CN115475632B - CN/Mn 2 O 3 Preparation method of/FTOp-n heterojunction material, and product and application thereof - Google Patents
CN/Mn 2 O 3 Preparation method of/FTOp-n heterojunction material, and product and application thereof Download PDFInfo
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a CN/Mn 2 O 3 Preparation method of/FTOp-n heterojunction material, and product and application thereof. The CN/Mn 2 O 3 The FTOp-n heterojunction material is prepared by dissolving melamine and cyanuric acid in concentrated sulfuric acid under ice bath condition, adding potassium permanganate, stirring for reaction to obtain mixed colloid; then heating the mixed colloid to react, dropwise adding hydrogen peroxide, centrifuging and drying to obtain melamine-cyanuric acid supermolecule precursor (MCS); finally, the melamine-cyanuric acid supermolecule precursor is coated on the FTO glass, and hydrogen plasma treatment is carried out to obtain the glass. The heterojunction can be used as photoelectrode for water decomposition, solar cell and H 2 O 2 The production and other photocatalytic reactions have the characteristics of stable structure, excellent photoelectric and cycle performance and the like, and can effectively solve the problem that the traditional powder photocatalyst is difficult to recycle.
Description
Technical Field
The invention relates to a CN/Mn 2 O 3 A preparation method of/FTOp-n heterojunction material, a product and application thereof belong to the technical field of photoelectrocatalysis material electrodes.
Background
Photoelectrochemical (PEC) technology has attracted tremendous interest in the last decades as a promising alternative to alleviate today's global energy and environmental problems. Despite great progress, howeverPEC technology is still limited by the lack of efficient photocatalysts for practical use. This motivated extensive research into photocatalysts to pursue low cost, reproducibility, and appropriate reduction and oxidation potentials for water decomposition. Recently, graphite carbon nitride (g-C 3 N 4 CN) as PEC battery, PEC water-splitting, CO due to its high visible light response, remarkable chemical and thermal stability 2 Photoelectrodes of reduction and environmental remediation have attracted increasing attention. Numerous studies have been conducted to improve the chemical, optical and electronic properties of CN, including the construction of heterojunctions, metal/nonmetal doping, plasma surface modification, and the introduction of C and/or N vacancies, among others. However, most of the improved processes of CN are generally based on thermal condensation and eventually all come in the form of CN powder. This would result in a complicated recovery step, thereby hampering practical use. Heretofore, the synthesis of CN photoelectrodes has been mainly achieved by common deposition methods such as screen printing, drop coating and spin coating, resulting in weak adhesion on common solid substrates (ITO and FTO) and poor CN coverage. Various attempts have been made to improve the performance of CN in (opto) electronic devices, such as solid state deposition, chemical vapor deposition and hot vapor condensation. However, these methods only produce a fairly thin CN layer, resulting in low light absorption, poor conductivity and weak photocurrent. These defects make CN films insufficient to act as active layers in photoelectrochemical cells or photovoltaic devices. Furthermore, the thickness and uniformity of CN films deposited by these methods are largely dependent on the surface properties. Thus, alternative routes to CN photoelectrode preparation would be challenging and significant. Recently, oxides of manganese, in particular Mn 2 O 3 Have been used as photocatalysts to enhance light absorption and charge separation because of their narrow band gap and high responsiveness. Many PEC water splitting studies have shown Mn 3+ Importance of ions in evolution O is separated from water due to excellent electrochemical Oxygen Evolution Reaction (OER) activity 2 . Thus, mn 2 O 3 Is a very promising PEC water splitting photocatalyst. More attractive are CN and Mn 2 O 3 Will become a custom-made photocatalyst to overcome the limitation of pure CN high carrier recombination.
Disclosure of Invention
The invention aims to: a first object of the present invention is to provide a CN/Mn 2 O 3 Preparation method of/FTOp-n heterojunction material; a second object of the present invention is to provide a CN/Mn obtained by the production method 2 O 3 FTOp-n heterojunction material; a third object of the present invention is to provide a CN/Mn 2 O 3 The FTOp-n heterojunction material is applied to the field of photoelectrochemistry as a photoelectrode.
The technical scheme is as follows: the invention relates to a CN/Mn 2 O 3 The preparation method of the/FTOp-n heterojunction material comprises the following steps:
(1) Under ice bath condition, melamine and cyanuric acid are dissolved in concentrated sulfuric acid, potassium permanganate is added, and the mixed colloid is obtained through stirring reaction;
(2) Heating the mixed colloid for reaction, dripping hydrogen peroxide, centrifugally separating, and drying the precipitate to obtain melamine-cyanuric acid supermolecule precursor (MCS powder);
(3) Coating melamine-cyanuric acid supermolecule precursor on FTO glass, and performing hydrogen plasma treatment to obtain CN/Mn 2 O 3 FTO p-n heterojunction material.
In the step (1), the mass-volume ratio of the melamine to the concentrated sulfuric acid is 1-2.5:10-20 g/mL, and the mass ratio of the melamine, the cyanuric acid and the potassium permanganate is 1-2.5:1-2.5: 0.25 to 1.
Wherein in the step (1), the temperature of the stirring reaction is 30-50 ℃, and the time of the stirring reaction is 1-3 h.
In the step (2), the volume ratio of the mixed colloid to the hydrogen peroxide is 1:1 to 3, and the mass concentration of the hydrogen peroxide is 20 to 30 weight percent.
In the step (2), the temperature of the heating reaction is 80-98 ℃, the time of the heating reaction is 1-2 h, the temperature of the drying reaction is 60-100 ℃, and the temperature of the drying reaction is 18-36h.
In the step (3), the flow rate of the hydrogen gas in the hydrogen plasma treatment is 10-100 sccm, the heating rate of the hydrogen plasma treatment is 5-15 ℃/min, the treatment temperature is 350-520 ℃, the heat preservation time is 1-4 h, and the treatment pressure is 100-500 pa.
Wherein the heating rate of the hydrogen plasma treatment is 5-10 ℃/min, the hydrogen plasma treatment temperature is 400-500 ℃, the heat preservation time is 1.5-3 h, and the treatment pressure is 100-200 pa.
In the step (3), the specification of the FTO glass is as follows: 20X 2.2mm 3 ，10Ωsq -1 The area of the melamine-cyanuric acid supermolecule precursor coated on the FTO glass is 1cm to 1.5cm 2 The thickness is 0.5-2mm.
The preparation method of the invention prepares CN/Mn 2 O 3 FTOp-n heterojunction material.
CN/Mn of the invention 2 O 3 FTOp-n heterojunction material as photoelectrode CN/Mn 2 O 3 FTO is used in the field of photoelectrochemistry.
The preparation principle of the invention is as follows: in the low temperature (ice bath) stage, melamine and cyanuric acid self-assemble in sulfuric acid solution through hydrogen bonds to form a supramolecular (MCS) precursor; meanwhile, in the subsequent reaction process, the potassium permanganate and the supermolecule precursor can be fully contacted and reacted, then the MCS powder is transferred into the FTO, and then hydrogen plasma treatment is carried out under certain conditions, wherein the reaction is carried out at a medium temperature (30-50 ℃) and then at a high temperature (80-98 ℃). When the heating temperature approaches H 2 SO 4 At the boiling point (338 ℃), the hydrogen bonds of the MCS begin to break and form a liquid phase in which Mn ions are free to dissolve and disperse. Due to H 2 SO 4 The liquid mixture becomes metastable, and free moving Mn ions readily form Mn with oxygen ions 2 O 3 . Moreover, under the conditions of high temperature and low pressure, the N atoms move from C-N=C, promoting NH 3 Is beneficial to the formation of a porous structure. When the heating temperature exceeds H 2 SO 4 Due to NH at the boiling point of (C) 3 And low pressure, a mixture having a hollow 3D structure can be formed. The metastable liquid phase is in close contact with the FTO surface, resulting in goodGood cycle performance and mechanical performance, and provides effective basis for practical application.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) CN/Mn prepared by the invention 2 O 3 the/FTO p-n heterojunction materials exhibit enhanced light absorption properties due to Mn 2 O 3 This will promote photocatalytic oxidation reactions;
(2) CN/Mn of the present invention 2 O 3 The preparation method of the/FTO heterojunction material is simple and easy to operate, and CN/Mn with any size can be prepared by optimizing process parameters 2 O 3 FTO p-n heterojunction material.
(3) The invention prepares CN/Mn by simply adjusting the addition amount of potassium permanganate 2 O 3 The FTO p-n material is used as a photoelectrode, so that the problem that a uniform and stable CN photoelectrode with excellent mechanical strength cannot be deposited on a solid substrate due to the existing technology including drop casting and spin coating can be effectively solved;
(4) CN/Mn prepared by the invention 2 O 3 The FTOp-n junction material is uniform and stable, has excellent mechanical strength on FTO, is favorable for recycling and is used as CN/Mn 2 O 3 The FTO photoelectrode can effectively overcome the characteristics of the powder photocatalyst shedding electrode and the problem of difficult recovery, and compared with the photoelectrode prepared by the common spin-coating method, the CN/Mn photoelectrode has the advantages that 2 O 3 The FTO photoelectrodes exhibit significantly enhanced PEC performance and the internal electric field of the p-n heterojunction contact interface can promote the transfer of photoelectrons, resulting in electrons and holes in the valence band and Mn of CN 2 O 3 The conduction band of the material is accumulated, and the material has wide application prospect in the field of photoelectrochemistry.
Drawings
FIG. 1 is a CN/Mn prepared in example 1 2 O 3 FTOp-n heterojunction material flow diagram;
FIG. 2 shows MCS and CN/Mn prepared in example 1 2 O 3 SEM images of FTOp-n heterojunction materials at different magnifications;
FIG. 3 is a CN/Mn prepared in example 1 2 O 3 High resolution TEM images of the/FTO p-n heterojunction material;
FIG. 4 is MCS, CN/FTO and CN/Mn 2 O 3 XRD spectrum of FTO;
FIG. 5 is MCS, CN/FTO and CN/Mn 2 O 3 FTIR spectrum of FTO;
FIG. 6 is the CN/Mn of example 1 2 O 3 XPS measurement spectrograms of/FTO and CN/FTO;
FIG. 7 is the CN/Mn of example 1 2 O 3 EDX profile of FTO;
FIG. 8 is a TG/DSC plot of the MCS in example 1;
FIG. 9 is a diagram of CN/FTO and CN/Mn 2 O 3 EPR spectrogram of/FTO;
FIG. 10 is a CN/Mn prepared in example 1 2 O 3 High-resolution XPS spectrogram of/FTO and structure model schematic diagram;
FIG. 11 is a diagram of CN/FTO and CN/Mn 2 O 3 LSV plot of FTO;
FIG. 12 is a diagram of CN/FTO and CN/Mn 2 O 3 Open circuit photovoltage decay (OCVD) plot of/FTO;
FIG. 13 is a diagram of CN/FTO and CN/Mn 2 O 3 Mott-Schottky plot of/FTO;
FIG. 14 is a diagram of CN/FTO and CN/Mn 2 O 3 EIS Nyquist plot of FTO;
FIG. 15 is a diagram of CN/FTO and CN/Mn 2 O 3 A transient photocurrent response diagram of/FTO;
FIG. 16 is a diagram of CN/FTO and CN/Mn 2 O 3 A long-time photocurrent response plot of/FTO;
Detailed Description
EXAMPLE 1CN/Mn 2 O 3 Preparation of/FTOp-n heterojunction material
CN/Mn 2 O 3 The preparation flow of the FTOp-n heterojunction material is shown in figure 1, and 2.5g of melamine and 2.5g of cyanuric acid are respectively dissolved in 10mL of concentrated sulfuric acid at the temperature of 0 ℃ in an ice bath to obtain mixed colloid. Next, 0.75g of KMnO was added under ice bath conditions 4 Adding into the mixed colloid. Subsequently, the mixed colloid was heated at 35℃for 2h, then heating at 98 ℃ for 1.5h; subsequently, 50 ml of a 20% hydrogen peroxide solution was dropwise added, the resulting viscous mixture was centrifuged to remove an upper layer solution, and the resulting precipitate was dried at 80℃for 48 hours to obtain a melamine-cyanuric acid supermolecule precursor (MCS). MCS was coated onto FTO glass (20X 2.2 mm) 3 ，10Ωsq -1 ) Area of 1cm 2 The thickness was 0.5mm.
Then transferring the material into a tube furnace for hydrogen plasma treatment, wherein parameters are set as follows: the hydrogen temperature is 500 ℃, the heating rate is 10 ℃/min, the heat preservation time is 2 hours, the pressure is 150pa, and the CN/Mn is obtained 2 O 3 FTOp-n heterojunction material, CN/Mn 2 O 3 FTOp-n heterojunction materials, i.e. photoelectrodes CN/Mn 2 O 3 /FTO。
MCS and CN/Mn obtained in this example 2 O 3 The result of scanning electron microscope analysis of the/FTOp-n heterojunction material is shown in FIG. 2, and FIG. 2 shows MCS and CN/Mn prepared in example 1 2 O 3 SEM pictures of FTOp-n heterojunction materials under different magnifications, wherein (a) is the SEM picture of MCS under 10 μm, and (b) is CN/Mn 2 O 3 FTOp-n heterojunction material SEM images at 10 μm. SEM images confirm that the precursor surface contains colloids, which are determining factors for liquid phase growth. And CN/Mn 2 O 3 The FTOp-n heterojunction material has a porous structure that can be effectively contacted with the reactants to increase its optoelectronic properties.
CN/Mn obtained in this example 2 O 3 The FTOp-n heterojunction material was subjected to transmission electron microscopy analysis and the results are shown in FIG. 3. FIG. 3 is a CN/Mn prepared in example 1 2 O 3 High resolution TEM image of/FTOp-n heterojunction material, where (a) is CN/Mn 2 O 3 TEM image of FTOp-n heterojunction material at 200nm, (b) CN/Mn 2 O 3 TEM image of FTOp-n heterojunction material at 5 nm. FIG. 3 shows Mn 2 O 3 Is proved to be CN/Mn 2 O 3 Formation of heterojunction.
EXAMPLE 2 preparation of CN/FTO
The preparation and experimental process of CN/FTO are implemented in the same wayExample 1, wherein KMnO was not added alone 4 The others are identical.
MCS obtained in example 1, photoelectrode CN/Mn 2 O 3 XRD analysis was performed on/FTO and CN/FTO obtained in this example, and the results are shown in FIG. 4. FIG. 4 is MCS, CN/FTO and CN/Mn 2 O 3 As can be seen from FIG. 4, by comparing Mn 2 O 3 The PDF card of the invention can find the CN/Mn prepared by the invention 2 O 3 the/FTO contains Mn 2 O 3 Is a characteristic peak of (2). TEM and XRD patterns combined with FIG. 3 confirm successful synthesis of CN/Mn 2 O 3 And a heterojunction.
MCS, CN/Mn prepared in example 1 2 O 3 FTIR spectrum contrast analysis was performed on the FTO and the CN/FTO prepared in this example, and the results are shown in FIG. 5. FIG. 5 is MCS, CN/FTO and CN/Mn 2 O 3 FTIR spectrum of FTO, characteristic peak of CN can be seen from FIG. 5, showing CN/Mn 2 O 3 Presence of CN in/FTO.
CN/Mn prepared in example 1 2 O 3 XPS measurement analysis was performed on/FTO and the CN/FTO obtained in this example, and the results are shown in FIG. 6. FIG. 6 is CN/Mn 2 O 3 XPS measurement spectrograms of/FTO and CN/FTO; from FIG. 6, it can be derived that example 1CN/Mn 2 O 3 the/FTO contains Mn 2 O 3 It was further confirmed that example 1 successfully synthesizes CN/Mn 2 O 3 And a heterojunction.
CN/Mn prepared in example 1 2 O 3 the/FTO was subjected to EDX spectroscopy, and the results are shown in FIG. 7. FIG. 7 is the CN/Mn of example 1 2 O 3 EDX profile of FTO; wherein (a) is CN/Mn 2 O 3 SEM pictures of FTO, and (b) - (f) are CN/Mn 2 O 3 Corresponding element maps in/FTO correspond to C, N, O, mn, S, respectively. As can be seen from fig. 7, the individual elements are equally distributed over the surface of the material. Successful preparation of CN/Mn through structural characterization 2 O 3 p-n heterojunction.
TGDSC thermogram of the MCS prepared in example 1 was performed and the results are shown in fig. 8. FIG. 8 is a TG/DSC plot of the MCS in example 1; the phase changes at various stages of the MCS can be seen from fig. 8.
For CN/Mn prepared in example 1 2 O 3 EPR spectroscopic analysis was carried out on/FTO and the CN/FTO prepared in this example, and the results are shown in FIG. 9. FIG. 9 is a diagram of CN/FTO and CN/Mn 2 O 3 EPR spectrogram of/FTO; as can be seen from FIG. 9, the CN/Mn prepared in example 1 2 O 3 N vacancies exist in/FTO.
For CN/Mn prepared in example 1 2 O 3 The results of the high-resolution XPS spectrum analysis of the/FTO are shown in FIG. 10. FIG. 10 is a CN/Mn prepared in example 1 2 O 3 XPS spectrogram and structure model schematic diagram of FTO; wherein (a) - (d) are respectively corresponding element high resolution diagrams, and correspond to elements C, N, O and Mn in sequence, so that the chemical bond structure of the heterojunction can be further known, and (e) is CN/Mn 2 O 3 Structural model diagram of FTO. Combining EPR and XPS data analysis to obtain CN/Mn 2 O 3 A structural model of the/FTO is shown in the figure (e), wherein the CN structural model contains N vacancies and is matched with Mn 2 O 3 A heterostructure is formed.
EXAMPLE 3CN/Mn 2 O 3 Preparation of/FTOp-n heterojunction material
1g of melamine and 2g of cyanuric acid were dissolved in 20mL of concentrated sulfuric acid at-5℃respectively, followed by 0.25g of KMnO under ice bath conditions 4 Adding into the mixed colloid. Subsequently, the mixed colloid was heated at 35℃for 1 hour, and then heated at 70℃for 1 hour; subsequently, 30ml of 30% hydrogen peroxide was added dropwise to the resulting viscous mixture, and the supernatant solution was removed by centrifugation, and the resulting precipitate was dried at 60℃for 48 hours to obtain a melamine-cyanuric acid supermolecule precursor (MCS). Then it was coated on FTO glass (20X 2.2 mm) 3 ，10Ωsq -1 ) Area of 1.5cm 2 The thickness was 0.5mm.
Then transferring the material into a tube furnace for hydrogen plasma treatment, wherein parameters are set as follows: the temperature is 400 ℃, the heating rate is 5 ℃/min, the heat preservation time is 1.5h, the pressure is 200pa, and the CN/Mn is obtained 2 O 3 FTO photoelectrodes.
EXAMPLE 4CN/Mn 2 O 3 Preparation of/FTOp-n heterojunction material
2g of melamine and 1g of cyanuric acid were dissolved in 20mL of concentrated sulfuric acid at-10deg.C, followed by 1g of KMnO under ice bath conditions 4 Adding into the mixed colloid. Subsequently, the mixed colloid was heated at 45℃for 2 hours, and then at 98℃for 2 hours; subsequently, 100mL of 20% hydrogen peroxide was added dropwise to the resulting viscous mixture, the supernatant solution was removed by centrifugation, and the resulting precipitate was dried at 90℃for 28 hours to give a melamine-cyanuric acid supermolecule precursor (MCS). Then it was coated on FTO glass (20X 2.2 mm) 3 ，10Ωsq -1 ) Area of 1cm 2 The thickness was 2mm.
Then transferring the material into a tube furnace for hydrogen plasma treatment, wherein parameters are set as follows: the temperature is 450 ℃, the heating rate is 10 ℃/min, the heat preservation time is 3 hours, the pressure is 100pa, and the CN/Mn is obtained 2 O 3 FTO photoelectrodes.
Example 5:
CN/Mn prepared in example 1 2 O 3 FTO photoelectrodes and CN/FTO electrodes prepared in example 2 photoelectrochemical measurements were carried out under a three electrode system using an electrochemical workstation (CHI 660E, shanghai, china). Platinum foil and saturated Ag/AgCl were used as counter and reference electrodes, respectively. CN/FTO and CN/Mn 2 O 3 The FTOs are respectively directly used as working photoelectrodes. For comparison, the corresponding working electrode, labeled CN/Mn, was prepared by drop coating the photocatalyst in powder form 2 O 3 Coating. Typically, 5mg of photocatalyst, 1mL of N, N-Dimethylformamide (DMF) and 40uL of Nafion were mixed under sonication for 30 minutes to give a mixed solution. Then 20uL of the mixed solution was dropped on an area of 1cm 2 Is dried at room temperature for 24h. Using 0.1M Na in the irradiation reactor 2 SO 4 Solutions and 300W xenon lamp (PLS-SXE 300D/300DUV,Beijing Perfect light) were tested. The results are shown in FIGS. 11-16.
FIG. 11 is a diagram of CN/FTO and CN/Mn 2 O 3 As can be seen from FIG. 11, the LSV graph of the/FTO, CN/Mn 2 O 3 the/FTO has a smaller starting voltage.
FIG. 12 is a diagram of CN/FTO and CN/Mn 2 O 3 As can be seen from FIG. 12, CN/Mn is shown in an open circuit photovoltage decay (OCVD) chart of/FTO 2 O 3 The time of the/FTO decay was 14.3s longer than the CN/FTO.
FIG. 13 is a diagram of CN/FTO and CN/Mn 2 O 3 As can be seen from FIG. 13, the Mott-Schottky image of the FTO contains both positive and negative slopes, confirming the CN/Mn prepared 2 O 3 FTO is a p-n heterojunction, and CN is an n-type semiconductor, mn 2 O 3 As a p-type semiconductor.
FIG. 14 is a diagram of CN/FTO and CN/Mn 2 O 3 EIS Nyquist diagram of/FTO As can be seen from FIG. 14, CN/Mn 2 O 3 The small radius of the/FTO semicircle indicates that it has a smaller electrochemical impedance.
FIG. 15 is a diagram of CN/FTO and CN/Mn 2 O 3 As can be seen from FIG. 15, the transient photocurrent response of the/FTO, CN/Mn 2 O 3 The photocurrent density of/FTO is significantly higher than that of CN/FTO, indicating that CN/Mn 2 O 3 the/FTO has a better photocurrent response.
FIG. 16 is a diagram of CN/FTO and CN/Mn 2 O 3 Long time current diagram of/FTO. As can be seen from FIG. 16, CN/Mn 2 O 3 The curve of/FTO is smoother than that of CN/FTO, indicating CN/Mn 2 O 3 the/FTO has better electrochemical stability than CN/FTO.
Claims (3)
1. CN/Mn 2 O 3 The preparation method of the FTOp-n heterojunction material is characterized by comprising the following steps of:
(1) Under ice bath condition, melamine and cyanuric acid are dissolved in concentrated sulfuric acid, potassium permanganate is added, and the mixed colloid is obtained through stirring reaction; the mass volume ratio of the melamine to the concentrated sulfuric acid is 1-2.5:10-20 g/mL, the mass ratio of the melamine to the cyanuric acid to the potassium permanganate is 1-2.5:1-2.5:0.25-1, the temperature of the stirring reaction is 30-50 ℃, and the time of the stirring reaction is 1-3 h;
(2) Heating the mixed colloid for reaction, dropwise adding hydrogen peroxide, centrifugally separating, and drying to obtain melamine-cyanuric acid supermolecule precursor (MCS); the volume ratio of the mixed colloid to the hydrogen peroxide is 1: 1-3, wherein the mass concentration of hydrogen peroxide is 20-30wt%, the temperature of the heating reaction is 80-98 ℃, the time of the heating reaction is 1-2 h, the drying temperature is 60-100 ℃, and the drying temperature time is 18-36h;
(3) Coating melamine-cyanuric acid supermolecule precursor on FTO glass, and performing hydrogen plasma treatment to obtain CN/Mn 2 O 3 FTO heterojunction material; the hydrogen gas flow rate of the hydrogen plasma treatment is 10-100 sccm, the heating rate of the hydrogen plasma treatment is 5-15 ℃/min, the treatment temperature is 350-520 ℃, the heat preservation time is 1-4 h, the treatment pressure is 100-500 pa, and the specification of the FTO glass is as follows: 20X 2.2mm 3 ，10 Ωsq -1 The area of the melamine-cyanuric acid supermolecule precursor coated on the FTO glass is 1-1.5cm 2 The thickness is 0.5-2mm.
2. The process of claim 1 to obtain CN/Mn 2 O 3 FTOp-n heterojunction material.
3. The CN/Mn of claim 2 2 O 3 The FTOp-n heterojunction material is applied to the field of photoelectrochemistry as a photoelectrode.
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