CN114950511B - Molybdenum-oxide-based photocatalyst with rich lattice defect sites, preparation method thereof and application thereof in photocatalytic nitrogen fixation - Google Patents
Molybdenum-oxide-based photocatalyst with rich lattice defect sites, preparation method thereof and application thereof in photocatalytic nitrogen fixation Download PDFInfo
- Publication number
- CN114950511B CN114950511B CN202210707546.5A CN202210707546A CN114950511B CN 114950511 B CN114950511 B CN 114950511B CN 202210707546 A CN202210707546 A CN 202210707546A CN 114950511 B CN114950511 B CN 114950511B
- Authority
- CN
- China
- Prior art keywords
- tio
- molybdenum
- mass
- preparation
- time
- 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.)
- Active
Links
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 40
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- 230000007547 defect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 18
- 229910000476 molybdenum oxide Inorganic materials 0.000 title description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 17
- 239000011733 molybdenum Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims abstract description 15
- 239000008213 purified water Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 9
- 235000019441 ethanol Nutrition 0.000 claims abstract description 9
- 239000008103 glucose Substances 0.000 claims abstract description 9
- UQJSLVWCKFZHFO-UHFFFAOYSA-N molybdenum(4+) oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Mo+4] UQJSLVWCKFZHFO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000007146 photocatalysis Methods 0.000 claims description 7
- 238000005286 illumination Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000004408 titanium dioxide Substances 0.000 abstract description 3
- 238000001132 ultrasonic dispersion Methods 0.000 abstract description 3
- 241000282326 Felis catus Species 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910039444 MoC Inorganic materials 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000004065 semiconductor Substances 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
- 101000801040 Homo sapiens Transmembrane channel-like protein 1 Proteins 0.000 description 1
- 101000638069 Homo sapiens Transmembrane channel-like protein 2 Proteins 0.000 description 1
- 101000638078 Homo sapiens Transmembrane channel-like protein 3 Proteins 0.000 description 1
- 101000638096 Homo sapiens Transmembrane channel-like protein 4 Proteins 0.000 description 1
- 102100033690 Transmembrane channel-like protein 1 Human genes 0.000 description 1
- 102100032054 Transmembrane channel-like protein 2 Human genes 0.000 description 1
- 102100032048 Transmembrane channel-like protein 3 Human genes 0.000 description 1
- 102100032041 Transmembrane channel-like protein 4 Human genes 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
- 125000003729 nucleotide group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 pharmacy Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
-
- 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)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a titanium dioxide molybdenum-based photocatalyst with rich lattice defect sites, and preparation and application thereof in photocatalytic nitrogen fixation. Adding molybdenum acetylacetonate and glucose into a mixed solvent of ethanol and purified water, adding sodium chloride, and stirring for the second time for 8-12min to obtain a precursor solution; then placing the precursor solution into a tube furnace, calcining for 1-3h in an inert atmosphere at 600-1000 ℃, naturally cooling to room temperature to obtain Mo 2 C@C; mo is added with 2 C@C and TiO 2 Adding absolute ethyl alcohol for ultrasonic dispersion. TiO prepared by the invention 2 /Mo 2 C@C composite materials have planar regular shapes and a abundance of lattice defect sites. TiO (titanium dioxide) 2 /Mo 2 C@C heterojunction photocatalyst does not involve the use of a sacrificial agent in the photocatalytic nitrogen fixation process, can effectively separate photo-generated electrons from holes, and can enable the catalyst to convert nitrogen into ammonia with better selectivity by utilizing light energy.
Description
Technical Field
The invention belongs to the field of semiconductor materials, relates to a titanium dioxide molybdenum-based photocatalyst with rich lattice defect sites, preparation and application thereof in photocatalysis nitrogen fixation, and in particular relates to TiO 2 /Mo 2 C@C heterojunction photocatalytic material.
Background
Ammonia is an important compound in human production and life, and is not only an important molecule for forming amino acid and nucleotide, but also applied to the aspects of synthetic fertilizer, pharmacy, synthetic fiber and the like. Nitrogen is the most abundant gas in natural air, accounting for about 78% of the air volume. Nitrogen is difficult to participate in some chemical reactions due to the stability of the triple bond of nitrogen and nitrogen (940.95 KJ/mol) in nitrogen. The current industry synthesizes ammonia gas by the Haber-Bosch process using nitrogen and hydrogen under high temperature and pressure conditions of an iron-based catalyst, which requires consumption of a large amount of fossil energy and discharge of a large amount of carbon dioxide. Therefore, nitrogen fixation at normal temperature is one of important research subjects in the chemical community.
Currently, human beings use light energy or electric energy to convert nitrogen into ammonia under the action of a catalyst. In particular to photocatalysis nitrogen fixation, and reasonable utilization of light energy accords with the concept of sustainable development in the future. Hitherto, catalysts including metal oxides, sulfides, metal-organic frameworks (MOFs), and the like have been studied. In the field of photocatalysis, tiO 2 Is most widely used due to TiO 2 Can generate high-energy electrons and oxidize water into oxygen to reduce the use of hole sacrificial agents, but due to TiO 2 The lack of nitrogen active sites generally requires modification methods such as doping, heterojunction construction and the like to improve TiO in the field of photocatalysis nitrogen fixation 2 In photocatalytic nitrogen fixation applications (X.Bian, et al ACS materials. Letters.2021, 11:1521-152). Mo-based materials have been demonstrated in the NRR field by theoretical calculations to possess the ability to activate a nitrogen-nitrogen triple bond. Hexagonal molybdenum carbide (abbreviated as Mo) 2 C) As a catalyst, it has good conductivity and hydrogen evolution capability, and has wide application in the field of photoelectrocatalysis (xu.X, et al applied Catalysis B: environmental.2020,272: 118984.).
The invention is achieved by combining TiO 2 With Mo 2 C@C the construction of the composite material enhances the corresponding ability to light, and the sintering of glucose and molybdenum acetylacetonate to prepare molybdenum carbide increases the surface area and the active site of the reaction. Preparation of Mo by tube furnace sintering 2 C@C and then Mo 2 C@C TiO is added 2 The nano particles are dispersed by ultrasonic and evaporated and dried to obtain TiO 2 /Mo 2 C@C photocatalyst. Work shows that with pure TiO 2 In comparison with TiO 2 /Mo 2 C@C heterojunction photocatalyst can effectively separate photo-generated electrons from holes, and can enable the catalyst to convert nitrogen into ammonia with better selectivity by utilizing light energy.
Disclosure of Invention
The first object of the invention is to provide a preparation method of a titanium dioxide molybdenum-based photocatalyst with rich lattice defect sites, aiming at the defects of the prior art.
A preparation method of a titanium dioxide molybdenum-based photocatalyst with rich lattice defect sites comprises the following steps:
step (1) Mo 2 Preparation of C@C composite materials
Adding molybdenum acetylacetonate and glucose into a mixed solvent of ethanol and purified water, stirring for 10-20min at 40-70 ℃ for the first time, adding sodium chloride, and stirring for the second time for 8-12min to obtain a precursor solution; transferring the precursor solution into a square boat, evaporating to dryness, putting into a tube furnace, calcining for 1-3h at 600-1000 ℃ in inert atmosphere, naturally cooling to room temperature, washing and centrifuging the calcined black solid with purified water, and putting into a vacuum oven for drying;
preferably, the mass ratio of the molybdenum acetylacetonate to the glucose is 0.4:0.14;
preferably, the mass volume ratio of the molybdenum acetylacetonate to the mixed solvent is 0.4g:5mL;
preferably, the volume ratio of the ethanol to the purified water in the mixed solvent is 4:1;
preferably, the mass ratio of the molybdenum acetylacetonate to the sodium chloride is 0.4:0.1;
preferably, the first stirring time is 15min and the second stirring time is 10min in the preparation process of the precursor solution;
preferably, the calcination time is 2 hours;
preferably, argon is used as the inert atmosphere;
step (2) TiO 2 /Mo 2 Preparation of C@C composite materials
Mo prepared in the step (1) 2 C@C and a certain mass of TiO 2 Adding absolute ethyl alcohol, dispersing for a period of time by ultrasonic, evaporating the solvent to obtain Mo 2 C@C TiO with mass fraction of 10-40% 2 /Mo 2 C@C composite;
preferably, the Mo 2 C@C and TiO 2 The mass-volume ratio of the total mass to the absolute ethyl alcohol is 100mg:10mL;
preferably, the ultrasonic dispersion time is 30min.
A second object of the present invention is to provide a molybdenum-titania-based photocatalyst having a planar regular shape, particularly TiO 2 Attached to Mo 2 C@C surface, mo 2 C@C are wrapped.
The third object of the invention is to provide the application of the titanium dioxide molybdenum-based photocatalyst with rich lattice defect sites in photocatalysis nitrogen fixation, which is as follows:
TiO is prepared under normal temperature and normal pressure 2 /Mo 2 C@C the composite material is dissolved in deionized water, dispersed for a period of time in a dark place, and nitrogen is introduced into the composite material for nitrogen fixation under sunlight illumination.
The invention has the beneficial effects that:
1. the invention does not involve the use of a sacrificial agent in the photocatalysis nitrogen fixation process, and prepares TiO by an ultrasonic compounding method 2 /Mo 2 C@C composite the desired photocatalytic composite is then prepared by removing the solvent. The method does not cause harm to the environment.
2. TiO prepared by the invention 2 /Mo 2 C@C the composite has a planar regular shape, and is characterized by ESR by rich lattice defect sites.
Drawings
FIG. 1 is a diagram of TiO 2 /Mo 2 C@C scanning electron microscopy of composite wherein (a) is pure Mo 2 C@C, (b) is TiO 2 /Mo 2 C@C composite.
FIG. 2 is a diagram of TiO 2 /Mo 2 C@C composite XRD characterization.
FIG. 3 is a diagram of TiO 2 /Mo 2 C@C ESR characterization of the composite.
FIG. 4 is a graph showing nitrogen fixation performance.
In the figure TMC1 represents TiO 2 /Mo 2 C@C (10 wt%) TMC2 represents TiO 2 /Mo 2 C@C (20 wt%) TMC3 represents TiO 2 /Mo 2 C@C (30 wt%) TMC4 represents TiO 2 /Mo 2 C@C(40wt％)。
Detailed Description
As described above, in view of the shortcomings of the prior art, the present inventors have long studied and practiced in a large number of ways, and have proposed the technical solution of the present invention, which is based on at least: (1) TiO prepared by the invention 2 /Mo 2 C@C composite materials have planar regular shapes and a abundance of lattice defect sites. (2) TiO (titanium dioxide) 2 /Mo 2 C@C heterojunction photocatalyst does not involve the use of a sacrificial agent in the photocatalytic nitrogen fixation process, can effectively separate photo-generated electrons from holes, and can enable the catalyst to convert nitrogen into ammonia with better selectivity by utilizing light energy.
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In a first aspect, a method for preparing a molybdenum-titania-based photocatalyst having abundant lattice defect sites is provided, comprising the steps of:
step (1) Mo 2 Preparation of C@C composite materials
Adding molybdenum acetylacetonate and glucose into a mixed solvent of ethanol and purified water, stirring for 10-20min at 40-70 ℃ for the first time, adding sodium chloride, and stirring for the second time for 8-12min to obtain a precursor solution; transferring the precursor solution into a square boat, evaporating to dryness, putting into a tube furnace, calcining for 1-3h at 600-1000 ℃ in inert atmosphere, naturally cooling to room temperature, washing and centrifuging the calcined black solid with purified water, and putting into a vacuum oven for drying;
preferably, the mass ratio of the molybdenum acetylacetonate to the glucose is 0.4:0.14;
preferably, the mass volume ratio of the molybdenum acetylacetonate to the mixed solvent is 0.4g:5mL;
preferably, the volume ratio of the ethanol to the purified water in the mixed solvent is 4:1;
preferably, the mass ratio of the molybdenum acetylacetonate to the sodium chloride is 0.4:0.1;
preferably, the first stirring time is 15min and the second stirring time is 10min in the preparation process of the precursor solution;
preferably, the calcination time is 2 hours;
preferably, argon is used as the inert atmosphere;
step (2) TiO 2 /Mo 2 Preparation of C@C composite materials
Mo prepared in the step (1) 2 C@C and a certain mass of TiO 2 Adding absolute ethyl alcohol, dispersing for a period of time by ultrasonic, evaporating the solvent to obtain Mo 2 C@C TiO with mass fraction of 10-40% 2 /Mo 2 C@C composite;
preferably, the Mo 2 C@C and TiO 2 The mass-volume ratio of the total mass to the absolute ethyl alcohol is 100mg:10mL;
preferably, the ultrasonic dispersion time is 30min.
In a second aspect, there is provided a molybdenum-based photocatalyst of titania having a large number of lattice defect sites, having a planar regular shape, in particular TiO 2 Attached to Mo 2 C@C surface, mo 2 C@C are wrapped.
In a third aspect, there is provided the use of a molybdenum titania-based photocatalyst having an abundance of lattice defect sites for photocatalytic nitrogen fixation, in particular:
TiO is prepared under normal temperature and normal pressure 2 /Mo 2 C@C the composite material is dissolved in deionized water, dispersed for a period of time in a dark place, and nitrogen is introduced into the composite material for nitrogen fixation under sunlight illumination.
In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention will be further analyzed with reference to specific examples.
Example 1.
(1)Mo 2 Preparation of C@C: to a solution of 4ml ethanol and 1ml purified water, 0.4g molybdenum acetylacetonate and 0.14g glucose were added. Stirring at 70deg.C for about 15min, adding 0.1g sodium chloride, stirring for 10min, dissolvingTransferring the solution to a square boat, and evaporating to dryness. Placing into a tube furnace, introducing argon to remove air, maintaining at 800 ℃ for 2h, and naturally cooling to room temperature. Washing and centrifuging the burned black solid with purified water, and drying in a vacuum oven at 80deg.C to obtain target product Mo 2 C@C。
(2) Ultrasonic composite preparation of TiO 2 /Mo 2 C@C: mo obtained in the step (1) 2 C@C adding 90mg TiO into 10ml ethanol with mass of 10mg 2 Ultrasonic treatment at room temperature for 30min; evaporating the solvent to dryness to prepare the target product TiO 2 /Mo 2 C@C(10wt％)。
Example 2.
Other than the same as in example 1, mo was added 2 C@C content is 20mg, tiO 2 The addition amount is 80mg to prepare the target product TiO 2 /Mo 2 C@C(20wt％)。
Example 3.
Other than the same as in example 1, mo was added 2 C@C content is 30mg, tiO 2 The addition amount is 70mg to prepare the target product TiO 2 /Mo 2 C@C(30wt％)。
Example 4.
Other than the same as in example 1, mo was added 2 C@C content is 40mg, tiO 2 The addition amount is 60mg to prepare the target product TiO 2 /Mo 2 C@C(40wt％)。
In order to evaluate the feasibility, morphology and distribution of the preparation of the semiconductor composite material, the invention utilizes a scanning microscope to carry out TiO (titanium dioxide) preparation 2 /Mo 2 C@C composite materials were characterized. As a result of observation by a scanning electron microscope, FIG. 1 (a) shows pure Mo 2 C@C is a layered planar hexagonal structure. FIG. 1 (b) is TiO 2 /Mo 2 C@C composite material, ultrafine TiO can be seen 2 Attached to Mo 2 C@C Mo is mixed with 2 C@C is wrapped with TiO on the surface 2 Better absorbs light and transfers photogenerated electrons to Mo 2 C@C.
Characterization of different mass fractions of TiO by XRD 2 /Mo 2 C@C composite. Mo can be seen in FIG. 2 2 C@C broad diffraction peaks at 39.4, 34.4, 61.5 with Mo 2 C (PDFNo. 35-0787). Different mass fractions of TiO 2 /Mo 2 C@C the sample shows a broad diffraction peak at 25.3℃with anatase TiO 2 (PDF No. 21-1272) corresponds to a small peak at 27.4℃with rutile TiO 2 (PDF No. 21-1276) and follows Mo 2 C@C increases the amount of Mo at 39.4 deg 2 C characteristic peak is more obvious, tiO 2 The characteristic peak is weakened. XRD shows TiO 2 Effective compounding with MC through ultrasonic method to obtain TiO 2 /Mo 2 C@C photocatalyst.
To examine TiO 2 /Mo 2 C@C composite lattice defects. ESR characterization of samples, FIG. 3 sample TiO 2 With mass fraction of 30% TiO 2 /Mo 2 C@C the signal peak of crystal defect (g=2.001), pure TiO 2 The defect signal peak is hardly detected, but it has a significant signal peak, and lattice defects (carbon vacancies) possibly generated by high temperature inert gas sintering are generated. The lattice defects provide active sites for nitrogen to convert to ammonia.
The following are different catalysts for catalytic reduction of N 2 The results of the activity experiments of (2) were analyzed:
the light source used in the laboratory is a 300W xenon lamp light source, sunlight can also be used, and an indophenol blue spectrophotometry is adopted to detect NH 4 + Concentration.
Application example 1
The photocatalytic nitrogen fixation experiment was performed under a nitrogen atmosphere at room temperature. By 5mgTiO 2 The catalyst and 30ml of purified water were placed in the reactor and sonicated for 5min to disperse the catalyst in the water. Under dark conditions before illumination with N 2 Aeration was carried out for 30min (rate 80 ml/min) and stirring rate was 700r/min. Then irradiating the reactor with 300W xenon lamp light source, extracting 1mL of the reaction solution every 1h, filtering with 0.22 μm filter, removing the photocatalyst, and detecting NH at 697.5nm by indophenol blue spectrophotometry 4 + Concentration.
Application example 2
The photocatalytic nitrogen fixation experiment was performed under a nitrogen atmosphere at room temperature. By 5mgTiO 2 /Mo 2 C@C compositePhotocatalyst and 30ml purified water were placed in a reactor and sonicated for 5min to disperse the catalyst in the water. Under dark conditions before illumination with N 2 Aeration was carried out for 30min (rate 80 ml/min) and stirring rate was 700r/min. Then irradiating the reactor with 300W xenon lamp light source, extracting 1mL of the reaction solution every 1h, filtering with 0.22 μm filter, removing the photocatalyst, and detecting NH at 697.5nm by indophenol blue spectrophotometry 4 + Concentration.
Except for the difference of materials, other experimental links are consistent.
FIG. 4 pure TiO 2 The ammonia conversion efficiency of nitrogen was 27.8. Mu.g/g cat /h。TiO 2 /Mo 2 C@C (10 wt%) nitrogen fixation efficiency was 120.0. Mu.g/g cat /h,TiO 2 /Mo 2 C@C (20 wt%) nitrogen fixation efficiency was 144.0. Mu.g/g cat /h,TiO 2 /Mo 2 C@C (30 wt%) has a nitrogen fixation efficiency of 437.7. Mu.g/g cat /h,TiO 2 /Mo 2 C@C (40 wt%) nitrogen fixation efficiency was 186.8. Mu.g/g cat /h。
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and falls within the scope of the present invention as long as the present invention meets the requirements.
Claims (8)
1. The application of the titanium dioxide molybdenum-based photocatalyst with rich lattice defect sites in photocatalysis nitrogen fixation is characterized in that the titanium dioxide molybdenum-based photocatalyst has a plane regular shape, in particular to TiO 2 Attached to Mo 2 C@C surface, mo 2 C@C are wrapped; the molybdenum-titanium-dioxide-based photocatalyst is prepared by the following method:
step (1) Mo 2 Preparation of C@C composite materials
Adding molybdenum acetylacetonate and glucose into a mixed solvent of ethanol and purified water, stirring for 10-20min at 40-70 ℃ for the first time, adding sodium chloride, and stirring for the second time for 8-12min to obtain a precursor solution; transferring the precursor solution into a square boat, evaporating to dryness, putting into a tube furnace, calcining for 1-3h at 600-1000 ℃ in inert atmosphere, naturally cooling to room temperature, washing and centrifuging the calcined black solid with purified water, and putting into a vacuum oven for drying; the mass ratio of the molybdenum acetylacetonate to the glucose is 0.4:0.14;
step (2) TiO 2 /Mo 2 Preparation of C@C composite materials
Mo prepared in the step (1) 2 C@C and a certain mass of TiO 2 Adding absolute ethyl alcohol, dispersing for a period of time by ultrasonic, evaporating the solvent to obtain Mo 2 C@C TiO 30% by mass 2 /Mo 2 C@C the titanium dioxide molybdenum-based photocatalyst.
2. Use according to claim 1, characterized in that the mass ratio of molybdenum acetylacetonate to sodium chloride in step (1) is 0.4:0.1.
3. use according to claim 1, characterized in that the mass to volume ratio of molybdenum acetylacetonate to mixed solvent in step (1) is 0.4g:5mL; the volume ratio of the ethanol to the purified water in the mixed solvent is 4:1.
4. The method according to claim 1, wherein the first stirring time is 15min and the second stirring time is 10min during the preparation of the precursor solution in step (1).
5. The method according to claim 1, wherein the inert atmosphere in step (1) is argon.
6. The use according to claim 1, characterized in that in step (2) the Mo 2 C@C and TiO 2 The mass-volume ratio of the total mass to the absolute ethyl alcohol is 100mg:10mL.
7. The use according to claim 1, characterized in that the ultrasound dispersion time in step (2) is 30min.
8. Use according to claim 1, characterized in that it comprises in particular:
normal temperature and normal conditionUnder the condition of pressure, tiO 2 /Mo 2 C@C the composite material is dissolved in deionized water, dispersed for a period of time in a dark place, and nitrogen is introduced into the composite material for nitrogen fixation under sunlight illumination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210707546.5A CN114950511B (en) | 2022-06-21 | 2022-06-21 | Molybdenum-oxide-based photocatalyst with rich lattice defect sites, preparation method thereof and application thereof in photocatalytic nitrogen fixation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210707546.5A CN114950511B (en) | 2022-06-21 | 2022-06-21 | Molybdenum-oxide-based photocatalyst with rich lattice defect sites, preparation method thereof and application thereof in photocatalytic nitrogen fixation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114950511A CN114950511A (en) | 2022-08-30 |
| CN114950511B true CN114950511B (en) | 2023-10-24 |
Family
ID=82964897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210707546.5A Active CN114950511B (en) | 2022-06-21 | 2022-06-21 | Molybdenum-oxide-based photocatalyst with rich lattice defect sites, preparation method thereof and application thereof in photocatalytic nitrogen fixation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114950511B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105772048A (en) * | 2016-03-26 | 2016-07-20 | 吉林大学 | Molybdenum carbide and titanium dioxide compounded photocatalytic water-decomposing hydrogen production catalyst and preparation method of molybdenum carbide and titanium dioxide compounded photocatalytic water-decomposing hydrogen production catalyst |
| CN109999840A (en) * | 2019-04-10 | 2019-07-12 | 中南大学 | A kind of molybdenum carbide (MoC) hydrogen sulfide selective oxidation-desulfurizing catalyst and preparation method thereof |
| CN111468151A (en) * | 2020-04-24 | 2020-07-31 | 宁夏大学 | Mo with lamellar structure2C cocatalyst, preparation and application |
-
2022
- 2022-06-21 CN CN202210707546.5A patent/CN114950511B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105772048A (en) * | 2016-03-26 | 2016-07-20 | 吉林大学 | Molybdenum carbide and titanium dioxide compounded photocatalytic water-decomposing hydrogen production catalyst and preparation method of molybdenum carbide and titanium dioxide compounded photocatalytic water-decomposing hydrogen production catalyst |
| CN109999840A (en) * | 2019-04-10 | 2019-07-12 | 中南大学 | A kind of molybdenum carbide (MoC) hydrogen sulfide selective oxidation-desulfurizing catalyst and preparation method thereof |
| CN111468151A (en) * | 2020-04-24 | 2020-07-31 | 宁夏大学 | Mo with lamellar structure2C cocatalyst, preparation and application |
Non-Patent Citations (1)
| Title |
|---|
| Molybdenum Carbide Nanodots Enable Efficient Electrocatalytic Nitrogen Fixation under Ambient Conditions;Hui Cheng等;Advanced Materials;第30卷(第46期);第1803694（1-7）页、补充文件第S1-S9页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114950511A (en) | 2022-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112169819B (en) | g-C 3 N 4 /(101)-(001)-TiO 2 Preparation method and application of composite material | |
| Chen et al. | Noble-metal-free Ni 3 N/gC 3 N 4 photocatalysts with enhanced hydrogen production under visible light irradiation | |
| CN112007681A (en) | Preparation method and application of nitrogen-doped biological carbon-loaded monatomic iron | |
| Li et al. | Carbon vacancies improved photocatalytic hydrogen generation of g-C3N4 photocatalyst via magnesium vapor etching | |
| CN112371146A (en) | Preparation method and application of Z-type carbon nitride-iron oxide catalyst containing nitrogen defect structure | |
| CN113663693A (en) | Preparation method of indium zinc sulfide-titanium dioxide composite material and application of indium zinc sulfide-titanium dioxide composite material in production of hydrogen peroxide for wastewater treatment | |
| CN109225222B (en) | Composite photocatalyst and application thereof | |
| CN113908829A (en) | High-dispersion platinum-titanium dioxide photocatalyst and preparation method and application thereof | |
| CN113578358B (en) | Pt/NVC-g-C 3 N 4 Photocatalytic material and preparation method and application thereof | |
| Su et al. | Excellent dispersion and charge separation of SrTiO3-TiO2 nanotube derived from a two-step hydrothermal process for facilitating hydrogen evolution under sunlight irradiation | |
| CN111482172A (en) | Composite nano material of CuO/defect titanium dioxide and application thereof | |
| CN114950511B (en) | Molybdenum-oxide-based photocatalyst with rich lattice defect sites, preparation method thereof and application thereof in photocatalytic nitrogen fixation | |
| WO2024011905A1 (en) | Metal-supported spinel nickel manganite nanosphere aerogel, preparation method therefor and use thereof | |
| CN115430451B (en) | Iron-titanium co-doped porous graphite phase carbon nitride photo-Fenton catalyst and preparation method and application thereof | |
| CN109078644B (en) | Graphene-loaded Bi-BiOCl-TiO2Photocatalyst and preparation method thereof | |
| CN107442098B (en) | Strontium titanate catalyst for preparing hydrogen by photolyzing water by adopting visible light and preparation method | |
| CN114308061B (en) | NiAu bimetallic alloy nano-catalyst and synthesis and application thereof | |
| CN113680359A (en) | Tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material and preparation method and application thereof | |
| CN110523425B (en) | Molybdenum dioxide/nitrogen doped reduced graphene full-spectrum response photocatalyst and preparation method thereof | |
| CN113546658A (en) | Two-dimensional layered ternary nano composite photocatalyst and preparation method and application thereof | |
| CN109225297B (en) | Composite catalyst QDs-SISCN and preparation method and application thereof | |
| Yang et al. | Aerogel for Highly Efficient Photocatalytic Degradation | |
| CN114289065B (en) | Preparation method and application of metal ion doped x-MOF-74 photocatalyst | |
| CN114797932B (en) | Bimetallic 3D unique honeycomb-shaped carbon dioxide reduction catalyst and preparation method and application thereof | |
| CN113019403B (en) | Double Z-type Bi loaded with cocatalyst2MoO6/Bi2WO6\ AgI/Ag photocatalyst and application thereof |
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 |