.
Wherein the concentration of the aqueous methanol solution can be 0.001-1.0 mol/L, preferably 0.02mol/L;
the volume ratio of the catalyst mass to the reaction solution can be 0.1-1 g/L, preferably 0.2g/L;
the aeration rate of nitrogen may be 10 to 200mL/min, preferably 100mL/min.
By g-C 3 N 4 Morphology control of (c) and high activity semiconductors with narrower band gapsThe material is subjected to composite modification, and is one of effective ways for improving light absorption and light-excited hole-electron transfer, so that the photo-generated hole-electron recombination rate is reduced. Thus, by designing 3D porous carbon nitride (3 DPCN) supported oxygen-enriched defective indium oxide (V O -In 2 O 3 ) Formation of 3DPCN/V O -In 2 O 3 Can increase the active interface of carbon nitride, inhibit hole-electron recombination and promote N pair 2 Activation properties of the molecules.
The invention discloses the following technical effects:
the invention combines 3D porous carbon nitride with oxygen-enriched defective V O -In 2 O 3 Successfully prepares the visible light response type 3DPCN/V O -In 2 O 3 The catalyst is applied to the photocatalysis of nitrogen fixation to produce ammonia. Experimental results show that the prepared catalyst has good photocatalytic nitrogen fixation and ammonia production performances, is simple to operate, has popularization effect on photocatalytic green synthesis of ammonia, and has the advantages of energy conservation and environmental protection.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of 3DPCN-4 prepared in example 4 of the present invention;
FIG. 2 is an In prepared In comparative example 1 of the present invention 2 O 3 SEM images of (a);
FIG. 3 is a 3DPCN-4/V prepared in example 4 of the present invention O -In 2 O 3 -SEM image of 4;
FIG. 4 is a 3DPCN-4/V prepared in example 4 of the present invention O -In 2 O 3 3 DPCN/In-4 and comparative example 4 2 O 3 EPR map of (c).
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The invention is described in further detail below with reference to examples:
the melamine, cyanuric acid, ethylenediamine, indium nitrate, methanol, ethanol, isopropanol, and dimethyl sulfoxide used in the examples of the present invention were all purchased from national pharmaceutical group chemical reagent limited.
Example 1
A preparation method of a 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst comprises the following steps:
(1) 800mg of melamine and 1000mg of cyanuric acid are added to methanol at 10℃min -1 Heating to 550 ℃ under nitrogen protection for 2h, cooling to room temperature, and grinding into powder 3DPCN-1 by an agate mortar.
(2) 120mg of indium nitrate and 120mg of 3DPCN-1 were dissolved in 45mL of absolute ethanol at a mass ratio of indium nitrate to 3DPCN of 1:1. Then 50mL of ethylenediamine was added dropwise to the above solution with stirring. After stirring for 15min, the resulting slurry was transferred to a 100mL autoclave (polytetrafluoroethylene liner). The autoclave was then sealed and incubated in an oven at 180℃for 16h. After the reaction, the autoclave was taken out and naturally cooled to room temperature, and the suspension was separated by centrifugation to obtain a precipitate, which was then washed three times with deionized water and absolute ethyl alcohol, respectively. Drying the precipitate at 70deg.C, heating to 500deg.C at 5deg.C/min In a muffle furnace, and maintaining for 2 hr to obtain 3DPCN-1/In 2 O 3 -1。
(3) 1g of 3DPCN-1/In was weighed out 2 O 3 -1 placing the ceramic boat, calcining for 2 hours in a tubular furnace at 500 ℃ under an air atmosphere, wherein the heating rate is 10 ℃ and min -1 . The resulting sample was labeled 3DPCN-1/V O -In 2 O 3 -1。
50mg of 3DPCN-1/V was added to 500mL of an aqueous methanol solution (0.001 mol/L) at normal temperature and normal pressure O -In 2 O 3 -1 catalyst, sonicated for 10min. Under the irradiation of visible light, nitrogen was introduced at 10 mL/min. Reacting for 120min, taking clear liquid, and measuring the ammonia production efficiency to be 0.32 mu mol/L/min by adopting a Nahner reagent spectrophotometry method.
Example 2
(1) 900mg of melamine and 1000mg of cyanuric acid are added to dimethyl sulfoxide at 8℃for min -1 Heating to 500 ℃ under nitrogen protection for 2h, cooling to room temperature, and grinding into powder 3DPCN-2 by an agate mortar.
(2) To be used forThe mass ratio of indium nitrate to 3DPCN is 1:5, and 100mg of indium nitrate and 500mg of 3DPCN-2 are dissolved in 34mL of absolute ethanol. 34mL of ethylenediamine was then added dropwise to the above solution with stirring. After stirring for 15min, the resulting slurry was transferred to a 100mL autoclave (polytetrafluoroethylene liner). The autoclave was then sealed and incubated in an oven at 180℃for 16h. After the reaction, the autoclave was taken out and naturally cooled to room temperature, and the suspension was separated by centrifugation to obtain a precipitate, which was then washed three times with deionized water and absolute ethyl alcohol, respectively. Drying the precipitate at 80deg.C, heating to 500deg.C at 5deg.C/min In a muffle furnace, and maintaining for 2 hr to obtain 3DPCN-2/In 2 O 3 -2。
(3) 1g of 3DPCN-2/In was weighed out 2 O 3 -2 placing the ceramic boat, calcining for 3 hours in a tubular furnace at 500 ℃ under air atmosphere, wherein the heating rate is 16 ℃ min -1 . The resulting sample was labeled 3DPCN-2/V O -In 2 O 3 -2。
50mg of 3DPCN-2/V was added to 500mL of an aqueous methanol solution (0.001 mol/L) at normal temperature and normal pressure O -In 2 O 3 -2 catalyst, sonicated for 10min. Under the irradiation of visible light, nitrogen was introduced at 10 mL/min. Reacting for 120min, taking clear liquid, and measuring the ammonia production efficiency to be 0.55 mu mol/L/min by adopting a Nahner reagent spectrophotometry method.
Example 3
(1) 1000mg of melamine and 1000mg of cyanuric acid are added to ethanol at 12℃min -1 Heating to 600 ℃ under nitrogen protection for 2h, cooling to room temperature, and grinding into powder 3DPCN-3 by an agate mortar.
(2) 300.83mg of indium nitrate and 2406.64mg of 3DPCN-3 were dissolved in 30mL of absolute ethanol at a mass ratio of indium nitrate to 3DPCN of 1:8. Then 30mL of ethylenediamine was added dropwise to the above solution with stirring. After stirring for 20min, the resulting slurry was transferred to a 100mL autoclave (polytetrafluoroethylene liner). The autoclave was then sealed and incubated in an oven at 180℃for 12h. After the reaction, the autoclave was taken out and naturally cooled to room temperature, and the suspension was separated by centrifugation to obtain a precipitate, which was then washed three times with deionized water and absolute ethyl alcohol, respectively.Drying the precipitate at 60deg.C, heating to 500deg.C at 5deg.C/min In a muffle furnace, and maintaining for 2 hr to obtain 3DPCN-3/In 2 O 3 -3。
(3) 1g of 3DPCN-3/In was weighed out 2 O 3 -3 placing the ceramic boat, calcining for 2 hours in a tubular furnace at 500 ℃ under air atmosphere, wherein the heating rate is 20 ℃ and min -1 . The resulting sample was labeled 3DPCN-3/V O -In 2 O 3 -3。
50mg of 3DPCN-3/V was added to 500mL of an aqueous methanol solution (0.001 mol/L) at normal temperature and normal pressure O -In 2 O 3 -3 catalyst, sonicated for 10min. Under the irradiation of visible light, nitrogen was introduced at 10 mL/min. The reaction is carried out for 120min, clear liquid is taken, and the ammonia production efficiency is measured to be 0.71 mu mol/L/min by adopting a Nahner reagent spectrophotometry.
Example 4
(1) 1000mg of melamine and 1000mg of cyanuric acid are added to dimethyl sulfoxide at 10 ℃ for min -1 The temperature was raised to 550℃and heated under nitrogen for 2 hours, then cooled to room temperature, and ground into 3DPCN-4 (SEM image of 3DPCN-4 in FIG. 1) in powder form by means of an agate mortar.
(2) 300.83mg of indium nitrate and 2406.64mg of 3DPCN-4 were dissolved in 30mL of absolute ethanol at a mass ratio of indium nitrate to 3DPCN of 1:8. 34mL of ethylenediamine was then added dropwise to the above solution with stirring. After stirring for 15min, the resulting slurry was transferred to a 100mL autoclave (polytetrafluoroethylene liner). The autoclave was then sealed and incubated in an oven at 180℃for 16h. After the reaction, the autoclave was taken out and naturally cooled to room temperature, and the suspension was separated by centrifugation to obtain a precipitate, which was then washed three times with deionized water and absolute ethyl alcohol, respectively. Drying the precipitate at 60deg.C, heating to 500deg.C at 5deg.C/min In a muffle furnace, and maintaining for 2 hr to obtain 3DPCN-4/In 2 O 3 -4 (3 DPCN-4/V in FIG. 3) O -In 2 O 3 -SEM image of 4).
(3) 1g of 3DPCN-4/In was weighed out 2 O 3 -4 placing the ceramic boat, calcining for 2 hours in a tubular furnace at 500 ℃ under an air atmosphere, wherein the heating rate is 10 ℃ and min -1 . The resulting sample was labeled 3DPCN-4/V O -In 2 O 3 -4 (as shown in figure 4).
50mg of 3DPCN-4/V was added to 500mL of an aqueous methanol solution (0.001 mol/L) at normal temperature and normal pressure O -In 2 O 3 -4 catalyst, sonicated for 10min. Under the irradiation of visible light, nitrogen was introduced at 10 mL/min. The reaction is carried out for 120min, clear liquid is taken, and the ammonia production efficiency is measured to be 1.10 mu mol/L/min by adopting a Nahner reagent spectrophotometry.
Example 5
(1) 1100mg of melamine and 1000mg of cyanuric acid are added to isopropanol at 10℃min -1 Heating to 500 ℃ under nitrogen protection for 2h, cooling to room temperature, and grinding into powder 3DPCN-5 by an agate mortar.
(2) 100mg of indium nitrate and 1000mg of 3DPCN-5 were dissolved in 50mL of methanol at a mass ratio of indium nitrate to 3DPCN of 1:10. Then 40mL of ethylenediamine was added dropwise to the above solution with stirring. After stirring for 15min, the resulting slurry was transferred to a 100mL autoclave (polytetrafluoroethylene liner). The autoclave was then sealed and incubated in an oven at 180℃for 16h. After the reaction, the autoclave was taken out and naturally cooled to room temperature, and the suspension was separated by centrifugation to obtain a precipitate, which was then washed three times with deionized water and absolute ethyl alcohol, respectively. Drying the precipitate at 40deg.C, heating to 500deg.C at 5deg.C/min In a muffle furnace, and maintaining for 3 hr to obtain 3DPCN-5/In 2 O 3 -5。
(3) 1g of 3DPCN-5/In was weighed out 2 O 3 -5 placing the ceramic boat, calcining for 2 hours in a tubular furnace at 500 ℃ under air atmosphere, wherein the heating rate is 10 ℃ min -1 . The resulting sample was labeled 3DPCN-5/V O -In 2 O 3 -5。
50mg of 3DPCN-5/V was added to 500mL of an aqueous methanol solution (0.001 mol/L) at normal temperature and normal pressure O -In 2 O 3 -5 catalyst, sonicated for 10min. Under the irradiation of visible light, nitrogen was introduced at 10 mL/min. Reacting for 120min, taking clear liquid, and measuring the ammonia production efficiency to be 0.86 mu mol/L/min by adopting a Nahner reagent spectrophotometry method.
Example 6
(1) 1200mg of melamine and1000mg cyanuric acid is added into dimethyl sulfoxide at 10 ℃ for min -1 Heating to 550 ℃ under nitrogen protection for 3h, cooling to room temperature, and grinding into powder 3DPCN-6 by an agate mortar.
(2) 50mg of indium nitrate and 750mg of 3DPCN-6 were dissolved in 40mL of absolute ethanol at a mass ratio of indium nitrate to 3DPCN of 1:15. Then 40mL of ethylenediamine was added dropwise to the above solution with stirring. After stirring for 15min, the resulting slurry was transferred to a 100mL autoclave (polytetrafluoroethylene liner). The autoclave was then sealed and incubated in an oven at 180℃for 15h. After the reaction, the autoclave was taken out and naturally cooled to room temperature, and the suspension was separated by centrifugation to obtain a precipitate, which was then washed three times with deionized water and absolute ethyl alcohol, respectively. Drying the precipitate at 60deg.C, heating to 500deg.C at 5deg.C/min In a muffle furnace, and maintaining for 2 hr to obtain 3DPCN-6/In 2 O 3 -6。
(3) 1g of 3DPCN-6/In was weighed out 2 O 3 -6 placing the ceramic boat, calcining for 2 hours in a tubular furnace at 500 ℃ under air atmosphere, wherein the heating rate is 10 ℃ min -1 . The resulting sample was labeled 3DPCN-6/V O -In 2 O 3 -6。
50mg of 3DPCN-6/V was added to 500mL of an aqueous methanol solution (0.001 mol/L) at normal temperature and normal pressure O -In 2 O 3 -6 catalyst, sonicated for 10min. Under the irradiation of visible light, nitrogen was introduced at 10 mL/min. The reaction is carried out for 120min, clear liquid is taken, and the ammonia production efficiency is measured to be 0.66 mu mol/L/min by adopting a Nahner reagent spectrophotometry.
Comparative example 1
The difference from example 4 is that In was produced by not adding 3DPCN and not calcining at high temperature to produce an oxygen-deficient structure 2 O 3 And (3) a sample.
In 2 O 3 Is prepared from the following steps: 523.5mg of indium nitrate was dissolved in 34mL of absolute ethanol. Then according to the volume ratio of 1: 34mL of ethylenediamine was added dropwise to the above solution with stirring. After stirring for 15min, the resulting white slurry was transferred to a 100mL autoclave (polytetrafluoroethylene liner). Then sealing the high-pressure reaction kettle and then putting the high-pressure reaction kettle into an oven at 180 DEG CPreserving heat for 16h. After the reaction was completed, the autoclave was taken out, naturally cooled to room temperature, and the suspension was separated by centrifugation to obtain a white precipitate, which was then washed three times with deionized water and absolute ethyl alcohol, respectively. Drying the white precipitate at 60deg.C, placing into a muffle furnace, heating to 500deg.C at 5deg.C/min, and maintaining for 2 hr to obtain In 2 O 3 (as shown in figure 2).
50mg of In was added to 500mL of an aqueous methanol solution (0.001 mol/L) at normal temperature and normal pressure 2 O 3 The catalyst was sonicated for 10min. Under the irradiation of visible light, nitrogen was introduced at 10 mL/min. The reaction is carried out for 120min, clear liquid is taken, and the ammonia production efficiency is measured to be 0.068 mu mol/L/min by adopting a Nahner reagent spectrophotometry.
Comparative example 2
The difference from example 4 is only that V was produced without adding 3DPCN O -In 2 O 3 And (3) a sample.
V O -In 2 O 3 Is prepared from the following steps: 523.5mg of indium nitrate was dissolved in 34mL of absolute ethanol. Then according to the volume ratio of 1: 34mL of ethylenediamine was added dropwise to the above solution with stirring. After stirring for 15min, the resulting white slurry was transferred to a 100mL autoclave (polytetrafluoroethylene liner). The autoclave was then sealed and incubated in an oven at 180℃for 16h. After the reaction was completed, the autoclave was taken out, naturally cooled to room temperature, and the suspension was separated by centrifugation to obtain a white precipitate, which was then washed three times with deionized water and absolute ethyl alcohol, respectively. Drying the white precipitate at 60deg.C, placing into a muffle furnace, heating to 500deg.C at 5deg.C/min, and maintaining for 2 hr to obtain In 2 O 3 。
1g of In was weighed out 2 O 3 Calcining in a muffle furnace at 500 deg.C for 2 hr at a heating rate of 10 deg.C/min -1 . The resulting sample was marked as V O -In 2 O 3 。
50mg of V was added to 500mL of an aqueous methanol solution (0.001 mol/L) at normal temperature and normal pressure O -In 2 O 3 The catalyst was sonicated for 10min. Under the irradiation of visible light, nitrogen was introduced at 10 mL/min. Reacting for 120min, collecting clear solution, and separating with Navier reagentThe ammonia production efficiency measured by the spectrophotometry is 0.19 mu mol/L/min.
Comparative example 3
The difference from example 4 is only that V is not added O -In 2 O 3 3DPCN samples were prepared.
Preparation of 3 DPCN: 1000mg of melamine and 1000mg of cyanuric acid are added to dimethyl sulfoxide at 10 ℃ for min -1 The temperature was raised to 550℃and heated under nitrogen for 2 hours, then cooled to room temperature, and ground into 3DPCN powder by means of an agate mortar.
50mg of the catalyst was added to 500mL of an aqueous methanol solution (0.001 mol/L) at normal temperature and normal pressure, followed by sonication for 10min. Under the irradiation of visible light, nitrogen was introduced at 10 mL/min. The reaction is carried out for 120min, clear liquid is taken, and the ammonia production efficiency is measured to be 0.0408 mu mol/L/min by adopting a Nahner reagent spectrophotometry.
Comparative example 4
The difference from example 4 is that 3DPCN/In was prepared without high-temperature calcination to produce an oxygen-deficient structure 2 O 3 And (3) a sample.
In 2 O 3 Is prepared from the following steps: 523.5mg of indium nitrate was dissolved in 34mL of absolute ethanol. Then according to the volume ratio of 1: 34mL of ethylenediamine was added dropwise to the above solution with stirring. After stirring for 15min, the resulting white slurry was transferred to a 100mL autoclave (polytetrafluoroethylene liner). The autoclave was then sealed and incubated in an oven at 180℃for 16h. After the reaction was completed, the autoclave was taken out, naturally cooled to room temperature, and the suspension was separated by centrifugation to obtain a white precipitate, which was then washed three times with deionized water and absolute ethyl alcohol, respectively. Drying the white precipitate at 60deg.C to obtain In 2 O 3 。
Preparation of 3 DPCN: 1000mg of melamine and 1000mg of cyanuric acid are added to dimethyl sulfoxide at 10 ℃ for min -1 The temperature was raised to 550℃and heated under nitrogen for 2 hours, then cooled to room temperature, and ground into 3DPCN powder by means of an agate mortar.
3DPCN/In 2 O 3 Is prepared from the following steps: weigh 100mg In 2 O 3 And 827mg of 3DPCN are respectively preparedMixing the dispersion, stirring for 4h under heating In water bath at 60deg.C, washing, and drying to obtain 3DPCN/In 2 O 3 。
50mg of the catalyst was added to 500mL of an aqueous methanol solution (0.001 mol/L) at normal temperature and normal pressure, followed by sonication for 10min. Under the irradiation of visible light, nitrogen was introduced at 10 mL/min. The reaction is carried out for 120min, clear liquid is taken, and the ammonia production efficiency is measured to be 0.376 mu mol/L/min by adopting a Nahner reagent spectrophotometry method.
FIG. 4 is 3DPCN-4/V of example 4 O -In 2 O 3 3 DPCN/In-4 and comparative example 4 2 O 3 The introduction of oxygen vacancies in the examples of the present invention can be seen.
The results showed that 3DPCN and In 2 O 3 Z-type 3DPCN/VO-In prepared by compounding constructed oxygen defects 2 O 3 The catalyst has excellent photocatalytic reduction nitrogen fixation and ammonia production performance. Under the irradiation of visible light, 50mg of catalyst is added into the system, 100mL/min of nitrogen is introduced into the system for reaction for 120min, the efficiency of nitrogen fixation and ammonia production by photocatalytic reduction can reach 1.10 mu mol/L/min, and the Z-type 3DPCN/V prepared by the invention O -In 2 O 3 The construction strategy of the Z-type carrier transfer system is demonstrated. The introduction and structural design of oxygen vacancies are also beneficial to the construction of solar energy conversion materials, such as pollutant degradation materials, and the catalyst has great development and application prospects in the aspect of photocatalytic green synthesis of ammonia.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.

Claims (2)

1. The application of the 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst in the photocatalytic nitrogen fixation and ammonia production is characterized in that the preparation method of the 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst comprises the following steps:
(1) Adding melamine and cyanuric acid into a solvent, and reacting under the protection of nitrogen to obtain 3D porous carbon nitride;
(2) Mixing the 3D porous carbon nitride with indium nitrate In the presence of a solvent, adding ethylenediamine, performing solvothermal reaction on the obtained reaction system, collecting precipitate, drying, and performing heating treatment to obtain 3DPCN/In 2 O 3 A composite catalyst;
(3) The 3DPCN/In 2 O 3 Calcining the composite catalyst to obtain the 3D porous carbon nitride composite oxygen-enriched defect indium oxide composite catalyst;
the mole ratio of the melamine to the cyanuric acid is 0.5:1-1.5:1;
the reaction temperature of the step (1) is 400-600 ℃ and the reaction time is 1-5 h;
the solvothermal reaction temperature of the step (2) is 120-250 ℃ and the reaction time is 1-24 h;
in the step (2), the mass ratio of the indium nitrate to the 3D porous carbon nitride is 1:1-1:20; the temperature of the heating treatment in the step (2) is 400-600 ℃ and the time is 1-5 h; the temperature of the calcination treatment in the step (3) is 300-600 ℃, and the calcination time is 1-5 h.
2. The use according to claim 1, wherein the drying temperature in step (2) is 30-90 ℃.
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