CN110152711A - A kind of CeO2@MoS2/g-C3N4Three-element composite photocatalyst and preparation method thereof - Google Patents

A kind of CeO2@MoS2/g-C3N4Three-element composite photocatalyst and preparation method thereof Download PDF

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CN110152711A
CN110152711A CN201910481070.6A CN201910481070A CN110152711A CN 110152711 A CN110152711 A CN 110152711A CN 201910481070 A CN201910481070 A CN 201910481070A CN 110152711 A CN110152711 A CN 110152711A
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mos
ceo
preparation
composite photocatalyst
mixed solution
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CN110152711B (en
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鲜啟鸣
朱成章
王鋙葶
李昱升
刘安鼐
孙成
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Nanjing Shengbin Environmental Research Institute Co Ltd
Nanjing University
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Nanjing Shengbin Environmental Research Institute Co Ltd
Nanjing University
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/082Decomposition and pyrolysis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341Irradiation 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
    • B01J37/343Irradiation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042Decomposition of water
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0266Processes for making hydrogen or synthesis gas containing a decomposition step
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/38Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention belongs to field of nano material preparation, disclose a kind of CeO2@MoS2/g‑C3N4Composite photocatalyst material and preparation method thereof, comprising: (1) six hydrous cerias are added in the mixed solution of butylamine, toluene, after gained mixed solution hydrothermal treatment, then reaction product are calcined, obtain CeO2It is nanocrystalline;(2) by two molybdic acid hydrate sodium, g-C3N4For nanometer sheet ultrasonic disperse in L-cysteine and dimethyl sulfoxide mixed solution, gained mixed solution hydrothermal treatment obtains MoS2/g‑C3N4Nanometer sheet;(3) by CeO2Nanocrystalline and MoS2/g‑C3N4Ultrasonic disperse is in methanol solution, and after methanol volatilization, collection products therefrom is CeO2‑MoS2/g‑C3N4Composite material;(4) by CeO2‑MoS2/g‑C3N4Composite material is placed in tube furnace, under nitrogen atmosphere calcination processing, obtains CeO2@MoS2/g‑C3N4Three-element composite photocatalyst.Preparation method of the present invention is simple, controllability is strong, and resulting composite photo-catalyst has excellent Photocatalytic Degradation Property.

Description

A kind of CeO2@MoS2/g-C3N4Three-element composite photocatalyst and preparation method thereof
Technical field
The invention belongs to nano material preparations and photocatalysis environmental energy and pollutant control technical field more particularly to one Kind CeO2@MoS2/g-C3N4Composite photocatalyst material and preparation method thereof.
Background technique
With the fast development of modern industrialization, environmental pollution and problem of energy crisis, which seem, to become increasingly conspicuous.Based on partly leading Body and its derived material are the photocatalysis technology of medium, as a kind of Driven by Solar Energy, pollution-free and cost-effective means, just The new energy research direction popular as one.Ceria (CeO2) it is the rare earth metal oxidation that China's essential industry is applied Object, rich content, at low cost, pollution-free and chemical stability are good, have in photocatalysis, production hydrogen and photoelectricity field good Application prospect.But CeO2There are two big defects, firstly, the band gap of ceria is 3.2eV, broad-band gap chemical property leads to it It can only be by ultraviolet excitation;Secondly, the internal charge rate of transform of ceria is relatively low, electron hole pair recombination rate is higher, causes CeO2Photon utilization rate is relatively low in photocatalysis chemical reaction process.
The building of hetero-junctions can effectively be promoted composite material absorbing properties and Pair production quick separating with Transfer, therefore the oxidation and reducing power that effectively material can be avoided to lose by charge recombination.In recent years, novel organic poly- Close object g-C3N4Yin Qiyi preparation, high-specific surface area and excellent electrical conductivity and be concerned, typical two-dimensional sheet structure And surface functional group can provide effective support for other semiconductors to form heterojunction structure.As good co-catalyst, Effective alternative compounds of noble metal, MoS2Because the edge of its exposure has a large amount of unsaturated Mo and S element, can effectively live Change active site, to enhance the visible light utilization efficiency of wide band gap semiconducter.Therefore, two-dimentional MoS2/g-C3N4Heterojunction structure is not only More support carriers are capable of providing, while can effectively enhance light absorpting ability and reduce the compound of photo-generate electron-hole pairs Rate.However, up to the present without CeO2@MoS2/g-C3N4The preparation of hetero-junctions and the report of photocatalytic applications.Therefore, this hair It is bright to provide a kind of visible light-responded CeO2@MoS2/g-C3N4The preparation method of heterojunction material, it is therefore an objective to excellent by constructing Heterojunction structure promote service life of photo-generated carrier, and then promote the quick separating of light induced electron and hole and enhance heterogeneous Tie the photocatalysis Decomposition aquatic products hydrogen and contaminant removal capacity of material.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a kind of CeO2@MoS2/g-C3N4It is multiple Light combination catalysis material and preparation method thereof.
The present invention is to realize above-mentioned technical purpose by following technological means:
A kind of CeO2@MoS2/g-C3N4The preparation method of Three-element composite photocatalyst, including following preparation step:
(1) six hydrous cerias are added in the mixed solution of butylamine, toluene, are uniformly dissolved, gained mixed solution warp After hydro-thermal process, then reaction product calcined, obtains CeO2It is nanocrystalline;
(2) by two molybdic acid hydrate sodium, g-C3N4Nanometer sheet ultrasonic disperse is mixed in L-cysteine and dimethyl sulfoxide (DMSO) It closes in solution, gained mixed solution hydrothermal treatment, reaction product is washed, dry, obtains MoS2/g-C3N4Composite material;
(3) by CeO2Nanocrystalline and MoS2/g-C3N4Compound material ultrasound is scattered in methanol solution, normal-temperature reaction until Methanol volatilizees completely, and collection products therefrom is CeO2-MoS2/g-C3N4Composite material;
(4) by CeO2-MoS2/g-C3N4Composite material is placed in tube furnace, under nitrogen atmosphere calcination processing, with enhancing CeO2Crystal and MoS2/g-C3N4The interfacial reaction of nanostructure, obtains CeO2@MoS2/g-C3N4Trielement composite material.The present invention The CeO of the preparation method preparation2@MoS2/g-C3N4Ce is existed simultaneously in composite photo-catalyst3+、Ce4+, wherein Ce3+And Ce4 +It is reversible electron to form, is able to extend the service life of charge;Ce4+Electronics can be captured to prevent the quick of electron hole pair It is compound;Ce3+Can the stronger reducing power of system, while can be reactant H2O molecule provides a large amount of adsorption site, in turn Its adsorption energy is reduced, water decomposition is promoted.
MoS in the present invention2Compound has unique two-dimensional nanostructure, the g-C with graphite-like structure3N4It can pass through Pi-pi accumulation effect combines.MoS2On the one hand nanometer sheet has strong absorption to visible light, on the other hand as electricity Sub- conducting shell can effectively improve the conduction velocity of electron-hole pair.And CeO2The introducing of hetero-junctions can be in MoS2/g-C3N4It receives A new energy level is introduced in rice chip architecture, the photoresponse effect of composite photo-catalyst under visible light is also remarkably reinforced.
Preferably, the mass volume ratio of six hydrous cerias described in step (1), butylamine, toluene and distilled water is (0.2 ~0.6) g:(0.05~0.25) ml:(10~30) ml:(20~30) ml.
Preferably, hydro-thermal process temperature described in step (1) is 160~180 DEG C, and hydrothermal conditions are for 24 hours;It is described to forge Burning temperature is 180 DEG C, and calcination time is for 24 hours.
Preferably, step (2) the two molybdic acid hydrates sodium, L-cysteine, g-C3N4Nanometer sheet, the quality volume of DMSO Than for (0.20~0.40) g:(0.3~0.6) ml:(0.05~0.15) g:(20~40) ml.
Preferably, step (2) the hydro-thermal process temperature is 180~200 DEG C, hydrothermal conditions 36h.
Preferably, step (3) CeO2Nanocrystalline, MoS2/g-C3N4The mass volume ratio of composite material and methanol is (0.01~0.03) g:(0.02~0.06) g:50ml.
Preferably, stream of nitrogen gas flow is 0.3~1.5L/ during calcination processing under step (4) described nitrogen atmosphere Minmm, calcination temperature are 180 DEG C, calcination time 1h.
It is a further object of the present invention to provide a kind of CeO prepared by the present invention2@MoS2/g-C3N4The use of composite photo-catalyst On the way.
By CeO prepared by the present invention2@MoS2/g-C3N4Composite photo-catalyst is used for the use of hydrogen production by water decomposition under visible light On the way.
By CeO prepared by the present invention2@MoS2/g-C3N4Three-element composite photocatalyst is used under visible light tetracycline of degrading Purposes.
In above-mentioned technical proposal, distillation water consumption is that soluble solids can be made to be completely dissolved.
The invention has the benefit that
(1) MoS in the composite photo-catalyst prepared by the present invention2Compound has unique two-dimensional nanostructure, with class The g-C of graphite-structure3N4It can be acted on and be combined by pi-pi accumulation.MoS2On the one hand nanometer sheet has strongly visible light On the other hand absorption can effectively improve the conduction velocity of electron-hole pair as electronic conductive layer.And it is forged by high temperature It burns, it can be in MoS2/g-C3N4CeO is introduced in nanometer chip architecture2Composite photo-catalyst is also remarkably reinforced visible in new energy level Photoresponse effect under light.
(2) CeO prepared by the present invention2@MoS2/g-C3N4Ce is existed simultaneously in composite photo-catalyst3+、Ce4+, wherein Ce3 +And Ce4+It is reversible electron to form, is able to extend the service life of charge;Ce4+Electronics can be captured to prevent electron hole pair It is quickly compound;Ce3+Can the stronger reducing power of system, while can be reactant H2O molecule provides a large amount of adsorption site, And then its adsorption energy is reduced, promote water decomposition.
(3) CeO prepared by the present invention2@MoS2/g-C3N4Three-element composite photocatalyst has excellent visible light effect, real Photo-generate electron-hole is showed to efficiently separating.
(4) MoS in the present invention2/g-C3N4Nanometer sheet is rich and easy to get, and biggish specific surface area is conducive to improve CeO2's Dispersion performance.
Detailed description of the invention
Fig. 1 is CeO prepared by the present invention2@MoS2/g-C3N4The transmission electron microscope picture of composite photo-catalyst;
Fig. 2 is the X-ray diffractogram and x-ray photoelectron spectroscopy of catalyst prepared by the present invention;
Fig. 3 is CeO prepared by the present invention2@MoS2/g-C3N4Uv-visible absorption spectra, the fluorescence of composite photo-catalyst Spectrum and optogalvanic spectra;
Fig. 4 is MoS prepared by the present invention2/g-C3N4With CeO2@MoS2/g-C3N4The contact angle experiments of composite photo-catalyst, Infrared absorption spectrum and electron spin resonance map;
Fig. 5 is CeO prepared by the present invention2@MoS2/g-C3N4The XPS map of composite photo-catalyst;
Fig. 6 is that photochemical catalyst prepared by the present invention produces hydrogen figure;
Fig. 7 is tetracycline photocatalytic degradation effect figure under radiation of visible light.
Specific embodiment
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair It is bright, but the invention is not limited to following embodiments.
The activity rating of the photocatalytic degradation of prepared photochemical catalyst in the present invention: in the bright general limited public affairs of science and technology in Shenzhen It takes charge of in the photocatalytic degradation instrument of preparation and carries out, use the xenon lamp of 200W as light source, wherein having 420nm filter plate;50mg catalysis Agent is scattered in 100mL 20mg/L tetracycline;Before turning on light, sufficiently ultrasonic and logical N230min has completely removed air, protects It holds anaerobic condition and catalyst obtains uniform light irradiation, measure its optical absorption intensity after extraction sample centrifugation in every 5 minutes.
The activity rating of the photocatalysis hydrogen production of prepared photochemical catalyst in the present invention: Lang Pu Science and Technology Ltd., Shenzhen Photocatalysis hydrogen production instrument, be 80.0mWcm with intensity-23W UV-Leds light irradiation, wherein have 420nm filter plate; 50mg catalyst is scattered in containing 0.5M Na2SO3With 0.5M Na2In the 80mL solution of S;Before turning on light, sufficiently ultrasonic and logical N2, 30min has completely removed air, maintains anaerobic conditions within and catalyst obtains uniform light irradiation.
Embodiment 1
(1) it takes 5g urea to be placed in Muffle furnace, is uniformly warming up to 550 DEG C with the heating rate of 2 DEG C/min, forges at a constant temperature It burns 6 hours, after natural cooling, obtained solid is ground into fine powder to get g-C is arrived3N4Nanometer sheet.Such as Fig. 1,2,3,4,5 it is found that Pure g-C3N4Pattern be two-dimensional sheet structure, without apparent packing phenomenon, and in X-ray diffractogram, x-ray photoelectron spectroscopy The middle energy characteristic peak visible in detail for belonging to C and N element, this shows the g-C for being applicable in this method synthesis3N4Nanometer sheet has High purity.
(2) six hydrous ceria of 0.2g can be taken to be dissolved in the mixed of 0.05ml butylamine, 10ml toluene and 20ml distilled water in It closing in solution, is evenly stirred until after being completely dissolved, gained mixed solution is transferred in hydrothermal reaction kettle, after sealing reaction kettle, It is placed in 160~180 DEG C of baking ovens and carries out hydro-thermal process 24 hours.After reaction, ethyl alcohol, deionization are used products therefrom repeatedly Water washing, 60 DEG C of drying after filtering, then the reaction product of drying is calcined for 24 hours under 180 DEG C of environment, obtain CeO2It is nanocrystalline.
(3) bis- molybdic acid hydrate sodium of 0.20g, 0.05g-C are taken3N4Nanometer sheet ultrasonic disperse in 0.3ml L-cysteine and In the mixed solution of 20ml dimethyl sulfoxide (DMSO), gained mixed solution is transferred in hydrothermal reaction kettle, sealing reaction kettle it Afterwards, it is placed in 180 DEG C of baking ovens and carries out hydro-thermal process 36 hours.After reaction, ethyl alcohol, deionized water are used products therefrom repeatedly Washing, 60 DEG C of drying, obtain MoS after filtering2/g-C3N4Composite material.
(4) 0.01g CeO is taken2Nanocrystalline and 0.02g MoS2/g-C3N4Compound material ultrasound is scattered in 50ml methanol solution In, until methanol volatilizees completely, collection products therefrom is CeO for reaction under normal temperature condition2-MoS2/g-C3N4Presoma.
(5) 5g CeO is weighed2-MoS2/g-C3N4Presoma is placed in tube furnace, is 0.3L/ in stream of nitrogen gas flow It is warming up to 180 DEG C under the nitrogen atmosphere of minmm, 1h is calcined, to enhance CeO2Crystal and MoS2/g-C3N4The boundary of nanostructure Face reaction, obtains CeO2@MoS2/g-C3N4Trielement composite material.
Embodiment 2
(1) it takes 5g urea to be placed in Muffle furnace, is uniformly warming up to 550 DEG C with the heating rate of 2 DEG C/min, forges at a constant temperature It burns 6 hours, after natural cooling, obtained solid is ground into fine powder to get g-C is arrived3N4Nanometer sheet.
(2) six hydrous ceria of 0.4g is taken to be dissolved in the mixed solution of 0.15ml butylamine, 20ml toluene and 30ml distilled water In, it is evenly stirred until after being completely dissolved, gained mixed solution is transferred in hydrothermal reaction kettle, after sealing reaction kettle, is placed in 170 It is carried out hydro-thermal process 24 hours in DEG C baking oven.After reaction, products therefrom is washed with ethyl alcohol, deionized water repeatedly, is filtered 60 DEG C of drying afterwards, then the reaction product of drying is calcined for 24 hours under 170 DEG C of environment, obtain CeO2It is nanocrystalline.
(3) bis- molybdic acid hydrate sodium of 0.30g, 0.10g g-C are taken3N4Nanometer sheet ultrasonic disperse in 0.4ml L-cysteine and In the mixed solution of 30ml dimethyl sulfoxide (DMSO), gained mixed solution is transferred in hydrothermal reaction kettle, sealing reaction kettle it Afterwards, it is placed in 200 DEG C of baking ovens and carries out hydro-thermal process 36 hours.After reaction, ethyl alcohol, deionized water are used products therefrom repeatedly Washing, 60 DEG C of drying, obtain MoS after filtering2/g-C3N4Composite material.
(4) 0.02g CeO is taken2Nanocrystalline and 0.04g MoS2/g-C3N4Compound material ultrasound is scattered in 50ml methanol solution In, until methanol volatilizees completely, collection products therefrom is CeO for reaction under normal temperature condition2-MoS2/g-C3N4Presoma.
(5) 5g CeO is weighed2-MoS2/g-C3N4Presoma is placed in tube furnace, is 1.5L/ in stream of nitrogen gas flow It is warming up to 180 DEG C under the nitrogen atmosphere of minmm, 1h is calcined, to enhance CeO2Crystal and MoS2/g-C3N4The boundary of nanostructure Face reaction, obtains CeO2@MoS2/g-C3N4Trielement composite material.Fig. 1 is CeO2@MoS2/g-C3N4The transmission of composite photo-catalyst Electron microscope, as shown, the CeO of preparation method preparation through this embodiment2Crystal is evenly distributed, without stacking phenomenon, partial size Size is about 19.7nm, MoS2Structure in the form of sheets, and be evenly distributed, by projection Electronic Speculum it is found that CeO2Crystal, MoS2Nanometer sheet With g-C3N4Nanometer sheet triplicity is close, forms apparent heterojunction structure.Fig. 2 is CeO2@MoS2/g-C3N4Complex light is urged Agent X-ray diffractogram and x-ray photoelectron spectroscopy, as seen from the figure, CeO in X-ray diffractogram2@MoS2/g-C3N4Complex light Do not occur apparent MoS in catalyst2With g-C3N4Characteristic peak, this may be due to CeO2Peak intensity it is too big, mask The characteristic peak of the two, it is also possible to because of MoS2With g-C3N4Load capacity it is few, characteristic peak is weaker.And x-ray photoelectron spectroscopy is then Demonstrate MoS in the composite photocatalyst2Nanometer sheet and g-C3N4The presence of nanometer sheet.
Fig. 3 is CeO manufactured in the present embodiment2@MoS2/g-C3N4It is the uv-visible absorption spectra of composite photo-catalyst, glimmering Light and photoelectric current.By Fig. 3 a it is found that compared to g-C3N4、CeO2/g-C3N4Equal catalysis materials, MoS2The introducing of nanometer sheet is very big The absorption to visible light is improved to degree, and by Fig. 3 b and 3c it is found that CeO2@MoS2/g-C3N4Composite photo-catalyst occurs The obvious phenomenon of fluorescent quenching and the enhancing of photo-current intensity, this explanation is in each comparison system, CeO2@MoS2/g-C3N4It is compound The photoproduction of photochemical catalyst-electron hole pair separation rate highest, recombination rate are minimum.
Embodiment 3
(1) it takes 5g urea to be placed in Muffle furnace, is uniformly warming up to 600 DEG C with the heating rate of 5 DEG C/min, forges at a constant temperature It burns 4 hours, after natural cooling, obtained solid is ground into fine powder to get g-C is arrived3N4Nanometer sheet.
(2) six hydrous ceria of 0.6g is taken to be dissolved in the mixed solution of 0.25ml butylamine, 30ml toluene and 25ml distilled water In, it is evenly stirred until after being completely dissolved, gained mixed solution is transferred in hydrothermal reaction kettle, after sealing reaction kettle, is placed in 180 It is carried out hydro-thermal process 24 hours in DEG C baking oven.After reaction, products therefrom is washed with ethyl alcohol, deionized water repeatedly, is filtered 60 DEG C of drying afterwards, then the reaction product of drying is calcined for 24 hours under 180 DEG C of environment, obtain CeO2It is nanocrystalline.
(3) bis- molybdic acid hydrate sodium of 0.40g, 0.15g g-C are taken3N4Nanometer sheet ultrasonic disperse in 0.6ml L-cysteine and In the mixed solution of 40ml dimethyl sulfoxide (DMSO), gained mixed solution is transferred in hydrothermal reaction kettle, sealing reaction kettle it Afterwards, it is placed in 200 DEG C of baking ovens and carries out hydro-thermal process 36 hours.After reaction, ethyl alcohol, deionized water are used products therefrom repeatedly Washing, 60 DEG C of drying, obtain MoS after filtering2/g-C3N4Composite material.
(4) 0.03g CeO is taken2Nanocrystalline and 0.06g MoS2/g-C3N4Compound material ultrasound is scattered in 50ml methanol solution In, until methanol volatilizees completely, collection products therefrom is CeO for reaction under normal temperature condition2-MoS2/g-C3N4Composite material.
(5) 5g CeO is weighed2-MoS2/g-C3N4Presoma is placed in tube furnace, is 1.0L/ in stream of nitrogen gas flow It is warming up to 180 DEG C under the nitrogen atmosphere of minmm, 1h is calcined, to enhance CeO2Crystal and MoS2/g-C3N4The boundary of nanostructure Face reaction, obtains CeO2@MoS2/g-C3N4Trielement composite material.
Fig. 4 is the MoS of the present embodiment preparation method preparation2/g-C3N4With CeO2@MoS2/g-C3N4Composite photo-catalyst Contact angle experiments.By Fig. 4 a, b it is found that CeO2@MoS2/g-C3N4Three-element composite photocatalyst contact angle is less than MoS2/g-C3N4Two First composite photo-catalyst, this illustrates that it has obtained greatly being promoted to the absorbability of water reactant, not only improves in absorption water Pollutant, be also beneficial to photocatalysis hydrolytic hydrogen production reaction progress.Fig. 4 C is the infrared suction of catalyst manufactured in the present embodiment Hydroxyl stretching vibration peak after receiving spectral adsorption hydrone, as seen from the figure, CeO2@MoS2/g-C3N4Three-element composite photocatalyst exists The peak 3000-3600 broadens, and it is stronger to further demonstrate in contact angle experiments ternary material absorption water energy amount, and it is anti-to be conducive to photocatalysis Physical absorption during answering, to enhance its light-catalyzed reaction rate.Fig. 4 d is the electron spin resonance map of the present embodiment, As seen from the figure, CeO2、CeO2@g-C3N4And CeO2@MoS2/g-C3N4G=in Three-element composite photocatalyst electron spin resonance map 1.96, this illustrates CeO2There are trivalents (3 by the Ce on surface+), and with compared to CeO2、CeO2@g-C3N4, CeO2@MoS2/g- C3N4The EPR peak intensity of Three-element composite photocatalyst also enhances, and illustrating it, there are more trivalent Ce ions.Importantly, Ce3+With Ce4+It is reversible electron to form, is able to extend the service life of charge;Ce4+Electronics can be captured to prevent the fast of electron hole pair Reply immediately conjunction;Ce3+Can the stronger reducing power of system, while can be reactant H2O molecule provides a large amount of adsorption site, into And its adsorption energy is reduced, promote water decomposition, therefore its light-catalyzed reaction ability is obviously improved.
Embodiment 4
(1) it takes 5g urea to be placed in Muffle furnace, is uniformly warming up to 550 DEG C with the heating rate of 2 DEG C/min, forges at a constant temperature It burns 6 hours, after natural cooling, obtained solid is ground into fine powder to get g-C is arrived3N4Nanometer sheet.
(2) six hydrous ceria of 0.5g is taken to be dissolved in the mixed solution of 0.20ml butylamine, 15ml toluene and 20ml distilled water In, it is evenly stirred until after being completely dissolved, gained mixed solution is transferred in hydrothermal reaction kettle, after sealing reaction kettle, is placed in 170 It is carried out hydro-thermal process 24 hours in DEG C baking oven.After reaction, products therefrom is washed with ethyl alcohol, deionized water repeatedly, is filtered 60 DEG C of drying afterwards, then the reaction product of drying is calcined for 24 hours under 180 DEG C of environment, obtain CeO2It is nanocrystalline.
(3) bis- molybdic acid hydrate sodium of 0.25g, 0.10g g-C are taken3N4Nanometer sheet ultrasonic disperse in 0.5ml L-cysteine and In the mixed solution of 25ml dimethyl sulfoxide (DMSO), gained mixed solution is transferred in hydrothermal reaction kettle, sealing reaction kettle it Afterwards, it is placed in 200 DEG C of baking ovens and carries out hydro-thermal process 36 hours.After reaction, ethyl alcohol, deionized water are used products therefrom repeatedly Washing, 60 DEG C of drying, obtain MoS after filtering2/g-C3N4Composite material.
(4) 0.015g CeO is taken2Nanocrystalline and 0.03g MoS2/g-C3N4It is molten that compound material ultrasound is scattered in 50ml methanol In liquid, until methanol volatilizees completely, collection products therefrom is CeO for reaction under normal temperature condition2-MoS2/g-C3N4Composite material.
(5) 5g CeO is weighed2-MoS2/g-C3N4Presoma is placed in tube furnace, is 0.5L/ in stream of nitrogen gas flow It is warming up to 180 DEG C under the nitrogen atmosphere of minmm, 1h is calcined, to enhance CeO2Crystal and MoS2/g-C3N4The boundary of nanostructure Face reaction, obtains CeO2@MoS2/g-C3N4Trielement composite material.
Fig. 5 is the MoS of the present embodiment preparation method preparation2/g-C3N4With CeO2@MoS2/g-C3N4Composite photo-catalyst XPS map, as seen from the figure, CeO2@MoS2/g-C3N4Middle Ce3+And Ce4+Ion is simultaneously deposited, and the electron spin in 4 is total in conjunction with the embodiments Map shake it is found that CeO2@MoS2/g-C3N4In there are more Ce3+, then it represents that CeO2@MoS2/g-C3N4It must in composite catalyst Surely there are more Lacking oxygens, and the presence of Lacking oxygen will be more advantageous to the generation of photocatalytic redox reaction.
Fig. 6 is the MoS of the present embodiment preparation method preparation2/g-C3N4With CeO2@MoS2/g-C3N4Composite photo-catalyst Photochemical catalyst produces hydrogen experiment, as shown in Figure 5 c, CeO2@MoS2/g-C3N4Composite photo-catalyst passes through holding in 12 weeks, and light is urged Change hydrogen manufacturing performance and has no significant difference, and and g-C3N4、MoS2/g-C3N4It compares, CeO2-MoS2/g-C3N4Composite photo-catalyst exists In the case of non precious metal exists, producing hydrogen rate and be up to 65.4 μm of ol/L, quantum efficiency is up to 10.35% at 420nm, and with wave Long increase, there are still the sub- efficiency of a certain amount, this illustrates CeO2-MoS2/g-C3N4Composite photo-catalyst to visible light there are still Good utilization rate is a kind of visible light catalyst having a high potential.
Embodiment 5
(1) it takes 5g urea to be placed in Muffle furnace, is uniformly warming up to 600 DEG C with the heating rate of 5 DEG C/min, forges at a constant temperature It burns 4 hours, after natural cooling, obtained solid is ground into fine powder to get g-C is arrived3N4Nanometer sheet.
(2) six hydrous ceria of 0.2g is taken to be dissolved in 0.25ml butylamine, 30ml toluene and molten with the mixing of 12ml distilled water It in liquid, is evenly stirred until after being completely dissolved, gained mixed solution is transferred in hydrothermal reaction kettle, after sealing reaction kettle, is placed in It is carried out hydro-thermal process 24 hours in 160 DEG C of baking ovens.After reaction, products therefrom is washed with ethyl alcohol, deionized water repeatedly, mistake 60 DEG C of drying after filter, then the reaction product of drying is calcined for 24 hours under 180 DEG C of environment, obtain CeO2It is nanocrystalline.
(3) bis- molybdic acid hydrate sodium of 0.40g, 0.05g g-C are taken3N4Nanometer sheet ultrasonic disperse in 0.3ml L-cysteine and In the mixed solution of 40ml dimethyl sulfoxide (DMSO), gained mixed solution is transferred in hydrothermal reaction kettle, sealing reaction kettle it Afterwards, it is placed in 200 DEG C of baking ovens and carries out hydro-thermal process 36 hours.After reaction, ethyl alcohol, deionized water are used products therefrom repeatedly Washing, 60 DEG C of drying, obtain MoS after filtering2/g-C3N4Composite material.
(4) 0.03g CeO is taken2Nanocrystalline and 0.02g MoS2/g-C3N4Compound material ultrasound is scattered in 50ml methanol solution In, until methanol volatilizees completely, collection products therefrom is CeO for reaction under normal temperature condition2-MoS2/g-C3N4Composite material.
(5) 5g CeO is weighed2-MoS2/g-C3N4Presoma is placed in tube furnace, is 0.8L/ in stream of nitrogen gas flow 180 DEG C of calcining 1h are warming up under the nitrogen atmosphere of minmm, to enhance CeO2Crystal and MoS2/g-C3N4The interface of nanostructure Reaction, obtains CeO2@MoS2/g-C3N4Trielement composite material.
Fig. 7 is tetracycline photocatalytic degradation effect figure under radiation of visible light, as seen from the figure, compared to g-C3N4、MoS2/g- C3N4Equal catalysis materials, CeO2@MoS2/g-C3N4Three-element composite photocatalyst is under visible light illumination 20mg/L's to concentration The more apparent degradation effect of tetracycline, degradation rate are obviously improved, its photocatalytic degradation efficiency reaches within the 120min period To 95%.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields, Similarly it is included within the scope of the present invention.

Claims (9)

1. a kind of CeO2@MoS2/g-C3N4The preparation method of Three-element composite photocatalyst, which is characterized in that including preparing step as follows It is rapid:
(1) six hydrous cerias are added in the mixed solution of butylamine, toluene and distilled water, are uniformly dissolved, gained mixing is molten After liquid hydrothermal treatment, then reaction product calcined, obtains CeO2It is nanocrystalline;
(2) by two molybdic acid hydrate sodium, g-C3N4Nanometer sheet ultrasonic disperse in L-cysteine and dimethyl sulfoxide mixed solution, It washed, dried after gained mixed solution hydrothermal treatment, obtain MoS2/g-C3N4Nanometer sheet;
(3) by CeO2Nanocrystalline and MoS2/g-C3N4Nanometer sheet ultrasonic disperse is in methanol solution, and normal-temperature reaction is until methanol is complete Volatilization, collection products therefrom are CeO2-MoS2/g-C3N4Composite material;
(4) by CeO2-MoS2/g-C3N4Composite material is placed in tube furnace, under nitrogen atmosphere calcination processing, to enhance CeO2It is brilliant Body and MoS2/g-C3N4The interfacial reaction of nanostructure, obtains CeO2@MoS2/g-C3N4Three-element composite photocatalyst.
2. a kind of CeO according to claim 12@MoS2/g-C3N4The preparation method of Three-element composite photocatalyst, feature Be: six hydrous cerias described in step (1), butylamine, toluene and distilled water mass volume ratio be (0.2~0.6) g: (0.05~0.25) ml:(10~30) ml:(20~30) ml.
3. a kind of CeO according to claim 12@MoS2/g-C3N4The preparation method of Three-element composite photocatalyst, feature Be: hydro-thermal process temperature described in step (1) is 160~180 DEG C, and hydrothermal conditions are for 24 hours;The calcination temperature is 180 DEG C, calcination time is for 24 hours.
4. a kind of CeO according to claim 12@MoS2/g-C3N4The preparation method of Three-element composite photocatalyst, feature It is: step (2) the two molybdic acid hydrates sodium, L-cysteine, g-C3N4Nanometer sheet, dimethyl sulfoxide mass volume ratio be (0.20~0.40) g:(0.3~0.6) ml:(0.05~0.15) g:(20~40) ml.
5. a kind of CeO according to claim 12@MoS2/g-C3N4The preparation method of Three-element composite photocatalyst, feature Be: step (2) the hydro-thermal process temperature is 180~200 DEG C, hydrothermal conditions 36h.
6. a kind of CeO according to claim 12@MoS2/g-C3N4The preparation method of Three-element composite photocatalyst, feature It is: step (3) described CeO2Nanocrystalline, MoS2/g-C3N4The mass volume ratio of composite material and methanol is (0.01~0.03) G:(0.02~0.06) g:50ml.
7. a kind of CeO according to claim 12@MoS2/g-C3N4The preparation method of Three-element composite photocatalyst, feature Be: stream of nitrogen gas flow is 0.3~1.5L/minmm, calcining during calcination processing under step (4) described nitrogen atmosphere Temperature is 180 DEG C, calcination time 1h.
8. CeO made from any one preparation method according to claim 1~72@MoS2/g-C3N4Three-element composite photocatalyst Purposes, it is characterised in that: by CeO2@MoS2/g-C3N4Composite photo-catalyst is used for the purposes of hydrogen production by water decomposition under visible light.
9. CeO made from any one preparation method according to claim 1~72@MoS2/g-C3N4Three-element composite photocatalyst Purposes, it is characterised in that: by CeO2@MoS2/g-C3N4Composite photocatalyst is used for the purposes of degradation tetracycline under visible light.
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