CN114939405A - 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 PDFInfo
- Publication number
- CN114939405A CN114939405A CN202210687929.0A CN202210687929A CN114939405A CN 114939405 A CN114939405 A CN 114939405A CN 202210687929 A CN202210687929 A CN 202210687929A CN 114939405 A CN114939405 A CN 114939405A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- carbon nitride
- 3dpcn
- catalyst
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 35
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 239000001301 oxygen Substances 0.000 title claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000007547 defect Effects 0.000 title claims abstract description 15
- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 15
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 29
- 230000001699 photocatalysis Effects 0.000 claims abstract description 23
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000004729 solvothermal method Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000002244 precipitate Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- 238000002798 spectrophotometry method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000004809 Teflon Substances 0.000 description 9
- 229920006362 Teflon® Polymers 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 241000257465 Echinoidea Species 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000002113 nanodiamond Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-shaped catalyst, a preparation method and nitrogen fixation application thereof, and relates to the technical field of synthesis of photocatalytic materials. The preparation method comprises the steps of firstly preparing 3D porous carbon nitride by using melamine and cyanuric acid as raw materials through a supramolecular assembly method, then mixing the 3D porous carbon nitride with indium nitrate and ethylenediamine, and preparing 3DPCN/In through solvothermal reaction 2 O 3 The composite catalyst is calcined to obtain 3D porous carbon nitride composite oxygen-rich defect indium oxide 3DPCN/V O ‑In 2 O 3 And (3) compounding a catalyst. The catalyst prepared by the invention has better performance of photocatalytic nitrogen fixation and ammonia production, is simple to operate, has a popularization effect on photocatalytic green synthesis of ammonia, and has the advantages of energy conservation and environmental protection.
Description
Technical Field
The invention relates to the technical field of synthesis of photocatalytic materials, in particular to a 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst, a preparation method and a nitrogen fixation application thereof.
Background
Ammonia is one of the largest industrial synthetic chemicals in the world, and is widely applied to the fields of modern industry, agriculture and the like due to 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 earth ecosystems. At present, the Haber-Bosch method mainly used for artificial nitrogen fixation is performed by using nitrogen (N) under the condition of iron-based catalyst 2 ) And hydrogen (H) 2 ) The reaction process is carried out under the severe conditions of high temperature and high pressure. The Haber-Bosch process consumes about 2% of the world's total energy annually; meanwhile, the process discharges 3 hundred million tons of greenhouse gases every year, thereby causing huge environmental pollution.
In order to alleviate the problems of high energy consumption and large environmental pollution of the existing industrial ammonia synthesis process, the nitrogen reduction ammonia synthesis reaction can be driven by utilizing renewable resources (such as solar energy), and the method is always one of hot spots and continuously pursued targets of industrial and academic interests worldwide. The technology for synthesizing ammonia by photocatalytic nitrogen reduction 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 arouses the intense attention of the industrial and academic circles. Therefore, the development of the catalyst with high-efficiency photocatalytic nitrogen fixation activity for realizing energy-saving and environment-friendly nitrogen fixation for synthesizing ammonia has important research significance.
Graphite phase carbon nitride (g-C) 3 N 4 ) Has unique electronic structure and excellent chemical stability. However, conventionally synthesized blocky g-C 3 N 4 Small surface active interface, easy electron-hole recombination and N pair in photocatalysis reaction 2 Weak adsorption of molecules and the like. Indium oxide (In) 2 O 3 ) The semiconductor is an n-type semiconductor, and the direct forbidden band width is 3.6eV, and the indirect forbidden band width is 2.6 eV. In 2 O 3 Having two crystal phases, i.e. cubic (C-In) 2 O 3 ) And hexagonal phase (H-In) 2 O 3 ). Under normal conditions, In 2 O 3 The crystal structure of cubic manganese ore (space group Ia3, crystal lattice containing 16 units) is easily crystallized. In 2 O 3 Due to their remarkable chemical properties, high electronic conductivity and optical transparency, and large forbidden bandwidth, they have attracted much attention in recent years.
J.Inorg.chem.2009:903-909, reports the use of H-In the form of sea urchin 2 O 3 The nano structure degrades rhodamine B (RhB), and the experimental result shows that H-In the shape of sea urchin 2 O 3 Can effectively degrade RhB and has a photocatalytic efficiency ratio In 2 O 3 The nano-diamonds are high. H-In of sea urchin shape 2 O 3 The high photocatalytic efficiency is due to the high surface oxygen vacancies, the special morphology and the high specific surface area. But does not relate to the composite design with carbon nitride material and the design of Z-type photocatalytic system, and does not relate to the research of reducing and fixing nitrogen.
ACS Applied Materials&Interfaces,2019,11:27686-27696, reports that by designing a Z-type photocatalytic structure, reaction sites with stronger redox capability can be reserved on the basis of inhibiting electron-hole recombination. The study teaches that the design of electron transfer routes can effectively improve photon utilization, but does not involve the adjustment of catalyst structure to N 2 Influence of molecular adsorption/activation properties.
J.Phys.chem.C,2010,114,6157-6162, reported the utilization of In by a modified co-precipitation method 2 O 3 Rod-shaped NaNbO modified by nano particles 3 The component compound is found to improve the photocatalytic methanol solution H under visible light 2 The efficiency is generated, and the efficiency of water photolysis under ultraviolet light is improved. The characterization results demonstrate that the photocatalytic activity is improved because the forming component compounds can promote the transfer of photogenerated holes, thereby inhibiting the recombination of electron-hole pairs. However, the research is not related to the construction of oxygen-rich defective photocatalysts, and the nitrogen fixation performance research is not related yet.
Disclosure of Invention
The invention aims to provide a 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-shaped catalyst, a preparation method and a nitrogen fixation application thereof, so as to solve the problems in the prior art, and the catalyst has good photocatalytic nitrogen fixation and ammonia production performance and the advantage of simple preparation method.
In order to achieve the purpose, the invention provides the following scheme:
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 (3DPCN) and indium nitrate In the presence of a solvent, adding ethylenediamine, carrying out solvothermal reaction on the obtained reaction system, cooling after the reaction is finished, collecting precipitate, drying, and heating to prepare the 3DPCN/In 2 O 3 A composite catalyst;
(3) mixing 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 in the step (1) is supramolecular 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 h.
Further, the temperature rise 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 16 h.
Further, in the step (2), the mass ratio of the indium nitrate to the 3DPCN (3D porous carbon nitride) is 1:1 to 1: 20.
Further, the drying temperature of the step (2) is 30-90 ℃, and 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 treatment in the step (2) has a heating rate of 2-8 ℃/min. Preferably 5 deg.C/min.
Further, the solvent in the step (2) is methanol, ethylene glycol or absolute ethyl alcohol. Preferably anhydrous ethanol.
Further, the volume ratio of the solvent to the ethylenediamine in the step (2) is 0.5: 1-2: 1. preferably 1: 1.
further, the method also comprises a stirring step after the ethylenediamine is added in the step (2), wherein the stirring time is 10-30 min, preferably 15 min.
Further, the temperature of the calcination treatment in the step (3) is 300-600 ℃, and the calcination time is 1-5 h. Preferably, the temperature of the calcination treatment is 500 ℃ and the calcination time is 2 h.
The temperature rise 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 verification experiment for producing ammonia by photocatalytic nitrogen fixation comprises the following steps:
under the condition of normal temperature and normal pressure, the prepared catalyst is added into 500mL of methanol water solution, and ultrasonic treatment is carried out to ensure that the catalyst is uniformly dispersed. Under the condition of light, nitrogen (N) is introduced into the dispersion liquid at a certain aeration rate 2 ) Sampling for a certain time, carrying out centrifugal separation, taking clear liquid, and measuring the ammonia production efficiency by adopting a nano-grade reagent spectrophotometry.
Wherein the concentration of the methanol aqueous solution can be 0.001-1.0 mol/L, preferably 0.02 mol/L;
the volume ratio of the mass of the catalyst to the reaction solution can be 0.1-1 g/L, preferably 0.2 g/L;
the aeration rate of the nitrogen gas can be 10-200 mL/min, preferably 100 mL/min.
Through g-C 3 N 4 The morphology control and the high-activity semiconductor material composite modification with narrower band gap are one of effective ways for improving the light absorption and the light excited hole-electron transfer, thereby reducing the photogenerated hole-electron recombination rate. Thus, loading of oxygen-rich defective indium oxide (V) by 3D porous carbon nitride (3DPCN) was designed O -In 2 O 3 ) Formation of 3DPCN/V O -In 2 O 3 Can increase the active interface of carbon nitride, inhibit the recombination of hole-electron and increase the p-N 2 The activating properties of the molecule.
The invention discloses the following technical effects:
the invention compounds 3D porous carbon nitride with oxygen-enriched defect type V O -In 2 O 3 Successfully prepare visible light response type 3DPCN/V O -In 2 O 3 The catalyst is applied to photocatalysis for nitrogen fixation and ammonia production. Experimental results show that the prepared catalyst has good photocatalytic nitrogen fixation and ammonia production performance, is simple to operate, has a 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 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 it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is an SEM photograph of 3DPCN-4 prepared in example 4 of the present invention;
FIG. 2 is In prepared In comparative example 1 of the present invention 2 O 3 SEM picture of (1);
FIG. 3 shows 3DPCN-4/V prepared in example 4 of the present invention O -In 2 O 3 SEM picture of-4;
FIG. 4 shows 3DPCN-4/V prepared in example 4 of the present invention O -In 2 O 3 -4 and 3DPCN/In comparative example 4 2 O 3 EPR map of.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description 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 the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, 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 herein 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 present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The present invention will be described in further detail with reference to the following examples:
the melamine, cyanuric acid, ethylenediamine, indium nitrate, methanol, ethanol, isopropanol and dimethyl sulfoxide used in the examples of the invention are all purchased from national drug 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 were added to methanol at 10 ℃ min -1 The temperature is increased to 550 ℃, the mixture is heated for 2 hours under the protection of nitrogen, then the mixture is cooled to room temperature, and the mixture is ground into powder 3DPCN-1 through an agate mortar.
(2) 120mg of indium nitrate and 120mg of 3DPCN-1 were dissolved in 45mL of anhydrous ethanol at a mass ratio of 1:1 of indium nitrate to 3 DPCN. 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 (Teflon lined). Then the autoclave is sealed and then is kept warm in an oven at 180 ℃ for 16 h. After the reaction, the autoclave was taken out and naturally cooled to room temperature, and the precipitate was obtained by centrifugal separation of the suspension, and then washed three times with deionized water and anhydrous ethanol, respectively. Drying the precipitate at 70 deg.C, heating to 500 deg.C at 5 deg.C/min in a muffle furnace and holding for 2h to obtain 3DPCN-1/In 2 O 3 -1。
(3) Weighing 1g of 3DPCN-1/In 2 O 3 -1 placing the mixture in a porcelain boat, calcining the mixture for 2 hours in a tubular furnace at 500 ℃ under the air atmosphere, wherein the heating rate is 10 ℃ per minute -1 . The obtained sample was labeled 3DPCN-1/V O -In 2 O 3 -1。
At normal temperature and pressure, 50mg of 3DPCN-1/V was added to 500mL of an aqueous methanol solution (0.001mol/L) O -In 2 O 3 1 catalyst, and performing ultrasonic treatment for 10 min. Under the irradiation of visible light, nitrogen gas was introduced at 10 mL/min. Reacting for 120min, taking clear liquid, and measuring the ammonia production efficiency by adopting a Nassner reagent spectrophotometry to be 0.32 mu mol/L/min.
Example 2
(1) 900mg of melamine and 1000mg of cyanuric acid are added to dimethyl sulfoxide at 8 ℃ min -1 Heating to 500 ℃, heating for 2h under the protection of nitrogen, then cooling to room temperature, and grinding into powder 3DPCN-2 through an agate mortar.
(2) 100mg of indium nitrate and 500mg of 3DPCN-2 were dissolved in 34mL of anhydrous ethanol at a mass ratio of 1:5 of indium nitrate to 3 DPCN. Then, 34mL of ethylenediamine was added dropwise to the above solution with stirring. After stirring for 15min, the resulting slurry was transferred to a 100mL autoclave (Teflon lined). Then the autoclave is sealed and then is kept warm in an oven at 180 ℃ for 16 h. After the reaction is finished, the autoclave is taken out and naturally cooled to room temperature, the precipitate is obtained by centrifugal separation of suspension, and then the precipitate is washed by deionized water and absolute ethyl alcohol for three times respectively. Drying the precipitate at 80 deg.C, heating to 500 deg.C at 5 deg.C/min In muffle furnace, and maintaining for 2 hr to obtain 3DPCN-2/In 2 O 3 -2。
(3) Weighing 1g of 3DPCN-2/In 2 O 3 -2 placing the mixture in a porcelain boat, calcining the mixture for 3 hours in a tubular furnace at 500 ℃ under the air atmosphere, wherein the heating rate is 16 ℃ per minute -1 . The obtained 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 (0.001mol/L) at ordinary temperature and pressure O -In 2 O 3 -2 catalyst, ultrasonic 10min. Under the irradiation of visible light, nitrogen gas 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 nano reagent spectrophotometry.
Example 3
(1) 1000mg of melamine and 1000mg of cyanuric acid were added to ethanol at 12 ℃ min -1 Heating to 600 ℃, heating for 2h under the protection of nitrogen, then cooling to room temperature, and grinding into powder 3DPCN-3 through an agate mortar.
(2) 300.83mg of indium nitrate and 2406.64mg of 3DPCN-3 were dissolved in 30mL of anhydrous ethanol at a mass ratio of 1:8 of indium nitrate to 3 DPCN. Then, 30mL of ethylenediamine was added dropwise to the above solution with stirring. After stirring was continued for 20min, the resulting slurry was transferred to a 100mL autoclave (Teflon lined). Then the autoclave is sealed and then is kept warm for 12h in an oven at 180 ℃. After the reaction, the autoclave was taken out and naturally cooled to room temperature, and the precipitate was obtained by centrifugal separation of the suspension, and then washed three times with deionized water and anhydrous ethanol, respectively. Drying the precipitate at 60 deg.C, heating to 500 deg.C at 5 deg.C/min In muffle furnace, and maintaining for 2 hr to obtain 3DPCN-3/In 2 O 3 -3。
(3) Weighing 1g of 3DPCN-3/In 2 O 3 -3 placing the mixture in a porcelain boat, calcining the mixture for 2 hours in a tubular furnace at 500 ℃ under the air atmosphere, wherein the heating rate is 20 ℃ per minute -1 . The obtained sample was labeled 3DPCN-3/V O -In 2 O 3 -3。
At normal temperature and pressure, 50mg of 3DPCN-3/V was added to 500mL of an aqueous methanol solution (0.001mol/L) O -In 2 O 3 3 catalyst, ultrasonic treatment for 10 min. Under the irradiation of visible light, nitrogen gas was introduced at 10 mL/min. Reacting for 120min, taking clear liquid, and measuring the ammonia production efficiency to be 0.71 mu mol/L/min by adopting a nano reagent spectrophotometry.
Example 4
(1) 1000mg of melamine and 1000mg of cyanuric acid were added to dimethyl sulfoxide at 10 ℃ min -1 Heating to 550 deg.C, heating under nitrogen for 2 hr, cooling to room temperature, and grinding into powder 3DPCN-4 (SE of 3DPCN-4 in FIG. 1) with agate mortarM picture).
(2) 300.83mg of indium nitrate and 2406.64mg of 3DPCN-4 were dissolved in 30mL of anhydrous ethanol at a mass ratio of 1:8 of indium nitrate to 3 DPCN. Then, 34mL of ethylenediamine was added dropwise to the above solution with stirring. After stirring for 15min, the resulting slurry was transferred to a 100mL autoclave (Teflon lined). Then the autoclave was sealed and kept at 180 ℃ in an oven for 16 h. After the reaction is finished, the autoclave is taken out and naturally cooled to room temperature, the precipitate is obtained by centrifugal separation of suspension, and then the precipitate is washed by deionized water and absolute ethyl alcohol for three times respectively. Drying the precipitate at 60 deg.C, heating to 500 deg.C at 5 deg.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 picture of 4).
(3) Weighing 1g of 3DPCN-4/In 2 O 3 -4 placing the mixture in a porcelain boat, calcining the mixture for 2 hours in a tubular furnace at 500 ℃ under the air atmosphere, wherein the heating rate is 10 ℃ per minute -1 . The obtained 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 (0.001mol/L) at ordinary temperature and pressure O -In 2 O 3 4 catalyst, ultrasonic treatment for 10 min. Under the irradiation of visible light, nitrogen gas was introduced at 10 mL/min. Reacting for 120min, taking clear liquid, and measuring the ammonia production efficiency to be 1.10 mu mol/L/min by adopting a nano reagent spectrophotometry.
Example 5
(1) 1100mg of melamine and 1000mg of cyanuric acid were added to isopropanol at 10 ℃ C. min -1 Heating to 500 ℃, heating for 2h under the protection of nitrogen, then cooling to room temperature, and grinding into powder 3DPCN-5 through an agate mortar.
(2) 100mg of indium nitrate and 1000mg of 3DPCN-5 were dissolved in 50mL of methanol at a mass ratio 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 (Teflon lined). Then the autoclave is sealed and then is kept warm in an oven at 180 ℃ for 16 h. After the reaction is finished, taking outThe autoclave was then naturally cooled to room temperature, and the suspension was centrifuged to obtain a precipitate, which was then washed three times with deionized water and absolute ethanol. Drying the precipitate at 40 deg.C, heating to 500 deg.C at 5 deg.C/min In a muffle furnace, and maintaining for 3 hr to obtain 3DPCN-5/In 2 O 3 -5。
(3) Weighing 1g of 3DPCN-5/In 2 O 3 -5 placing the mixture in a porcelain boat, calcining the mixture for 2 hours in a tubular furnace at 500 ℃ under the air atmosphere, wherein the heating rate is 10 ℃ per minute -1 . The obtained sample was labeled 3DPCN-5/V O -In 2 O 3 -5。
At normal temperature and pressure, 50mg of 3DPCN-5/V was added to 500mL of an aqueous methanol solution (0.001mol/L) O -In 2 O 3 5 catalyst, ultrasonic treatment for 10 min. Under the irradiation of visible light, nitrogen gas 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 nano reagent spectrophotometry.
Example 6
(1) 1200mg of melamine and 1000mg of cyanuric acid were added to dimethyl sulfoxide at 10 ℃ min -1 Heating to 550 ℃, heating for 3h under the protection of nitrogen, then cooling to room temperature, and grinding into powder 3DPCN-6 through an agate mortar.
(2) 50mg of indium nitrate and 750mg of 3DPCN-6 were dissolved in 40mL of anhydrous ethanol at a mass ratio 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 (Teflon lined). Then the autoclave is sealed and then is kept in an oven at 180 ℃ for 15 h. After the reaction, the autoclave was taken out and naturally cooled to room temperature, and the precipitate was obtained by centrifugal separation of the suspension, and then washed three times with deionized water and anhydrous ethanol, respectively. Drying the precipitate at 60 deg.C, heating to 500 deg.C at 5 deg.C/min In a muffle furnace, and maintaining for 2 hr to obtain 3DPCN-6/In 2 O 3 -6。
(3) Weighing 1g of 3DPCN-6/In 2 O 3 -6 placing the mixture in a porcelain boat, calcining the mixture for 2 hours in a tubular furnace at 500 ℃ under the air atmosphere, wherein the heating rate is 10 ℃ per minute -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 (0.001mol/L) at ordinary temperature and pressure O -In 2 O 3 -6 catalysts, 10min of ultrasound. Under the irradiation of visible light, nitrogen gas was introduced at 10 mL/min. Reacting for 120min, taking clear liquid, and measuring the ammonia production efficiency to be 0.66 mu mol/L/min by adopting a nano reagent spectrophotometry.
Comparative example 1
The only difference from example 4 was that In was prepared without adding 3DPCN and without performing high-temperature calcination to form an oxygen-deficient structure 2 O 3 And (3) sampling.
In 2 O 3 The preparation of (1): 523.5mg of indium nitrate were dissolved in 34mL of anhydrous ethanol. Then, mixing the components in a volume ratio of 1:1 to the above solution, 34mL of ethylenediamine was added dropwise with stirring. After stirring for 15min, the resulting white slurry was transferred to a 100mL autoclave (Teflon lined). Then the autoclave is sealed and then is kept warm in an oven at 180 ℃ for 16 h. After the reaction, the autoclave was taken out and naturally cooled to room temperature, and a white precipitate was obtained by centrifugal separation of the suspension, and then washed three times with deionized water and anhydrous ethanol, respectively. Drying the white precipitate at 60 deg.C, placing into a muffle furnace, heating to 500 deg.C at 5 deg.C/min, and maintaining for 2 hr to obtain In 2 O 3 (as shown in fig. 2).
50mg of In was added to 500mL of an aqueous methanol solution (0.001mol/L) at ordinary temperature and pressure 2 O 3 And (5) carrying out ultrasonic treatment on the catalyst for 10 min. Under the irradiation of visible light, nitrogen gas was introduced at 10 mL/min. Reacting for 120min, taking clear liquid, and measuring the ammonia production efficiency to be 0.068 mu mol/L/min by adopting a nano reagent spectrophotometry.
Comparative example 2
Differs from example 4 only in that no 3DPCN is added, preparation V O -In 2 O 3 And (4) sampling.
V O -In 2 O 3 The preparation of (1): 523.5mg of indium nitrate were dissolved in 34mL of anhydrous ethanol. Then, mixing the components in a volume ratio of 1:1 to the above solution, 34mL of ethylenediamine was added dropwise with stirring. Continuously stirringAfter 15min, the resulting white slurry was transferred to a 100mL autoclave (Teflon lined). Then the autoclave is sealed and then is kept warm in an oven at 180 ℃ for 16 h. After the reaction, the autoclave was taken out and naturally cooled to room temperature, white precipitates were obtained by centrifugal separation of the suspension, and then washed three times with deionized water and absolute ethyl alcohol, respectively. Drying the white precipitate at 60 deg.C, placing into a muffle furnace, heating to 500 deg.C at 5 deg.C/min, and maintaining for 2 hr to obtain In 2 O 3 。
Weighing 1g of In 2 O 3 Placing in a porcelain boat, calcining in a muffle furnace at 500 deg.C under air atmosphere for 2h at a heating rate of 10 deg.C/min -1 . The resulting sample was labeled V O -In 2 O 3 。
50mg of V was added to 500mL of an aqueous methanol solution (0.001mol/L) at ordinary temperature and pressure O -In 2 O 3 And (5) carrying out catalyst treatment by ultrasonic treatment for 10 min. Under the irradiation of visible light, nitrogen gas was introduced at 10 mL/min. Reacting for 120min, taking clear liquid, and measuring the ammonia production efficiency to be 0.19 mu mol/L/min by adopting a nano reagent spectrophotometry.
Comparative example 3
Differs from example 4 only in 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 were added to dimethyl sulfoxide at 10 ℃ min -1 The temperature is increased to 550 ℃, the mixture is heated for 2 hours under the protection of nitrogen, then the mixture is cooled to room temperature, and the mixture is ground into powder 3DPCN through an agate mortar.
50mg of the catalyst was added to 500mL of an aqueous methanol solution (0.001mol/L) at ordinary temperature and pressure, and the mixture was sonicated for 10 min. Under the irradiation of visible light, nitrogen gas was introduced at 10 mL/min. Reacting for 120min, collecting the clear liquid, and measuring the ammonia production efficiency by adopting a nano reagent spectrophotometry to be 0.0408 mu mol/L/min.
Comparative example 4
The difference from example 4 is only that 3DPCN/In was prepared without performing high-temperature calcination to form an oxygen-deficient structure 2 O 3 And (3) sampling.
In 2 O 3 The preparation of (1): 523.5mg of indium nitrate were dissolved in 34mL of anhydrous ethanol. Then, mixing the components in a volume ratio of 1:1 to the above solution, 34mL of ethylenediamine was added dropwise with stirring. After stirring for 15min, the resulting white slurry was transferred to a 100mL autoclave (Teflon lined). Then the autoclave is sealed and then is kept warm in an oven at 180 ℃ for 16 h. After the reaction, the autoclave was taken out and naturally cooled to room temperature, and a white precipitate was obtained by centrifugal separation of the suspension, and then washed three times with deionized water and anhydrous ethanol, respectively. Drying the white precipitate at 60 deg.C to obtain In 2 O 3 。
Preparation of 3 DPCN: 1000mg of melamine and 1000mg of cyanuric acid were added to dimethyl sulfoxide at 10 ℃ min -1 The temperature is increased to 550 ℃, the mixture is heated for 2 hours under the protection of nitrogen, then the mixture is cooled to room temperature, and the mixture is ground into powder 3DPCN through an agate mortar.
3DPCN/In 2 O 3 The preparation of (1): weighing 100mg of In 2 O 3 Respectively preparing into dispersion solutions with 827mg3DPCN, mixing, stirring at 60 deg.C water bath for 4 hr, washing, and drying to obtain 3DPCN/In 2 O 3 。
50mg of the catalyst was added to 500mL of an aqueous methanol solution (0.001mol/L) at ordinary temperature and pressure, and the mixture was sonicated for 10 min. Under the irradiation of visible light, nitrogen gas was introduced at 10 mL/min. Reacting for 120min, taking clear liquid, and measuring the ammonia production efficiency by adopting a Nassner reagent spectrophotometry to be 0.376 mu mol/L/min.
FIG. 4 shows 3DPCN-4/V in example 4 O -In 2 O 3 -4 and 3DPCN/In comparative example 4 2 O 3 The EPR map of (a) shows the introduction of oxygen vacancies in the examples of the invention.
The results show that 3DPCN is In 2 O 3 Compounding Z-type 3DPCN/VO-In prepared after oxygen defect construction 2 O 3 The catalyst has excellent performance of producing ammonia by photocatalytic reduction of nitrogen fixation. Under the irradiation of visible light, 50mg of catalyst is added into the system, nitrogen is introduced at 100mL/min for reaction for 120min, the efficiency of producing ammonia by photocatalytic reduction nitrogen fixation can reach 1.10 mu mol/L/min, and the Z-shaped 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 of oxygen vacancy and the structural design 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 green synthesis of ammonia through photocatalysis.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (9)
1. A preparation method of a 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst is characterized by comprising 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 and indium nitrate In the presence of a solvent, adding ethylenediamine, carrying out solvothermal reaction on the obtained reaction system, collecting and drying the precipitate, and then carrying out heating treatment to prepare 3DPCN/In 2 O 3 A composite catalyst;
(3) mixing the 3DPCN/In 2 O 3 And calcining the composite catalyst to obtain the 3D porous carbon nitride composite indium oxide composite catalyst with oxygen-rich defects.
2. The method according to claim 1, wherein the molar ratio of melamine to cyanuric acid is 0.5:1 to 1.5: 1.
3. The preparation method according to claim 1, wherein the reaction temperature in the step (1) is 400-600 ℃ and the reaction time is 1-5 h.
4. The preparation method according to claim 1, wherein the solvothermal reaction temperature in the step (2) is 120-250 ℃ and the reaction time is 1-24 hours.
5. The preparation method according to claim 1, wherein the mass ratio of the indium nitrate to the 3D porous carbon nitride in the step (2) is 1:1 to 1: 20.
6. The method according to claim 1, wherein the drying temperature in the step (2) is 30 to 90 ℃; the temperature of the heating treatment is 400-600 ℃, and the time is 1-5 h.
7. The method according to claim 1, wherein the calcination treatment in step (3) is carried out at a temperature of 300 to 600 ℃ for 1 to 5 hours.
8. The 3D porous carbon nitride composite oxygen-rich defect indium oxide Z-type catalyst prepared by the preparation method of any one of claims 1 to 7.
9. Use of the catalyst of claim 8 for photocatalytic nitrogen fixation and ammonia production.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210687929.0A CN114939405B (en) | 2022-06-17 | 2022-06-17 | 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst, preparation method and nitrogen fixation application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210687929.0A CN114939405B (en) | 2022-06-17 | 2022-06-17 | 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst, preparation method and nitrogen fixation application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114939405A true CN114939405A (en) | 2022-08-26 |
CN114939405B CN114939405B (en) | 2023-05-26 |
Family
ID=82910284
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210687929.0A Active CN114939405B (en) | 2022-06-17 | 2022-06-17 | 3D porous carbon nitride composite oxygen-enriched defect indium oxide Z-type catalyst, preparation method and nitrogen fixation application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114939405B (en) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106622326A (en) * | 2016-12-13 | 2017-05-10 | 南京理工大学 | Core-shell carbon nitride material and preparation method thereof |
CN107790163A (en) * | 2017-09-27 | 2018-03-13 | 阜阳师范学院 | A kind of photochemical catalyst In2O3/g‑C3N4B preparation and application |
CN109225194A (en) * | 2018-09-11 | 2019-01-18 | 同济大学 | Photocatalysis fixed nitrogen Zn doped indium oxide photocatalyst material and its preparation method and application |
CN109999836A (en) * | 2019-04-28 | 2019-07-12 | 大连工业大学 | A kind of preparation of indium oxide/indium sulfide heterojunction semiconductor material and photochemical catalyst purposes and solar energy fixed nitrogen application |
CN110697667A (en) * | 2019-10-08 | 2020-01-17 | 河海大学 | Visible light responsive tubular g-C3N4Preparation method of (1) |
CN112371146A (en) * | 2020-10-14 | 2021-02-19 | 江苏大学 | Preparation method and application of Z-type carbon nitride-iron oxide catalyst containing nitrogen defect structure |
CN112871195A (en) * | 2020-09-27 | 2021-06-01 | 江南大学 | Multi-morphology carbon nitride synthesized by salt assistance, and preparation method and application thereof |
CN113976155A (en) * | 2021-10-09 | 2022-01-28 | 江苏大学 | Preparation method of porous carbon nitride-ferrite composite catalyst with nitrogen/oxygen-containing double defect structure and application of photocatalyst in nitrogen fixation |
CN114452989A (en) * | 2022-01-30 | 2022-05-10 | 江苏大学 | Porous structure carbon nitride composite catalyst and preparation method and application thereof |
-
2022
- 2022-06-17 CN CN202210687929.0A patent/CN114939405B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106622326A (en) * | 2016-12-13 | 2017-05-10 | 南京理工大学 | Core-shell carbon nitride material and preparation method thereof |
CN107790163A (en) * | 2017-09-27 | 2018-03-13 | 阜阳师范学院 | A kind of photochemical catalyst In2O3/g‑C3N4B preparation and application |
CN109225194A (en) * | 2018-09-11 | 2019-01-18 | 同济大学 | Photocatalysis fixed nitrogen Zn doped indium oxide photocatalyst material and its preparation method and application |
CN109999836A (en) * | 2019-04-28 | 2019-07-12 | 大连工业大学 | A kind of preparation of indium oxide/indium sulfide heterojunction semiconductor material and photochemical catalyst purposes and solar energy fixed nitrogen application |
CN110697667A (en) * | 2019-10-08 | 2020-01-17 | 河海大学 | Visible light responsive tubular g-C3N4Preparation method of (1) |
CN112871195A (en) * | 2020-09-27 | 2021-06-01 | 江南大学 | Multi-morphology carbon nitride synthesized by salt assistance, and preparation method and application thereof |
CN112371146A (en) * | 2020-10-14 | 2021-02-19 | 江苏大学 | Preparation method and application of Z-type carbon nitride-iron oxide catalyst containing nitrogen defect structure |
CN113976155A (en) * | 2021-10-09 | 2022-01-28 | 江苏大学 | Preparation method of porous carbon nitride-ferrite composite catalyst with nitrogen/oxygen-containing double defect structure and application of photocatalyst in nitrogen fixation |
CN114452989A (en) * | 2022-01-30 | 2022-05-10 | 江苏大学 | Porous structure carbon nitride composite catalyst and preparation method and application thereof |
Non-Patent Citations (3)
Title |
---|
SHAO-WEN CAO ET AL.: ""Solar-to-fuels conversion over In2O3/g-C3N4 hybrid photocatalysts"" * |
ZHENMIN LI ET AL.: ""In2O3 nanoporous nanosphere: A highly efficient photocatalyst for decomposition of perfluorooctanoic acid"" * |
陆杨: ""超分子预组装法可控合成氮化碳基光催化剂及光解水性能研究"" * |
Also Published As
Publication number | Publication date |
---|---|
CN114939405B (en) | 2023-05-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
He et al. | Indium sulfide nanotubes with sulfur vacancies as an efficient photocatalyst for nitrogen fixation | |
CN100411730C (en) | Zeolite based nano-titanium dioxide double function material and its prepn. method | |
Zhu et al. | Construction of 2D/2D TiO2/g-C3N4 nanosheet heterostructures with improved photocatalytic activity | |
CN102039118B (en) | Preparation method of supported nano TiO2 photocatalytic material with diatomite filter aid as carrier | |
CN106552651B (en) | Bi12O17Br2Synthesis and application method of photocatalyst | |
CN107837816B (en) | Fe2O3/g-C3N4Composite system, preparation method and application | |
CN112023938B (en) | Bimetallic ion doped nano composite photocatalyst and preparation method thereof | |
CN102631919B (en) | Preparation method of copper-titanium-oxide mesomorphism material | |
CN107983353B (en) | TiO 22-Fe2O3Preparation method and application of composite powder | |
CN112958061B (en) | Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof | |
CN110721698B (en) | Bismuth vanadate/copper vanadate composite photocatalyst and preparation method and application thereof | |
CN102039117A (en) | Method for preparing loaded nano TiO2 composite material by using precipitated white carbon black as carrier | |
Shen et al. | Photoinduced defect engineering: enhanced photocatalytic performance of 3D BiOCl nanoclusters with abundant oxygen vacancies | |
Khan et al. | Efficient CO2 conversion and organic pollutants degradation over Sm3+ doped and rutile TiO2 nanorods decorated-GdFeO3 nanorods | |
CN110745864B (en) | Perovskite type lanthanum titanate material and preparation method and application thereof | |
CN106362742A (en) | Ag/ZnO nano-composite, preparation method thereof and application of composite | |
CN109289849A (en) | Controllable preparation novel C eO2The method of the renewable surface reinforced Raman active catalysis material of/Ag | |
CN109382088B (en) | SnO2/α~Bi2O3/β~Bi2O3Composite material and preparation method thereof | |
Cui et al. | Heterojunction g-C3N4/CeO2/Bi2O3 composite for the photocatalytic purification of exhaust gas | |
CN108704660B (en) | Preparation and application of nitrogen vacancy modified oxygen-enriched titanium dioxide nano composite material | |
Wang et al. | Free-standing and flexible 0D CeO 2 nanodot/1D La (OH) 3 nanofiber heterojunction net as a novel efficient and easily recyclable photocatalyst | |
Zhang et al. | Enhanced electron density of the π-conjugated structure and in-plane charge transport to boost photocatalytic H2 evolution of g-C3N4 | |
Jing et al. | Surfactant-induced photocatalytic performance enhancement of europium oxide nanoparticles | |
Sang et al. | Fabrication of the hydrogen-evolving photocatalyst with mesoporous structure | |
CN112774703A (en) | Elemental red phosphorus-loaded titanium dioxide composite catalyst for efficient photocatalytic decomposition of water to produce hydrogen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |