CN114481168B - 3D flower-shaped Z-shaped heterojunction photoelectric catalyst Zn 3 In 2 S 6 @Bi 2 WO 6 Preparation method and application thereof - Google Patents
3D flower-shaped Z-shaped heterojunction photoelectric catalyst Zn 3 In 2 S 6 @Bi 2 WO 6 Preparation method and application thereof Download PDFInfo
- Publication number
- CN114481168B CN114481168B CN202210169081.2A CN202210169081A CN114481168B CN 114481168 B CN114481168 B CN 114481168B CN 202210169081 A CN202210169081 A CN 202210169081A CN 114481168 B CN114481168 B CN 114481168B
- Authority
- CN
- China
- Prior art keywords
- shaped
- deionized water
- flower
- added
- mixed solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 229960000583 acetic acid Drugs 0.000 claims abstract description 8
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000011941 photocatalyst Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
Abstract
The 3D flower-shaped Z-shaped heterojunction photocatalyst Zn 3 In 2 S 6 @Bi 2 WO 6 And a preparation method and application thereof. The technical scheme adopted is as follows: bi (NO) 3 ) 3 ·5H 2 O is dissolved in the mixed solution of deionized water and glacial acetic acid, and Na is added after the mixture is uniformly mixed 2 WO 4 ·2H 2 O aqueous solution, then adding Zn to the obtained mixed solution 3 In 2 S 6 Stirring for 1h, transferring into an autoclave for hydrothermal reaction, washing and drying the product to obtain Zn 3 In 2 S 6 @Bi 2 WO 6 . The photoelectric catalyst Zn prepared by the invention 3 In 2 S 6 @Bi 2 WO 6 For the efficient and rapid production of H 2 O 2 Is helpful to promote the application of the photoelectrocatalysis technology in the field of clean energy production.
Description
Technical Field
The invention belongs to the field of photoelectrocatalysis, and in particular relates to a 3D flower-shaped Z-shaped heterojunction photoelectrocatalyst Zn 3 In 2 S 6 @Bi 2 WO 6 And a preparation method and application thereof.
Background
The effects of global climate change are obviously related to the sustained production of carbon dioxide from fossil fuel use. In order to reduce the current reliance on fossil fuels, inexpensive and efficient methods of producing fuels using renewable energy sources have become an increasingly important goal. Hydrogen peroxide (H) 2 O 2 ) Is widely applied as a green environment-friendly productIs used in textile, environment protection, food, paper making, electronics, medicine and other industries, and becomes an important inorganic chemical raw material.
Currently, H is produced 2 O 2 Industrial routes such as anthraquinone processes or direct synthesis, often require large energy inputs and are environmentally hazardous. Therefore, a green and environment-friendly way for synthesizing H is needed 2 O 2 . Photoelectrocatalysis for producing H 2 O 2 Can be carried out by an anode Water Oxidation (WOR) reaction (2H) 2 O＝H 2 O 2 +2H + +2e - E(H 2 O/H 2 O 2 ) = +1.77v vs. rhe) may also be carried out by cathodic oxygen reduction (ORR) reaction (O 2 +2H + +2e - ＝H 2 O 2 E(O 2 /H 2 O 2 ) = +0.68V vs. RHE). Although more and more photocatalysts are being explored with H production by photoelectrocatalysis 2 O 2 But H 2 O 2 The poisoning of (2), the rapid recombination of photo-generated charges and the assistance of sacrificial agents greatly limit the development of the catalyst. Therefore, a high-efficiency and stable catalyst is needed to be designed for the photoelectrocatalysis to produce H 2 O 2 。
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a 3D flower-shaped Z-shaped heterojunction photoelectric catalyst Zn 3 In 2 S 6 @Bi 2 WO 6 For the efficient and rapid production of H 2 O 2 Is helpful to promote the application of the photoelectrocatalysis technology in the field of clean energy production.
The technical scheme adopted by the invention is as follows: 3D flower-shaped Z-shaped heterojunction photoelectric catalyst Zn 3 In 2 S 6 @Bi 2 WO 6 The preparation method comprises the following steps: bi (NO) 3 ) 3 ·5H 2 O is dissolved in the mixed solution of deionized water and glacial acetic acid, and Na is added after the mixture is uniformly mixed 2 WO 4 ·2H 2 O aqueous solution, then adding Zn to the obtained mixed solution 3 In 2 S 6 Stirring for 1h, transferring into an autoclavePerforming hydrothermal reaction, washing and drying a product to obtain Zn 3 In 2 S 6 @Bi 2 WO 6 。
Further, in the mixed solution of deionized water and glacial acetic acid, the volume ratio of deionized water to glacial acetic acid=5:3.
Further, the hydrothermal reaction is carried out at 160 ℃ for 16 hours.
Further, the Zn 3 In 2 S 6 The preparation method of the (C) comprises the following steps: znSO is added to 4 ·7H 2 After O and thioacetamide are dissolved in deionized water, inCl is added 3 Stirring the aqueous solution for 30-40min, transferring the obtained mixed solution into an autoclave, performing hydrothermal reaction at 160 ℃ for 12h, washing, and drying to obtain Zn 3 In 2 S 6 。
The 3D flower-shaped Z-shaped heterojunction photoelectric catalyst Zn provided by the invention 3 In 2 S 6 @Bi 2 WO 6 Photoelectrocatalysis for producing H as catalyst 2 O 2 Is used in the field of applications.
Further, the method comprises the following steps: zn is added 3 In 2 S 6 @Bi 2 WO 6 Coating on carbon paper as working electrode, platinum sheet as counter electrode and Ag/AgCl as reference electrode to form three-electrode system, placing the three-electrode system in electrolyte solution, blowing O into the electrolyte solution under dark condition 2 For 30min, and then under illumination, producing H by photoelectrocatalysis 2 O 2 。
Further, the photoelectrocatalysis conditions are: the bias voltage is-0.6V, the light source is a 300W xenon lamp, lambda>420nm, and the average light intensity is 100mW cm -2 。
Further, the concentration was 0.1mol L at pH=3.0 -1 Na of (2) 2 SO 4 Is an electrolyte solution.
The beneficial effects of the invention are as follows:
1. the photoelectric catalyst Zn provided by the invention 3 In 2 S 6 @Bi 2 WO 6 Is a heterojunction with Z-type charge conduction mode and has high-efficiency photoelectric catalyst. Photoexcitation enablesElectrons in the semiconductor transition from the Valence Band (VB) to the Conduction Band (CB) to form electron-hole pairs, and e is the position of the semiconductor CB - H with another other VB position + Preferably, charge separation is realized, and photo-generated charges with stronger oxidation/reduction capability are respectively reserved on the semiconductors, so that the original oxidation/reduction capability is maintained.
2. The photoelectric catalyst Zn provided by the invention 3 In 2 S 6 @Bi 2 WO 6 The 3D flower-like structure has rich folds, increases the specific surface area of the catalyst, increases the reactive sites of the catalyst, is beneficial to the mass transfer of the catalyst and electrolyte solution, and improves the photoelectrocatalysis performance.
3. The photoelectric catalyst Zn provided by the invention 3 In 2 S 6 @Bi 2 WO 6 The performance in the photoelectric system is far higher than that of a single photocatalysis system and an electrocatalytic system, so that the photoelectric synergistic effect is achieved.
Drawings
FIG. 1 is Zn 3 In 2 S 6 (a) And Zn 3 In 2 S 6 @Bi 2 WO 6 (b) SEM images of (a).
FIG. 2 is Bi 2 WO 6 ，Zn 3 In 2 S 6 And Zn 3 In 2 S 6 @Bi 2 WO 6 Is a XRD pattern of (C).
FIG. 3 is Bi 2 WO 6 ，Zn 3 In 2 S 6 And Zn 3 In 2 S 6 @Bi 2 WO 6 Performance contrast for photoelectrocatalytic production of hydrogen peroxide.
FIG. 4 is Zn 3 In 2 S 6 @Bi 2 WO 6 And the catalytic effects under the combined action of pure light, pure electricity and photoelectricity are compared.
FIG. 5 is Zn 3 In 2 S 6 @Bi 2 WO 6 Kinetic profile of catalytic process.
Fig. 6 is a radical trapping principle.
FIG. 7Is a speculative O 2 Reduction to H 2 O 2 Reaction mechanism.
Detailed Description
Example 1 3D flower-like Z-heterojunction photocatalyst Zn 3 In 2 S 6 @Bi 2 WO 6
The preparation method (one) is as follows
1、Zn 3 In 2 S 6 Is prepared from
0.5865g InCl 3 ·4H 2 O was dissolved in 25mL deionized water, 0.8711g ZnSO 4 ·7H 2 O and 0.4545g of thioacetamide are dissolved in 45mL of deionized water, the two solutions are mixed and stirred for 30min, the obtained mixed solution is transferred into an autoclave to be subjected to hydrothermal reaction at 160 ℃ for 12h, washed and dried, and yellow powdery solid Zn is obtained 3 In 2 S 6 。
2、Zn 3 In 2 S 6 @Bi 2 WO 6 Is prepared from
1.9403g Bi(NO 3 ) 3 ·5H 2 O was dissolved in a mixed solution of 25ml deionized water and 15ml glacial acetic acid, 0.6598g Na 2 WO 4 ·2H 2 O was dissolved in 10ml deionized water, and after combining the two solutions, 0.09g Zn was added 3 In 2 S 6 Adding into the mixed solution, stirring for 1h, transferring into an autoclave, performing hydrothermal reaction at 160 ℃ for 16h, washing the product, and drying to obtain Zn 3 In 2 S 6 @Bi 2 WO 6 。
(II) detection
FIG. 1 is Zn 3 In 2 S 6 (a) And Zn 3 In 2 S 6 @Bi 2 WO 6 (b) SEM image. As can be seen from FIG. 1 a, zn 3 In 2 S 6 A good 3D hierarchical flower-like structure was developed. As can be seen from FIG. 1 b, the load Bi 2 WO 6 After that, the original 3D flower-like layered structure is not obviously changed, and a large number of nanowires are wound outside the flower.
FIG. 2 is Bi 2 WO 6 ，Zn 3 In 2 S 6 And Zn 3 In 2 S 6 @Bi 2 WO 6 Is a XRD pattern of (C). As can be seen from FIG. 2, pure Bi 2 WO 6 In the spectra of (2) theta = 28.30, 32.79, 47.15, 55.82, the diffraction peaks are due to Bi respectively 2 WO 6 (131) (002), (202) and (133) crystal planes (JCPLDS No. 979-2381). For Zn alone 3 In 2 S 6 The diffraction peaks at 2θ=26.99, 28.23 and 46.92 for the samples were attributed to Zn 3 In 2 S 6 (101), (102) and (110) crystal planes (JCPLDS No. 80-0835). In Zn 3 In 2 S 6 @Bi 2 WO 6 Shows only weaker Bi 2 WO 6 Due to Bi 2 WO 6 The content in the composite material is low.
Example 2 Zn 3 In 2 S 6 @Bi 2 WO 6 In the photoelectrocatalysis to produce H 2 O 2 Application in (a)
Evaluation of catalytic Activity
The method comprises the following steps: 3mg Zn 3 In 2 S 6 @Bi 2 WO 6 Coating on carbon paper as working electrode, platinum sheet as counter electrode, ag/AgCl as reference electrode, bias voltage of-0.6V, and light source of 300W xenon lamp (lambda)>420 nm) with an average light intensity of 100mW cm -2 At 0.1 mol.L -1 Na 2 SO 4 (ph=3.0) is an electrolyte solution, O is blown into the electrolyte solution 2 . By H 2 O 2 Representation of Zn production rate 3 In 2 S 6 @Bi 2 WO 6 Is a catalyst activity of (a). Blowing O in the dark before the electric/optical start 2 For 30min to reach O 2 Balance. Quantitative analysis of ultraviolet visible absorption at 350nm by KI chromogenic method, and measuring H every 30min 2 O 2 Concentration.
(II) evaluation of Performance
FIG. 3 is Bi 2 WO 6 ，Zn 3 In 2 S 6 And Zn 3 In 2 S 6 @Bi 2 WO 6 Performance contrast for photoelectrocatalytic production of hydrogen peroxide. As can be seen from fig. 3, the phasesCompared with Bi alone 2 WO 6 And Zn 3 In 2 S 6 ，Zn 3 In 2 S 6 @Bi 2 WO 6 The composite material exhibits a significantly enhanced performance in the photoelectrocatalytic production of hydrogen peroxide, wherein Zn 3 In 2 S 6 @Bi 2 WO 6 The hydrogen peroxide production amount reaches 1600 mu mol/L, and is respectively Zn alone 3 In 2 S 6 And Bi (Bi) 2 WO 6 Four times and two times.
FIG. 4 is Zn 3 In 2 S 6 @Bi 2 WO 6 And the catalytic effects under the combined action of pure light, pure electricity and photoelectricity are compared. As can be seen from fig. 4, the photo-catalysis also shows significantly enhanced catalytic activity compared to the photo-catalysis and electro-catalysis alone, demonstrating the synergistic effect of the photoelectricity. The amount of hydrogen peroxide produced by photocatalysis and electrocatalysis is 100 mu mol/L and 50 mu mol/L respectively, which is far less than that produced by photocatalysis.
FIG. 5 is Zn 3 In 2 S 6 @Bi 2 WO 6 Kinetic profile of catalytic process. As can be seen from FIG. 5, the reaction process is consistent with quasi-zero order kinetics, compared to Bi alone 2 WO 6 And Zn 3 In 2 S 6 ，Zn 3 In 2 S 6 @Bi 2 WO 6 The composite material shows higher rate constant, and the reaction rate constant is 7.78154min -1 。
(III) catalytic mechanism
In the catalytic process, a variety of active ions are typically present, including O 2 - And h + Etc. To further study Zn 3 In 2 S 6 @Bi 2 WO 6 The mechanism of photoelectrocatalysis of the composite material to hydrogen peroxide was tested for capture (fig. 6). When silver nitrate (e) - Capture agent), produced H 2 O 2 A substantial decrease in H 2 O 2 Generation of the requirement e - . P-benzoquinone (O) 2 - Capture agent) is added into the reaction system, H is generated 2 O 2 The same is also greatly reduced, indicating that O 2 - Is to generate H 2 O 2 Is a major active ingredient of (a) a compound. Citric acid (h) + Capture agent) is added into the reaction system, H 2 O 2 There is a smaller increase in the amount of (h), possibly due to h + Promotes the separation of electrons and holes, thereby generating more H 2 O 2 . Based on the standard electrode potential (O) for generating reactive particles 2 /·O 2 - (-0.33 ev vs. nhe)), in combination with the trapping experiment results and their bandgap structure, the Z-conduction is considered to be the charge conduction mode of the heterojunction (fig. 7).
Claims (3)
1.3D flower-shaped Z-shaped heterojunction photocatalyst Zn 3 In 2 S 6 @Bi 2 WO 6 Photoelectrocatalysis for producing H as catalyst 2 O 2 Is characterized in that the method comprises the following steps: zn is added 3 In 2 S 6 @Bi 2 WO 6 Coating on carbon paper as working electrode, platinum sheet as counter electrode and Ag/AgCl as reference electrode to form three-electrode system, placing the three-electrode system in electrolyte solution, blowing O into the electrolyte solution under dark condition 2 30min, and then under illumination, producing H by photoelectrocatalysis 2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The photoelectrocatalysis conditions are as follows: the bias voltage is-0.6V, the light source is a 300W xenon lamp, lambda>420nm, average light intensity of 100mW cm -2 ；
The 3D flower-shaped Z-shaped heterojunction photoelectric catalyst Zn 3 In 2 S 6 @Bi 2 WO 6 The preparation method comprises the following steps: bi (NO) 3 ) 3 ·5H 2 O is dissolved in the mixed solution of deionized water and glacial acetic acid, and Na is added after the mixture is uniformly mixed 2 WO 4 ·2H 2 O aqueous solution, then adding Zn to the obtained mixed solution 3 In 2 S 6 Stirring for 1h, transferring to an autoclave at 160 ℃ for hydrothermal reaction for 16h, washing and drying the product to obtain Zn 3 In 2 S 6 @Bi 2 WO 6 ；
In the mixed solution of deionized water and glacial acetic acid, the volume ratio of deionized water to glacial acetic acid=5:3.
2. The use according to claim 1, characterized in that the Zn 3 In 2 S 6 The preparation method of the (C) comprises the following steps: znSO is added to 4 ·7H 2 After O and thioacetamide are dissolved in deionized water, inCl is added 3 Stirring the aqueous solution for 30-40min, transferring the obtained mixed solution into an autoclave, performing hydrothermal reaction at 160 ℃ for 12h, washing, and drying to obtain Zn 3 In 2 S 6 。
3. The use according to claim 1, wherein the concentration is 0.1mol L at ph=3.0 -1 Na of (2) 2 SO 4 Is an electrolyte solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210169081.2A CN114481168B (en) | 2022-02-23 | 2022-02-23 | 3D flower-shaped Z-shaped heterojunction photoelectric catalyst Zn 3 In 2 S 6 @Bi 2 WO 6 Preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210169081.2A CN114481168B (en) | 2022-02-23 | 2022-02-23 | 3D flower-shaped Z-shaped heterojunction photoelectric catalyst Zn 3 In 2 S 6 @Bi 2 WO 6 Preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114481168A CN114481168A (en) | 2022-05-13 |
| CN114481168B true CN114481168B (en) | 2024-03-22 |
Family
ID=81483711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210169081.2A Active CN114481168B (en) | 2022-02-23 | 2022-02-23 | 3D flower-shaped Z-shaped heterojunction photoelectric catalyst Zn 3 In 2 S 6 @Bi 2 WO 6 Preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114481168B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923779A (en) * | 2012-11-14 | 2013-02-13 | 陕西科技大学 | Preparation method of flower-shaped spherical Bi2MoO6 microcrystal |
| CN108505062A (en) * | 2018-05-04 | 2018-09-07 | 厦门大学 | A kind of method that electro-catalysis reduction oxygen generates hydrogen peroxide |
| CN111261413A (en) * | 2019-12-27 | 2020-06-09 | 武汉科技大学 | Ti-doped α -Fe2O3Nanorod composite MOFs heterojunction photo-anode and preparation method and application thereof |
| CN111437840A (en) * | 2020-05-22 | 2020-07-24 | 辽宁大学 | 3D hierarchical flower-like MoS2@CoMoS4Z-type heterostructure photoelectric catalyst and preparation method and application thereof |
| CN111437824A (en) * | 2020-05-18 | 2020-07-24 | 辽宁大学 | 3D layered micro-flower structure CoWO4@Bi2WO6Z-type heterojunction composite catalyst and preparation method and application thereof |
| CN113856703A (en) * | 2021-10-15 | 2021-12-31 | 泉州师范学院 | Indium zinc sulfide and bismuth molybdate nanosheet composite photocatalyst with nanoflower structure and preparation method and application thereof |
-
2022
- 2022-02-23 CN CN202210169081.2A patent/CN114481168B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923779A (en) * | 2012-11-14 | 2013-02-13 | 陕西科技大学 | Preparation method of flower-shaped spherical Bi2MoO6 microcrystal |
| CN108505062A (en) * | 2018-05-04 | 2018-09-07 | 厦门大学 | A kind of method that electro-catalysis reduction oxygen generates hydrogen peroxide |
| CN111261413A (en) * | 2019-12-27 | 2020-06-09 | 武汉科技大学 | Ti-doped α -Fe2O3Nanorod composite MOFs heterojunction photo-anode and preparation method and application thereof |
| CN111437824A (en) * | 2020-05-18 | 2020-07-24 | 辽宁大学 | 3D layered micro-flower structure CoWO4@Bi2WO6Z-type heterojunction composite catalyst and preparation method and application thereof |
| CN111437840A (en) * | 2020-05-22 | 2020-07-24 | 辽宁大学 | 3D hierarchical flower-like MoS2@CoMoS4Z-type heterostructure photoelectric catalyst and preparation method and application thereof |
| CN113856703A (en) * | 2021-10-15 | 2021-12-31 | 泉州师范学院 | Indium zinc sulfide and bismuth molybdate nanosheet composite photocatalyst with nanoflower structure and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Wu, Yan等.Construction of hierarchical 2D-2D Zn3In2S6/fluorinated polymeric carbon nitride nanosheets photocatalyst for boosting photocatalytic degradation and hydrogen production performance.《Applied Catalysis, B: Environmental》.2018,第233卷第58-69页. * |
| 许雪棠等.Fe/Bi_2WO_6水热合成及其光催化性能研究.无机盐工业.2016,第48卷(第03期),第72-76页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114481168A (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108686710B (en) | Two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalytic hydrogen evolution material and preparation method thereof | |
| CN107012474B (en) | A kind of method of large-scale solar energy photocatalysis-photoelectrocatalysis hydrogen production by water decomposition | |
| Xie et al. | A solar responsive photocatalytic fuel cell with a heterostructured ZnFe2O4/TiO2-NTs photoanode and an air-breathing cathode | |
| CN107761127B (en) | Preparation method of polyacid and phthalocyanine jointly modified nano porous bismuth vanadate oxygen evolution electrode | |
| He et al. | NiFe-layered double hydroxide decorated BiVO4 photoanode based bi-functional solar-light driven dual-photoelectrode photocatalytic fuel cell | |
| CN107020075A (en) | Carbon dioxide electrochemical reduction simple substance bismuth catalyst and its preparation and application | |
| CN104549214A (en) | Tin dioxide multi-stage structured nanosphere carbon dioxide electrochemical reduction catalyst, preparation method and application of tin dioxide multi-stage structured nanosphere carbon dioxide electrochemical reduction catalyst | |
| CN107299362B (en) | A kind of preparation method and its electrochemical applications of activated carbon supported cobalt-nickel alloy material | |
| JP7434372B2 (en) | Method for producing nickel-iron catalyst material, use in oxygen evolution reaction, method for producing hydrogen and/or oxygen by water electrolysis, and method for producing liquid solar fuel | |
| Chen et al. | A solar responsive cubic nanosized CuS/Cu2O/Cu photocathode with enhanced photoelectrochemical activity | |
| CN111437840B (en) | 3D hierarchical flower-like MoS2@CoMoS4Z-type heterostructure photoelectric catalyst and preparation method and application thereof | |
| CN112206830A (en) | CuPc@Ti3C2TxMXene catalytic material, electrode and application in nitrate radical reduction | |
| Wang et al. | Integration of zirconium-based metal–organic framework with CdS for enhanced photocatalytic conversion of CO 2 to CO | |
| CN111450849B (en) | 3D hierarchical cube-shaped alpha-MnS@CuS Z heterostructure photoelectric catalyst and preparation method and application thereof | |
| CN111468120B (en) | CoFeNiO X Layered hollow nanocage electrocatalyst and preparation method and application thereof | |
| CN113104862A (en) | Method for rapidly preparing Prussian blue or analogues thereof in batches and application of method | |
| CN114011398B (en) | 3D flower-like Zn 3 In 2 S 6 @Bi 2 O 4 /β-Bi 2 O 3 double-Z-type heterojunction photocatalyst and application thereof | |
| Zhou et al. | In situ growth of CdIn2S4 on NH2-MIL-125 as efficient photocatalysts for H2 production under visible-light irradiation | |
| Savino et al. | Tandem devices for simultaneous CO2 reduction at the cathode and added-value products formation at the anode | |
| CN112657515B (en) | 3D flower-shaped Z-shaped heterojunction photoelectric catalyst Zn 3 In 2 S 6 @α-Fe 2 O 3 Preparation method and application thereof | |
| WO2022068491A1 (en) | Lead nanosheet-graphene two-dimensional composite, preparation method and application thereof | |
| CN114481168B (en) | 3D flower-shaped Z-shaped heterojunction photoelectric catalyst Zn 3 In 2 S 6 @Bi 2 WO 6 Preparation method and application thereof | |
| CN109972149B (en) | Bi2Te3/Bi2O3/TiO2Preparation method of ternary heterojunction film | |
| CN110038641B (en) | Bismuth vanadate/chromium porphyrin/graphene quantum dot two-dimensional composite Z-type photocatalytic material, preparation method and application | |
| Lashgari et al. | A cost-effective H2S pollutant electro-transformation to hydrogen clean fuel and value-added semiconducting materials: A green alternative to Claus process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |