CN105935594A - Bismuth oxyiodide / nitrogen doped graphene composite photocatalyst and preparation method thereof - Google Patents
Bismuth oxyiodide / nitrogen doped graphene composite photocatalyst and preparation method thereof Download PDFInfo
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- CN105935594A CN105935594A CN201610054452.7A CN201610054452A CN105935594A CN 105935594 A CN105935594 A CN 105935594A CN 201610054452 A CN201610054452 A CN 201610054452A CN 105935594 A CN105935594 A CN 105935594A
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- graphene
- nitrogen
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- composite photocatalyst
- basic bismuth
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 116
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 title abstract 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 46
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 39
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000004202 carbamide Substances 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000012265 solid product Substances 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 39
- ORZGULPODBRYCV-UHFFFAOYSA-M bismuth;oxygen(2-);iodide Chemical compound [O-2].[I-].[Bi+3] ORZGULPODBRYCV-UHFFFAOYSA-M 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 235000013877 carbamide Nutrition 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 2
- 239000004809 Teflon Substances 0.000 abstract 1
- 229920006362 Teflon® Polymers 0.000 abstract 1
- PIMIKCFPAJSEQM-UHFFFAOYSA-N bismuth;trinitrate;hydrate Chemical compound O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PIMIKCFPAJSEQM-UHFFFAOYSA-N 0.000 abstract 1
- 238000005119 centrifugation Methods 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 description 47
- 239000007788 liquid Substances 0.000 description 18
- 238000007146 photocatalysis Methods 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- -1 OH Chemical class 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000004224 protection Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- BDJYZEWQEALFKK-UHFFFAOYSA-N bismuth;hydrate Chemical compound O.[Bi] BDJYZEWQEALFKK-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- WPQVKKFPOFIUFF-UHFFFAOYSA-M fluorolead Chemical compound [Pb]F WPQVKKFPOFIUFF-UHFFFAOYSA-M 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- B01J35/39—
-
- B01J35/60—
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/38—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a BiOI / N doped graphene composite photocatalyst and a preparation method thereof. The method mainly comprises the following steps: 1) preparing a graphene oxide colloidal suspension mixing with urea by stirring, drying, conducting high vacuum thermal reduction to obtain N doped graphene; 2) conducting ultrasonic dispersion on the N doped graphene in the glycol solution of potassium iodide, and stirring and mixing without bismuth nitrate hydrate glycol solution; and 3) transferring the above mixed solution into an autoclave with teflon liner, conducting hydrothermal reaction to obtain a solid product; and conducting repeated centrifugation, washing and drying on the solid product. The BiOI / N doped graphene composite photocatalyst prepared by the invention comprises bismuth oxyiodide in flower-like particles and nitrogen doped graphene coated with the bismuth oxyiodide particles, and forms a p-n heterojunction on the interface. The catalyst prepared by the invention has excellent performance in the field of photocatalytic degradation of organic pollutants, and has potential application value in the field of photocatalytic treatment of sewage.
Description
Technical field
The present invention relates to photocatalysis field, particularly to a kind of BiOX composite photo-catalyst and preparation method thereof.
Background technology
Problem of environmental pollution is the huge challenge that contemporary mankind faces.Along with industrialized development, dirty containing organic toxic
The trade effluent yield of dye thing acutely increases.The method that traditional wastewater processes, cost is high, and energy consumption is big.Conductor photocatalysis is degraded
Organic pollutant wastewater, becomes a kind of method of wastewater treatment having application prospect.Semiconductor light-catalyst, utilizes the sun
Can, organic substance is degraded, there is the advantages such as energy-conservation, non-secondary pollution, environmental protection, the suitability be wide.
The principle of the degradable organic pollutant of semiconductor light-catalyst is: photon energy is equal to or more than the light of energy gap
When irradiating quasiconductor, the part electrons in its valence band is excited, and transits to conduction band from valence band, such that it is able in conduction band and valence band
Forming light induced electron and photohole respectively, photo-generated carrier moves to the surface of photocatalyst and with absorption at catalyst surface
Hydroxyl (OH) and oxygen molecule (O2) etc. react, produce there is the hydroxyl radical free radical (OH) of Strong oxdiative ability, peroxide divides
Son (H2O2), superoxide radical (O2) etc.；These active substances and some radical reaction in organic molecule, it is achieved Organic substance
Degraded.
Titanium dioxide, as the earliest by the catalysis material of human research, has with low cost, and stable chemical nature etc. is excellent
Point.But owing to the energy gap of titanium dioxide is relatively big, the photon of ultraviolet waves in sunlight can only be absorbed, and UV energy
Only accounting for the 3-4% of solar energy, this solar energy utilization ratio resulting in titanium dioxide is relatively low, and photocatalysis efficiency is low.In order to extend two
The absorption bands of titanium oxide, uses some means to be modified titanium dioxide, such as dye sensitization, element doping etc..Although expanding
Open up absorbing wavelength, but created substantial amounts of defect and complex centre, limit photocatalysis efficiency.Therefore, research is at visible ray
The high-performance optical catalysis material of wave band response causes the concern of more scholar.
Basic bismuth iodide (BiOI) is one of bismuth oxyhalide with visible light catalytic performance, has the straight of 1.7ev
Tape splicing gap, can absorb visible ray；In tetragonal structure structure, its crystal structure is by Bi2O2Layer and intersect at bilayer therein
The layer structure that halogen atom is constituted；As a kind of novel photocatalyst, because of the electronic structure of its uniqueness, special stratiform knot
Structure and suitably energy gap become the focus of catalysis material research.But as single photocatalyst applications, BiOI
Photo-generate electron-hole during from vivo migration to surface, major part is combined, higher compound of its photo-generated carrier
Rate limits its photocatalysis performance；Additionally its stability, repeatable usability need to improve further.Therefore, BiOI is entered
Row study on the modification, the novel photocatalysis agent material in hgher efficiency to obtaining Photocatalytic Activity for Degradation, become in actual industrial
Seek the effective way of efficient organic wastewater degraded.
Summary of the invention
It is an object of the invention to the complex light proposing that there is under a kind of visible ray the Basic bismuth iodide of high efficiency photocatalysis activity
Catalyst and preparation method thereof.The present invention carries out compound acquisition by p-type BiOI and the nitrogen of N-shaped are mixed Graphene to have p-n different
The BiOI/N of matter junction interface structure mixes graphene composite photocatalyst；It is intended to utilize N to mix the electronic transmission performance that Graphene is excellent
And hetero-junctions can effectively facilitate the separation of electron hole, thus improve its photocatalysis efficiency.
The invention provides a kind of Basic bismuth iodide/nitrogen and mix the preparation method of graphene composite photocatalyst, comprise following step
Rapid:
Step one): with graphite powder as raw material, preparing graphene oxide by Hume's method, graphene oxide is through deionized water, ethanol
Repeatedly after filtering and washing, obtain graphene oxide suspension with deionized water for solvent；
Then, by graphene oxide suspension and carbamide mix and blend more than 12 hours, wherein graphene oxide and urea quality
Compare 0.1:1；Post-drying, grind and obtain the hybrid solid powder of graphene oxide and carbamide；Above-mentioned hybrid solid powder is existed
900-1100 DEG C of annealing under vacuum environment, obtains nitrogen and mixes Graphene.
In this process, the thermal reduction under high temperature high vacuum environment of the mixture of Graphene and carbamide, obtain oxygen-containing group
Group is few, and the nitrogen that electrical conductivity is high mixes Graphene.
Step 2): first, by described step one) nitrogen that obtains mixes in the ethylene glycol solution that Graphene adds potassium iodide, super
Sound dispersion obtains the first solution；Five nitric hydrate bismuths are dissolved in ethylene glycol and obtain the second solution；
Wherein nitrogen mixes the mass ratio of Graphene and five nitric hydrate bismuths is 0.006～0.041:1, potassium iodide and five nitric hydrate bismuths
The amount of material than for 1:1；Then, by described first solution, the second solution mixing, and stir, obtain mixed solution.
Step 3): first, by step 2) prepared mixed solution adds in autoclave, 140～180 DEG C of reactions 8
～15h；During this, under hydrothermal reaction condition, the crystallization and the nitrogen that complete Basic bismuth iodide are mixed Graphene and are aoxidized with iodine simultaneously
Bismuth compound, obtains Basic bismuth iodide and nitrogen and mixes the complex solid product of Graphene；Then, the solid product after hydro-thermal reaction is divided
Dissipate in deionized water, centrifugal rear redispersion recentrifuge in ethanol, after washing for several times, it is dried, obtains Basic bismuth iodide/nitrogen and mix
Graphene composite photocatalyst.
In this step, under specified temp and environment under high pressure, the crystallization and BiOI Yu N that complete BiOI mix Graphene simultaneously
Compound, realize nitrogen and mix the most compound of Graphene and Basic bismuth iodide；At compound interface, form heterogeneous p-n structure simultaneously, should
Structure can effectively suppress the compound of photo-generate electron-hole, improves photocatalysis performance.
As preferably, step one) temperature of described annealing is 1100 DEG C.
As preferably, step 2) described nitrogen mixes Graphene and the mass ratio 0.006:1 of five nitric hydrate bismuths.
As preferably, step 3) described in mixed solution reaction temperature in autoclave be 160 DEG C, during reaction
Between 12 hours.
Present invention also offers a kind of Basic bismuth iodide/nitrogen prepared according to method made above and mix Graphene composite photocatalyst
Agent, in this composite catalyst, described Basic bismuth iodide presents the most flower-shaped rule particle pattern, has multilamellar scale structure, its
Granularity is in 1 μm～5 μm；Nitrogen is mixed Graphene and is wrapped in flower-shaped Basic bismuth iodide granule, and both combine closely, and forms nitrogen and mixes Graphene
Composite interface structures with Basic bismuth iodide；And this composite interface structures is p-n heterojunction interfacial structure.
The present invention has the significant advantage that compared with prior art
(1) using hydro-thermal reaction method to prepare the flower-shaped BiOI granule of multilamellar scale structure, specific surface area is big, high adsorption capacity,
Be conducive to improving photocatalysis performance.
(2) it is different from traditional photocatalyst to be combined with Graphene, uses p-type BiOI and N-shaped N to mix Graphene and be combined, system
The interface mixing Graphene at BiOI Yu N for the composite photo-catalyst gone out forms heterogeneous p-n structure, advantageously in carrier
Separation, be effectively improved photocatalysis performance；Utilize N to mix the electronic transmission performance that Graphene is excellent simultaneously, improve further
The visible light photocatalysis efficiency of composite catalyst.
(3) preparation method that the present invention uses is simple and with low cost, good process repeatability, is suitable for industrial operation.
(4) result that dyestuff RhB carries out photocatalytic degradation shows, the iodine oxidation obtained according to the process of the present invention
It is that one has highly active catalyst under visible light that bismuth/nitrogen mixes graphene composite photocatalyst.
Accompanying drawing explanation
Fig. 1 is the SEM figure that the BiOI/N that embodiment 1 prepares mixes graphene composite photocatalyst.
Fig. 2 be the BiOI/N that embodiment 1 prepares mix graphene composite photocatalyst electrochemical workstation carry out Mo Te-
The result that Schottky figure (Mott-schottky) is tested.
Fig. 3 is that the BiOI/N that embodiment 1 prepares mixes the XRD figure of graphene composite photocatalyst and (meets the PDF card of BiOI
JCPDS NO. 10-0445).
Fig. 4 is that the BiOI/N that embodiment 1 prepares mixes graphene composite photocatalyst and comparative example prepares BiOI is mono-to be urged
Agent is degraded the curve of RhB under the same conditions.
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is explained in further detail, clear based on technical scheme in the embodiment of the present invention
Chu, complete description, those skilled in the art can need not additional inventive work according to this explanation again just can reproduce this
A little embodiments.
The BiOI/N that the present invention proposes is mixed graphene composite photocatalyst and is mainly prepared by hydrothermal crystallization reaction method, at water
Complete the crystallization of BiOI and N under thermal rection condition simultaneously and mix the compound of Graphene and BiOI.Its concrete preparation process is mainly wrapped
Include following three big steps.
Step (one) high temperature reduction method is prepared N and is mixed Graphene:
First, with graphite powder as raw material, preparing graphene oxide by Hume's method, graphene oxide is many through deionized water, ethanol
After secondary filtering and washing, obtain graphene oxide suspension with deionized water for solvent；
Then, by graphene oxide suspension and carbamide mix and blend more than 12 hours, post-drying, grind and obtain graphite oxide
The hybrid solid powder of alkene and carbamide；Wherein graphene oxide and the mass ratio 0.1:1 of carbamide；
Finally, by above-mentioned hybrid solid powder 900-1100 DEG C of annealing under certain vacuum environment, obtain N and mix Graphene.
Step (two) N mixes the dispersion of Graphene and the preparation of precursor solution:
First, being mixed by the N that step () obtains in the ethylene glycol solution that Graphene adds potassium iodide, ultrasonic disperse 2h obtains first
Solution；Five nitric hydrate bismuths are dissolved in ethylene glycol and obtain the second solution.Wherein N mixes Graphene and the quality of five nitric hydrate bismuths
Ratio is 0.006～0.041:1, and the amount of the material of potassium iodide and five nitric hydrate bismuths is than for 1:1.
Then, by the first solution, the second solution mixing, and stir 1h, obtain mixed solution.
Step (three) hydrothermal crystallization reacts:
First, mixed solution step (two) prepared adds in teflon-lined autoclave, 140～180 DEG C
Reaction 8～15h.During this, under hydrothermal reaction condition, the crystallization and the N that complete BiOI mix Graphene and BiOI's simultaneously
Compound, obtain BiOI Yu N and mix the complex solid product of Graphene.
Then, being disperseed in deionized water by the solid product after hydro-thermal reaction, centrifugal rear redispersion is the most again
Centrifugal, after washing for several times, it is dried, obtains BiOI/N and mix graphene composite photocatalyst.
By above-mentioned preparation method, prepare BiOI Yu N and mix the composite photo-catalyst of Graphene, by adulterating in Graphene
Nitrogen, it is thus achieved that the nitrogen of N-type mixes Graphene, is combined it with the BiOI of p-type, to obtaining the heterojunction interface structure with p-n junction
Composite photo-catalyst, be effectively improved photocatalysis efficiency；Utilize N to mix the electronic transmission performance that Graphene is excellent, further simultaneously
Improve the visible light photocatalysis efficiency of composite catalyst.
Part specific embodiment is presented herein below.Based on the embodiment in the present invention, those skilled in the art are not making
The every other embodiment obtained under creative work premise, broadly falls into the scope of protection of the invention.
Embodiment 1:
The first step: 1) with graphite powder as raw material, prepare graphene oxide by Hume's method, with deionized water, ethanol repeatedly sucking filtration
After washing, obtain graphene oxide suspension (2mg/mL) with deionized water for solvent；2) by 50mL graphene oxide suspension
With 1g carbamide (i.e. the mass ratio 0.1:1 of graphene oxide and carbamide) mix and blend more than 12 hours, then drying, grinding obtains
The hybrid solid powder of graphene oxide and carbamide；3) by above-mentioned hybrid solid powder in less than the vacuum environment of 1Pa 1100
DEG C annealing, obtain N and mix Graphene.
Second step: 1) 1.66g(10mM) potassium iodide is dissolved in 30mL ethylene glycol, and add the N that the first step obtains and mix Graphene
30mg, ultrasonic disperse 2h obtain A liquid.4.85g(10mM) (with the amount of the materials such as potassium iodide, and N mixes Graphene to five nitric hydrate bismuths
It is 0.006:1 with the mass ratio of five nitric hydrate bismuths) it is dissolved in 30mL ethylene glycol and obtains B liquid；2) by A liquid, the mixing of B liquid, and
It is stirred vigorously 1h.
3rd step: 1) mixed solution that obtained by second step adds in teflon-lined autoclave, and 160 DEG C
Hydro-thermal reaction 8h；2) being disperseed in deionized water by the solid product after hydro-thermal reaction, centrifugal rear redispersion is the most again
Centrifugal, after washing for several times, 60 DEG C are dried, obtain BiOI/N and mix graphene composite photocatalyst.
Embodiment 2:
The first step: 1) with graphite powder as raw material, prepare graphene oxide by Hume's method, repeatedly will take out with deionized water, ethanol
After filter washing, obtain graphene oxide suspension (1mg/mL) with deionized water for solvent；2) 100mL graphene oxide is suspended
Liquid and 1g carbamide (i.e. graphene oxide is 0.1:1 with the mass ratio of carbamide) mix and blend more than 12 hours, then dries, grinds
Obtain the hybrid solid powder of graphene oxide and carbamide；3) by above-mentioned hybrid solid powder less than in the vacuum environment of 1Pa
1100 DEG C of annealings, obtain N and mix Graphene.
Second step: 1) 0.83g(5mM) potassium iodide is dissolved in 30mL ethylene glycol, and add the N that the first step obtains and mix Graphene
30mg, ultrasonic disperse 2h obtain A liquid.2.42g(5mM) five nitric hydrate bismuths are dissolved in 30mL ethylene glycol and obtain B liquid, and wherein N mixes
The mass ratio of Graphene and five nitric hydrate bismuths is 0.012:1；2) by A liquid, the mixing of B liquid, and it is stirred vigorously 1h.
3rd step: 1) mixed solution that obtained by second step adds in teflon-lined autoclave, and 150 DEG C
Hydro-thermal reaction 8h；2) being disperseed in deionized water by the solid product after hydro-thermal reaction, centrifugal rear redispersion is the most again
Centrifugal, after washing for several times, 60 DEG C are dried, obtain BiOI/N and mix graphene composite photocatalyst.
Embodiment 3:
The first step: 1) with graphite powder as raw material, prepare graphene oxide by Hume's method, repeatedly will take out with deionized water, ethanol
After filter washing, obtain graphene oxide suspension (2mg/mL) with deionized water for solvent；2) 50mL graphene oxide is suspended
Liquid and 1g carbamide (i.e. graphene oxide is 0.1:1 with the mass ratio of carbamide) mix and blend more than 12 hours, then dries, grinds
Obtain the hybrid solid powder of graphene oxide and carbamide；3) by above-mentioned hybrid solid powder less than in the vacuum environment of 1Pa
1100 DEG C of annealings, obtain N and mix Graphene.
Second step: 1) 0.42g(2.5mM) potassium iodide is dissolved in 30mL ethylene glycol, and add the N that the first step obtains and mix Graphene
50mg, ultrasonic disperse 2h obtain A liquid.1.21g(2.5mM) five nitric hydrate bismuths are dissolved in 30mL ethylene glycol and obtain B liquid, wherein N
The mass ratio mixing Graphene and five nitric hydrate bismuths is 0.041:1；2) by A liquid, the mixing of B liquid, and it is stirred vigorously 1h.
3rd step: 1) mixed solution that obtained by second step adds in teflon-lined autoclave, and 160 DEG C
Hydro-thermal reaction 12h；2) being disperseed in deionized water by the solid product after hydro-thermal reaction, centrifugal rear redispersion is the most again
Centrifugal, after washing for several times, 60 DEG C are dried, obtain BiOI/N and mix graphene composite photocatalyst.
Comparative example 1:
The first step: 1) 1.66g(10mM) potassium iodide is dissolved in 30mL ethylene glycol, obtains A liquid.4.85g(10mM) five nitric hydrate
Bismuth is dissolved in 30mL ethylene glycol and obtains B liquid；2) by A liquid, B liquid mixes, and is stirred vigorously 1h.
Second step: 1) mixed solution that the first step obtained adds in teflon-lined autoclave, and 160 DEG C
Hydro-thermal reaction 8h；2) being disperseed in deionized water by the solid product after hydro-thermal reaction, centrifugal rear redispersion is the most again
Centrifugal, after washing for several times, 60 DEG C are dried, obtain BiOI photocatalyst.
Performance test:
The BiOI/N finally prepared the various embodiments described above mixes graphene composite photocatalyst and has carried out a series of performance test,
Including 1) observe, by scanning electron microscope (SEM), the BiOI/N that the present invention formed and mix the microcosmic of graphene composite photocatalyst
Pattern；2) prepared BiOI/N is mixed graphene composite photocatalyst electrochemical workstation carry out Mo Te-Schottky figure (
Mott schottky) test, reference electrode is Ag/AgCl；3) tested by X-Ray diffraction (XRD figure spectrum), analyze BiOI/N
Mix crystalline condition and the crystalline phase of graphene composite photocatalyst；4) BiOI/N that each embodiment of contrast test prepares mixes stone
The photocatalytic degradation effect of the BiOI monomer photocatalyst prepared in ink alkene composite photo-catalyst and comparative example: at 300W xenon lamp
Under (adding 420nm optical filter cut-off ultraviolet light) irradiates, test its photocatalytic degradation curve to dyestuff RhB, use photocatalyst
100mg, the RhB solution being degraded is 100mL, its concentration is 50mg/L, forms the light degradation curve of RhB.
The main properties of catalyst prepared the present invention as a example by the test result of embodiment 1 is retouched in more detail
State, such as Fig. 1～4, for the result figure of embodiment more than 1 performance test.Wherein, as it is shown in figure 1, be the prepared BiOI/ of embodiment 1
N mixes the SEM figure of graphene composite photocatalyst.From the figure, it can be seen that BiOI granule-morphology is regular, present the most flower-shaped,
Having multilamellar scale structure, its granularity is in 1 μm～5 μm；N mixes Graphene and is wrapped in flower-shaped BiOI, N mix Graphene and BiOI it
Between be tightly combined, form N and mix the composite interface structures of Graphene and BiOI.Again as in figure 2 it is shown, be that embodiment 1 is prepared
BiOI/N mixes the result that the Mo Te-Schottky figure (Mott schottky) of graphene composite photocatalyst is tested, and this curve is V
Type, illustrates that this photocatalyst is mixed at the compound interface of Graphene at BiOI and N, defines p-n heterojunction structure.On the one hand, many
The flower-like structure of layer scale structure has bigger specific surface area, can strengthen the catalysis activity of light Cui's agent；On the other hand, heavier
Want, the structure of this Graphene parcel BiOI formed just, and its p-n heterojunction constituted at interface, it is possible to promote
Light induced electron and the high efficiency separation in hole, being combined of suppression photo-generated carrier, improve quantum efficiency and photocatalytic activity, thus obtain
To high performance composite photo-catalyst.The XRD figure spectrum of Fig. 3 shows that the BiOI that BiOI/N mixes in graphene composite photocatalyst is
The cubic fluorine lead ore phase that degree of crystallinity is higher, high crystalline also can further enhance the catalysis activity of catalyst.In Fig. 4, display
Be the light degradation curve of the photocatalyst for degrading RhB that embodiment 1 and comparative example prepare.It can be seen that BiOI with N mixes in figure
After Graphene is compound, compared with the mono-catalyst of BiOI that comparative example prepares, under the same conditions, its Photocatalytic Degradation Property obtains
It is greatly improved.
The composite photo-catalyst that the present invention prepares has efficient visible light photocatalysis efficiency, and its preparation method raw material holds
Easily obtaining, reaction unit is simple, has application prospect at field of Environment Protections such as photocatalysis degradation organic contaminants.It is above the present invention
Part preferred embodiment, based on the embodiment in the present invention, those skilled in the art are not making creative work premise
Lower obtained every other embodiment, broadly falls into the scope of protection of the invention.
Claims (5)
1. Basic bismuth iodide/nitrogen mixes the preparation method of graphene composite photocatalyst, it is characterised in that comprise the steps of:
Step one):
With graphite powder as raw material, preparing graphene oxide by Hume's method, graphene oxide is through deionized water, ethanol repeatedly sucking filtration
After washing, obtain graphene oxide suspension with deionized water for solvent；
Then, by graphene oxide suspension and carbamide mix and blend more than 12 hours, wherein graphene oxide and urea quality
Compare 0.1:1；Post-drying, grind and obtain the hybrid solid powder of graphene oxide and carbamide；Above-mentioned hybrid solid powder is existed
900-1100 DEG C of annealing under vacuum environment, obtains nitrogen and mixes Graphene；
Step 2):
First, by described step one) nitrogen that obtains mixes in the ethylene glycol solution that Graphene adds potassium iodide, and ultrasonic disperse obtains the
One solution；Five nitric hydrate bismuths are dissolved in ethylene glycol and obtain the second solution；
Wherein nitrogen mixes the mass ratio of Graphene and five nitric hydrate bismuths is 0.006～0.041:1, potassium iodide and five nitric hydrate bismuths
The amount of material than for 1:1；
Then, by described first solution, the second solution mixing, and stir, obtain mixed solution；
Step 3):
First, by step 2) prepared mixed solution adds in autoclave, 140～180 DEG C of reactions 8～15h；This process
In, under hydrothermal reaction condition, complete the crystallization of Basic bismuth iodide simultaneously and nitrogen mixes the compound of Graphene and Basic bismuth iodide, obtain
Basic bismuth iodide and nitrogen mix the complex solid product of Graphene；
Then, the solid product after hydro-thermal reaction is disperseed in deionized water, centrifugal rear redispersion recentrifuge in ethanol,
After washing for several times, it is dried, obtains Basic bismuth iodide/nitrogen and mix graphene composite photocatalyst.
A kind of Basic bismuth iodide/nitrogen the most according to claim 1 mixes the preparation method of graphene composite photocatalyst, its feature
It being: step one) temperature of described annealing is 1100 DEG C.
A kind of Basic bismuth iodide/nitrogen the most according to claim 1 mixes the preparation method of graphene composite photocatalyst, its feature
It is: described nitrogen mixes Graphene and the mass ratio 0.006:1 of five nitric hydrate bismuths.
A kind of Basic bismuth iodide/nitrogen the most according to claim 1 mixes the preparation method of graphene composite photocatalyst, its feature
Be: step 3) described in mixed solution reaction temperature in autoclave be 160 DEG C, 12 hours response time.
5. Basic bismuth iodide/the nitrogen prepared according to Claims 1-4 any one preparation method mixes graphene composite photocatalyst,
It is characterized in that: described Basic bismuth iodide presents the most flower-shaped rule particle pattern, has multilamellar scale structure, and its granularity is at 1 μ
M～5 μm；Nitrogen is mixed Graphene and is wrapped in flower-shaped Basic bismuth iodide granule, and both combine closely, and forms nitrogen and mixes Graphene and iodine oxidation
The composite interface structures of bismuth；And this composite interface structures is p-n heterojunction interfacial structure.
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