CN116078409B - Iron-bismuth composite photocatalyst with visible light response and preparation method and application thereof - Google Patents
Iron-bismuth composite photocatalyst with visible light response and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- RDQSSKKUSGYZQB-UHFFFAOYSA-N bismuthanylidyneiron Chemical compound [Fe].[Bi] RDQSSKKUSGYZQB-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 230000004298 light response Effects 0.000 title abstract description 9
- 239000000779 smoke Substances 0.000 claims abstract description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
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- 238000003756 stirring Methods 0.000 claims description 24
- 238000009210 therapy by ultrasound Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052797 bismuth Inorganic materials 0.000 claims description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- -1 potassium halide Chemical class 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 29
- 230000031700 light absorption Effects 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 16
- 239000003546 flue gas Substances 0.000 description 16
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
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- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
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- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-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
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
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- LTKWZIUEGOOERX-UHFFFAOYSA-N trihydridoarsenic(.1+) Chemical compound [AsH3+] LTKWZIUEGOOERX-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Abstract
The invention belongs to the technical field of photocatalysis-smoke control, and particularly relates to an iron-bismuth composite photocatalyst with visible light response, and a preparation method and application thereof. The Fe 2O3 in the invention can make BiOX (X=Cl, I, br) have better visible light absorption capability, so that the BiOX has very high removal capability of Hg 0 and AsH 3 under the irradiation of visible light, and the aim of removing two pollutants of AsH 3 and Hg 0 by high-efficiency photocatalytic oxidation is fulfilled.
Description
Technical Field
The invention belongs to the technical field of photocatalysis-smoke control, and particularly relates to a preparation method of an iron-bismuth composite photocatalyst and application of the iron-bismuth composite photocatalyst in high-efficiency catalysis removal of gaseous mercury and arsine in smoke under visible light.
Background
Energy crisis and environmental pollution become major challenges worldwide, with the problem of managing heavy metal pollution in industrial waste gas being particularly prominent. Research results on treatment of atmospheric heavy metals are mainly focused on the aspect of controlling heavy metal pollution in oxidizing atmospheres such as coal-fired flue gas and the like at present. The carbothermic reduction method has wide application in the industries of chemical industry, metallurgy and the like, the carbothermic smelting tail gas is a secondary resource with great economic value, and the recovery of the resource is seriously affected by heavy metals such as gaseous mercury (Hg 0), arsine (AsH 3) and the like. Therefore, the development of a safe, efficient and environment-friendly gaseous heavy metal removal technology is a key for realizing resource recovery.
According to the state-of-the-art analysis of control of Hg 0 and AsH 3, the technology for removing Hg 0 and AsH 3 from flue gas is mainly two: adsorption technology and catalytic oxidation technology. The adsorption technology utilizes unbalanced chemical bonds or molecular attractive force on the surface of the adsorbent to adsorb Hg 0 and AsH 3 in the flue gas on the solid surface for removal, the performance of the adsorbent determines the effect of the adsorption purification process, and the adsorption type arsenic and mercury removal technology is difficult to apply on a large scale due to higher cost; the thermal catalytic technology has the problems of high energy consumption, large potential safety hazard, easy secondary pollution and the like, and the photocatalytic oxidation technology is a novel method for removing Hg 0 and AsH 3 and has the characteristics of mild reaction conditions, stable chemical properties, high oxidation efficiency and the like.
Bismuth oxyhalide (BiOX, X=Cl, I, br) has a unique two-dimensional layered structure, a proper energy band structure and excellent photoelectric property, is applied to photocatalytic removal of Hg 0 in oxidative flue gas, and simultaneously obtains better performance under the condition of ultraviolet light, the performance of the BiOX (X=Cl, I, br) under the condition of visible light is still to be further improved due to the limit of band gap, and the problems of ozone generation and the like of ultraviolet light possibly bring secondary pollution to the environment, so that the application of the bismuth oxyhalide in the field of gas purification is greatly limited; the research content for removing the AsH 3 in the flue gas by utilizing the photocatalytic oxidation technology is less, the effect is not ideal, and meanwhile, no related report for removing the AsH 3 in the flue gas by utilizing the visible photocatalytic oxidation is found. Therefore, development of efficient photocatalyst for removing Hg 0 and AsH 3 from catalytic reduction flue gas under visible light is particularly important.
Disclosure of Invention
In view of the above, the invention aims to provide the iron-bismuth composite photocatalyst with visible light response and the preparation method thereof, which aim to overcome the defects of the prior art, realize the simultaneous removal of Hg 0 and AsH 3 and also facilitate the collection and utilization of industrial raw material gas.
It should be noted that the technical points of the disclosure and protection of the present invention are as follows:
Firstly, photocatalytic removal of AsH 3 in flue gas is not widely studied, and a series of iron-based catalysts are developed to be applied to photocatalytic removal of AsH 3 by utilizing the characteristic that iron oxide (Fe 2O3) is an activating agent for enhancing arsenic removal in the current application situation of photocatalytic arsenic removal in a water body; secondly, the removal of Hg 0 is mainly concentrated in the ultraviolet light catalytic range in the oxidizing atmosphere, and in order to realize the efficient removal of Hg 0 in the reducing smoke in one step, bismuth oxyhalide (BiOX (X=Cl, br, I)) photocatalyst with good visible light response is directly selected to remove Hg 0. By combining the importance of iron-based on AsH 3 removal and good light response of bismuth-based materials, fe 2O3 and BiOX (X=Cl, br, I) are combined to construct the Fe 2O3/BiOX (X=Cl, br, I) composite photocatalyst with visible light catalytic capability, so that the aim of improving the photocatalytic efficiency is fulfilled, and the simultaneous removal of Hg 0 and AsH 3 in reducing flue gas is realized.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The first technical purpose of the invention is to provide a Fe 2O3/BiOX (X=Cl, br, I) composite photocatalyst with visible light catalytic capability for removing Hg 0 and AsH 3.
The second technical aim of the invention is to provide a preparation method of the iron-bismuth composite photocatalyst.
The Fe 2O3/BiOX (X=Cl, I, br) composite photocatalyst is synthesized by a hydrothermal method, the preparation method is simple, the cost is low, the material has good photocatalytic performance, and the simultaneous removal of AsH 3 and Hg 0 in reducing smoke can be realized.
According to the preparation method, fe 2O3 can be easily loaded on the surface of the BiOX (X=Cl, I, br) through a hydrothermal method, and the Fe 2O3/BiOX (X=Cl, I, br) heterostructure is constructed and formed, so that the crystallinity and the specific surface area of the material are improved. This not only can exert the advantage of Fe 2O3 in promoting AsH 3 removal, but also can form heterojunction with bismuth-based materials to enhance charge transfer, and the appropriate band gap can promote more excellent visible light catalytic performance.
The preparation method of the iron-bismuth composite photocatalyst comprises the following steps:
(1) Preparation of a bisx (x=br, I, cl) photocatalyst:
Adding 0.01-0.02mol of Bi (NO 3)3·H2 O into 20mL of glacial acetic acid), performing ultrasonic treatment until Bi (NO 3)3·H2 O is completely dissolved, and performing magnetic stirring to obtain a tan suspension A;
adding 0.01-0.02mol of KX (X=Cl, br, I) into 20mL of deionized water, and performing ultrasonic treatment until the KX is completely dissolved to obtain colorless and transparent solution B;
While stirring the solution A, dropwise adding the solution B into the solution A, and then continuously stirring for 30min; transferring the obtained suspension into a hydrothermal kettle, performing hydrothermal treatment at 160-200 ℃ for 12-18h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying in a 60 ℃ oven for 8h to obtain the BiOX (X=Cl, br, I) photocatalyst.
(2) Preparation of Fe 2O3/bisx (x=cl, br, I) composite photocatalyst:
adding 0.1-0.3g of BiOX (X=Cl, br, I) photocatalyst into 40mL of deionized water, performing ultrasonic treatment for 10min until the sample is completely dispersed, and stirring to obtain solution C;
Adding 0.07-0.21g of Fe (NO 3)3 into 40mL of deionized water, and stirring until the Fe is completely dissolved to obtain solution D;
Then adding the solution D into the solution C dropwise under the condition of continuously stirring the solution C, continuously magnetically stirring for 20min, transferring the obtained mixed solution into a hydrothermal kettle, carrying out hydrothermal treatment at 150-200 ℃ for 12-18h, cooling to room temperature, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and drying in a 60 ℃ oven for 8h to obtain the Fe 2O3/BiOX composite photocatalyst.
According to the invention, fe 2O3 is loaded on the surface of BiOX (X=Cl, I, br) to form the composite photocatalytic material, and the prepared material has larger adsorption capacity and can exert high photocatalytic property. The addition of Fe 2O3 increases the specific surface area of BiOX (X=Cl, I, br), provides more catalytic active sites for the photocatalytic reaction process, and in addition, fe 2O3 has a band gap of 2.2eV, so that sunlight can be utilized in a wider range.
Therefore, by utilizing the compounding of Fe 2O3, a BiOX (X=Cl, I, br) semiconductor photocatalyst with low energy band gap and enhanced visible light absorption can be obtained, and the photocatalytic efficiency to AsH 3 and Hg 0 can be improved; meanwhile, fe 2O3 and BiOX (X=Cl, I, br) form a heterojunction, so that the recombination rate of a photogenerated carrier can be reduced more effectively, effective separation of photogenerated electrons and holes is realized, and the photocatalysis performance of the material can be greatly improved by realizing the efficient photocatalysis effect.
Specifically, the composite catalyst can be used for photocatalytic removal of AsH 3 and Hg 0, and the reaction mechanism is as follows:
Fe2O3/BiOX(X＝Cl,I,Br)+hv→Fe2O3/BiOX(X＝Cl,I,Br)+(e-+h+) (1)
O2+4H++4e-→H2O(ad) (2)
O2(g)+e-→·O2 - (3)
H2O+h+→·OH+H+ (4)
Hg0(g)→Hg0 (ad) (5)
Hg0+·O2 -/·OH→HgO(ad) (6)
AsH3+·O2 -/·OH→As2O3(ad)+As2O5(ad) (7)
Compared with the prior art, the invention discloses and provides the iron-bismuth composite photocatalyst with visible light response, and the preparation method and the application thereof, and has the excellent effects that:
(1) The formation of heterojunction between Fe 2O3 and bisx (x=cl, I, br) improves the basic properties of bismuth-based materials comprehensively, and also reduces the electron-hole recombination rate of the sample and its ability to absorb visible light. So that the sample can keep high-efficiency photocatalysis performance and has good stability.
(2) The Fe 2O3 is loaded, so that the BiOX (X=Cl, I, br) has better visible light absorption capacity, and very high removal capacities of Hg 0 and AsH 3 are obtained under the irradiation of visible light, and the aim of removing two pollutants of AsH 3 and Hg 0 by high-efficiency photocatalytic oxidation is fulfilled.
(3) Aiming at research and development of Hg 0 and AsH 3 photocatalysis removal catalysts in reducing atmosphere, performance test and removal mechanism disclosure, theory and basic application can be provided for the subsequent photocatalysis technology applied to the field of treatment of heavy metals in reducing waste gas.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
Fig. 1 (a) shows a performance chart of the photocatalytic removal of Hg 0 by the BiOX (x=cl, I, br) under the irradiation of visible light, and (b) shows a performance chart of the photocatalytic removal of AsH 3 by the BiOX (x=cl, I, br) under the irradiation of visible light.
Fig. 2 (a) shows a performance chart of Fe 2O3/bisox (x=cl, I, br) photocatalytic removal of Hg 0 under visible light irradiation, and (b) shows a performance chart of Fe 2O3/bisox (x=cl, I, br) photocatalytic removal of AsH 3 under visible light irradiation.
Fig. 3 is an X-ray diffraction (XRD) pattern of BiOX (x=cl, I, br).
Fig. 4 is an X-ray diffraction (XRD) pattern of Fe 2O3/bisx (x=cl, I, br).
Fig. 5 is a (a) ultraviolet-visible diffuse reflectance (UV-Vis) spectrum and (b) two-photon energy (eV 2) diagram of BiOX (x=cl, I, br).
Fig. 6 is a (a) ultraviolet-visible diffuse reflectance (UV-Vis) spectrum and (b) two-photon energy (eV 2) plot of Fe 2O3/bisox (x=cl, I, br).
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention discloses a preparation method of an iron-bismuth composite photocatalyst with visible light response and application of the iron-bismuth composite photocatalyst in removing Hg 0 and AsH 3 simultaneously.
The present invention will be further specifically illustrated by the following examples, which are not to be construed as limiting the invention, but rather as falling within the scope of the present invention, for some non-essential modifications and adaptations of the invention that are apparent to those skilled in the art based on the foregoing disclosure.
Example 1
1. Preparation of bismuth-based photocatalyst
0.01Mol of Bi (NO 3)3·H2 O) is added into 20mL of glacial acetic acid, ultrasonic treatment is carried out for 10min, stirring is carried out, thus obtaining a tan suspension A, 0.01mol of KCl is added into 20mL of deionized water, ultrasonic treatment is carried out for 10min, and colorless transparent solution B is obtained.
And (3) dropwise adding the solution B into the solution A while stirring, continuously stirring for 30min, transferring the obtained suspension into a hydrothermal kettle, performing hydrothermal treatment at 160 ℃ for 12h, respectively washing with deionized water and absolute ethyl alcohol for 3 times after cooling to room temperature, and drying in a 60 ℃ oven for 8h to obtain the BiOCl photocatalyst.
2. Preparation of iron-bismuth composite photocatalyst
Adding 0.1g of BiOCl photocatalyst into 40mL of deionized water, and stirring after ultrasonic treatment for 10min to obtain solution C; 0.07g of Fe (NO 3)3 was added to 40mL of deionized water and stirred until completely dissolved, giving solution D.
And then dropwise adding the solution D into the solution C under the condition that the solution C is continuously stirred, continuously stirring for 20min, transferring the mixed solution into a hydrothermal kettle, maintaining at 160 ℃ for 12h, cooling to room temperature, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and drying in a 60 ℃ oven for 8h to obtain the Fe 2O3/BiOCl composite photocatalyst.
3. Catalytic performance test:
0.1g of BiOCl and Fe 2O3/BiOCl prepared in the example are respectively weighed for the research of photocatalysis under visible light and simultaneous removal of Hg 0 and AsH 3 in simulated flue gas. The simulated flue gas is: 1%O 2, an inlet concentration AsH 3＝150mg/m3,Hg0＝400μg/m3, a gas flow rate of 500mL/min, a visible light source provided by a xenon lamp, a wavelength of more than 400nm and a power of 300W.
As can be seen from fig. 1, the removal efficiency of BiOCl on Hg 0 and AsH 3 under visible light irradiation conditions was 23.94% and 14.65%, respectively. In FIG. 2, the heterojunction is formed by compounding Fe 2O3, and the removal effect of Hg 0 and AsH 3 of Fe 2O3/BiOCl is remarkably improved, namely 82.85% and 75.47% respectively, which are 3.5 times and 5.2 times that of BiOCl. FIGS. 3 and 4 show that BiOCl and Fe 2O3/BiOCl have a good structure and good crystallinity. In addition, as can be seen from fig. 5 and 6, the combination of Fe 2O3 widens the light absorption range of BiOCl, promotes the absorption rate of visible light, and in addition, the forbidden bandwidth is reduced from 3.38eV to 1.99eV by the formula αhv= (hv-E g)n, which indicates that better photocatalytic performance can be obtained under visible light.
Example 2
1. Preparation of bismuth-based photocatalyst
0.02Mol of Bi (NO 3)3·H2 O is added into 20mL of glacial acetic acid, ultrasonic treatment is carried out for 10min, stirring is carried out, thus obtaining a tan suspension A, 0.02mol of KI is added into 20mL of deionized water, ultrasonic treatment is carried out for 10min, and colorless transparent solution B is obtained.
And (3) dropwise adding the solution B into the solution A while stirring, continuously stirring for 30min, transferring the obtained suspension into a hydrothermal kettle, carrying out hydrothermal treatment at 180 ℃ for 15h, respectively washing with deionized water and absolute ethyl alcohol for 3 times after cooling to room temperature, and drying in a 60 ℃ oven for 8h to obtain the BiOI photocatalyst.
2. Preparation of iron-bismuth composite photocatalyst
Adding 0.2g of BiOI photocatalyst into 40mL of deionized water, performing ultrasonic treatment for 10min, and stirring to obtain solution C; 0.14g of Fe (NO 3)3 was added to 40mL of deionized water and stirred until completely dissolved, giving solution D.
And then dropwise adding the solution D into the solution C under the condition of continuously stirring the solution C, continuously stirring for 20min, transferring the mixed solution into a hydrothermal kettle, keeping the temperature at 180 ℃ for 15h, cooling to room temperature, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and drying in a 60 ℃ oven for 8h to obtain the Fe 2O3/BiOI composite photocatalyst.
3. Catalytic performance test:
0.1g of BiOI and Fe 2O3/BiOI prepared in this example were weighed separately for use in a visible light photocatalytic study to simultaneously remove Hg 0 and AsH 3 from simulated flue gas. The simulated flue gas is: 1%O 2, an inlet concentration AsH 3＝150mg/m3,Hg0＝400μg/m3, a gas flow rate of 500mL/min, a visible light source provided by a xenon lamp, a wavelength of more than 400nm and a power of 300W.
As can be seen from fig. 1, the removal efficiency of the BiOI on Hg 0 and AsH 3 under the condition of visible light irradiation is 44.72% and 29.58%, respectively, which is superior to that of the BiOCl and the BiOBr, and as can be seen from fig. 5, the BiOI shows an extended visible light absorption region, has a smaller band gap, is about 1.9eV, and is beneficial to improving the light response capability. The characteristic peak of Fe 2O3/BiOI in FIG. 4 is changed compared to BiOI in FIG. 3, and part of the characteristic peak is weakened due to Fe 2O3 loading. In addition, the heterojunction is formed by the recombination of Fe 2O3, and the removal efficiency of Fe 2O3/BiOI to Hg 0 and AsH 3 in FIG. 2 is highest and reaches 97.14% and 92.72% respectively, which are 2.2 times and 3.1 times that of BiOI. In fig. 6, fe 2O3/BiOI shows a better light absorption capacity in the visible light region, has a minimum band gap, and is calculated to be about 1.89eV, so that high-efficiency simultaneous removal of Hg 0 and AsH 3 in the reducing flue gas under visible light can be realized.
Example 3
1. Preparation of bismuth-based photocatalyst
0.02Mol of Bi (NO 3)3·H2 O is added into 20mL of glacial acetic acid, ultrasonic treatment is carried out for 10min, stirring is carried out, thus obtaining a tan suspension A, 0.02mol of KBr is added into 20mL of deionized water, ultrasonic treatment is carried out for 10min, and colorless transparent solution B is obtained.
And (3) dropwise adding the solution B into the solution A while stirring, continuously stirring for 30min, transferring the obtained suspension into a hydrothermal kettle, performing hydrothermal treatment at 200 ℃ for 18h, respectively washing with deionized water and absolute ethyl alcohol for 3 times after cooling to room temperature, and drying in a 60 ℃ oven for 8h to obtain the BiOBr photocatalyst.
2. Preparation of iron-bismuth composite photocatalyst
Adding 0.3g of BiOBr photocatalyst into 40mL of deionized water, and performing ultrasonic treatment for 10min to obtain solution C; 0.21g of Fe (NO 3)3 was added to 40mL of deionized water and stirred until completely dissolved, giving solution D.
And then dropwise adding the solution D into the solution C under the condition that the solution C is continuously stirred, continuously stirring for 20min, transferring the mixed solution into a hydrothermal kettle, keeping the temperature at 200 ℃ for 18h, cooling to room temperature, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and drying in a 60 ℃ oven for 8h to obtain the Fe 2O3/BiOBr composite photocatalyst.
3. Catalytic performance test:
0.1g of BiOBr and Fe 2O3/BiOBr prepared in this example were weighed separately for use in a visible light photocatalytic study to simultaneously remove Hg 0 and AsH 3 from simulated flue gas. The simulated flue gas is: 1%O 2, an inlet concentration AsH 3＝150mg/m3,Hg0＝400μg/m3, a gas flow rate of 500mL/min, a visible light source provided by a xenon lamp, a wavelength of more than 400nm and a power of 300W.
As can be seen from fig. 1, the removal efficiencies of the BiOBr on Hg 0 and AsH 3 under the irradiation of visible light were 35.89% and 21.84%, respectively. In FIG. 2, after the Fe 2O3 is compounded, the Hg 0 and AsH 3 removal effects of Fe 2O3/BiOBr are remarkably improved, namely 90.98% and 84.39% respectively, which are 2.5 times and 3.9 times that of BiOBr. Due to the loading of Fe 2O3, fe 2O3/BiOI in FIG. 4 reduces part of the characteristic peaks compared to BiOI in FIG. 3. In addition, as can be seen by combining fig. 5 and 6, compared with the BiOBr, the light absorption range of Fe 2O3/BiOBr is widened, the forbidden bandwidth is reduced by 2.04eV from 2.88eV, the absorption rate of visible light is promoted, and the photocatalytic performance of Hg 0 and AsH 3 is improved.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. The application of the iron-bismuth composite photocatalyst is characterized in that the molecular structural formula of the catalyst is Fe 2O3/BiOX; x is Cl, br or I;
The catalyst is used for simultaneously removing AsH 3 and Hg 0 in the reducing smoke under the response of visible light.
2. The application of the iron-bismuth composite photocatalyst according to claim 1, wherein the preparation method of the iron-bismuth composite photocatalyst specifically comprises the following steps:
(1) Preparation of bismuth oxyhalide BiOX photocatalyst:
Adding bismuth nitrate pentahydrate Bi (NO 3)3·5H2 O into glacial acetic acid, and performing ultrasonic treatment until Bi (NO 3)3·H2 O is completely dissolved to obtain a tan suspension A;
Adding potassium halide KX into deionized water, and performing ultrasonic treatment until KX is completely dissolved to obtain colorless and transparent solution B;
Dropwise adding the solution B into the suspension A stirred at normal temperature, continuously stirring, transferring the obtained suspension into a hydrothermal kettle for reaction, cooling to room temperature after the reaction is finished, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying to obtain the bismuth oxyhalide BiOX photocatalyst;
the hydrothermal reaction temperature is 150-200 ℃ and the reaction time is 12-18h; the drying temperature is 60 ℃ and the drying time is 8 hours;
(2) Preparation of Fe 2O3/BiOX composite photocatalyst:
adding the BiOX photocatalyst prepared in the step (1) into deionized water, and performing ultrasonic treatment until the sample is completely dispersed to obtain a solution C;
adding Fe (NO 3)3 into deionized water, and stirring until the Fe is completely dissolved to obtain a solution D;
and (3) dropwise adding the solution D into the solution C which is continuously stirred, continuously stirring, transferring the obtained mixed solution into a hydrothermal kettle for reaction, washing with deionized water and absolute ethyl alcohol for 3 times respectively after the reaction is finished, and drying the solid to obtain the iron-bismuth composite photocatalyst.
3. The use of the iron bismuth composite photocatalyst according to claim 2, wherein in the step (1), bi (NO 3)3 ·5H2 O in an amount of 0.01 to 0.02mol, KX in an amount of 0.01 to 0.02mol, bi (NO 3)3·H2 O to KX molar ratio of 1:1, volumes of glacial acetic acid and deionized water are 20 mL).
4. The use of the iron bismuth composite photocatalyst according to claim 2, wherein in the step (2), the mass of the bisox photocatalyst is 0.1-0.3g, the mass of fe (NO 3)3 ) is 0.07-0.21g, and the deionized volume is 40mL.
5. The use of the iron-bismuth composite photocatalyst according to claim 2, wherein the hydrothermal reaction temperature in step (2) is 150-200 ℃ and the reaction time is 12-18h; the drying temperature was 60℃and the drying time was 8 hours.
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