CN108579773B - A kind of perovskite-based composite nano materials and preparation method and purposes - Google Patents

A kind of perovskite-based composite nano materials and preparation method and purposes Download PDF

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CN108579773B
CN108579773B CN201810335846.9A CN201810335846A CN108579773B CN 108579773 B CN108579773 B CN 108579773B CN 201810335846 A CN201810335846 A CN 201810335846A CN 108579773 B CN108579773 B CN 108579773B
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composite nano
nano materials
perovskite
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based composite
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CN108579773A (en
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梁希萌
高梦涵
陈敏
姜德立
李娣
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Hefei Liandunke Intelligent Technology Co ltd
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Jiangsu University
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    • 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
    • B01J27/06Halogens; Compounds thereof
    • B01J27/138Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • B01J35/39
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam
    • 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
    • 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 present invention relates to a kind of perovskite-based composite nano materials and preparation methods and purposes, belong to material preparation and light-catalysed technical field.BiOCl/K is prepared using hydro-thermal method+Ca2Nb3O10 Hetero-junctions compound nanometer photocatalyst, detailed process is as follows: taking K+Ca2Nb3O10 It is mixed in a certain amount of water, after mixing evenly, Bi (NO is added3)3·5H2O, gained mixed solution is transferred in hydrothermal reaction kettle by KCl solid after being sufficiently mixed, and for 24 hours, centrifuge washing vacuum drying obtains BiOCl/K for 160 DEG C of reactions+Ca2Nb3O10 Hetero-junctions composite nano materials.Products obtained therefrom photocatalytic activity is good, and stability is high, and production process is environmentally protective, is expected to large-scale industrial production.

Description

A kind of perovskite-based composite nano materials and preparation method and purposes
Technical field
The present invention relates to a kind of perovskite-based composite nano materials and preparation method and purposes, belongs to material preparation and light is urged The technical field of change.
Technical background
In recent years, photocatalysis technology is because having the various features such as low energy consumption, reaction condition be mild and without secondary pollution, by To the extensive concern of researcher.Photocatalysis technology can convert the solar energy of low-density to highdensity chemical energy (Hydrogen Energy), Can degrade and organic pollutant and antibiotic in mineralising environment again, thus it solution energy crisis in problem of environmental pollution Have important application value.
In numerous two-dimensional semiconductor materials, from Dion-Jacobson phase (M [An-1BnO3n+1]) laminated perovskite structure niobium The two-dimentional calcium niobate potassium (K that hydrochlorate separates+Ca2Nb3O10 -) poly metal oxide nano piece energy with good stability, especially It is that the conduction band of the nanosheet photocatalytic material is made of the Nb 4d track of high level, and the light induced electron of generation has very strong Reducing power.But simple two-dimentional K+Ca2Nb3O10 -Catalysis material lacks enough active sites, causes its surface a large amount of Light induced electron is quenched with hole recombination, to reduce photocatalysis efficiency.In order to solve this problem, simple K+Ca2Nb3O10 - It is often used to especially construct with the composite photocatalyst material of the compound preparation binary of the progress such as oxide or sulfide, ternary Heterojunction material;The heterojunction material of this special designing can effectively promote the separation in light induced electron and hole, inhibit photoproduction Electronics and hole it is compound, finally improve photocatalysis efficiency.
In numerous photocatalytic semiconductor materials, bismuth oxychloride (BiOCl) is connected to two Cl because having-[Bi2O2]2+ Two-dimensional layered structure, and show excellent physicochemical property.(001) crystal face of BiOCl possess higher end oxygen atom density and Lacking oxygen is formed, its photocatalytic activity is improved.Because possessing the band structure to match, BiOCl and the photocatalysis of laminated perovskite type Material K+Ca2Nb3O10 -It is compound to form II type hetero-junctions, possess the separative efficiency in higher light induced electron and hole, Jin Erti Highlight catalytic active.Meanwhile compared to zero dimension/two dimension, one-dimensional/two dimensional heterostructures, two-dimentional BiOCl/ two dimension K+Ca2Nb3O10 - The formation of hetero-junctions possesses more active sites, improves light capture ability.
So far, it is not yet found that people prepares BiOCl/K using hydro-thermal method+Ca2Nb3O10 -Hetero-junctions composite Nano material Material, K used+Ca2Nb3O10 -With stable physicochemical property, raw material are cheap and easy to get, nontoxic, and are prepared using it as carrier BiOCl/K+Ca2Nb3O10 -The reaction process of hetero-junctions composite nano materials is simple, and products obtained therefrom photocatalytic activity is good, stability Height, production process is environmentally protective, is expected to large-scale industrial production.
Summary of the invention
It is new under cryogenic that it is an object of the present invention to provide one kind, with simple and easy hydro-thermal method fabricated in situ Z-type BiOCl/K+Ca2Nb3O10 -The method of hetero-junctions composite nano materials.
The present invention is realized by following steps:
(1) calcium niobate potassium nanometer sheet (K is prepared+Ca2Nb3O10 -): weigh the K of a certain amount of drying2CO3、CaCO3And Nb2O5In In mortar, it is fully ground mixing and is placed in semi-enclosed crucible, crucible is then transferred to the heating of auto-programming temperature control It is calcined in tube furnace.It after room temperature, takes out, with mortar grinder to after powdered, is added to 5molL-1HNO3 A couple of days is stirred in solution, carries out protonation processing.The white precipitate deionized water and washes of absolute alcohol that protonation is obtained Remove HNO3, then be centrifuged, it is dried to obtain white solid HCa2Nb3O10.Weigh a certain amount of HCa2Nb3O10A certain amount of quality is added After tetrabutylammonium hydroxide solution and appropriate amount of deionized water stirring a couple of days of score 10%, it is centrifuged to obtain upper layer colloidal substance. Colloidal substance is finally added dropwise to 2molL-1Obtain white precipitate in KCl solution, by above-mentioned precipitating deionized water and Washes of absolute alcohol, centrifugation are dried in vacuo (ChemSusChem, 2016,9,396-402).
(2) bismuth oxychloride/calcium niobate potassium hetero-junctions composite nano materials (BiOCl/K is prepared+Ca2Nb3O10 -): it weighs certain The K of amount+Ca2Nb3O10 -It is scattered in deionized water, obtains the suspension of stable homogeneous through ultrasound, stir process.In the feelings of stirring Under condition, a certain amount of Bi (NO is added3)3·5H2O and KCl is sufficiently mixed in above-mentioned suspension.Reaction solution, which is transferred to liner, is In the reaction kettle of polytetrafluoroethylene (PTFE), it is placed in hydro-thermal reaction in baking oven, obtained product deionized water and dehydrated alcohol is cleaned, from The heart, vacuum drying obtain bismuth oxychloride/calcium niobate potassium hetero-junctions composite nano materials.
In the calcium niobate potassium nanometer sheet synthesis process, K+、Ca2+And Nb5+Molar ratio be 1.1:2:3.HCa2Nb3O10With The ratio of tetrabutylammonium hydroxide is 1g:5ml.
In the bismuth oxychloride/calcium niobate potassium hetero-junctions composite nano materials, bismuth oxychloride accounts for bismuth oxychloride/calcium niobate potassium The 10%-50% of hetero-junctions composite nano materials gross mass, preferably 40%.
The power of ultrasonic machine used in the ultrasonic disperse is 250W, sonication treatment time 0.5-1h.
The stir process uses magnetic stirring apparatus, and the stir process time is 1-1.5h.
The temperature of the hydro-thermal reaction is 150-200 DEG C, reaction time 18-24h.
Utilize X-ray diffractometer (XRD), transmission electron microscope (TEM) and high resolution transmission electron microscopy (HRTEM) micromorphology analysis is carried out to product, is that target dyestuff carries out photocatalysis with quadracycline (TC, 35mg/L) solution Degradation experiment measures absorbance by ultraviolet-visible spectrophotometer, to assess its Photocatalytic Degradation Property.
Detailed description of the invention
Fig. 1 is K+Ca2Nb3O10 -, BiOCl and BiOCl/K+Ca2Nb3O10 -The XRD diffraction of hetero-junctions nano-photocatalyst Spectrogram, as can be seen from the figure BiOCl/K+Ca2Nb3O10 -XRD spectrum mainly by BiOCl and K+Ca2Nb3O10 -Diffraction maximum structure At.
Fig. 2A, B, C are respectively simple K+Ca2Nb3O10 -Sample, simple BiOCl sample, BiOCl/K+Ca2Nb3O10 -Hetero-junctions The transmission electron microscope photo of composite nano materials;D is BiOCl/K+Ca2Nb3O10 -The high-resolution of hetero-junctions composite nano materials transmits Electromicroscopic photograph.As seen from the figure, BiOCl nanometer sheet is successfully compounded in K+Ca2Nb3O10 -Nanometer sheet surface.
Fig. 3 is that the catalysis material of different quality ratio is degraded the when m- degradation rate relational graph of TC solution, prepared 40% BiOCl/K+Ca2Nb3O10 -Hetero-junctions composite nano materials have most excellent photocatalytic activity, and sample reacts 150min in catalysis TC solution degradation rate has reached 94.5% afterwards.
Specific embodiment
1 calcium niobate potassium nanometer sheet (K of embodiment+Ca2Nb3O10 -) preparation
The preparation of calcium niobate potassium nanometer sheet uses high-temperature solid phase reaction method: weighing 0.3406g K2CO3、0.8968g CaCO3 With 1.7865g Nb2O5It in mortar, is fully ground mixing and is placed in semi-enclosed crucible, be then transferred to crucible certainly 1200 DEG C of calcining 10h in the heating tube furnace of dynamic program temperature control.After naturally cool to being taken out after room temperature, with mortar grinder to powder After shape, 4g is taken to be added to 200ml 5molL-1HNO33d is stirred in solution, carries out protonation processing.Protonation is obtained white Color precipitating uses 3 removing HNO of deionized water and washes of absolute alcohol respectively3, then be centrifuged through 6000rad/min, 60 DEG C of drying 12h Obtain white solid HCa2Nb3O10.Take 0.1g HCa2Nb3O10With the tetrabutylammonium hydroxide solution of 0.5ml mass fraction 10% It is scattered in 100ml deionized water stirring 7d, is centrifuged to obtain upper layer colloid object through 1500rad/min.Dropwise by colloid object finally It is added to 100ml 2molL-1White precipitate is obtained in KCl solution, above-mentioned precipitating is used into deionized water and dehydrated alcohol respectively Cleaning 3 times, is centrifuged through 6000rad/min, is finally placed in 60 DEG C of vacuum ovens and dries for 24 hours.
2 40%BiOCl/K of embodiment+Ca2Nb3O10 -The preparation of hetero-junctions composite nano materials
BiOCl/K+Ca2Nb3O10 -The preparation of hetero-junctions composite nano materials uses traditional hydro-thermal method: weighing 0.0391g K+Ca2Nb3O10 -It is scattered in 65ml deionized water, sonicated 1h and stir process 1.5h obtain the suspended of stable homogeneous Liquid.In the case of stirring, 0.0485g Bi (NO is added3)3·5H2O and 0.0075g KCl is sufficiently mixed in above-mentioned suspension It closes.It is to be put into 160 DEG C of water in baking oven in the reaction kettle of 100ml that by above-mentioned reaction solution, to be transferred to liner, which be polytetrafluoroethylene (PTFE) capacity, For 24 hours, cooled to room temperature, obtained product uses deionized water and washes of absolute alcohol 3 times to thermal response respectively, through 4500rad/ Min centrifugation is finally placed in 60 DEG C of vacuum ovens dry 12h and obtains 40%BiOCl/K+Ca2Nb3O10 -Hetero-junctions composite Nano Material.
Embodiment 3CdIn2S4/g-C3N4The experiment of/GO composite material photocatalytic activity
(1) compound concentration is the TC solution of 35mg/L, and the solution prepared is kept in dark place.
(2) BiOCl/K of different quality ratio is weighed+Ca2Nb3O10 -Hetero-junctions composite nano materials 0.035g, is respectively placed in In photo catalysis reactor, the target degradation solution that 35mL step (1) is prepared, the lower magnetic agitation 60min of dark, to BiOCl/ is added K+Ca2Nb3O10 -Hetero-junctions composite nano materials be uniformly dispersed and with TC reach absorption-desorption balance after, open cooling water and 300W xenon source carries out photocatalytic degradation experiment.
(3) every 30min draws the photocatalytic degradation liquid in reactor, and the measurement of UV-visible absorbance is used for after centrifugation.
(4) prepared BiOCl/K as seen from Figure 3+Ca2Nb3O10 -There is hetero-junctions composite nano materials excellent light to urge Change activity, especially 40%BiOCl/K+Ca2Nb3O10 -Sample catalysis react 150min after TC solution degradation rate have reached 94.5%.

Claims (8)

1. a kind of preparation method of perovskite-based composite nano materials, which is characterized in that the perovskite-based composite nano materials It is using one step hydro thermal method fabricated in situ Z-type BiOCl/K+Ca2Nb3O10 -Hetero-junctions composite nano materials, specific steps are as follows: weigh A certain amount of K+Ca2Nb3O10 -It is scattered in deionized water, obtains the suspension of stable homogeneous through ultrasound, stir process;It is stirring In the case where, a certain amount of Bi (NO is added3)3·5H2O and KCl is sufficiently mixed in above-mentioned suspension;Reaction solution is transferred to interior Lining is to be placed in hydro-thermal reaction in baking oven in the reaction kettle of polytetrafluoroethylene (PTFE) and carry out fabricated in situ, obtained product deionized water It is cleaned with dehydrated alcohol, centrifugation, vacuum drying obtains bismuth oxychloride/calcium niobate potassium hetero-junctions composite nano materials.
2. a kind of preparation method of perovskite-based composite nano materials as described in claim 1, which is characterized in that BiOCl receives Rice piece is compounded in K+Ca2Nb3O10 -Nanometer sheet surface.
3. a kind of preparation method of perovskite-based composite nano materials as described in claim 1, which is characterized in that the chlorine oxygen Change in bismuth/calcium niobate potassium hetero-junctions composite nano materials, bismuth oxychloride accounts for bismuth oxychloride/calcium niobate potassium hetero-junctions composite Nano material Expect the 10%-50% of gross mass.
4. a kind of preparation method of perovskite-based composite nano materials as claimed in claim 3, which is characterized in that bismuth oxychloride Account for bismuth oxychloride/calcium niobate potassium hetero-junctions composite nano materials gross mass 40%.
5. a kind of preparation method of perovskite-based composite nano materials as described in claim 1, which is characterized in that the ultrasound The power for dispersing ultrasonic machine used is 250W, sonication treatment time 0.5-1h.
6. a kind of preparation method of perovskite-based composite nano materials as described in claim 1, which is characterized in that the stirring Processing uses magnetic stirring apparatus, and the stir process time is 1-1.5h.
7. a kind of preparation method of perovskite-based composite nano materials as described in claim 1, which is characterized in that the hydro-thermal The temperature of reaction is 150-200 DEG C, reaction time 18-24h.
8. the purposes of perovskite-based composite nano materials prepared by the preparation method as described in claim 1-7 is any, feature exist In for photocatalytic degradation quadracycline.
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CN109174143B (en) * 2018-10-26 2021-08-03 江苏大学 Perovskite-based composite nano photocatalytic material and preparation method and application thereof
CN112717958B (en) * 2021-01-22 2022-06-21 江苏大学 Oxygen-rich vacancy BiOBr/HNb3O8Preparation method and application of nanosheet photocatalyst
CN113877608A (en) * 2021-09-18 2022-01-04 盐城工学院 Based on La2Ce2O7Preparation method and application of BiOCl-and-photocatalytic composite material

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CN107262085A (en) * 2017-07-21 2017-10-20 江苏大学 A kind of preparation method of bismuth/calcium niobate potassium plasma nano composite

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CN104511293A (en) * 2014-10-31 2015-04-15 北京理工大学 Bismuth oxychloride-iron bismuth titanate composite photocatalyst and preparation method thereof
CN106563485A (en) * 2016-11-08 2017-04-19 江苏大学 Carbon nitride/potassium calcium niobate composite material and preparing method and application thereof
CN107262085A (en) * 2017-07-21 2017-10-20 江苏大学 A kind of preparation method of bismuth/calcium niobate potassium plasma nano composite

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