CN107537521A - A kind of preparation method and application of the BiOBr micro-flowers photochemical catalysts of the high exposure ratio of { 001 } active crystal face - Google Patents

A kind of preparation method and application of the BiOBr micro-flowers photochemical catalysts of the high exposure ratio of { 001 } active crystal face Download PDF

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CN107537521A
CN107537521A CN201710908415.2A CN201710908415A CN107537521A CN 107537521 A CN107537521 A CN 107537521A CN 201710908415 A CN201710908415 A CN 201710908415A CN 107537521 A CN107537521 A CN 107537521A
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biobr
preparation
flowers
micro
photochemical catalysts
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李新勇
孙娟娟
肇启东
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Dalian University of Technology
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Dalian University of Technology
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Abstract

The invention discloses the preparation method of the BiOBr micro-flowers photochemical catalysts of the high exposure ratio of a kind of { 001 } active crystal face, belong to environment pollution control and technical field.First, KBr dispersion liquids are prepared；Then by equivalent molar than Bi (NO3)3·5H2O is added in KBr dispersion liquids, is transferred into afterwards in reactor, carries out hydro-thermal reaction；Sample is naturally cooled into room temperature afterwards, products therefrom is collected by centrifugation, is washed for several times with deionized water and absolute ethyl alcohol, sample obtained by last re-dry is the BiOBr micro-flowers photochemical catalysts with hierarchy.The BiOBr photochemical catalysts that the present invention synthesizes are visible light-responded strong, and catalytic activity is high, has a good application prospect and is worth in the degraded field of organic pollution.

Description

A kind of preparation of the BiOBr micro-flowers photochemical catalysts of the high exposure ratio of { 001 } active crystal face Method and application
Technical field
The invention belongs to field of environment pollution control, is related to a kind of preparation side of tetragonal crystal system pentabromo- bismuth oxide catalyst Method, concretely relate to the BiOBr micro-flowers photochemical catalysts of the high exposure ratio of a kind of { 001 } active crystal face preparation method and Using.
Background technology
Bismuth oxybromide (BiOBr) is because of its unique electronic structure, suitable position of energy band and excellent light absorpting ability (Eg =2.7eV), higher catalytic activity is made it have, increasing attention is received in photocatalytic pollutant degradation field. BiOBr crystal structure is tetragonal crystal system, belongs to PbFCl types, wherein [Bi2O2]2+Layer and Br-Ion layer is alternately arranged to be formed Typical layer structure, and the layer structure of this opening not only contributes to photo-generated carrier and shortens electric charge in the transmission of interlayer The distance in surface-active site is reached, reduces the recombination probability of photogenerated charge；And provided for polarization relevant atomic and track Much room is so as to generating perpendicular to [Bi2O2]2+Layer and Br-The internal stationary electric field of sheath so that photogenerated charge is easy to (W.Wang, et al., Phys.Chem.Chem.Phys., 2012,14,2450-2454 is separated in [001] direction； K.L.Zhang,Appl.Catal.,B,2006,68,125–129).Relative to other lamellar compounds such as g-C3N4, BiOBr layers Intermolecular forces are not only Van der Waals force and ionic bonding forces be present, therefore it is more stable.Huo etc. (Y.Huo, et al., Appl.Catal.B, 2012,111-112,334-341) by contrast the photocatalytic activity of the BiOBr after 6 circulations, brilliant degree and Microscopic appearance, it is found that BiOBr has very high photocatalysis stability and great practical application potentiality.
Further, since crystal face is the important component of crystalline material, different crystal faces have different geometries and Electronic structure so that crystalline material has different intrinsic reactivity and physicochemical characteristics on different crystal faces.Grind Study carefully and show, BiOBr { 001 } crystal face photo-generate electron-hole separation rate is higher, and largely exposure { 001 } crystal face can be with one Determine to improve its photocatalysis performance (D.Zhang, et al., J.Mater.Chem.A, 2013,1,8622-8629 in degree； F.Duan,Phys.Chem.Chem.Phys.,2016,18,6113–6121).The hydro-thermal method that first passage of the present invention simply saves The BiOBr micro-flowers catalysis materials formed by ultra-thin two-dimension nanometer sheet self assembly are prepared for, { 001 } crystal face exposure ratio is up to 98%, test result indicates that the catalyst has good visible absorption ability, photogenerated charge separation rate is high and photocatalysis is lived Property is strong.
The content of the invention
Present invention aims at providing a kind of preparation method and applications of novel photocatalyst, this method is simple to operate, Relative energy-conservation.Using this method synthesis material under visible light photocatalytic degradation gas phase o-dichlorohenzene activity it is higher.
Technical scheme：
The preparation method of the BiOBr micro-flowers photochemical catalysts of the high exposure ratio of a kind of { 001 } active crystal face, step are as follows：
1) preparation of KBr dispersion liquids：KBr is dissolved in absolute ethyl alcohol, 0.5-1.5h is stirred vigorously after ultrasonic 10-30min, Form KBr dispersion liquids.
2) preparation of mixed solution：By Bi (NO3)·5H2O is slowly added into KBr dispersion liquids, stirring at normal temperature 1-3h, is obtained To mixed solution in Bi (NO3)·5H2O is identical with KBr mol ratios；
3) crystallization：Above-mentioned mixed solution is placed in reactor, the hydro-thermal reaction 8-15h under the conditions of 100-200 DEG C, obtained Sample；
4) collect：After sample after crystallization is naturally cooled into room temperature, then centrifuged, collect sediment；
5) wash：Sediment is washed several times successively with deionized water and absolute ethyl alcohol respectively；
6) dry：Sample after washing is dried in 40 DEG C of -80 DEG C of baking ovens, obtains BiOBr micro-flowers photocatalysis Agent.
Ultrasonic time in described step 1) is 15min, and it is 1h to be stirred vigorously the time.
Hydrothermal temperature in described step 3) is 140, the hydro-thermal reaction time 12h.
Described BiOBr micro-flowers photochemical catalyst is used for volatile organic contaminant of degrading.
Beneficial effects of the present invention：The present invention has synthesized BiOBr micro-flowers photochemical catalysts using simple hydro-thermal method, and should The BiOBr catalyst of kind method synthesis is visible light-responded strong, and catalytic activity is high, has in the degraded field of organic pollutant good Good application value and prospect.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of the BiOBr photochemical catalysts prepared.
Fig. 2 is ESEM (SEM) figure of the BiOBr photochemical catalysts prepared
Fig. 3 (a) is that the ratio scale of the BiOBr photochemical catalysts prepared is 200nm transmission electron microscope (TEM) figure.
Fig. 3 (b) is that the TEM that ratio scale is 50nm schemes.
Fig. 3 (c) is the high power transmission plot (HRTEM) of the BiOBr photochemical catalysts prepared
Fig. 3 (d) is the SEAD figure (SAED) of the BiOBr photochemical catalysts prepared.
Fig. 4 (a) is the full spectrogram of the x-ray photoelectron spectroscopy (XPS) of the BiOBr photochemical catalysts prepared.
Fig. 4 (b) is Bi 4f XPS spectrum figure.
Fig. 4 (c) is Br 3d XPS spectrum figure.
Fig. 4 (d) is O 1s XPS spectrum figure.In figure：With reference to Lattice Oxygen can be belonged in 529.9eV characteristic peak, with reference to energy It is as caused by the absorption oxygen of catalyst surface at 532.1eV peak.
Fig. 5 (a) is the UV-vis DRS spectrum of the BiOBr photochemical catalysts prepared.
Fig. 5 (b) is (α h υ)1/2The graph of a relation of corresponding light energy.
Fig. 6 is the surface photovoltage figure of BiOBr photochemical catalysts.
Fig. 7 be the BiOBr photochemical catalysts prepared under visible light conditions to the degradation efficiency figure of o-dichlorohenzene.
Embodiment
Describe the specific embodiment of the present invention in detail below in conjunction with technical scheme and accompanying drawing.
Wherein embodiment 1-5 is the BiOBr micro-flowers catalyst prepared under different condition.
Embodiment 1
1.5mmol KBr is added in 16mL absolute ethyl alcohols, after ultrasonic 15min, is vigorously agitated again 1h, is formed scattered Liquid A.Then by equivalent molar than Bi (NO3)·5H2O is slowly added into above-mentioned dispersion liquid, after stirring at normal temperature 2h, will be mixed Solution is poured into 20mL ptfe autoclave, and 12h is reacted at 140 DEG C, it is naturally cooled to room temperature, and centrifugation is received Collection gained reaction product, respectively with deionized water and washes of absolute alcohol several times after, the drying BiOBr in 60 DEG C of baking oven Micro-flowers catalyst.
Embodiment 2
According to the preparation method of the present invention of embodiment 1, KBr addition is increased into 4.5mmol, is dissolved in 48mL anhydrous second In alcohol, Bi (NO3)3·5H2O addition equally increases to 4.5mmol, and BiOBr micro-flowers catalyst is made.
Embodiment 3
According to the preparation method of the present invention of embodiment 1, hydrothermal temperature is changed to 160 DEG C, reacts 12h, then divided From washing and drying.Obtain BiOBr micro-flowers catalyst.
Embodiment 4
According to the preparation method of the present invention of embodiment 1, at 140 DEG C, hydro-thermal reaction 14h, then separated, wash and do It is dry.Obtain BiOBr micro-flowers catalyst.
Embodiment 5
According to the preparation method of the present invention of embodiment 1, at 120 DEG C, hydro-thermal reaction 12h, then separated, wash and do It is dry.Obtain BiOBr micro-flowers catalyst.
Application of the photochemical catalyst of embodiment 6 in volatile organic contaminant of degrading
According to BiOBr micro-flowers catalyst of the present invention made from the preparation method of embodiment 1, with the Lei bis- Evil compared with difficult degradation The o-dichlorohenzene of English is target contaminant, has investigated its photocatalysis performance.It is and real using FTIS in situ When monitored degradation reaction process, photocatalytic degradation efficiency of the catalyst to o-dichlorohenzene has been investigated by gas-chromatography, drop Efficiency is solved as shown in fig. 7, after radiation of visible light 6h, 69% is reached to the degradation rate of o-dichlorohenzene.Show that example 1 is prepared compound Photochemical catalyst has preferable photocatalytic activity, has larger application potential in terms of degraded to environmental pollutants.

Claims (4)

  1. The preparation method of the BiOBr micro-flowers photochemical catalysts of the high exposure ratio of a kind of 1. { 001 } active crystal face, it is characterised in that step It is rapid as follows：
    1) preparation of KBr dispersion liquids：KBr is dissolved in absolute ethyl alcohol, 0.5-1.5h is stirred vigorously after ultrasonic 10-30min, is formed KBr dispersion liquids；
    2) preparation of mixed solution：By Bi (NO3)·5H2O is slowly added into KBr dispersion liquids, stirring at normal temperature 1-3h, is obtained Bi (NO in mixed solution3)·5H2O is identical with KBr mol ratios；
    3) crystallization：Above-mentioned mixed solution is placed in reactor, the hydro-thermal reaction 8-15h under the conditions of 100-200 DEG C, obtains sample Product；
    4) collect：After sample after crystallization is naturally cooled into room temperature, then centrifuged, collect sediment；
    5) wash：Sediment is washed several times successively with deionized water and absolute ethyl alcohol respectively；
    6) dry：Sample after washing is dried in 40 DEG C of -80 DEG C of baking ovens, obtains BiOBr micro-flowers photochemical catalysts.
  2. 2. preparation method according to claim 1, it is characterised in that the ultrasonic time in described step 1) is 15min, it is 1h to be stirred vigorously the time.
  3. 3. preparation method according to claim 1 or 2, it is characterised in that the hydro-thermal reaction temperature in described step 3) Spend for 140, the hydro-thermal reaction time 12h.
  4. 4. the BiOBr micro-flowers photochemical catalyst that the preparation method of claim 1 or 2 obtains is used for volatile organic contaminant of degrading.
CN201710908415.2A 2017-09-29 2017-09-29 A kind of preparation method and application of the BiOBr micro-flowers photochemical catalysts of the high exposure ratio of { 001 } active crystal face Withdrawn CN107537521A (en)

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CN108281642A (en) * 2018-01-17 2018-07-13 南京信息工程大学 A kind of flower-like structure BiOBr electrode materials and preparation method thereof and electrochemical energy storage application
CN108940323A (en) * 2018-07-09 2018-12-07 王子韩 A kind of preparation method and applications of BiOBr nanometer rods
CN109289878A (en) * 2018-09-18 2019-02-01 哈尔滨理工大学 A kind of BiOI micron ring and preparation method
CN109821565A (en) * 2019-03-26 2019-05-31 南昌航空大学 A kind of sheet g-C3N4The preparation method of compound petal-shaped BiOBr catalysis material
CN111744505A (en) * 2020-07-08 2020-10-09 大连工业大学 Niobium-doped bismuth oxybromide catalyst and preparation and use methods thereof
CN112371140A (en) * 2020-11-12 2021-02-19 景德镇陶瓷大学 Coralline MoS2Photocatalyst and MoS2Preparation method of-BiOBr heterojunction composite photocatalytic material
CN112588304A (en) * 2020-12-16 2021-04-02 江苏大学 Preparation method of bismuth oxybromide efficient photocatalyst with homogenous crystal face junction

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CN108281642A (en) * 2018-01-17 2018-07-13 南京信息工程大学 A kind of flower-like structure BiOBr electrode materials and preparation method thereof and electrochemical energy storage application
CN108281642B (en) * 2018-01-17 2020-05-05 南京信息工程大学 Flower-shaped structure BiOBr electrode material, preparation method and electrochemical energy storage application thereof
CN108940323A (en) * 2018-07-09 2018-12-07 王子韩 A kind of preparation method and applications of BiOBr nanometer rods
CN109289878A (en) * 2018-09-18 2019-02-01 哈尔滨理工大学 A kind of BiOI micron ring and preparation method
CN109821565A (en) * 2019-03-26 2019-05-31 南昌航空大学 A kind of sheet g-C3N4The preparation method of compound petal-shaped BiOBr catalysis material
CN111744505A (en) * 2020-07-08 2020-10-09 大连工业大学 Niobium-doped bismuth oxybromide catalyst and preparation and use methods thereof
CN112371140A (en) * 2020-11-12 2021-02-19 景德镇陶瓷大学 Coralline MoS2Photocatalyst and MoS2Preparation method of-BiOBr heterojunction composite photocatalytic material
CN112588304A (en) * 2020-12-16 2021-04-02 江苏大学 Preparation method of bismuth oxybromide efficient photocatalyst with homogenous crystal face junction
CN112588304B (en) * 2020-12-16 2023-04-07 江苏大学 Preparation method of bismuth oxybromide efficient photocatalyst with homogenous crystal face junction

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Application publication date: 20180105