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 PDFInfo
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- 229910052961 molybdenite Inorganic materials 0.000 title claims abstract description 105
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 105
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 54
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 28
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 26
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000047 product Substances 0.000 claims abstract description 19
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000002086 nanomaterial Substances 0.000 claims abstract description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 239000004201 L-cysteine Substances 0.000 claims abstract description 8
- 235000013878 L-cysteine Nutrition 0.000 claims abstract description 8
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 5
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 25
- 229910001868 water Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- 239000004098 Tetracycline Substances 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 229960002180 tetracycline Drugs 0.000 claims description 6
- 229930101283 tetracycline Natural products 0.000 claims description 6
- 235000019364 tetracycline Nutrition 0.000 claims description 6
- 150000003522 tetracyclines Chemical class 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 238000010406 interfacial reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000001035 drying Methods 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004435 EPR spectroscopy Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y40/00—Manufacture or treatment of nanostructures
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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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
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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