CN108607593B - Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application thereof - Google Patents
Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application thereof Download PDFInfo
- Publication number
- CN108607593B CN108607593B CN201810388355.0A CN201810388355A CN108607593B CN 108607593 B CN108607593 B CN 108607593B CN 201810388355 A CN201810388355 A CN 201810388355A CN 108607593 B CN108607593 B CN 108607593B
- Authority
- CN
- China
- Prior art keywords
- nanorod
- niobium pentoxide
- nitrogen
- cadmium sulfide
- doped graphene
- 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
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 64
- 239000002073 nanorod Substances 0.000 title claims abstract description 63
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 41
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 35
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 230000001699 photocatalysis Effects 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- -1 cadmium sulfide nanoparticle-modified niobium pentoxide Chemical class 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 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 description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 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 1
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 19
- 239000004065 semiconductor Substances 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 8
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 7
- 229910052979 sodium sulfide Inorganic materials 0.000 description 7
- 229910052724 xenon Inorganic materials 0.000 description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/39—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- 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
- 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
Abstract
The invention discloses a cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application thereof. The nitrogen-doped graphene is used as a carrier and an electron receiver of the photocatalyst with a multilevel structure, and the niobium pentoxide nanorod modified by the cadmium sulfide nanoparticles is used as a light capture body and an electron transfer body of the photocatalyst.
Description
The invention belongs to a cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst, a preparation method and application thereof, and a divisional application of patent applications with application numbers of 201610050573.4 and application dates of 2016, 1 and 26, and belongs to a product and an application part thereof.
Technical Field
The invention relates to a novel semiconductor-graphene composite photocatalyst for preparing hydrogen by catalytic decomposition reaction of water under visible light, in particular to a cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application of photocatalytic hydrogen production.
Background
The hydrogen energy has the characteristics of cleanness, high efficiency, environmental friendliness and the like, and is an ideal secondary energy source. At present, the main methods for producing hydrogen in large scale industry include water gas, water electrolysis, an ammonia decomposition method, a reaction of active metal and acid, a reaction of strong base and aluminum or silicon, a methanol cracking method and the like. The traditional hydrogen preparation method has the characteristics of mature and simple process and the like. But the reaction conditions are harsh, the requirements on production equipment are high, a large amount of energy is consumed, and the production cost is high. Some methods generate waste water and waste residues, and have certain influence on the environment. In addition, the hydrogen production by using fossil fuel only converts fossil energy into hydrogen energy, and cannot solve the problems of energy shortage and environmental pollution.
The hydrogen production method by photocatalytic water decomposition has shown wide application prospect in the aspects of solving the environmental pollution and energy crisis, and is generally concerned by researchers at home and abroad. The photocatalytic decomposition of water to produce hydrogen is the best way to convert solar energy into storable, readily available chemical energy. The photocatalytic water splitting hydrogen production has the advantages of mild reaction conditions, no secondary pollution, simple equipment, less investment and the like. The principle of hydrogen production by photolysis of water by taking a semiconductor as a catalyst is that solar light is absorbed by the catalyst, electrons of a valence band of the semiconductor are excited to a conduction band, and reduction reaction is carried out under the action of the electrons and water of the conduction band to produce hydrogen; the holes in the valence band of the semiconductor react with water to form oxygen. Therefore, a suitable photocatalytic water splitting catalyst should have appropriate conduction and valence band positions (the conduction band potential should be higher than the hydrogen electrode potential E (H)+/H2) Slightly negative, and the valence band potential should be higher than the oxygen electrode potential E (O)2/H2O) slightly positive). In addition, the catalyst for hydrogen production by photolysis of water also needs to satisfy the conditions of appropriate band gap (capable of absorbing sunlight), high stability, no light corrosion, low price and the like.
The niobium-based photocatalyst has the characteristics of good stability, no toxicity and the like, and is a semiconductor photocatalyst with development potential. But due to Nb2O5The band gap of the energy band is wide (3.1 eV), and the utilization rate of sunlight is low. All in oneIn the case of the photocatalyst, the photo-generated electrons and the photo-generated holes are easy to recombine, and the quantum efficiency is low, so that the photocatalytic activity is low. The niobium-based semiconductor and other semiconductors with narrow band gaps are compounded to form a heterojunction structure, so that the photoresponse range of the heterojunction structure can be expanded, the compounding of photo-generated electrons and electron holes is reduced, and the photocatalytic activity is improved.
Disclosure of Invention
The invention provides a preparation method of a cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst. The nitrogen-doped graphene is used as a carrier and an electron receiver of the photocatalyst with a multilevel structure, and the niobium pentoxide nanorod modified by the cadmium sulfide nanoparticles is used as a light capture body and an electron transfer body of the photocatalyst.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a preparation method of a cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst comprises the following steps:
(1) preparation of niobium pentoxide nanorod (NbR)
The niobium pentoxide nano-rod is synthesized by a hydrothermal method.
Ultrasonically dispersing the niobic acid into the mixed solvent, and stirring to obtain a mixed solution; then putting the mixed solution into a polytetrafluoroethylene inner sleeve high-pressure reaction kettle, aging at 100-200 ℃ for 20-40 hours, and sequentially carrying out suction filtration, deionized water washing and drying to obtain a solid; then heating the solid in a muffle furnace from room temperature to 400-700 ℃ at the speed of 5-20 ℃/min, then carrying out heat preservation roasting for 2-10 hours, and naturally cooling to room temperature to obtain NbR;
(2) preparation of cadmium sulfide nanoparticle modified niobium pentoxide nanorod composite semiconductor (NbR/CdS)
Dispersing niobium pentoxide nanorods in an alcohol solvent, and adding a cadmium ion trapping agent after ultrasonic dispersion; then carrying out reflux reaction for 2-5 hours, cooling to room temperature, then dropwise adding a cadmium acetate solution, and stirring for 50-75 minutes; then Na is added2S solution(ii) a Stirring for 50-75 minutes to obtain a mixture; placing the mixture in a polytetrafluoroethylene inner sleeve high-pressure reaction kettle, and reacting for 20-30 hours at 150-200 ℃; then, carrying out suction filtration, deionized water washing and drying on the reaction solution in sequence to obtain a cadmium sulfide nanoparticle modified niobium pentoxide nanorod (NbR/CdS);
(3) preparation of cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst (NbR/CdS/NGR)
Mixing the cadmium sulfide nanoparticle modified niobium pentoxide nanorod NbR/CdS prepared in the step with the nitrogen-doped graphene suspension and deionized water, and carrying out ultrasonic reaction for 1-3 hours; then carrying out centrifugal treatment, washing the obtained solid by deionized water, and drying to obtain the cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst; the mass ratio of the cadmium sulfide nano particle modified niobium pentoxide nanorod, the nitrogen-doped graphene suspension and the deionized water is 1: 0.01-0.06: 30-50.
In the technical scheme, in the step (1), the mass ratio of the niobic acid to the mixed solvent is 1: 50-3000; the mixed solvent is a mixture of ethanol and water; the volume ratio of the ethanol to the water is preferably 1: 1; stirring for 20-50 minutes; in a muffle furnace, the heating rate is 10 ℃/min, and the roasting time is 5 hours. The invention adopts the polytetrafluoroethylene inner sleeve high-pressure reaction kettle, and the reaction can be carried out at high temperature and high pressure (when water medium is used, the reaction pressure can reach 2.1 MPa), but impurities can not be introduced. The NbR with perfect crystal form can be obtained by accurately controlling the temperature rising rate and the roasting time.
In the above technical solution, in the step (2), the alcohol solvent is a small molecule alcohol solvent, such as methanol, isopropanol, ethanol, propanol, etc., preferably ethanol; the ultrasonic dispersion time is 50-75 minutes, preferably 60 minutes; the cadmium ion trapping agent is one or more of 3-aminopropyl triethoxysilane (APTES), D-glucose and polyethylene glycol, and the polyethylene glycol is preferably polyethylene glycol 400; the reflux reaction time is 3 hours; the concentration of the cadmium acetate solution is 4 mg/mL; na (Na)2The concentration of the S solution is 25 mg/mL; the mixture is placed in a polytetrafluoroethylene inner sleeve under high pressureReacting for 20-25 hours at 160-180 ℃ in a reaction kettle; the drying condition is vacuum drying at 70-80 ℃.
In the above technical scheme, in the step (2), the niobium pentoxide nanorod, the cadmium ion trapping agent, the cadmium acetate and the Na2The molar ratio of S is (1.5-2): (4-4.5): (0.5-1): (0.8-1.2).
In the technical scheme, in the step (3), the nitrogen doping amount of the nitrogen-doped graphene is 1-5 atm%; the concentration of the nitrogen-doped graphene suspension is 0.1 mg/mL; the ultrasonic reaction time is 1.5-2.5 hours; the centrifugal treatment process is 1800-2200 revolutions per minute, and the centrifugal time is 25-40 minutes; the drying condition is vacuum drying at 70-80 ℃.
In the invention, after the reaction is finished, the reaction solution is filtered to obtain a filter cake, and the filter cake is heated and dried after passing through deionized water, so that a corresponding solid product is obtained.
The invention further discloses a cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst prepared according to the method; wherein the niobium pentoxide nanorod is 0.5-1.0 mu m long and 90-130 nm in diameter; the particle size of the cadmium sulfide is 5-20 nm. The niobium pentoxide nanorod with a proper length-diameter ratio is beneficial to directional transmission of photo-generated electrons, can reduce the recombination probability of the photo-generated electrons and holes, and improves the utilization efficiency of light quanta. Meanwhile, when cadmium sulfide is compounded with NbR with a proper length-diameter ratio, the CdS nanoparticles generated on NbR have moderate particle size and are uniformly distributed on NbR, so that the composite semiconductor material has the characteristics of higher photocatalytic activity and the like.
The composite catalyst of the invention not only has high photocatalytic activity under the irradiation of ultraviolet-visible light, but also has good activity under the irradiation of visible light; the stability is good, and the high photocatalytic activity can be still maintained after long-time reaction; therefore, the invention further discloses the application of the cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst in photocatalytic hydrogen production; furthermore, the cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst can perform photocatalytic hydrogen production reaction under normal temperature and pressure and visible light.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1) the invention successfully solves the problem of low self activity of the existing niobium pentoxide, can effectively expand the photoresponse range of the niobium pentoxide, and has high photocatalytic activity under the irradiation of ultraviolet-visible light and good activity under the irradiation of visible light.
2) The invention compounds cadmium sulfide and niobium pentoxide, thereby combining a lower energy gap and a high band gap to form a compound semiconductor, and changing Nb2O5The structure expands the absorption range of incident light, can fully utilize visible light, and improves the photocatalytic activity of the visible light, thereby improving the photoresponse range and the photocatalytic performance.
3) The invention changes the appearance of the semiconductor and prepares the semiconductor into a nano rod-shaped structure, thereby not only obtaining the photocatalytic material with large specific surface area and high crystallinity, but also reducing the recombination of photo-generated electrons and electron holes in the photocatalytic process and effectively improving the photocatalytic activity.
4) In the composite photocatalyst disclosed by the invention, graphene has a large specific surface area and can be used as an excellent carrier of the catalyst, and after the semiconductor photocatalyst is compounded with the graphene, the excellent conductivity of the graphene is beneficial to timely separation of photo-generated electrons and holes, so that the photocatalytic activity of the catalyst can be further improved.
5) The preparation method disclosed by the invention is simple, the obtained composite catalyst has good stability, and the high catalytic activity can be maintained after long-time photocatalytic reaction.
6) The cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst disclosed by the invention has simple requirements on hydrogen production conditions, can be subjected to catalytic hydrogen production reaction at normal temperature and normal pressure, and has high catalytic activity under visible light.
Drawings
FIG. 1 is a scanning electron microscope image of niobium pentoxide nanorods in example one;
FIG. 2 is a scanning electron microscope image of cadmium sulfide nanoparticle-modified niobium pentoxide nanorods in example one;
FIG. 3 is a scanning electron microscope image of the cadmium sulfide nanoparticle-modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst of example one.
Detailed Description
Example one
1) Preparation of niobium pentoxide nanorod (NbR)
Weighing 0.5 g of niobic acid, ultrasonically dispersing into 200 mL of ethanol/deionized water (1:1), and stirring for 30 min to obtain a mixed solution; and putting the obtained mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene inner sleeve, aging for 38 hours at 180 ℃, performing suction filtration, washing with deionized water, and drying. Heating the obtained solid to 600 ℃ in a muffle furnace at the speed of 10 ℃/min, keeping for 5 hours, and naturally cooling to room temperature to obtain NbR;
2) preparation of cadmium sulfide nanoparticle modified niobium pentoxide nanorod composite semiconductor (NbR/CdS)
0.5 g NbR is weighed and dispersed in 100 mL absolute ethyl alcohol, after 1.0 hour of ultrasonic stirring, 4.2 mmol of 3-aminopropyl triethoxysilane (APTES) is added as a Cd ion capturing agent, the mixture is refluxed for 3.0 hours at 70 ℃, and 35 mL of cadmium acetate (4 mg mL) is slowly added after the mixture is cooled to room temperature-1) The solution was stirred for 1.0 hour, and 3 mL of Na was added2S solution (25 mg mL)-1). After stirring and reacting for 1.0 hour, putting the obtained mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene inner sleeve to react for 24 hours at 180 ℃. Cooling to room temperature, performing suction filtration, washing the obtained solid with deionized water, and performing vacuum drying at 70 ℃ to obtain the cadmium sulfide nanoparticle modified niobium pentoxide nanorod composite semiconductor (NbR/CdS);
3) preparation of cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst (NbR/CdS/NGR)
NbR/CdS compound semiconductor prepared by the steps and NGR (0.1 mg mL)-1The nitrogen doping amount is 5 atm%) and deionized water are mixed according to the mass ratio of 1:0.02:40, and then the mixture is treated by an ultrasonic-assisted in-situ reaction method 2And after the reaction is carried out for hours, centrifuging, washing the obtained solid by deionized water, and carrying out vacuum drying at 70 ℃ to obtain the cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst.
FIG. 1 is a scanning electron microscope image of the niobium pentoxide nanorod; the niobium pentoxide nanorod is about 0.5-1.0 μm long and the rod diameter is about 100 nm.
FIG. 2 is a scanning electron microscope image of the cadmium sulfide nanoparticle-modified niobium pentoxide compound semiconductor; the niobium pentoxide nanorod is about 0.5-1.0 μm long and the diameter of the nanorod is about 110 nm; the cadmium sulfide nano particles are uniformly distributed on the niobium pentoxide nano rods, and the particle size is about 10 nm.
FIG. 3 is a scanning electron microscope image of the cadmium sulfide nanoparticle-modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst, wherein the cadmium sulfide/niobium pentoxide nanorods are uniformly distributed on the surface of the nitrogen-doped graphene.
4) Photocatalytic water splitting reaction
0.25 mg of the above catalyst was mixed with 70 mL of 0.35M Na2S and 0.25M Na2SO3The aqueous solution of (a) was mixed, ultrasonically stirred for 0.5 hour, and then added to a photocatalytic reactor. Visible light (150W xenon lamp, lambda) at a reaction temperature of 25 ℃>400 nm) for 8 hours under the irradiation, the hydrogen yield is 800 mu mol g-1。
Example two
In the first embodiment, the step (1) of aging at 180 ℃ for 38 hours is changed into the step of aging at 150 ℃ for 30 hours, and the step (2) of reacting in a high-pressure reaction kettle with a polytetrafluoroethylene inner sleeve at 180 ℃ for 24 hours is changed into the step of reacting in the high-pressure reaction kettle with the polytetrafluoroethylene inner sleeve at 160 ℃ for 20 hours; and obtaining the product cadmium sulfide nano particle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst.
0.25 mg of the above catalyst was mixed with 70 mL of 0.35M Na2S and 0.25M Na2SO3The aqueous solution of (a) was mixed, ultrasonically stirred for 0.5 hour, and then added to a photocatalytic reactor. At a reaction temperature of 25 ℃ in the visible (150W xenon lamp, lambda)>400 nm) for 8 hours under the irradiation, the hydrogen yield is 605μmol g-1。
EXAMPLE III
The preparation methods of the niobium pentoxide nanorod (NbR) and the cadmium sulfide nanoparticle modified niobium pentoxide nanorod composite semiconductor (NbR/CdS) are the same as those in the first embodiment. However, when preparing the composite semiconductor catalyst, NbR/CdS composite semiconductor and nitrogen-doped graphene NGR suspension (0.1 mg mL)-1And the nitrogen doping amount is 5 atm%) and deionized water are mixed according to the mass ratio of 1:0.01:40, and the preparation steps and conditions are the same as those in the first embodiment, so that the cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst is obtained.
0.25 mg of the above catalyst was mixed with 70 mL of 0.35M Na2S and 0.25M Na2SO3The aqueous solution of (a) was mixed, ultrasonically stirred for 0.5 hour, and then added to a photocatalytic reactor. At a reaction temperature of 25 ℃ in the visible (150W xenon lamp, lambda)>400 nm) for 8 hours under the irradiation, the hydrogen yield is 550 mu mol g-1。
Example four
The mass ratio of NbR to CdS in the first step and the second step of the embodiment is changed to 1:0.1, so that the cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst is obtained.
0.25 mg of the above catalyst was mixed with 70 mL of 0.35M Na2S and 0.25M Na2SO3The aqueous solution of (a) was mixed, ultrasonically stirred for 0.5 hour, and then added to a photocatalytic reactor. At a reaction temperature of 25 ℃ in the visible (150W xenon lamp, lambda)>400 nm) for 8 hours under the irradiation, the hydrogen yield is 495 mu mol g-1。
EXAMPLE five
And changing the Cd ion capture agent into D-glucose in the second step of the first embodiment, changing the mass ratio of NbR to CdS into 1:0.3, and obtaining the product cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst under the same other preparation conditions as the first embodiment.
0.25 mg of the above catalyst was mixed with 70 mL of 0.35M Na2S and 0.25M Na2SO3Is dissolved in waterMixing the solutions, ultrasonically stirring for 0.5 hour, and adding into a photocatalytic reactor. At a reaction temperature of 25 ℃ in the visible (150W xenon lamp, lambda)>400 nm) for 8 hours under the irradiation, the hydrogen yield is 521 mu mol g-1。
EXAMPLE six
The cadmium sulfide nanoparticle-modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst obtained in the first embodiment is adopted. 0.25 mg of catalyst and 70 mL of catalyst containing 0.35M Na2S and 0.25M Na2SO3The aqueous solution of (a) was mixed, ultrasonically stirred for 0.5 hour, and then added to a photocatalytic reactor. At a reaction temperature of 25 ℃ in the visible (150W xenon lamp, lambda)>400 nm) for 8 hours under the irradiation, the hydrogen yield is respectively 800, 810, 795, 790 and 795 mu mol g-1. The average hydrogen yield was 798. mu. mol g-1。
EXAMPLE seven
The cadmium sulfide nanoparticle-modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst obtained in the first embodiment is adopted. 0.25 mg of the above catalyst was mixed with 70 mL of 0.35M Na2S and 0.25M Na2SO3The aqueous solution of (a) was mixed, ultrasonically stirred for 0.5 hour, and then added to a photocatalytic reactor. The catalytic reaction is carried out for 8 hours under the irradiation of ultraviolet-visible light (150W xenon lamp) at the reaction temperature of 25 ℃, and the yield of hydrogen is 1576 mu mol g-1。
The above embodiments show that the cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst prepared by the invention has high photocatalytic activity under the action of ultraviolet light; but also has better photocatalytic activity under the action of visible light; the catalyst has good cycle stability, and still has high photocatalytic activity after five cycles; meanwhile, the catalyst of the invention has simple and reasonable preparation process and simple application condition, and is suitable for industrial production.
Claims (7)
1. The preparation method of the cadmium sulfide nanoparticle-modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst is characterized by comprising the following steps of:
(1) ultrasonically dispersing the niobic acid into the mixed solvent, and stirring to obtain a mixed solution; then putting the mixed solution into a polytetrafluoroethylene inner sleeve high-pressure reaction kettle, aging at 180 ℃ for 38 hours, and sequentially carrying out suction filtration, deionized water washing and drying to obtain a solid; then heating the solid in a muffle furnace from room temperature to 400-700 ℃ at the speed of 5-20 ℃/min, then roasting for 2-10 hours at the temperature, and naturally cooling to room temperature to obtain niobium pentoxide nanorods; the mixed solvent is a mixture of ethanol and water;
(2) dispersing niobium pentoxide nanorods in an alcohol solvent, performing ultrasonic dispersion, adding a cadmium ion capture agent, performing reflux reaction for 2-5 hours, cooling to room temperature, adding a cadmium acetate solution, and stirring for 50-75 minutes; then Na is added2S solution; stirring for 50-75 minutes, placing the mixture into a polytetrafluoroethylene inner sleeve high-pressure reaction kettle, and reacting for 20-25 hours at 160-180 ℃; then carrying out suction filtration, deionized water washing and drying on the reaction solution in sequence to obtain the cadmium sulfide nanoparticle modified niobium pentoxide nanorod; the alcohol solvent is a micromolecular alcohol solvent; the niobium pentoxide nanorod, the cadmium ion trapping agent, cadmium acetate and Na2The molar ratio of S is (1.5-2): (4-4.5): (0.5-1): (0.8-1.2);
(3) mixing the cadmium sulfide nanoparticle modified niobium pentoxide nanorod prepared in the step (2), the nitrogen-doped graphene suspension and deionized water, and then carrying out ultrasonic reaction for 1-3 hours at room temperature; then carrying out centrifugal treatment, washing the obtained solid by deionized water, and drying to obtain the cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst; the mass ratio of the cadmium sulfide nanoparticle modified niobium pentoxide nanorod, the nitrogen-doped graphene suspension and the deionized water is 1:0.02: 40; the nitrogen doping amount of the nitrogen-doped graphene is 1-5 atm%;
the niobium pentoxide nanorod is 0.5-1.0 mu m in length and 90-130 nm in diameter; the particle size of the cadmium sulfide is 5-20 nm.
2. The cadmium sulfide nanoparticle-modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst as claimed in claim 1, wherein: in the step (1), the mass ratio of the niobic acid to the mixed solvent is 1: 50-3000; stirring for 20-50 minutes; in a muffle furnace, the heating rate is 10 ℃/min, and the roasting time is 5 hours.
3. The cadmium sulfide nanoparticle-modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst as claimed in claim 1, wherein: in the step (2), the ultrasonic dispersion time is 50-75 minutes; the cadmium ion trapping agent is one or more of 3-aminopropyl triethoxysilane, D-glucose and polyethylene glycol; the reflux reaction time is 3 hours; the concentration of the cadmium acetate solution is 4 mg/mL; na (Na)2The concentration of the S solution is 25 mg/mL; the drying condition is vacuum drying at 70-80 ℃.
4. The cadmium sulfide nanoparticle-modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst as claimed in claim 3, wherein: in the step (2), the alcohol solvent is methanol, isopropanol, ethanol or propanol; the time of ultrasonic dispersion is 1 hour; the polyethylene glycol is polyethylene glycol 400.
5. The cadmium sulfide nanoparticle-modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst as claimed in claim 1, wherein: in the step (3), the concentration of the nitrogen-doped graphene suspension is 0.1 mg/mL; the ultrasonic reaction time is 1.5-2.5 hours; the centrifugal treatment process is 1800-2200 revolutions per minute, and the centrifugal time is 25-40 minutes; the drying condition is vacuum drying at 70-80 ℃.
6. The application of the cadmium sulfide nanoparticle-modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst in photocatalytic hydrogen production.
7. Use according to claim 6, characterized in that: the photocatalytic hydrogen production is carried out at normal temperature and normal pressure under visible light.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810388355.0A CN108607593B (en) | 2016-01-26 | 2016-01-26 | Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810388355.0A CN108607593B (en) | 2016-01-26 | 2016-01-26 | Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application thereof |
CN201610050573.4A CN105709793B (en) | 2016-01-26 | 2016-01-26 | Niobium pentoxide nano stick/nitrogen-doped graphene composite photo-catalyst, preparation method and application of cadmium sulfide nano-particles modification |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610050573.4A Division CN105709793B (en) | 2016-01-26 | 2016-01-26 | Niobium pentoxide nano stick/nitrogen-doped graphene composite photo-catalyst, preparation method and application of cadmium sulfide nano-particles modification |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108607593A CN108607593A (en) | 2018-10-02 |
CN108607593B true CN108607593B (en) | 2021-01-12 |
Family
ID=56154056
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810388355.0A Active CN108607593B (en) | 2016-01-26 | 2016-01-26 | Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application thereof |
CN201610050573.4A Active CN105709793B (en) | 2016-01-26 | 2016-01-26 | Niobium pentoxide nano stick/nitrogen-doped graphene composite photo-catalyst, preparation method and application of cadmium sulfide nano-particles modification |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610050573.4A Active CN105709793B (en) | 2016-01-26 | 2016-01-26 | Niobium pentoxide nano stick/nitrogen-doped graphene composite photo-catalyst, preparation method and application of cadmium sulfide nano-particles modification |
Country Status (1)
Country | Link |
---|---|
CN (2) | CN108607593B (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106582881A (en) * | 2016-12-06 | 2017-04-26 | 河南理工大学 | Niobium hydroxide visible-light-driven photocatalyst having wide-spectral catalytic performance and grafting with aromatic alcohol on surface, and preparation and application thereof |
CN108786854A (en) * | 2017-05-06 | 2018-11-13 | 佛山市洁灏环保科技有限公司 | A kind of compound cadmium sulfide photochemical catalyst |
CN107626338A (en) * | 2017-10-11 | 2018-01-26 | 南通科技职业学院 | The preparation method of the mesoporous niobium pentaoxide of molybdenum sulfide Nanoparticle Modified/nitrogen-doped graphene composite photo-catalyst |
CN107519897B (en) * | 2017-10-12 | 2020-04-10 | 辽宁大学 | Ternary Z-shaped structured photocatalyst and preparation method and application thereof |
CN108435210B (en) * | 2018-03-30 | 2020-10-09 | 福州大学 | Cadmium niobate/cadmium sulfide composite photocatalyst and preparation method thereof |
CN109980210B (en) * | 2019-04-19 | 2021-01-29 | 陕西科技大学 | Niobium pentoxide three-dimensional doped graphene composite material and preparation method and application thereof |
CN113731497B (en) * | 2021-09-13 | 2023-06-16 | 福州大学 | CdS QDs supported BPEI modified niobium pentoxide catalyst and preparation method and application thereof |
CN113769763B (en) * | 2021-10-11 | 2023-11-07 | 陕西科技大学 | CdS-Au nano-catalyst and preparation method and application thereof |
CN114618527B (en) * | 2022-03-23 | 2023-05-23 | 河南大学 | Au nanoparticle and CdS quantum dot modified niobate composite nanomaterial and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102176382A (en) * | 2011-01-31 | 2011-09-07 | 中国科学院上海硅酸盐研究所 | Method for preparing grapheme-quantum dot composite film and solar battery structured by using same |
CN102180518A (en) * | 2011-01-25 | 2011-09-14 | 湖北大学 | Large-scale preparation method of niobium pentoxide nanowires and hydrogen-sensitive element thereof |
CN103521244A (en) * | 2013-09-29 | 2014-01-22 | 南昌航空大学 | Photocatalytic water-splitting hydrogen production material CdS/Sr1.6Zn0.4Nb2O7 and preparation method thereof |
CN105214689A (en) * | 2015-09-07 | 2016-01-06 | 上海应用技术学院 | A kind of TiO 2/ CdS/ Graphene composite photocatalyst material and preparation method thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101391770B (en) * | 2008-10-24 | 2010-09-29 | 哈尔滨工业大学 | Method for preparing niobium pentoxide nano stick |
CN102266787A (en) * | 2010-06-07 | 2011-12-07 | 付文甫 | Preparation method of novel noble-metal-free catalyst for photolysis of water to produce hydrogen |
CN103657687A (en) * | 2012-09-19 | 2014-03-26 | 中国科学院理化技术研究所 | Compound type semiconductor photocatalyst and preparation method thereof as well as photocatalytic system and hydrogen production method |
CN103657630A (en) * | 2013-12-21 | 2014-03-26 | 海安县吉程机械有限公司 | Preparation of compound photocatalyst of rodlike niobium pentoxide and reduced graphene oxide |
CN105107528A (en) * | 2015-07-31 | 2015-12-02 | 武汉理工大学 | Ternary compound optical catalyst and preparation method therefor and application thereof |
-
2016
- 2016-01-26 CN CN201810388355.0A patent/CN108607593B/en active Active
- 2016-01-26 CN CN201610050573.4A patent/CN105709793B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102180518A (en) * | 2011-01-25 | 2011-09-14 | 湖北大学 | Large-scale preparation method of niobium pentoxide nanowires and hydrogen-sensitive element thereof |
CN102176382A (en) * | 2011-01-31 | 2011-09-07 | 中国科学院上海硅酸盐研究所 | Method for preparing grapheme-quantum dot composite film and solar battery structured by using same |
CN103521244A (en) * | 2013-09-29 | 2014-01-22 | 南昌航空大学 | Photocatalytic water-splitting hydrogen production material CdS/Sr1.6Zn0.4Nb2O7 and preparation method thereof |
CN105214689A (en) * | 2015-09-07 | 2016-01-06 | 上海应用技术学院 | A kind of TiO 2/ CdS/ Graphene composite photocatalyst material and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
"Highly durable N-doped graphene/CdS nanocomposites with enhanced photocatalytic hydrogen evolution from water under visible light irradiation";Li Jia et al.;《The Journal of Physical Chemistry C》;20110524;第115卷;第11467页左栏第3段,第11471页左栏第1段 * |
"Nb2O5/CdS纳米粒子的制备及其光催化性能研究";黄正喜 等;《中南民族大学学报》;20141231;第33卷(第4期);第26页右栏第2段,第27页左栏第4段 * |
Also Published As
Publication number | Publication date |
---|---|
CN105709793A (en) | 2016-06-29 |
CN108607593A (en) | 2018-10-02 |
CN105709793B (en) | 2018-07-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108607593B (en) | Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application thereof | |
CN110773213B (en) | One-dimensional cadmium sulfide/two-dimensional titanium carbide composite photocatalyst and preparation method and application thereof | |
CN108067281B (en) | Porous g-C3N4Photocatalyst and preparation method and application thereof | |
CN111203231B (en) | Indium zinc sulfide/bismuth vanadate composite material and preparation method and application thereof | |
CN111203262B (en) | Method for rapidly preparing carbon nitride nanosheet loaded nano-copper, product and application thereof | |
CN110252352B (en) | Carbon quantum dot modified bismuth tungstate/ordered macroporous fluorine-doped tin oxide composite photocatalyst and preparation method and application thereof | |
CN113058617B (en) | Photocatalyst and preparation method and application thereof | |
CN110280281B (en) | Preparation method of zinc ferrite/black phosphorus microsphere compound and application of zinc ferrite/black phosphorus microsphere compound in photocatalysis field | |
CN111957354A (en) | Preparation method of oxygen-deficient titanium dioxide/TpPa-1-COF heterojunction photocatalyst | |
CN112675831A (en) | Preparation method of MOF-derived zinc oxide composite titanium dioxide heterojunction and application of heterojunction in photoelectric water decomposition | |
CN110102349B (en) | alpha-Fe2O3Preparation of TpPa-2 composite material and hydrogen production by photolysis of water | |
CN113967481B (en) | Spherical MoP-HCCN-like composite photocatalyst and preparation method and application thereof | |
CN113699549A (en) | Ruthenium and tin bimetallic oxide electrocatalytic material and preparation method and application thereof | |
CN113617376A (en) | P-doped g-C3N4Catalyst for hydrogen production by water photolysis through MoP and preparation method thereof | |
CN111939957A (en) | Preparation method of photocatalytic nitrogen fixation material porous carbon nitride nanofiber/graphene | |
CN108855193B (en) | TaN/BiVO4Heterojunction composite material and preparation method and application thereof | |
CN113398997B (en) | Platinum doped ultrathin Zr-MOFs nano thin layer composite photocatalyst and preparation method and application thereof | |
CN113289661B (en) | Dual-polarization site co-modified carbon nitride photocatalyst and preparation method thereof | |
CN110629245B (en) | Nitrogen-doped carbon-coated copper cadmium sulfide catalyst for photoelectric reduction of CO2Method of producing a composite material | |
CN113546658A (en) | Two-dimensional layered ternary nano composite photocatalyst and preparation method and application thereof | |
CN113070063A (en) | In-situ synthesis method of metal-loaded tungsten trioxide-based nano heterojunction material | |
CN112371161A (en) | Carbon-point-modified graphite-phase carbon nitride hollow sphere photocatalyst and preparation method and application thereof | |
CN112717958A (en) | Oxygen-rich vacancy BiOBr/HNb3O8Preparation method and application of nanosheet photocatalyst | |
CN116371425B (en) | CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Preparation and application of composite catalyst | |
CN115672352B (en) | Single-atom Ti-modified CdS nano-catalyst and preparation method 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 |