CN109201100A - A kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7Nanocomposite and preparation method thereof - Google Patents

A kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7Nanocomposite and preparation method thereof Download PDF

Info

Publication number
CN109201100A
CN109201100A CN201810840791.7A CN201810840791A CN109201100A CN 109201100 A CN109201100 A CN 109201100A CN 201810840791 A CN201810840791 A CN 201810840791A CN 109201100 A CN109201100 A CN 109201100A
Authority
CN
China
Prior art keywords
nanocomposite
junctions
silver
type hetero
grain
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
Application number
CN201810840791.7A
Other languages
Chinese (zh)
Inventor
魏昂
武德伟
位威
叶茂
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.)
Nanjing Post and Telecommunication University
Nanjing University of Posts and Telecommunications
Original Assignee
Nanjing Post and Telecommunication University
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 Nanjing Post and Telecommunication University filed Critical Nanjing Post and Telecommunication University
Priority to CN201810840791.7A priority Critical patent/CN109201100A/en
Publication of CN109201100A publication Critical patent/CN109201100A/en
Pending legal-status Critical Current

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
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/70Treatment of water, waste water, or sewage by reduction
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/22Chromium or chromium compounds, e.g. chromates
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts

Abstract

The invention discloses a kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7Nanocomposite and preparation method thereof, the nanocomposite are g-C3N4、Bi4O7, silver nano-grain composition trielement composite material, wherein g-C3N4With laminar structured, silver nano-grain is dispersed in g-C3N4Lamella on, g-C3N4With Bi4O7It is built into Z-type heterojunction structure, and there is sharp interface;In the nanocomposite, the content of silver nano-grain is 1~10wt%, Bi4O7Content be 10~80wt%, silver nano-grain and Bi4O7Crystallization is good.A kind of Z-type hetero-junctions g-C of load silver is prepared using the method that repeatedly heat treatment combines light deposition in the present invention3N4@Bi4O7Nanocomposite.The nanocomposite each component content is adjustable, and adjustable extent is big, it is seen that photo-reduction metal chromium ions efficiency is good.

Description

A kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7Nanocomposite and its preparation Method
Technical field
The present invention relates to Material Fields, more particularly, to a kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7It is nano combined Material and preparation method thereof.
Background technique
With the rapid development of industry, Heavy Metals in Water Environment ionic soil is got worse, and common heavy metal ion is dirty Dye is primarily referred to as mercury, lead, chromium, uranium etc..Since heavy metal ion toxicity is big, is difficult to degrade, and there is chronicity and accumulation property, holds It is easily enriched in vivo, and then humans and animals vivo protein and enzyme denaturation is caused to inactivate, seriously threaten biology and the mankind's Health.The common method of processing Heavy Metals in Waters has the precipitation method, extraction, absorption method and membrane separation process etc. at present, these sides Fado can be along with energy consumption is high, processing is not thorough, secondary pollution problems.It is using photochemical catalyst redox heavy metal ion A kind of novel heavy metal ion processing technique developed in recent years, can be synchronous to remove in environment under normal temperature and pressure conditions Oxidized and reduced pollutant, reaction thoroughly and do not generate secondary pollution, shows in processing effluent containing heavy metal ions Unique advantage, the concern by more and more people.
1989, the researcher in California, USA university Berli gram branch school synthesized successfully beta-phase carbon nitride (β-for the first time C3N4), so that carbonitride (C3N4) initially enter the visual field of scientific research academia.1996, Virginia, US Polytechnics Researcher is calculated by first principle demonstration and has deduced carbonitride and have 5 kinds of structures, be respectively α phase, β phase, quasi- cubic phase, Cubic phase and class graphite-phase (g-C3N4).2009, Wang etc. reported g-C on Nature Materials for the first time3N4In light Application in catalysis.g-C3N4Highest occupied molecular orbital (HOMO ,+1.4V) and lowest unoccupied molecular orbital (LUMO ,- Band gap between 1.3V) is 2.7eV, therefore has certain visible light-responded ability.
Bismuth-based oxide is a kind of novel catalysis material, and common Bi-O system is containing there are many phases, such as Bi2O3(point For four kinds of crystal form α-, β-, γ-and δ-Bi2O3), Bi2O4, Bi2O2-x, Bi8O11, Bi6O7, Bi4O7And BiO.Hu etc. is reported not When synthermal lower sintering, Bi2O4Significant transformation behavior is shown, and is prepared for a series of bismuth oxide material (Bi4O7, α- Bi2O3With β-Bi2O3), it the article pointed out Bi2O4It can be converted Bi at 250 DEG C4O7。Bi4O7It is a kind of bismuthino of mixed valence Oxide, bandwidth 1.89eV, light absorption cutoff wavelength belong to narrow bandgap semiconductor material at 656nm, and having can Light-exposed absorbability.
In the research of photocatalysis at present it is the most commonly used it is two kinds of it is heterogeneous become II type hetero-junctions and Z-type hetero-junctions, II Type hetero-junctions is different the carrier transfer path in separation process with Z-type hetero-junctions photo-generate electron-hole.For II type Hetero-junctions, the conduction band and valence band location of two kinds of semiconductors are close, and band curvature, light can be generated at contact interface after the two contact Raw electrons are shifted along interface knee, and equally, photohole can also be shifted along interface knee, just realize partly lead in this way The separation of the photo-generate electron-hole pair of body-semiconductor composite under light illumination.For Z-type hetero-junctions, carrier transfer Path and II type hetero-junctions are entirely different, when the valence band of one of semiconductor connects compared with the conduction band positions of another semiconductor When close, light induced electron meeting and photohole can be compound inside two kinds of semiconductor contact interfaces, and in turn, two kinds of semiconductors generate Light induced electron and photohole can remain respectively, carry out subsequent photo catalytic reduction/oxidation reaction.
2008, Japanese AWAZU etc. had developed the Ag/TiO for having wide spectrum Absorption Characteristics in visible light region2Light is urged Change material, the surface plasma body resonant vibrations of the discovery noble metal nano particles such as Au, Ag (Surface Plasmon Resonance, SPR) there is apparent improvement result to the photocatalytic activity of semiconductor, and be prepared for a variety of Ag (Au)/partly lead on this basis Body nano composite photo-catalyst has been put forward for the first time surface plasma photochemical catalyst (Plasmonic Photocatalyst) Concept.Since then, SPR has received the concern of more and more researchers to the research of the visible light photocatalysis active of optimization semiconductor.
Chinese patent CN107398293A discloses a kind of Z-type photochemical catalyst TiO2/g-C3N4Preparation method, by quiet Electrospun and in-situ crystallization calcination method, method of electrostatic spinning operation is difficult to control, and TiO2For wide bandgap semiconductor materials, although structure Z-type structure is built, but visible light activity improvement is still limited.Chinese patent CN106975507A discloses a kind of Ag/g-C3N4It is multiple The preparation method of light combination catalyst, this method are g-C with melamine3N4Raw material, the g-C of preparation3N4Lamella fuzzy, than Surface area is little.
Summary of the invention
To overcome the above-mentioned problems in the prior art, the object of the present invention is to provide a kind of Z-type of load silver is heterogeneous Tie g-C3N4@Bi4O7Nanocomposite and preparation method thereof, the nanocomposite each component content is adjustable, and adjustable extent Greatly, it is seen that photo-reduction metal chromium ions efficiency is good.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7Nanocomposite, the nanocomposite are g-C3N4、 Bi4O7, silver nano-grain composition trielement composite material, wherein g-C3N4With laminar structured, silver nano-grain uniformly divides It is dispersed in g-C3N4Lamella on, g-C3N4With Bi4O7It is built into Z-type heterojunction structure, and there is sharp interface;It is described nano combined In material, the content of silver nano-grain is 1~10wt%, Bi4O7Content be 10~80wt%.
The specific surface area of the nanocomposite is 60~100m2g-1, silver nano-grain partial size is 10~20nm.
A kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7The preparation method of nanocomposite, comprising the following steps:
(1) g-C will be prepared3N4Raw material carry out thermal polycondensation in air atmosphere, obtain block shape g-C3N4
(2) the block shape g-C for taking step (1) to obtain3N4Hot soarfing is carried out in air atmosphere from obtaining g-C3N4Nanometer sheet;
(3) Bi will be prepared4O7Stock dispersion in deionized water, then carry out hydro-thermal process, obtained after dry brick-red Powder;
(4) g-C that the brick-red powder and step (2) for taking step (3) to obtain obtain3N4Nanometer sheet is dispersed in organic solvent In, ultrasonic treatment to uniform mixing;Then drying is volatilized completely to organic solvent, then obtained mixed-powder is transferred to Muffle In furnace, calcining obtains Z-type hetero-junctions g-C in air atmosphere3N4@Bi4O7Nanocomposite;
(5) the Z-type hetero-junctions g-C for obtaining step (4)3N4@Bi4O7Nanocomposite disperses in deionized water, to surpass Sonication is to evenly dispersed;Addition prepares the raw material and hole sacrifice agent of silver nano-grain, obtains the Z of load silver by light deposition Type hetero-junctions g-C3N4@Bi4O7Nanocomposite.
In step (1), g-C is prepared3N4Raw material be one of urea, melamine, dicyandiamide or cyanamide or a variety of Mixture;The condition of thermal polycondensation are as follows: temperature is 400~700 DEG C, and the time is 2~5 hours, and heating rate is 1~5 DEG C/min.
In step (2), hot soarfing from condition are as follows: temperature be 450~750 DEG C, the time be 3~6 hours, heating rate 1 ~10 DEG C/min.
In step (3), Bi is prepared4O7Raw material be sodium bismuthate, bismuth nitrate one or more mixtures;Prepare Bi4O7 Raw material in deionized water concentration be 5~20mg/mL;The condition of hydro-thermal process are as follows: temperature is 120~200 DEG C, the time 4 ~12 hours.
In step (4), organic solvent is ethyl alcohol, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, tetrahydrofuran, diformazan One kind of ether or acetone;Brick-red powder and g-C3N4The mass ratio of nanometer sheet is 0.1~0.8, and two kinds of powder are in organic solvent Total concentration be 2~10mg/mL.
In step (4), the condition of calcining are as follows: temperature is 200~350 DEG C, and the time is 2~5 hours, and heating rate is 1~5 ℃/min。
In step (5), prepares the raw material of silver nano-grain and mixed for silver nitrate, silver chlorate, the one or more of silver iodide Close object;Hole sacrifice agent is one or more mixtures of sodium citrate, methanol, ethylene glycol;Z-type hetero-junctions g-C3N4@ Bi4O7Concentration is 0.1~2mg/mL to nanocomposite in deionized water;The raw material of silver nano-grain is prepared in deionized water Middle concentration is 0.5~2mM;Concentration is 0.5~2mM to hole sacrifice agent in deionized water;Prepare the raw material of silver nano-grain with The molar ratio of hole sacrifice agent is 1:1~1:2.
In step (5), the condition of light deposition are as follows: 200~700nm of wavelength, 40~70W of power, luminous range be 20~ 40cm, light application time are 0.5~3 hour.
The utility model has the advantages that the present invention is respectively with urea, melamine, dicyandiamide g-C3N4Raw material, with sodium bismuthate, nitric acid Bismuth is Bi4O7Raw material light deposition is combined using multiple heat treatment using silver nitrate, silver chlorate, silver iodide as the raw material of nano silver Method, be prepared for it is a kind of load silver Z-type hetero-junctions g-C3N4@Bi4O7Nanocomposite.The composite material has larger Specific surface area, Z-type heterojunction boundary is obvious, and silver nano-grain is uniform, your gold of Z-type hetero-junctions-can be cooperateed in photocatalytic process The effect of metal surface plasma resonance.
Compared with prior art, the present invention has obtained a kind of load silver using the method that repeatedly heat treatment combines light deposition Z-type hetero-junctions g-C3N4@Bi4O7Nanocomposite.By controlling heat treatment process, different g-C are prepared3N4Pattern;Pass through Deploy Bi4O7And g-C3N4Feed ratio, construct Z-type heterojunction structure, and deploy Bi4O7And g-C3N4Mass ratio.Pass through control Light deposition process controls the size and content of Ag nano particle.
The Z-type hetero-junctions g-C of load silver prepared by the present invention3N4@Bi4O7Nanocomposite has biggish specific surface Product (60~100m2g-1), Z-type heterojunction boundary is obvious, and silver nano-grain is dispersed in g-C3N4Lamella on, silver nanoparticle Grain partial size is in 10~20nm.In trielement composite material, silver content is 1~10wt%, Bi4O7Content is about 10~80wt%.This is multiple Condensation material has good absorbing properties, especially in visible-range, compared with block shape g-C3N4And g-C3N4Nanometer sheet is inhaled Receipts are remarkably reinforced.g-C3N4With Bi4O7The Z-type heterojunction structure of building promotes the separation of electron hole, with SPR performance Nano silver further promotes the reducing property of light induced electron.Pass through (420~700nm of wavelength), heavy metal chromium under visible light conditions The analysis of ion (Cr (VI)) reducing property, the degradation efficiency of the trielement composite material is approximately block shape g-C3N430~50 times, Heavy metal ion in processing industrial wastewater has broad application prospects.
Detailed description of the invention
Fig. 1 is block shape g-C prepared by embodiment 13N4(Bulk g-C3N4) and g-C3N4Nanometer sheet characteristic X-ray spreads out Penetrate (XRD) map;
Fig. 2 is g-C prepared by embodiment 23N4@Bi4O7With Ag@g-C3N4@Bi4O7Composite material distinctive X-ray diffraction (XRD) map;
Fig. 3 is block shape g-C prepared by embodiment 1 and embodiment 23N4、g-C3N4Nanometer sheet, g-C3N4@Bi4O7With Ag@ g-C3N4@Bi4O7Composite material feature nitrogen adsorption-desorption isotherm (BET);
Fig. 4 is g-C prepared by embodiment 23N4@Bi4O7With Ag@g-C3N4@Bi4O7The transmission electron microscopy of composite material Mirror (TEM) figure and high power transmission electron microscope (HRTEM);
Fig. 5 is g-C prepared by embodiment 1 and embodiment 33N4Nanometer sheet, g-C3N4@Bi4O7With Ag@g-C3N4@Bi4O7 Composite material fluorescence spectra (PL);
Fig. 6 is g-C prepared by embodiment 1 and embodiment 43N4Nanometer sheet, g-C3N4@Bi4O7With Ag@g-C3N4@Bi4O7 Composite material ultraviolet-visible absorption spectroscopy;
Fig. 7 is Ag@g-C prepared by embodiment 53N4@Bi4O7Transmission electron microscope (TEM) figure of composite material;
Fig. 8 is Ag@g-C prepared by embodiment 63N4@Bi4O7Transmission electron microscope (TEM) figure of composite material.
Specific embodiment
A kind of Z-type hetero-junctions g-C of load silver of the invention3N4@Bi4O7Nanocomposite, the nanocomposite are g-C3N4、Bi4O7, silver nano-grain composition trielement composite material, wherein g-C3N4With laminar structured, silver nano-grain It is dispersed in g-C3N4Lamella on, g-C3N4With Bi4O7It is built into Z-type heterojunction structure, and there is sharp interface;It is described to receive In nano composite material, the content of silver nano-grain is 1~10wt%, Bi4O7Content be 10~80wt%, silver nano-grain and Bi4O7Crystallization is good.
Wherein, the specific surface area of nanocomposite is 60~100m2g-1, silver nano-grain partial size is 10~20nm.
A kind of Z-type hetero-junctions g-C of load silver of the invention3N4@Bi4O7The preparation method of nanocomposite, including with Lower step:
(1) g-C will be prepared3N4Raw material carry out thermal polycondensation in air atmosphere, obtain block shape g-C3N4
Wherein, g-C is prepared3N4Raw material be one of urea, melamine, dicyandiamide or cyanamide or a variety of mixed Close object;The condition of thermal polycondensation are as follows: temperature is 400~700 DEG C, and the time is 2~5 hours, and heating rate is 1~5 DEG C/min;
(2) the block shape g-C for taking step (1) to obtain3N4Hot soarfing is carried out in air atmosphere from obtaining g-C3N4Nanometer sheet;
Wherein, hot soarfing from condition are as follows: temperature be 450~750 DEG C, the time be 3~6 hours, heating rate be 1~10 ℃/min;
(3) Bi will be prepared4O7Stock dispersion in deionized water, then carry out hydro-thermal process, obtained after dry brick-red Powder;
Wherein, Bi is prepared4O7Raw material be sodium bismuthate, bismuth nitrate one or more mixtures;Prepare Bi4O7Original Concentration is 5~20mg/mL to material in deionized water;The condition of hydro-thermal process are as follows: temperature is 120~200 DEG C, and the time is 4~12 Hour;
(4) g-C that the brick-red powder and step (2) for taking step (3) to obtain obtain3N4Nanometer sheet is dispersed in organic solvent In, ultrasonic treatment to uniform mixing;Then drying is volatilized completely to organic solvent, then obtained mixed-powder is transferred to Muffle In furnace, calcining obtains Z-type hetero-junctions g-C in air atmosphere3N4@Bi4O7Nanocomposite;
Wherein, organic solvent be ethyl alcohol, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, tetrahydrofuran, dimethyl ether or One kind of acetone;Brick-red powder and g-C3N4The mass ratio of nanometer sheet is 0.1~0.8, two kinds of powder in organic solvent total Concentration is 2~10mg/mL;The condition of calcining are as follows: temperature is 200~350 DEG C, and the time is 2~5 hours, and heating rate is 1~5 ℃/min;
(5) the Z-type hetero-junctions g-C for obtaining step (4)3N4@Bi4O7Nanocomposite disperses in deionized water, to surpass Sonication is to evenly dispersed;Addition prepares the raw material and hole sacrifice agent of silver nano-grain, obtains the Z of load silver by light deposition Type hetero-junctions g-C3N4@Bi4O7Nanocomposite;
Wherein, the raw material for preparing silver nano-grain is one or more mixtures of silver nitrate, silver chlorate, silver iodide; Hole sacrifice agent is one or more mixtures of sodium citrate, methanol, ethylene glycol;Z-type hetero-junctions g-C3N4@Bi4O7Nanometer Concentration is 0.1~2mg/mL to composite material in deionized water;Preparing the raw material of silver nano-grain, concentration is in deionized water 0.5~2mM;Concentration is 0.5~2mM to hole sacrifice agent in deionized water;Prepare the raw material and hole sacrifice of silver nano-grain The molar ratio of agent is 1:1~1:2;The condition of light deposition are as follows: 200~700nm of wavelength, 40~70W of power, luminous range be 20~ 40cm, light application time are 0.5~3 hour.
The present invention is described in detail combined with specific embodiments below.
Protection scope of the present invention is not limited to embodiment, and only protection is specifically addressed.For example, graphite-phase in embodiment The raw material of carbonitride selects dicyandiamide, can also select urea, melamine or cyanamide replacement;Hole is sacrificial during light deposition What domestic animal agent was selected is sodium citrate, is also possible to methanol, ethylene glycol replacement.The raw material of nano silver is silver nitrate, is also possible to chlorine Change silver, silver iodide, the organic solvent of dispersed sample can also use methanol, ethyl alcohol, normal propyl alcohol, isopropanol, just in addition to ethyl alcohol Butanol, tetrahydrofuran, dimethyl ether or acetone.
Embodiment 1
Weigh 10g dicyandiamide addition have in the alumina crucible of lid, under the conditions of air atmosphere, Muffle furnace with 2 DEG C/ Min heating rate is warming up to 550 DEG C, keeps the temperature 4 hours, and obtaining yellow powder sample is block shape g-C3N4.By block shape g-C3N4 It is laid in uncovered ceramics Noah's ark bottom.Under the conditions of air atmosphere, Muffle furnace is warming up to 500 DEG C with the heating rate of 5 DEG C/min, It is kept for 3 hours, obtained pale yellow powder sample, as g-C3N4Nanometer sheet.
Embodiment 2
By 0.7g sodium bismuthate (NaBiO3) be distributed in 75mL water, it is transferred to 100mL polytetrafluoroethyllining lining later not It becomes rusty in steel water heating kettle, is then heated 6 hours at 160 DEG C using baking oven.After reaction, red-brown precipitation object passes through centrifuge separation, It is dried after deionized water washing, obtained brick-red powder.It takes 60mL ethyl alcohol, the brick-red powder of 0.084g and 0.21g is added g-C3N4Nanometer sheet is ultrasonically treated 50min.By dispersion liquid at 60 DEG C the dry removing of volatilization in 4 hours ethyl alcohol, then will obtain Powder is put into crucible with cover, is warming up at 250 DEG C and is heated 3 hours with the heating rate of 2 DEG C/min in Muffle furnace, obtained Sample is Z-type hetero-junctions g-C3N4@Bi4O7Nanocomposite is abbreviated as g-C3N4@Bi4O7
By 500mg Bi4O7@g-C3N4Composite material is dispersed in 500mL deionized water, then ultrasound 60min.It is mixed to this It closes and 0.8g AgNO is added in solution3With 0.15g sodium citrate.After stirring 40min, suspension is transferred to the UV lamp case of sealing It is middle to irradiate 60min with UV light (wavelength 365nm, power 56W, operating distance 30cm).Finally, deionized water centrifuge washing, dry Obtaining sample afterwards is the Z-type hetero-junctions g-C for loading silver3N4@Bi4O7Nanocomposite is abbreviated as Ag@g-C3N4@Bi4O7
Embodiment 3
By 0.7g sodium bismuthate (NaBiO3) be distributed in 100mL water, it is transferred to 100mL polytetrafluoroethyllining lining later not It becomes rusty in steel water heating kettle, is then heated 6 hours at 200 DEG C using baking oven.After reaction, red-brown precipitation object passes through centrifuge separation, It is dried after deionized water washing, obtained brick-red powder.It takes 60mL ethyl alcohol, the brick-red powder of 0.021g and 0.21g is added g-C3N4Nanometer sheet (g-C3N4The preparation of nanometer sheet is with embodiment 1), it is ultrasonically treated 50min.By dispersion liquid dry 4 at 60 DEG C Hour volatilization removes ethyl alcohol, is then put into obtained powder in crucible with cover, with the heating speed of 2 DEG C/min in Muffle furnace Rate is warming up at 300 DEG C and heats 3 hours, and obtaining sample is Z-type hetero-junctions g-C3N4@Bi4O7Nanocomposite.
By 500mg Bi4O7@g-C3N4Composite material is dispersed in 500mL deionized water, then ultrasound 60min.It is mixed to this It closes and 0.8g AgNO is added in solution3With 0.15g sodium citrate.After stirring 40min, suspension is transferred to the UV lamp case of sealing It is middle to irradiate 60min with UV light (wavelength 365nm, power 56W, operating distance 30cm).Finally, deionized water centrifuge washing, dry Obtaining sample afterwards is the Z-type hetero-junctions g-C for loading silver3N4@Bi4O7Nanocomposite.
Embodiment 4
By 0.7g sodium bismuthate (NaBiO3) be distributed in 50mL water, it is transferred to 100mL polytetrafluoroethyllining lining later not It becomes rusty in steel water heating kettle, is then heated 6 hours at 160 DEG C using baking oven.After reaction, red-brown precipitation object passes through centrifuge separation, It is dried after deionized water washing, obtained brick-red powder.It takes 60mL ethyl alcohol, the brick-red powder of 0.042g and 0.21g is added g-C3N4Nanometer sheet (g-C3N4The preparation of nanometer sheet is with embodiment 1), it is ultrasonically treated 50min.By dispersion liquid dry 4 at 60 DEG C Hour volatilization removes ethyl alcohol, is then put into obtained powder in crucible with cover, with the heating speed of 2 DEG C/min in Muffle furnace Rate is warming up at 250 DEG C and heats 3 hours, and must obtain sample is Z-type hetero-junctions g-C3N4@Bi4O7Nanocomposite.
By 500mg Bi4O7@g-C3N4Composite material is dispersed in 500mL deionized water, then ultrasound 60min.It is mixed to this It closes and 0.8g AgNO is added in solution3With 0.20g sodium citrate.After stirring 40min, suspension is transferred to the UV lamp case of sealing It is middle to be irradiated 2 hours with UV light (wavelength 365nm, power 56W, operating distance 30cm).Finally, deionized water centrifuge washing, dry Obtaining sample afterwards is the Z-type hetero-junctions g-C for loading silver3N4@Bi4O7Nanocomposite.
Embodiment 5
By 0.7g sodium bismuthate (NaBiO3) be distributed in 75mL water, it is transferred to 100mL polytetrafluoroethyllining lining later not It becomes rusty in steel water heating kettle, is then heated 6 hours at 160 DEG C using baking oven.After reaction, red-brown precipitation object passes through centrifuge separation, It is dried after deionized water washing, obtained brick-red powder.It takes 60mL ethyl alcohol, the brick-red powder of 0.126g and 0.21g is added g-C3N4Nanometer sheet (g-C3N4The preparation of nanometer sheet is with embodiment 1), it is ultrasonically treated 50min.By dispersion liquid dry 4 at 60 DEG C Hour volatilization removes ethyl alcohol, is then put into obtained powder in crucible with cover, with the heating speed of 2 DEG C/min in Muffle furnace Rate is warming up at 250 DEG C and heats 3 hours, and obtaining sample is Z-type hetero-junctions g-C3N4@Bi4O7Nanocomposite.
By 500mg Bi4O7@g-C3N4Composite material is dispersed in 500mL deionized water, then ultrasound 60min.It is mixed to this It closes and 0.8g AgNO is added in solution3With 0.15g sodium citrate.After stirring 40min, suspension is transferred to the UV lamp case of sealing It is middle to be irradiated 1.5 hours with UV light (wavelength 365nm, power 56W, operating distance 30cm).Finally, deionized water centrifuge washing, does It is the Z-type hetero-junctions g-C for loading silver that sample is obtained after dry3N4@Bi4O7Nanocomposite.
Embodiment 6
By 0.7g sodium bismuthate (NaBiO3) be distributed in 50mL water, it is transferred to 100mL polytetrafluoroethyllining lining later not It becomes rusty in steel water heating kettle, is then heated 6 hours at 160 DEG C using baking oven.After reaction, red-brown precipitation object passes through centrifuge separation, It is dried after deionized water washing, obtained brick-red powder.It takes 60mL ethyl alcohol, the brick-red powder of 0.168g and 0.21g is added g-C3N4Nanometer sheet is ultrasonically treated 50min.By dispersion liquid at 60 DEG C the dry removing of volatilization in 4 hours ethyl alcohol, then will obtain Powder is put into crucible with cover, is warming up at 250 DEG C and is heated 3 hours with the heating rate of 2 DEG C/min in Muffle furnace, obtained Sample is Z-type hetero-junctions g-C3N4@Bi4O7Nanocomposite.
By 500mg Bi4O7@g-C3N4Composite material is dispersed in 500mL deionized water, then ultrasound 60min.It is mixed to this It closes and 0.8g AgNO is added in solution3With 0.15g sodium citrate.After stirring 40min, suspension is transferred to the UV lamp case of sealing It is middle to irradiate 60min with UV light (wavelength 365nm, power 56W, operating distance 30cm).Finally, deionized water centrifuge washing, dry Obtaining sample afterwards is the Z-type hetero-junctions g-C for loading silver3N4@Bi4O7Nanocomposite.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7Nanocomposite, it is characterised in that: the nanocomposite is g-C3N4、Bi4O7, silver nano-grain composition trielement composite material, wherein g-C3N4With laminar structured, silver nano-grain It is dispersed in g-C3N4Lamella on, g-C3N4With Bi4O7It is built into Z-type heterojunction structure, and there is sharp interface;It is described to receive In nano composite material, the content of silver nano-grain is 1~10wt%, Bi4O7Content be 10~80wt%.
2. the Z-type hetero-junctions g-C of load silver according to claim 13N4@Bi4O7Nanocomposite, it is characterised in that: The specific surface area of the nanocomposite is 60~100m2g-1, silver nano-grain partial size is 10~20nm.
3. a kind of Z-type hetero-junctions g-C of any load silver of claims 1 or 23N4@Bi4O7The preparation of nanocomposite Method, it is characterised in that: the following steps are included:
(1) g-C will be prepared3N4Raw material carry out thermal polycondensation in air atmosphere, obtain block shape g-C3N4
(2) the block shape g-C for taking step (1) to obtain3N4Hot soarfing is carried out in air atmosphere from obtaining g-C3N4Nanometer sheet;
(3) Bi will be prepared4O7Stock dispersion in deionized water, then carry out hydro-thermal process, obtain brick red toner after dry End;
(4) g-C that the brick-red powder and step (2) for taking step (3) to obtain obtain3N4Nanometer sheet disperses in organic solvent, to surpass Sonication is mixed to uniform;Then drying is volatilized completely to organic solvent, then obtained mixed-powder is transferred in Muffle furnace, Calcining obtains Z-type hetero-junctions g-C in air atmosphere3N4@Bi4O7Nanocomposite;
(5) the Z-type hetero-junctions g-C for obtaining step (4)3N4@Bi4O7Nanocomposite disperses in deionized water, at ultrasound It manages to evenly dispersed;Addition prepares the raw material and hole sacrifice agent of silver nano-grain, and the Z-type for obtaining load silver by light deposition is different Matter knot g-C3N4@Bi4O7Nanocomposite.
4. the Z-type hetero-junctions g-C of load silver according to claim 33N4@Bi4O7The preparation method of nanocomposite, It is characterized in that: in step (1), preparing g-C3N4Raw material be one of urea, melamine, dicyandiamide or cyanamide or more The mixture of kind;The condition of thermal polycondensation are as follows: temperature be 400~700 DEG C, the time be 2~5 hours, heating rate be 1~5 DEG C/ min。
5. the Z-type hetero-junctions g-C of load silver according to claim 33N4@Bi4O7The preparation method of nanocomposite, Be characterized in that: in step (2), hot soarfing from condition are as follows: temperature be 450~750 DEG C, the time be 3~6 hours, heating rate 1 ~10 DEG C/min.
6. the Z-type hetero-junctions g-C of load silver according to claim 33N4@Bi4O7The preparation method of nanocomposite, It is characterized in that: in step (3), preparing Bi4O7Raw material be sodium bismuthate, bismuth nitrate one or more mixtures;Preparation Bi4O7Raw material in deionized water concentration be 5~20mg/mL;The condition of hydro-thermal process are as follows: temperature is 120~200 DEG C, the time It is 4~12 hours.
7. the Z-type hetero-junctions g-C of load silver according to claim 33N4@Bi4O7The preparation method of nanocomposite, Be characterized in that: in step (4), organic solvent is ethyl alcohol, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, tetrahydrofuran, two One kind of methyl ether or acetone;Brick-red powder and g-C3N4The mass ratio of nanometer sheet is 0.1~0.8, and two kinds of powder are in organic solvent In total concentration be 2~10mg/mL.
8. the Z-type hetero-junctions g-C of load silver according to claim 33N4@Bi4O7The preparation method of nanocomposite, Be characterized in that: in step (4), the condition of calcining are as follows: temperature be 200~350 DEG C, the time be 2~5 hours, heating rate be 1~ 5℃/min。
9. the Z-type hetero-junctions g-C of load silver according to claim 33N4@Bi4O7The preparation method of nanocomposite, It is characterized in that: in step (5), preparing the raw material of silver nano-grain and mixed for silver nitrate, silver chlorate, the one or more of silver iodide Close object;Hole sacrifice agent is one or more mixtures of sodium citrate, methanol, ethylene glycol;Z-type hetero-junctions g-C3N4@ Bi4O7Concentration is 0.1~2mg/mL to nanocomposite in deionized water;The raw material of silver nano-grain is prepared in deionized water Middle concentration is 0.5~2mM;Concentration is 0.5~2mM to hole sacrifice agent in deionized water;Prepare the raw material of silver nano-grain with The molar ratio of hole sacrifice agent is 1:1~1:2.
10. the Z-type hetero-junctions g-C of load silver according to claim 33N4@Bi4O7The preparation method of nanocomposite, It is characterized by: in step (5), the condition of light deposition are as follows: 200~700nm of wavelength, 40~70W of power, luminous range is 20~ 40cm, light application time are 0.5~3 hour.
CN201810840791.7A 2018-07-27 2018-07-27 A kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7Nanocomposite and preparation method thereof Pending CN109201100A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810840791.7A CN109201100A (en) 2018-07-27 2018-07-27 A kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7Nanocomposite and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810840791.7A CN109201100A (en) 2018-07-27 2018-07-27 A kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7Nanocomposite and preparation method thereof

Publications (1)

Publication Number Publication Date
CN109201100A true CN109201100A (en) 2019-01-15

Family

ID=64990272

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810840791.7A Pending CN109201100A (en) 2018-07-27 2018-07-27 A kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7Nanocomposite and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109201100A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110327487A (en) * 2019-07-22 2019-10-15 西南大学 Has light-operated antibacterial functions g-C3N4/TiO2Coating and preparation method
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
CN110464854A (en) * 2019-09-06 2019-11-19 南京邮电大学 A method of mould is killed using photocatalysis principle
CN112844479A (en) * 2020-12-31 2021-05-28 中南大学 ZIF-8-loaded silver nanoparticle catalyst and preparation method and application thereof
CN113426467A (en) * 2021-06-16 2021-09-24 郑州大学 Z-type boron-doped carbon nitride and silver iodide composite visible light catalyst and preparation method thereof
CN114433107A (en) * 2022-01-11 2022-05-06 西安建筑科技大学 Co3O4/Bi4O7/Bi2O3Heterojunction photocatalyst and application thereof
CN114433107B (en) * 2022-01-11 2024-04-12 西安建筑科技大学 Co (cobalt) 3 O 4 /Bi 4 O 7 /Bi 2 O 3 Heterojunction photocatalyst and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102167437A (en) * 2011-03-28 2011-08-31 河南理工大学 Photochemical method for removing organic phenolic pollutants and hexavalent chromium in water body and preparation method of catalytic agent
CN103586064A (en) * 2013-11-26 2014-02-19 中国科学院福建物质结构研究所 Metal/graphite-like carbon nitride compound catalyst and preparing method thereof
CN106215967A (en) * 2016-07-21 2016-12-14 吉林师范大学 A kind of g C3n4the quantum dot sensitized Bi of quantum dot, Ag2moO6the preparation method of nanometer sheet
CN106238089A (en) * 2016-08-24 2016-12-21 徐州工程学院 A kind of visible light-responded g C3n4/ SnS2the preparation method of composite photo-catalyst
WO2018020356A1 (en) * 2016-07-28 2018-02-01 Sabic Global Technologies B.V. Nitrogen rich carbon nitride materials with a three dimensional cubic mesoporosity from diaminotetrazine

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102167437A (en) * 2011-03-28 2011-08-31 河南理工大学 Photochemical method for removing organic phenolic pollutants and hexavalent chromium in water body and preparation method of catalytic agent
CN103586064A (en) * 2013-11-26 2014-02-19 中国科学院福建物质结构研究所 Metal/graphite-like carbon nitride compound catalyst and preparing method thereof
CN106215967A (en) * 2016-07-21 2016-12-14 吉林师范大学 A kind of g C3n4the quantum dot sensitized Bi of quantum dot, Ag2moO6the preparation method of nanometer sheet
WO2018020356A1 (en) * 2016-07-28 2018-02-01 Sabic Global Technologies B.V. Nitrogen rich carbon nitride materials with a three dimensional cubic mesoporosity from diaminotetrazine
CN106238089A (en) * 2016-08-24 2016-12-21 徐州工程学院 A kind of visible light-responded g C3n4/ SnS2the preparation method of composite photo-catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MAO YE ET AL.: "Silver nanoparticles/graphitic carbon nitride nanosheets for improved visible-light-driven photocatalytic performance", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A: CHEMISTRY》 *
MENG SUN ET AL.: "Fabrication of a novel Z-scheme g-C3N4/Bi4O7 heterojunction photocatalyst with enhanced visible light-driven activity toward organic pollutants", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110327487A (en) * 2019-07-22 2019-10-15 西南大学 Has light-operated antibacterial functions g-C3N4/TiO2Coating and preparation method
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
CN110464854A (en) * 2019-09-06 2019-11-19 南京邮电大学 A method of mould is killed using photocatalysis principle
CN112844479A (en) * 2020-12-31 2021-05-28 中南大学 ZIF-8-loaded silver nanoparticle catalyst and preparation method and application thereof
CN112844479B (en) * 2020-12-31 2022-02-11 中南大学 ZIF-8-loaded silver nanoparticle catalyst and preparation method and application thereof
CN113426467A (en) * 2021-06-16 2021-09-24 郑州大学 Z-type boron-doped carbon nitride and silver iodide composite visible light catalyst and preparation method thereof
CN113426467B (en) * 2021-06-16 2024-03-12 郑州大学 Z-type boron-doped carbon nitride and silver iodide composite visible light catalyst and preparation method thereof
CN114433107A (en) * 2022-01-11 2022-05-06 西安建筑科技大学 Co3O4/Bi4O7/Bi2O3Heterojunction photocatalyst and application thereof
CN114433107B (en) * 2022-01-11 2024-04-12 西安建筑科技大学 Co (cobalt) 3 O 4 /Bi 4 O 7 /Bi 2 O 3 Heterojunction photocatalyst and application thereof

Similar Documents

Publication Publication Date Title
CN109201100A (en) A kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7Nanocomposite and preparation method thereof
Aghdam et al. Precipitation dispersion of various ratios of BiOI/BiOCl nanocomposite over g-C3N4 for promoted visible light nanophotocatalyst used in removal of acid orange 7 from water
Rajendran et al. g-C3N4/TiO2/CuO S-scheme heterostructure photocatalysts for enhancing organic pollutant degradation
CN103920479B (en) Biomass modified TiO2the preparation method and applications of visible-light photocatalyst
CN100522350C (en) Hydrothermal method for preparing superstructure visible light responsive Bi2WO6 photcatalyst
El-Shabasy et al. A green synthetic approach using chili plant supported Ag/Ag2O@ P25 heterostructure with enhanced photocatalytic properties under solar irradiation
Hassan et al. A review on self-modification of zirconium dioxide nanocatalysts with enhanced visible-light-driven photodegradation of organic pollutants
CN102039117B (en) Method for preparing loaded nano TiO2 composite material by using precipitated white carbon black as carrier
Yu et al. Enhanced catalytic performance of a bio-templated TiO2 UV-Fenton system on the degradation of tetracycline
CN102039118B (en) Preparation method of supported nano TiO2 photocatalytic material with diatomite filter aid as carrier
CN105944711B (en) A kind of visible light-responded BiVO4/TiO2/ graphene Three-element composite photocatalyst and preparation method thereof
Zhou et al. Enhanced photocatalytic degradation of xylene by blackening TiO2 nanoparticles with high dispersion of CuO
CN105664995B (en) A kind of multielement codoped nanaotitania catalysis material
CN1321743C (en) Bismuth contained composite oxide BiMO4 and Bi2NO6 semiconductor photocatalyst, preparation and use
CN107812520A (en) A kind of loading type silver catalyst preparation method for purifying formaldehyde
CN107362793A (en) A kind of CeVO4‑La2O3The preparation method and purposes of@HNTs composite photo-catalysts
CN107376964A (en) A kind of composite photo-catalyst using adulterated with Ca and Ti ore as carrier prepares and its application
CN109603809A (en) A kind of preparation and application of pucherite quantum dot and titanium dioxide nano-belts composite photo-catalyst
Cheng et al. Plasmonic Z-scheme α/β-Bi 2 O 3–Ag–AgCl photocatalyst with enhanced visible-light photocatalytic performance
CN107008473A (en) A kind of three-dimensional structure bismuth titanates nanometer sheet/perite nanometer piece composite photo-catalyst and preparation method thereof
CN105905940A (en) Preparation method of nickel titanate/titanium dioxide composite nanomaterial
CN105728008A (en) Method for preparing AgCl/Bi2O2CO3 composite photocatalytic material and product of material
Tashkandi et al. Visible-light driven of heterostructured LaFeO3/TiO2 photocatalysts for degradation of antibiotics: Ciprofloxacin as case study
Yin et al. Synergistically enhanced photocatalytic degradation of tetracycline hydrochloride by Z-scheme heterojunction MT-BiVO4 microsphere/P-doped g-C3N4 nanosheet composite
CN106238084A (en) The preparation method and application of visible ray synergy ozone catalytic degradation organic acid catalyst

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: 20190115

RJ01 Rejection of invention patent application after publication