CN107876069A - BiOCl photochemical catalysts and its synthetic method with highlight catalytic active - Google Patents
BiOCl photochemical catalysts and its synthetic method with highlight catalytic active Download PDFInfo
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- CN107876069A CN107876069A CN201711222753.7A CN201711222753A CN107876069A CN 107876069 A CN107876069 A CN 107876069A CN 201711222753 A CN201711222753 A CN 201711222753A CN 107876069 A CN107876069 A CN 107876069A
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- biocl
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- aqueous solution
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- catalytic active
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000010189 synthetic method Methods 0.000 title claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 230000001699 photocatalysis Effects 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 230000004044 response Effects 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- FIMTUWGINXDGCK-UHFFFAOYSA-H dibismuth;oxalate Chemical compound [Bi+3].[Bi+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O FIMTUWGINXDGCK-UHFFFAOYSA-H 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- 239000000243 solution Substances 0.000 description 19
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 18
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 14
- 229940012189 methyl orange Drugs 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000001103 potassium chloride Substances 0.000 description 9
- 235000011164 potassium chloride Nutrition 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- -1 bismuthino compound Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 239000001509 sodium citrate Substances 0.000 description 5
- 235000011083 sodium citrates Nutrition 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 238000002372 labelling Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/10—One-dimensional structures
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses a kind of BiOCl photochemical catalysts and its synthetic method with highlight catalytic active, the photocatalytic activity of the BiOCl photochemical catalysts is higher, and its pattern is not reported with synthetic method.In addition, Bi will be contained3+、[C6O7H5]3‑And Cl‑The aqueous solution carry out heating response the step of, wherein, Bi in the aqueous solution3+With [C6O7H5]3‑The ratio between the amount of material be 6:15, you can obtaining this has the BiOCl photochemical catalysts of highlight catalytic active, and synthetic method is simple, has higher application value.
Description
Technical field
The present invention relates to nano material, in particular it relates to a kind of BiOCl photochemical catalysts with highlight catalytic active and its
Synthetic method and application.
Background technology
Fossil fuel is all indispensable in the links that we live, and the non-renewable and reserves that gradually decrease are
Through causing energy crisis, and also along with serious environmental pollution during consumption.At present, Photocatalitic Technique of Semiconductor is considered as
It is to solve the more promising technology of the two problems, by generation of hydrogen by dissociation of water, photocatalytic reduction of carbon oxide produces hydrocarbon
Fuel, and light degradation is carried out to toxic pollutant to make up problem of environmental pollution.
In recent years, BiOCl synthesis and photocatalytic activity research cause the great interest of people, main cause one：
BiOCl has [Bi2O2] and two dimension (2D) crystal structure for interlocking of double halogen atom.Spontaneous interior electricity be present in this layer structure
, be advantageous to quick separating and the transmission of photo-generated charge carriers, activity is urged so as to effectively improve light；Reason two：BiOCl has
Preferable photostability, valence band hole position and conduction band electron position are Strong oxdiative also original position.Its photocatalytic activity it is remote by force with
Star's material TiO2。
Therefore, the patterns such as BiOCl nanometer sheets, the micron ball of hierarchy, micro-flowers and their photocatalytic activity are all
There are numerous studies.But the claimed BiOCl micro/nano materials of this patent, its pattern have no report with synthetic method.Separately
Outside, the higher photocatalytic activity of product is also the outstanding person in the bismuthino compound photochemical catalyst reported at present.
The content of the invention
, should it is an object of the invention to provide a kind of BiOCl photochemical catalysts and its synthetic method with highlight catalytic active
The photocatalytic activity of BiOCl photochemical catalysts is higher, equal better than in general bismuthino compound photochemical catalyst, its pattern and synthetic method
Have no report.In addition, Bi will be contained3+、[C6O7H5]3-And Cl-The aqueous solution carry out heating response the step of, wherein, in the aqueous solution
Bi3+With [C6O7H5]3-The ratio between the amount of material be 6:1-5, you can obtaining this has the BiOCl photocatalysis of highlight catalytic active
Agent, synthetic method is simple, has higher application value.
To achieve these goals, the invention provides a kind of conjunction of the BiOCl photochemical catalysts with highlight catalytic active
Into method, including Bi will be contained3+、[C6O7H5]3-And Cl-The aqueous solution carry out heating response the step of, wherein, Bi in the aqueous solution3 +With [C6O7H5]3-The ratio between the amount of material be 6:1-5.
The present invention also provides a kind of BiOCl light with highlight catalytic active synthesized according to previously described synthetic method
Catalyst.
Pass through above-mentioned technical proposal, there is provided a kind of BiOCl photochemical catalysts and its synthetic method with highlight catalytic active,
The photocatalytic activity of the BiOCl photochemical catalysts is higher, better than in general bismuthino compound photochemical catalyst, its pattern and synthetic method
It is not reported.In addition, Bi will be contained3+、[C6O7H5]3-And Cl-The aqueous solution carry out heating response the step of, wherein, the aqueous solution
Middle Bi3+With [C6O7H5]3-The ratio between the amount of material be 6:1-5, you can obtaining this has the BiOCl photocatalysis of highlight catalytic active
Agent, synthetic method is simple, has higher application value.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is to detect the X-ray diffractogram in example 1；
Fig. 2 is to detect ESEM (SEM) figure in example 2；
Fig. 3 is ESEM (SEM) figure of the product in embodiment 3；
Fig. 4 is ESEM (SEM) figure of the product in embodiment 4；
Fig. 5 is MO (10mg/L) degradation curve in the presence of the different catalysts in application examples 1；
Fig. 6 be application examples 2 in BiOCl-0.2g as photochemical catalyst, to the degradation curve of various concentrations MO solution；
Fig. 7 is RhB (10mg/L) degradation curve in the presence of the different catalysts in application examples 3；
Fig. 8 is the degradation curve of phenol (10mg/L) in the presence of the different catalysts in application examples 4；
Fig. 9 is the BiOCl-0.2g in application examples 5 to 10mg/L Photocatalytic Degradation of Methyl Orange recycling rate of waterused figures；
Figure 10 is the X-ray diffractogram in application examples 5.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
To achieve these goals, the invention provides a kind of conjunction of the BiOCl photochemical catalysts with highlight catalytic active
Into method, including Bi will be contained3+、[C6O7H5]3-And Cl-The aqueous solution carry out heating response the step of, wherein, Bi in the aqueous solution3 +With [C6O7H5]3-The ratio between the amount of material be 6:1-5.
Pass through above-mentioned technical proposal, there is provided a kind of BiOCl photochemical catalysts and its synthetic method with highlight catalytic active,
The photocatalytic activity of the BiOCl photochemical catalysts is higher, better than in general bismuthino compound photochemical catalyst, its pattern and synthetic method
It is not reported.In addition, Bi will be contained3+、[C6O7H5]3-And Cl-The aqueous solution carry out heating response the step of, wherein, the aqueous solution
Middle Bi3+With [C6O7H5]3-The ratio between the amount of material be 6:1-5, you can obtaining this has the BiOCl photocatalysis of highlight catalytic active
Agent, synthetic method is simple, has higher application value.
In a kind of preferred embodiment of the present invention, in order to obtain the BiOCl photochemical catalysts with highlight catalytic active,
Preferably, Bi in the aqueous solution3+、[C6O7H5]3-And Cl-The ratio between the amount of material be 6:1-5：6.
In a kind of preferred embodiment of the present invention, in order to obtain the BiOCl photochemical catalysts with highlight catalytic active,
Preferably, Bi in the aqueous solution3+Concentration be 20-30mmol/L.
In a kind of preferred embodiment of the present invention, in order to obtain the BiOCl photochemical catalysts with highlight catalytic active,
Preferably, the temperature of heating response is 120-180 DEG C.
In a kind of preferred embodiment of the present invention, in order to obtain the BiOCl photochemical catalysts with highlight catalytic active,
Preferably, the time of heating response is 8-12h.
Pass through above-mentioned technical proposal is the BiOCl photochemical catalysts that can obtain having highlight catalytic active, in order to be had
The BiOCl photochemical catalysts of highlight catalytic active, it is preferable that the formation of the aqueous solution includes：Cl will be provided-Material and offer
[C6O7H5]3-Material be pre-dissolved in water, then ultrasonic disperse is added dropwise to be pre-dissolved and is provided with Bi3+Material the aqueous solution in, mix
Close.
It is the BiOCl photochemical catalysts that can obtain that there is highlight catalytic active according to above-mentioned synthetic method, further, is
The higher BiOCl photochemical catalysts with highlight catalytic active of photocatalytic activity are obtained, the formation of the aqueous solution includes：Will
Cl is provided-Material and offer [C6O7H5]3-Material be pre-dissolved in water, then ultrasonic disperse is added dropwise to be pre-dissolved and is provided with Bi3+
Material the aqueous solution in, mixing.
In the above-mentioned technical solutions, it is pre-dissolved and is provided with Cl-Material and offer [C6O7H5]3-Material the aqueous solution with it is pre-
Dissolving is provided with Bi3+The volume ratio of the aqueous solution of material can be adjusted in relative broad range, as long as meet above-mentioned concentration or
The amount requirement of material, in order to obtain the BiOCl micron bars of the regular exposure of crystalline form (110) crystal face, it is preferable that in advance dissolved with carrying
For Cl-Material and offer [C6O7H5]3-Material the aqueous solution and be pre-dissolved and be provided with Bi3+Material the aqueous solution volume ratio
For 1:0.8-1.2.
In the above-mentioned technical solutions, those skilled in the art are for providing Cl-Material can be adjusted in relative broad range
It is whole, such as, there is provided Cl-Material to contain Cl-Salt or contain Cl-Acid, can be achieved the present invention.In order to further make original
Expect simple and easy to get, it is preferable that Cl is provided-Material be sodium chloride, potassium chloride and hydrochloric acid in one or more.
In the above-mentioned technical solutions, those skilled in the art are for providing [C6O7H5]3-Material can enter in relative broad range
Row adjustment, in order to further make raw material simple and easy to get, it is preferable that [C is provided6O7H5]3-Material be citrate and/or lemon
Acid.
In the above-mentioned technical solutions, those skilled in the art are for providing Bi3+Material can be adjusted in relative broad range
It is whole, in order to further make raw material simple and easy to get, it is preferable that provide Bi3+Material be bismuth nitrate and/or bismuth oxalate.
Terminate the processing of rear product for reaction, those skilled in the art can be adjusted flexibly, it is preferable that the synthetic method
It is additionally included in after heating response terminates and naturally cools to room temperature, product is washed with water and/or ethanol afterwards, then dried
The step of.
The present invention also provides a kind of BiOCl light with highlight catalytic active synthesized according to previously described synthetic method
Catalyst.
The photocatalytic activity of the BiOCl photochemical catalysts is better than in general bismuthino compound photochemical catalyst, its pattern and synthesis
Method is not reported.
Further, BiOCl photochemical catalysts have the one-dimensional rod-like structure accumulated and formed by BiOCl nanometer sheets.
The present invention also provides a kind of method of photocatalytic pollutant degradation, including by pollutant under illumination condition and above
The step of described BiOCl photochemical catalysts with highlight catalytic active are contacted.
The method of photocatalytic pollutant degradation has the characteristics of efficiency high, BiOCl photochemical catalysts are easily recycled.
In the above-mentioned technical solutions, pollutant has the one or more in methyl orange, phenol and rhodamine B.
In such scheme, enter in the one or more that the condition of photocatalytic degradation is included in soil, water, organic solvent
The row contact.
The present invention will be described in detail by way of examples below.
In following examples, all raw materials are commercially available product.
Embodiment 1
By 1mmol Bi (NO3)3·5H2O and 1mmol KCl are added separately in 20mL distilled water, are connected at 20 DEG C of room temperature
Continuous stirring forms solution, 0.68mmol (0.2g) sodium citrate is added in above-mentioned KCl solution, ultrasonic disperse, then by it
Mixed solution is added drop-wise to above-mentioned Bi (NO3)3·5H2In O solution, stir 30 minutes；
It is then transferred in autoclave, 160 DEG C are heated 8 hours, after reaction terminates, naturally cool to room temperature；
Product distilled water, ethanol washing, is dried to constant weight.Product Labeling is BiOCl-0.2g.
Embodiment 2
By 1mmol Bi (NO3)3·5H2O is added in 25mL distilled water, and 1mmol KCl are added separately into 25mL distillations
In water, continuously stir to form solution respectively at 20 DEG C of room temperature, 0.83mmol sodium citrates be added in above-mentioned KCl solution,
Ultrasonic disperse, then it is mixed solution and is added drop-wise to above-mentioned Bi (NO3)3·5H2In O solution, stir 30 minutes；
It is then transferred in autoclave, 120 DEG C are heated 12 hours, after reaction terminates, naturally cool to room temperature；
Product distilled water, ethanol washing, is dried to constant weight.
Embodiment 3
By 1mmol Bi (NO3)3·5H2O is added in 18mL distilled water, and 1mmol KCl are added separately into 17mL distillations
In water, continuously stir to form solution respectively at 20 DEG C of room temperature, 0.17mmol (0.05g) sodium citrate is added to above-mentioned KCl
In solution, ultrasonic disperse, then it is mixed solution and is added drop-wise to above-mentioned Bi (NO3)3·5H2In O solution, stir 30 minutes；
It is then transferred in autoclave, 180 DEG C are heated 10 hours, after reaction terminates, naturally cool to room temperature；
Product distilled water, ethanol washing, is dried to constant weight.Product Labeling is BiOCl-0.05g.
Embodiment 4
By 1mmol Bi (NO3)3·5H2O and 1mmol KCl are added separately in 20mL distilled water, are connected at 20 DEG C of room temperature
Continuous stirring forms solution, 0.34mmol (0.1g) sodium citrate is added in above-mentioned KCl solution, ultrasonic disperse, then by it
Mixed solution is added drop-wise to above-mentioned Bi (NO3)3·5H2In O solution, stir 30 minutes；
It is then transferred in autoclave, 160 DEG C are heated 8 hours, after reaction terminates, naturally cool to room temperature；
Product distilled water, ethanol washing, is dried to constant weight.Product Labeling is BiOCl-0.1g
Comparative example 1
BiOCl is synthesized according to the method for embodiment 1, the difference is that being added without sodium citrate, keeps obtaining under the same terms
Sample be labeled as BiOCl-001 (BiOCl-0g).
Detect example 1
The BiOCl photochemical catalysts obtained in X-ray diffraction analysis embodiment 1, embodiment 3, embodiment 4, in corresponding diagram
BiOCl-001 (0g curve in corresponding diagram) in 0.2g, 0.05g, 0.1g curve, and comparative example 1, and and standard card
BiOCl (JCPDS No.06-0249) is compareed, and obtained X-ray diffractogram (XRD) is as shown in Figure 1.
It will be seen from figure 1 that BiOCl photochemical catalysts (001) crystal face diffracted intensity substantially subtracts than BiOCl-001 diffracted intensity
It is weak, and the BiOCl-001 of (110) crystal face diffracted intensity is strong.
Detect example 2
The BiOCl photochemical catalysts that ESEM (SEM) analysis embodiment 1 obtains, as a result as shown in Figure 2.Can from Fig. 2
Go out, product BiOCl is accumulated by substantial amounts of BiOCl nanometer sheets, forms one-dimensional rod-like structure.
Similarly, the BiOCl photochemical catalysts obtained in ESEM (SEM) analysis embodiment 3, embodiment 4, it is as a result right respectively
It should show that product BiOCl is accumulated by substantial amounts of BiOCl nanometer sheets such as Fig. 3, Fig. 4, form one-dimensional rod-like structure.
Application examples 1
In the case where temperature is 30 DEG C and illumination condition by the BiOCl in embodiment 1, embodiment 3, embodiment 4 and comparative example 1
Photochemical catalyst 0.04g is contacted with the aqueous solution 40mL containing methyl orange (MO) (10mg/L).As shown in figure 5, BiOCl-
0.2g samples show highest photocatalytic activity, and 100% MO (10mg/L) can be complete in 4 minutes under sunshine irradiation
Degraded.BiOCl-0.1g, BiOCl-0.05g degradation efficiency are also superior to the sample in comparative example.
It can be seen that BiOCl of the invention light urges agent to have preferable photocatalytic activity, photocatalytic degradation of the invention pollution
The method of thing has the characteristics of efficiency high.
Application examples 2
It it is 30 DEG C and under the conditions of sunshine irradiation by temperature, by methyl orange (MO) water of 40mL various concentrations
Solution is contacted to evaluate the work of BiOCl-0.2g photochemical catalysts in embodiment 1 with applying BiOCl-0.2g photochemical catalysts 0.04g in example 1
Property, the concentration of wherein methyl orange (MO) aqueous solution are 10mg/L, 20mg/L, 30mg/L and 40mg/L, as a result as shown in fig. 6,
BiOCl-0.2g samples also have extraordinary degradation capability to the MO of high concentration, as 40mg/L MO can be complete at 30 minutes
Degradable, degradation efficiency are higher.
Application examples 3
In the case where temperature is 30 DEG C and illumination condition, by embodiment 1, embodiment 3, embodiment 4 and comparative example 1
BiOCl photochemical catalysts 0.04g is contacted to evaluate embodiment with the 40mL aqueous solution for containing rhodamine B (RhB) (10mg/L)
1st, in embodiment 3, embodiment 4 and comparative example 1 BiOCl photocatalytic activity.As shown in fig. 7, BiOCl-0.05g, BiOCl-
0.1g and BiOCl-0.2g is compared to BiOCl-0g, under showing that more preferable photocatalytic activity, sunshine irradiate, 10mg/L's
RhB is degradable in 3 minutes, 6 minutes and 7 minutes respectively.
It can be seen that BiOCl of the invention light urges agent to have preferable photocatalytic activity, photocatalytic degradation of the invention pollution
The method of thing has the characteristics of efficiency high.
Application examples 4
In the case where temperature is 30 DEG C and illumination condition, by embodiment 1, embodiment 3, embodiment 4 and comparative example 1
BiOCl photochemical catalysts 0.04g is contacted to evaluate embodiment 1, embodiment with the 40mL aqueous solution for containing phenol (10mg/L)
3rd, in embodiment 4 and comparative example 1 BiOCl photocatalytic activity.As shown in figure 8, BiOCl-0.05g, BiOCl-0.1g and
BiOCl-0.2g shows more preferable photocatalytic activity, under sunshine irradiation, 10mg/L phenol divides compared to BiOCl-0g
It is degradable interior degradable not in 30 minutes, 35 minutes and 30 minutes.
It can be seen that BiOCl of the invention light urges agent to have preferable photocatalytic activity, photocatalytic degradation of the invention pollution
The method of thing has the characteristics of efficiency high.
Application examples 5
According to the method for application examples 1, using the BiOCl-0.2g samples in 0.04g embodiments 1 to 40mL10mg/L methyl
Orange aqueous solution photocatalytic degradation carries out repeating degraded 5 times, and the degradation efficiency after observation recycling as a result as shown in figure 9, can
See, BiOCl-0.2g stability in photocatalytic process is preferable, and recycling rate of waterused is higher.
Five forward and backward diffraction patterns of circulation are being carried out using X-ray diffraction analysis BiOCl-0.2 photochemical catalysts, as a result such as
Shown in Figure 10, BiOCl-0.2 photochemical catalysts circulate for five times forward and backward diffraction maximum change substantially it is small, it is seen then that BiOCl-0.2g
Stability is preferable in photocatalytic process, and recycling rate of waterused is higher.
As can be seen here, BiOCl photochemical catalysts of the invention have excellent photocatalytic activity and reusing；And because
Product is one-dimensional micro/nano structure, has larger size, and recovery is beneficial in actual sewage degradation process.Therefore, this product
It is the high efficiency photocatalyst with practical value.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of synthetic method of the BiOCl photochemical catalysts with highlight catalytic active, it is characterised in that including Bi will be contained3+、
[C6O7H5]3-And Cl-The aqueous solution carry out heating response the step of, wherein, Bi in the aqueous solution3+With [C6O7H5]3-Material amount
The ratio between be 6:1-5.
2. synthetic method according to claim 1, wherein, Bi in the aqueous solution3+、[C6O7H5]3-And Cl-Material amount it
Than for 6:1-5：6.
3. synthetic method according to claim 1, wherein, Bi in the aqueous solution3+Concentration be 20-30mmol/L.
4. synthetic method according to claim 1, wherein, the temperature of heating response is 120-180 DEG C；And/or
The time of heating response is 8-12h.
5. according to the synthetic method described in claim any one of 1-4, wherein, the formation of the aqueous solution includes：Cl will be provided-
Material and offer [C6O7H5]3-Material be pre-dissolved in water, then ultrasonic disperse is added dropwise to be pre-dissolved and is provided with Bi3+Material
The aqueous solution in, mixing.
6. synthetic method according to claim 5, wherein, it is pre-dissolved and is provided with Cl-Material and offer [C6O7H5]3-Thing
The aqueous solution of matter is provided with Bi with being pre-dissolved3+Material the aqueous solution volume ratio be 1:0.8-1.2.
7. synthetic method according to claim 5, wherein, there is provided Cl-Material to contain Cl-Salt or contain Cl-'s
Acid；And/or
[C is provided6O7H5]3-Material be citrate and/or citric acid.
8. synthetic method according to claim 5, wherein, there is provided Bi3+Material be bismuth nitrate and/or bismuth oxalate.
9. the BiOCl photocatalysis with highlight catalytic active of the synthetic method synthesis according to claim any one of 1-8
Agent.
10. BiOCl photochemical catalysts according to claim 9, wherein, BiOCl photochemical catalysts have by BiOCl nanometer sheet heaps
The one-dimensional rod-like structure that product is formed.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107857333A (en) * | 2017-11-29 | 2018-03-30 | 安徽师范大学 | The method of photocatalytic pollutant degradation |
| CN108579770A (en) * | 2018-05-15 | 2018-09-28 | 安徽师范大学 | A method of carrying out degradation of contaminant using BiOCl nano-rings |
| CN108940323A (en) * | 2018-07-09 | 2018-12-07 | 王子韩 | A kind of preparation method and applications of BiOBr nanometer rods |
| TWI776041B (en) * | 2019-04-08 | 2022-09-01 | 鋐錕實業股份有限公司 | Method for reducing carbon dioxide to manufacture carbon compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104386746A (en) * | 2014-11-19 | 2015-03-04 | 北京大学 | Method for preparing small-size bismuth oxychloride wafer by use of hydrothermal method |
| CN105032452A (en) * | 2015-07-14 | 2015-11-11 | 聊城大学 | Preparation method for high-visible-light-activity K-doped BiOCl photocatalyst |
| CN107215894A (en) * | 2017-06-09 | 2017-09-29 | 北京华腾新材料股份有限公司 | A kind of heat-insulated granules of pigments of bismoclite near-infrared high reflection and preparation method |
-
2017
- 2017-11-29 CN CN201711222753.7A patent/CN107876069A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104386746A (en) * | 2014-11-19 | 2015-03-04 | 北京大学 | Method for preparing small-size bismuth oxychloride wafer by use of hydrothermal method |
| CN105032452A (en) * | 2015-07-14 | 2015-11-11 | 聊城大学 | Preparation method for high-visible-light-activity K-doped BiOCl photocatalyst |
| CN107215894A (en) * | 2017-06-09 | 2017-09-29 | 北京华腾新材料股份有限公司 | A kind of heat-insulated granules of pigments of bismoclite near-infrared high reflection and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| XIULANHU ET.AL: "Controllable hydrothermal synthesis of BiOCl nanoplates with high exposed {001} facets", 《MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107857333A (en) * | 2017-11-29 | 2018-03-30 | 安徽师范大学 | The method of photocatalytic pollutant degradation |
| CN107857333B (en) * | 2017-11-29 | 2021-03-16 | 安徽师范大学 | Method for photocatalytic degradation of pollutants |
| CN108579770A (en) * | 2018-05-15 | 2018-09-28 | 安徽师范大学 | A method of carrying out degradation of contaminant using BiOCl nano-rings |
| CN108579770B (en) * | 2018-05-15 | 2020-03-24 | 安徽师范大学 | Method for degrading pollutants by using BiOCl nanoring |
| CN108940323A (en) * | 2018-07-09 | 2018-12-07 | 王子韩 | A kind of preparation method and applications of BiOBr nanometer rods |
| CN108940323B (en) * | 2018-07-09 | 2021-04-09 | 王子韩 | Preparation method and application of BiOBr nanorod |
| TWI776041B (en) * | 2019-04-08 | 2022-09-01 | 鋐錕實業股份有限公司 | Method for reducing carbon dioxide to manufacture carbon compound |
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