CN115572985A - Cobalt-doped CsPbBr 3 Quantum dot photoelectric catalyst and preparation method and application thereof - Google Patents
Cobalt-doped CsPbBr 3 Quantum dot photoelectric catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of photoelectric catalysts, and particularly relates to cobalt-doped CsPbBr 3 A quantum dot photoelectric catalyst, a preparation method and application thereof. The invention realizes the stable cubic phase by doping, and the cobalt-doped CsPbBr with the cobalt-lead molar ratio of 0.03-0.10 percent 3 The preparation of the quantum dot photocatalyst ensures that the quantum dot photocatalyst has high photoelectrocatalysis activity and efficiency, visible light response and fluorescence quenching property can be modulated by cobalt doping concentration; the compound can be used as a photo-anode catalytic material in photoelectrocatalysis application, can still maintain 50% of stability in water within 5500 seconds, and realizes CsPbBr 3 The possibility of operating the quantum dot photoelectric catalyst in water. The preparation process is simple, the cost is greatly reduced, and meanwhile, the single junction photovoltaic meets the minimum voltage required by water decomposition, so that the single junction photovoltaic is an ideal high-efficiency photoelectric catalyst material. Overcomes the defects of the existing photoelectric catalyst such as the transmission obstacle of photon-generated carriers and electron holesThe problem of fast recombination provides an enlightenment for the inorganic perovskite quantum dot to be used in PEC photoelectrocatalysis.
Description
Technical Field
The invention belongs to the technical field of photoelectric catalysts, and particularly relates to cobalt-doped CsPbBr 3 Quantum dotsA photoelectric catalyst, a preparation method and application thereof.
Background
In recent years, with the increasing problems of global environmental climate pollution and energy shortage, green and clean renewable energy sources are searched for in all countries around the world to realize green and healthy development. Hydrogen energy is one of important hot spots for research in the energy field as a clean, zero-carbon, renewable and high-energy secondary clean energy. Solar energy is converted into hydrogen energy through water decomposition by utilizing photoelectrocatalysis, and the method is an ideal hydrogen production mode. However, most semiconductor materials have the defect of poor photoelectrocatalysis activity nowadays, and the development of efficient photoelectrocatalysts is still an important focus in the field of photoelectrocatalysis water decomposition.
At present, common photocatalysts comprise elemental metal photocatalysts, metal oxide photocatalysts and the like. The wide application of the metal elementary substance photoelectric catalyst is limited due to the expensive price and scarcity of the metal elementary substance photoelectric catalyst, and the metal oxide photoelectric catalyst can only utilize the ultraviolet part of solar light due to the large band gap of the metal oxide photoelectric catalyst. The quantum dots as the quasi-zero-dimensional material have the unique properties of quantum confinement effect, dielectric confinement effect and the like, have the advantages of adjustable components, doping possibility, adjustable size, easy surface passivation, high defect tolerance, high phase stability and the like, and are widely applied to the field of photoelectrocatalysis for preparing high-efficiency photocatalysts.
At present, various types of quantum dots such as AgInS, pbS and other photocatalysts are widely applied to the field of photoelectrocatalysis and show excellent performance, but the preparation process is complex, the production cost is high, and the industrial production and application of the quantum dots are severely restricted. CsPbBr 3 The quantum dot has the advantages of simple preparation and low cost, responds in visible light, and simultaneously meets the minimum voltage required by water decomposition by single junction photovoltaic, thereby being an ideal material for preparing the high-efficiency photoelectric catalyst. But the photoelectrocatalysis activity and efficiency of the photoelectrocatalysis material still need to be improved due to factors such as transmission obstacle of photogenerated carriers, recombination of electron hole pairs and the like.
Disclosure of Invention
Aiming at the problems or the defects, the method aims to solve the problems of high cost, photoelectrocatalysis activity and poor photoelectrocatalysis activity of the existing quantum dot photocatalystThe invention provides a cobalt-doped CsPbBr, which has low efficiency 3 A quantum dot photoelectric catalyst, a preparation method and application thereof.
Cobalt-doped CsPbBr 3 The crystal structure of the quantum dot photoelectric catalyst is a cubic phase, the molar ratio of cobalt to lead is 0.03-0.10%, and the quantum dot photoelectric catalyst absorbs light at a wavelength of 500-520 nm to realize visible light response and has a fluorescence quenching characteristic. Can effectively solve CsPbBr 3 The quantum dot carrier transmission barrier and the electron hole pair are quickly compounded, so that the separation efficiency of the electron hole pair and the service life of the carrier are improved. The standard sunlight irradiation and 1.23V are realized RHE Under bias, the photocurrent density is as high as 1.944mA/cm 2 And is stabilized at 1mA/cm 2 The time is 5000-5500 seconds, and the photocatalyst has better photoelectrocatalysis activity and water stability.
The cobalt-doped CsPbBr 3 The preparation method of the quantum dot photoelectric catalyst comprises the following steps:
step 1, in an inert gas atmosphere, mixing a cesium source and a solvent, and heating to 100-120 ℃ to uniformly disperse the cesium source and the solvent to prepare a cesium precursor solution, wherein the concentration of cesium is 0.8-1 mol/L.
And 3, purifying the mixed solution prepared in the step 2, and then drying in vacuum to obtain the cobalt-doped CsPbBr 3 A quantum dot photocatalyst.
Further, in the step 1, the cesium source is cesium carbonate, and the solvent is a mixed solution of octadecene and oleic acid with purity of more than or equal to 90% and a volume ratio of 9.5-12.
Further, in the step 2, the ligand and the solvent are an oleic acid solution, an oleylamine solution and octadecene in a volume ratio of 1-1.2. The ligand and the solvent enable the quantum dots to stably exist in the solution.
Furthermore, the purification process in the step 3 adopts a toluene and ethyl acetate mixed solution with the concentration of more than or equal to 99.8% and the volume ratio of 1-1.2 to ensure that the cobalt is doped with CsPbBr 3 The mixed solution of the quantum dots is completely dispersed and then completely centrifuged, and the precipitate at the lower part is purified cobalt-doped CsPbBr 3 Quantum dots to remove most of the solvent and unreacted PbBr during synthesis 2 。
Further, the temperature of vacuum drying in the step 3 is 50-80 ℃ to remove the cobalt-doped CsPbBr 3 The solvent in the quantum dots is remained and kept stable without inactivation.
The cobalt-doped CsPbBr 3 The quantum dot photoelectric catalyst is coated on a photoelectric anode with the thickness of 40-60 nm and is used as a photoelectric catalyst applied to the field of photoelectric catalysis.
In conclusion, the invention provides the CsPbBr 3 The quantum dots are doped with cobalt to realize the stable cubic phase cobalt doping CsPbBr 3 The preparation of the quantum dot photoelectric catalyst further solves the problems of transmission barrier of a photon-generated carrier and rapid recombination of an electron hole pair of the existing photoelectric catalyst, so that the photoelectric catalyst has high photoelectric catalytic activity and efficiency, visible light response and can modulate fluorescence quenching characteristics through cobalt doping concentration; the compound can be used as a photo-anode catalytic material in photoelectrocatalysis application, can still maintain 50% of stability in water within 5500 seconds, and realizes CsPbBr 3 The possibility of operating the quantum dot photoelectric catalyst in water. The preparation process is simple, the cost is greatly reduced, and meanwhile, the single junction photovoltaic meets the minimum voltage required by water decomposition, so that the single junction photovoltaic is an ideal high-efficiency photoelectric catalyst material. Provides an enlightenment for the inorganic perovskite quantum dots to be used in PEC photoelectrocatalysis.
Drawings
FIG. 1 is an XRD pattern of samples obtained in examples 1 to 4 and comparative example 1;
FIG. 2 is a graph showing UV-Vis spectral absorptions of samples obtained in examples 1 to 4 and comparative example 1;
FIG. 3 is a photoluminescence spectrum of samples obtained in examples 1 to 4 and comparative example 1;
FIG. 4 is a plot of linear sweep voltammograms of examples 1-4 and comparative example 1 applied to a photoanode device under visible light;
fig. 5 is a stability test chart of the photoanode device applied to example 2 in an aqueous solution.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
Cobalt-doped CsPbBr 3 The preparation method of the quantum dot photoelectric catalyst comprises the following steps:
step 1, under the atmosphere of nitrogen at 120 ℃, 130mgCs 2 CO 3 Adding into 6mL of mixed solution of 90% octadecene and 0.5mL of 90% oleic acid, mixing, drying for 1 hr, and heating to 150 deg.C to Cs 2 CO 3 And completely dissolving to obtain cesium precursor solution.
And 3, centrifuging the mixed solution prepared in the step 2, removing the lower-layer precipitate, purifying by using a mixed solution of 1.5mL of methylbenzene and 4.5mL of ethyl acetate, centrifuging at the speed of 9000 r/min, and removing the lower-layer precipitate to obtain the purified cobalt-doped CsPbBr 3 And (4) quantum dots. Purified cobalt-doped CsPbBr 3 Putting the quantum dots in a vacuum drying oven for drying to obtain the cobalt-doped CsPbBr 3 The quantum dot photocatalyst has a molar ratio of cobalt to lead of 0.03%.
Example 2
The cobalt content of the oleylamine solution containing cobalt chloride in step 2 was adjusted in the same manner as in example 1 by carrying outPreparation procedure in example 1, cobalt-doped CsPbBr was prepared 3 The quantum dot photocatalyst has a molar ratio of cobalt to lead of 0.05%.
Example 3
In the same manner as in example 1, the cobalt content in the oleylamine solution containing cobalt chloride in step 2 was adjusted, and cobalt-doped CsPbBr was prepared through the preparation process in example 1 3 The quantum dot photocatalyst has a molar ratio of cobalt to lead of 0.06%.
Example 4
In the same manner as in example 1, the cobalt content in the oleylamine solution containing cobalt chloride in step 2 was adjusted, and cobalt-doped CsPbBr was prepared through the preparation process in example 1 3 The quantum dot photocatalyst has a molar ratio of cobalt to lead of 0.10%.
Comparative example 1
CsPbBr 3 The preparation method of the quantum dot photoelectric catalyst comprises the following steps:
step 1, under the atmosphere of nitrogen at 120 ℃, 130mgCs 2 CO 3 Adding into 6mL of mixed solution of 90% octadecene and 0.5mL of 90% oleic acid, mixing, drying for 1 hr, and heating to 150 deg.C to Cs 2 CO 3 And completely dissolving to obtain cesium precursor solution.
Cobalt-doped CsPbBr obtained in examples 1-4 3 Quantum dot photocatalyst and CsPbBr obtained in comparative example 1 3 The quantum dot photoelectric catalyst is respectively mixed and dispersed with a polar solvent uniformlyHomogenizing and knife coating to sinter TiO with a thickness of 200nm 2 Coating the FTO glass with a coating thickness of 50nm, and then packaging the coating layer by using low-temperature conductive carbon paste to obtain the CsPbBr based on cobalt doping 3 A photoelectric anode device of quantum dot photoelectric catalyst.
Application examples
FIG. 1 shows CsPbBr obtained in examples 1 to 4 and comparative example 1 3 XRD characterization results of quantum dot photocatalysts, cobalt-doped CsPbBr obtained in examples 1-4 3 Quantum dot photocatalyst and CsPbBr obtained in comparative example 1 3 Compared with the quantum dot photoelectric catalyst, the crystal structure is not changed after doping, and the CsPbBr is compared with the cubic phase CsPbBr 3 The crystal diffraction peaks (PDF # 18-0364) remained consistent. The following table shows CsPbBr obtained in examples 1 to 4 3 ICP-MS test is carried out on the quantum dot photoelectric catalyst, and the cobalt content is respectively 0.03%, 0.05%, 0.06% and 0.10%.
Table 1: cobalt-doped CsPbBr obtained in examples 1 to 4 3 Perovskite quantum dot ICP-MS data table
| Sample(s) | Cobalt content | Lead content | Molar ratio of |
| Example 1 | 40.1ug/L | 457.7mg/L | 0.03％ |
| Example 2 | 65.6ug/L | 442.8mg/L | 0.05％ |
| Example 3 | 230ug/L | 1325.8mg/L | 0.06％ |
| Example 4 | 158.6ug/L | 571.5mg/L | 0.10％ |
FIG. 2 shows CsPbBr synthesized in examples 1 to 4 and comparative example 1 3 The ultraviolet-visible spectrum absorption diagram of the quantum dot photocatalyst is used for comparing the light absorption performance of the quantum dot photocatalyst. The quantum dot catalyst absorbs light at wavelengths of 500 to 520nm and, with doping of cobalt, csPbBr 3 The absorption intensity of the quantum dot photoelectric catalyst is obviously enhanced, but the absorption intensity is reduced to a certain extent along with the further increase of the cobalt doping concentration, and the most suitable cobalt doping concentration is 0.05%. Meanwhile, no new absorption band appears after cobalt doping, namely, the cobalt pair CsPbBr is doped 3 The electronic structure of the quantum dot photocatalyst has little effect.
FIG. 3 shows CsPbBr synthesized in examples 1 to 4 and comparative example 1 3 Photoluminescence of the quantum dot photocatalyst is shown, and the separation efficiency of electron-hole pairs is studied. Synthetic CsPbBr 3 Quantum dot photocatalyst and cobalt-doped CsPbBr 3 The quantum dot photocatalyst emits light at the wavelength of 520-518 nm, and the half-peak width is 22.24nm. However, obvious fluorescence quenching phenomenon occurs after cobalt doping, which indicates that the cobalt-doped CsPbBr 3 The quantum dot photocatalyst has higher electron-hole pair separation efficiency and carrier transport efficiency.
In a photoelectrocatalysis test system, a working electrode is a photoelectric anode to be testedThe device comprises a platinum electrode as a counter electrode, an Ag/AgCl reference electrode as a reference electrode and 1mol/L potassium hydroxide aqueous solution as electrolyte. The electrochemical test instrument is CHI760e electrochemical workstation of Shanghai Chenghua instrument, the light source is 500W xenon lamp light source with 1.5G filter, and the light power is 100mW/cm 2 . The test method is linear scanning cyclic voltammetry, and the test range is 0.5V-1.5V vs.
FIG. 4 is a photo-electric diagram of examples 1 to 4 and comparative example 1. Photoelectrode devices obtained in examples 1 to 4 and comparative example 1 are depicted by a photocurrent under irradiation with visible light, at irradiation with visible light and 1.23V RHE CsPbBr-based material prepared in comparative example 1 under bias 3 The photocurrent density of the quantum dot photoanode device is 0.422mA/cm 2 The photocurrent density is small. But cobalt doped CsPbBr 3 Then, the photocurrent density is obviously improved, and when the cobalt doping concentration reaches 0.05 percent, csPbBr is doped based on cobalt 3 The current density of the photoelectric anode device of the quantum dot photoelectric catalyst is improved to 1.944mA/cm 2 The result shows that the cobalt doping can be effectively improved based on CsPbBr 3 The photoelectrocatalysis activity of the quantum dot photoelectrode device.
FIG. 5 shows CsPbBr doped based on Co prepared in example 2 3 And (3) testing the stability of the quantum dot photoanode device in an aqueous solution. At 1.23V RHE Continuous illumination under bias voltage, based on cobalt-doped CsPbBr 3 The photocurrent density of the quantum dot photoanode device is stabilized at 1mA/cm 2 The length of the water-soluble polymer reaches 5500s, and the water-soluble polymer has better water stability.
As can be seen from the above examples and comparative examples and subsequent testing, the cobalt-doped CsPbBr 3 The quantum dot photoelectric catalyst absorbs light at the wavelength of 500-520 nm to realize visible light response, can generate obvious fluorescence quenching along with cobalt doping, can effectively inhibit electron-hole pair recombination, improves the transmission rate of a photon-generated carrier, further enhances the photoelectric catalytic activity of the photocatalyst, and promotes the application of the photocatalyst in water.
Claims (7)
1. Cobalt-doped CsPbBr 3 The quantum dot photocatalyst is characterized in that: the crystal structure is a cubic phase, the molar ratio of cobalt to lead is 0.03-0.10%, and the crystal absorbs light at the wavelength of 500-520 nm, realizes visible light response and has fluorescence quenching property; under standard sunlight irradiation and 1.23V RHE Under bias, the photocurrent density is as high as 1.944mA/cm 2 And is stabilized at 1mA/cm 2 The time is 5000-5500 seconds.
2. The cobalt-doped CsPbBr of claim 1 3 The preparation method of the quantum dot photoelectric catalyst is characterized by comprising the following steps of:
step 1, in an inert gas atmosphere, mixing a cesium source and a solvent, and heating to 100-120 ℃ to uniformly disperse the cesium source and the solvent to prepare a cesium precursor solution, wherein the concentration of cesium is 0.8-1 mol/L;
step 2, under the inert gas atmosphere, adding PbBr 2 Adding the mixture into a mixed solution of a ligand containing cobalt and a solvent, heating the mixture to 100-120 ℃, uniformly mixing the mixture at a constant temperature, drying the mixture to remove moisture, heating the mixture to 160-180 ℃, adding the cesium precursor solution obtained in the step (1), keeping the temperature for 5-9 s, and quenching the mixture to obtain cobalt-doped CsPbBr 3 The mixed solution of quantum dots, wherein the molar ratio of cobalt to lead is 0.03-0.10%;
and 3, purifying the mixed solution prepared in the step 2, and then drying in vacuum to obtain the cobalt-doped CsPbBr 3 A quantum dot photocatalyst.
3. The cobalt-doped CsPbBr of claim 2 3 The preparation method of the quantum dot photoelectric catalyst is characterized by comprising the following steps of;
in the step 1, the cesium source is cesium carbonate, and the solvent is a mixed solution of octadecene and oleic acid with the purity of more than or equal to 90% and the volume ratio of 9.5-12.
4. The cobalt-doped CsPbBr of claim 2 3 The preparation method of the quantum dot photoelectric catalyst is characterized by comprising the following steps of;
in the step 2, the ligand and the solvent are oleic acid solution, oleylamine solution and octadecene with the volume ratio of 1-1.2.
5. The cobalt-doped CsPbBr of claim 2 3 The preparation method of the quantum dot photoelectric catalyst is characterized by comprising the following steps of;
the purification process of the step 3 adopts a toluene and ethyl acetate mixed solution with the concentration of more than or equal to 99.8 percent and the volume ratio of 1-1.2 to ensure that the cobalt is doped with CsPbBr 3 The mixed solution of the quantum dots is completely dispersed and then completely centrifuged, and the precipitate at the lower part is purified cobalt-doped CsPbBr 3 Quantum dots to remove most of the solvent and unreacted PbBr during synthesis 2 。
6. The cobalt-doped CsPbBr of claim 2 3 The preparation method of the quantum dot photoelectric catalyst is characterized by comprising the following steps of; the temperature of vacuum drying in the step 3 is 50-80 ℃.
7. The cobalt-doped CsPbBr of claim 1 3 The application of the quantum dot photocatalyst is characterized in that; doping cobalt with CsPbBr 3 The quantum dot photoelectric catalyst is coated on a photoelectric anode with the thickness of 40-60 nm and is used as a photoelectric catalyst applied to the field of photoelectric catalysis.
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