CN110876951A - Composite material containing metal oxide, preparation method and application thereof - Google Patents
Composite material containing metal oxide, preparation method and application thereof Download PDFInfo
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- CN110876951A CN110876951A CN201811039766.5A CN201811039766A CN110876951A CN 110876951 A CN110876951 A CN 110876951A CN 201811039766 A CN201811039766 A CN 201811039766A CN 110876951 A CN110876951 A CN 110876951A
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- composite material
- metal oxide
- carbon nitride
- metal
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- 239000002131 composite material Substances 0.000 title claims abstract description 102
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 86
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 98
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011159 matrix material Substances 0.000 claims abstract description 32
- 239000002923 metal particle Substances 0.000 claims abstract description 23
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005286 illumination Methods 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 78
- 239000002184 metal Substances 0.000 claims description 78
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 230000001699 photocatalysis Effects 0.000 claims description 40
- 239000000758 substrate Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 17
- 238000006317 isomerization reaction Methods 0.000 claims description 16
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 15
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 15
- 235000002867 manganese chloride Nutrition 0.000 claims description 15
- 239000011565 manganese chloride Substances 0.000 claims description 15
- 229940099607 manganese chloride Drugs 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000446 fuel Substances 0.000 abstract description 10
- 230000005284 excitation Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 description 48
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 20
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- 229910021642 ultra pure water Inorganic materials 0.000 description 15
- 239000012498 ultrapure water Substances 0.000 description 15
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- 229920000877 Melamine resin Polymers 0.000 description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 229910052724 xenon Inorganic materials 0.000 description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 7
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- 238000009210 therapy by ultrasound Methods 0.000 description 6
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
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- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/31—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of rings
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/86—Ring systems containing bridged rings containing four rings
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention provides a composite material and a preparation method and application thereof. Wherein the composite material comprises: a carbon nitride matrix having a sheet structure; the auxiliary agent is loaded on the carbon nitride matrix and comprises metal oxide particles and elemental metal particles, wherein the metal oxide particles are suitable for attracting holes, and the elemental metal particles are suitable for attracting electrons. The inventor finds that the composite material is simple in structure and easy to realize, has high reducing capacity under the excitation of sunlight, can effectively reduce water to obtain hydrogen under the illumination condition, and can also isomerize norbornadiene with high efficiency to obtain tetracyclic heptane, so that novel fuel hydrogen energy and tetracyclic heptane can be prepared by utilizing renewable energy, and the composite material is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a composite material, a preparation method and application thereof, and more particularly relates to a composite material, a preparation method of the composite material and application of the composite material in photocatalytic hydrogen production and preparation of tetracycloheptane by photochemical isomerization of norbornadiene.
Background
At present, the development and utilization of renewable energy sources are more urgent. Renewable energy mainly includes solar energy, wind energy, water energy, etc., wherein solar energy is considered as one of the most promising alternative energy sources, and efficient utilization and conversion of solar energy is a current research hotspot. At present, the synthesis of new fuels by using solar energy is receiving more and more attention.
The synthesis of the novel fuel has important significance in the fields of machinery, war industry, aerospace and the like. The hydrogen energy has the advantages of high heat value, cleanness, environmental protection and the like, and is one of green energy sources with the greatest prospect. The double-component low-temperature liquid propellant consisting of liquid hydrogen and liquid oxygen has important application in communication satellites, space shuttles and other carrier rockets. Besides liquid hydrogen, tetracycloheptane is also a high-energy aerospace hydrocarbon fuel with excellent performance. Tetracycloheptane is a typical high-tension cage-like liquid hydrocarbon with a density of up to 0.98g cm-3The freezing point is lower than-40 ℃, the stability is good, the catalyst can be safely stored and transported, and the catalyst can be prepared by photocatalysis isomerization of norbornadiene. The development of a novel and efficient synthesis method of hydrogen and tetracycloheptane is a research focus from the past.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a composite material which can effectively generate electrons and holes under the excitation of sunlight, has low recombination rate of the electrons and the holes and strong reduction capability, and is suitable for photocatalytic hydrogen production or preparation of tetracycloheptane by photochemical isomerization of norbornadiene.
In one aspect of the invention, the invention provides a composite material. According to an embodiment of the invention, the composite material comprises: a carbon nitride matrix having a sheet structure; the auxiliary agent is loaded on the carbon nitride matrix and comprises metal oxide particles and elemental metal particles, wherein the metal oxide particles are suitable for attracting holes, and the elemental metal particles are suitable for attracting electrons. The inventor finds that the composite material is simple in structure and easy to realize, under the excitation action of sunlight, the carbon nitride can generate electrons and holes, the metal oxide attracts the holes, the metal simple substance attracts electrons, the utilization rate of the electrons and the holes is improved, the utilization rate of light energy can be improved, the electrons and the holes can be effectively separated under the combined action of the metal oxide and the metal simple substance, the recombination rate of the electrons and the holes is reduced, the composite material has high reduction capacity, water can be effectively reduced under the illumination condition to obtain hydrogen, norbornadiene can be efficiently isomerized to obtain tetracycloheptane, and therefore novel fuel hydrogen energy and tetracycloheptane can be prepared by utilizing renewable energy sources, and the composite material is suitable for large-scale production.
According to an embodiment of the present invention, the elemental metal particles are formed on the surfaces of the carbon nitride substrate and the metal oxide particles. Therefore, the position relation between the metal simple substance and the metal oxide is more favorable for separating electrons and holes, so that the composite material has stronger reducing capability, and the capability of preparing hydrogen by photocatalysis and preparing tetracycloheptane by photocatalysis and isomerization of norbornadiene is stronger.
According to an embodiment of the present invention, the metal oxide particles have a particle size of 10 nm to 20 nm. Therefore, the specific surface area of the metal oxide particles is appropriate, the capacity of capturing holes is strong, and the holes can be effectively separated from electrons.
According to the embodiment of the invention, the particle size of the metal simple substance particles is 3 nm-8 nm. Therefore, the specific surface area of the metal simple substance is appropriate, the capability of capturing electrons is strong, and the electrons and the holes can be effectively separated.
According to an embodiment of the invention, the composite material comprises, based on the total mass of the composite material: 0.5 to 10 wt% of said metal oxide; 0.1-5 wt% of the elemental metal; and the balance of the carbon nitride matrix. Therefore, the composite material has stronger capability of separating and transmitting electrons and holes and stronger reduction capability, and is more favorable for preparing hydrogen by photocatalysis and preparing tetracycloheptane by photocatalysis and isomerization of norbornadiene.
According to an embodiment of the present invention, the metal oxide includes manganese oxide, and the elemental metal includes at least one of platinum, gold, and silver. Therefore, the metal oxide has low price, strong capacity of attracting and transmitting holes and strong capacity of attracting and transmitting electrons by the metal, can efficiently utilize light energy, improves the utilization rate of photo-generated electrons and holes, has high separation efficiency of the electrons and the holes, and ensures that the composite material has strong reduction capacity.
In another aspect of the invention, the invention provides a method of making a composite material as hereinbefore described. According to an embodiment of the invention, the method comprises: providing a carbon nitride substrate; metal oxide particles and elemental metal particles are formed on the surface of the carbon nitride substrate. The inventor finds that the method is simple and convenient to operate and easy to implement, and the composite material with the characteristics and the advantages can be prepared.
According to an embodiment of the present invention, forming the metal oxide particles and the elemental metal particles on the surface of the carbon nitride substrate includes: performing a first reaction after mixing the carbon nitride substrate, the metal salt and the sodium hydroxide solution to support the metal oxide particles on the carbon nitride substrate; and mixing the carbon nitride matrix loaded with the metal oxide particles with a metal precursor, and carrying out a second reaction under the illumination condition so as to obtain the composite material. Therefore, the metal oxide particles form rich active sites for adsorption and deposition of the metal simple substance particles, so that part of the metal simple substance particles are formed on the surfaces of the metal oxide particles, and stronger interaction between the metal oxide and the metal simple substance is formed, so that the separation of electrons and holes is more efficient, the photocatalytic performance of the composite material is improved, and the photocatalytic hydrogen production and the isomerization of norbornadiene to generate tetracycloheptane are facilitated.
According to an embodiment of the invention, the temperature of the first reaction is 40-80 ℃ and the time is 2-4 h. Therefore, the effect of forming the metal oxide particles is better, and further, the separation of the photo-generated electrons and the holes is facilitated.
According to an embodiment of the invention, the concentration of the sodium hydroxide solution is 4-12 g/L. The size of the metal oxide particles can thereby be optimized to enhance the catalytic activity of the composite material.
According to an embodiment of the invention, the time of the second reaction is 2-4 h. Therefore, the effect of forming the metal simple substance particles is better, even partial metal simple substance particles can be effectively formed on the surfaces of the metal oxide particles, the interaction between the metal simple substance and the metal oxide is favorably improved, and the separation efficiency of electrons and holes is favorably improved.
According to an embodiment of the invention, the metal salt is selected from at least one of manganese chloride, manganese nitrate and manganese sulphate. Thus, the metal salt is widely available and inexpensive, and the metal oxide particles obtained from the metal salt have a strong ability to attract electrons.
According to an embodiment of the present invention, the metal precursor includes at least one of chloroplatinic acid, chloroauric acid, and silver nitrate. Therefore, the metal precursor is suitable for being reduced into metal simple substance particles under the illumination condition, the reduction efficiency is high, the obtained metal simple substance particles have high electron attracting capacity, and the separation efficiency of photo-generated electrons and holes is improved.
In another aspect of the invention, the invention provides the use of the composite material in photocatalytic hydrogen production and photochemical isomerization of norbornadiene to produce tetracycloheptane. The inventor finds that the composite material has high efficiency in preparing hydrogen and tetracyclic heptane by photocatalysis, is beneficial to obtaining novel fuels, and is suitable for large-scale application.
The invention can at least obtain the following beneficial effects:
1. by simple means (e.g. atmospheric oil bath)2Closely grown at g-C3N4The electronic transmission between the two is facilitated; pt is grown on g-C by means of photo-deposition without any chemical reducing agent and organic solvent3N4The above step (1);
2. in g-C3N4Adding MnO simultaneously2And Pt, which is helpful for promoting the generation of hydrogen and the occurrence of norbornadiene isomerization reaction;
3. the norbornadiene photocatalytic isomerization reaction is carried out under the condition of no solvent, so that the separation of products and the recovery of a catalyst are facilitated.
4. The catalyst has the advantages of simple preparation method, low price of raw materials, rich sources, simple and convenient operation of the preparation process and low preparation cost.
5. The photocatalytic hydrogen production activity and norbornadiene isomerization activity of the composite material are respectively improved by 4-39 times and 5-10 times compared with pure carbon nitride.
Drawings
FIG. 1 is a schematic flow diagram of a method for preparing a composite material according to one embodiment of the present invention.
Fig. 2 is a schematic flow chart of a method for forming metal oxide particles and elemental metal particles on the surface of a carbon nitride substrate according to an embodiment of the present invention.
FIG. 3 is a transmission electron micrograph of the composite material of example 1.
Fig. 4 is an X-ray diffraction pattern (XRD pattern) of the carbon nitride matrix and the composite material in example 1.
FIG. 5 is an infrared spectrum of the composite material of example 1.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the invention, the invention provides a composite material. According to an embodiment of the invention, the composite material comprises: a carbon nitride matrix having a sheet structure; the auxiliary agent is loaded on the carbon nitride matrix and comprises metal oxide particles and elemental metal particles, wherein the metal oxide particles are suitable for attracting holes, and the elemental metal particles are suitable for attracting electrons. The inventor finds that the composite material is simple in structure and easy to realize, has high reducing capacity under the irradiation of sunlight, can effectively reduce water to obtain hydrogen under the illumination condition, and can also efficiently isomerize norbornadiene to obtain tetracyclic heptane, so that novel fuel hydrogen energy and tetracyclic heptane can be prepared by utilizing renewable energy photocatalysis, and the composite material is suitable for large-scale production.
According to the embodiment of the invention, under the excitation of sunlight, carbon nitride (g-C)3N4) The matrix can generate electrons and holes, the metal oxide loaded on the surface of the carbon nitride matrix attracts the holes, the metal simple substance attracts the electrons, the electrons and the holes can be effectively separated, the recombination rate of the electrons and the holes is reduced, the number of the electrons in the composite material is large, the composite material has high reduction capability, the utilization rate of the electrons and the holes can be improved under the combined action of the metal oxide and the metal simple substance, the utilization rate of light energy can be improved, water can be effectively reduced under the illumination condition to obtain hydrogen, and norbornadiene can be efficiently isomerized to obtain tetracycloheptane; when the composite material is used for preparing hydrogen or tetracycloheptane under the excitation of sunlight, the effect of preparing novel fuel hydrogen energy and tetracycloheptane by using renewable energy sources can be realized, the preparation cost is low, and the preparation method is suitable for large-scale production. According to the embodiment of the invention, if the catalyst only contains the carbon nitride substrate, electrons and holes generated under the illumination condition are easy to recombine, so that the reduction capability of the catalyst is weak, and hydrogen and tetracycloheptane can hardly be produced by photocatalysis; if the composite material only contains the carbon nitride matrix and the metal oxide particles or metal simple substance particles loaded on the carbon nitride matrix, the separation effect of electrons and holes generated by the carbon nitride matrix under the illumination condition is poor, so that the quantity of usable photogenerated electrons in the composite material is less, the reduction capability of the composite material is weaker, the quantity of photocatalytic hydrogen production is less, the yield of tetracycloheptane is lower, the catalytic activity is lower, and the requirement for synthesizing a novel fuel cannot be met.
According to the embodiment of the invention, in order to enable the composite material to have high catalytic activity, the metal oxide and the metal simple substance are in a granular shape. Therefore, the specific surface area of the metal oxide and the metal simple substance is proper, the capability of attracting electrons and holes is strong, the capability of separating photo-generated electrons and holes is excellent, and the composite material has more available photo-generated electrons under the illumination condition, so that the composite material has strong reducibility, and the photocatalytic activity of the composite material can be obviously improved.
In some embodiments of the present invention, in order to make the catalytic activity of the composite material higher, the elemental metal particles are formed on the surfaces of the carbon nitride matrix and the metal oxide particles. Therefore, the structure between the metal simple substance particles and the metal oxide particles is tighter, the separation efficiency of electrons and holes is more favorably improved, the available electron quantity in the composite material is higher, the reduction capability is stronger, and the capability of preparing hydrogen by photocatalysis and preparing tetracycloheptane by photocatalysis and isomerization of norbornadiene is stronger.
According to embodiments of the present invention, the metal oxide particles have a particle size of 10 nm to 20 nm (e.g., 10 nm, 10.5 nm, 11 nm, 11.5 nm, 12 nm, 12.5 nm, 13 nm, 13.5 nm, 14 nm, 14.5 nm, 15 nm, 15.5 nm, 16 nm, 16.5 nm, 17 nm, 17.5 nm, 18 nm, 18.5 nm, 19 nm, 19.5 nm, 20 nm, etc.). Therefore, the specific surface area of the metal oxide particles is appropriate, the capacity of capturing holes is strong, and the holes can be effectively separated. With respect to the above diameter range, when the particle diameter of the metal oxide particles is too small, the ability of the metal oxide to capture holes and transport holes is relatively weak, resulting in relatively poor photo-generated charge separation effect; when the particle size of the metal oxide particles is too large, the specific surface area of the metal oxide particles is small, and the ability to attract holes is relatively weak, resulting in relatively poor photo-generated charge separation effect. The particle diameter of the metal oxide particle refers to the maximum value of the distance between any two points in the metal oxide particle.
According to the embodiment of the invention, the particle size of the elemental metal particles is 3 nm to 8 nm (e.g., 3 nm, 3.5 nm, 4 nm, 4.5 nm, 5 nm, 5.5 nm, 6 nm, 6.5 nm, 7 nm, 7.5 nm, 8 nm, etc.). Therefore, the specific surface area of the metal simple substance particles is appropriate, the capability of capturing electrons is strong, and the electrons can be effectively separated. Compared with the diameter range, when the particle size of the metal simple substance particles is too small, the electron capturing capability and the electron transferring capability of the metal simple substance are relatively weak, so that the photo-generated charge separation effect is relatively poor; when the particle size of the metal simple substance particles is too large, the specific surface area of the metal simple substance is small, and the ability of attracting electrons is relatively weak, so that the effect of separating photo-generated charges is relatively poor. The particle size of the metal simple substance particles refers to the maximum value of the distance between any two points in the metal simple substance particles.
According to an embodiment of the present invention, the metal oxide includes manganese oxide, and the elemental metal includes at least one of platinum, gold, and silver. Therefore, the metal oxide has low price, strong capacity of attracting and transmitting holes, strong capacity of attracting and transmitting electrons by the metal simple substance, effective utilization of light energy, improvement of the utilization rate of photo-generated electrons and holes, high separation efficiency of the electrons and the holes and strong reduction capacity of the composite material.
According to an embodiment of the invention, the composite material comprises, based on the total mass of the composite material: 0.5 to 10 wt% (e.g., 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, etc.) of the metal oxide; 0.1-5 wt% (e.g., 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, etc.) of the elemental metal; and the balance of the carbon nitride matrix. Therefore, the content of the metal oxide and the metal simple substance is proper, the metal oxide particles or the metal simple substance particles can be prevented from becoming charge recombination centers, the composite material has stronger capability of separating and transmitting electrons and holes and stronger reduction capability, and is more favorable for preparing hydrogen by photocatalysis and preparing tetracycloheptane by photocatalysis and isomerization of norbornadiene. Compared with the content range, when the content of the metal oxide particles is too high or the content of the metal simple substance particles is too high, the light absorption active sites on the surface of the carbon nitride can be covered, so that the quantity of photo-generated electrons is relatively small, and the catalytic reaction efficiency is further reduced; when the content of the metal oxide particles is too low or the content of the metal simple substance particles is too low, sufficient charge separation and reactive sites are not provided enough to improve the catalytic activity of the composite material and further promote the reaction.
In another aspect of the invention, the invention provides a method of making a composite material as hereinbefore described. According to an embodiment of the present invention, referring to fig. 1, the method includes:
s100: a carbon nitride substrate is provided.
According to an embodiment of the present invention, the carbon nitride matrix is obtained by calcining a nitrogen-containing precursor. Therefore, the operation is simple and convenient, and the carbon nitride matrix with good service performance can be obtained. According to an embodiment of the invention, the nitrogen-containing precursor comprises at least one of melamine, dicyandiamide and urea. Therefore, the material has wide sources and low price, and the carbon nitride matrix obtained by roasting has good service performance.
According to an embodiment of the present invention, the specific steps of preparing the carbon nitride matrix may be: the nitrogen-containing precursor is calcined under the condition of 520-550 ℃ (such as 520 ℃, 530 ℃, 540 ℃, 550 ℃ and the like) in the air atmosphere for 2-4h (such as 2h, 2.5h, 3h, 3.5h, 4h and the like). Therefore, the operation is simple and convenient, the realization is easy, and the prepared carbon nitride matrix can effectively generate electrons and holes under the illumination condition so as to be beneficial to separating the electrons and the holes by the metal oxide and the metal simple substance.
S200: metal oxide particles and elemental metal particles are formed on the surface of the carbon nitride substrate.
According to an embodiment of the present invention, referring to fig. 2, forming metal oxide particles and elemental metal particles on a surface of the carbon nitride substrate includes:
s210: the carbon nitride substrate, the metal salt, and the sodium hydroxide solution are mixed and then subjected to a first reaction to support the metal oxide particles on the carbon nitride substrate.
According to an embodiment of the present invention, before the first reaction is performed, the carbon nitride matrix may be ultrasonically dispersed in water, and then the mixed solution may be placed in a constant temperature water bath for dispersion, so as to facilitate the subsequent steps.
According to an embodiment of the invention, the metal salt is selected from at least one of manganese chloride, manganese nitrate and manganese sulphate. Thus, the metal salt is widely available and inexpensive, and the metal oxide particles obtained from the metal salt have a strong ability to attract electrons.
According to an embodiment of the invention, the concentration of the sodium hydroxide solution is 4-12g/L (e.g., 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L, 11g/L, 12g/L, etc.). The particle size of the manganese dioxide can be optimized to improve the catalytic activity of the composite material and thus improve the reaction efficiency. When the concentration of the sodium hydroxide solution is too low, the metal salt precursor cannot be completely precipitated, and the effect of forming the metal oxide is relatively poor; when the concentration of the sodium hydroxide solution is too high, the particle size of the metal oxide particles is relatively too large and the particles are easily agglomerated.
According to an embodiment of the present invention, the temperature of the first reaction is 40-80 ℃ (e.g., 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, etc.) and the time is 2-4h (e.g., 2h, 2.5h, 3h, 3.5h, 4h, etc.). Therefore, the metal oxide particles can be grown on the surface of the carbon nitride substrate in situ, the effect of forming the metal oxide particles is better, and the separation of photo-generated electrons and holes is further facilitated. When the temperature of the first reaction is too high or the time is too long with respect to the above reaction temperature and time ranges, the resulting metal oxide particles may be agglomerated; when the temperature of the first reaction is too low or the time is too short, the precipitation of the metal oxide is incomplete, and the effect of forming metal oxide particles is relatively poor. According to the embodiment of the invention, the first reaction can be carried out under the condition of a normal-pressure oil bath, and the operation is simple and convenient.
The metal salt and sodium hydroxide can form a metal oxide under the conditions of the first reaction.
S220: and mixing the carbon nitride matrix loaded with the metal oxide particles with a metal precursor, and carrying out a second reaction under the illumination condition so as to obtain the composite material.
According to the embodiment of the invention, the metal oxide particles loaded on the carbon nitride substrate provide abundant active sites for the adsorption and deposition of the metal simple substance particles, so that part of the metal simple substance particles can be formed on the surfaces of the metal oxide particles, the structures of the metal oxide particles and the metal simple substance particles are tighter, and stronger interaction between the metal oxide and the metal simple substance is formed, so that the separation of electrons and holes is more efficient, the photocatalysis performance of the composite material is improved, the process of synthesizing the metal simple substance particles is green and pollution-free, and no chemical oxidant or reducing agent is needed.
According to an embodiment of the present invention, the metal precursor includes at least one of chloroplatinic acid, chloroauric acid, and silver nitrate. Therefore, the metal precursor is suitable for being reduced into a metal simple substance under the illumination condition, the metal simple substance can be synthesized in situ, the reduction efficiency is high, the obtained metal simple substance has high capability of attracting electrons, and the separation efficiency of photo-generated electrons and holes is improved.
According to an embodiment of the present invention, the above-mentioned lighting condition may be as follows: using a 300W xenon lamp at constant power (60-120 Mw/cm)2) The second reaction is carried out for 2-4h (such as 2h, 2.5h, 3h, 3.5h, 4h and the like). Therefore, the metal simple substance particles can be deposited on the surfaces of the carbon nitride matrix or the metal oxide particles in situ, the effect of forming the metal simple substance particles is good, the interaction between the metal simple substance and the metal oxide is favorably improved, and the separation efficiency of electrons and holes is favorably improved. Compared with the above reaction time, when the second reaction time is too short, the effect of photo-reduction of the metal precursor is relatively poor, and the effect of forming a metal simple substance is relatively poor, resulting in relatively poor photocatalytic activity of the composite material; when the time of the second reaction is too long, energy is wasted.
According to an embodiment of the invention, the second reaction is carried out under stirring. Therefore, the shape of the metal simple substance is favorably regulated and controlled, the shape of the metal simple substance is metal simple substance particles, and the photocatalytic activity of the composite material is higher.
According to an embodiment of the present invention, the specific steps for preparing the composite material may be as follows:
(1) preparation of carbon nitride matrix: weighing a certain mass of nitrogen-containing precursor, and roasting at 520-550 ℃ for 2-4h in an air atmosphere.
(2) Forming metal oxide particles on a carbon nitride substrate: weighing 0.1-3 g of carbon nitride matrix, ultrasonically dispersing the carbon nitride matrix in a round bottom flask containing 100mL of water, placing the flask in an oil bath at 60 ℃ for 30min, adding 0.01-0.3 g of anhydrous manganese chloride into the system, stirring to fully dissolve the anhydrous manganese chloride, adding 2-48 mL of 4g/L NaOH solution, reacting for 3h, centrifugally separating the solid in the system, washing, and drying to obtain MnO2/g-C3N4。
(3) Forming elemental metal particles on the carbon nitride substrate on which the metal oxide particles are formed: weighing 0.1-3 g MnO2/g-C3N4In a photocatalytic reactor containing 100-150 mL of water and triethanolamine, uniformly dispersing by ultrasonic waves, adding a metal precursor, stirring, and illuminating for 2-4h under a 300W xenon lamp constant current (60-120mW/cm 2). And recovering the obtained solid, and drying the solid overnight in vacuum at the temperature of 60 ℃ to obtain the required composite material.
In another aspect of the invention, the invention provides the use of the composite material in photocatalytic hydrogen production and photochemical isomerization of norbornadiene to produce tetracycloheptane. The inventor finds that the composite material has high efficiency in preparing hydrogen and tetracyclic heptane by photocatalysis, is beneficial to obtaining novel fuels, and is suitable for large-scale application.
According to the embodiment of the invention, the hydrogen production by photocatalysis of the composite material is to put the composite material into water and carry out the hydrogen production by photocatalysis under the illumination condition, and the hydrogen production principle is as follows: under the condition of illumination, a large number of photo-generated electrons and photo-generated holes are generated in the composite material, the holes are consumed by utilizing a hole sacrificial agent (such as triethanolamine), and the large number of photo-generated electrons in the composite material can reduce water to generate hydrogen when meeting water. In some embodiments of the present invention, the photocatalytic hydrogen production is performed by: A300W xenon lamp is used as a light source (the current is controlled to be 15A), the reaction temperature of photocatalytic hydrogen production is 0 ℃, 0.05g of composite material is dispersed into an aqueous solution containing 10% volume fraction of cavity sacrificial agent triethanolamine during reaction, argon is introduced to purge a mixed solution for 30min, the lamp is turned on for reaction, samples are taken every half an hour during the reaction, and the gas product is subjected to chromatographic quantitative analysis. Therefore, the operation is simple and convenient, and the realization is easy.
According to the embodiment of the invention, the specific operation steps for isomerizing norbornadiene photochemical valence bond by using the composite material to prepare the tetracycloheptane can be as follows: dispersing the composite material into a norbornadiene solution containing a photosensitizer (e.g., tetraethyl michael ketone, etc.) to obtain a mixed solution, irradiating the mixed solution with light to obtain tetracycloheptane, compared with the traditional process for preparing the tetracycloheptane by catalyzing norbornadiene photochemical valence bond isomerization by using the liquid photosensitizer, the composite material and the photosensitizer have the migration of photo-generated charges, promote the charge separation and improve the efficiency of the photo-generated charges for isomerization reaction, so that the tetracycloheptane has higher yield and lower preparation cost, and the solvent is not used in the preparation method, and the yield of the tetracycloheptane is still higher, which shows that the dependence on the solvent can be eliminated when the composite material is used for preparing the tetracycloheptane, so that the improvement of the amount of reactants treated by the composite material in unit volume is facilitated, the composite material can be recycled, and the preparation cost is further reduced.
Embodiments of the present application are described below.
Examples
1. Photocatalytic hydrogen production
The photocatalytic hydrogen production reaction adopts an external illumination type quartz reactor, a light source is a 300W xenon lamp (light emitted by the xenon lamp is used for simulating sunlight), the current is controlled to be 15A, and the reaction temperature is 0 ℃. And (3) dispersing 0.05g of the composite material into a water solution containing 10% of triethanolamine by volume fraction during reaction, introducing argon to purge for 30min, then turning on a lamp to perform reaction, sampling every half an hour during the reaction process, and performing chromatographic quantitative analysis on a gas product.
2. Tetracycloheptane synthesis
The tetracycloheptane synthesis reaction adopts an internal illumination type quartz reactor, a 400W high-pressure mercury lamp as a light source, and the reaction temperature is room temperature. Mixing 150mL of norbornadiene and 3g of tetraethyl michael ketone, adding 1.5g of composite catalyst, fully stirring and mixing, transferring the mixture into a reactor, turning on a lamp, continuously stirring in the reaction process, transferring the product into a rotary evaporator after reacting for 20 hours, and distilling at the temperature of 60-70 ℃ under normal pressure to obtain the tetracycloheptane product.
Example 1
Preparing a composite material:
weighing 15g of melamine, roasting the melamine in a tubular atmosphere furnace at 550 ℃ for 4h in the air atmosphere at the heating rate of 2 ℃/min, grinding the obtained yellow-white solid, centrifuging, washing with water and ethanol for a plurality of times to obtain carbon nitride (g-C)3N4) And (5) standby. Weighing 3g of carbon nitride in a round-bottom flask, adding 100mL of ultrapure water, performing ultrasonic treatment for 1h to uniformly disperse the carbon nitride, performing oil bath at 60 ℃ for 30min, adding 0.15g of anhydrous manganese chloride into the system, stirring to fully dissolve the anhydrous manganese chloride, dropwise adding 10mL of 12g/L NaOH solution, continuously stirring in the reaction process, centrifugally separating the reaction solution after 3h, washing, and drying to obtain a solid, namely MnO2/g-C3N4. Weighing 2g MnO2/g-C3N4Adding 90mL of ultrapure water and 10mL of triethanolamine as a cavity sacrificial agent into a photocatalytic reactor, ultrasonically dispersing the ultrapure water and the triethanolamine uniformly, adding 0.04g of chloroplatinic acid, stirring, and illuminating for 3 hours under the constant current (15A) of a 300W xenon lamp. Centrifuging the obtained solid, washing, and vacuum drying at 60 deg.C overnight to obtain the desired catalyst (MnO)2-Pt/g-C3N4)。
The transmission electron microscope test result of the composite material is shown in figure 3, and the XRD characterization result and the infrared spectrogram of the composite material are respectively referred to figure 4 and figure 5.
Example 2:
weighing 15g of melamine, roasting the melamine in a tubular atmosphere furnace at 550 ℃ for 4h in the air atmosphere at the heating rate of 2 ℃/min, grinding the obtained yellow-white solid, centrifuging, washing with water and ethanol for several times to obtain carbon nitrideThe application is as follows. Weighing 3g of carbon nitride in a round-bottom flask, adding 100mL of ultrapure water, performing ultrasonic treatment for 1h to uniformly disperse the carbon nitride, performing oil bath at 60 ℃ for 30min, adding 0.06g of anhydrous manganese chloride into the system, stirring to fully dissolve the anhydrous manganese chloride, dropwise adding 4mL of 12g/L NaOH solution, continuously stirring in the reaction process, centrifugally separating the reaction solution after 3h, washing, and drying to obtain a solid, namely MnO2/g-C3N4. Weighing 2gMnO2/g-C3N4Adding 90mL of ultrapure water and 10mL of triethanolamine into a photocatalytic reactor, performing ultrasonic treatment to uniformly disperse the ultrapure water and the triethanolamine, adding 0.04g of chloroauric acid, stirring, and illuminating for 3 hours under a 300W xenon lamp constant current (15A). Centrifuging the obtained solid, washing, and vacuum drying at 60 deg.C overnight to obtain the desired catalyst (MnO)2-Au/g-C3N4)。
Examples 3 to 14
Examples 3-14 composites were prepared as in example 1, except as indicated in the following table:
comparative example 1
Preparing a composite material:
weighing 15g of melamine, roasting the melamine in a tubular atmosphere furnace at 550 ℃ for 4h in the air atmosphere at the heating rate of 2 ℃/min, grinding the obtained yellow-white solid, centrifuging, washing with water and ethanol for a plurality of times to obtain carbon nitride (g-C)3N4) And (5) standby. Weighing 3g of carbon nitride in a round-bottom flask, adding 100mL of ultrapure water, performing ultrasonic treatment for 1h to uniformly disperse the carbon nitride, performing oil bath at 60 ℃ for 30min, adding 0.15g of anhydrous manganese chloride into the system, stirring to fully dissolve the anhydrous manganese chloride, dropwise adding 10mL of 12g/L NaOH solution, continuously stirring in the reaction process, centrifugally separating the reaction solution after 3h, washing, and drying to obtain a solid, namely MnO2/g-C3N4。
Comparative example 2
Preparing a composite material:
weighing 2g g-C3N4Adding 90mL of ultrapure water and 10mL of triethanolamine into a photocatalytic reactor, ultrasonically dispersing the ultrapure water and the triethanolamine uniformly, adding 0.04g of chloroplatinic acid, stirring, and illuminating for 3 hours under a 300W xenon lamp constant current (15A). Centrifuging the obtained solid, washing, and vacuum drying at 60 deg.C overnight to obtain the desired catalyst (Pt/g-C)3N4)。
Comparative example 3
The preparation of the composite material is the same as that of comparative example 2, except that the metal precursor in the comparative example is chloroauric acid, and the obtained composite material is Au/g-C3N4。
Comparative example 4
The preparation of the composite material is the same as that of comparative example 2, except that in the comparative example, the metal precursor is silver nitrate, and the obtained composite material is Ag/g-C3N4。
Comparative example 5
The preparation method of the composite material comprises the following steps:
weighing 15g of melamine, roasting the melamine in a tubular atmosphere furnace at 550 ℃ for 4h in the air atmosphere at the heating rate of 2 ℃/min, grinding the obtained yellow-white solid, centrifuging, washing with water and ethanol for a plurality of times to obtain carbon nitride (g-C)3N4) And (5) standby. Weighing 3g of carbon nitride in a round-bottom flask, adding 100mL of ultrapure water, performing ultrasonic treatment for 1h to uniformly disperse the carbon nitride, performing oil bath at 60 ℃ for 30min, adding 0.15g of anhydrous manganese chloride into the system, stirring to fully dissolve the anhydrous manganese chloride, dropwise adding 10mL of 5g/L NaOH solution, continuously stirring in the reaction process, centrifugally separating the reaction solution after 3h, washing, and drying to obtain a solid, namely MnO2/g-C3N4. Weighing 2g MnO2/g-C3N4Adding 90mL of ultrapure water and 10mL of triethanolamine as a cavity sacrificial agent into a photocatalytic reactor, ultrasonically dispersing the ultrapure water and the triethanolamine uniformly, adding 0.02g of chloroauric acid, stirring, and illuminating for 3 hours under the constant current (12A) of a 300W xenon lamp. Centrifuging the obtained solid, washing, and vacuum drying at 60 deg.C overnight to obtain the desired composite material (MnO)2-Au/g-C3N4)。
Comparative example 6
The preparation method of the composite material comprises the following steps:
weighing 15g of melamine, roasting the melamine in a tubular atmosphere furnace at 550 ℃ for 4h in the air atmosphere at the heating rate of 2 ℃/min, grinding the obtained yellow-white solid, centrifuging, washing with water and ethanol for a plurality of times to obtain carbon nitride (g-C)3N4) And (5) standby. Weighing 3g of carbon nitride in a round-bottom flask, adding 100mL of ultrapure water, performing ultrasonic treatment for 1h to uniformly disperse the carbon nitride, performing oil bath at 60 ℃ for 30min, adding 0.15g of anhydrous manganese chloride into the system, stirring to fully dissolve the anhydrous manganese chloride, dropwise adding 10mL of 24g/L NaOH solution, continuously stirring in the reaction process, centrifugally separating the reaction solution after 3h, washing, and drying to obtain a solid, namely MnO2/g-C3N4. Weighing 2g MnO2/g-C3N4Adding 90mL of ultrapure water and 10mL of triethanolamine as a cavity sacrificial agent into a photocatalytic reactor, ultrasonically dispersing the ultrapure water and the triethanolamine uniformly, adding 0.04g of chloroauric acid, stirring the mixture, and illuminating the mixture for 3 hours under the constant current (20A) of a 300W xenon lamp. Centrifuging the obtained solid, washing, and vacuum drying at 60 deg.C overnight to obtain the desired composite material (MnO)2-Au/g-C3N4)。
Comparative example 7
The composite material was prepared in the same manner as in example 1, except that the content of the metal oxide particles was 20 wt% and the content of the metal particles was 8 wt% in this comparative example.
Comparative example 8
The composite material was prepared in the same manner as in example 1, except that the content of the metal oxide particles was 0.2 wt% and the content of the metal particles was 0.05 wt% in this comparative example.
The experimental data for examples 1-14 and comparative examples 1-8 are shown in the following table.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A composite material, comprising:
a carbon nitride matrix having a sheet structure;
the auxiliary agent is loaded on the carbon nitride matrix and comprises metal oxide particles and elemental metal particles, wherein the metal oxide particles are suitable for attracting holes, and the elemental metal particles are suitable for attracting electrons.
2. The composite material according to claim 1, wherein the elemental metal particles are formed on the surfaces of the carbon nitride matrix and the metal oxide particles.
3. The composite material of claim 1, wherein the metal oxide particles have a particle size of 10 nm to 20 nm;
optionally, the particle size of the elemental metal particles is 3 nm to 8 nm.
4. The composite material according to claim 1, comprising, based on the total mass of the composite material:
0.5 to 10 wt% of said metal oxide;
0.1-5 wt% of the elemental metal; and
the balance of the carbon nitride matrix.
5. The composite material of claim 1, wherein the metal oxide comprises manganese oxide and the elemental metal comprises at least one of platinum, gold, and silver.
6. A method of making the composite material of any one of claims 1-5, comprising:
providing a carbon nitride substrate;
metal oxide particles and elemental metal particles are formed on the surface of the carbon nitride substrate.
7. The method of claim 6, wherein forming metal oxide particles and elemental metal particles on the surface of the carbon nitride substrate comprises:
performing a first reaction after mixing the carbon nitride substrate, the metal salt and the sodium hydroxide solution to support the metal oxide particles on the carbon nitride substrate;
and mixing the carbon nitride matrix loaded with the metal oxide particles with a metal precursor, and carrying out a second reaction under the illumination condition so as to obtain the composite material.
8. The method according to claim 7, wherein the temperature of the first reaction is 40-80 ℃ and the time is 2-4 h;
optionally, the concentration of the sodium hydroxide solution is 4-12 g/L;
optionally, the time of the second reaction is 2-4 h.
9. The method according to any one of claims 6 to 8, wherein the metal salt is selected from at least one of manganese chloride, manganese nitrate and manganese sulfate;
optionally, the metal precursor includes at least one of chloroplatinic acid, chloroauric acid, and silver nitrate.
10. Use of the composite material according to any one of claims 1 to 5 for photocatalytic hydrogen production and photochemical isomerization of norbornadiene to tetracycloheptane.
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