CN107159264A - A kind of high-efficient full-spectrum response CuS/ graphene composite photocatalysts and preparation method thereof - Google Patents
A kind of high-efficient full-spectrum response CuS/ graphene composite photocatalysts and preparation method thereof Download PDFInfo
- Publication number
- CN107159264A CN107159264A CN201710213349.7A CN201710213349A CN107159264A CN 107159264 A CN107159264 A CN 107159264A CN 201710213349 A CN201710213349 A CN 201710213349A CN 107159264 A CN107159264 A CN 107159264A
- Authority
- CN
- China
- Prior art keywords
- cus
- graphene
- efficient full
- graphene composite
- preparation
- 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.)
- Pending
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000001228 spectrum Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000004044 response Effects 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 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 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims 1
- 239000004005 microsphere Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract 1
- 239000000975 dye Substances 0.000 abstract 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 229910001923 silver oxide Inorganic materials 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- -1 rare earth ion Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003256 environmental substance Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Toxicology (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of high-efficient full-spectrum response CuS/ graphene composite photocatalysts and preparation method thereof, the composite photo-catalyst is that CuS microballoons are attached on graphene film, and graphene is two-dimensional sheet structure, and CuS microballoons are assembled by CuS nano particles.The CuS/ graphene composite photocatalysts of the present invention have good light absorbs in ultraviolet, visible or even infrared light region, and show excellent activity in photocatalytic degradation benzene series and dyestuff contaminant and reducing heavy metal ion, with pollution-free, it is nontoxic, with low cost the advantages of, be a kind of photochemical catalyst of high-efficient full-spectrum (ultraviolet, visible and infrared light) response.The preparation technology of the present invention is simple, and mild condition is easy to operate, with low cost, it is easy to accomplish industrial scale application.
Description
Technical field
The present invention relates to field of photocatalytic material, and in particular to one kind can high-efficient full-spectrum response CuS/ graphene complex lights
Catalyst and preparation method thereof.
Background technology
Environmental pollution and energy shortage are two hang-ups that 21 century human kind sustainable development is faced, and how to seek one kind
New, environment-friendly and economically viable technical solution is urgent of pendulum in face of government and researcher
Business.Solar energy and semiconductor photocatalysis technology is acknowledged as solving the most promising green environmental protection technique of this two hang-up, tool
Have the advantages that energy consumption is low, simple to operate, reaction condition is gentle, non-secondary pollution.Typical photochemical catalyst has TiO2,CdS,C3N4Deng.
Meanwhile, researcher passes through the methods pair such as semiconductors coupling, co-catalyst, metal or nonmetallic ion-doped, dye sensitization
Semiconductor is modified, and is presented and excellent is removed removal organic polluter and heavy metal ion, the activity of photodissociation aquatic products hydrogen.Although
Great achievement is achieved, still, this field is all confined to Uv and visible light region mostly, and accounts for the infrared light of solar energy 50%
It is not utilized.In order to effectively utilize solar energy, exploitation efficiently, stable, full spectrum (it is ultraviolet, it is seen that and near-infrared) ring
The novel photochemical catalyst answered is key issue in the urgent need to address, is one of study hotspot of field of semiconductor photocatalyst.
Recently, the photochemical catalyst that researcher is responded for near-infrared is studied.Patent application
(CN101642702A；CN102489288A；CN102125828A CN103316703A) disclose a kind of semiconductor/upper conversion
Material cladding photochemical catalyst, using the characteristic of up-conversion, absorbs near infrared light so that shown under Infrared irradiation excellent
Different photocatalytic activity.But, it is just with the light of 980nm wavelength in solar spectral, and the utilization rate to solar energy compares
It is low.Meanwhile, rare earth material costly, causes photochemical catalyst cost high, there is rare earth ion losing issue, meeting during use
Environment is polluted.Patent application (CN103127946A；CN104174413A；CN105664981A；CN103301834A)
Disclose a kind of photochemical catalyst such as Cu of near infrared light response2(OH)PO4, Ag2S2O7/Ag2O, BiOBr/BiOCl, Bi2WO6, but
It is that they are merely capable of responding visible or near infrared light region.Patent application (CN103272584A) discloses a kind of full spectrum
Photochemical catalyst and preparation method thereof, Bi2WO6/TiO2Composite photo-catalyst shows under ultraviolet, visible and near infrared light
Good activity.But, the activity under Infrared irradiation is somewhat low, and only 70% or so.Patent application
(CN104353454A) preparation method of ultraviolet, visible and infrared photochemical catalyst silver oxide is disclosed, the silver oxide photochemical catalyst
Excellent activity is respectively provided with ultraviolet, visible and near infrared light.But, in During Illumination, silver oxide easily occurs
Photochemical corrosion, causes active reduction, and stability is poor.Therefore, the photochemical catalyst of high-efficient full-spectrum response is explored, is still one to choose greatly
War.
CuS has unique light, electricity and physicochemical characteristics, its energy gap 1.7-2.0eV, can have as one kind
The photochemical catalyst of potentiality, while being widely used in the fields such as solar cell, lithium ion battery.Patent application
(CN103752329A；CN105502475A；CN103638950A CuS photocatalyst and preparation method thereof) is disclosed, is shown
Outstanding photocatalytic activity and good cyclical stability.But, photo-generated carrier is compound in photocatalytic process, may still lead to
CuS catalytic activity limits its practical application than relatively low.It is a kind of expansion light absorbs and promotion to construct semiconductor composite
The effective ways that photo-generated carrier is shifted and separated.CuS base composite photocatalysts, which are reported, presents good activity.Graphene
It is a kind of typical two-dimensional layer material, it is excellent with high, the unique photoelectricity characteristic of specific surface area, good chemical stability etc.
Point, therefore it is counted as preferable semiconductor support material.Graphene has high surface area, can during light-catalyzed reaction
To provide more avtive spots.Particularly, the unique network structure of graphene and good electrical conductivity, can extend photoproduction load
The life-span of son is flowed, is combined so as to suppress it, and then reach the purpose of enhancing photocatalytic activity.Therefore, graphite is coupled in CuS
Alkene, forms CuS/ graphene composite photocatalysts, is a kind of arranging for simple and effective exploitation high-efficient full-spectrum responsive photocatalyst
Apply.However, up to the present, relevant CuS and its compound are used for light-catalysed report (Langmuir 2012,28,12893；
RSC Advance 2014,4,63447；Journal of Environmental Chemical Engineering 2016,
4,4600；Journal of Physics and Chemistry of Solids 2017,103,201；Materials
Letters 2014,126,220), all only for visible region, responded for full spectrum (ultraviolet, visible and infrared light)
CuS/ graphene composite photocatalysts, be also rarely reported.
At present, CuS preparation method mainly has solvent-thermal method, photochemical method (CN103752329A；CN105502475A；
CN103638950A) etc..But these methods more or less have deficiency, such as preparation technology is complex, takes, be difficult
Operation, cost are high, and there is certain insecurity.Therefore, a kind of simple preparation CuS/ graphene composite photocatalysts are sought
The method of agent, is conducive to furtheing investigate it and popularization and application.
The content of the invention
Regarding the issue above, the present invention provides a kind of high-efficient full-spectrum response CuS/ graphene composite photocatalysts
Agent and preparation method thereof.The full spectral response CuS/ graphene composite photocatalysts of the present invention shine in ultraviolet, visible and infrared light
Penetrate down and all show excellent photocatalytic activity, it is pollution-free, it is nontoxic and with low cost.The microwave method that the present invention is used has heating
Speed is fast, homogeneous heating, high, energy-efficient and pollution-free product purity the advantages of, it is adaptable to industrialized production.
To achieve these goals, the technical scheme that provides of the present invention is：A kind of high-efficient full-spectrum responds composite photocatalyst
Agent, described photochemical catalyst is CuS/ graphene complexes, and described compound is attached on graphene film for CuS microballoons, institute
The graphene stated is two-dimensional sheet structure, and CuS microballoons are assembled by CuS nano particles.
In above-mentioned technical proposal, it is preferred that described CuS bulb diameters are usually 200-500nm.
It is preferred that, described graphene and CuS mass ratio are 0.5%~2%.
Described composite photo-catalyst is respectively provided with excellent activity under ultraviolet, visible or even near infrared light.
The present invention also provides the preparation method that a kind of high-efficient full-spectrum responds CuS/ graphene composite photocatalysts, including with
Lower step：
The first step, copper source and graphene oxide are dissolved in deionized water together, and ultrasonic disperse is uniformly mixed molten
Liquid A；
Second step, sulphur source is dissolved in deionized water, and ultrasonic disperse obtains solution B；
3rd step, solution B is added drop-wise in solution A, stirring, obtains mixed solution C, solution C then is transferred into microwave
Pipe, is positioned in microwave reactor, is reacted 5-20 minutes under 120~160 DEG C of constant temperature, cleans, and dries, obtains high-efficient full-spectrum
Respond CuS/ graphene composite photocatalysts.
In the above method, it is preferred that described copper source is at least one in copper chloride, copper nitrate, copper sulphate, copper acetate
Kind, described graphene oxide is the graphite after oxidation, and described sulphur source is vulcanized sodium, thiocarbamide, thioacetamide, the Guang ammonia of L- half
At least one of acid.
It is preferred that, the concentration in described copper source is 0.05~0.2mol/L, the mol ratio in described sulphur source and copper source for 1~
2。
The CuS/ graphene composite photocatalysts of the present invention, under ultraviolet, visible or even Infrared irradiation, are respectively provided with excellent
Photocatalytic activity, it is nontoxic with pollution-free, be a kind of efficiently potential high-efficient full-spectrum response the advantages of with low cost
Photochemical catalyst.Meanwhile, preparation method of the invention is simply easy, and mild condition is easy to operate, it is easy to accomplish industrial scale should
With.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the CuS/ graphenes synthesized in the embodiment of the present invention 1.
Fig. 2 is the X-ray diffractogram of the CuS/ graphenes synthesized in the embodiment of the present invention 1.
Fig. 3 is the light absorbs spectrogram of the CuS/ graphenes synthesized in the embodiment of the present invention 1.
Fig. 4 is the photocatalysis efficiency figure of the CuS/ graphenes synthesized in embodiment 1 in the present invention.
Embodiment：
With reference to specific embodiment mode, the present invention is further elaborated.It should be understood that these embodiments are only used for
It is bright the present invention rather than for limiting the scope of the present invention.In addition, after present disclosure has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the appended claims restriction of the application institute
Scope.
Embodiment 1
1) preparation of photochemical catalyst
1.6mg graphite oxides are added in 10ml 0.1mol/l copper-baths, ultrasonic disperse, by 10ml
0.1mol/l thioacetyl amine aqueous solutions are added drop-wise in above-mentioned solution, are stirred 30 minutes, are formed dispersed mixed solution, are put into
In 35ml microwave tube.Then, microwave tube is placed in microwave reaction synthesizer, reacted 10 minutes at 150 DEG C, cleaned, done
It is dry, obtain CuS/ graphene complexes.
Fig. 1 is the scanning electron microscope (SEM) photograph of the CuS/ graphenes synthesized.From the figure, it can be seen that graphene is transparent, accordion
Laminated structure.Pure CuS is chondritic, and diameter is about 200-500nm, and spherical CuS is by nano particle assembling
Into, CuS microballoons are well dispersed on graphene film.
Fig. 2 is the X-ray diffractogram of the CuS/ graphenes synthesized.Found from figure, in the XRD diffraction spectras of CuS/ graphenes
Only there was only CuS diffraction maximum.The diffraction maximum of graphene is not observed, it may be possible to because the content of graphene is too in compound
It is low.
Fig. 3 is the light absorbs spectrogram of the CuS/ graphenes synthesized.From the figure, it can be seen that CuS/ graphenes it is ultraviolet, can
See that even region of ultra-red all has very strong light absorbs, a kind of photochemical catalyst of efficient full spectral response can be used as.
2) photocatalysis is tested
The above-mentioned photochemical catalyst (1g/L) prepared is put into Cr (VI) solution (100ml) that concentration is 40ppm, in magnetic
Under power stirring condition, after dark reaction 30 minutes, high-pressure sodium lamp (being used as ultraviolet source) and xenon source are opened, is put during using xenon lamp
The optical filter that cutoff wavelength is 400nm (as visible light source) and 800nm (as infrared light supply) is put, photocatalysis is carried out respectively anti-
Should.A certain amount of Cr (VI) solution is taken at regular intervals, and the absorption spectrum of solution is tested with ultraviolet-visible spectrophotometer,
Cr (VI) percent reduction can be calculated by the change of absorption peak strength.
Fig. 4 is the photocatalysis efficiency figure of the CuS/ graphenes synthesized.Wherein abscissa is light application time, and ordinate is nitro
The normalization concentration of benzole soln change.Percent reduction of the CuS/ graphenes to Cr (VI) is shown in figure.With the change of light application time
Change curve.It is seen that as light application time increases, Cr (VI) percent reduction is significantly improved.Ultraviolet, visible and red
Under outer light irradiation, CuS/ graphenes Cr (VI) percent reduction reaches more than 90%.
Embodiment 2
3.6mg graphite oxides are added in 10ml 0.15mol/l copper chloride solutions, ultrasonic disperse, by 10ml
0.2mol/l sodium sulfide solutions are added drop-wise in above-mentioned solution, are stirred 30 minutes, are formed dispersed mixed solution, are put into 35ml
Microwave tube in.Then, microwave tube is placed in microwave reaction synthesizer, reacted 10 minutes at 160 DEG C, cleaned, dried, obtain
To CuS/ graphene complexes.
Photochemical catalyst made from this example is tested under ultraviolet, visible and Infrared irradiation to nitre using 1 methods described is implemented
The degrading activity of base benzene.Its photocatalysis performance sees table 1.
Embodiment 3
1.9mg graphite oxides are added in 10ml 0.1mol/l copper nitrate solutions, ultrasonic disperse, by 10ml
0.2mol/l thiourea solutions are added drop-wise in above-mentioned solution, are stirred 30 minutes, are formed dispersed mixed solution, are put into 35ml's
In microwave tube.Then, microwave tube is placed in microwave reaction synthesizer, reacted 10 minutes at 140 DEG C, cleaned, dried, obtain
CuS/ graphene complexes.
Photochemical catalyst made from this example is tested under ultraviolet, visible and Infrared irradiation to promise using 1 methods described is implemented
Red bright B degrading activity.Its photocatalysis performance sees table 1.
Embodiment 4
4mg graphite oxides are added in 10ml 0.2mol/l acetic acid copper solutions, ultrasonic disperse, by 10ml 0.3mol/l
Cys solution is added drop-wise in above-mentioned solution, is stirred 30 minutes, is formed dispersed mixed solution, is put into the micro- of 35ml
In wave duct.Then, microwave tube is placed in microwave reaction synthesizer, reacted 10 minutes at 150 DEG C, cleaned, dried, obtain
CuS/ graphene complexes.
Photochemical catalyst made from this example is tested under ultraviolet, visible and Infrared irradiation to benzene using 1 methods described is implemented
The degrading activity of phenol.Its photocatalysis performance sees table 1.
Table 1
| Ultraviolet catalytic activity | Visible light catalysis activity | Infrared photocatalytic activity | |
| Embodiment 1 | 98% | 93% | 92% |
| Embodiment 2 | 99% | 99% | 96% |
| Embodiment 3 | 97% | 98% | 98% |
| Embodiment 4 | 99% | 99% | 96% |
It can be seen that, CuS/ graphenes of the invention have excellent ultraviolet, visible and infrared photocatalytic activity, pollution-free, nothing
Poison, the low series of advantages of cost is a kind of photochemical catalyst of high-efficient full-spectrum response.The preparation technology of the present invention is simple, temperature
Relatively low, mild condition is spent, it is easy to operate, it is with low cost, it is suitable for industrialized production.
It is above the description to case study on implementation of the present invention, by the described above to disclosed case study on implementation, makes ability
Domain professional and technical personnel can realize or using the present invention.A variety of modifications to these case study on implementation rescue the people in water to this area
Aobvious face is clear to for ignition technique personnel, generic principles defined herein can not depart from the present invention spirit or
In the case of scope, realized in other case study on implementation.Therefore the present invention will not be restricted to these implementation cases shown in this article
In example together, the features such as being to fit to principles disclosed herein and novelty thinks consistent widest range.
Claims (7)
1. a kind of high-efficient full-spectrum responds CuS/ graphene composite photocatalysts, it is characterised in that the photochemical catalyst is CuS/ stones
The compound of black alkene, described compound is attached on graphene film for CuS microballoons, and described CuS microballoons are by CuS nano particles
Assemble, described graphene is two-dimensional sheet structure.
2. high-efficient full-spectrum according to claim 1 responds CuS/ graphene composite photocatalysts, it is characterised in that described
CuS microsphere diameters be 200-500nm.
3. high-efficient full-spectrum according to claim 1 responds CuS/ graphene composite photocatalysts, it is characterised in that described
Graphene and CuS mass ratio be 0.5%~2%.
4. a kind of high-efficient full-spectrum responds the preparation method of CuS/ graphene composite photocatalysts, it is characterised in that including following
Step：
The first step, copper source and graphene oxide is dissolved in deionized water together, ultrasonic disperse, get a uniform mixture A；
Second step, sulphur source is dissolved in deionized water, and ultrasonic disperse obtains solution B；
3rd step, solution B is added drop-wise in solution A, stirring, obtains mixed solution C, solution C then is transferred into microwave tube, put
It is placed in microwave reactor, is reacted 5-20 minutes under 120~160 DEG C of constant temperature, cleaned, dried, obtains high-efficient full-spectrum response
CuS/ graphene composite photocatalysts.
5. high-efficient full-spectrum according to claim 4 responds the preparation method of CuS/ graphene composite photocatalysts, it is special
Levy and be, described copper source is at least one of copper chloride, copper nitrate, copper sulphate, copper acetate.
6. high-efficient full-spectrum according to claim 4 responds the preparation method of CuS/ graphene composite photocatalysts, it is special
Levy and be, described sulphur source is at least one of vulcanized sodium, thiocarbamide, thioacetamide, Cys.
7. high-efficient full-spectrum according to claim 4 responds the preparation method of CuS/ graphene composite photocatalysts, it is special
Levy and be, in described solution A, the concentration in copper source is 0.05~0.2mol/L, the mol ratio in described sulphur source and copper source for 1~
2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710213349.7A CN107159264A (en) | 2017-04-01 | 2017-04-01 | A kind of high-efficient full-spectrum response CuS/ graphene composite photocatalysts and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710213349.7A CN107159264A (en) | 2017-04-01 | 2017-04-01 | A kind of high-efficient full-spectrum response CuS/ graphene composite photocatalysts and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107159264A true CN107159264A (en) | 2017-09-15 |
Family
ID=59848960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710213349.7A Pending CN107159264A (en) | 2017-04-01 | 2017-04-01 | A kind of high-efficient full-spectrum response CuS/ graphene composite photocatalysts and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107159264A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117062A (en) * | 2018-02-06 | 2018-06-05 | 叶剑 | A kind of preparation method of graphite alkenes nano material |
| CN109225273A (en) * | 2018-10-18 | 2019-01-18 | 中国计量大学 | A kind of copper sulfide/tungsten sulfide composite photo-catalyst and preparation method thereof |
| CN109627867A (en) * | 2018-11-02 | 2019-04-16 | 清远市美若科新材料有限公司 | Modified fireproof coating of a kind of graphene and preparation method thereof |
| CN110368979A (en) * | 2019-08-08 | 2019-10-25 | 南京邮电大学 | A kind of tubulose g-C3N4/CuS/Cu2S nanocomposite and its preparation method and application |
| CN110841680A (en) * | 2019-11-04 | 2020-02-28 | 淮阴师范学院 | Preparation method of nitrogen and sulfur-doped graphene-CuS composite material |
| CN111504976A (en) * | 2020-04-29 | 2020-08-07 | 青岛粲耀新材料科技有限责任公司 | graphene/Cu-Cu2S composite material and preparation method thereof |
| CN111943252A (en) * | 2020-08-14 | 2020-11-17 | 武汉理工大学 | CuS/graphene nanocomposite material, preparation method thereof and application thereof in microwave absorption field |
| CN113145170A (en) * | 2020-12-31 | 2021-07-23 | 东北电力大学 | Preparation method of visible light full-absorption saturated phosphomolybdate composite material with Keggin structure |
| CN115487850A (en) * | 2022-10-28 | 2022-12-20 | 南京工程学院 | Photo-thermal catalytic composite material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105958037A (en) * | 2016-07-08 | 2016-09-21 | 华东师范大学 | Copper sulphide/graphene composite material for negative electrode of sodium-ion battery and preparation method |
-
2017
- 2017-04-01 CN CN201710213349.7A patent/CN107159264A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105958037A (en) * | 2016-07-08 | 2016-09-21 | 华东师范大学 | Copper sulphide/graphene composite material for negative electrode of sodium-ion battery and preparation method |
Non-Patent Citations (4)
| Title |
|---|
| JINGJING SHI ET AL.: "Sonochemical synthesis of CuS/reduced graphene oxide nanocomposites with enhanced absorption and photocatalytic performance", 《MATERIALS LETTERS》 * |
| PRIYAKSHREE BORTHAKUR ET AL.: "Microwave assisted synthesis of CuS-reduced graphene oxide nanocomposite with efficient photocatalytic activity towards azo dye degradation", 《JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING》 * |
| YINGWEI ZHANG ET AL.: "Biomolecule-Assisted, Environmentally Friendly, One-Pot Synthesis of CuS/Reduced Graphene Oxide Nanocomposites with Enhanced Photocatalytic Performance", 《LANGMUIR》 * |
| 徐磊等: "纳米硫化铜近红外吸收材料", 《光学学报》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117062A (en) * | 2018-02-06 | 2018-06-05 | 叶剑 | A kind of preparation method of graphite alkenes nano material |
| CN109225273A (en) * | 2018-10-18 | 2019-01-18 | 中国计量大学 | A kind of copper sulfide/tungsten sulfide composite photo-catalyst and preparation method thereof |
| CN109225273B (en) * | 2018-10-18 | 2021-03-23 | 中国计量大学 | Copper sulfide/tungsten sulfide composite photocatalyst and preparation method thereof |
| CN109627867A (en) * | 2018-11-02 | 2019-04-16 | 清远市美若科新材料有限公司 | Modified fireproof coating of a kind of graphene and preparation method thereof |
| CN109627867B (en) * | 2018-11-02 | 2021-07-16 | 清远市美若科新材料有限公司 | Graphene modified fireproof coating and preparation method thereof |
| CN110368979A (en) * | 2019-08-08 | 2019-10-25 | 南京邮电大学 | A kind of tubulose g-C3N4/CuS/Cu2S nanocomposite and its preparation method and application |
| CN110368979B (en) * | 2019-08-08 | 2022-04-22 | 南京邮电大学 | Tubular g-C3N4/CuS/Cu2S nano composite material and preparation method and application thereof |
| CN110841680A (en) * | 2019-11-04 | 2020-02-28 | 淮阴师范学院 | Preparation method of nitrogen and sulfur-doped graphene-CuS composite material |
| CN111504976B (en) * | 2020-04-29 | 2021-12-28 | 深圳米瑞科信息技术有限公司 | graphene/Cu-Cu2S composite material and preparation method thereof |
| CN111504976A (en) * | 2020-04-29 | 2020-08-07 | 青岛粲耀新材料科技有限责任公司 | graphene/Cu-Cu2S composite material and preparation method thereof |
| CN111943252A (en) * | 2020-08-14 | 2020-11-17 | 武汉理工大学 | CuS/graphene nanocomposite material, preparation method thereof and application thereof in microwave absorption field |
| CN111943252B (en) * | 2020-08-14 | 2022-09-02 | 武汉理工大学 | CuS/graphene nanocomposite material, preparation method thereof and application thereof in microwave absorption field |
| CN113145170A (en) * | 2020-12-31 | 2021-07-23 | 东北电力大学 | Preparation method of visible light full-absorption saturated phosphomolybdate composite material with Keggin structure |
| CN115487850A (en) * | 2022-10-28 | 2022-12-20 | 南京工程学院 | Photo-thermal catalytic composite material and preparation method and application thereof |
| CN115487850B (en) * | 2022-10-28 | 2023-10-24 | 南京工程学院 | Photo-thermal catalytic composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107159264A (en) | A kind of high-efficient full-spectrum response CuS/ graphene composite photocatalysts and preparation method thereof | |
| Yan et al. | Enhanced photocatalytic activity of ternary Ag3PO4/GO/g-C3N4 photocatalysts for Rhodamine B degradation under visible light radiation | |
| CN104128184B (en) | A kind of float type CoFe2O4/TiO2/ float bead composite photochemical catalyst and preparation method thereof | |
| CN103801284B (en) | A kind of preparation method of pucherite-graphene composite photocatalyst | |
| CN106902810A (en) | Individual layer Bismuth tungstate nano-sheet composite photo-catalyst of carbon quantum dot modification and its preparation method and application | |
| CN110227453B (en) | Preparation method of AgCl/ZnO/GO composite visible light catalyst | |
| CN109225273B (en) | Copper sulfide/tungsten sulfide composite photocatalyst and preparation method thereof | |
| CN108940332B (en) | High-activity MoS2/g-C3N4/Bi24O31Cl10Preparation method of composite photocatalyst | |
| CN107952464B (en) | Novel photocatalytic material and double-photocatalytic-electrode self-bias pollution control system | |
| CN107362833B (en) | A kind of preparation method of animal hair class photochemical catalyst | |
| CN102580742A (en) | Activated carbon-loaded cuprous oxide photocatalyst and preparation method thereof | |
| CN102107138A (en) | Photocatalyst, preparation method and application thereof | |
| CN108067267B (en) | Visible light response cadmium telluride/titanium dioxide Z-type photocatalyst and preparation method and application thereof | |
| CN103861621B (en) | A kind of Bi 7o 9i 3/ Graphene composite visible light catalyst and preparation method thereof | |
| CN102861567B (en) | Floating type BiVO4/floating bead composite photocatalyst and preparation method and application thereof | |
| CN110639555A (en) | CdS/CdIn with visible light response2S4Preparation method and application of composite nano-structured photocatalyst | |
| CN106607063A (en) | Floating visible-light-induced photocatalyst, and preparation method and application thereof | |
| CN106334554A (en) | ZnO/Ag composite nano-photocatalyst with high-efficiency photocatalytic activity under visible lights | |
| CN108704662A (en) | A kind of metalloporphyrin/graphite phase carbon nitride composite photo-catalyst | |
| CN106944074A (en) | A kind of visible-light response type composite photo-catalyst and its preparation method and application | |
| CN102671674A (en) | Magnetically supported silver bromide photochemical catalysis material and preparation method thereof | |
| CN106622293A (en) | Preparation method of H-TiO2/CdS/Cu(2-x)S nanoribbon | |
| CN106975503A (en) | A kind of preparation method of the modified phosphotungstic acid/titanium dioxide composite film catalyst of silver | |
| CN106693996A (en) | Preparation method and application for bismuth sulfide-bismuth ferrate composite visible-light photocatalyst | |
| CN103721713B (en) | A kind of three-phase composite visible of efficient degradation dyestuff |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170915 |
|
| RJ01 | Rejection of invention patent application after publication |