CN110957142A - CdS nanoparticle modified TiO2Nano composite photoelectric material, preparation and application - Google Patents
CdS nanoparticle modified TiO2Nano composite photoelectric material, preparation and application Download PDFInfo
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- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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- H01G9/20—Light-sensitive devices
- H01G9/2054—Light-sensitive devices comprising a semiconductor electrode comprising AII-BVI compounds, e.g. CdTe, CdSe, ZnTe, ZnSe, with or without impurities, e.g. doping materials
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Abstract
The invention belongs to the field of improving photoelectrochemical conversion performance, and particularly relates to superfine highly branched TiO modified by CdS nano-particles2A nano-composite photoelectric material and a preparation method and application thereof. The composite photoelectric material is TiO with a superfine highly branched nano lawn structure2CdS nano-particles are deposited on the surface of a photoanode substrate of the material to form a composite photoelectric material of a composite heterojunction system. According to the invention, through the combination of the CdS nano-particles, the heterojunction structure well integrates the transmission performance of electrons, so that the photoelectric conversion efficiency of solar energy is improved. The method has the advantages of simple experimental operation steps, cheap and easily-obtained raw materials, and has important significance for preparing the nano material with high photoelectrochemical conversion performance.
Description
Technical Field
The invention belongs to the field of improving photoelectrochemical conversion performance, and particularly relates to superfine highly branched TiO modified by CdS nano-particles2A nano-composite photoelectric material and a preparation method and application thereof.
Background
TiO2The material is a semiconductor material which is most widely applied at present, and has the advantages of low price, high stability, environmental friendliness and the like, so that the material is widely applied to the fields of solar cells, hydrogen production by water photolysis, photocatalytic degradation and the like. However, TiO2But has larger forbidden band width, can only respond to ultraviolet light in sunlight, and generates light carrierThe fluid is easily recombined, thereby limiting its utilization of solar energy. Thus to TiO2The current research focus is to perform morphology regulation and modification to improve the photoresponse capability of the optical fiber.
Aiming at the defect that photogenerated carriers are easy to compound, researchers find that TiO with special nano-morphology is prepared2The nano material such as one-dimensional (nano rod, nano tube) and the like can provide a direct electronic path for the rapid transmission of photo-generated electrons, effectively reduce the crystal boundary, improve the collection efficiency of photo-generated carriers and realize effective charge separation and transfer. In addition, the light absorption area can be further increased by constructing a nano-branched structure, more electron active sites are generated, and the channel for electron transmission is increased. Furthermore, the ultrafining of the nano-branches can further improve the rapid transfer of photo-generated charge carriers and reduce the charge transfer barrier. The superfine nanowires are mutually connected, can provide more electron transmission channels, is easy for electrolyte permeation, can further improve the conductivity, and enriches electrochemical active sites.
For TiO2The defects of large band gap and narrow light absorption range can expand the optical absorption area by coupling with other sensitizers and thus improve the solar energy utilization rate. Meanwhile, researches find that the compact heterojunction structure can also help to effectively separate photogenerated electrons and holes in different semiconductors, so that the photogenerated electrons and holes in different semiconductors can show extremely high photoelectrochemical properties compared with single-component materials, and the electrons can be more easily transferred between interfaces due to sufficient interface combination between two semiconductor heterojunctions, so that the separation of electron holes is promoted, the manufacture of high-efficiency semiconductor heterojunction materials is facilitated, and the photoelectric conversion performance of the materials is improved.
Thus, against the above TiO2The method aims to adopt corresponding measures to improve the carrier transmission and expand the light utilization range, mainly focuses on constructing a photoelectrode with special nano-morphology and compounding a sensitizer corresponding to visible light on the photoelectrode to enhance the photoelectric conversion activity of the photoelectrode, so as to better utilize the solar energy.
Disclosure of Invention
Aiming at the improvement of TiO2Semiconductor materialThe invention relates to the problem of photoelectrochemical conversion performance of a material, and aims to provide superfine highly branched TiO modified by CdS nano particles2A nano-composite photoelectric material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
CdS nanoparticle modified TiO2The nano composite photoelectric material is TiO with a superfine highly branched nano lawn structure2CdS nano-particles are deposited on the surface of a photoanode substrate of the material to form a composite photoelectric material of a composite heterojunction system.
The deposition is through successive ionic layer adsorption reactions(SILAR)Cyclic deposition of CdS nanoparticles to ultrafine highly branched TiO2And a photo-anode substrate.
TiO with superfine highly branched nano lawn structure2Immersing the material photo-anode substrate into the solution b for 20-30 seconds, taking out and washing with deionized water, then immersing into the solution c for 20-30 seconds, taking out and washing with deionized water again to form a CdS immersion deposition cycle, and repeating the immersion deposition cycle until 10-15 circulating CdS nanoparticles are deposited; the CdS nano-particle deposition amount is 10-15 immersion deposition cycles.
The solution b is 0.002-0.003M Cd (NO)3)2A solution; the solution c is 0.002-0.003M Na2And (5) preparing an S solution.
TiO with superfine highly branched nano lawn structure formed on the photoanode substrate2The material is directly grown with TiO on a substrate by a one-step hydrothermal method2An optoelectronic material.
Placing the pretreated substrate in an inner container of a high-pressure reaction kettle, placing the conductive surface of the substrate at an angle of 45 degrees with the kettle wall, adding the solution a into the high-pressure reaction kettle to immerse the substrate, heating the substrate at 190 ℃ for 6-12 hours at 170 ℃ and directly growing TiO with the ultrafine highly branched nano lawn structure on the substrate2A material;
the solution a is prepared by adding titanium potassium oxalate powder into a diethylene glycol aqueous solution and obtaining anatase with the shape of a nano lawn through a one-step hydrothermal methodTiO of mineral phase2A photovoltaic material; wherein the aqueous solution of diethylene glycol is deionized water (H)2O) and diethylene glycol (DEG) in a volume ratio of (1: 2) - (1: 4) the final concentration of the titanium potassium oxalate powder in the aqueous solution of diethylene glycol is 1.98-2.02 mM.
CdS nanoparticle modified TiO2A process for preparing the nano-class composite photoelectric material used for preparing the superfine highly-branched nano lawn2Immersing the material photo-anode substrate into the solution b for 20-30 seconds, taking out and washing with deionized water, then immersing into the solution c for 20-30 seconds, taking out and washing with deionized water again to form a CdS immersion deposition cycle, and repeating the immersion deposition cycle until the required amount of CdS nano-particles are doped; the deposition amount of the CdS nano particles is 10-15 cycles; the solution b is 0.002-0.003MCd (NO)3)2A solution; the solution c is 0.002-0.003M Na2And (5) preparing an S solution.
CdS nanoparticle modified TiO2The application of the nano composite photoelectric material, and the composite photoelectric material is used as a material with photoelectric conversion performance.
The photoelectric material is used for a photo-anode and generates photo-generated current density under the irradiation of simulated sunlight, thereby realizing the application in the light-electricity conversion.
CdS nanoparticle modified superfine highly branched TiO2Nanocomposite photoelectrode, TiO2The nano-structure film directly grows on the surface of the conductive substrate through hydrothermal reaction, and CdS nano-particles are deposited on the prepared TiO with the nano lawn-like appearance through an SILAR method2A substrate surface.
TiO modified by CdS nano-particles prepared by the method for improving photoelectric and chemical conversion performance2The nano composite photoelectric material is used for testing the photoelectric chemical conversion performance, and is characterized by the change of photo-generated current density and an incident photon-electron conversion efficiency (IPCE) spectrum. Wherein the change in the photo-generated current density is measured by recording information on the change in the photo-generated current density with time under on/off light conditions. The specific measurement device is CHI660D electrochemical workstation, and uses three-electrode system and Pt electrodes respectivelyAg/AgCl electrode and prepared TiO2The nano composite photo anode is used as a counter electrode, a reference electrode and a working electrode for measurement, as shown in fig. 2. The electrolyte used was 0.25M Na2S+0.35M Na2SO3And (3) solution. Simulating sunlight (AM1.5) by using a xenon lamp as a light source, wherein the optical power density is 100mW cm-2. At the center of the front face of the cell there is a quartz window of about 30mm in diameter through which the incident light impinges on the surface of the photoelectrode. The PEC conversion efficiency of the photoanode was studied based on monochromatic incident photon-electron conversion efficiency (IPCE) spectroscopy, which was measured with a monochromator, also using the three-electrode system as above.
The basic principle of the invention is as follows: CdS is a visible light-responsive sensitizer with a forbidden band width (Eg) of 2.4 eV; and TiO 22Has a forbidden band width of 3.2eV, and mainly responds to ultraviolet light. CdS and TiO under simulated sunlight irradiation2Electrons in the valence band may be excited into the conduction band to produce photogenerated electrons. TiO due to the conduction band potential ratio of CdS2More negative of (2), TiO2Is more positive than CdS, resulting in the transfer of photo-generated electrons generated at the conduction band of CdS to TiO2To reduce its energy, TiO2The photo-generated holes generated on the valence band of CdS will be transferred to the valence band of CdS, thus achieving separation of electrons and holes. At the same time, TiO2The photoanode substrate with the superfine highly branched nano structure promotes the rapid transfer of photo-generated charges and reduces TiO2And the interface transfer potential barrier between the CdS and the CdS finally provides a quick charge transmission path. In addition, the interlaced elongated nanostructures of the loose porous structure also give a large number of light trapping regions and electron collection sites. Therefore, the quantum efficiency of the composite material is greatly improved, and the photoelectric conversion efficiency is greatly improved.
The invention has the advantages that:
the invention leads the TiO with the superfine highly branched nano lawn structure2The photoanode substrate is combined with the ultrafine CdS nanoparticles corresponding to visible light, and the transmission performance of electrons is well integrated through the multiphase heterojunction structure, so that the photoelectric conversion efficiency of solar energy is improved; in particular to：
1. The invention synthesizes TiO by a one-step hydrothermal method2The CdS nano-particles are modified on the surface of the nano-material through SILAR, the method is simple in operation steps, raw materials are cheap and easy to obtain, and the obtained nano-composite material has good photoelectrochemical conversion performance.
2. CdS nanoparticle modified TiO of the invention2The nano composite photoelectric material firstly has a loose porous structure and a staggered and slender nano structure, and can realize a large number of light capture areas and electron collection sites; secondly, the heterojunction system promotes the rapid transfer of photo-generated charges and reduces TiO2And the interface transfer potential barrier between the CdS and the CdS finally provides a quick charge transmission path. Thereby leading the composite material to realize good photoelectrochemistry conversion performance.
3. The photo-generated current density of the composite photo-anode prepared by the invention can reach 5.6 mA-cm under the irradiation of simulated sunlight (AM1.5)-2The photo-generated current density can reach 3.8mA cm under the irradiation of simulated visible light-2The photoelectric conversion performance is greatly improved.
Drawings
FIG. 1 shows CdS nanoparticle modified TiO provided by an embodiment of the invention2The preparation process of the nano composite photoelectric material.
FIG. 2 shows TiO provided in an embodiment of the present invention2The device diagram of the photo-generated current density test of the composite light anode.
FIG. 3 is a SEM, TEM and HRTEM image of the present invention. Wherein a and b are respectively TiO with superfine highly branched nano lawn structure2SEM and TEM images of the photoanode substrate; c and d are respectively TiO of superfine highly branched nano lawn structure modified by CdS nano particles2TEM, HRTEM images of the composite photoanode.
FIG. 4 shows an example of the present invention, which provides a TiO with an ultra-fine highly-branched nano lawn structure2Photoanode and CdS nanoparticle modified superfine highly branched TiO lawn structure2The composite light anode is used for intermittently simulating the change curve of photo-generated current density with time under the irradiation of sunlight and visible light.
FIG. 5 shows an example of the present invention, which provides a TiO with an ultra-fine highly-branched nano lawn structure2Photoanode and CdS nanoparticle modified superfine highly branched TiO lawn structure2Monochromatic incident photon-electron conversion efficiency (IPCE) spectra of the composite photoanode.
Detailed Description
The invention will be further described, by way of example, without in any way being restricted to the following figures.
Examples
CdS nanoparticle modified TiO for improving photoelectrochemical conversion performance2Preparing a nano composite photoelectric material:
1) preparation of FTO conductive glass: firstly, cutting FTO glass into 20 x 10mm2Size, then ultrasonic cleaning in analytically pure acetone for 5 minutes, then deionized water for 5 minutes, and then drying the FTO glass for later use.
2) Preparation of hydrothermal solution: titanium potassium oxalate (PTO), 0.708g in mass, was added to 10mL of deionized water, stirred under magnetic stirring for 15 minutes, and then 30mL of diethylene glycol (DEG) was added and stirring was continued for 15 minutes.
3) Ultra-fine highly branched TiO2Preparation of the photo-anode: placing the FTO conductive glass obtained in the step 1) in an inner container of a high-pressure reaction kettle, wherein the conductive surface is placed downwards and forms a certain angle with the kettle wall. Adding the solution obtained in the step 2) into a reaction kettle, and then heating the solution at 180 ℃ for 9 hours to obtain the superfine highly branched nano lawn structure TiO2A substrate (fig. 3a and 3 b).
4) Modification of CdS nanoparticles to TiO2Surface of the nano material: circularly depositing CdS nano-particles to the superfine highly branched TiO prepared in the step 3) by a continuous ion layer adsorption reaction technology2And a photo-anode substrate. Firstly, TiO prepared in the step 3) is treated2The substrate photoanode was immersed in the solution b for 20 seconds and rinsed with deionized water, then immersed in the solution c for another 20 seconds and rinsed again with deionized water. This impregnation procedure is called one cycle of CdS deposition, which is repeated 12 times until the desired amount of CdS nanoparticles is incorporated (fig. 3c and 3 d). Wherein the solution b is0.0025M Cd(NO3)2Solution (cationic precursor); solution c is 0.0025M Na2S solution (cationic precursor). The specific preparation flow chart is shown in figure 1.
The obtained TiO is2The composite material was rinsed with deionized water, dried, and placed in a muffle furnace at 450 ℃ for 1 hour. Then coating insulating silica gel, and pasting a copper adhesive tape to prepare the photo-anode for measuring the photoelectrochemical conversion performance.
For TiO obtained by the above preparation2The photoelectrode is used for testing the photoelectrochemical conversion performance: on the device shown in the schematic diagram of the experimental device 2, CHI660D electrochemical workstation of Shanghai Chenghua instruments company is adopted, and the monitoring is carried out under a three-electrode system by 0.25M Na2S+0.35M Na2SO3The solution was used as an electrolyte to simulate the change in the photo-generated current density (fig. 4) of the photoelectrode under the irradiation of intermittent sunlight and visible light, and the monochromatic incident photon-electron conversion efficiency (IPCE) was measured using a monochromator (fig. 5).
The superfine highly branched nano lawn structure TiO prepared can be seen from figure 3a2The specific SEM image consists of a series of superfine nanowires and a plurality of superfine nanometer branches, and has a loose and porous structure, and the diameter of the main trunk of each superfine nanowire is about 200 nm; from the TEM image of FIG. 3b, it is clear that the diameter of the nano-branches is only 5-10 nm. FIG. 3c shows the prepared CdS nanoparticle modified superfine highly branched nano lawn structure TiO2TEM images, comparing fig. 3b, show that CdS nanoparticles are uniformly distributed on the ultrafine nano-branches, with a size of only about 5nm, indicating that the deposited CdS nanoparticles are also ultrafine. FIG. 3d shows CdS/TiO2HRTEM image of (1), a lattice spacing of 0.352nm corresponds to anatase TiO2And the lattice spacing of the nanoparticles on the nano-branches of 0.336nm corresponds to the (111) plane of CdS. This ultrafine highly branched nanostructure will contribute to TiO2The CdS nano particles are fully combined, a superfine transmission path of light-induced electrons is provided, the electron transmission resistance is reduced, the electrolyte easily enters the inner surface of the composite material due to a loose porous structure, and the transfer distance of charge carriers is shortened. In addition, theThe large surface area of the structure may also promote interconnect light scattering and promote photon absorption by the fabricated photoanode.
From FIG. 4, it can be seen that TiO prepared under intermittent simulated sunlight and visible light illumination2And CdS/TiO2The change in the intensity of the photo-induced current of the photoelectrode. Under simulated sunlight, TiO with single nanometer lawn structure2The photo-generated current density of the photo-anode is about 100 muA cm-2And hardly responds under visible light. And CdS nanoparticle modified TiO2The current density of the photoelectrode is as high as 5.6mA cm-2The photo-generated current density can reach 3.8mA cm under the irradiation of simulated visible light-2. TiO of superfine highly branched nano lawn structure modified by CdS nano particles2The photoelectrochemical conversion performance of the composite photo-anode is obviously improved.
The TiO produced can be seen from FIG. 52And CdS/TiO2Spectrum of incident photon-electron conversion efficiency (IPCE) of photoelectrode. Pure TiO2The photoanode exhibits a light response only at incident wavelengths of 300 to 400nm and has an IPCE value (11.3% maximum) to CdS/TiO2The IPCE value of the photo-anode is much smaller. And CdS/TiO2The IPCE values of the photoanode showed significantly enhanced photoresponse, especially at incident wavelengths of 300 to 520 nm. This phenomenon is caused by the deposited CdS nanoparticles acting as light absorbers causing a photoresponse, which absorbers have a strong light absorption in this region. CdS/TiO in the incident wavelength range of 300-520nm2The IPCE of the photoanode reached 27.3-74.8%, and the maximum IPCE was about 74.8% at an incident wavelength of 320 nm. This result demonstrates that TiO is modified with CdS nanoparticles2The photo-anode can obviously improve the photon-electron conversion efficiency, namely enhance the photoelectrochemical conversion performance.
Claims (10)
1. CdS nanoparticle modified TiO2The nano-composite photoelectric material is characterized in that: the composite photoelectric material is TiO with a superfine highly branched nano lawn structure2CdS nano-particles are deposited on the surface of a photoanode substrate of the material to form a composite photoelectric material of a composite heterojunction system.
2. CdS nanoparticle modified TiO as defined in claim 12The nano-composite photoelectric material is characterized in that: the deposition is that CdS nano-particles are circularly deposited to superfine highly branched TiO through continuous ion layer adsorption reaction2And a photo-anode substrate.
3. CdS nanoparticle modified TiO according to claim 1 or 22The nano-composite photoelectric material is characterized in that: TiO with superfine highly branched nano lawn structure2And (3) immersing the material photoanode substrate into the solution b for 20-30 seconds, taking out and washing with deionized water, then immersing the material photoanode substrate into the solution c for 20-30 seconds, taking out and washing with deionized water again to form a CdS immersion deposition cycle, and repeating the immersion deposition cycle until 10-15 CdS nanoparticles are deposited.
4. CdS nanoparticle modified TiO as defined in claim 32The nano-composite photoelectric material is characterized in that: the solution b is 0.002-0.003M Cd (NO)3)2A solution; the solution c is 0.002-0.003M Na2And (5) preparing an S solution.
5. CdS nanoparticle modified TiO as defined in claim 32The nano-composite photoelectric material is characterized in that: TiO with superfine highly branched nano lawn structure formed on the photoanode substrate2The material is directly grown with TiO on a substrate by a one-step hydrothermal method2An optoelectronic material.
6. CdS nanoparticle modified TiO as claimed in claim 52The nano-composite photoelectric material is characterized in that: placing the pretreated substrate in an inner container of a high-pressure reaction kettle, placing the conductive surface of the substrate at an angle of 45 degrees with the kettle wall, adding the solution a into the high-pressure reaction kettle to immerse the substrate, heating the substrate at 190 ℃ for 6-12 hours at 170 ℃ and directly growing TiO with the ultrafine highly branched nano lawn structure on the substrate2A material;
the solution isThe liquid a is prepared by adding titanium potassium oxalate powder into a diethylene glycol aqueous solution and obtaining TiO of anatase phase with nano lawn morphology by a one-step hydrothermal method2A photovoltaic material; wherein the aqueous solution of diethylene glycol is deionized water (H)2O) and diethylene glycol (DEG) in a volume ratio of (1: 2) - (1: 4) the final concentration of the titanium potassium oxalate powder in the aqueous solution of diethylene glycol is 1.98-2.02 mM.
7. The CdS nanoparticle-modified TiO of claim 12The preparation method of the nano-composite photoelectric material is characterized by comprising the following steps: TiO with superfine highly branched nano lawn structure2Immersing the material photo-anode substrate into the solution b for 20-30 seconds, taking out and washing with deionized water, then immersing into the solution c for 20-30 seconds, taking out and washing with deionized water again to form a CdS immersion deposition cycle, and repeating the immersion deposition cycle until the required amount of CdS nano-particles are doped; the solution b is 0.002-0.003MCd (NO)3)2A solution; the solution c is 0.002-0.003M Na2And (5) preparing an S solution.
8. The CdS nanoparticle-modified TiO of claim 12The application of the nano composite photoelectric material is characterized in that: the composite photoelectric material is used as a material with photoelectric conversion performance.
9. CdS nanoparticle modified TiO as defined in claim 82The application of the nano composite photoelectric material is characterized in that: the photoelectric material is used for a photo-anode and generates photo-generated current density under the irradiation of simulated sunlight, thereby realizing the application in the light-electricity conversion.
10. CdS nanoparticle modified superfine highly branched TiO2The nano composite photoelectrode is characterized in that: TiO 22The nano-structure film directly grows on the surface of the conductive substrate through hydrothermal reaction, and CdS nano-particles are deposited on the prepared TiO with the nano lawn-like appearance through an SILAR method2A substrate surface.
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