CN114655978B - Preparation and application of three-component sulfide photoelectric material with hollow hierarchical heterostructure - Google Patents

Preparation and application of three-component sulfide photoelectric material with hollow hierarchical heterostructure Download PDF

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CN114655978B
CN114655978B CN202210197281.9A CN202210197281A CN114655978B CN 114655978 B CN114655978 B CN 114655978B CN 202210197281 A CN202210197281 A CN 202210197281A CN 114655978 B CN114655978 B CN 114655978B
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CN114655978A (en
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高文华
彭靖俊
陈佳阳
郑德论
林镇彬
陈耀文
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Shantou University
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    • C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
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Abstract

The invention discloses preparation and application of a three-component sulfide photoelectric material with a hollow hierarchical heterostructure, which is used for coordination polymer Cd 3 (C 3 N 3 S 3 ) 2 The material is used as a self-template material, and three-component ZnIn with a hollow hierarchical heterostructure is prepared by a one-step solvothermal synthesis method 2 S 4 /CnIn 2 S 4 /CdS material. The method comprises the following steps: (1) first, octahedron with adjustable size is prepared. (2) Zn (NO) 3 ) 2 ·6H 2 O，InCl 3 ·4H 2 O and thioacetamide as ZnIn 2 S 4 Precursor of component and self-template Cd 3 (C 3 N 3 S 3 ) 2 The material is subjected to solvothermal reaction to obtain three-component ZnIn with a hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 /CdS (ZIS/CIS/CdS-HHOC). The preparation method omits the complicated process of removing the template, is extremely easy to operate, and provides a method for preparing the photoelectric active material with excellent photoelectric conversion performance. The prepared material has large specific surface area, matched energy band structure and tightly contacted interface, high light utilization rate, and thin shell layer and nano sheet, and can degrade CO in photocatalysis 2 The method has extremely wide application prospect in the fields of reduction, hydrogen production, photo synthesis, antibiosis and photoelectric sensing.

Description

Preparation and application of three-component sulfide photoelectric material with hollow hierarchical heterostructure
Technical Field
The invention belongs to the field of novel nano functional materials and photoelectrochemistry, and particularly relates to preparation and application of a three-component sulfide photoelectric material with a hollow hierarchical heterostructure.
Background
Photoelectrochemistry is a powerful discipline developed from electrochemistry and is aimed at exploring the conversion of light energy into electrical energy and the interconversion of electrical energy and chemical energy. The working principle of photoelectrochemistry is to study the oxidation or reduction reaction condition, rule and application of substance molecules or ions in a ground state or an excited state on the basis of combining photochemistry and electrochemistry, thereby realizing the technical means of substance energy conversion, energy utilization, analysis and detection and other purposes. The photoelectrochemical reaction process mainly comprises the following steps: the photoelectric active material can excite electrons (participate in reduction reaction) and holes (participate in oxidation reaction) under the irradiation of light, and the generated photo-generated electron-hole pairs are separated by the electric field of the photoelectric active material/electrolyte junction and then undergo oxidation-reduction reaction with ions in the solution, so that the photoelectric active material has the advantages of environmental protection, low cost, high safety, mild reaction conditions and the like. Since most photoelectrochemical systems such as photocatalysis, PEC water of decomposition, PEC biosensors and the like are based on high-activity photo-generated electron-hole pairs, a photoactive material with excellent photoelectric conversion capability plays a key role in the photoelectrochemical systems. To date, a large number of researchers have been devoted to developing excellent photoactive materials and have proposed the use of materials such as transition metal chalcogenides, metal organic frameworks, transition metal carbides/nitrides to achieve the desired PEC systems. Cadmium sulfide (CdS) has been extensively studied as an n-type semiconductor and ideal photoactive material due to its strong visible light absorption, high electron mobility, suitable band structure driving redox reactions and adjustable morphology. However, cdS of bulk or single-component structure suffers from inherent defects such as high photo-corrosion and rapid recombination of photo-excited electron-hole pairs, resulting in limited photoelectric activity.
In recent years, nanomaterials having different hollow hierarchical structures have attracted great attention in both basic research and practical applications in the PEC field. Hollow structures, particularly nanomaterials with hierarchical structures, have many unique properties compared to bulk structural materials. For example, the internal cavity structure provides multiple light scattering effects, increasing light collection efficiency, while the outer shell reduces the distance for charge transport and charge directional separation. On the other hand, a larger specific surface area provides more active sites for surface-related photooxidation-reduction reactions. In addition, the incorporation of reasonable components into a hollow nanostructure would be advantageous for further improvement of photoelectric conversion efficiency due to the synergistic properties between the components. However, creating nanomaterials with hollow hierarchical structures typically involves lengthy and complex synthesis steps. In particular, the integration of hybrid materials with tandem band structures and tight interfaces into a hollow framework has not been fully investigated due to the lack of efficient manufacturing strategies.
Disclosure of Invention
The invention aims to provide a Cd-based optical fiber 3 (C 3 N 3 S 3 ) 2 Derived three-component ZnIn with hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 The preparation method omits the complicated process of removing the template, is extremely easy to operate, and provides a method for preparing the photoelectric active material with excellent photoelectric conversion performance. The prepared three-component ZnIn with the hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 The CdS material has large specific surface area, matched energy band structure and tightly contacted interface, high light utilization rate, and thin shell layer and nano sheet, and can be used for photocatalytic degradation, CO 2 The Jing Ben invention provides a heuristic strategy for designing nano materials with excellent photoelectric activity and has extremely wide application in the fields of reduction, hydrogen production, photo synthesis, antibiosis and photoelectric sensingHas potential application value in chemical catalysis, energy storage, environmental protection and biochemical sensing.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a three-component sulfide photoelectric material with a hollow hierarchical heterostructure comprises the following steps:
A. preparation of octahedral coordination Polymer Cd 3 (C 3 N 3 S 3 ) 2 ；
B. The Cd is treated with 3 (C 3 N 3 S 3 ) 2 Adding the mixture into the solution, and dispersing to obtain a suspension;
C. zn (NO) 3 ) 2 ·6H 2 O、InCl 3 ·4H 2 Sequentially adding the solution of O and thioacetamide into the suspension, stirring, and putting the suspension into a reaction kettle for reaction after stirring is completed to obtain yellow precipitate;
D. washing and drying the yellow precipitate to obtain the three-component ZnIn with the hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 /CdS material.
Preferably, the method comprises the following steps:
A. obtaining the Cd 3 (C 3 N 3 S 3 ) 2 ；
B. The Cd is treated with 3 (C 3 N 3 S 3 ) 2 Adding the mixture into a mixed solution of ethanol and glycerol, and dispersing to obtain a suspension;
C. zn (NO) 3 ) 2 ·6H 2 Ethanol solution of O, inCl 3 ·4H 2 Sequentially adding the ethanol solution of O into the suspension, magnetically stirring for 20min, adding the ethanol solution of thioacetamide, magnetically stirring for half an hour, and then placing the mixture into a reaction kettle for reaction after stirring is completed to obtain yellow precipitate;
D. washing and drying the yellow precipitate to obtain the three-component ZnIn 2 S 4 /CnIn 2 S 4 /CdS material.
Through strong magnetic stirring at high rotation speed (900-1100 rpm) for 20min and Cd 3 (C 3 N 3 S 3 ) 2 Dangling bonds of the surface will be Zn 2+ And In 3+ Ion aggregation to Cd 3 (C 3 N 3 S 3 ) 2 A surface; then adding the thioacetamide ethanol solution, and magnetically stirring for half an hour at 400-600 rpm.
Cd 3 (C 3 N 3 S 3 ) 2 The template material has adjustable microcosmic morphology, can provide a sulfur source and a cadmium source, and is beneficial to the morphology regulation and control of the later-stage material and the regulation and control of heterojunction components. During the solvothermal reaction, cd 3 (C 3 N 3 S 3 ) 2 The template material is thermally degraded to generate Cd 2+ And S is 2- Then slowly forming CdS, finally completely disappearing the template material when the reaction is finished to obtain pure three-component ZnIn with hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 /CdS material. Through regulating and controlling the reaction time and the precursor dosage, the smart coordination of the growth and the microcosmic morphology regulation of different components is realized, and finally, the pure three-component ZnIn with a hollow hierarchical heterostructure is obtained 2 S 4 /CnIn 2 S 4 /CdS material.
Preferably, in the step B, the volume ratio of the ethanol to the glycerol in the mixed solution of the ethanol and the glycerol is 3.5:1; in step B, the Cd 3 (C 3 N 3 S 3 ) 2 The mass volume ratio of the mixed solution of ethanol and glycerol is 30-85 mg: 15-35 mL.
The ethanol solvent is mainly used for controlling Cd 3 (C 3 N 3 S 3 ) 2 The degradation rate of the template material is favorable for forming a hollow heterojunction structure. If in an aqueous system, cd 3 (C 3 N 3 S 3 ) 2 The degradation speed of the template material is too high, the morphology can collapse, and the regulation and control are difficult. While the effect of glycerol is to increase the dispersibility of the material in favor of uniformity of the size of the synthesized powder.
Generally weighing 36.5-82.2 mg (0.06 m)mol～0.138mmol)Cd 3 (C 3 N 3 S 3 ) 2 Dispersed into the ethanol glycerol mixed solution (total volume 27 mL) to form a homogeneous pale yellow suspension. More preferably, cd 3 (C 3 N 3 S 3 ) 2 The mass of the powder was 54.8mg (0.09 mmol), and the reaction time was 12 hours.
Preferably, in step C, zn (NO 3 ) 2 ·6H 2 The concentration of the ethanol solution of O is 0.04 to 0.20mol.L -1 ，InCl 3 ·4H 2 The concentration of the ethanol solution of O is 0.08 to 0.40 mol.L -1 The concentration of the thioacetamide ethanol solution is 0.16 to 0.80 mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the In step C, cd 3 (C 3 N 3 S 3 ) 2 、Zn(NO 3 ) 2 ·6H 2 O、InCl 3 ·4H 2 The molar ratio of O to thioacetamide is 1:1:1:2.
preferably, in the step C, the reaction kettle is a polytetrafluoroethylene reaction kettle and reacts for 6-16 hours at 160 ℃ with a heating rate of 5 ℃/hour; in step D, the yellow precipitate is washed three times with ethanol and then dried in a vacuum environment at 60 ℃ for 12 hours to obtain the three-component ZnIn 2 S 4 /CnIn 2 S 4 /CdS material.
The pale yellow precipitate obtained by the reaction is treated with ethanol by three washing centrifugal cycles and finally dried for 12 hours in a vacuum environment at 60 ℃.
Preferably, the specific operation of step a includes:
a1, cdCl 2 Dissolving in ultrapure water and stirring to form transparent solution A;
a2, dissolving cyanuric acid in a NaOH solution to form a yellow solution B;
a3, under the condition of strong stirring, dropwise adding the yellow solution B into the transparent solution A, and slowly stirring for reaction after the dropwise addition is completed;
a4, washing and drying after the reaction is finished to obtain the Cd 3 (C 3 N 3 S 3 ) 2 。
Preferably, the specific operation of step a includes:
a1, cdCl 2 According to the mass volume ratio of 1.8332 g-4.1247 g: 80-180 mL of the transparent solution A is formed by dissolving the transparent solution A in ultrapure water and stirring;
a2, mixing the cyanuric acid according to the mass volume ratio of 1.1818 g-2.6591 g:70 mL-150 mL of the solution is dissolved in 0.15 mol.L -1 The yellow solution B is formed in NaOH solution;
a3, under the condition of strong stirring, according to CdCl 2 The yellow solution B is dropwise added into the transparent solution A according to the mass ratio of the cyanuric acid to the cyanuric acid of 3:2, and the mixture is slowly stirred at room temperature for reaction for 12-24 hours after the dropwise addition is completed;
a4, after the reaction is finished, washing with ethanol, centrifugally collecting, circulating for three times, and finally drying to obtain the Cd 3 (C 3 N 3 S 3 ) 2 。
Cd-based photoelectric material prepared by preparation method of three-component sulfide material with hollow hierarchical heterostructure 3 (C 3 N 3 S 3 ) 2 Derived three-component ZnIn with hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 /CdS material.
As described above, three components ZnIn 2 S 4 /CnIn 2 S 4 The use of a/CdS material, characterized in that it is used for photocatalytic degradation of CO 2 Reduction, hydrogen production, photosynthesis, antimicrobial and photoelectric sensing fields.
Preferably, the method is used for quantitative detection of the biomarker CA19-9 by photoelectrochemical sensing; the bacteria used for resisting bacteria include one or more of Escherichia coli, staphylococcus aureus, and Candida albicans.
Compared with the prior art, the implementation of the invention has the following beneficial effects:
(1) The invention takes coordination polymer as self-template, and prepares three-component ZnIn with hollow hierarchical heterostructure by one-step solvothermal synthesis method 2 S 4 /CnIn 2 S 4 Cd material, cd as template after preparation 3 (C 3 N 3 S 3 ) 2 The preparation method omits the complicated process of removing the template, is extremely easy to operate, and opens up a new way for preparing the material with the hollow hierarchical heterostructure rapidly.
(2) The invention first prepares octahedra with adjustable size. Reuse of Zn (NO) 3 ) 2 ·6H 2 O，InCl 3 ·4H 2 O and thioacetamide as ZnIn 2 S 4 Precursor of component and self-template Cd 3 (C 3 N 3 S 3 ) 2 The material is subjected to solvothermal reaction to obtain three-component ZnIn with a hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 /CdS (ZIS/CIS/CdS-HHOC), three-component ZnIn of the hollow graded heterostructure is realized 2 S 4 /CnIn 2 S 4 And (3) accurately regulating and controlling the morphology of the CdS material.
(3) The invention combines the advantages of hollow graded hetero-materials and composite hetero-junction materials. Three-component ZnIn with hollow hierarchical heterostructure prepared by solvothermal reaction derived and regulated by coordination polymer 2 S 4 /CnIn 2 S 4 the/CdS material has multiple light absorption effects, a matched band structure, a tightly contacted heterojunction interface, a large specific surface area, a large number of exposed active sites, a thin shell layer, and nanoplatelet micro-units. The multiple light absorption effect enables the hollow three-component ZnIn to be realized 2 S 4 /CnIn 2 S 4 the/CdS material has higher light absorption efficiency, and generates more photogenerated carriers under illumination. The tightly contacted heterojunction interface and the matched energy band structure enable the hollow three-component ZnIn 2 S 4 /CnIn 2 S 4 the/CdS material has the ability to rapidly separate the photogenerated carriers. On the other hand, a large number of exposed active sites, high light utilization, thin shell layers and nanoplatelet microelements are also beneficial for the surface-related photoredox reactions. Overall, the synergistic effect of the morphology of the ZIS/CIS/CdS-HHOC material with the appropriate multicomponent characteristics enhances its overall photoemission. Because the invention has hollow gradingThree-component ZnIn heterostructure 2 S 4 /CnIn 2 S 4 the/CdS material has wide application potential in the field of photoelectrochemistry.
(4) The method is simple and convenient, has low cost, is easy to operate and control, has good repeatability and lower growth temperature, and the highest growth temperature is only 160 ℃, thereby reducing the requirement on equipment; the performance is excellent, and the large-scale application is expected to be realized.
(5) Based on three-component ZnIn with hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 The photoelectrochemical sensing platform constructed by the CdS material realizes detection of the biomarker CA19-9, and shows good linear range (0.001U mL -1 To 10U mL -1 ) And detection limit (0.76 mU mL) -1 ). Compared with the traditional detection method, the biological photoelectrochemical detection method provided by the invention has the characteristics of simple operation, simple equipment, high sensitivity, low detection cost and the like.
Drawings
FIG. 1 is a three-component ZnIn with a hollow hierarchical heterostructure according to the invention 2 S 4 /CnIn 2 S 4 Schematic diagram of preparation process of CdS material;
FIG. 2 is a diagram of (A) Cd of the invention 3 (C 3 N 3 S 3 ) 2 (B-D) ZIS/CIS/CdS-HHOC (E-F) ZIS/CIS/CdS-HHOC TEM image, (G) ZIS/CIS/CdS-HHOC element distribution image;
FIG. 3 is an XRD spectrum of a ZIS/CIS/CdS-HHOC material (A) of the invention; (B) XPS full spectrum of ZIS/CIS/CdS-HHOC; (C-F) ZIS/CIS/CdS-HHOC high resolution XPS spectrum;
FIG. 4 is a TEM image of (A) ZIS/CIS/CdS-HHOC (ZIS/CIS/CdS-HHOC heterostructure) of the ZIS/CIS/CdS-HHOC material of the invention; (B-C) ZIS/CIS/CdS-HHOC HRTEM images and SAED images; (D) XRD pattern of intermediate; (E) ZIS/CIS/CdS-HHOC synthesized in an aqueous system; (F) ZIS/CIS/CdS-HHOC, cdS and Cd 3 (C 3 N 3 S 3 ) 2 An XRD pattern of (a);
FIG. 5 shows (A-C) ZnIn of the ZIS/CIS/CdS-HHOC material of the invention 2 S 4 、CdIn 2 S 4 Tauc equation diagram of CdS component, (D-F) ZnIn 2 S 4 、CdIn 2 S 4 XPS valence spectrum of CdS component;
FIG. 6 is a graph of (A) transient photocurrent, (B) photoelectric conversion efficiency, (C) solid UV absorbance spectra, (D) Mott-Schottky test patterns, (E) Bode phase angle characterization, (F) CIMVS, (G) electrochemical impedance, (H) photoluminescence test, (I) CIMPS characterization of the ZIS/CIS/CdS-HHOC material of the present invention;
FIG. 7 is a graph of (A) photocurrent response of a ZIS/CIS/CdS-HHOC material sensing application of the present invention, (B) Nyquist plot: (a) ZIS/CIS/CdS-HHOC, (b) ZIS/CIS/CdS-HHOC/CS/GA, (C) ZIS/CIS/CdS-HHOC/CS/GA/Ab, (D) ZIS/CIS/CdS-HHOC/CS/GA/Ab/BSA, (e) ZIS/CIS/CdS-HHOC/CS/GA/Ab/BSA/Ag, (C) linear regression equations for detecting CA19-9 at different concentrations, (D-F) sensor selectivity, stability and reproducibility.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1
Three-component ZnIn with hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 The preparation of the/CdS material, as shown in FIG. 1, mainly comprises the following steps:
(1) Preparation of Cd 3 (C 3 N 3 S 3 ) 2 ；
Preparation of Cd by stirring at room temperature 3 (C 3 N 3 S 3 ) 2 Octahedron, mainly comprising: 2.7498g of CdCl was weighed out 2 Dissolving in 100mL of ultrapure water solution, stirring to form transparent solution A, weighing 1.7727g of cyanuric acid, and dissolving in 100mL 0.015M NaOH to form solution B; dropwise adding the solution B into the solution A under the condition of strong stirring; then, the mixture is stirred vigorously for 5 minutes, and the mixture reacts for 12 hours under slow stirring at room temperature; after completion of the reaction, the white product obtained was washed by centrifugation and collected by washing with ethanol (three cycles) Finally, it was placed in a vacuum oven at 60℃for 12 hours. Scanning Electron Microscopy (SEM) to observe the synthesized Cd 3 (C 3 N 3 S 3 ) 2 The size and morphology of Cd as shown in FIG. 2A 3 (C 3 N 3 S 3 ) 2 The size of the octahedron is about 800 nm. Demonstration of Cd by XRD characterization analysis 3 (C 3 N 3 S 3 ) 2 Has a good crystal structure (fig. 4F). At the same time, XRD characterization analysis of the intermediate product showed that ZnIn preferentially grown 2 S 4 The layer can be prepared by combining Cd 3 (C 3 N 3 S 3 ) 2 Degradation of Cd produced 2+ The reaction part is changed into CdIn 2 S 4 A three-component graded heterojunction structure is formed (fig. 4D).
(2) Synthesis of three-component ZnIn with hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 CdS material
54.8mg Cd was added 3 (C 3 N 3 S 3 ) 2 Adding the mixture into a mixed solution of 21mL of ethanol and 6mL of glycerol, and performing ultrasonic dispersion for 10 minutes to obtain Cd 3 (C 3 N 3 S 3 ) 2 Then 1mL of Zn (NO) 3 ) 2 ·6H 2 O(0.04mol·L -1 ) And InCl 3 ·4H 2 O(0.08mol·L -1 ) Adding mother solution into the suspension and stirring for 10 minutes; next, 1mL of thioacetamide mother liquor (0.16 mol.L) -1 ) And magnetically stirred for half an hour. After stirring, the mixture is put into a polytetrafluoroethylene reaction kettle and reacted for 12 hours at 160 ℃ with a heating rate of 5 ℃/hour. The resulting yellow precipitate was washed three times with ethanol and collected by centrifugation, and then dried in a vacuum environment at 60 ℃ for 12 hours. SEM and TEM characterization results of the prepared ZIS/CIS/CdS-HHOC show that the prepared octahedral structure still maintaining the template has a large cavity structure and nano-sheet micro units (figures 2B-F), and the enlarged TEM image further confirms the hierarchical heterostructure (figure 4A). The particle size of ZIS/CIS/CdS-HHOC is uniformly distributed at about 1 μm, and the thickness of the nanosheet micro-unit is about 15 nm. While the water bodyThe particle size distribution of ZIS/CIS/CdS-HHOC (FIG. 4E) synthesized under the system was about 5. Mu.m. As shown In FIG. 2G, the element surface scanning pattern shows that the prepared ZIS/CIS/CdS-HHOC mainly contains four elements of Zn, in, cd and S and is uniformly distributed; selective electron diffraction analysis showed that the material prepared was polycrystalline and demonstrated ZnIn 2 S 4 、CnIn 2 S 4 And the presence of CdS components (fig. 2G). XRD characterization of ZIS/CIS/CdS-HHOC in FIG. 3A did not reveal the removal of ZnIn 2 S 4 、CnIn 2 S 4 And a hetero peak other than CdS component, indicating that Cd as a template was reacted 3 (C 3 N 3 S 3 ) 2 Is completely removed. As shown In FIGS. 3B-F, XPS test was performed on sample ZIS/CIS/CdS-HHOC to further confirm the composition and chemical valence of the sample, demonstrating the presence of Zn, in, cd and S elements.
Example 2
Based on three-component ZnIn with hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 Photoelectrochemical sensor of/CdS material
(1) Cleaning of ITO electrode and preparation of modified electrode
Preparation of ZIS/CIS/CdS-HHOC/ITO electrode: ITO conductive substrate (3.0X1.0 cm) 2 ) NaOH placed in 1M (Vwater: vacetone=1: 1) Ultrasonic treatment is carried out for 30min in the solution, then the solution is respectively washed by absolute ethyl alcohol and ultrapure water for three times, and then the solution is placed in a 65 ℃ oven for drying for 45min. And (5) placing the ITO conductive substrate obtained by cleaning in a shade place for preservation. 3mg of the prepared ZIS/CIS/CdS-HHOC powder was weighed out and dispersed into 1mL of ultrapure water, and stirred for 6 hours to mix. 10 mu L of the mixture with the concentration of 3 mg.mL is taken -1 Is dripped on the pretreated ITO conductive glass, and the active area is 0.0961cm 2 After drying in an oven at 60℃for 12h, it was cooled to room temperature to give a stable ZIS/CIS/CdS-HHOC/ITO electrode.
(2) Preparation of chemical biological immunity sensor
The resulting ZIS/CIS/CdS-HHOC/ITO modified electrode was added dropwise with 8. Mu.L of 0.1wt% Chitosan (CS), and dried at 60℃for 30 minutes; then 8 mu L of 2.5wt% glutaraldehyde solution is added dropwise, and inoculated for 1 hour at room temperatureWhen PBS buffer was used, excess Glutaraldehyde (GA) was washed off; subsequently, 6. Mu.L of 20. Mu.g.mL was added dropwise -1 Incubating the CA19-9antibody solution for 2 hours at room temperature, and washing off excessive CA19-9antibody by using a PBS buffer solution to obtain a CA19-9 anti-body/GA/CS/ZIS/CIS/CdS-HHOC/ITO electrode; then, 6. Mu.L of 0.5wt% Bovine Serum Albumin (BSA) solution was dropped to block the non-specific site, and the surface of the obtained BSA/CA19-9 anti-body/GA/CS/ZIS/CIS/CdS-HHOC/ITO electrode was washed with PBS solution to obtain an immunosensor electrode.
(3) Photoelectrochemical biosensor for detecting biomarker CA19-9
mu.L was added at a concentration of 0.001U mL -1 To 10U mL -1 CA19-9 of (B) was added dropwise to BSA/CA19-9 anti-body/GA/CS/ZIS/CIS/CdS-HHOC/ITO electrode, respectively, and incubated at room temperature for 2h. Finally, PBS containing 12mL of 0.1M ascorbic acid (pH=7.4, 0.1mol L -1 ) In a quartz cell of the solution, an ITO electrode is used as a working electrode, a saturated Ag/AgCl is used as a reference electrode, a platinum wire is used as a counter electrode, and a German Zahner electrochemical workstation is used for photoelectrochemical analysis.
FIG. 7 (C) shows the correspondence between CA19-9 and the photocurrent response value obtained in the present invention, and it can be seen from the graph that the photocurrent gradually decreases with increasing CA19-9 concentration. As in FIG. 7 (C), at 0.001U mL -1 To 10U mL -1 In the concentration interval of (2), the logarithmic value of the CA19-9 concentration and the photocurrent response value show good linear relation, and the detection limit can reach 0.76mU mL -1 . Next, we explored the specificity of the sensor by comparing transient current responses of potentially interfering proteins, including cancer antigen 15-3 (CA 15-3), cardiac troponin (cTnI), alpha fetoprotein (PSA), and cancer antigen (CEA). FIG. 7D shows that the cells were incubated with CA19-9 (0.01U mL -1 ) Is incubated with interferents (0.01 ng mL) -1 Or 0.01U mL -1 ) No significant change in sensor photocurrent, indicating good selectivity of the sensor. In addition, the photocurrent response of the sensor at 20 on/off irradiation cycles remained stable, and the Relative Standard Deviation (RSD) of the photocurrent peak was 0.43%, indicating good stability of the sensor (fig. 7E). Finally, by constructing 5 PEC sensors individuallyIncubation with 0.1U mL -1 CA19-9 and parallel measurement of photocurrent (fig. 7F) with no significant difference in photocurrent response (rsd=3.58%) demonstrated that the reproducibility of the sensor was reliable.
Example 3
Three-component ZnIn with hollow hierarchical heterostructure prepared in example 1 2 S 4 /CnIn 2 S 4 Use of/CdS material in photocatalytic hydrogen production.
Catalyst performance was tested using a medium teaching gold source photocatalytic reaction system and gas chromatography, and 50mg of ZIS/CIS/CdS-HHOC material prepared in example 1 was dispersed in a solution containing 90vt% deionized water and 10vt% lactic acid. The photocatalysis reaction is carried out in 250mL closed reaction, and before the reaction, nitrogen is introduced for 30min to remove redundant air in the system. A300W Xe lamp is used as a light source, and a 420nm cut-off filter is assembled to filter ultraviolet light in the light source. During the reaction, the suspension was continuously stirred and thoroughly exposed to light. In addition, the reaction temperature is controlled to be about 25 ℃ by externally connecting condensed water. Stirring is continuously carried out in the reaction process, and the generated hydrogen amount is measured by a gas chromatograph every 60 min. Test results show that the ZIS/CIS/CdS-HHOC material prepared by the invention has more excellent photo-hydrogen production activity than the material prepared by the invention, and the invention can lead the photo-catalytic hydrogen production rate to be the composite material ZnIn prepared by simple physical mixing 2 S 4 -CnIn 2 S 4 5.56mmol g of-CdS -1 h -1 To 20.58mmol g -1 h -1 The performance is improved by 3.7 times. The ZIS/CIS/CdS-HHOC material prepared by the invention has the characteristics of multiple light absorption effect, large specific surface area, large exposed active sites, thin shell layers, nanosheet micro units, compact heterojunction interfaces and energy band structures matched among components, and is beneficial to improving the efficiency of the material in photoelectrochemical hydrogen production.
Example 4
Three-component ZnIn with hollow hierarchical heterostructure prepared in example 1 2 S 4 /CnIn 2 S 4 the/CdS material is applied to the visible light catalytic degradation of p-chloronitrobenzene (p-CNB).
And (3) taking a 300W Xe lamp as a light source, assembling a 420nm cut-off filter to filter ultraviolet light in the light source, and performing a photocatalytic degradation experiment, wherein the distance between a sample and the light source is 10 cm. 50mg of the photocatalyst was added to 50mL of a p-CNB solution at a concentration of 0.1mM, and stirred in a dark room for 1 hour to reach adsorption equilibrium. Then, the Xe lamp was turned on to irradiate for 6 hours to perform a photocatalytic reaction. Measuring p-CNB concentration by High Performance Liquid Chromatography (HPLC) with mobile phase of methanol/water (70/30) and flow rate of 1.0 mL-min -1 The detection wavelength was 280nm. The anion concentration in the degradation process of p-CNB is detected by adopting an IC-600 ion chromatography, TOC in the degradation process is analyzed by adopting a TOC analyzer, and an intermediate product is monitored by adopting liquid-liquid extraction GC-MS. The ZIS/CIS/CdS-HHOC material prepared in example 1 was measured to have a TOC degradation rate of 50.5% for p-CNB within 6 hours. The ZIS/CIS/CdS-HHOC material prepared by the method has multiple light absorption effects, so that the ZIS/CIS/CdS-HHOC material with a hollow hierarchical heterostructure has higher light absorption efficiency, and generates more photo-generated carriers under illumination. The large specific surface area and rich active sites enable the three-component ZnIn with a hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 The CdS material can efficiently adsorb pollutants and accelerate the catalytic reaction. On the other hand, the thin shell layer and the nano-sheet micro-unit are also beneficial to the surface-related photooxidation-reduction reaction, and the separation and transmission of the photo-generated carriers are accelerated by the tight heterojunction interface and the energy band structure matched with the components.
Example 5
Three-component ZnIn with hollow hierarchical heterostructure prepared in example 1 2 S 4 /CnIn 2 S 4 the/CdS material is applied to visible light catalytic degradation of antibiotics.
And (3) taking a 300W Xe lamp as a light source, assembling a 420nm cut-off filter to filter ultraviolet light in the light source, and performing a photocatalytic degradation experiment, wherein the distance between a sample and the light source is 10 cm. 50mg of photocatalyst was added to 100mL of the solution at a concentration of 25mg L -1 Is stirred in a dark room for 90min to reach adsorption equilibrium. Taking 3mL of antibiotic every 12minThe solutions were centrifuged and the extent of degradation of tetracycline, aureomycin, demeclocycline, doxycycline and oxytetracycline at different times was determined by the intensity changes of the absorbance peaks at 356nm,272nm, 365 nm,345nm and 353 nm. And (3) recovering the catalyst for experiments, filtering and washing, drying, then performing secondary operation, and testing the stability of the composite material. Three-component ZnIn with hollow hierarchical heterostructure prepared in example 1 was measured 2 S 4 /CnIn 2 S 4 The degradation rate of the/CdS material for different antibiotics within 120min is 95%.
Example 6
20mg of prepared three-component ZnIn with a hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 5ml of Triethanolamine (TEOA) and 45ml of ultrapure water were dispersed in a quartz tube and connected to a gas closed circulation system. Before illumination, the suspension was evacuated and then backfilled with several carbon dioxide until the air was completely removed. And (3) using a 300W Xe lamp as a light source, assembling a 420nm cut-off filter to filter ultraviolet light in the light source, wherein the distance between a sample and the light source is 10cm, and calibrating the average intensity of radiation by a spectrum radiometer to perform a photoreduction experiment. During the reaction, the quartz tube was kept at room temperature by circulating water of a metal jacket. Analysis of CO and CH by off-line gas chromatography 4 Is contained in the composition. Three-component ZnIn with hollow hierarchical heterostructure after reaction 2 S 4 /CnIn 2 S 4 the/CdS material was centrifuged and washed with water, and the recovered sample was further used for cycling experiments at 60℃after vacuum drying. The main gas products of the gas chromatographic analysis are CO and CH 4 The liquid phase was detected by ion chromatography to contain trace amounts of HCOOH. The final carbon monoxide yield was 16.58. Mu. Mol. G -1 ·h -1 ，CH 4 Yield 1.05. Mu. Mol g -1 ·h -1 。
Example 7
Three-component ZnIn with hollow hierarchical heterostructure prepared in example 1 2 S 4 /CnIn 2 S 4 the/CdS material is applied to the environmental protection shaving board antibiosis.
The antibacterial performance of the shaving board is improved by the composite antibacterial additive composed of chitosan, tourmaline powder and the prepared ZIS/CIS/CdS-HHOC material. Specifically, the mass ratio of the chitosan to tourmaline powder to ZIS/CIS/CdS-HHOC material is 10:2:1, mixing and adding the mixture into wood fibers, and finally bonding the plates through an environment-friendly formaldehyde-free adhesive to obtain the environment-friendly antibacterial shaving board. Through tests, the composite antibacterial additive based on ZIS/CIS/CdS-HHOC material can obviously improve the antibacterial performance of the prepared shaving board, negative oxygen ions released by ZIS/CIS/CdS-HHOC material can enable biological cells to carry negative charges so as to inhibit the attack capability of viruses on the cells, and excellent antibacterial effects (the antibacterial rates of strains such as escherichia coli, staphylococcus aureus and candida albicans respectively reach 98.3%,97.8% and 98.1%) are provided for the board.
Example 8 application example of antibacterial fiber
The prepared ZIS/CIS/CdS-HHOC material is used as an antibacterial agent, and HDPE resin is used as a raw material to prepare the antibacterial fiber. The dosage of the prepared ZIS/CIS/CdS-HHOC material is 1% -5% of that of HDPE resin, the HDPE resin and ZIS/CIS/CdS-HHOC material are uniformly mixed and added into a charging barrel with the temperature of about 230 ℃, extrusion parameters of an extruder are set, wherein the melt pressure of the extruder is 10.0-12.0 MPa, the residence time of the material in a spinning machine is 10-12min, the extrusion capacity is 2.0kg/h, the screw rotating speed is 23r/min, the length-diameter ratio L/D=25 of the extruder screw is 10 times, and the monofilament fineness is 420 denier. Extruding and spinning to obtain HDPE monofilament with antibacterial performance, and weaving filter net with weaving density of 15×15/cm in air freshener 2 Is a conventional size of (c) a. And (5) performing an antibacterial test on the prepared filter screen. The results show that the antibacterial rates of the bacteria such as escherichia coli, staphylococcus aureus, candida albicans and the like respectively reach 98.3%,99.1% and 98.6%.
EXAMPLE 9 application example of antimicrobial precoating film
The antibacterial barrier of BOPP (polypropylene film) composite film is modified by using polyvinyl alcohol, nano calcium carbonate, prepared ZIS/CIS/CdS-HHOC material and other components with different proportions and concentrations to form nano modified PV with optimal oxygen, water and antibacterial propertiesAnd A, pre-coating film. Specifically, firstly, 3:1:1, physically mixing nano calcium carbonate, molybdenum trioxide and prepared ZIS/CIS/CdS-HHOC powder. Then premixing raw material components of polyvinyl alcohol, a surfactant (prepared from succinic anhydride, sorbitan and polyethylene glycol), molybdenum trioxide, a regulator (methanol or ethanol), borax and water (deionized water, distilled water or purified water), and then adding the prepared modified nano powder, stirring and keeping the mass ratio of the powder to be 2.5%. And finally, preparing the antibacterial barrier BOPP composite film by matching the raw material components of the nano modified PVA mixed solution with the processes of uniform coating modes with different coating amounts and coating times, curing at different temperatures and times and the like. According to experimental analysis, the oxygen permeability of the prepared nano modified BOPP composite film antibacterial barrier film is less than or equal to 5cm 3 /(m 2 24 h.0.1 MPa), water vapor transmission rate of 4.5 g/(m) 2 24 h), and can effectively inhibit the proliferation of bacteria such as escherichia coli, staphylococcus aureus, candida albicans and the like.
Example 10 application example of antibacterial anti-fog masterbatch
ZIS/CIS/CdS-HHOC material is taken as an antibacterial active material, and is uniformly mixed with polypropylene or polyethylene, an antioxidant (antioxidant 1010), a coupling agent (silane coupling agent) and a dispersing agent (polypropylene wax) according to different proportions, and an antibacterial master batch with antibacterial performance and good processing performance is obtained after extrusion, cooling and granulating. The preparation method comprises the following steps: the antibacterial and antifogging master batch is prepared by uniformly mixing 55% of polyethylene, 34% of ZIS/CIS/CdS-HHOC material, 4% of antioxidant 1010, 1% of silane coupling agent, 2% of antifogging agent and 4% of polypropylene wax by weight percent, adding the mixture into a hopper with the temperature of 80-95 ℃ for heating for 1 hour, extruding the mixture in a double screw at the temperature of 180-210 ℃, cooling and granulating the extruded mixture. And finally, mixing the obtained antibacterial and anti-fog master batch with polypropylene according to the mass ratio of 2:100, and performing melt extrusion and biaxial stretching to prepare the BOPP film with antibacterial and anti-fog effects. The antibacterial performance test (escherichia coli, staphylococcus aureus and candida albicans are used as test strains) shows that the antibacterial rate of the three strains respectively reaches 98.5 percent (escherichia coli), 98.2 percent (staphylococcus aureus) and 99.0 percent (candida albicans). The prepared refrigerator door sealing strip has good antibacterial performance and can effectively inhibit the propagation of bacteria such as escherichia coli, staphylococcus aureus, candida albicans and the like.
Example 11 application example of antibacterial paint
The cationic emulsion (cationic polyurethane emulsion), the curing agent (isocyanate), the prepared ZIS/CIS/CdS-HHOC material, the dispersing agent (alkyl fatty amine), the leveling agent (organic silicon), the thickening agent (acrylic acid) and water (deionized water, distilled water or purified water) are ultrasonically stirred and mixed to form the antibacterial coating with long-acting sterilization and bacteriostasis functions. The method comprises the following steps: 1) Adding 0.8g of curing agent and 20g of deionized water into a beaker, carrying out ultrasonic treatment for 1 hour, and then stirring and dispersing uniformly to prepare a curing agent pre-dispersion liquid; 2) Adding the curing agent pre-dispersion liquid into 9.5g of cationic emulsion, and continuously stirring and dispersing uniformly; 3) Adding 2.7g of ZIS/CIS/CdS-HHOC material into the dispersion liquid obtained in the step 2, and continuously stirring and dispersing uniformly; 4) And (3) respectively adding 0.05g of flatting agent, 0.1g of dispersing agent and 0.3g of thickening agent into the dispersion liquid obtained in the step (3), and stirring and dispersing uniformly to prepare the antibacterial coating. And (3) selecting escherichia coli, staphylococcus aureus and candida albicans as test strains for the antibacterial performance of the prepared coating. By measurement, the antibacterial rates of the three strains respectively reach 98.5 percent (escherichia coli), 97.9 percent (staphylococcus aureus) and 98.3 percent (candida albicans), which shows that the prepared antibacterial coating has good antibacterial performance.
5. Three-component ZnIn with hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 CdS material application characterization
Transient photocurrent was taken to study the modification process of the photoelectrochemical aptamer sensor. As shown in fig. 7A, the prepared ZIS/CIS/CdS-HHOC/ITO electrode exhibited enhanced photocurrent signals due to the advantages of having multiple light absorption effects, a matched band structure, a tightly contacted heterojunction interface, a large specific surface area, a large number of exposed active sites, a thin shell layer, and a nanoplatelet micro-unit. After stepwise modification of chitosan, glutaraldehyde, CA19-9antibody, BSA and CA19-9 antigen specific binding, the electrode photocurrent was significantly reduced. This is due to the insulating and steric effects of these modified materials, which hinder the reaction between photoexcited holes at the electrode surface and diffused AA.
Characterization of electrode modification Using electrochemical impedance
To further demonstrate the modification process of the sensor, [ Fe (CN) 6 ] 3-/4- Electrochemical Impedance (EIS) tests were performed as redox probes under visible light. The value of the electron transport impedance is approximately equal to the semi-circular diameter of the EIS curve. As shown in FIG. 7B, the prepared ZIS/CIS/CdS-HHOC/ITO electrode gradually increased in Ret value after stepwise modification of chitosan, glutaraldehyde, CA19-9antibody, BSA. Next, the Ret value is further expanded after further modification of the CA19-9 antigen due to increased steric hindrance caused by the strong specific binding between the CA19-9antibody and the CA19-9 antigen. Thus, from the impedance change of the EIS curve and the change in photocurrent in the transient photocurrent curve, it can be seen that the photoelectrochemical aptamer sensor was successfully constructed.
Performance testing
1. X-ray diffraction pattern
XRD spectrum of prepared ZIS/CIS/CdS-HHOC proves that composite material contains cubic CdIn 2 S 4 Hexagonal ZnIn 2 S 4 And CdS, which is consistent with the analysis results of HRTEM and SAED (fig. 3A, 4B, 4C). Wherein, the cubic CdIn 2 S 4 The characteristic peaks of (JCPDS No. 27-0060) are 23.2 DEG, 27.3 DEG, 33.0 DEG, 43.3 DEG and 47.4 DEG, respectively, corresponding to the (220), (311), (400), (511) and (440) crystal planes thereof. Whereas the strong diffraction peaks at 24.9 °, 26.5 °, 28.2 °, 43.8 °, 47.8 ° and 51.9 ° are hexagonal CdS (JCPDS No. 65-3414). While hexagonal ZnIn 2 S 4 Peaks at 21.6 °, 27.7 ° and 47.2 ° are shifted to lower diffraction angles than the standard value of the (JCPDS No. 65-2023) card, which is probably due to Cd 2+ Partially dope into ZnIn 2 S 4 In the crystal lattice, the interplanar spacing is increased.
2. Ultraviolet visible light absorption spectrum and optical band gap calculation
By means ofUltraviolet-visible Diffuse Reflectance Spectroscopy (DRS) and XPS valence band spectroscopy (E) VB ) For ZnIn 2 S 4 、CdIn 2 S 4 The optical properties and band structure of CdS and ZIS/CIS/CdS-HHOC were analyzed. As shown in fig. 6C, all of the prepared photoactive materials exhibited light absorption in the visible region. But due to CdIn 2 S 4 The narrow band gap of the components allows the light absorption region of ZIS/CIS/CdS-HHOC to be extended. In addition, the well-structured ZIS/CIS/CdS-HHOC has a stronger light capturing capacity than ZIS/CIS/CdS-PM due to the multiple light scattering effect. According to Tauc equation (ah v) 2 Calculation of =a (hν -Eg) gives ZnIn 2 S 4 、CdIn 2 S 4 The band gaps (Eg) of CdS were 2.75eV, 2.36eV and 2.53eV, respectively (fig. 5A-C). The valence band positions of the above materials were calculated to be 1.10eV (vs NHE), 1.37eV (vs NHE) and 1.65eV (vs NHE), respectively, by XPS test (FIGS. 5D-F). From eg=e CB -E VB The formula is available, znIn 2 S 4 、CdIn 2 S 4 And the conduction band positions of CdS are-1.65 eV, -0.99eV and-0.88 eV in order. Therefore, the staggered energy band structure and closely contacted ternary components in ZIS/CIS/CdS-HHOC can form a type II heterojunction on the material interface, which is beneficial to the separation of photogenerated carriers and the inhibition of the recombination of photogenerated electron-hole pairs.
4. Three-component ZnIn with hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 Photoelectrochemical characterization of/CdS materials
The electrochemical properties of the prepared photoactive materials were first determined by chopped photovoltaic method. As shown in fig. 5B, the photocurrent-time curve was achieved by several on/off lights with a period of 20s, resulting in a rapidly increasing and stable photocurrent curve, indicating that the prepared material was sensitive to visible light (fig. 6A). And control group ZnIn 2 S 4 、CdIn 2 S 4 The photocurrent signal of the well-designed ZIS/CIS/CdS-HHOC was significantly improved (about 39.8 μa) compared to CdS. In addition, the photocurrent of ZIS/CIS/CdS-HHOC is about that of the physically mixed ZnIn 2 S 4 /CnIn 2 S 4 4 times (about 9.7. Mu.A) of the/CdS material (ZIS/CIS/CdS-PM), implying hollow delaminationThe construction of the texture is effective for enhancing photoelectric conversion. Likewise, the improvement in photoelectric conversion efficiency in ZIS/CIS/CdS-HHOC was also demonstrated in the incident optoelectronic conversion efficiency (IPCE) test (FIG. 6B). ZIS/CIS/CdS-HHOC has a higher IPCE value and a broader visible light response than ZIS/CIS/CdS-PM, further indicating that the hollow layered heterostructure of ZIS/CIS/CdS-HHOC plays an indispensable role in enhancing PEC performance.
To gain insight into ZIS/CIS/CdS-HHOC electronic properties and interfacial kinetics, we performed a series of electrochemical test characterization. The fermi level (E) of the material is obtained by the concept of the intersection of the mot schottky curve tangent (fig. 6D) with the abscissa f ) Size of the product. The apparent positive shift in potential in ZIS/CIS/CdS-HHOC (-0.84V vs. Ag/AgCl) compared to control CdS (-1.05V vs. Ag/AgCl) demonstrates the tight formation of the heterojunction, resulting in a balance between their fermi levels (FIG. 6D). Under a tight n-nII heterojunction, the photoexcited electron-hole pairs can be easily separated and their recombination process suppressed, which is measured in terms of electron lifetime (τ) at the phase angle of the material n ) This was confirmed in the analysis. The characteristic peaks of ZIS/CIS/CdS-HHOC shifted to lower frequencies compared to control CdS and ZIS/CIS/CdS-PM (fig. 6E), which means that the electron transfer process in ZIS/CIS/CdS-HHOC was faster than for a typical physically mixed heterojunction, because of the frequency (f max ) Inversely proportional to electron lifetime (τ n ＝1/2πf max ). The final calculated electron lifetimes were 148.8 μs, 118.6 μs and 84.4 μs for ZIS/CIS/CdS-HHOC, ZIS/CIS/CdS-PM and CdS, respectively.
Next, ZIS/CIS/CdS-HHOC electron transport and recombination processes were further studied by controlled intensity modulated photoelectro-current spectroscopy (CIMPS) and controlled intensity modulated photovoltage spectroscopy (CIMVS), electron transport time (τ D ) And electron lifetime (tau) n ) Can be obtained by the following formula:
τ D ＝1/(2πf CIMPS ) Equ(1)
τ n ＝1/(2πf CIMVS ) Equ(2)
wherein f CIMPS And f CIMVS The smallest imaginary component of the fourth quadrant in the CIMPS and CIMVS diagrams, respectivelyIs a frequency of (a) is a frequency of (b). The electron lifetimes of ZIS/CIS/CdS-HHOC, ZIS/CIS/CdS-PM, cdS were calculated to be 570ms, 140ms, and 180ms, respectively (FIG. 6F). τ from CIMVS n In terms of values, ZIS/CIS/CdS-HHOC possesses the longest electron lifetime reflecting its smallest photo-generated electron-hole pair recombination rate, consistent with the results of the Bode plot (FIG. 6E) analysis. Notably, the electron lifetime values obtained in CIMVS are greater than the Bode test, which is due to the different test solution system from CIMVS and the fact that the Bode test is performed in dark conditions. At the same time, the steady state PL signal of ZIS/CIS/CdS-HHOC quenching further reflects the effective inhibition of photogenerated electron-hole recombination in ZIS/CIS/CdS-HHOC (FIG. 6H). In addition, ZIS/CIS/CdS-HHOC has a smaller electron transfer resistance (R) than the simple physically mixed ZIS/CIS/CdS-PM material et ) The rapid electron injection process between ZIS/CIS/CdS-HHOC material and the electrolyte was demonstrated (fig. 6H). This is all attributable to the in situ formation of a dense heterostructure and the thin surface of the ZIS/CIS/CdS-HHOC secondary microcell structure which accelerates the transfer of photogenerated carriers. Whereas CIMPS test results (FIG. 6I) found τ for ZIS/CIS/CdS-HHOC and ZIS/CIS/CdS-PM and CdS materials D The values (0.33 ms) are comparable, indicating that the hierarchical heterostructure built in ZIS/CIS/CdS-HHOC has no effect on the electron transport process between the material and the electrode (fig. 6G). Thus according to the formula eta cc ＝1-τ D /τ n (η cc For charge collection efficiency) can be calculated as η of ZIS/CIS/CdS-HHOC, ZIS/CIS/CdS-PM and CdS cc 0.9994, 0.9976 and 0.9982, respectively, and the results indicate that ZIS/CIS/CdS-HHOC enhances the charge collection efficiency of the photoanode by effectively separating carriers and inhibiting their recombination process. All the above results show that the hierarchical heterostructure built in ZIS/CIS/CdS-HHOC material facilitates the separation and transfer process of its carriers.
The foregoing disclosure is merely illustrative of the preferred embodiments of the present invention and is not intended to limit the scope of the claims herein, as equivalent changes may be made in the claims herein without departing from the scope of the invention.

Claims (10)

1. The preparation method of the three-component sulfide photoelectric material with the hollow hierarchical heterostructure is characterized by comprising the following steps of:
A. preparation of octahedral coordination Polymer Cd 3 (C 3 N 3 S 3 ) 2 ；
B. The Cd is treated with 3 (C 3 N 3 S 3 ) 2 Adding into a mixed solution of ethanol and glycerol, and dispersing to obtain a suspension; the volume ratio of ethanol to glycerol in the ethanol and glycerol mixed solution is 3.5:1;
C. zn (NO) 3 ) 2 ·6H 2 O、InCl 3 ·4H 2 Sequentially adding the solution of O and thioacetamide into the suspension, stirring, and putting the suspension into a reaction kettle for reaction after stirring is completed to obtain yellow precipitate;
D. washing and drying the yellow precipitate to obtain the three-component ZnIn with the hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 /CdS material.
2. The method for preparing the hollow hierarchical heterostructure three-component sulfide photoelectric material according to claim 1, comprising the following steps:
A. obtaining the Cd 3 (C 3 N 3 S 3 ) 2 ；
B. The Cd is treated with 3 (C 3 N 3 S 3 ) 2 Adding the mixture into a mixed solution of ethanol and glycerol, and dispersing to obtain a suspension;
C. zn (NO) 3 ) 2 ·6H 2 Ethanol solution of O, inCl 3 ·4H 2 Sequentially adding the ethanol solution of O into the suspension, magnetically stirring for 20min, adding the ethanol solution of thioacetamide, magnetically stirring for half an hour, and then placing the mixture into a reaction kettle for reaction after stirring is completed to obtain yellow precipitate;
D. washing and drying the yellow precipitate to obtain the three-component ZnIn 2 S 4 /CnIn 2 S 4 /CdS material.
3. The method for preparing a three-component sulfide photoelectric material with a hollow hierarchical heterostructure according to claim 2, wherein in the step B, the Cd 3 (C 3 N 3 S 3 ) 2 The mass volume ratio of the mixed solution of ethanol and glycerol is 30-85 mg: 15-35 mL.
4. The method for preparing a hollow hierarchical heterostructure three-component sulfide photovoltaic material of claim 1, wherein in step C, zn (NO 3 ) 2 ·6H 2 The concentration of the ethanol solution of O is 0.04 to 0.20mol.L -1 ，InCl 3 ·4H 2 The concentration of the ethanol solution of O is 0.08 to 0.40 mol.L -1 The concentration of the thioacetamide ethanol solution is 0.16 to 0.80 mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the In step C, cd 3 (C 3 N 3 S 3 ) 2 、Zn(NO 3 ) 2 ·6H 2 O、InCl 3 ·4H 2 The molar ratio of O to thioacetamide is 1:1:1:2.
5. the method for preparing the three-component sulfide photoelectric material with the hollow hierarchical heterostructure according to claim 1, wherein in the step C, the reaction kettle is a polytetrafluoroethylene reaction kettle and reacts for 6-16 hours at 160 ℃, and the heating rate is 5 ℃/hour; in step D, the yellow precipitate is washed three times with ethanol and then dried in a vacuum environment at 60 ℃ for 12 hours to obtain the three-component ZnIn 2 S 4 /CnIn 2 S 4 /CdS material.
6. The method for preparing the hollow hierarchical heterostructure three-component sulfide photoelectric material according to claim 1, wherein the specific operation of the step a comprises:
a1, cdCl 2 Dissolving in ultrapure water and stirring to form transparent solution A;
a2, dissolving cyanuric acid in a NaOH solution to form a yellow solution B;
a3, under the condition of strong stirring, dropwise adding the yellow solution B into the transparent solution A, and slowly stirring for reaction after the dropwise addition is completed;
a4, washing and drying after the reaction is finished to obtain the Cd 3 (C 3 N 3 S 3 ) 2 。
7. The method for preparing the hollow hierarchical heterostructure three-component sulfide photovoltaic material of claim 6, wherein the specific operation of step a comprises:
a1, cdCl 2 According to the mass volume ratio of 1.8332 g-4.1247 g: 80-180 mL of the transparent solution A is formed by dissolving the transparent solution A in ultrapure water and stirring;
a2, mixing the cyanuric acid according to the mass volume ratio of 1.1818 g-2.6591 g:70 mL-150 mL of the solution is dissolved in 0.15 mol.L -1 The yellow solution B is formed in NaOH solution;
a3, under the condition of strong stirring, according to CdCl 2 The yellow solution B is dropwise added into the transparent solution A according to the mass ratio of the cyanuric acid to the cyanuric acid of 3:2, and the mixture is slowly stirred at room temperature for reaction for 12-24 hours after the dropwise addition is completed;
a4, after the reaction is finished, washing with ethanol, centrifugally collecting, circulating for three times, and finally drying to obtain the Cd 3 (C 3 N 3 S 3 ) 2 。
8. Cd-based photovoltaic material of three-component sulfide with hollow hierarchical heterostructure obtained by the method of preparation of the material according to claim 1 3 (C 3 N 3 S 3 ) 2 Derived three-component ZnIn with hollow hierarchical heterostructure 2 S 4 /CnIn 2 S 4 /CdS material.
9. A three-component ZnIn as claimed in claim 8 2 S 4 /CnIn 2 S 4 The use of a/CdS material, characterized in that it is used for photocatalytic degradation of CO 2 Reduction, hydrogen production, photosynthesis, antimicrobial and photoelectric sensing fields.
10. The three-component ZnIn of claim 9 2 S 4 /CnIn 2 S 4 The application of the CdS material is characterized by being used for quantitative detection of the biomarker CA19-9 by photoelectrochemical sensing; the bacteria used for resisting bacteria include one or more of Escherichia coli, staphylococcus aureus, and Candida albicans.
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