CN117324009A - Bi-doped ZnIn 2 S 4 Photocatalyst, preparation method and application thereof - Google Patents

Bi-doped ZnIn 2 S 4 Photocatalyst, preparation method and application thereof Download PDF

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Publication number
CN117324009A
CN117324009A CN202311509414.2A CN202311509414A CN117324009A CN 117324009 A CN117324009 A CN 117324009A CN 202311509414 A CN202311509414 A CN 202311509414A CN 117324009 A CN117324009 A CN 117324009A
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znin
photocatalyst
doped
water
reaction
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范晓星
史连娟
裴丽
许鸿璐
于洁
刘欣宇
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Liaoning University
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Liaoning University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04Sulfides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042Decomposition of water
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0266Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step

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Abstract

The invention discloses a Bi-doped ZnIn 2 S 4 A photocatalyst, a preparation method and application thereof. Dissolving bismuth nitrate pentahydrate in ZnIn 2 S 4 In the precursor solution of (2) by changing the molar ratio of bismuth source to obtain ZnIn with different molar ratios 2 S 4 -x% Bi composite material which can be applied in the field of photocatalytic decomposition of water-splitting hydrogen. Compared with the existing photocatalyst, the Bi-doped ZnIn of the invention 2 S 4 The catalyst has good controllability, is favorable for further improving the separation efficiency of carriers, and has higher hydrogen yield and better stability when being applied to photocatalytic decomposition of water. The invention is green and environment-friendly, has simple method, convenient operation and low material preparation cost, accords with the environment-friendly concept advocated at present, and has wide application marketScene prospect.

Description

Bi-doped ZnIn 2 S 4 Photocatalyst, preparation method and application thereof
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to Bi-doped ZnIn 2 S 4 A photocatalyst, a preparation method and application thereof.
Background
In recent years, the problems of energy shortage and environmental destruction severely restrict the sustainable development of society, and the development of efficient green hydrogen resources is the focus of most researchers. Hydrogen is becoming increasingly popular as an environmentally friendly, sustainable and renewable energy source because it potentially alleviates the energy shortfall caused by the abuse of fossil fuels. To date, a number of methods for generating hydrogen energy have been established, including pyrolysis of water and electrocatalytic water splitting. In particular, photocatalytic water splitting hydrogen production is easy to operate and widely used, is a potential environmental protection technology, but it is not easy to achieve efficient hydrogen production. Therefore, a key problem in high performance photocatalytic water splitting hydrogen evolution technology is the search for photocatalysts that can effectively achieve charge separation.
ZnIn 2 S 4 The method has received extensive attention and application because of the remarkable advantages of simple synthesis, environmental friendliness, good stability and proper energy band structure. However, pure ZnIn 2 S 4 The photocatalytic efficiency of a photocatalyst is generally limited, mainly due to its significantly lower efficiency of development for sunlight and the large recombination of photo-generated charges. Thus, various modification techniques have been designed to enhance ZnIn 2 S 4 Photocatalytic efficiency of photocatalytic hydrogen production, however Bi-doped ZnIn 2 S 4 There have been no reports on hydrogen evolution as a photocatalyst.
Disclosure of Invention
In order to solve the problems existing in the prior art, the invention provides a Bi doped ZnIn 2 S 4 A photocatalyst, a preparation method and application thereof.
The invention adopts the technical scheme that: bi-doped ZnIn 2 S 4 Photocatalyst, mole percent, doping amount of Bi is ZnIn 2 S 4 1-5% of (C).
Bi-doped ZnIn 2 S 4 The preparation method of the photocatalyst comprises the following steps: znCl 2 、InCl 3 And Thioacetamide (TAA) are added into water and stirred to form a uniform precursor solution; bi (NO) 3 )·5H 2 O is added into the precursor solution, after being stirred uniformly, the mixture is transferred into a high-pressure reaction kettle for hydrothermal reaction, after the reaction is finished, the mixture is cooled to room temperature, centrifugally washed and dried, and the Bi doped ZnIn is obtained 2 S 4 A photocatalyst.
Preferably, znCl is used in molar ratio 2 :InCl 3 Thioacetamide=1:2:4.
Preferably, the hydrothermal reaction is: the reaction is carried out at 180 ℃ for 24 hours.
The Bi doped ZnIn provided by the invention 2 S 4 The application of the photocatalyst in preparing hydrogen by photocatalytic decomposition of water under irradiation of visible light.
Preferably, the method is as follows: doping Bi with ZnIn 2 S 4 The photocatalyst is uniformly dispersed in a mixed solution of deionized water, triethanolamine (TEOA) and chloroplatinic acid, argon is continuously introduced at a constant flow rate, and the photocatalyst is irradiated under the irradiation condition of visible light.
Preferably, the concentration of the triethanolamine is 7.2mmol/mL; the concentration of the chloroplatinic acid is 0.75 weight percent.
Preferably, the Bi is doped with ZnIn according to the solid-to-liquid ratio 2 S 4 Deionized water: triethanolamine chloroplatinic acid = 20mg:18ml:3ml:15 μl.
The beneficial effects of the invention are as follows:
1. the invention prepares Bi-doped ZnIn by utilizing a hydrothermal method 2 S 4 After the Bi doping modification, the photocatalyst generates a impurity level in the original energy band structure, reduces an electron transition potential barrier, can effectively reduce the recombination of photo-generated electrons and holes, and improves the separation efficiency of carriers, thereby obviously improving the visible light response of the catalyst and enhancing the photocatalytic activity.
2. Bi doped ZnIn prepared by the invention 2 S 4 Photocatalysts with larger specific surface area and more efficient photo-generated electron and hole separation capability, and with stronger lightCatalytic reduction capability, participation in catalytic reaction, is an effective way to improve visible light catalytic activity.
3. Bi doped ZnIn prepared by the invention 2 S 4 The photocatalyst has better photocatalytic hydrogen evolution performance, and the method is simple and convenient to operate, low in cost, mild in condition and beneficial to large-scale production.
Drawings
FIG. 1 shows ZnIn prepared in example 1 2 S 4 、ZnIn 2 S 4 -1% Bi and ZnIn 2 S 4 -X-ray diffraction pattern of 2% bi photocatalyst.
FIG. 2 shows ZnIn prepared in example 1 2 S 4 、ZnIn 2 S 4 -1% Bi and ZnIn 2 S 4 Photocurrent-time curve of 2% bi photocatalyst.
FIG. 3 shows ZnIn prepared in example 1 2 S 4 、ZnIn 2 S 4 -1% Bi and ZnIn 2 S 4 -2% bi photocatalyst decomposition water hydrogen evolution activity comparison graph.
Detailed Description
EXAMPLE 1Bi doped ZnIn 2 S 4 Photocatalyst (one) ZnIn 2 S 4 Is prepared from
0.4mmol ZnCl 2 、0.8mmol InCl 3 And 1.6mmol of TAA are put into 36mL of water, stirred to form uniform precursor solution, put into a hydrothermal kettle for hydrothermal reaction at 180 ℃ for 24 hours, naturally cooled to room temperature, respectively washed with distilled water and ethanol for three times, and dried at 60 ℃ to obtain ZnIn 2 S 4
ZnIn with Bi doping amount of 1% 2 S 4 Preparation of photocatalyst
0.4mmol ZnCl 2 、0.8mmol InCl 3 And 1.6mmol of TAA were put into 36mL of water, stirred to form a uniform precursor solution, and 0.004mmol of Bi (NO 3 ) 3 ·5H 2 O, after fully stirring, transferring into a high-pressure reaction kettle, carrying out hydrothermal reaction for 24 hours at 180 ℃, naturally cooling to room temperature after the reaction is finished, respectively centrifugally washing with distilled water and ethanol for three times, and drying at 60 ℃ to obtain the Bi doped amount of1% ZnIn 2 S 4 Photocatalyst, labeled ZnIn 2 S 4 -1%Bi。
ZnIn with Bi doping amount of 2% 2 S 4 Preparation of photocatalyst
0.4mmol ZnCl 2 、0.8mmol InCl 3 And 1.6mmol of TAA were put into 36mL of water, stirred to form a uniform precursor solution, and 0.008mmol of Bi (NO 3 ) 3 ·5H 2 O, after fully stirring, transferring into a high-pressure reaction kettle, carrying out hydrothermal reaction for 24 hours at 180 ℃, naturally cooling to room temperature after the reaction is finished, respectively centrifugally washing with distilled water and ethanol for three times, and drying at 60 ℃ to obtain ZnIn with the Bi doping amount of 2 percent 2 S 4 Photocatalyst, labeled ZnIn 2 S 4 -2%Bi。
(IV) detection
FIG. 1 shows ZnIn prepared in example 1 2 S 4 、ZnIn 2 S 4 -1% Bi and ZnIn 2 S 4 -X-ray diffraction pattern of 2% bi photocatalyst. In fig. 1, 8 distinct characteristic diffraction peaks at 2θ=21.6 °,27.8 °,37.4 °,30.4 °,40 °,47.2 °,52.1, 56.1 and 75.9 correspond to ZnIn, respectively 2 S 4 (006), (102), (102), (104), (108), (112), (1012), (1012), (202) and (213) crystal planes (standard card PDF#65-2023). No characteristic peak of other impurities was observed from FIG. 1, which shows Bi-doped ZnIn 2 S 4 After that still retains ZnIn 2 S 4 Original structure.
EXAMPLE 2Bi doped ZnIn 2 S 4 Application of photocatalyst in catalyzing and decomposing water to hydrogen evolution under illumination
The method comprises the following steps: 18mL of deionized water, 3mL of TEOA solution having a concentration of 7.2mmol/mL and 15. Mu.L of an aqueous solution of chloroplatinic acid having a concentration of 0.75% by weight were added to the vessel at normal temperature and pressure, followed by addition of 20mg of ZnIn prepared in example 1, respectively 2 S 4 、ZnIn 2 S 4 -1% Bi and ZnIn 2 S 4 -2% bi photocatalyst, sonicated for 10min, dispersing the solution. Argon is introduced into the container at a rate of 40mL/min for 30min, the container is sealed, under the condition of visible light irradiation,every 30min, taking 1000 mu L of gas in a container by using a microinjector, detecting the gas components of the sample by using a gas chromatographic separation technology method, and measuring the concentration of hydrogen evolution.
FIG. 2 shows ZnIn prepared in example 1 2 S 4 、ZnIn 2 S 4 -1% Bi and ZnIn 2 S 4 Photocurrent-time curve of 2% bi photocatalyst. The results show that ZnIn 2 S 4 The photocurrent intensity of 2% Bi is about 9.84. Mu.A.cm -2 Is pure ZnIn 2 S 4 (4.26μA·cm -2 ) Is 2.31 times that of (c). The doping of Bi improves the separation efficiency of photo-generated carriers of the semiconductor, thereby improving the photoelectrochemical property of the semiconductor.
FIG. 3 shows ZnIn prepared in example 1 2 S 4 、ZnIn 2 S 4 -1% Bi and ZnIn 2 S 4 -2% bi photocatalyst decomposition water hydrogen evolution activity comparison graph. As can be seen from FIG. 3, after 30min of the illumination reaction, znIn 2 S 4 The hydrogen yield is 10.54mmol/L, znIn 2 S 4 1% Bi to H 2 The amount was 11.14mmol/L, znIn 2 S 4 2% Bi to H 2 The amount was 19.18mmol/L. ZnIn doped with Bi 2 S 4 The catalytic hydrogen production performance of the photocatalyst is purer than that of ZnIn 2 S 4 Has great lifting. Indicating that Bi is doped with ZnIn 2 S 4 After that, the photo-generated electrons have stronger transmission and transfer capability and the electron holes have stronger oxidation-reduction capability.

Claims (8)

1. Bi-doped ZnIn 2 S 4 The photocatalyst is characterized in that the doping amount of Bi is ZnIn in mole percent 2 S 4 1-5% of (C).
2. A Bi-doped ZnIn according to claim 1 2 S 4 The preparation method of the photocatalyst is characterized by comprising the following steps: znCl 2 、InCl 3 And thioacetamide are added into water and stirred to form uniform precursor solution; bi (NO) 3 )·5H 2 O is added into the precursor solution, and is transferred to a high temperature after being stirred uniformlyIn the autoclave, carrying out hydrothermal reaction, cooling to room temperature after the reaction is finished, centrifugally washing and drying to obtain Bi doped ZnIn 2 S 4 A photocatalyst.
3. The process according to claim 2, wherein ZnCl is present in molar ratio 2 :InCl 3 Thioacetamide=1:2:4.
4. The method of claim 2, wherein the hydrothermal reaction is: the reaction is carried out at 180 ℃ for 24 hours.
5. The Bi-doped ZnIn of claim 1 2 S 4 The application of the photocatalyst in the hydrogen production by catalyzing and decomposing water under the irradiation of visible light.
6. The use according to claim 5, characterized in that the method is as follows: doping Bi with ZnIn 2 S 4 The photocatalyst is uniformly dispersed in a mixed solution of deionized water, triethanolamine and chloroplatinic acid, argon is continuously introduced at a constant flow rate, and the photocatalyst is irradiated under the irradiation condition of visible light.
7. The use according to claim 6, characterized in that the concentration of triethanolamine is 7.2mmol/mL; the concentration of the chloroplatinic acid is 0.75 weight percent.
8. The use according to claim 7, wherein the Bi is doped with ZnIn in solid-to-liquid ratio 2 S 4 Deionized water: triethanolamine chloroplatinic acid = 20mg:18ml:3ml:15 μl.
CN202311509414.2A 2023-11-14 2023-11-14 Bi-doped ZnIn 2 S 4 Photocatalyst, preparation method and application thereof Pending CN117324009A (en)

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Cited By (1)

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CN118002155A (en) * 2024-02-05 2024-05-10 辽宁大学 Heterojunction CoTiO3/ZnIn2S4Photocatalyst, preparation method and application thereof

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CN113509932A (en) * 2021-05-17 2021-10-19 电子科技大学长三角研究院(湖州) Semiconductor photocatalyst and preparation method thereof
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CN113509932A (en) * 2021-05-17 2021-10-19 电子科技大学长三角研究院(湖州) Semiconductor photocatalyst and preparation method thereof
CN114950483A (en) * 2022-04-18 2022-08-30 淮阴工学院 High-hydrophobic three-dimensional flower-shaped ZnIn2S4/Sn3O4 composite structure material and preparation method and application thereof
CN115837279A (en) * 2022-08-29 2023-03-24 南昌航空大学 CdS and ZnIn constructed by in-situ load 2 S 4 Method of heterojunction

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118002155A (en) * 2024-02-05 2024-05-10 辽宁大学 Heterojunction CoTiO3/ZnIn2S4Photocatalyst, preparation method and application thereof

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