CN111790394A - Synthesis method of bismuth vanadate photocatalytic material selectively modified by hydroxyl ferric oxide cocatalyst - Google Patents
Synthesis method of bismuth vanadate photocatalytic material selectively modified by hydroxyl ferric oxide cocatalyst Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 22
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 11
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000001308 synthesis method Methods 0.000 title claims description 5
- -1 hydroxyl ferric oxide Chemical compound 0.000 title claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title description 3
- 229910002588 FeOOH Inorganic materials 0.000 claims abstract description 82
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 76
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 22
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003426 co-catalyst Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000005286 illumination Methods 0.000 claims description 14
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 229960004887 ferric hydroxide Drugs 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 26
- 239000011941 photocatalyst Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000012986 modification Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 230000004048 modification Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000005215 recombination Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011697 sodium iodate Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 229910002703 Al K Inorganic materials 0.000 description 1
- 244000298903 Basella rubra Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- C01B3/042—Decomposition of water
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Abstract
The synthesis process of bismuth vanadate as photocatalytic material selectively modified with ferric hydroxide as co-catalyst includes the following steps: 1) preparing a copper ion solution; 2) taking a certain amount of BiVO4Dispersing in deionized water to form a uniform suspension; 3) uniformly mixing the copper ion solution and the suspension; 4) adding a certain amount of water-soluble ferrous salt into the suspension obtained in the step 3); 5) introducing the suspension obtained in the step 4) for a certain time N2Then, stirring at room temperature, and illuminating for a certain time; 6) filtering, washing and drying the reaction product illuminated in the step 5) to obtain the FeOOH cocatalyst selectively modified in BiVO4{110} plane photocatalytic material. The preparation method disclosed by the invention is simple to operate, does not need to add any surfactant, is green, environment-friendly and pollution-free, and the selectively modified FeOOH cocatalyst has the advantages of rich reserves, low price, stable property and the like.
Description
Technical Field
The invention relates to a preparation technology of a bismuth vanadate {110} crystal face selectively modified iron oxyhydroxide cocatalyst, in particular to a synthesis method of a bismuth vanadate photocatalytic material selectively modified by an iron oxyhydroxide cocatalyst.
Technical Field
In the face of the current global energy crisis and the severe dilemma of environmental pollution, the energy problem is solved by utilizing solar energy through the photocatalysis technologyEnvironmental pollution problems are one of the most promising strategies. Among them, photocatalytic water splitting is an effective method for converting solar energy into green and sustainable energy. Over the past decades, various photocatalysts have been synthesized, such as TiO2、C3N4、BiVO4And the like. They are used for water decomposition, but the photocatalytic water decomposition activity is low. In order to improve the performance of the photocatalyst, modification is needed, wherein the modification of the cocatalyst is one of effective means for improving the activity. Therefore, the search for high-activity cocatalyst modified photocatalytic materials is the focus of the technical research.
According to research in recent years, BiVO exposing crystal planes of 010 and 110 simultaneously4The decahedral photocatalyst is capable of forming an internal electric field. Under the irradiation of visible light, photoproduction electrons and holes are directionally transmitted under the drive of an endogenous electric field, so that crystal faces of {010} and {110} are rich in electrons and holes respectively, and BiVO (BiVO) is effectively reduced4The recombination efficiency of photogenerated carriers in vivo. Generally, the photocatalytic efficiency of a semiconductor photocatalyst is determined by three aspects: 1) the absorption and utilization rate of sunlight; 2) transfer and separation efficiency of photogenerated carriers; 3) efficiency of interfacial redox reactions. Can be found in BiVO4The surface of the photocatalyst is selectively modified with a proper redox cocatalyst, so that the photocatalytic performance of the photocatalyst can be further improved. IrO is commonly used in photocatalytic water splitting oxygen generation systems2And RuO2And the like to promote photoproduction electron-hole separation and simultaneously provide rich active sites to improve interface catalytic reaction. However, the use of noble metal promoters significantly increases production costs, preventing their large-scale use. FeOOH is a material with rich earth crust content, is a cocatalyst with very large application potential, and has the advantages of low cost, high stability and the like. For example, k.s.choi et al (j.am.chem.soc.2012,134, 2186-2192) reported BiVO4The coated FeOOH photocatalyst has significantly enhanced water oxidation performance. Therefore, the FeOOH cocatalyst is selectively modified in BiVO4The {110} crystal face has important significance for improving the photocatalytic water decomposition performance. However, at presentIn BiVO4Related preparation technologies of selectively modified FeOOH cocatalyst on a {110} crystal face are not reported yet.
Disclosure of the invention
In order to solve BiVO4The invention discloses a method for synthesizing a bismuth vanadate photocatalytic material selectively modified by a hydroxyl ferric oxide cocatalyst, and aims to solve the problems of high recombination efficiency and low catalytic reaction efficiency of a photocatalyst photogenerated charge carrier4The {110} crystal face of the photocatalyst.
The technical scheme adopted by the invention for solving the technical problems is as follows: the synthesis method of the bismuth vanadate photocatalytic material selectively modified by the ferric oxyhydroxide cocatalyst is characterized by comprising the following steps:
1) preparing a copper ion solution with a certain concentration;
2) taking a certain amount of BiVO4Dispersing in deionized water to form a uniform suspension;
3) uniformly mixing a certain amount of the copper ion solution obtained in the step 1) with the suspension obtained in the step 2);
4) adding a certain amount of water-soluble ferrous salt into the suspension obtained in the step 3);
5) introducing the suspension obtained in the step 4) for a certain time N2Then, stirring at room temperature, and illuminating for a certain time;
6) filtering, washing and drying the reaction product illuminated in the step 5) to obtain the FeOOH cocatalyst selectively modified in BiVO4{110} plane photocatalytic material.
According to the scheme, the copper ion solution in the step 1) is copper sulfate, copper chloride, copper nitrate or copper acetate; wherein the concentration of copper ions is 0.1-5 mol/L.
According to the scheme, the ratio of the amount of the copper ion solution and the ferrous salt added in the step 3) is controlled to be 1: 1-50: 1.
According to the scheme, the ferrous salt in the step 4) is ferrous chloride, ferrous nitrate, ferrous sulfate or ferrous acetate, wherein the addition amount of the ferrous salt is equal to BiVO4The mass ratio of (A) to (B) is controlled to be 0.005: 1-2: 1.
According to the scheme, the illumination time in the step 5) is 0.5-6 h.
The general formula of the composition of the photocatalytic material is as follows: FeOOH/{110} BiVO4. The invention discloses a BiVO with exposed {010} and {110} crystal faces and simultaneously having a decahedral structure4Is a photocatalyst main body material (prepared according to the synthesis of the literature Li., et al, Crystal growth Des.2017,17, 2923-2928). Making ferrous ion in BiVO by light deposition method4The {110} crystal face is oxidized to generate FeOOH catalyst promoter. The basic principle of improving the photocatalytic activity is as follows: BiVO is made by selective modification of FeOOH cocatalyst4The photogenerated carriers produced under the excitation of illumination are efficiently separated, and rich reaction active sites are provided to accelerate the rate of the interface catalytic oxidation reaction, so that BiVO is realized4The photocatalytic activity of the photocatalyst is effectively improved.
Compared with the prior art, the invention uses BiVO4Using light deposition method to make ferrous ion in BiVO as main material4The {110} crystal face is oxidized to generate FeOOH, thereby preparing FeOOH/{110} BiVO4A photocatalyst. The preparation method is simple to operate, does not need to add any surfactant, is green, environment-friendly and pollution-free, and the selectively modified FeOOH cocatalyst has the advantages of rich reserves, low price, stable property and the like. In FeOOH/{110} BiVO4Expensive equipment and devices and high-temperature and high-pressure reaction conditions are not needed in the whole synthesis process of the photocatalyst, and the photocatalyst is easy to synthesize in large quantities; meanwhile, the synthesized photocatalyst has high activity of decomposing water into oxygen by photocatalysis, and has great development potential for development and utilization of new energy.
Drawings
FIG. 1 is a FESEM and corresponding EDS spectra for each sample of example 1 (inset): (A) BiVO4,(B)3wt％FeOOH/{110}BiVO4,(C)10wt％FeOOH/{110}BiVO4,(D)50wt％FeOOH/{110}BiVO4,(E)100wt％FeOOH/{110}BiVO4。
Figure 2 is the XRD pattern of each sample of example 1: (a) BiVO4,(b)3wt％FeOOH/{110}BiVO4,(c)10wt％FeOOH/{110}BiVO4,(d)50wt％FeOOH/{110}BiVO4,(e)100wt％FeOOH/{110}BiVO4。
FIG. 3(A) is an XPS survey of the different samples of example 1 and high resolution XPS spectra of the different elements (B) Fe 2p, (C) Cu 2p, (D) O1 s: (a) BiVO4,(b)3wt％FeOOH/{110}BiVO4,(c)50wt％FeOOH/{110}BiVO4,(d)100wt％FeOOH/{110}BiVO4。
FIG. 4 is a plot of the UV-vis absorption spectra and corresponding optical plots for each of the samples of example 1: (a) BiVO4,(b)3wt％FeOOH/{110}BiVO4,(c)10wt％FeOOH/{110}BiVO4,(d)50wt％FeOOH/{110}BiVO4,(e)100wt％FeOOH/{110}BiVO4。
FIG. 5 is a graph of the rate of photocatalytic decomposition of water to produce oxygen for different samples in example 1: (a) BiVO4,(b)3wt％FeOOH/{110}BiVO4,(c)10wt％FeOOH/{110}BiVO4,(d)50wt％FeOOH/{110}BiVO4,(e)100wt％FeOOH/{110}BiVO4。
Detailed Description
The present invention will be described in further detail with reference to examples, but the following description should not be construed as limiting the present invention.
Example 1:
first, 50mL of 0.1mol/L Cu (NO) was prepared3)2The solution was placed in a beaker and then 100mg of BiVO was weighed4Dispersed in a three-necked flask containing 80mL of pure water. Subsequently, the above Cu (NO) is taken3)2948. mu.L of the solution was injected into BiVO4-in a pure water system; then adding FeSO with different mass4·7H2O in the solution, and introducing N2Removing dissolved O in the solution for 30min2. Stirring at room temperature for 30min allowed complete dissolution of the solid. Finally, four LED lamps (20mW cm) were used-2λ ═ 420nm) for 4 h. Collecting the product after the reaction is finished, washing the product for 2-3 times by using deionized water and absolute ethyl alcohol respectively, and drying the product at the temperature of 60 ℃ to obtain FeOOH/{110} BiVO4A photocatalytic material. In which FeSO of different masses is added4·7H2O and BiVO4The mass ratio of (A) to (B) is selectively modified in BiVO4The FeOOH cocatalysts of {110} planes are 0, 3,10. 50 and 100 wt%.
FeOOH/{110} BiVO was prepared by the following method4And (3) carrying out characterization on the photocatalyst: the morphological characteristics of the samples were measured by observation with a JSM-7500 field emission scanning electron microscope (FESEM, JEOL, Japan), while the chemical composition of the samples was studied with an energy dispersive X-ray spectrometer (EDX). The crystal structure and composition of the sample were characterized by using an UltimaIII X-ray diffractometer (Cu K α is a radiation source) manufactured by Rigaku, japan. The surface elements of the samples were analyzed by using XPS system (krataxsam 800, target source Al K α) produced in uk, with reference to the standard carbon element peak C1s 284.8 eV. The UV-visible absorption spectrum of the sample was measured by a solid UV-visible spectrophotometer (Shimadzu, Japan, UV-2450) using BaSO4And (5) making a standard base sample.
In FIG. 1, A is decahedral BiVO4The FESEM image of (B) shows BiVO4A very regular decahedral structure is presented, wherein the upper four sides and the lower four sides and the side surfaces of the eight trapezoidal surfaces respectively correspond to {010} crystal planes and {110} crystal planes, the size is about 1-3 μm, and the thickness is about 1 μm. FIGS. 1B-E are 3 wt% FeOOH/{110} BiVO4,10wt％FeOOH/{110}BiVO4，50wt％FeOOH/{110}BiVO4And 100 wt% FeOOH/{110} BiVO4The FESEM spectrum of the catalyst shows that the catalyst promoter FeOOH is selectively deposited on BiVO4The {110} crystal face of (A) shows fine granular shape, and when the added Fe source is increased to 50 wt%, the FeOOH granules on the {110} crystal face show short needle shape. The presence of iron element, the content of which increases with increasing amount of added Fe salt, is demonstrated from the embedded EDS inset.
Figure 2 is an XRD pattern of different photocatalysts. Compared with the prior art, the experimental synthesized BiVO4The samples were all monoclinic scheelite type (JCPDS card number: 14-0688). Different amounts of FeOOH modified samples (b-c) and BiVO4(a) The XRD patterns are similar, which shows that the selective modification of FeOOH does not affect the crystal structure, and no diffraction peak of FeOOH is found in the patterns (FIG. 2b-e) of the samples modified with different FeOOH contents, which is probably because the FeOOH selectively modified by the light deposition exists in an amorphous form.
FIG. 3 shows XPS spectra of different samples. As can be seen from FIG. 3A, these samples all contain Bi, V, O and C, wherein the Bi, V and O are mainly derived from BiVO4Whereas the C element may originate from an external carbon source in the XPS tester. Sample after FeOOH modification (FeOOH/{110} BiVO)4) The XPS full spectrogram has a strong characteristic peak of Fe element, which indicates that the substance containing Fe element is successfully modified in BiVO4A surface. Further more detailed elemental information of the sample was obtained by high resolution XPS spectroscopy analysis, fig. 3B, C and D are XPS high resolution spectra of Fe 2p, Cu 2p and O1s, respectively. As can be seen from FIG. 3B, varying amounts of FeOOH/{110} BiVO were modified4The sample has two characteristic peaks at the binding energy of 711.18eV and 724.83eV, which respectively correspond to Fe 2p3/2And Fe 2p1/2Peak, this is in comparison with the Fe 2p in FeOOH reported in the literature (J.Yan., et al., J.Mater. chem.A., 2017,5, 21478-3/2Orbital electron binding energies 711.3eV and Fe 2p1/2The electron binding energy of the orbitals is 725.0eV is consistent, and the valence state of Fe is +3, which proves that the valence state is that in BiVO4The FeOOH cocatalyst is successfully modified on the photocatalyst. As can be seen from FIG. 3-C, NO Cu element was detected on all the sample surfaces, which indicates that Cu (NO) was added to the solution during the synthesis of FeOOH by photo-deposition3)2The Cu (II) of (a) is reduced into Cu (I) by photo-generated electrons and is not reduced on the surface of the sample in the form of solid particles. As can be seen from FIG. 3-D, it is related to BiVO4In contrast, the peak of O1s shows a slightly enhanced shoulder at 532eV, which indicates that the modified FeOOH has a certain influence on the O element of the sample. The above results demonstrate FeOOH/{110} BiVO4The photocatalytic material is successfully synthesized.
FIG. 4 is a graph of UV-vis spectra for different samples. As can be seen from the figure, pure BiVO4And the absorption band edge of the sample modified by FeOOH is about 540nm, but the sample shows different light absorption capacity. When FeOOH is selectively modified to BiVO4After the {110} crystal face, as can be seen from the optical diagram of the sample in the illustration, the color of the sample is gradually changed from bright yellow to brown yellow, and the light absorption intensity in the range of 400-800 nm is higher than that of pure BiVO4The light absorption intensity of the photocatalytic material is increased along with the increase of the FeOOH modification amountAnd is further enhanced. The above results further indicate that FeOOH has been successfully modified in BiVO4A surface.
BiVO4Selectively modifying BiVO with FeOOH cocatalyst4The oxygen production performance of photocatalytic decomposition water by the photocatalyst is evaluated as follows: 80mg of photocatalyst was weighed and dispersed in a solution containing 80mL of 0.02mol/L NaIO3In a three-necked flask of (1), wherein NaIO3As a sacrificial reagent to capture photogenerated electrons. Introducing N before illumination2Purging for 30min to remove air from the reaction flask, and then stirring the reaction solution with four LED lamps (420nm, 20mW cm)-2) And (4) irradiating. Subsequently, 0.4mL of the reaction gas was withdrawn every 0.5h using a tube equipped with a thermal conductivity detector and
gas chromatography determination of molecular Sieve column (Shimadzu GC-2014C, Japan; N2Carrier gas) analysis of precipitated O2And (4) content.
FIG. 5 is a graph showing the oxygen production rate of photocatalytic decomposition water of different samples. As can be seen from the figure, pure BiVO4The rate of oxygen generation was only 54. mu. mol/L/h. FeOOH/{110} BiVO with increasing FeOOH modification4O of sample2The formation rate showed a tendency to increase and then decrease, especially 50 wt% FeOOH/{110} BiVO4The oxygen production rate of the sample was maximized to 609. mu. mol/L/h. This phenomenon may be attributed to the selective modification of BiVO with a moderate amount of FeOOH co-catalyst4On the {110} crystal face, the separation of photon-generated carriers is effectively promoted, and simultaneously, a large number of photocatalytic active sites are provided, so that the photocatalytic oxygen evolution reaction is obviously enhanced; and excessive modified FeOOH cocatalyst can possibly generate new photon-generated carrier recombination centers, and recombination occurs on the surface of the new photon-generated carrier recombination centers, so that the photocatalytic activity is reduced.
Experimental example 2:
in order to examine the influence of the ferrous salt dissolved in water on the selective modification of the FeOOH cocatalyst, the reaction conditions such as the type of copper salt, the amount of copper ions added, and the illumination time were the same as those in example 1, except that the type of the ferrous salt dissolved in water was different. When ferrous chloride, ferrous nitrate and ferric nitrate are used respectively,When ferrous sulfate, ferrous acetate and the like are used as iron sources, FeOOH can be selectively deposited on BiVO4{110} plane.
Experimental example 3:
in order to examine the influence of the addition amount of the ferrous salt dissolved in water on the selective modification of the FeOOH cocatalyst, the reaction conditions of the ferrous salt species, the addition amount of the copper ions, the illumination time and the like are the same as those in example 1 except that the addition amount of the ferrous salt is different. The experimental result shows that when the addition amount of the ferrous salt is relative to BiVO4When the mass of (B) is more than 200 wt%, FeOOH will be in BiVO4On different sides of the substrate. Thus, in BiVO4The {110} crystal face selectively modifies FeOOH cocatalyst, and the addition of ferrous salt is preferably controlled within 200 wt%.
Experimental example 4:
in order to test the selective modification of different water-soluble copper salt types (copper sulfate, copper chloride, copper nitrate and copper acetate) on FeOOH cocatalyst in BiVO4The influence of the {110} crystal plane was the same as in example 1 except that the kind of the copper salt solution was changed, and other conditions such as a ferrous salt dissolved in water, an irradiation time, an amount of copper ions added, and the like were changed. The experimental result shows that when copper sulfate, copper chloride, copper nitrate and copper acetate are respectively used as the electron capture agents, FeOOH can be selectively deposited on BiVO better4The {110} crystal plane.
Experimental example 5:
in order to examine the influence of the addition of copper ions on the selective modification of the FeOOH cocatalyst, the reaction conditions of ferrous salt species, copper ion species, illumination time and the like are the same as those in example 1 except that the addition of the copper ion salt solution is different. The experimental result shows that when the addition amount of the copper ion salt solution is more than the amount of the modified FeOOH substance, FeOOH is better and selectively deposited on BiVO4The {110} crystal plane. When the addition amount of the copper ions is less than 0.8mL, the ferrous ions in the solution can not be completely deposited and modified on BiVO4{110} crystal face; when the addition amount of the copper ions is more than 5mL, the copper ions in the solution are excessive, so that a certain amount of copper ions are in FeOOH/{110} BiVO4And (4) surface adsorption. Thus, in BiVO4{110} surface-selectively modified FeOOH cocatalystThe addition amount of the oxidant and the copper ion salt solution is preferably controlled to be 0.8-5 mL.
Experimental example 6:
in order to examine the influence of the illumination time on the selective modification of the FeOOH cocatalyst, other reaction conditions such as the types of ferrous salts, copper salts and the amount of added copper ions dissolved in water were the same as in example 1 except for the illumination time conditions. When the illumination time is 0.5h, BiVO4The {110} crystal face has a small amount of fine FeOOH generated, which indicates that only a small amount of ferrous ions in the solution participate in the reaction. When the illumination time is 6h, BiVO4The {110} crystal face is FeOOH-generated and has a short needle-like structure. When the illumination time is continuously prolonged, FeOOH is deposited on BiVO4The deposition of the {110} crystal plane was not significantly changed from that of the illumination of 6 h. Therefore, in the preparation process of selective modification of the FeOOH cocatalyst, the optimal illumination time is 0.5-6 h.
Claims (5)
1. The synthesis method of the bismuth vanadate photocatalytic material selectively modified by the ferric oxyhydroxide cocatalyst is characterized by comprising the following steps:
1) preparing a copper ion solution with a certain concentration;
2) taking a certain amount of BiVO4Dispersing in deionized water to form a uniform suspension;
3) uniformly mixing a certain amount of the copper ion solution obtained in the step 1) with the suspension obtained in the step 2);
4) adding a certain amount of water-soluble ferrous salt into the suspension obtained in the step 3);
5) introducing the suspension obtained in the step 4) for a certain time N2Then, stirring at room temperature, and illuminating for a certain time;
6) filtering, washing and drying the reaction product illuminated in the step 5) to obtain the FeOOH cocatalyst selectively modified in BiVO4{110} plane photocatalytic material.
2. The method for synthesizing the bismuth vanadate photocatalytic material selectively modified by the ferric oxyhydroxide co-catalyst according to claim 1, wherein the copper ion solution in the step 1) is copper sulfate, copper chloride, copper nitrate or copper acetate; wherein the concentration of copper ions is 0.1-5 mol/L.
3. The method for synthesizing the selectively modified bismuth vanadate photocatalytic material as claimed in claim 1, wherein the ratio of the amount of the added copper ion solution to the amount of the ferrous salt substance in the step 3) is controlled to be 1: 1-50: 1.
4. The method for synthesizing a bismuth vanadate photocatalytic material selectively modified by an iron oxyhydroxide co-catalyst according to claim 1, wherein the ferrous salt in the step 4) is ferrous chloride, ferrous nitrate, ferrous sulfate or ferrous acetate, wherein the addition amount of the ferrous salt is equal to that of BiVO4The mass ratio of (A) to (B) is controlled to be 0.005: 1-2: 1.
5. The method for synthesizing the bismuth vanadate photocatalytic material selectively modified by the iron oxyhydroxide co-catalyst according to claim 1, wherein the illumination time in the step 5) is 0.5-6 h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112717932A (en) * | 2020-12-31 | 2021-04-30 | 武汉理工大学 | Preparation method and application of copper-doped ferric oxide nano disc |
| CN113235124A (en) * | 2021-05-18 | 2021-08-10 | 西北师范大学 | S-FeOOH/bismuth vanadate composite photo-anode and preparation method thereof |
| CN113293393A (en) * | 2020-11-02 | 2021-08-24 | 台州学院 | Bismuth vanadate/sodium phytate/iron oxyhydroxide composite photoelectrode and preparation method and application thereof |
| CN113441145A (en) * | 2021-07-30 | 2021-09-28 | 陕西科技大学 | Preparation method of barium titanate/iron oxyhydroxide photocatalyst |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105536770A (en) * | 2016-01-27 | 2016-05-04 | 厦门大学 | Pucherite-based photocatalyst and preparation method and application thereof |
| CN109772355A (en) * | 2019-03-11 | 2019-05-21 | 辽宁石油化工大学 | Amorphous FeOOH/alum acid bismuth composite photocatalyst material preparation method |
| CN110201679A (en) * | 2019-06-24 | 2019-09-06 | 武汉理工大学 | The method of NiOOH auxiliary agent selective modification on pucherite { 110 } face |
-
2020
- 2020-07-31 CN CN202010759386.XA patent/CN111790394A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105536770A (en) * | 2016-01-27 | 2016-05-04 | 厦门大学 | Pucherite-based photocatalyst and preparation method and application thereof |
| CN109772355A (en) * | 2019-03-11 | 2019-05-21 | 辽宁石油化工大学 | Amorphous FeOOH/alum acid bismuth composite photocatalyst material preparation method |
| CN110201679A (en) * | 2019-06-24 | 2019-09-06 | 武汉理工大学 | The method of NiOOH auxiliary agent selective modification on pucherite { 110 } face |
Non-Patent Citations (1)
| Title |
|---|
| 廖丹: "助剂选择性修饰增强单晶钒酸铋光催化性能的研究" * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113293393A (en) * | 2020-11-02 | 2021-08-24 | 台州学院 | Bismuth vanadate/sodium phytate/iron oxyhydroxide composite photoelectrode and preparation method and application thereof |
| CN113293393B (en) * | 2020-11-02 | 2022-03-18 | 台州学院 | Bismuth vanadate/sodium phytate/iron oxyhydroxide composite photoelectrode and preparation method and application thereof |
| CN112717932A (en) * | 2020-12-31 | 2021-04-30 | 武汉理工大学 | Preparation method and application of copper-doped ferric oxide nano disc |
| CN113235124A (en) * | 2021-05-18 | 2021-08-10 | 西北师范大学 | S-FeOOH/bismuth vanadate composite photo-anode and preparation method thereof |
| CN113441145A (en) * | 2021-07-30 | 2021-09-28 | 陕西科技大学 | Preparation method of barium titanate/iron oxyhydroxide photocatalyst |
| CN114452969A (en) * | 2022-01-21 | 2022-05-10 | 山东大学 | Double-promoter supported photocatalyst and preparation method and application thereof |
| CN114452969B (en) * | 2022-01-21 | 2023-05-30 | 山东大学 | Double-cocatalyst-supported photocatalyst and preparation method and application thereof |
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