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%.