CN108940332A - A kind of high activity MoS2/g-C3N4/Bi24O31Cl10The preparation method of composite photo-catalyst - Google Patents

A kind of high activity MoS2/g-C3N4/Bi24O31Cl10The preparation method of composite photo-catalyst Download PDF

Info

Publication number
CN108940332A
CN108940332A CN201810576978.0A CN201810576978A CN108940332A CN 108940332 A CN108940332 A CN 108940332A CN 201810576978 A CN201810576978 A CN 201810576978A CN 108940332 A CN108940332 A CN 108940332A
Authority
CN
China
Prior art keywords
mos
solution
catalyst
prepared
methanol
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.)
Granted
Application number
CN201810576978.0A
Other languages
Chinese (zh)
Other versions
CN108940332B (en
Inventor
王敏
张宇
刘施羽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northeastern University China
Original Assignee
Northeastern University China
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Northeastern University China filed Critical Northeastern University China
Priority to CN201810576978.0A priority Critical patent/CN108940332B/en
Publication of CN108940332A publication Critical patent/CN108940332A/en
Application granted granted Critical
Publication of CN108940332B publication Critical patent/CN108940332B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • B01J35/39
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents

Abstract

The invention belongs to new material, utilization of new energy resources and technical field of environment pollution control, are related to a kind of high activity MoS2/g‑C3N4/Bi24O31Cl10The preparation method of composite photo-catalyst.Using bismuth nitrate, ammonium chloride, citric acid as raw material, Bi is prepared using improved solution combustion method24O31Cl10;Using melamine, acetic acid as raw material, g-C is prepared using a step thermal polymerization3N4;Using ammonium molybdate, thiocarbamide as raw material, dimethylformamide is solvent, prepares MoS using hydro-thermal method2;The Bi that will be handled through ultrasonic disperse24O31Cl10With g-C3N4、MoS2In methanol solution after ultrasonic mixing reaction, washing, centrifugation, drying are to get the composite photo-catalyst.This method is simple and easy, low in cost, reproducible, is with a wide range of applications in fields such as photodegradation water, photochemical catalytic oxidation environmental contaminants.

Description

A kind of high activity MoS2/g-C3N4/Bi24O31Cl10The preparation method of composite photo-catalyst
Technical field
The invention belongs to new material, utilization of new energy resources and technical field of environment pollution control, are related to a kind of high activity MoS2/ g-C3N4/Bi24O31Cl10The preparation method of composite photo-catalyst.
Background technique
With the increasingly exacerbation of problem of environmental pollution, photocatalysis technology is in terms of photolysis water hydrogen and degradable organic pollutant More and more paid attention to.Wherein, TiO2Have many advantages, such as that at low cost, photocatalysis stability is good, photocatalysis efficiency is high, is light Common used material in catalytic field.But TiO2Photochemical catalyst is since its forbidden bandwidth is wide, about 3.1eV, can only by ultraviolet excitation, and Ultraviolet light only accounts for 5% or so of solar spectrum, low to the utilization rate of sunlight, limits it to a certain extent in environmental improvement The application of aspect.Therefore, utmostly to utilize solar energy, R and D can be mesh by the new catalyst of excited by visible light Preceding research emphasis and hot spot.
Bismuth series catalysts are current a kind of novel visible catalysts of greatest concern, it becomes at aspect of curbing environmental pollution It is now good, increasingly liked by domestic and international researcher.Their most prominent advantages are exactly that forbidden bandwidth is relatively narrow, this Feature is conducive to its organic pollutant in photocatalytic degradation environment under visible light.Wherein Bi24O31Cl10As a kind of oxygen-enriched Bismuth series catalysts, due to having the advantage that forbidden bandwidth is small, about 2.8eV can be by excited by visible light;It is chemically and physically stable Property is good;It is high with unique crystal structure, quantum efficiency, just becoming research hotspot in recent years.Such as Jin uses hydro-thermal legal system For with a thickness of 300nm, the Bi that width is 1-3 μm24O31Cl10Photochemical catalyst, compared with BiOCl, Bi24O31Cl10In visible light Visible light can be preferably absorbed under (> 420 nm) irradiation, and effectively can generate O by activating molecules oxygen2·-, to enhance Bi24O31Cl10Visible light photocatalysis active.The method that Yin etc. is combined using hydro-thermal and heat treatment, is prepared for Bi24O31Cl10 Nanometer sheet is used for the degradation of quadracycline, illumination 150min under visible light, to the degradation rate of quadracycline up to 80% with On.However, pure Bi24O31Cl10Photoproduction-electron hole it is easily compound, and specific surface area is smaller, causes its photocatalytic activity lower, Actual industrial application is not able to satisfy still, for this purpose, also need to adopt various measures to improve its photocatalytic activity, such as by energy band position It is compound to set the different semiconductor materials progress to match, forms hetero-junctions, the compound of material internal electrons and holes can be reduced Rate.
MoS2It is the photon that a type graphene hexagonal closs packing layer structure material can absorb visible frequency, and it is led The edge current potential of band and valence band is high, when compound with other photochemical catalysts, can effectively enhance the absorbability to light, and can play fast The effect of speed transmission electronics.And g-C3N4It is a kind of polymer semiconductor similar to graphene-structured, C, N atom are with sp2 hydridization Form the pi-conjugated system of height delocalization.g-C3N4Have many advantages, such as that the from a wealth of sources of polymer material, price be low, chemical stabilization, And have certain absorption to visible light, there is preferable photocatalysis performance.And MoS2With g-C3N4Valence band and conduction band positions with Bi24O31Cl10Energy good match, forms hetero-junctions, on the one hand enhances Bi24O31Cl10Light absorpting ability, and can effectively subtract Few Bi24O31Cl10The recombination rate of internal electron and hole, and in Bi24O31Cl10The thin layer MoS of particle surface cladding2With g-C3N4 Nanometer sheet increases the specific surface area of catalyst, the pre- adsorbance of catalyst surface in organic pollutant is increased, to also have Conducive to the raising of light-catalyzed reaction efficiency.
In view of this, it is necessary to provide a kind of MoS2/g-C3N4/Bi24O31Cl10The preparation method of heterojunction photocatalyst.
Summary of the invention
To solve the above problems, the present invention provides a kind of high activity MoS2/g-C3N4/Bi24O31Cl10Composite photo-catalyst Preparation method.
Preparation method of the invention, first using bismuth nitrate, ammonium chloride, citric acid as raw material, the improvement solution combustion of use Method prepares Bi24O31Cl10, the then ultrasonic disperse in methanol solution;Secondly using melamine, acetic acid as raw material, using step heat Polymerization prepares g-C3N4, the then ultrasonic disperse in methanol solution;Using ammonium molybdate, thiocarbamide as raw material, dimethylformamide is molten Agent prepares MoS using hydro-thermal method2, ultrasonic disperse is handled in methanol solution.It will finally handle through ultrasonic disperse Bi24O31Cl10With g-C3N4、MoS2It is dry after then washed, centrifugation after ultrasonic mixing is sufficiently reacted in methanol solution, i.e., Obtain MoS2/g-C3N4/Bi24O31Cl10Composite photo-catalyst.
Technical solution of the present invention:
A kind of high activity MoS2/g-C3N4/Bi24O31Cl10The preparation method of composite photo-catalyst, steps are as follows:
(1) using bismuth nitrate, ammonium chloride, citric acid as raw material, Bi is prepared using improved solution combustion method24O31Cl10
Five nitric hydrate bismuths and citric acid are mixed and are dissolved in dust technology, dilute nitre of five nitric hydrate bismuths and citric acid is obtained The mixed solution of acid, wherein five nitric hydrate bismuths and citric acid molar ratio are 1:2;Ammonium chloride is dissolved in distilled water, until complete Dissolution, obtains ammonium chloride solution;Under agitation, ammonium chloride solution is added to dilute nitre of five nitric hydrate bismuths and citric acid In the mixed solution of acid, wherein five nitric hydrate bismuths are 1:1 with ammonium chloride molar ratio, are uniformly mixed to solution in clear state When, solution ph is adjusted to 5~6 with ammonium hydroxide;3~4h of heating stirring under the conditions of 60 DEG C~80 DEG C, then under the conditions of 600 DEG C 3h is calcined, obtains pale yellow powder, as pure Bi24O31Cl10
(2) using melamine, acetic acid as raw material, g-C is prepared using a step thermal polymerization3N4
Melamine is uniformly mixed with acetic acid according to the molar ratio of 10:1,2h is calcined at 500 DEG C, obtains yellowish toner End, as pure g-C3N4
(3) using ammonium molybdate, thiocarbamide as raw material, dimethylformamide is solvent, prepares MoS using hydro-thermal method2
Compound concentration is the mixed solution of the Ammonium Molybdate Tetrahydrate of 4.8~5.0g/L and the dimethylformamide of thiocarbamide, In, the mass ratio of Ammonium Molybdate Tetrahydrate and thiocarbamide is 1:2;Stirring, until the dimethylformamide of Ammonium Molybdate Tetrahydrate and thiocarbamide The transparent state of mixed solution;After reacting for 24 hours at 200 DEG C in a kettle, it is cooled to room temperature;Deionized water washing, centrifugation, Obtain black solid, by black solid dry 12 at 60 DEG C~100 DEG C~for 24 hours, obtain MoS2
(4) Bi that step (1) is prepared24O31Cl10Be added in methanol solution, ultrasound, obtain concentration be 40~ The Bi of 50g/L24O31Cl10With the mixed solution of methanol;The g-C that step (2) is prepared3N4It is added to Bi24O31Cl10With first In the mixed solution of alcohol, wherein g-C3N4With Bi24O31Cl10Mass ratio is 0.01~0.1;Continue ultrasound, be then centrifuged for, wash, It is centrifuged again, obtains solid matter;Solid matter is dried into for 24 hours~48h under the conditions of 60 DEG C~80 DEG C, grinds, obtains after cooling 1%~10%g-C3N4/ Bi24O31Cl10Composite photo-catalyst;
(5) 5%g-C that step (4) is prepared3N4/Bi24O31Cl10It is added in methanol solution, ultrasound obtains concentration For the 5%g-C of 40~50g/L3N4/Bi24O31Cl10With the mixed solution of methanol;The MoS that step (3) is prepared2It is added To 5%g-C3N4/Bi24O31Cl10In the mixed solution of methanol, wherein MoS2With 5%g-C3N4/Bi24O31Cl10Mass ratio It is 0.03~0.07;Continue ultrasound, is then centrifuged for, washs, is centrifuged again, obtain solid matter;By solid matter 60 DEG C~80 Dry 24~48h at DEG C, grinds after cooling to get 3%~7%MoS2/ 5%g-C3N4/Bi24O31Cl10Composite photo-catalyst.
Beneficial effects of the present invention: after tested, 5%MoS2/ 5%g-C3N4/Bi24O31Cl10To the catalytic degradation of rhodamine B Rate can reach 99%, while the composite catalyst can also reach 90% or more in 50min to the degradation rate of tetracycline, purer Bi24O31Cl10, 5%MoS2/Bi24O31Cl10, 5%g-C3N4/Bi24O31Cl10Photocatalysis efficiency be significantly improved.We Method is simple and easy, low in cost, reproducible, has in fields such as photodegradation water, photochemical catalytic oxidation environmental contaminants extensive Application prospect.
Detailed description of the invention
Fig. 1 is Bi24O31Cl1、MoS2、g-C3N4, 5%g-C3N4/Bi24O31Cl10, 5%MoS2/Bi24O31Cl10, 5% MoS2/ 5%g-C3N4/Bi24O31Cl10The XRD spectrum of photochemical catalyst;
Fig. 2 (a) is Bi24O31Cl10The SEM of photochemical catalyst schemes;
Fig. 2 (b) is 5%MoS2/ 5%g-C3N4/Bi24O31Cl10The SEM spectrum of photochemical catalyst;
Fig. 2 (c) is EDS map;
Fig. 3 is the UV-Vis map of photochemical catalyst;Wherein, a indicates Bi24O31Cl10, b indicate 5%g-C3N4/ Bi24O31Cl10, c indicate 5%MoS2/Bi24O31Cl10, d indicate 5%MoS2/ 5%g-C3N4/ Bi24O31Cl10, e indicate MoS2Light The UV-Vis map of catalyst;
Fig. 4 is Bi24O31Cl10, 5%g-C3N4/Bi24O31Cl10, 5%MoS2/Bi24O31Cl10, 5%MoS2/ 5%g- C3N4/Bi24O31Cl10The PL map of photochemical catalyst;
Fig. 5 is for photochemical catalyst to the degradation efficiency of rhodamine B under visible light photograph;Wherein, a indicates Bi24O31Cl10, b table Show 1%g-C3N4/Bi24O31Cl10, c indicate 3%g-C3N4/Bi24O31Cl10, d indicate 5%g-C3N4/Bi24O31Cl10, e indicate 10%g-C3N4/Bi24O31Cl10, f indicate 5%MoS2/Bi24O31Cl10, g indicate 3%MoS2/ 5%g-C3N4/Bi24O31Cl10、h Indicate 5%MoS2/ 5%g-C3N4/Bi24O31Cl10, i indicate 7%MoS2/ 5%g-C3N4/Bi24O31Cl10
The Bi of Fig. 6 preparation24O31Cl10, 5%g-C3N4/Bi24O31Cl10, 5%MoS2/Bi24O31Cl10, 5%MoS2/ 5% g-C3N4/Bi24O31Cl10Photochemical catalyst is under visible light photograph to the degradation efficiency of tetracycline.
Specific embodiment
Below in conjunction with attached drawing and technical solution, a specific embodiment of the invention is further illustrated.
Preparation method through the invention prepares 3%~7%MoS2/ 5%g-C3N4/Bi24O31Cl10Composite photo-catalyst, And prepare 5%MoS2/Bi24O31Cl10Composite photo-catalyst compares the effect of each composite photo-catalyst.
Embodiment 1
(1)Bi24O31Cl10Preparation: take five nitric hydrate bismuth of 0.01mol to be dissolved in the dust technology of 10% volumetric concentration of 50ml In, 0.02mol citric acid is then added, is uniformly mixed until being completely dissolved;In addition the ammonium chloride of 0.01mol is dissolved in 50ml In distilled water, it is uniformly mixed until being completely dissolved.Under constant temperature blender with magnetic force stirring, ammonium chloride solution is slowly injected to five water In the mixed solution for closing the dust technology of bismuth nitrate and citric acid, when being uniformly mixed to solution in clear state, adjusted using ammonium hydroxide Then mixed solution pH value continues heating stirring 4h at 60 DEG C, is poured into crucible with cover, then in muffle furnace to 6 3h is calcined at 600 DEG C, obtains pale yellow powder, as pure Bi24O31Cl10
(2)g-C3N4Preparation: 3g melamine is uniformly mixed with 10 milliliters of acetic acid (concentration 36%), has been put in lid In crucible, 2h then is calcined at 500 DEG C in muffle furnace, obtains pale yellow powder, as pure g-C3N4
(3)MoS2Preparation: 80 milligrams of Ammonium Molybdate Tetrahydrates and 160 milligrams of thiocarbamides are dissolved in 50 milliliters of dimethylformamides Solvent, magnetic agitation until reaction raw materials be dissolved as it is transparent, then go to 100 milliliters of liners be tetrafluoroethene stainless steel hydro-thermal Reaction kettle is reacted for 24 hours at 200 DEG C, is cooled to room temperature, then high speed centrifugation, distillation water washing 5 under 10000r/min revolving speed Black solid is obtained after secondary, drying for 24 hours, obtains MoS in drying box 60 DEG C2
(4) by 2 grams of Bi obtained by step (1)24O31Cl10It is separately added into 40 ml methanol solution, under 1000KW power Ultrasonic 1h, then in Bi24O31Cl10Be separately added into methanol mixed solution prepared by step (2) 0.02 gram, 0.06 gram, 0.10 gram and 0.2 gram of g-C3N4Powder then proceedes to the ultrasound 1h under 1000KW power, then solid and methanol solution exists It is centrifuged under 10000r/min revolving speed, is then washed with distilled water, then be centrifuged, the solid obtained after being repeated four times, in drying box Drying for 24 hours, is ground after cooling up to 1%~10%g-C at 60 DEG C3N4/Bi24O31Cl10Composite photo-catalyst.
(5) 1 gram of 5%g-C for obtaining step (4)3N4/Bi24O31Cl10Sample is added in 20 ml methanol solution, Ultrasound 1h under 1000KW power, then in 5%g-C3N4/Bi24O31Cl10It is made that step (3) is separately added into methanol mixed solution Standby 0.3g MoS2Powder then proceedes to the ultrasound 1h under 1000KW power, then by solid and methanol solution in 10000r/ It is centrifuged under min revolving speed, is then washed with distilled water, then be centrifuged, the solid obtained after being repeated four times is done in drying box 60 DEG C Dry 48h is ground after cooling up to 3%MoS2/ 5%g-C3N4/Bi24O31Cl10Composite photo-catalyst.
(6) by 1 gram of Bi obtained by step (1)24O31Cl10It is added in 20 ml methanol solution, it is ultrasonic under 1000KW power 1h, then in Bi24O31Cl10With 0.5 gram of MoS prepared by addition step (3) in methanol mixed solution2Powder then proceedes to Solid and methanol solution, are then centrifuged under 10000r/min revolving speed, then use distilled water by the ultrasound 1h under 1000KW power Washing, then be centrifuged, the solid obtained after being repeated four times, drying for 24 hours, is ground after cooling up to 5% in drying box 60 DEG C MoS2/Bi24O31Cl10Composite photo-catalyst.
Embodiment 2
(1)Bi24O31Cl10Preparation: take five nitric hydrate bismuth of 0.01mol to be dissolved in the dust technology of 10% volumetric concentration of 50ml In, 0.02mol citric acid is then added, is uniformly mixed until being completely dissolved;In addition the ammonium chloride of 0.01mol is dissolved in 50ml In distilled water, it is uniformly mixed until being completely dissolved.Under constant temperature blender with magnetic force stirring, ammonium chloride solution is slowly injected to five water In the mixed solution for closing the dust technology of bismuth nitrate and citric acid, when being uniformly mixed to solution in clear state, adjusted using ammonium hydroxide Then mixed solution pH value continues heating stirring 3h at 80 DEG C, is poured into crucible with cover, then in muffle furnace to 5 3h is calcined at 600 DEG C, obtains pale yellow powder, as pure Bi24O31Cl10
(2)g-C3N4Preparation: 3g melamine is uniformly mixed with 10 milliliters of acetic acid (concentration 36%), has been put in lid In crucible, 2h then is calcined at 500 DEG C in muffle furnace, obtains pale yellow powder, as pure g-C3N4
(3)MoS2Preparation: 60 milligrams of Ammonium Molybdate Tetrahydrates and 120 milligrams of thiocarbamides are dissolved in 36 milliliters of dimethylformamides Solvent, magnetic agitation until reaction raw materials be dissolved as it is transparent, then go to 50 milliliters of liners be tetrafluoroethene stainless steel hydro-thermal Reaction kettle is reacted for 24 hours at 200 DEG C, is cooled to room temperature, then high speed centrifugation, distillation water washing 5 under 10000r/min revolving speed Black solid is obtained after secondary, dry 12h, obtains MoS in drying box 100 DEG C2
(4) by 1 gram of Bi obtained by step (1)24O31Cl10It is separately added into 25 ml methanol solution, under 1000KW power Ultrasonic 1h, then in Bi24O31Cl10Be separately added into methanol mixed solution prepared by step (2) 0.01 gram, 0.03 gram, 0.05 gram and 0.1 gram of g-C3N4Powder then proceedes to the ultrasound 1h under 1000KW power, then solid and methanol solution exists It is centrifuged under 10000r/min revolving speed, is then washed with distilled water, then be centrifuged, the solid obtained after being repeated four times, in drying box Dry 48h, grinds after cooling up to 1%~10%g-C at 80 DEG C3N4/Bi24O31Cl10Composite photo-catalyst.
(5) 1.8 grams of 5%g-C for obtaining step (4)3N4/Bi24O31Cl10Sample is added in 40 ml methanol solution, Ultrasound 1h under 1000KW power, then in 5%g-C3N4/Bi24O31Cl10It is made that step (3) is separately added into methanol mixed solution Standby 0.09g MoS2Powder then proceedes to the ultrasound 1h under 1000KW power, then by solid and methanol solution in 10000r/ It is centrifuged under min revolving speed, is then washed with distilled water, then be centrifuged, the solid obtained after being repeated four times is done in drying box 80 DEG C It is dry for 24 hours, ground after cooling up to 5%MoS2/ 5%g-C3N4/Bi24O31Cl10Composite photo-catalyst.
(6) by 1 gram of Bi obtained by step (1)24O31Cl10It is added in 20 ml methanol solution, it is ultrasonic under 1000KW power 1h, then in Bi24O31Cl10With 0.5 gram of MoS prepared by addition step (3) in methanol mixed solution2Powder then proceedes to Solid and methanol solution, are then centrifuged under 10000r/min revolving speed, then use distilled water by the ultrasound 1h under 1000KW power Washing, then be centrifuged, the solid obtained after being repeated four times, drying for 24 hours, is ground after cooling up to 5% in drying box 60 DEG C MoS2/Bi24O31Cl10Composite photo-catalyst.
Embodiment 3
(1)Bi24O31Cl10Preparation: take five nitric hydrate bismuth of 0.01mol to be dissolved in the dust technology of 10% volumetric concentration of 50ml In, 0.02mol citric acid is then added, is uniformly mixed until being completely dissolved;In addition the ammonium chloride of 0.01mol is dissolved in 50ml In distilled water, it is uniformly mixed until being completely dissolved.Under constant temperature blender with magnetic force stirring, ammonium chloride solution is slowly injected to five water In the mixed solution for closing the dust technology of bismuth nitrate and citric acid, when being uniformly mixed to solution in clear state, adjusted using ammonium hydroxide Then mixed solution pH value continues heating stirring 3.5h at 60 DEG C, is poured into crucible with cover, then in muffle furnace to 6 In calcine 3h at 600 DEG C, obtain pale yellow powder, as pure Bi24O31Cl10
(2)g-C3N4Preparation: 3g melamine is uniformly mixed with 10 milliliters of acetic acid (concentration 36%), has been put in lid In crucible, 2h then is calcined at 500 DEG C in muffle furnace, obtains pale yellow powder, as pure g-C3N4
(3)MoS2Preparation: 45 milligrams of Ammonium Molybdate Tetrahydrates and 90 milligrams of thiocarbamides are dissolved in 27.5 milliliters of dimethyl formyls Amine solvent, magnetic agitation until reaction raw materials be dissolved as it is transparent, then go to 50 milliliters of liners be tetrafluoroethene stainless steel water Thermal response kettle is reacted for 24 hours at 200 DEG C, is cooled to room temperature, then high speed centrifugation, distillation water washing under 10000r/min revolving speed Black solid is obtained after 5 times, dry 18h, obtains MoS in drying box 80 DEG C2
(4) by 9 grams of Bi obtained by step (1)24O31Cl10It is separately added into 200 ml methanol solution, under 1000KW power Ultrasonic 1h, then in Bi24O31Cl10Be separately added into methanol mixed solution prepared by step (2) 0.09 gram, 0.27 gram, 0.45 gram and 0.9 gram of g-C3N4Powder then proceedes to the ultrasound 1h under 1000KW power, then solid and methanol solution exists It is centrifuged under 10000r/min revolving speed, is then washed with distilled water, then be centrifuged, the solid obtained after being repeated four times, in drying box Dry 36h, grinds after cooling up to 1%~10%g-C at 70 DEG C3N4/Bi24O31Cl10Composite photo-catalyst.
(5) 1.5 grams of 5%g-C for obtaining step (4)3N4/Bi24O31Cl10Sample is added in 30 ml methanol solution, Ultrasound 1h under 1000KW power, then in 5%g-C3N4/Bi24O31Cl10It is made that step (3) is separately added into methanol mixed solution Standby 0.105g MoS2Powder then proceedes to the ultrasound 1h under 1000KW power, then solid and methanol solution exists It is centrifuged under 10000r/min revolving speed, is then washed with distilled water, then be centrifuged, the solid obtained after being repeated four times, in drying box Dry 36h, grinds after cooling up to 7%MoS at 70 DEG C2/ 5%g-C3N4/Bi24O31Cl10Composite photo-catalyst.
(6) by 1 gram of Bi obtained by step (1)24O31Cl10It is added in 20 ml methanol solution, it is ultrasonic under 1000KW power 1h, then in Bi24O31Cl10With 0.5 gram of MoS prepared by addition step (3) in methanol mixed solution2Powder then proceedes to Solid and methanol solution, are then centrifuged under 10000r/min revolving speed, then use distilled water by the ultrasound 1h under 1000KW power Washing, then be centrifuged, the solid obtained after being repeated four times, drying for 24 hours, is ground after cooling up to 5% in drying box 60 DEG C MoS2/Bi24O31Cl10Composite photo-catalyst.
Structure and morphology characterization:
It will be seen from figure 1 that the Bi of preparation24O31Cl10With JCPDS standard card number (No.75-0887) tetragonal crystal system Bi24O31Cl10Diffraction maximum matches.5%g-C3N4/Bi24O31Cl10Without g-C in sample3N4Peak, 5%MoS2/Bi24O31Cl10、 Without MoS in sample2Peak, 5%MoS2/ 5%g-C3N4/Bi24O31Cl105% there are no g-C3N4And MoS2Peak, mainly by In compound g-C3N4And MoS2Amount it is less caused by.
From Fig. 2 (a), 2 (b) and 2 (c) as can be seen that the 5%MoS of preparation2/ 5%g-C3N4/Bi24O31Cl10In sample at Function is compounded with g-C3N4And MoS2
From figure 3, it can be seen that working as Bi24O31Cl10With MoS2Or g-C3N4After compound, the absorbing properties of sample are obtained obviously It is promoted, wherein compound MoS2The more compound g-C of the absorbing properties of sample afterwards3N4It is promoted more significant, works as MoS2With g-C3N4Simultaneously Compound Bi24O31Cl10When absorbing properties promoted maximum, have apparent light absorption within the scope of 200-800nm.
From fig. 4, it can be seen that 5%MoS2/ 5%g-C3N4/Bi24O31Cl10PL peak intensity it is minimum, illustrate the photochemical catalyst Minimum, the lower recombination rate of photoexcited electron-hole recombination rate, be conducive to the raising of photocatalytic activity.
Photocatalytic activity test experiments:
Taking initial concentration is 5mgL-1Rhodamine B (RhB) solution 100mL or 20mgL-1Quadracycline solution 50mL is placed in 250mL beaker as target degradation product, then adds 0.03g photochemical catalyst in rhodamine B or quadracycline In solution, it is uniformly mixed.Before illumination, first by this suspension in darkroom magnetic agitation 30min, make photochemical catalyst and rhodamine Reach adsorption-desorption balance between B or tetracycline, is then placed on visible light source (the 250W gold halogen away from liquid level 14cm Lamp) under carry out photocatalysis experiment.Light application time is 50min, wherein the rubber head dropper every 10min cleaning takes supernatant, Centrifugation is placed in cuvette, its absorbance, root are surveyed at the maximum absorption wavelength 554nm and 356nm of rhodamine B and tetracycline According to langbobier law, the removal rate D of rhodamine B or tetracycline can be calculated by formula (1):
D=(C0-C)/C0× 100%=(A0’-A)/A0' × 100% (1)
In formula: C0, C --- before illumination and illumination after the concentration of rhodamine B or tetracycline;
A0', A --- before illumination and illumination after the absorbance of rhodamine B or tetracycline
5%MoS as shown in Figure 52/ 5%g-C3N4/Bi24O31Cl10It can in 50min to the catalysis degradation modulus of rhodamine B Reach 90%, while the composite catalyst can also reach 88% or so (as shown in Figure 6) in 50min to the degradation rate of tetracycline, Purer Bi24O31Cl10, 5%MoS2/Bi24O31Cl10, 5%g-C3N4/ Bi24O31Cl10Photocatalysis efficiency obtained significantly mentioning Height illustrates using MoS2And g-C3N4It is compound to Bi simultaneously24O31Cl10Activity promoted it is obvious.

Claims (1)

1. a kind of high activity MoS2/g-C3N4/Bi24O31Cl10The preparation method of composite photo-catalyst, which is characterized in that step is such as Under:
(1) using bismuth nitrate, ammonium chloride, citric acid as raw material, Bi is prepared using improved solution combustion method24O31Cl10
Five nitric hydrate bismuths and citric acid are mixed and are dissolved in dust technology, the dust technology of five nitric hydrate bismuths and citric acid is obtained Mixed solution, wherein five nitric hydrate bismuths and citric acid molar ratio are 1:2;Ammonium chloride is dissolved in distilled water, until completely molten Solution, obtains ammonium chloride solution;Under agitation, ammonium chloride solution is added to the dust technology of five nitric hydrate bismuths and citric acid Mixed solution in, wherein five nitric hydrate bismuths and ammonium chloride molar ratio are 1:1, when being uniformly mixed to solution in clear state, Solution ph is adjusted to 5~6 with ammonium hydroxide;3~4h of heating stirring under the conditions of 60 DEG C~80 DEG C, is then forged under the conditions of 600 DEG C 3h is burnt, obtains pale yellow powder, as pure Bi24O31Cl10
(2) using melamine, acetic acid as raw material, g-C is prepared using a step thermal polymerization3N4
Melamine is uniformly mixed with acetic acid according to the molar ratio of 10:1,2h is calcined at 500 DEG C, obtains pale yellow powder, As pure g-C3N4
(3) using ammonium molybdate, thiocarbamide as raw material, dimethylformamide is solvent, prepares MoS using hydro-thermal method2Compound concentration is 4.8 The mixed solution of the dimethylformamide of the Ammonium Molybdate Tetrahydrate and thiocarbamide of~5.0g/L, wherein Ammonium Molybdate Tetrahydrate and thiocarbamide Mass ratio be 1:2;Stirring, until the transparent state of mixed solution of the dimethylformamide of Ammonium Molybdate Tetrahydrate and thiocarbamide; After reacting for 24 hours at 200 DEG C in a kettle, it is cooled to room temperature;Deionized water washing, centrifugation, obtain black solid, black are consolidated Body dry 12 at 60 DEG C~100 DEG C~for 24 hours, obtain MoS2
(4) Bi that step (1) is prepared24O31Cl10It is added in methanol solution, ultrasound, obtaining concentration is 40~50g/L Bi24O31Cl10With the mixed solution of methanol;The g-C that step (2) is prepared3N4It is added to Bi24O31Cl10With mixing for methanol It closes in solution, wherein g-C3N4With Bi24O31Cl10Mass ratio is 0.01~0.1;Continue ultrasound, be then centrifuged for, wash, again from The heart obtains solid matter;By solid matter under the conditions of 60 DEG C~80 DEG C it is dry for 24 hours~48h, ground after cooling, obtain 1%~ 10%g-C3N4/Bi24O31Cl10Composite photo-catalyst;
(5) 5%g-C that step (4) is prepared3N4/Bi24O31Cl10It is added in methanol solution, ultrasound, obtaining concentration is 40 The 5%g-C of~50g/L3N4/Bi24O31Cl10With the mixed solution of methanol;The MoS that step (3) is prepared2It is added to 5% g-C3N4/Bi24O31Cl10In the mixed solution of methanol, wherein MoS2With 5%g-C3N4/Bi24O31Cl10Mass ratio be 0.03 ~0.07;Continue ultrasound, is then centrifuged for, washs, is centrifuged again, obtain solid matter;Solid matter is done at 60 DEG C~80 DEG C Dry 24~48h is ground after cooling to get 3%~7%MoS2/ 5%g-C3N4/Bi24O31Cl10Composite photo-catalyst.
CN201810576978.0A 2018-06-04 2018-06-04 High-activity MoS2/g-C3N4/Bi24O31Cl10Preparation method of composite photocatalyst Active CN108940332B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810576978.0A CN108940332B (en) 2018-06-04 2018-06-04 High-activity MoS2/g-C3N4/Bi24O31Cl10Preparation method of composite photocatalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810576978.0A CN108940332B (en) 2018-06-04 2018-06-04 High-activity MoS2/g-C3N4/Bi24O31Cl10Preparation method of composite photocatalyst

Publications (2)

Publication Number Publication Date
CN108940332A true CN108940332A (en) 2018-12-07
CN108940332B CN108940332B (en) 2020-12-15

Family

ID=64493405

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810576978.0A Active CN108940332B (en) 2018-06-04 2018-06-04 High-activity MoS2/g-C3N4/Bi24O31Cl10Preparation method of composite photocatalyst

Country Status (1)

Country Link
CN (1) CN108940332B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111362303A (en) * 2020-04-09 2020-07-03 中国矿业大学 Hollow porous microspheric BiOCl photocatalytic material assembled by nanocrystals and preparation method thereof
CN112108130A (en) * 2020-09-10 2020-12-22 辽宁大学 Intelligent super-hydrophobic material and preparation method and application thereof
CN112156803A (en) * 2020-09-28 2021-01-01 东北大学 Photocatalytic composite material and preparation method and application thereof
CN113731448A (en) * 2021-08-20 2021-12-03 华南理工大学 Homogeneous Fenton cocatalyst, and preparation method and application thereof
CN114487058A (en) * 2021-12-10 2022-05-13 江苏大学 Preparation method and application of photoelectrochemical aptamer sensor for detecting fluoroquinolone antibiotics
CN114849789A (en) * 2022-04-14 2022-08-05 东北大学 Preparation method and application of MIL-125 loaded 1T-phase molybdenum sulfide composite photocatalyst

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012066545A3 (en) * 2010-11-16 2013-04-11 Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. Bismuth oxyhalide compounds useful as photocatalysts
CN103433077A (en) * 2013-09-11 2013-12-11 江南大学 Three-element composite photocatalyst and preparation method thereof
CN104475133A (en) * 2014-12-22 2015-04-01 聊城大学 Preparation method of Bi/BiOCl photocatalyst
CN106975511A (en) * 2017-04-24 2017-07-25 吉林师范大学 A kind of MoS2/C60/g‑C3N4Composite photo-catalyst and preparation method thereof
CN107115880A (en) * 2017-04-24 2017-09-01 吉林师范大学 A kind of MoS2/CNTs/g C3N4 composite photo-catalysts and preparation method thereof
CN107376971A (en) * 2017-07-25 2017-11-24 洛阳理工学院 The synthetic method of one species graphitic nitralloy carbon/molybdenum disulfide nano-composite material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012066545A3 (en) * 2010-11-16 2013-04-11 Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. Bismuth oxyhalide compounds useful as photocatalysts
CN103433077A (en) * 2013-09-11 2013-12-11 江南大学 Three-element composite photocatalyst and preparation method thereof
CN104475133A (en) * 2014-12-22 2015-04-01 聊城大学 Preparation method of Bi/BiOCl photocatalyst
CN106975511A (en) * 2017-04-24 2017-07-25 吉林师范大学 A kind of MoS2/C60/g‑C3N4Composite photo-catalyst and preparation method thereof
CN107115880A (en) * 2017-04-24 2017-09-01 吉林师范大学 A kind of MoS2/CNTs/g C3N4 composite photo-catalysts and preparation method thereof
CN107376971A (en) * 2017-07-25 2017-11-24 洛阳理工学院 The synthetic method of one species graphitic nitralloy carbon/molybdenum disulfide nano-composite material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111362303A (en) * 2020-04-09 2020-07-03 中国矿业大学 Hollow porous microspheric BiOCl photocatalytic material assembled by nanocrystals and preparation method thereof
CN112108130A (en) * 2020-09-10 2020-12-22 辽宁大学 Intelligent super-hydrophobic material and preparation method and application thereof
CN112108130B (en) * 2020-09-10 2021-11-30 辽宁大学 Intelligent super-hydrophobic material and preparation method and application thereof
CN112156803A (en) * 2020-09-28 2021-01-01 东北大学 Photocatalytic composite material and preparation method and application thereof
CN112156803B (en) * 2020-09-28 2021-09-10 东北大学 Photocatalytic composite material and preparation method and application thereof
CN113731448A (en) * 2021-08-20 2021-12-03 华南理工大学 Homogeneous Fenton cocatalyst, and preparation method and application thereof
CN114487058A (en) * 2021-12-10 2022-05-13 江苏大学 Preparation method and application of photoelectrochemical aptamer sensor for detecting fluoroquinolone antibiotics
CN114849789A (en) * 2022-04-14 2022-08-05 东北大学 Preparation method and application of MIL-125 loaded 1T-phase molybdenum sulfide composite photocatalyst

Also Published As

Publication number Publication date
CN108940332B (en) 2020-12-15

Similar Documents

Publication Publication Date Title
CN108940332A (en) A kind of high activity MoS2/g-C3N4/Bi24O31Cl10The preparation method of composite photo-catalyst
CN105032468B (en) A kind of Cu2O‑TiO2/g‑C3N4Ternary complex and its methods for making and using same
CN106824246B (en) A kind of TiO2/g-C3N4The preparation method of composite visible light catalyst
CN102335602B (en) Bismuth tungstate composite photocatalyst, preparation method thereof, and application thereof
CN109603880A (en) Hollow tubular carbon nitride photocatalyst and its preparation method and application
CN104801328B (en) Method for preparing TiO2/g-C3N4 composite photocatalyst at low temperature
CN101890350B (en) Method for preparing Fe3+doped TiO2 hollow sphere catalyst and application thereof
CN104001496B (en) A kind of BiVO 4nanometer sheet composite photocatalyst and its preparation method and application
CN101905153B (en) Preparation method and application of ZnO-doped TiO2 composite hollow sphere
CN102060330B (en) Method for synthetizing bismuth molybdate octahedral nanoparticle by microwave radiation heating
CN106268734A (en) A kind of preparation method of water dispersible ternary mixed crystal nano titanium dioxide photocatalyst
CN105668632A (en) Variable valency metal catalyzed and doped tungsten bronze nano-short rod particle and preparation method thereof
CN106391086A (en) Preparation method of C3N4/SiO2 heterojunction photocatalyst
CN109174082A (en) It is a kind of to prepare BiVO4/MnO2The method of composite photocatalyst oxidant
CN102600865B (en) Photocatalyst for degrading organic dye waste water pollutants and preparation method thereof
CN105536765B (en) A kind of shell base boron-doped titanium dioxide composite photo-catalyst and preparation method thereof
CN102500405A (en) Cerium, nitrogen and fluoride co-doped titanium dioxide photocatalyst and application thereof in degrading organic pollutants in visible light
CN106362742B (en) A kind of Ag/ZnO nano-complex and its preparation method and application
CN103721699A (en) NaInO2 photocatalyst and preparation method thereof
CN107362792A (en) A kind of preparation method of strontium titanates/niobic acid tin composite nano materials
CN106000460A (en) TiO2 photocatalyst modified by carbon quantum dot sensitization dendritic polyethyleneimine
CN109772421A (en) A kind of C, N codope TiO improving visible light activity2Photochemical catalyst and preparation method thereof
CN109382088A (en) SnO2/ α~Bi2O3/ β~Bi2O3Composite material and preparation method
CN109482238A (en) A kind of titanous-titanium dioxide-porphyrin/nitridation carbon composite photocatalyst and preparation method thereof
CN107308960A (en) A kind of niobic acid tellurium catalysis material and its preparation method and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant