CN110787812A - Hole assistant Ti (IV) and electron assistant Ni (OH)2Synergistically modified ZnIn2S4Method for preparing photocatalyst - Google Patents
Hole assistant Ti (IV) and electron assistant Ni (OH)2Synergistically modified ZnIn2S4Method for preparing photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 29
- 239000010936 titanium Substances 0.000 claims abstract description 64
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 claims abstract description 25
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 13
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
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- 238000005406 washing Methods 0.000 claims abstract description 6
- 150000003608 titanium Chemical class 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004202 carbamide Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 description 11
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 238000011068 loading method Methods 0.000 description 4
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- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 230000006798 recombination Effects 0.000 description 2
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- 239000012266 salt solution Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910002703 Al K Inorganic materials 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 238000000926 separation method Methods 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
- 238000001308 synthesis method Methods 0.000 description 1
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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
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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Abstract
The invention relates to a hole auxiliary agent Ti (IV) and an electron auxiliary agent Ni (OH)2Synergistically modified ZnIn2S4The preparation method of the photocatalyst comprises the following steps: 1) ZnIn2S4Mixing the photocatalytic material with deionized water, and fully stirring to form a suspension; 2) adding a water-soluble titanium salt to the suspension; 3) heating the suspension in water bath for a certain time while stirring; 4) filtering, washing and drying the precipitate to obtain the photocatalyst; 5) mixing a photocatalyst with deionized water, and stirring to form a uniform suspension; 6) adding a water-soluble nickel salt and urea solution to the suspension; 7) heating the suspension in water bath for a certain time while stirring; 8) filtering, washing and drying the precipitate to obtain the cavity assistant Ti (IV) and the electron assistant Ni (OH)2Synergistically modified ZnIn2S4A photocatalyst. The synthetic method has the advantages of simple operation, environmental protection, energy saving and no need of adding any organic surfactant.
Description
Technical Field
The invention relates to a hole auxiliary agent Ti (IV) and an electron auxiliary agent Ni (OH)2Synergistically modified ZnIn2S4The preparation method of the photocatalyst, in particular to a hole auxiliary agent Ti (IV) and an electron auxiliary agent Ni (OH)2The method of loading (1).
Technical Field
At present, the problem of energy shortage is increasingly serious, and solar energy is clean renewable energy, so that the solution of the environmental pollution problem and the energy problem by using the solar energy is one of the most potential strategies; wherein the photocatalytic technology can realize high-efficiency solar energyCapture and transformation are of great interest. The core of the photocatalysis technology is photocatalyst, but pure phase TiO2、CdS、C3N4、BiVO4The photocatalytic activity of the photocatalysts is very low, and the modification of the photocatalysts is needed, wherein the modification of the auxiliary agent is one of effective means for improving the activity of the photocatalysts. Therefore, the search for a preparation method of the high-activity-assistant modified photocatalyst is a hot spot and a focus of development in the technology.
Recent studies have shown that: ni (OH)2Can be used as an electron assistant to rapidly transfer photogenerated electrons and inhibit the recombination of the photogenerated electrons and photogenerated holes, thereby improving the ZnIn2S4The photocatalytic performance of (a). More importantly, Ni (OH)2After photo-generated electrons are absorbed, Ni can be absorbed2+The Ni simple substance can be used as an active site of the photocatalytic reaction, thereby accelerating the rate of the interface reduction reaction. It is well known that the semiconductor photocatalytic rate is determined by three important components: 1) the transmission rate of photogenerated electrons and holes, 2) the rate of interfacial reduction reaction, 3) the rate of interfacial oxidation reaction. Therefore, to further improve ZnIn2S4The photocatalytic performance of the composite material is that a hole auxiliary agent Ti (IV) is utilized to accelerate the rate of the interface oxidation reaction, and finally the ZnIn is improved2S4The purpose of the photocatalytic performance of (1).
Disclosure of the invention
Aiming at the technical problems, the invention provides a green environment-friendly hole auxiliary agent Ti (IV) and an electron auxiliary agent Ni (OH) which are simple to operate2Synergistically modified ZnIn2S4The preparation method of the photocatalyst comprises the steps of preparing a cavity assistant Ti (IV) and an electron assistant Ni (OH) by a low-temperature water bath method2Loaded on ZnIn2S4On the surface.
The technical scheme adopted for solving the technical problems is as follows: hole assistant Ti (IV) and electron assistant Ni (OH)2Synergistically modified ZnIn2S4The preparation method of the photocatalyst is characterized by comprising the following steps:
1)ZnIn2S4mixing the photocatalytic material with deionized waterFully stirring to form uniform suspension;
2) adding a water-soluble titanium salt to the suspension in step 1);
3) stirring the suspension liquid in the step 2) and heating in a water bath for a certain time;
4) filtering, washing and drying the precipitate in the step 3) to obtain the ZnIn modified by the cavity assistant Ti (IV)2S4；
5) Mixing the photocatalyst in the step 4) with deionized water, and stirring to form uniform suspension;
6) adding a water-soluble nickel salt and urea solution to the suspension in step 5);
7) heating the suspension liquid obtained in the step 6) in a water bath for a certain time while stirring;
8) filtering, washing and drying the precipitate in the step 7) to obtain the hole auxiliary agent Ti (IV) and the electron auxiliary agent Ni (OH)2Synergistically modified ZnIn2S4A photocatalyst.
According to the scheme, the water bath heating reaction temperature of the step 3) and the step 7) is 70-90 ℃, and the reaction time is 4-6 h.
According to the scheme, the titanium salt in the step 2) is titanium chloride or titanium sulfate.
According to the scheme, the nickel salt in the step 6) is nickel sulfate or nickel nitrate.
ZnIn of the invention2S4The preparation method of (1) is described in the literature (Z.Yan, X.Yu, A.Han, P.xu, P.Du, Journal of physical Chemistry C118 (2014)22896-22903), wherein ZnIn is2S4Is a hexagonal crystal form microsphere structure, and a certain amount of cavity auxiliary agent Ti (IV) and electron auxiliary agent Ni (OH) are loaded by a low-temperature water bath method2. The basic principle of the enhancement of the photocatalytic activity is as follows: hole assistant Ti (IV) and electron assistant Ni (OH)2Improve ZnIn2S4Separation efficiency of internal photogenerated carriers, and electron auxiliary agent Ni (OH)2Accelerates the rate of interfacial oxidation reaction, thereby increasing Ni (OH)2-Ti(IV)/ZnIn2S4Photocatalytic activity of (1).
The invention has the beneficial effects that: the invention provides ZnIn2S4As a precursor, divalent nickel ions are made to be ZnIn by a low-temperature water bath method2S4Surface formation of Ni (OH)2The synthesis method has the advantages of simple operation, environmental protection, energy saving, no need of adding any organic surfactant, wide raw material source, low price, no toxicity, no pollution, stable chemical property and the like. Meanwhile, the whole reaction process does not need various expensive processing and synthesizing equipment, high-temperature and high-pressure reaction devices and the like, and has the advantages of easiness in large-scale synthesis and the like. The prepared photocatalytic material has high visible light photocatalytic activity and is expected to generate good social and economic benefits.
Drawings
FIG. 1 shows ZnIn as sample (A) in example 12S4、(B)Ti(IV,0.5％)/ZnIn2S4、(C)Ni(OH)2(3％)/ZnIn2S4、 (D)Ni(OH)2(3％)-Ti(IV,0.5％)/ZnIn2S4FESEM image of (g). Wherein the patterns embedded in (A), (B), (C) and (D) are ZnIn, respectively2S4、Ti(IV,0.5％)/ZnIn2S4、Ni(OH)2/ZnIn2S4、Ni(OH)2-Ti(IV,0.5％)/ZnIn2S4An energy dispersive X-ray spectrometer (EDX) spectrum of (a);
figure 2 is the XRD patterns of different samples in example 1: (a) ZnIn2S4、(b)Ti(IV,0.5％)/ZnIn2S4、 (c)Ni(OH)2(3％)/ZnIn2S4、(d)Ni(OH)2(3％)-Ti(IV,0.5％))/ZnIn2S4；
FIG. 3(A) is an XPS survey of various samples of example 1 and high resolution XPS plots of various elements (B) Ti2p, (C) Ni 2p, (D) In 3D, (E) Zn 2p, (F) S2 p: (a) ZnIn2S4、(b)Ti(IV,0.5％)ZnIn2S4、(c)Ni(OH)2(3％)/ZnIn2S4、 (d)Ni(OH)2(3％)-Ti(IV,0.5％))/ZnIn2S4；
FIG. 4(A) is a graph of the rate of hydrogen production for different samples in example 1: (a) ZnIn2S4，(b)Ti(IV,0.5％)/ZnIn2S4，(c) Ni(OH)2(3％)-Ti(IV,0.5％)/ZnIn2S4FIG. 4(B) shows a photocatalytic cycle chart of (1), wherein Ni (OH)2(3％)/Ti(IV,0.5％)/ZnIn2S4The photocatalytic cycle chart of (1).
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:
hole assistant Ti (IV) and electron assistant Ni (OH)2Synergistically modified ZnIn2S4The preparation process of the photocatalyst is as follows: 30mL of deionized water was first charged to a three-necked flask, and 0.2g of ZnIn was then added2S4The powder was mixed with the above solution under magnetic stirring to form a homogeneous suspension, and 526. mu.L of TiCl was taken out with a pipette4(0.01mol/L) solution was added to the above suspension; then, the three-necked flask was placed at 75 ℃ in a water bath with stirring for 6 hours, the reaction product was washed three times with water and dried in an oven at 40 ℃ for 12 hours to obtain Ti (IV, 0.5%)/ZnIn2S4Photocatalytic Material 0.2g of the above photocatalytic material was then added to a solution containing 30mL of deionized water and 0.6mL of Ni (NO)3)2(10g/L) solution and 5mL of urea solution (1mol/L), then the three-necked flask was placed at 75 ℃ in a water bath with stirring for 6 hours, the reaction product was washed three times with water and dried in an oven at 40 ℃ for 12 hours to obtain Ni (OH)2(3％)-Ti(IV,0.5％)/ZnIn2S4A photocatalytic material.
Hole assistant Ti (IV) and electron assistant Ni (OH)2Synergistically modified ZnIn2S4The photocatalyst is characterized by that the morphology and structure of sample are observed and measured by JSM-7500 field emission scanning electron microscope (FESEM, JEOL, Japan), and the chemical composition of sample is studied by energy dispersive X-ray spectrometer (EDX). The crystal phase structure and phase composition of sample are characterized by using Ultima III X-ray diffractometer (Cu K α is ray source) produced by Rigaku corporation of Japan, and the surface elements of sample are characterized by KRATOA XSAM 800X-ray light produced in UKThe electron spectrum system (target source is Al K α) is used for analysis, and the binding energy of each sample element is taken as a reference of a standard carbon element peak C1s 284.8.8 eV.
In FIG. 1, A is ZnIn2S4Scanning Electron Microscope (SEM) image of microsphere structure, from which ZnIn can be seen2S4The size range of (A) is 1-2 μm. In FIG. 1, B is Ti (IV, 0.5%)/ZnIn2S4The SEM image shows that some amorphous substances exist between the petals of the microsphere structure, and the existence of Ti element is also proved by the embedded EDS image B in figure 1. In FIG. 1, C is Ni (OH)2(3％)/ZnIn2S4The SEM image also shows that some amorphous substances exist between the petals of the microsphere structure, and the embedded energy dispersive X-ray spectrogram also proves the existence of the nickel element. In FIG. 1, D is a cavity promoter Ti (IV) and an electron promoter Ni (OH)2Synergistically modified ZnIn2S4Photocatalyst, EDS chart also proves the existence of nickel element and Ti element
Figure 2 is an X-ray diffraction (XRD) pattern of different samples. As can be seen from the figure, the samples a prepared by the experiment are ZnIn in hexagonal crystal form2S4(PDF card number: 49-1562). XRD patterns for samples b, c and d similar to sample a, description and Ti (IV) and Ni (OH)2Adjuvant modified pair ZnIn2S4The crystal phase structure of the sample has no influence.
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) plot of different samples. As can be seen from A In FIG. 3, these samples all contain Zn, In, O, S and C, wherein the elements Zn, S and In are mainly derived from ZnIn2S4O may come from adsorbed water on the sample surface, while C element may originate from an external C source in the XPS test instrument. B, C, D, E, F In FIG. 3 show the high resolution XPS of Ti2p, Ni 2p, In 3d, Zn 2p, S2 p, respectively, as Ti (IV, 0.5%)/ZnIn2S4The high resolution XPS plots for the samples showed XPS peaks at 457.8 and 464.1eV, which correlates with 2p for Ti3/2And 2p1/2The characteristic peaks of (a) and (B) are relative to each other, so that the valence of Ti of the sample is +4 (see FIG. 3-B-B). As can be seen from C in FIG. 3, XPS peaks appear at 856.2 and 873.6eV, which is comparable to the 2p of Ni3/2And 2p1/2The characteristic peaks of (a) are consistent, so that the valence of Ni of the sample is + 4. The binding energy corresponding to Ni 2p is referred to in the literature (Z.Yan, X.Yu, A.Han, P.Xu, P.Du, Journal of Physical Chemistry C118 (2014) 22896-. The above data therefore demonstrate the auxiliaries Ti (IV) and Ni (OH)2Has been successfully loaded in ZnIn2S4On the surface of (a).
The evaluation basis of the photocatalytic activity of the sample is the hydrogen production rate of the sample in the photocatalytic process. The test conditions are as follows: at normal temperature and normal pressure, a flat-bottom three-necked flask of 100mL is used as a photocatalytic reaction container, the opening of the flask is sealed by a silica gel plug and a sealing film, a Light Emitting Diode (LED) lamp (lambda is 420nm) of 350W and filtering ultraviolet light is used as a light source of the photocatalytic reaction, and the light source is 20cm away from the three-necked flask. Meanwhile, the light intensity on the surface of the flask is measured to be 180mW cm by using an FZ-A type visible light meter produced by Beijing university of teachers-2. The specific photocatalysis experiment process is as follows: putting 50mg of sample into a flat-bottom three-mouth bottle with the volume of 100mL, adding 65mL of deionized water and 15mL of triethanolamine into the flat-bottom three-mouth bottle, wherein the triethanolamine has the function of consuming photoproduction holes generated in the photocatalysis process and avoiding the recombination of the photoproduction holes and photoproduction electrons, thereby improving the photocatalytic activity of the sample. The flask was purged with nitrogen for about 30min before irradiation with light to remove air and oxygen dissolved in water in the flask. Then, the reaction vessel was subjected to light treatment while stirring, in order to suspend the sample particles in the solution and to achieve sufficient reaction. After 0.5h of illumination, 400 μ L of gas in the flask was extracted with a gas injector through a silica gel plug at the seal of the flask, and then the content of hydrogen in the gas was detected with a gas chromatograph model GC-2014C manufactured by Shimadzu, Japan, equipped with a Thermal Conductivity Detector (TCD), nitrogen as carrier gas, and a capillary column as capillary column
The molecular sieve of (1).
In FIG. 4, A is that of example 1The hydrogen production rate chart of the same sample: (a) ZnIn2S4，(b)Ti(IV,0.5％)/ZnIn2S4，(c) Ni(OH)2(3％)/ZnIn2S4，(d-g)Ni(OH)2(1％,3％,5％,8％)/Ti(IV,0.5％)/ZnIn2S4. As can be seen from the figure, the photocatalyst Ni (OH)2(3％)/Ti(IV,0.5％)/ZnIn2S4The hydrogen production rate of (2) is 115.51 mu mol h-1Its activity is obviously higher than ZnIn2S4，Ti(IV,0.5％)/ZnIn2S4And Ni (OH)2(3％)/ZnIn2S4A photocatalyst. In FIG. 4, B is Ni (OH)2(3％)/Ti(IV,0.5％)/ZnIn2S4The photocatalytic cycle chart of (a) shows that the catalyst has good stability.
Experimental example 2:
to examine the loading of Ti on ZnIn by different water-soluble Ti salt solutions (titanium sulfate or titanium chloride)2S4The conditions such as bath temperature, bath time and the like were the same as in example 1 except that the water-soluble Ti salt solution was different. Experimental results show that when titanium sulfate or titanium chloride is respectively used as a Ti source, Ti can be well loaded on ZnIn2S4On the surface of (a).
Experimental example 3:
to check the bath temperature auxiliary agents Ti and Ni (OH)2The reaction conditions such as bath time and Ti, Ni source used were the same as in example 1 except that the bath temperature was varied. The experimental result shows that when the water bath temperature is lower than 65 ℃, the auxiliary agents Ti and Ni (OH)2Is not loaded on ZnIn2S4On the surface of (a). Because the low temperature environment can not be taken as auxiliary agents of Ti and Ni (OH)2The loading of (2) provides sufficient energy to be unfavorable for the auxiliaries Ti and Ni (OH)2The load of (2). When the temperature of the water bath is more than 90 ℃, the ZnIn is loaded2S4On the surface of Ti and Ni (OH)2There will be a crystal form. Therefore, in Ti (IV)/ZnIn2S4And Ni (OH)2/ZnIn2S4During the preparation process of the photocatalyst, the optimal water bath temperature is 70-90 ℃.
Experimental example 4:
to examine the water-soluble nickel salt versus auxiliary Ni (OH)2The effect of the loading was the same as in example 1 except that the nickel salt dissolved in water was different, and other conditions such as bath temperature, bath time and the like were changed. The experimental results show that when nickel sulfate or nickel nitrate is used as the nickel source, the auxiliary agent Ni (OH)2Can be well loaded in ZnIn2S4On the surface of (a).
Experimental example 5:
to check the bath time, auxiliaries Ti and Ni (OH)2The reaction conditions such as bath temperature and Ti, Ni source used, etc. were the same as in example 1 except for the time of the bath. When the water bath time is less than 4h, ZnIn2S4The photocatalytic hydrogen production rate is not obviously improved, which shows that only a small amount of nickel ions participate in the reaction in the solution. When the water bath time is more than 6h, ZnIn2S4The photocatalytic hydrogen production rate is improved to the extent that the water bath time is 4-6 h. Therefore, from the viewpoint of energy saving, Ni (OH)2-Ti(IV)/ZnIn2S4In the preparation process of the photocatalyst, the optimal water bath time is 4-6 h.
Claims (4)
1. Hole assistant Ti (IV) and electron assistant Ni (OH)2Synergistically modified ZnIn2S4The preparation method of the photocatalyst is characterized by comprising the following steps:
1)ZnIn2S4mixing the photocatalytic material with deionized water, and fully stirring to form uniform suspension;
2) adding a water-soluble titanium salt to the suspension in step 1);
3) stirring the suspension liquid in the step 2) and heating in a water bath for a certain time;
4) filtering, washing and drying the precipitate in the step 3) to obtain the ZnIn modified by the cavity assistant Ti (IV)2S4；
5) Mixing the photocatalyst in the step 4) with deionized water, and stirring to form uniform suspension;
6) adding a water-soluble nickel salt and urea solution to the suspension in step 5);
7) heating the suspension liquid obtained in the step 6) in a water bath for a certain time while stirring;
8) filtering, washing and drying the precipitate in the step 7) to obtain the hole auxiliary agent Ti (IV) and the electron auxiliary agent Ni (OH)2Synergistically modified ZnIn2S4A photocatalyst.
2. The hole promoter Ti (IV) and electron promoter Ni (OH) according to claim 12Synergistically modified ZnIn2S4The preparation method of the photocatalyst is characterized in that the water bath heating reaction temperature of the steps 3) and 7) is 70-90 ℃, and the reaction time is 4-6 h.
3. The hole promoter Ti (IV) and electron promoter Ni (OH) according to claim 12Synergistically modified ZnIn2S4The preparation method of the photocatalyst is characterized in that the titanium salt in the step 2) is titanium chloride or titanium sulfate.
4. The hole promoter Ti (IV) and electron promoter Ni (OH) according to claim 12Synergistically modified ZnIn2S4The preparation method of the photocatalyst is characterized in that the nickel salt in the step 6) is nickel sulfate or nickel nitrate.
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| CN112892555A (en) * | 2021-01-13 | 2021-06-04 | 华南师范大学 | ZnIn synergistically modified by cavity promoter Ti (IV) and electron promoter MXene QDs2S4Photocatalyst and process for producing the same |
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| CN107737597A (en) * | 2017-10-11 | 2018-02-27 | 肇庆市华师大光电产业研究院 | A kind of titanium doped indium sulfide zinc flower-like microsphere and its preparation method and application |
| CN107866234A (en) * | 2016-09-27 | 2018-04-03 | 中国地质大学（北京） | A kind of high activity ZnIn2S4/TiO2Z System Catalyst materials and preparation method thereof |
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| CN107866234A (en) * | 2016-09-27 | 2018-04-03 | 中国地质大学（北京） | A kind of high activity ZnIn2S4/TiO2Z System Catalyst materials and preparation method thereof |
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