CN111617784A - Preparation method and application of two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material - Google Patents
Preparation method and application of two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material Download PDFInfo
- Publication number
- CN111617784A CN111617784A CN202010581799.3A CN202010581799A CN111617784A CN 111617784 A CN111617784 A CN 111617784A CN 202010581799 A CN202010581799 A CN 202010581799A CN 111617784 A CN111617784 A CN 111617784A
- Authority
- CN
- China
- Prior art keywords
- doped modified
- preparation
- biocl
- bismuth oxychloride
- boc
- 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
Links
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 17
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 44
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005303 weighing Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229910001868 water Inorganic materials 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 15
- 239000011265 semifinished product Substances 0.000 claims description 15
- 238000006731 degradation reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 230000015556 catabolic process Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 28
- 150000003839 salts Chemical class 0.000 abstract description 17
- 239000011941 photocatalyst Substances 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000004298 light response Effects 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 47
- 229940073609 bismuth oxychloride Drugs 0.000 description 35
- 239000000243 solution Substances 0.000 description 18
- 230000008569 process Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000000137 annealing Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 150000002500 ions Chemical group 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- -1 morphology control Chemical compound 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000009284 supercritical water oxidation Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- 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
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of a two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material. Using novel molten salts (NaNO)3And KNO3) The method prepares pure BiOCl and Fe-doped modified BiOCl. Firstly, weighing NaNO with a certain mass ratio3And KNO3Mixing and grinding, then adding Bi (NO) into the mixed salt3)3•5H2O, KCl and Fe (NO)3)3•9(H2O), and uniformly mixing and grinding. And then placing the mixed powder into an alumina crucible for heat treatment to obtain the Fe-doped modified BiOCl. The invention has the advantages of low cost, high efficiency, environmental protection, safety and convenience, and simple processThe obtained Fe-doped modified BiOCl material has the advantages of a typical layer-layer structure, more surface active areas, visible light response and stable photocatalytic performance, and therefore has great potential application value in preparation of novel photocatalysts.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a preparation method and application of a two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material.
Background
With the continuous progress of industrialization and urbanization, the pollution problem caused by waste gas, organic matter, polymers, biomass, etc. becomes more severe. Among them, some of the artificially synthesized organic pollutants have high toxicity despite their low concentration in the environment, and thus it is necessary to convert the pollutants into non-toxic (or low-toxic) substances without generating secondary pollution through an efficient and "green" treatment technique. Currently, several physical and chemical methods have been used to solve this problem. The physical treatment technology mainly comprises adsorption, ultrafiltration, flocculation and the like, and the chemical treatment technology mainly comprises ozone oxidation, ultraviolet irradiation, hydrogen peroxide oxidation, semiconductor photocatalytic degradation, supercritical water oxidation, Fenton process, sound wave degradation, electrochemical treatment, electron beam treatment process, solvated electron reduction, iron permeation reaction wall, enzyme treatment process and the like. The semiconductor photocatalysis technology can completely eliminate organic pollutants, and has the advantages of high reaction speed, low process cost, mild operation conditions and environmental friendliness, so that the semiconductor photocatalysis technology becomes one of the most effective and green methods for removing organic pollutants.
At present, the photocatalytic material is limited in industrial production and practical application due to the complex synthesis process, low visible light utilization rate, low organic mineralization rate and poor catalyst stability.
In recent years, bismuth oxychloride (BiOCl) -based photocatalytic materials attract attention of many researchers due to the characteristics of rich sources, no toxicity, stability, unique optical and electrical properties and the like. BiOCl is a typical ternary semiconductor compound of main groups v-vi-viiIn which the halogen Cl ion forms [ Cl2]2-Layer, bismuth and oxygen form [ Bi2O2]2+And (3) a layer. [ Cl ]2]2-Layer and [ Bi ]2O2]2+The layers alternate to form a tetragonal crystal structure ([001 ] in the c-axis direction]). However, the BiOCl has a large band gap value and cannot be excited by visible light, so that the full utilization of solar energy is limited, and the practical application is hindered.
Many methods have been used to improve the visible light absorption and photocatalytic performance of BiOCl, such as morphology control, crystal plane modulation, complex heterojunctions, and element doping. Wherein the elemental doping strategy maintains a unique static internal electric field and high separation of photoionized charges. It is worth noting that the element doping can form band gap states near the conduction band edge and the valence band edge, so that absorption of visible light to sub-band energy is induced, and photon-generated carrier recombination is inhibited. Many elements are used to dope bioactive carbon, such as manganese, zinc, iron, cobalt, Ce, W, Sn, etc. Especially, Fe has attracted more and more attention as a promising method. Since the size of Fe ions is similar to that of bismuth ions, Bi ions are easily substituted in the crystal structure. In addition, oxygen vacancies generated by Fe doping can improve the conductivity, improve the separation and migration of electron-hole pairs, and further improve the photocatalytic performance.
The melting method is widely applied to synthesis of micro-materials due to the advantages of low cost, high efficiency, environmental friendliness, safety, convenience and the like. Particularly, the exposed ions can be directly transported and participate in the reaction process, so that the reaction caused by dehydration of the hydrated ions is limited, and the reaction speed in the molten salt is greatly accelerated. The mass transfer rate in molten salts is higher than in liquid phase processes. This facilitates homogeneous synthesis of the material. And simultaneously, impurity atoms can enter into a lattice structure.
In conclusion, the molten salt method not only provides a remarkable way for improving the photocatalytic performance, but also opens up a new technical route for designing a large amount of doped photocatalysts. No NaNO is adopted in the BiOCl preparation3-KNO3As a molten salt, material synthesis has been reported, and no studies have been made on material modification.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method and application of a two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material3And KNO3The prepared Fe-doped BOC modified material has stronger catalytic degradation activity of sunlight response, in addition, the preparation process is simple, the energy consumption is low, the prepared material has high catalytic efficiency, and the application of the prepared material in the field of photocatalysis is widened.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a preparation method of a two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material comprises the following steps:
step 1, mixing the raw materials in a mass ratio of 1:1 weighing raw material NaNO3And KNO3Mixing, placing in a mortar, and adding Bi (NO) into the mixed molten salt3)3•5H2O, 1.0000g KCl and a mass Fe (NO) satisfying the molar ratio Bi/Fe =1/x3)3•9(H2O), fully grinding for 3h to obtain mixed powder, wherein the Fe (NO) is3)3•9(H2O) and Bi (NO)3)3•5H2The molar ratio of O is a value x, wherein x is 0-0.20; the content of Fe doping is changed by changing Fe (NO)3)3•9(H2O)/Bi(NO3)3•5H2The mol ratio of O realizes the doping of Fe in a BiOCl bulk phase, and the doping can be marked as xFe-BOC (x = 0-0.20);
and 3, taking out the semi-finished product, repeatedly centrifuging and washing, and drying in an oven to obtain a finished product.
As a modification, the source used in step 1NaNO material3、KNO3、Bi(NO3)3•5H2O、KCl、Fe(NO3)3•9(H2O) are all analytically pure, x is 0.05.
The improvement is that the temperature rise speed of the muffle furnace synthesis in the step 2 is kept at 5-10 ℃/min.
As a modification, the rate of centrifugation in step 3 was 4000 r/min.
As an improvement, the specific steps of washing and drying in the step 3 are as follows: and (3) washing the semi-finished product with an absolute ethyl alcohol water solution with the volume ratio of 1:1 for 5-10 times, and drying in an oven environment at 80 ℃.
The two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material is applied to degradation of RhB solution.
The working principle is as follows: on one hand, the BiOCl nanosheet has a special energy band structure and certain visible light response capability; on the other hand, oxygen defect vacancies formed after metal Fe doping modification can facilitate the rapid separation of photo-generated electron-hole pairs, thereby improving the quantum yield, and further improving the photocatalytic degradation performance in the visible light response range.
Has the advantages that:
compared with the prior art, the preparation method of the two-dimensional layered bismuth oxychloride-Fe doped and modified photocatalytic material adopts novel molten salt (NaNO)3And KNO3) Pure BiOCl and metal (taking iron as an example) doping modified BiOCl thereof are prepared by the method. Firstly, weighing NaNO with a certain mass ratio3And KNO3Mixing and grinding, then adding Bi (NO) into the mixed salt3)3•5H2O, KCl and a weight of Fe (NO)3)3•9(H2O), and uniformly mixing and grinding. And then placing the mixed powder into an alumina crucible for heat treatment to obtain pure BiOCl-Fe doped and modified BiOCl.
The concrete advantages are as follows: the preparation method has the advantages of low cost, high efficiency, environmental friendliness, safety, convenience, simple process and the like, and the obtained Fe-doped modified BiOCl material has a typical layer-layer structure, more surface active regions, visible light response, stable photocatalytic performance and excellent degradation effect on RhB.
Drawings
FIG. 1 is an XRF pattern for a product of various embodiments of the present invention wherein (a) is BOC, xFe-BOC and (b) is BOC and 0.05 Fe-BOC;
FIG. 2 is an XPS spectrum of 0.05Fe-BOC of a sample obtained in example 3 of the present invention: (a) is a total map, (b) is a Bi 4f map, (c) is a Cl 2p map, (d) is a Fe2p map, and (e) is an O1 s map;
FIG. 3 is a SEM photograph and an EDS spectrum of example 3 of the present invention, wherein (a) is a SEM photograph of a sample BOC, (b) is a SEM photograph of 0.05Fe-BOC, (c) is an EDS spectrum of 0.05Fe-BOC, (d) is an EDS spectrum of Cl, (e) is an EDS spectrum of Bi, (f) is an EDS spectrum of O, and (g) is an EDS spectrum of Fe;
FIG. 4 is a UV-VIS absorption spectrum of BOC and Fe-BOC in example 3 of the present invention, wherein (a) is the UV-VIS absorption spectrum of BOC and Fe-BOC, and (b) is the converted UV-VIS bandgap spectrum;
FIG. 5 is a graph showing the effect of different proportions of Fe-BOC and BOC photocatalytic materials on simulated photocatalytic degradation of RhB solution in sunlight, wherein (a) is a concentration variation curve of Fe-BOC and BOC photocatalytic RhB dyes in different proportions under illumination, and (b) is a curve fitted according to kinetics of photocatalytic degradation of RhB;
FIG. 6 is a graph showing the effect of sunlight simulated photocatalytic degradation of RhB solution when the prepared 0.05Fe-BOC material is circulated for 5 times and the times are different;
FIG. 7 is a schematic view of the condensing apparatus of the present invention.
Detailed description of the preferred embodiment
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
(1) Preparing Fe body by molten salt methodAdding BiOCl, weighing 25g NaNO with the mass ratio of 1:13And KNO3Mixed and milled, then 1.9403 g Bi (NO) is added to the mixed salt3)3•5H2O, 1.0000g KCl and 0.0170 g Fe (NO)3)3•9(H2O), mixing and grinding for 3 hours to obtain mixed powder;
(2) then putting the mixed and ground powder into an alumina crucible, annealing for 3h at 400 ℃, and naturally cooling to ambient temperature to obtain a semi-finished product;
(3) taking out the semi-finished product, repeatedly washing the semi-finished product by using a mixed solution of deionized water and absolute ethyl alcohol, and then putting the washed semi-finished product powder into an oven at 80 ℃ for drying overnight, (abbreviated as 0.01 Fe-BOC).
Example 2
(1) Preparing Fe-phase-doped BiOCl by adopting a molten salt method, and weighing 25g of NaNO with the mass ratio of 1:13And KNO3Mixed and milled, then 1.9403 g Bi (NO) is added to the mixed salt3)3•5H2O, 1.0000g KCl and 0.0511 g Fe (NO)3)3•9(H2O), and milling for 3 h. .
(2) And then putting the mixed and ground powder into an alumina crucible, annealing for 3 hours at 400 ℃, and naturally cooling to the ambient temperature.
(3) Then, the mixture solution of deionized water and absolute ethyl alcohol is repeatedly washed. And finally, placing the semi-finished product powder in an oven at 80 ℃ for drying overnight. (abbreviated as 0.03 Fe-BOC).
Example 3
(1) Preparing Fe-phase-doped BiOCl by adopting a molten salt method, and weighing 25g of NaNO with the mass ratio of 1:13And KNO3Mixed and milled, then 1.9403 g Bi (NO) is added to the mixed salt3)3•5H2O, 1.0000g KCl and 0.0851 g Fe (NO)3)3•9(H2O), and milling for 3 h.
(2) And then putting the mixed and ground powder into an alumina crucible, annealing for 3 hours at 400 ℃, and naturally cooling to the ambient temperature.
(3) Then, the mixture solution of deionized water and absolute ethyl alcohol is repeatedly washed. And finally, placing the semi-finished product powder in an oven at 80 ℃ for drying overnight. (abbreviated as 0.05 Fe-BOC).
Example 4
(1) Preparing Fe-phase-doped BiOCl by adopting a molten salt method, and weighing 25g of NaNO with the mass ratio of 1:13And KNO3Mixed and milled, then 1.9403 g Bi (NO) is added to the mixed salt3)3•5H2O, 1.0000g KCl and 0.1191 g Fe (NO)3)3•9(H2O), and milling for 3 h.
(2) And then putting the mixed and ground powder into an alumina crucible, annealing for 3 hours at 400 ℃, and naturally cooling to the ambient temperature.
(3) Then, the mixture solution of deionized water and absolute ethyl alcohol is repeatedly washed. And finally, placing the semi-finished product powder in an oven at 80 ℃ for drying overnight. (abbreviated as 0.07 Fe-BOC).
Example 5
(1) Preparing Fe-phase-doped BiOCl by adopting a molten salt method, and weighing 25g of NaNO with the mass ratio of 1:13And KNO3Mixed and milled, then 1.9403 g Bi (NO) is added to the mixed salt3)3•5H2O, 1.0000g KCl and 0.1796 g Fe (NO)3)3•9(H2O), and milling for 3 h.
(2) And then putting the mixed and ground powder into an alumina crucible, annealing for 3 hours at 400 ℃, and naturally cooling to the ambient temperature.
(3) Then, the mixture solution of deionized water and absolute ethyl alcohol is repeatedly washed. And finally, placing the semi-finished product powder in an oven at 80 ℃ for drying overnight. (abbreviated as 0.10 Fe-BOC).
Example 6
(1) Preparing Fe-phase-doped BiOCl by adopting a molten salt method, and weighing 25g of NaNO with the mass ratio of 1:13And KNO3Mixed and milled, then 1.9403 g Bi (NO) is added to the mixed salt3)3•5H2O, 1.0000g KCl and 0.2852 g Fe (NO)3)3•9(H2O), and milling for 3 h.
(2) And then putting the mixed and ground powder into an alumina crucible, annealing for 3 hours at 400 ℃, and naturally cooling to the ambient temperature.
(3) Then, the mixture solution of deionized water and absolute ethyl alcohol is repeatedly washed. And finally, placing the semi-finished product powder in an oven at 80 ℃ for drying overnight. (abbreviated as 0.15 Fe-BOC).
Example 7
(1) Preparing Fe-phase-doped BiOCl by adopting a molten salt method, and weighing 25g of NaNO with the mass ratio of 1:13And KNO3Mixed and milled, then 1.9403 g Bi (NO) is added to the mixed salt3)3•5H2O, 1.0000g KCl and 0.4040 g Fe (NO)3)3•9(H2O), and milling for 3 h.
(2) And then putting the mixed and ground powder into an alumina crucible, annealing for 3 hours at 400 ℃, and naturally cooling to the ambient temperature.
(3) Then, the mixture solution of deionized water and absolute ethyl alcohol is repeatedly washed. Finally, the sample was placed in an oven at 80 ℃ to dry overnight. (abbreviated as 0.20 Fe-BOC).
Preparation of comparative example BiOCl alone
(1) Pure BiOCl is prepared by adopting a molten salt method, and 25g of NaNO with the mass ratio of 1:1 is weighed3And KNO3Mixed and milled, then 1.9403 g Bi (NO) is added to the mixed salt3)3•5H2O, 1.0000g KCl, and mixed grinding for 3 hours.
(2) And then putting the mixed and ground powder into an alumina crucible, annealing for 3 hours at 400 ℃, and naturally cooling to the ambient temperature.
(3) Then, the mixture solution of deionized water and absolute ethyl alcohol is repeatedly washed. Finally, the sample was placed in an oven at 80 ℃ to dry overnight. (abbreviated as BOC).
Performance testing
In order to verify and analyze the self-quality and catalytic performance of the two-dimensional layered bismuth oxychloride-Fe-doped modified photocatalytic material obtained in the embodiment of the invention, the experiment example tests the Fe-doped BiOCl photocatalyst obtained in the embodiments 1 to 7 and the single BiOCl, and the test and analysis results show that the performances are good, specifically:
firstly, the tested finished product is identified in the test example, and the pure BiOCl photocatalyst and the Fe-doped photocatalyst are respectively subjected to X-ray powder diffraction analysis test, so that the structure of the BiOCl photocatalyst and the Fe-doped photocatalyst is formedIf the XRD patterns of pure BiOCl, i.e., BOC and xFe-BOC, respectively, are shown in FIG. 1 (a), it can be seen that all the final products crystallize well, conforming to the BiOCl tetragonal structure (card number JCPDS:06-0249), and all the xFe-BOC has no iron oxide or other characteristic peaks of crystalline phases, indicating that iron enters the BiOCl bulk phase of hexagonal crystal structure. As shown in FIG. 1 (b), the characteristic peak of XRD of 0.05Fe-BOC appears shifted to the right according to the Bragg equation: 2dsin θ = n λ, due to Fe3+Ions enter Bi3+Lattice, Fe3+Atomic radius ratio Bi3+That the lattice distortion leads to a decrease in the grain boundary spacing d and an increase in the diffraction angle, and further confirms that Fe3+Doping of partially substituted Bi3+The above shows that the synthesis of xFe-BOC and BOC is successful by the molten salt method, rather than the lattice interstitial type.
To further confirm the surface chemical composition and chemical state of the doped BiOCl, FIG. 2 is an XPS spectrum of 0.05 Fe-BOC. FIG. 2(a) shows characteristic peaks of Bi, Fe, O, Cl and C. Wherein C1s is assigned to the characteristic peak of instrument test at 285 eV. FIG. 2(b) XPS spectrum shows two major peaks of Bi 4f with binding energies of 164.3 eV and 159.8 eV, respectively, corresponding to Bi3+Bi 4f of7/2And Bi 4f5/2. The Cl 2p XPS spectrum shows two main binding energy peaks at 197.7 and 199.3 eV as shown in FIG. 2(c), corresponding to Cl2 2-Cl 2p of3/2And Cl 2p1/2(FIG. 2 (b)). The high resolution XPS spectrum of Fe2p is shown in FIG. 2 (d). The peak at 711.4 eV for Fe2p can be attributed to Fe 3+2p of ion3/2. This is probably due to the Fe in the doped BiOCl crystal3+Substitute for Bi3+Bi-O-Fe bonds are formed. The matching peak of the O1 s spectrum shown in FIG. 2 (e) is 529.8eV, which belongs to the lattice oxygen of BiOCl, while the other 532eV peak with higher energy is not only due to the surface water oxygen radicals but also due to the surface oxygen vacancies BiOCl.
To further prove the partial speculation described above regarding the identification of substances and to further investigate the microscopic morphological features of the HTN, BiOCl and BHT photocatalytic materials, the experimental examples performed Scanning Electron Microscopy (SEM) and X-ray analysis on themEnergy spectrum analysis (EDS), and the test results are SEM photographs of pure-phase BiOCl and 0.05Fe-BOC as shown in FIG. 3(a) and FIG. 3 (b), respectively. The pure phase BOC synthesized by the sample at 400 ℃ for 3h consists of microcrystals with different sizes. Compared with BOC, the 0.05Fe-BOC has more disordered and irregular appearance and smaller volume. This is due to the fact that the molten salt greatly accelerates the mass transfer and reaction rates, resulting in Fe3+The BOC crystal structure is more easily accessible. However Fe3+The introduction of ions leads to the appearance of a new disordered structure when the BOC crystal grows, which is due to Fe3+The addition of the impurities inhibits the growth of BOC crystals in the direction of the flaky ab. The resulting structural disorder and particle size decrease shorten the diffusion path of the photon-generated carriers in the bulk phase, thereby promoting the effective separation of the carriers, improving the effective contact activity of the catalyst and the reactant, and improving the photocatalytic performance. As shown in FIGS. 3 (c) -3 (g), the element distribution can be obtained from the photographs of 0.05Fe-BOC X-ray spectral analysis (EDS) pictures, and the bright spots corresponding to Bi, Cl, O and Fe in the EDS pictures respectively indicate that Bi, Cl, O and Fe are main elements and Fe is uniformly distributed in the BOC crystal lattice.
The optical absorption properties were evaluated by uv-vis absorption spectroscopy. As shown in fig. 4(a), the original BOC exhibits negligible optical absorption in the visible region due to its large bandgap. In contrast, the absorption edge of Fe-BiOCl was red-shifted to the visible region, indicating Fe3+In addition, there is an overall red-shift rather than an additional shoulder-like light absorption tail, further confirming that bulk Fe doping rather than surface Fe doping the absorbance of BOC is generally and gradually enhanced over the range of 420-800 nm the band gap of indirect bandgap semiconductors can be calculated from the formula Ahv = α (hv-Eg)2FIG. 4 (b) shows that the bandgap of 0.05Fe-BiOCl (3.24eV) is significantly reduced (about 0.16eV) from that of BOC (3.4 eV). this may be due to the doping level after Fe doping approaching the valence band maximum of BiOCl.
Further, to verify the degradation capability of the BHT visible light catalyst, the test also performed a comprehensive visible light catalysis of the sample prepared in example 1A RhB degradation experiment is carried out by taking a 300W xenon lamp as a simulated sunlight source, simulating a sewage water body containing organic pollutants by using a RhB solution with the volume of 20mg/L, mainly comparing degradation effects of prepared two-dimensional layered bismuth oxychloride and a Fe-doped modified photocatalytic material thereof, carrying out a dark adsorption reaction on the photocatalyst with the addition content of 100mg before illumination to ensure that the catalyst is fully contacted with a target molecule and is in an adsorption saturation state, carrying out the photocatalytic reaction in a commercially available double-layer glass beaker as a condensing device (shown in figure 7) after illumination is started, removing the influence of thermal effect on catalytic performance in the illumination process, taking a group of samples at an interval of 10min, and testing the concentration change of the target solution RhB solution by liquid ultraviolet to represent the photocatalytic performance of the catalyst. As shown in fig. 5 (a), the photocatalytic activity of the sample was measured by RhB photodegradation under simulated irradiation with sunlight. The Fe doping obviously improves the photocatalytic performance, and the photocatalytic performance of the 0.05Fe-BOC sample is the best. After 60 minutes of irradiation, the degradation efficiency of the 0.05Fe-BOC finished product for the RhB dye was 94.91%, whereas the degradation efficiency of pure BiOC for the RhB dye was only 77.40%. The degradation process corresponds to a pseudo first order reaction, i.e. -ln (C)0/Ct) = kt, wherein C0And CtInitial and instantaneous concentrations of RhB, respectively, and k is the rate constant. FIG. 5 (b) shows the kinetic curve of the prepared finished product xFe-BOC, which is in accordance with the pseudo-first order reaction kinetics. By first order fitting rate constants, xFe-BOC (x =0, 0.01, 0.03, 0.05, 0.07, 0.10, 0.15, 0.2) rate constants are obtained of 0.01597, 0.01678, 0.02117, 0.04586, 0.01664, 0.04352, 0.02574, 0.03026min in sequence-1The kinetic constant of the 0.05Fe-BOC sample was the highest, approximately 3 times that of BOC.
Further, in order to investigate the stability of the 0.05Fe-BOC finished product prepared in example 3, the experimental example collected the photocatalyst by recycling, a circulation device consisting of a sand core funnel, an external vacuum pump, and an aqueous filter membrane with a pore size of 0.45 μm was used, the solution after each circulation reaction was placed in the sand core funnel, the vacuum pump was turned on, the reaction solution was removed by suction filtration, the solid catalyst was collected at the filter membrane and subjected to the next set of circulation, thereby obtaining RhB degraded under visible light irradiation, and the photodegradation stability result of 0.05Fe-BOC was studied. As shown in fig. 6, it can be clearly seen that after 5 times of repeated experiments, the photocatalyst is not significantly deactivated, and the inevitable loss of the catalyst during the collection process and the reduction degree of the catalytic performance are not changed, which indicates that the prepared layered Fe-BOC photocatalytic material shows excellent stability and activity of removing RhB.
In conclusion, the present invention uses a novel molten salt (NaNO)3And KNO3) Pure BiOCl and metal (taking iron as an example) doping modified BiOCl thereof are prepared by the method. The preparation method has the advantages of low cost, high efficiency, environmental friendliness, safety, convenience, simple process and the like, and the obtained Fe-doped modified BiOCl material has a typical layer-layer structure, more surface active regions, visible light response, stable photocatalytic performance and excellent degradation effect on RhB. Therefore, the preparation method of the layered BiOCl photocatalyst provided by the invention can be widely applied to the field of photocatalytic degradation of organic sewage.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
Claims (6)
1. A preparation method of a two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material is characterized by comprising the following steps of:
step 1, mixing the raw materials in a mass ratio of 1:1 weighing raw material NaNO3And KNO3Mixing, placing in a mortar, and adding Bi (NO) into the mixed molten salt3)3•5H2O, 1.0000g KCl and Fe (NO)3)3•9(H2O), fully grinding for 3h to obtain mixed powder, wherein the Fe (NO) is3)3•9(H2O) and Bi (NO)3)3•5H2The molar ratio of O is a value x, wherein x is 0-0.20; the content of Fe doping is changed by changing Fe (NO)3)3•9(H2O)/ Bi (NO3)3•5H2The mol ratio of O realizes the doping of Fe in a BiOCl bulk phase, and the doping can be marked as xFe-BOC (x = 0-0.20);
step 2, placing the mixed powder into an alumina crucible, synthesizing for 3 hours in a muffle furnace at 400 ℃, and naturally cooling to ambient temperature to obtain a semi-finished product;
and 3, taking out the semi-finished product, repeatedly carrying out centrifugal washing, and then placing the washed sample powder in an oven for drying.
2. The preparation method of the two-dimensional layered bismuth oxychloride-Fe-doped modified photocatalytic material as claimed in claim 1, wherein the raw material NaNO used in step 1 is3、KNO3、Bi(NO3)3•5H2O、KCl、Fe(NO3)3•9(H2O) are all analytically pure, x is 0.05.
3. The preparation method of the two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material as claimed in claim 1, wherein the heating rate of the muffle furnace synthesis in step 2 is kept at 5-10 ℃/min.
4. The preparation method of the two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material as claimed in claim 1, wherein the centrifugation speed in step 3 is 4000 r/min.
5. The preparation method of the two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material as claimed in claim 1, wherein the specific steps of washing and drying in step 3 are as follows: and (3) washing the semi-finished product with an absolute ethyl alcohol water solution with the volume ratio of 1:1 for 5-10 times, and drying in an oven environment at 80 ℃.
6. The application of the two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material disclosed by claim 1 in degradation of RhB solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010581799.3A CN111617784A (en) | 2020-06-23 | 2020-06-23 | Preparation method and application of two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010581799.3A CN111617784A (en) | 2020-06-23 | 2020-06-23 | Preparation method and application of two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111617784A true CN111617784A (en) | 2020-09-04 |
Family
ID=72268513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010581799.3A Pending CN111617784A (en) | 2020-06-23 | 2020-06-23 | Preparation method and application of two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111617784A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115007178A (en) * | 2022-08-09 | 2022-09-06 | 广东工业大学 | Preparation method and application of high-stability bismuth oxychloride photocatalytic material |
| CN115739118A (en) * | 2022-12-08 | 2023-03-07 | 烟台大学 | Iron-doped bismuth oxysulfide photocatalyst and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028264A (en) * | 2014-06-12 | 2014-09-10 | 哈尔滨工业大学 | Regularly quadrangular bismuth-series oxysalt Bi2WO6 and preparation method thereof |
| CN104368363A (en) * | 2014-09-19 | 2015-02-25 | 哈尔滨工业大学 | Flaky bismuth oxychloride photocatalyst material preparation method |
| CN104588047A (en) * | 2015-01-29 | 2015-05-06 | 扬州大学 | Preparation method of photocatalysis ferric oxide/bismuth oxychloride composite material |
| CN105197994A (en) * | 2015-11-05 | 2015-12-30 | 南昌航空大学 | Organic molten salt method for preparation of rod-assembled spherical BiOCl nanoparticles |
| CN106423225A (en) * | 2016-09-13 | 2017-02-22 | 天津科技大学 | Preparation method of composite photocatalyst-Fe-BiOCl |
| CN108067277A (en) * | 2016-11-15 | 2018-05-25 | 中国地质大学（北京） | High itrogen content of getter with nitrogen doped monocrystalline TiO2The preparation method of mesoporous material |
| CN108383160A (en) * | 2018-04-11 | 2018-08-10 | 湘潭大学 | A kind of preparation method and applications of metallic element doping BiOCl nanometer sheet materials |
| CN110773206A (en) * | 2019-11-27 | 2020-02-11 | 中国科学院青岛生物能源与过程研究所 | Fe with high catalytic degradation activity 2O 3BiOCl composite photocatalyst and preparation method and application thereof |
-
2020
- 2020-06-23 CN CN202010581799.3A patent/CN111617784A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028264A (en) * | 2014-06-12 | 2014-09-10 | 哈尔滨工业大学 | Regularly quadrangular bismuth-series oxysalt Bi2WO6 and preparation method thereof |
| CN104368363A (en) * | 2014-09-19 | 2015-02-25 | 哈尔滨工业大学 | Flaky bismuth oxychloride photocatalyst material preparation method |
| CN104588047A (en) * | 2015-01-29 | 2015-05-06 | 扬州大学 | Preparation method of photocatalysis ferric oxide/bismuth oxychloride composite material |
| CN105197994A (en) * | 2015-11-05 | 2015-12-30 | 南昌航空大学 | Organic molten salt method for preparation of rod-assembled spherical BiOCl nanoparticles |
| CN106423225A (en) * | 2016-09-13 | 2017-02-22 | 天津科技大学 | Preparation method of composite photocatalyst-Fe-BiOCl |
| CN108067277A (en) * | 2016-11-15 | 2018-05-25 | 中国地质大学（北京） | High itrogen content of getter with nitrogen doped monocrystalline TiO2The preparation method of mesoporous material |
| CN108383160A (en) * | 2018-04-11 | 2018-08-10 | 湘潭大学 | A kind of preparation method and applications of metallic element doping BiOCl nanometer sheet materials |
| CN110773206A (en) * | 2019-11-27 | 2020-02-11 | 中国科学院青岛生物能源与过程研究所 | Fe with high catalytic degradation activity 2O 3BiOCl composite photocatalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| KAIQIANG XU ET AL.: ""Molten-salt-mediated synthesis of bulk W doped BiOCl with highly enhanced visible-light photocatalytic performances"", 《APPLIED SURFACE SCIENCE》 * |
| MEICHAO GAO ET AL.: ""Combustion synthesis of Fe-doped BiOCl with high visible-light photocatalytic activities"", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115007178A (en) * | 2022-08-09 | 2022-09-06 | 广东工业大学 | Preparation method and application of high-stability bismuth oxychloride photocatalytic material |
| CN115739118A (en) * | 2022-12-08 | 2023-03-07 | 烟台大学 | Iron-doped bismuth oxysulfide photocatalyst and preparation method and application thereof |
| CN115739118B (en) * | 2022-12-08 | 2024-02-27 | 烟台大学 | Iron-doped bismuth oxygen sulfur photocatalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101972563B1 (en) | Zinc oxide/reduced graphene oxide nanocomposites photocatalytic controlled morphology with high photocatalytic performance and the preparation method thereof | |
| Baylan et al. | Highly efficient photocatalytic activity of stable manganese-doped zinc oxide (Mn: ZnO) nanofibers via electrospinning method | |
| CN108311164B (en) | Iron modified photocatalytic material and preparation method and application thereof | |
| Ma et al. | Simple thermal decomposition of bismuth citrate to Bi/C/α-Bi2O3 with enhanced photocatalytic performance and adsorptive ability | |
| CN110217850B (en) | Method for photocatalytic degradation of antibiotics in water body | |
| Mousavi-Kamazani et al. | Facile solvothermal synthesis of CeO 2–CuO nanocomposite photocatalyst using novel precursors with enhanced photocatalytic performance in dye degradation | |
| Yan et al. | Hydrothermal synthesis of Bi 2 WO 6 with a new tungsten source and enhanced photocatalytic activity of Bi 2 WO 6 hybridized with C 3 N 4 | |
| Wang et al. | Synthesis and their photocatalytic properties of Ni-doped ZnO hollow microspheres | |
| CN111617784A (en) | Preparation method and application of two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material | |
| Zhao et al. | Microstructure and photocatalytic activity of Ni-doped ZnS nanorods prepared by hydrothermal method | |
| Plubphon et al. | Rapid preparation of g-C3N4/Bi2O2CO3 composites and their enhanced photocatalytic performance | |
| Wei et al. | A stable and efficient La-doped MIL-53 (Al)/ZnO photocatalyst for sulfamethazine degradation | |
| Chen et al. | Synthesis of gC 3 N 4/diatomite/MnO 2 composites and their enhanced photo-catalytic activity driven by visible light | |
| CN111686770A (en) | Metal ion co-doped BiOBr microsphere, preparation method and application thereof | |
| Lu et al. | Preparation of self-assembled N-Zn2GeO4 nanocomposite and their photocatalytic properties | |
| CN113426461B (en) | Preparation method of silver-doped polycrystalline zinc ferrite photocatalytic nano material | |
| CN113731462A (en) | Based on La2Ce2O7And g-C3N4Preparation method and application of photocatalytic composite material | |
| CN113731461A (en) | CeTiO (CeTiO)4-（g-C3N4) Preparation method and application of photocatalytic composite material | |
| Feng et al. | Persistent photocatalysis effect of black peony-like BiOCl and its potential full-time photocatalytic applications | |
| Yu et al. | Efficient removal of tetracycline hydrochloride through novel Fe/BiOBr/Bi2WO6 photocatalyst prepared by dual-strategy under visible-light irradiation | |
| Liu et al. | Synthesis of BiOI/ZnCo-CLDH hybrid photocatalyst with highly efficient degradation of rhodamine B and tetracycline hydrochloride | |
| Peng et al. | Influence of ytterbium doping on the visible light photocatalytic activity of mixed phase TiO2 nanoparticles | |
| CN109589963B (en) | Lithium niobate type oxide/attapulgite nonlinear optical composite photocatalytic material and preparation method and application thereof | |
| CN113457706A (en) | Synthesis of N-BiOBr/CQDs/Fe by pollutant template element filling strategy3O4And applications thereof | |
| Shi et al. | Stoichiometry-controlled synthesis of pyrite and greigite particles for photo-Fenton degradation catalysis |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200904 |