CN115475632A - CN/Mn 2 O 3 Preparation method of/FTOp-n heterojunction material, product and application thereof - Google Patents
CN/Mn 2 O 3 Preparation method of/FTOp-n heterojunction material, product and application thereof Download PDFInfo
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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
- 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
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- B01J35/33—
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- B01J35/39—
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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
-
- 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
Abstract
The invention discloses CN/Mn 2 O 3 Preparation method of/FTOp-n heterojunction material, 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, and stirring to obtain mixed colloid; heating the mixed colloid for reaction, dropwise adding hydrogen peroxide, centrifuging, and drying to obtain a melamine-cyanuric acid supramolecular precursor (MCS); and finally, coating the melamine-cyanuric acid supramolecular precursor on FTO glass, and performing hydrogen plasma treatment to obtain the melamine-cyanuric acid supramolecular precursor. The heterojunction of the invention can be used as a photoelectrode for water decomposition, solar cells and H 2 O 2 The photocatalytic reaction such as production and the like has the characteristics of stable structure, excellent photoelectric and circulating performances 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 CN/Mn 2 O 3 A preparation method of/FTOp-n heterojunction material, a product and an application thereof belong to the technical field of photoelectrocatalysis material electrodes.
Background
As a promising alternative to mitigate today's global energy and environmental issues, photoelectrochemical (PEC) technologies have attracted great interest over the last decades. Despite great advances, PEC technology is still limited by the lack of efficient photocatalysts for practical applications. This has stimulated a great deal of research on photocatalysts in the pursuit of low cost, reproducibility, and appropriate reduction and oxidation potentials for water splitting. Recently, graphitic carbon nitride (g-C) 3 N 4 CN) as a PEC cell, PEC water splitting, CO due to its high visible light response, significant chemical and thermal stability 2 Reduction and environmental remediation photoelectrodes have attracted increasing attention. A great deal of research has been conducted to improve the chemical, optical and electronic properties of CN, including the construction of heterojunctions, metal/non-metal doping, plasma surface modification and the introduction of C and/or N vacancies, among others. However, most CN improvement methods are generally based on thermal condensation and are ultimately presented as CN powders. This results in a complicated recovery step, which hinders practical use. To date, 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, this is not soThese methods only produce rather thin CN layers, resulting in low light absorption, poor conductivity and weak photocurrent. These defects make CN thin films insufficient to serve as active layers in photoelectrochemical cells or photovoltaic devices. Furthermore, the thickness and uniformity of CN thin films deposited by these methods are largely dependent on surface properties. Therefore, an alternative route to CN photoelectrode fabrication would be challenging and meaningful. More recently, oxides of manganese, particularly Mn 2 O 3 Has been used as a photocatalyst to enhance light absorption and charge separation because of its 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 The combination of (a) would be a tailored photocatalyst to overcome the limitations of pure CN high carrier recombination.
Disclosure of Invention
The invention aims to: the first purpose of the invention is to provide a CN/Mn 2 O 3 A preparation method of the/FTOp-n heterojunction material; the second purpose of the invention is to provide CN/Mn obtained by the preparation method 2 O 3 a/FTOp-n heterojunction material; the third purpose of the invention is to provide a CN/Mn 2 O 3 the/FTOp-n heterojunction material is applied to the photoelectrode field.
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 the ice bath condition, dissolving melamine and cyanuric acid in concentrated sulfuric acid, adding potassium permanganate, and stirring for reaction to obtain a mixed colloid;
(2) Heating the mixed colloid for reaction, dropwise adding hydrogen peroxide, centrifugally separating, and drying the precipitate to obtain a melamine-cyanuric acid supramolecular precursor (MCS powder);
(3) Coating melamine-cyanuric acid supermolecule precursor on FTO glass, and performing hydrogen plasma treatment to obtainCN/Mn 2 O 3 the/FTO p-n heterojunction material.
In the step (1), the mass-to-volume ratio of melamine to concentrated sulfuric acid is 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 percent, and the mass concentration of the hydrogen peroxide is 20 to 30 weight percent.
In the step (2), the heating reaction temperature is 80-98 ℃, the heating reaction time is 1-2 h, the drying temperature is 60-100 ℃, and the drying temperature time is 18-36h.
In the step (3), the flow rate of the hydrogen gas for 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 temperature rise rate of the hydrogen plasma treatment is 5-10 ℃/min, the temperature of the hydrogen plasma treatment 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 specifications of the FTO glass are as follows: 20X 2.2mm 3 ，10Ωsq -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.
The preparation method of the invention prepares CN/Mn 2 O 3 a/FTOp-n heterojunction material.
CN/Mn of the invention 2 O 3 /FTOp-n heterojunction material as photoelectrode CN/Mn 2 O 3 the/FTO is applied to the field of photoelectrochemistry.
The preparation principle of the invention is as follows: in the low-temperature (ice bath) stage, melamine and cyanuric acid form a supramolecular (MCS) precursor in a sulfuric acid solution through hydrogen bond self-assembly; at the same time follow upIn the reaction process, the reaction is carried out at a medium temperature (30-50 ℃) and at a high temperature (80-98 ℃), because the potassium permanganate and the supermolecule precursor can be in full contact reaction, and then the MCS powder is transferred to the FTO, and then hydrogen plasma treatment is carried out under certain conditions. When the heating temperature is close to H 2 SO 4 At boiling point of (338 c), hydrogen bonds of MCS start to break and form a liquid phase in which Mn ions are freely dissolved and dispersed. Due to H 2 SO 4 The liquid mixture becomes metastable, and free moving Mn ions easily form Mn with oxygen ions 2 O 3 . Further, under the conditions of high temperature and low pressure, N atoms move from C-N = C, promoting NH 3 Is favorable for the formation of a porous structure. When the heating temperature exceeds H 2 SO 4 At the boiling point of (2), due to NH 3 With low pressure, a mixture with a hollow 3D structure can be formed. The metastable liquid phase is in close contact with the FTO surface, so that good cycle performance and mechanical performance are achieved, and an effective basis is provided for practical application.
Has the beneficial effects 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 material shows enhanced light absorption performance, which is attributed to Mn 2 O 3 A narrow band gap, which will promote the photocatalytic oxidation reaction;
(2) CN/Mn of the 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 an/FTO p-n heterojunction material.
(3) The invention prepares CN/Mn by simply adjusting the adding amount of potassium permanganate 2 O 3 The FTO p-n material is used as a photoelectrode, and can effectively solve the problem that the current technology comprises drop casting and spin coating and can not deposit a uniform and stable CN photoelectrode with excellent mechanical strength on a solid substrate;
(4) CN/Mn prepared by the invention 2 O 3 the/FTOp-n junction material is uniform and stable and has excellent performance on FTOMechanical strength, easy recycling, as CN/Mn 2 O 3 The FTO photoelectrode can effectively overcome the characteristics of a powder photocatalyst falling electrode and the problem of difficult recovery, and compared with a photoelectrode prepared by a common spin-coating method, the FTO photoelectrode has the advantages of CN/Mn 2 O 3 the/FTO photoelectrode exhibits significantly enhanced PEC performance, and the internal electric field at the p-n heterojunction contact interface can facilitate the transfer of photoelectrons, resulting in electrons and holes in the valence band and Mn of CN 2 O 3 The accumulation in the conduction band has wide application prospect in the photoelectrochemistry field.
Drawings
FIG. 1 shows CN/Mn prepared in example 1 2 O 3 a/FTOp-n heterojunction material flow diagram;
FIG. 2 shows the MCS and CN/Mn prepared in example 1 2 O 3 SEM images of/FTOp-n heterojunction materials at different magnifications;
FIG. 3 is CN/Mn prepared in example 1 2 O 3 High resolution TEM image of/FTO p-n heterojunction material;
FIG. 4 shows MCS, CN/FTO and CN/Mn 2 O 3 XRD spectrum of/FTO;
FIG. 5 shows MCS, CN/FTO and CN/Mn 2 O 3 FTIR spectrum of/FTO;
FIG. 6 shows CN/Mn in example 1 2 O 3 XPS measurement spectrograms of/FTO and CN/FTO;
FIG. 7 shows CN/Mn in example 1 2 O 3 EDX spectrum of/FTO;
FIG. 8 is a TG/DSC plot of the MCS of example 1;
FIG. 9 shows CN/FTO and CN/Mn 2 O 3 EPR spectrogram of/FTO;
FIG. 10 is CN/Mn prepared in example 1 2 O 3 A high-resolution XPS spectrogram and a structural model schematic diagram of/FTO;
FIG. 11 shows CN/FTO and CN/Mn 2 O 3 LSV plot for/FTO;
FIG. 12 shows CN/FTO and CN/Mn 2 O 3 Open circuit photovoltage decay (OCVD) plot for/FTO;
FIG. 13 shows CN/FTO and CN/Mn 2 O 3 Mott-Schottky diagram for/FTO;
FIG. 14 shows CN/FTO and CN/Mn 2 O 3 EIS Nyquist plot for FTO;
FIG. 15 shows CN/FTO and CN/Mn 2 O 3 Transient photocurrent response diagram of/FTO;
FIG. 16 shows CN/FTO and CN/Mn 2 O 3 Long-time photocurrent response curve 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 a mixed colloid. Then 0.75g of KMnO was added under ice bath conditions 4 Adding into the mixed colloid. Subsequently, the mixed colloid is heated for 2h at 35 ℃ and then heated for 1.5h at 98 ℃; subsequently, 50 ml of 20% hydrogen peroxide solution is dropwise added to obtain a viscous mixture, centrifugal separation is carried out to remove the upper layer solution, and the obtained precipitate is dried at 80 ℃ for 48 hours to obtain the melamine-cyanuric acid supramolecular precursor (MCS). MCS was coated onto FTO glass (20X 2.2 mm) 3 ，10Ωsq -1 ) Area of 1cm 2 The thickness is 0.5mm.
Then transferring the tube furnace to a tubular furnace for hydrogen plasma treatment, wherein the parameters are as follows: hydrogen temperature is 500 ℃, heating rate is 10 ℃/min, heat preservation time is 2h, pressure is 150pa, and CN/Mn is obtained 2 O 3 /FTOp-n heterojunction material, CN/Mn 2 O 3 the/FTOp-n heterojunction material, i.e. photoelectrode CN/Mn 2 O 3 /FTO。
The MCS and CN/Mn obtained in this example 2 O 3 The results of the scanning electron microscope analysis of the/FTOp-n heterojunction material are shown in FIG. 2, and FIG. 2 shows the MCS and CN/Mn prepared in example 1 2 O 3 SEM pictures of/FTOp-n heterojunction material under different magnifications, wherein (a) is SEM picture of MCS under 10 μm, and (b) is CN/Mn 2 O 3 the/FTOp-n heterojunction material is 10 muSEM image under m. The SEM images confirmed that the precursor surface contained colloids, which is a determining factor in liquid phase growth. And CN/Mn 2 O 3 the/FTOp-n heterojunction material has a porous structure, and can be effectively contacted with reactants, so that the photoelectric property of the material is improved.
The CN/Mn obtained in this example was used 2 O 3 The transmission electron microscope analysis of the/FTOp-n heterojunction material is shown in the figure 3. FIG. 3 is CN/Mn prepared in example 1 2 O 3 High resolution TEM image of/FTOp-n heterojunction material, wherein (a) is CN/Mn 2 O 3 TEM image of/FTOp-n heterojunction material at 200nm, (b) is CN/Mn 2 O 3 TEM image of/FTOp-n heterojunction material at 5 nm. FIG. 3 shows Mn 2 O 3 The crystal lattice fringes of (2), confirming CN/Mn 2 O 3 And (4) forming a heterojunction.
EXAMPLE 2 preparation of CN/FTO
CN/FTO preparation was carried out as in example 1 except that no KMnO was added 4 And the others are identical.
MCS obtained in example 1, photoelectrode CN/Mn 2 O 3 XRD analysis of/FTO and CN/FTO obtained in this example was carried out, and the results are shown in FIG. 4. FIG. 4 shows MCS, CN/FTO and CN/Mn 2 O 3 XRD pattern of/FTO, as can be seen from FIG. 4, by comparison of Mn 2 O 3 The present invention can find the CN/Mn prepared by the present invention 2 O 3 /FTO contains Mn 2 O 3 Characteristic peak of (2). The successful synthesis of CN/Mn is confirmed by combining the TEM image and XRD pattern of FIG. 3 2 O 3 A heterojunction.
MCS, CN/Mn prepared in example 1 2 O 3 FTIR comparative analysis was performed on/FTO and CN/FTO obtained in this example, and the results are shown in FIG. 5. FIG. 5 shows MCS, CN/FTO and CN/Mn 2 O 3 FTIR spectrogram of/FTO, the characteristic peak of CN can be seen from figure 5, and the CN/Mn is proved 2 O 3 Presence of CN in FTO.
CN/Mn prepared in example 1 2 O 3 XPS measurements of/FTO and CN/FTO obtained in this example are shown in FIG. 6. FIG. 6 shows 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 /FTO contains Mn 2 O 3 Further, it was confirmed that CN/Mn was successfully synthesized in example 1 2 O 3 A heterojunction.
CN/Mn prepared in example 1 2 O 3 EDX profiling was performed for/FTO and the results are shown in FIG. 7. FIG. 7 shows CN/Mn in example 1 2 O 3 EDX spectrum of FTO; wherein (a) is CN/Mn 2 O 3 SEM pictures of/FTO, CN/Mn in (b) - (f) 2 O 3 The corresponding element mapping maps in the/FTO correspond to C, N, O, mn and S respectively. As can be seen from fig. 7, the elements are equally distributed on the surface of the material. The successful preparation of CN/Mn is found through structural characterization 2 O 3 A p-n heterojunction.
TGDSC thermal analysis of the MCS prepared in example 1 is shown in FIG. 8. FIG. 8 is a TG/DSC plot of the MCS of example 1; the phase change of the various phases of the MCS can be seen from fig. 8.
For CN/Mn prepared in example 1 2 O 3 EPR spectral analysis was performed on/FTO and CN/FTO obtained in this example, and the results are shown in FIG. 9. FIG. 9 shows CN/FTO and CN/Mn 2 O 3 EPR spectrogram of/FTO; as can be seen in FIG. 9, CN/Mn prepared in example 1 2 O 3 An N vacancy is present for/FTO.
For CN/Mn prepared in example 1 2 O 3 The results of high resolution XPS spectroscopy performed by/FTO are shown in FIG. 10. FIG. 10 is CN/Mn prepared in example 1 2 O 3 XPS spectrogram and structural model schematic diagram of/FTO; wherein, (a) - (d) are respectively corresponding element high resolution diagrams, which are sequentially corresponding to elements C, N, O and Mn, and can further understand the chemical bond structure of the heterojunction, and (e) is CN/Mn 2 O 3 Structure model diagram of/FTO. Combining with the data analysis of EPR and XPS, CN/Mn can be obtained 2 O 3 The structure model of/FTO is shown in figure (e), wherein the CN structure model contains N vacant sites and is connected with Mn 2 O 3 A heterostructure is formed.
Example 3CN/Mn 2 O 3 /FTOpreparation of p-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 4 Adding into the mixed colloid. Subsequently, the mixed colloid is heated for 1h at 35 ℃ and then heated for 1h at 70 ℃; and then, dripping 30mL of 30% hydrogen peroxide to obtain a viscous mixture, performing centrifugal separation, removing an upper layer solution, and drying the obtained precipitate at 60 ℃ for 48 hours to obtain the melamine-cyanuric acid supramolecular precursor (MCS). It was then coated on FTO glass (20X 2.2 mm) 3 ，10Ωsq -1 ) Area of 1.5cm 2 The thickness is 0.5mm.
Then transferring the tube furnace to a tubular furnace for hydrogen plasma treatment, wherein the parameters are as follows: the temperature is 400 ℃, the heating rate is 5 ℃/min, the heat preservation time is 1.5h, and the pressure is 200pa, thus obtaining CN/Mn 2 O 3 an/FTO photoelectrode.
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-10 ℃ respectively, followed by 1g of KMnO under ice bath 4 Adding into the mixed colloid. Subsequently, the mixed colloid is heated at 45 ℃ for 2h and then at 98 ℃ for 2h; and then, dropwise adding 100mL of 20% hydrogen peroxide to obtain a viscous mixture, performing centrifugal separation, removing an upper layer solution, and drying the obtained precipitate at 90 ℃ for 28h to obtain a melamine-cyanuric acid supramolecular precursor (MCS). It was then coated on FTO glass (20X 2.2 mm) 3 ，10Ωsq -1 ) Area of 1cm 2 The thickness is 2mm.
Then transferring the tube furnace to a tubular furnace for hydrogen plasma treatment, wherein the parameters are as follows: the temperature is 450 ℃, the heating rate is 10 ℃/min, the heat preservation time is 3h, and the pressure is 100pa, thus obtaining CN/Mn 2 O 3 an/FTO photoelectrode.
Example 5:
CN/Mn prepared in example 1 2 O 3 FTO photoelectrode and CN/FTO electrode prepared in example 2 in a three electrode systemPhotoelectrochemical measurements were performed systematically 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/FTO respectively directly serves as a working photoelectrode. For comparison, the corresponding working electrodes, which are labeled CN/Mn, were produced by dropping a photocatalyst in powder form 2 O 3 And/coating. Generally, 5mg of photocatalyst, 1mL of N, N-Dimethylformamide (DMF), and 40uL of Nafion were mixed under sonication for 30 minutes to obtain a mixed solution. Then, 20uL of the mixed solution was dropped on a surface of 1cm 2 And dried at room temperature for 24h. Use of 0.1M Na in irradiation reaction vessel 2 SO 4 The solutions were tested with a 300W xenon lamp (PLS-SXE 300D/300DUV, beijing Perfect light). The results are shown in FIGS. 11-16.
FIG. 11 shows CN/FTO and CN/Mn 2 O 3 LSV plot of/FTO, CN/Mn, as can be seen from FIG. 11 2 O 3 the/FTO has a smaller starting voltage.
FIG. 12 shows CN/FTO and CN/Mn 2 O 3 the/FTO open circuit photovoltage decay (OCVD) plot, from FIG. 12, CN/Mn 2 O 3 The decay time for/FTO was 14.3s, which is longer than that for CN/FTO.
FIG. 13 shows CN/FTO and CN/Mn 2 O 3 Mott-Schottky plot of/FTO, as can be seen in FIG. 13, the Mott-Schottky plot contains both a positive and negative slope, confirming the CN/Mn produced 2 O 3 the/FTO is a p-n heterojunction and CN as n-type semiconductor, mn 2 O 3 As a p-type semiconductor.
FIG. 14 shows CN/FTO and CN/Mn 2 O 3 EIS Nyquist plot for/FTO, as can be seen in FIG. 14, CN/Mn 2 O 3 The small radius of the/FTO semicircle indicates that it has a smaller electrochemical impedance.
FIG. 15 shows CN/FTO and CN/Mn 2 O 3 Transient photocurrent response diagram of/FTO, CN/Mn, can be seen from FIG. 15 2 O 3 The photocurrent density of/FTO is significantly higher than that of CN/FTO, which shows that CN/Mn 2 O 3 the/FTO has better photocurrent response.
FIG. 16 shows CN/FTO and CN/Mn 2 O 3 Long time timing current diagram of/FTO. As can be seen from FIG. 16, CN/Mn 2 O 3 the/FTO curve is more stable than the CN/FTO curve, which shows that CN/Mn 2 O 3 the/FTO has better electrochemical stability than CN/FTO.
Claims (10)
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 the ice bath condition, dissolving melamine and cyanuric acid in concentrated sulfuric acid, adding potassium permanganate, and stirring for reaction to obtain a mixed colloid;
(2) Heating the mixed colloid for reaction, dropwise adding hydrogen peroxide, centrifugally separating, and drying to obtain a melamine-cyanuric acid supramolecular precursor (MCS);
(3) Coating melamine-cyanuric acid supermolecule precursor on FTO glass, and performing hydrogen plasma treatment to obtain CN/Mn 2 O 3 an/FTO heterojunction material.
2. CN/Mn according to claim 1 2 O 3 The preparation method of the/FTOp-n heterojunction material is characterized in that in the step (1), the mass volume ratio of melamine to concentrated sulfuric acid is 1-2.5.
3. CN/Mn according to claim 1 2 O 3 The preparation method of the/FTOp-n heterojunction material is characterized in that in the step (1), the temperature of the stirring reaction is 30-50 ℃, and the time of the stirring reaction is 1-3 h.
4. CN/Mn according to claim 1 2 O 3 The preparation method of the/FTOp-n heterojunction material is characterized in that 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.
5. CN/Mn according to claim 1 2 O 3 The preparation method of the/FTOp-n heterojunction material is characterized in that in the step (2), the heating reaction temperature is 80-98 ℃, the heating reaction time is 1-2 h, the drying temperature is 60-100 ℃, and the drying temperature time is 18-36h.
6. CN/Mn according to claim 1 2 O 3 The preparation method of the/FTOp-n heterojunction material is characterized in that in the step (3), the flow rate of hydrogen gas for hydrogen plasma treatment is 10-100 sccm, the temperature rise 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.
7. CN/Mn according to claim 6 2 O 3 The preparation method of the/FTOp-n heterojunction material is characterized in that the temperature rise rate of hydrogen plasma treatment is 5-10 ℃/min, the temperature of the hydrogen plasma treatment is 400-500 ℃, the heat preservation time is 1.5-3 h, and the treatment pressure is 100-200 pa.
8. CN/Mn according to claim 1 2 O 3 The preparation method of the/FTOp-n heterojunction material is characterized in that in the step (3), the FTO glass has the specification that: 20X 2.2mm 3 ，10Ωsq -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.
9. CN/Mn obtained by the production method according to any one of claims 1 to 8 2 O 3 a/FTOp-n heterojunction material.
10. CN/Mn as claimed in claim 1 2 O 3 the/FTOp-n heterojunction material is applied to the photoelectrode field.
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