CN115410829B - Quantum dot sensitized oxide electrode and preparation method and application thereof - Google Patents
Quantum dot sensitized oxide electrode and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a quantum dot sensitized oxide electrode and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving cuprous iodide, zinc acetate and indium acetate in dodecyl mercaptan and oleylamine, heating, adding sulfur oleylamine solution, continuing heating, and quenching reaction to obtain a first reaction solution; adding dodecyl mercaptan and octadecene into the mixture, degassing, heating, quenching to obtain a second reaction solution, adding toluene and ethanol, mixing uniformly, centrifuging, dispersing in toluene again to obtain an electrophoretic deposition solution, and carrying out electrophoretic deposition by taking two oxide electrodes as working electrodes to obtain the quantum dot sensitized oxide electrode. The photoelectrochemical cell built by the electrode structure of the invention has high activity and high stability, and no external bias voltage is needed when the photoelectrochemical cell with a two-electrode system is built. The invention relates to the technical field of photoelectrochemical cells, and solves the problems of low activity, low stability, high toxicity and external bias voltage requirement of the existing photoelectrochemical cell.
Description
Technical Field
The invention relates to the technical field of photoelectrochemical cells, in particular to a quantum dot sensitized oxide electrode, a preparation method and application thereof.
Background
The quantum dot sensitized photoelectrochemical cell technology is a novel cell technology which directly utilizes light energy through a light response semiconductor and converts the light energy into chemical energy, and generally consists of a quantum dot sensitized photoelectrode with light activity, electrolyte and a circuit, has a simple structure, and has lower device cost and device complexity compared with the technology of generating electricity by photovoltaic and then generating hydrogen by electrolyzing water; compared with photoelectrochemical cell technology without quantum dot sensitization, the quantum dot with the adjustable band gap can fully absorb sunlight of ultraviolet, visible and near infrared, and can fully realize effective utilization of light energy. The current large-scale application of the quantum dot sensitized photoelectrochemical cell hydrogen production technology is mainly limited in the following aspects: firstly, the activity and stability of the whole battery are low due to insufficient contact between the quantum dots and the photoelectrode; secondly, the quantum dot sensitized photoelectrochemical cell usually needs an external power supply, and a certain bias voltage is applied to enable the device to obtain considerable performance; thirdly, although quantum dots are widely used in photoelectrochemical cells due to the characteristics of adjustable energy band structure, wide spectrum absorption and the like, most quantum dots contain toxic metals such as lead, cadmium and the like, and the development of the technology is hindered from the perspective of green and environmental protection.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a quantum dot sensitized oxide electrode, and a preparation method and application thereof, so as to solve the problems of poor contact, low activity, low stability, high toxicity and external bias voltage requirement of the traditional quantum dot sensitized photoelectrochemical cell.
The technical scheme for solving the technical problems is as follows: the preparation method of the quantum dot sensitized oxide electrode comprises the following steps:
(1) Completely dissolving cuprous iodide, zinc acetate and indium acetate in mixed solution of dodecyl mercaptan and oleylamine, heating at 200-250deg.C for 8-12min, dropwise adding oleylamine solution of sulfur, continuously heating at 180-220deg.C for 18-22min, and quenching to obtain first reaction solution, namely quantum dot ZnCuInS coated with oleylamine and dodecyl mercaptan 2 A solution;
(2) Adding the first reaction solution prepared in the step (1) into a mixed solution of dodecyl mercaptan and octadecene, degassing for 28-32min under the conditions of vacuum and 45-55 ℃, heating to 100-150 ℃, keeping for 10-20min, and then carrying out quenching reaction to obtain a second reaction solution, namely the dodecyl mercaptan coated quantum dot ZnCuInS 2 A solution;
(3) And (3) adding toluene and ethanol into the second reaction solution prepared in the step (2), uniformly mixing, centrifuging, dispersing the precipitate in toluene again to obtain an electrophoretic deposition solution, and carrying out electrophoretic deposition by taking two oxide electrodes as working electrodes to obtain the oxide electrode sensitized by the quantum dots.
The beneficial effects of the invention are as follows: the dodecyl mercaptan ligand has one mercapto group at one end and long chain alkyl at one end, the ligand coated quantum dot is mercapto contact quantum dot, and the alkyl is exposed to form outer hydrophobic quantum dot structure.
According to the invention, the quantum dots are coated by the dodecyl mercaptan ligand, then the oxide electrode is sensitized by the quantum dots, and the prepared quantum dot sensitized oxide electrode can effectively contact with the oxide electrode, so that the effective contact problem of the traditional quantum dot sensitized photoelectrode is solved based on different ligand lengths, ligand intensities and ligand loading amounts on the surface of the quantum dots, and meanwhile, the quantum dot sensitized oxide electrode does not contain toxic heavy metals; the quantum dot sensitized oxide electrode constructs a photoelectrochemical cell, particularly has high activity and high stability, and does not need external bias voltage when constructing a photoelectrochemical cell of a two-electrode system.
Based on the technical scheme, the invention can also be improved as follows:
further, in the step (1), the molar volume ratio of the cuprous iodide, the zinc acetate, the indium acetate, the dodecathiol and the oleylamine is 0.4-0.6mmol:0.4-0.6mmol:0.8-1.2mmol:4-6mL:4-6mL.
Further, in the step (1), degassing is carried out for 28-32min under vacuum and at 80-100 ℃, then heating is carried out to 130-150 ℃ under nitrogen atmosphere, and the dissolution process is completed after 10-20 min.
Further, in the step (1), the concentration of sulfur in the sulfur oleylamine solution is 0.3 to 0.8mol/L.
Further, in the step (1), the volume ratio of the dodecyl mercaptan to the sulfur oleylamine solution is 2-3:2.
further, in the step (2), the volume ratio of the first reaction solution, the dodecathiol and the octadecene is 2-4:4-6:8-12.
Further, in the step (2), heating is performed under a nitrogen atmosphere.
Further, in the step (3), the oxide electrode is a bismuth vanadate electrode or a cuprous oxide electrode.
Further, the bismuth vanadate electrode is prepared by the following method:
(3.11) adding potassium iodide, lactic acid and bismuth nitrate into water to obtain a mixed solution, regulating the pH value, then dropwise adding a p-benzoquinone ethanol solution, and stirring to obtain a deposition solution;
(3.12) taking the deposition liquid prepared in the step (3.11) as an electrochemical deposition liquid, taking conductive glass FTO as a working electrode, and performing electrophoretic deposition in a three-electrode system;
(3.13) dropwise adding dimethyl sulfoxide solution of vanadyl acetylacetonate onto the working electrode prepared in the step (3.12), heating to 400-500 ℃, keeping for 1.5-2.5h, then immersing into potassium hydroxide solution for dissolution, and washing to obtain the bismuth vanadate electrode.
Further, in the step (3.11), the concentrations of potassium iodide, lactic acid and bismuth nitrate in the mixed solution are respectively 0.3-0.5mol/L and 0.02-0.04mol/L:0.01-0.02mol/L.
Further, in the step (3.11), the pH value is adjusted to 1.5-2 by using a nitric acid solution.
Further, in the step (3.11), the volume ratio of the mixed solution to the p-benzoquinone ethanol solution is 45-55:15-25.
Further, in the step (3.11), the concentration of the p-benzoquinone ethanol solution is 0.04-0.05mol/L.
Further, in the step (3.12), the conditions of the electrophoretic deposition are: the reference electrode Ag/AgCl is applied to the electrode platinum sheet, voltage is firstly applied to-0.3 to-0.4V, deposition is carried out for 18-22s, then voltage is applied to-0.08 to-0.12V, and deposition is carried out for 250-350s.
Further, in the step (3.13), the concentration of the dimethyl sulfoxide solution of vanadyl acetylacetonate is 0.18 to 0.22mol/L.
Further, in the step (3.13), the concentration of the potassium hydroxide solution is 0.8 to 1.2mol/L.
Further, the cuprous oxide electrode is prepared by the following method:
(3.21) adding copper sulfate, dipotassium hydrogen phosphate and lactic acid into water, and adjusting the pH value to prepare a deposition solution;
(3.22) taking the deposition liquid prepared in the step (3.21) as an electrochemical deposition liquid, taking conductive glass FTO as a working electrode, and performing electrophoretic deposition in a two-electrode system;
(3.23) washing the working electrode obtained in the step (3.22), and obtaining the cuprous oxide electrode.
Further, in the step (3.21), the mass-volume ratio of the copper sulfate, the dipotassium hydrogen phosphate, the lactic acid and the water is 1-2g:4-5g:10-15g:45-55mL.
Further, in the step (3.21), the pH value is adjusted to 10-12 by adopting potassium hydroxide solution.
Further, in step (3.22), the conditions for electrophoretic deposition are: counter electrode platinum sheet, current density of-0.08 to-0.12 mA/cm 2 The deposition time is 2.5-3.5h.
Further, in the step (3), the volume ratio of the second reaction solution to the added toluene and ethanol is 2-4:5-10:3-8; the volume ratio of the second reaction liquid to the toluene which is dispersed and precipitated is 2-4:5-10.
Further, in the step (3), the electrophoretic deposition conditions are: the distance between electrodes is 0.8-1.2cm, and the electrode area is 1×1cm 2 Applying 180-220V voltage for 1.5-2.5 hr.
The invention also provides the quantum dot sensitized oxide electrode prepared by the preparation method of the quantum dot sensitized oxide electrode.
The invention also provides application of the quantum dot sensitized oxide electrode in preparation of a photoelectrochemical cell.
The invention also provides a photoelectrochemical cell comprising the oxide electrode sensitized by the quantum dots.
Further, the electrolyte of the photoelectrochemical cell was a potassium borate solution of 0.5mol/L at pH 9.
The invention has the following beneficial effects:
1. the invention provides a scheme for respectively sensitizing a bismuth vanadate anode and a cuprous oxide cathode by using green and environment-friendly quantum dots, and builds a serial unbiased photoelectrochemical cell group, so as to solve a series of problems of low activity, low stability, high toxicity and external bias of the existing photoelectrochemical cell.
2. According to the invention, a quantum dot simultaneous sensitization technology for different oxide electrodes is developed, and the doping energy level of the quantum dot is controlled, so that the energy band of the quantum dot can be sensitized with a cathode oxide and an anode oxide respectively, the preparation flow of the device is optimized, and the complexity of the whole device is reduced.
3. The unbiased photoelectrochemical cell constructed by the invention does not contain any toxic heavy metal, does not need an external access power supply to apply bias, and in addition, the electrolyte is sodium borate solution, the pH value of the electrolyte is only 9, compared with the pH value (generally 12.5) of other quantum dot sensitized photoelectrochemical cells, the pH value is lower, the consumption of alkali is reduced, and meanwhile, the requirement on battery equipment for resisting alkalinity is reduced; more importantly, the photoelectrochemical cell can realize the conversion efficiency from sunlight to hydrogen energy of 0.65% under the condition of simulated solar illumination, and maintains the stability of 99.9% within 2 hours of continuous illumination, thereby achieving the optimal activity and stability of the same type of unbiased photoelectrochemical cell based on quantum dots.
Drawings
FIG. 1 is a schematic diagram of the structure of a quantum dot sensitized oxide electrode according to example 1;
FIG. 2 is a cut-away SEM image of a quantum dot sensitized oxide electrode of example 1;
FIG. 3 is a schematic diagram of the structure of a quantum dot sensitized oxide electrode according to example 2;
FIG. 4 is a cut-away SEM image of a quantum dot sensitized oxide electrode of example 2;
fig. 5 is a photograph of the unbiased photoelectrochemical cell of example 3 when operated.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
the preparation method of the quantum dot sensitized oxide electrode comprises the following steps:
(1) Preparation of bismuth vanadate electrode
(1.1) preparing 50mL of mixed solution containing 0.4mol/L potassium iodide, 0.03mol/L lactic acid and 0.015mol/L bismuth nitrate, adding a nitric acid solution to adjust the pH value to 1.8, slowly dropwise adding 20mL of p-benzoquinone ethanol solution with the concentration of 0.046mol/L, and stirring for 20min until the pH value is stable to prepare a deposition solution;
(1.2) in a three-electrode deposition system in which the deposition solution obtained in the step (1.1) is used as an electrochemical deposition solution and the counter electrode is a platinum sheet electrode in a Ag/AgCl reference electrode containing 4mol/L potassium chloride, the concentration of the deposition solution is 1X 1cm 2 The conductive glass FTO is used as a working electrode, voltage of-0.35V is applied to a reference electrode, 20s is deposited firstly, then voltage of-0.1V is applied, and 300s is deposited, so that the bismuth oxyiodide-loaded working electrode is obtained;
dropwise adding 50 mu L of dimethyl sulfoxide solution of vanadyl acetylacetonate with the concentration of 0.18-0.22mol/L onto the bismuth oxyiodide prepared in the step (1.2) by using a pipetting gun, heating to 450 ℃ in a muffle furnace at the heating rate of 2 ℃/min, maintaining for 2h, naturally cooling to obtain a working electrode responsible for the mixture of bismuth vanadate and vanadium pentoxide, immersing into a potassium hydroxide solution with the concentration of 1mol/L to dissolve the vanadium pentoxide, and finally washing with deionized water to obtain the bismuth vanadate electrode;
(2) Placing cuprous iodide, zinc acetate, indium acetate, dodecathiolol and oleylamine into a three-necked flask, degassing under vacuum and 90 ℃ for 30min, heating to 140 ℃ under nitrogen atmosphere, keeping for 15min to ensure complete dissolution, forming copper indium zinc solution, heating at 230 ℃ for 10min to nucleate quantum dots, dropwise adding 4mL of oleylamine solution with concentration of 0.5mol/L sulfur into the solution by using a syringe, continuing heating at 200 ℃ for 20min to grow the quantum dots, and finally placing the three-necked flask into a three-necked flaskQuenching in cold water to obtain a first reaction solution, namely the quantum dot ZnCuInS coated by the oleylamine and the dodecyl mercaptan 2 A solution; wherein, the molar volume ratio of the cuprous iodide, the zinc acetate, the indium acetate, the dodecathiol and the oleylamine is 0.5mmol:0.5mmol:1mmol:5mL:5mL;
(3) Placing dodecyl mercaptan and octadecene in a three-necked flask, adding the first reaction liquid prepared in the step (2), degassing for 30min under the conditions of vacuum and 50 ℃, heating to 120 ℃ under nitrogen atmosphere, keeping for 15min to enable the ligand on the surface of the quantum dot to be fully exchanged, placing the three-necked flask in cold water, and carrying out quenching reaction to obtain a second reaction liquid, namely the dodecyl mercaptan coated quantum dot ZnCuInS 2 A solution; wherein, the volume ratio of the first reaction liquid, the dodecathiol and the octadecene is 3:5:10;
(4) Adding 7mL of toluene and 5mL of ethanol into 3mL of the second reaction solution prepared in the step (3), fully oscillating and uniformly mixing, centrifuging to obtain a precipitate, dispersing the precipitate in 7mL of toluene again to obtain an electrophoretic deposition solution, and performing electrophoretic deposition by taking the bismuth vanadate electrode prepared in the two steps (1) as a working electrode, wherein the electrode distance is 1cm and the electrode area is 1 multiplied by 1cm 2 And applying voltage of 200V and depositing for 2h to obtain the quantum dot sensitized bismuth vanadate electrode, namely the quantum dot sensitized oxide electrode.
A photoelectrochemical cell, the method of making comprising the steps of: the quantum dot sensitized bismuth vanadate electrode is used as a working electrode, a platinum sheet is used as a counter electrode, ag/AgCl containing 4mol/L potassium chloride is used as a reference electrode, and a 0.5mol/L potassium borate solution with the pH value of 9 is used as an electrolyte, so that the bias three-electrode system photoelectrochemical cell is constructed.
Example 2:
the preparation method of the quantum dot sensitized oxide electrode comprises the following steps:
(1) Preparing a cuprous oxide electrode:
(1.1) preparing 50mL of a mixed solution containing 1.6g of copper sulfate, 4.4g of dipotassium hydrogen phosphate and 13.5g of lactic acid, and adjusting the pH value to 12 by adopting a potassium hydroxide solution to prepare a deposition solution;
(1.2) the process of step (1.1)The obtained deposition solution is electrochemical deposition solution, and is 1×1cm 2 In a two-electrode system with the conductive glass FTO as a working electrode and the platinum sheet as a counter electrode, the relative counter electrode is at-0.1 mA/cm 2 Constant current deposition is carried out at current density for 3h to obtain a working electrode loaded with cuprous oxide;
(1.3) washing the cuprous oxide-loaded working electrode prepared in the step (1.2) with deionized water to prepare a cuprous oxide electrode;
in the step (4), the cuprous oxide electrode sensitized by the quantum dots, namely the oxide electrode sensitized by the quantum dots, is prepared by taking the cuprous oxide electrode prepared in the step (1) as a working electrode.
The procedure is as in example 1.
A photoelectrochemical cell, the method of making comprising the steps of: the quantum dot sensitized cuprous oxide electrode is used as a working electrode, the platinum sheet is used as a counter electrode, the Ag/AgCl containing 4mol/L potassium chloride is used as a reference electrode, and the 0.5mol/L potassium borate solution with the pH value of 9 is used as an electrolyte, so that the bias three-electrode system photoelectrochemical cell is constructed.
Example 3:
the preparation method of the quantum dot sensitized oxide electrode comprises the following steps:
(1) Bismuth vanadate electrode was prepared as in example 1; preparation of cuprous oxide electrode the same as in example 2;
in the step (4), the bismuth vanadate electrode and the cuprous oxide electrode prepared in the step (1) are respectively used as working electrodes, and the quantum dot sensitized bismuth vanadate electrode and the quantum dot sensitized cuprous oxide electrode, namely the quantum dot sensitized oxide electrode, are respectively prepared.
The procedure is as in example 1.
A photoelectrochemical cell, the method of making comprising the steps of: the method comprises the steps of using a quantum dot sensitized cuprous oxide electrode as a photo-anode, using the quantum dot sensitized cuprous oxide electrode as a cathode, and using a potassium borate solution with the pH value of 9 and 0.5mol/L as electrolyte to construct a bias-free photoelectrochemical cell of a two-electrode system.
Example 4:
the preparation method of the quantum dot sensitized oxide electrode comprises the following steps:
(1) Preparation of bismuth vanadate electrode
(1.1) preparing 45mL of mixed solution containing 0.3mol/L potassium iodide, 0.02mol/L lactic acid and 0.01mol/L bismuth nitrate, adding a nitric acid solution to adjust the pH value to 1.5, slowly dropwise adding 15mL of p-benzoquinone ethanol solution with the concentration of 0.04mol/L, and stirring for 20min until the pH value is stable to prepare a deposition solution;
(1.2) in a three-electrode deposition system in which the deposition solution obtained in the step (1.1) is used as an electrochemical deposition solution and the counter electrode is a platinum sheet electrode in a Ag/AgCl reference electrode containing 4mol/L potassium chloride, the concentration of the deposition solution is 1X 1cm 2 The conductive glass FTO is used as a working electrode, voltage of-0.3V is applied to a reference electrode, 22s is deposited firstly, then voltage of-0.08V is applied, and 350s is deposited, so that the bismuth oxyiodide-loaded working electrode is obtained;
dropwise adding 50 mu L of dimethyl sulfoxide solution of vanadyl acetylacetonate with the concentration of 0.18mol/L onto the bismuth oxyiodide prepared in the step (1.2) by using a pipetting gun, heating to 400 ℃ in a muffle furnace at the heating rate of 2 ℃/min, maintaining for 2.5h, naturally cooling to obtain a working electrode responsible for the mixture of bismuth vanadate and vanadium pentoxide, immersing into potassium hydroxide solution with the concentration of 0.8mol/L to dissolve the vanadium pentoxide, and finally washing with deionized water to obtain the bismuth vanadate electrode;
(2) Placing cuprous iodide, zinc acetate, indium acetate, dodecyl mercaptan and oleylamine into a three-necked flask, degassing under vacuum and 80 ℃ for 32min, heating to 130 ℃ under nitrogen atmosphere, keeping for 20min to ensure complete dissolution, forming copper indium zinc solution, heating at 200 ℃ for 12min to nucleate quantum dots, dropwise adding 4mL of oleylamine solution with concentration of 0.3mol/L sulfur into the solution by using a syringe, continuing heating at 180 ℃ for 22min to grow quantum dots, finally placing the three-necked flask into cold water, quenching to obtain a first reaction solution, namely quantum dots ZnCuInS coated by the oleylamine and the dodecyl mercaptan together 2 A solution; wherein, the molar volume ratio of the cuprous iodide, the zinc acetate, the indium acetate, the dodecathiol and the oleylamine is 0.4mmol:0.4mmol:0.8mmol:4mL:4mL;
(3) Twelve sulfurPlacing alcohol and octadecene in a three-necked flask, adding the first reaction solution prepared in the step (2), degassing for 32min under vacuum and 45 ℃, heating to 100 ℃ under nitrogen atmosphere, keeping for 20min to enable ligands on the surfaces of the quantum dots to be fully exchanged, placing the three-necked flask in cold water, and performing quenching reaction to obtain a second reaction solution, namely the dodecyl mercaptan coated quantum dots ZnCuInS 2 A solution; wherein, the volume ratio of the first reaction liquid, the dodecathiol and the octadecene is 2:4:8, 8;
(4) Adding 5mL of toluene and 3mL of ethanol into 2mL of the second reaction solution prepared in the step (3), fully oscillating and uniformly mixing, centrifuging to obtain a precipitate, dispersing the precipitate in 5mL of toluene again to obtain an electrophoretic deposition solution, and performing electrophoretic deposition by taking the bismuth vanadate electrode prepared in the two steps (1) as a working electrode, wherein the electrode distance is 0.8cm, and the electrode area is 1 multiplied by 1cm 2 And applying voltage 180V, and depositing for 2.5h to obtain the quantum dot sensitized bismuth vanadate electrode, namely the quantum dot sensitized oxide electrode.
A photoelectrochemical cell, the method of making comprising the steps of: the quantum dot sensitized bismuth vanadate electrode is used as a working electrode, a platinum sheet is used as a counter electrode, ag/AgCl containing 4mol/L potassium chloride is used as a reference electrode, and a 0.5mol/L potassium borate solution with the pH value of 9 is used as an electrolyte, so that the bias three-electrode system photoelectrochemical cell is constructed.
Example 5:
the preparation method of the quantum dot sensitized oxide electrode comprises the following steps:
(1) Preparation of bismuth vanadate electrode
(1.1) preparing 55mL of a mixed solution containing 0.5mol/L potassium iodide, 0.04mol/L lactic acid and 0.02mol/L bismuth nitrate, adding a nitric acid solution to adjust the pH value to 2, slowly dropwise adding 25mL of a p-benzoquinone ethanol solution with the concentration of 0.05mol/L, and stirring for 20min until the pH value is stable to prepare a deposition solution;
(1.2) in a three-electrode deposition system in which the deposition solution obtained in the step (1.1) is used as an electrochemical deposition solution and the counter electrode is a platinum sheet electrode in a Ag/AgCl reference electrode containing 4mol/L potassium chloride, the concentration of the deposition solution is 1X 1cm 2 Conductive glass FTO is used as a working electrode and is applied relative to a reference electrode-depositing for 18s at a voltage of 0.4V, and then applying a voltage of-0.12V for 200s to obtain a working electrode loaded with bismuth oxyiodide;
dropwise adding 50 mu L of dimethyl sulfoxide solution of vanadyl acetylacetonate with the concentration of 0.22mol/L onto the bismuth oxyiodide prepared in the step (1.2) by using a pipetting gun, heating to 550 ℃ in a muffle furnace at the heating rate of 2 ℃/min, maintaining for 1.5h, naturally cooling to obtain a working electrode responsible for the mixture of bismuth vanadate and vanadium pentoxide, immersing into potassium hydroxide solution with the concentration of 1.2mol/L to dissolve the vanadium pentoxide, and finally washing with deionized water to obtain the bismuth vanadate electrode;
(2) Putting cuprous iodide, zinc acetate, indium acetate, dodecyl mercaptan and oleylamine into a three-necked flask, degassing for 28min under vacuum and 100 ℃, heating to 150 ℃ under nitrogen atmosphere, keeping for 10min to ensure complete dissolution, forming copper indium zinc solution, heating for 8min under 250 ℃ to nucleate quantum dots, dropwise adding 4mL of oleylamine solution with concentration of 0.8mol/L sulfur into the solution by using a syringe, continuing heating for 18min under 220 ℃ to enable the quantum dots to grow, finally putting the three-necked flask into cold water, quenching, and obtaining a first reaction solution, namely quantum dot ZnCuInS coated by the oleylamine and dodecyl mercaptan together 2 A solution; wherein, the molar volume ratio of the cuprous iodide, the zinc acetate, the indium acetate, the dodecathiol and the oleylamine is 0.6mmol:0.6mmol:1.2mmol:6mL:6mL;
(3) Placing dodecyl mercaptan and octadecene in a three-necked flask, adding the first reaction liquid prepared in the step (2), degassing for 28min under the conditions of vacuum and 55 ℃, heating to 150 ℃ under nitrogen atmosphere, keeping for 10min to enable the ligand on the surface of the quantum dot to be fully exchanged, placing the three-necked flask in cold water, and carrying out quenching reaction to obtain a second reaction liquid, namely the dodecyl mercaptan coated quantum dot ZnCuInS 2 A solution; wherein, the volume ratio of the first reaction liquid to the dodecathiol to the octadecene is 4:6:12;
(4) Adding 10mL of toluene and 8mL of ethanol into 4mL of the second reaction solution prepared in the step (3), sufficiently oscillating and uniformly mixing, centrifuging to obtain a precipitate, and dispersing the precipitate in 10mL of toluene again to obtain an electrophoresis deposition solution, thereby obtaining the electrophoresis deposition solutionTwo bismuth vanadate electrodes prepared in the step (1) are used as working electrodes, electrophoretic deposition is carried out, the distance between the electrodes is 1.2cm, and the electrode area is 1 multiplied by 1cm 2 And applying 220V voltage for 1.5h to prepare the quantum dot sensitized bismuth vanadate electrode, namely the quantum dot sensitized oxide electrode.
A photoelectrochemical cell, the method of making comprising the steps of: the quantum dot sensitized bismuth vanadate electrode is used as a working electrode, a platinum sheet is used as a counter electrode, ag/AgCl containing 4mol/L potassium chloride is used as a reference electrode, and a 0.5mol/L potassium borate solution with the pH value of 9 is used as an electrolyte, so that the bias three-electrode system photoelectrochemical cell is constructed.
Example 6:
the preparation method of the quantum dot sensitized oxide electrode comprises the following steps:
(1) Preparation of cuprous oxide electrode
(1.1) preparing 45mL of a mixed solution containing 1g of copper sulfate, 4g of dipotassium hydrogen phosphate and 10g of lactic acid, and adjusting the pH value to 10 by adopting a potassium hydroxide solution to prepare a deposition solution;
(1.2) the deposition solution obtained in the step (1.1) was used as an electrochemical deposition solution at a concentration of 1X 1cm 2 In a two-electrode system with the conductive glass FTO as a working electrode and the platinum sheet as a counter electrode, the relative counter electrode is at-0.08 mA/cm 2 Constant current deposition is carried out at current density for 3.5h to obtain a working electrode loaded with cuprous oxide;
(1.3) washing the cuprous oxide-loaded working electrode prepared in the step (1.2) with deionized water to prepare a cuprous oxide electrode;
in the step (4), the cuprous oxide electrode sensitized by the quantum dots, namely the oxide electrode sensitized by the quantum dots, is prepared by taking the cuprous oxide electrode prepared in the step (1) as a working electrode.
The procedure is as in example 4.
A photoelectrochemical cell, the method of making comprising the steps of: the quantum dot sensitized cuprous oxide electrode is used as a working electrode, the platinum sheet is used as a counter electrode, the Ag/AgCl containing 4mol/L potassium chloride is used as a reference electrode, and the 0.5mol/L potassium borate solution with the pH value of 9 is used as an electrolyte, so that the bias three-electrode system photoelectrochemical cell is constructed.
Example 7:
the preparation method of the quantum dot sensitized oxide electrode comprises the following steps:
(1) Preparation of cuprous oxide electrode
(1.1) preparing 55mL of a mixed solution containing 2g of copper sulfate, 5g of dipotassium hydrogen phosphate and 15g of lactic acid, and adjusting the pH value to 11 by adopting a potassium hydroxide solution to prepare a deposition solution;
(1.2) the deposition solution obtained in the step (1.1) was used as an electrochemical deposition solution at a concentration of 1X 1cm 2 In a two-electrode system with the conductive glass FTO as a working electrode and the platinum sheet as a counter electrode, the relative counter electrode is at-0.12 mA/cm 2 Constant current deposition is carried out at current density for 3h to obtain a working electrode loaded with cuprous oxide;
(1.3) washing the cuprous oxide-loaded working electrode prepared in the step (1.2) with deionized water to prepare a cuprous oxide electrode;
in the step (4), the cuprous oxide electrode sensitized by the quantum dots, namely the oxide electrode sensitized by the quantum dots, is prepared by taking the cuprous oxide electrode prepared in the step (1) as a working electrode.
The procedure is as in example 5.
A photoelectrochemical cell, the method of making comprising the steps of: the quantum dot sensitized cuprous oxide electrode is used as a working electrode, the platinum sheet is used as a counter electrode, the Ag/AgCl containing 4mol/L potassium chloride is used as a reference electrode, and the 0.5mol/L potassium borate solution with the pH value of 9 is used as an electrolyte, so that the bias three-electrode system photoelectrochemical cell is constructed.
Example 8:
the preparation method of the quantum dot sensitized oxide electrode comprises the following steps:
(1) Bismuth vanadate electrode was prepared as in example 4 and cuprous oxide electrode was prepared as in example 6.
In the step (4), the bismuth vanadate electrode and the cuprous oxide electrode prepared in the step (1) are respectively used as working electrodes, and the quantum dot sensitized bismuth vanadate electrode and the quantum dot sensitized cuprous oxide electrode, namely the quantum dot sensitized oxide electrode, are respectively prepared.
The procedure is as in example 4.
A photoelectrochemical cell, the method of making comprising the steps of: the method comprises the steps of using a quantum dot sensitized cuprous oxide electrode as a photo-anode, using the quantum dot sensitized cuprous oxide electrode as a cathode, and using a potassium borate solution with the pH value of 9 and 0.5mol/L as electrolyte to construct a bias-free photoelectrochemical cell of a two-electrode system.
Example 9:
the preparation method of the quantum dot sensitized oxide electrode comprises the following steps:
(1) Bismuth vanadate electrode was prepared as in example 5 and cuprous oxide electrode was prepared as in example 7.
In the step (4), the bismuth vanadate electrode and the cuprous oxide electrode prepared in the step (1) are respectively used as working electrodes, and the quantum dot sensitized bismuth vanadate electrode and the quantum dot sensitized cuprous oxide electrode, namely the quantum dot sensitized oxide electrode, are respectively prepared.
The procedure is as in example 5.
A photoelectrochemical cell, the method of making comprising the steps of: the method comprises the steps of using a quantum dot sensitized cuprous oxide electrode as a photo-anode, using the quantum dot sensitized cuprous oxide electrode as a cathode, and using a potassium borate solution with the pH value of 9 and 0.5mol/L as electrolyte to construct a bias-free photoelectrochemical cell of a two-electrode system. Comparative example 1:
an oxide electrode, the preparation method of which comprises the following steps: step (1) was performed as in example 1.
A photoelectrochemical cell, the method of making comprising the steps of: the method is characterized in that a bismuth vanadate electrode is used as a working electrode, a platinum sheet is used as a counter electrode, ag/AgCl containing 4mol/L potassium chloride is used as a reference electrode, and a 0.5mol/L potassium borate solution with the pH value of 9 is used as an electrolyte, so that a bias three-electrode system photoelectrochemical cell is constructed.
Comparative example 2:
the preparation method of the quantum dot sensitized oxide electrode comprises the following steps:
(1) Bismuth vanadate electrodes were prepared as in example 1;
(2) A first reaction solution was prepared as in example 1;
(3) Preparing a second reaction solution, namely the quantum dot ZnCuInS coated by the oleylamine 2 Solution: the dodecyl mercaptan in the step (3) of the example 1 is replaced by oleylamine, and the rest is the same as the step (3) of the example 1;
the procedure is as in example 1.
A photoelectrochemical cell, the method of making comprising the steps of: the quantum dot sensitized bismuth vanadate electrode is used as a working electrode, a platinum sheet is used as a counter electrode, ag/AgCl containing 4mol/L potassium chloride is used as a reference electrode, and a 0.5mol/L potassium borate solution with the pH value of 9 is used as an electrolyte, so that the bias three-electrode system photoelectrochemical cell is constructed.
Comparative example 3:
the preparation method of the quantum dot sensitized oxide electrode comprises the following steps: step (3) was omitted and the remainder was the same as in example 1.
A photoelectrochemical cell, the method of making comprising the steps of: the quantum dot sensitized bismuth vanadate electrode is used as a working electrode, a platinum sheet is used as a counter electrode, ag/AgCl containing 4mol/L potassium chloride is used as a reference electrode, and a 0.5mol/L potassium borate solution with the pH value of 9 is used as an electrolyte, so that the bias three-electrode system photoelectrochemical cell is constructed.
Comparative example 4:
the preparation method of the quantum dot sensitized oxide electrode comprises the following steps:
(1) Bismuth vanadate electrodes were prepared as in example 1;
(2) A first reaction solution was prepared as in example 1;
(3) Placing 4mL of mercaptopropionic acid and 24mL of dimethylformamide into a three-necked flask, adding 2mL of the first reaction solution prepared in the step (2), degassing for 30min under the conditions of vacuum and 50 ℃, heating to 120 ℃ under the nitrogen atmosphere, keeping for 15min to enable the ligand on the surface of the quantum dot to be fully exchanged, placing the three-necked flask into cold water for quenching reaction, finally settling with 30mL of n-propanol, dissolving the sediment with 30mL of deionized water, and preparing a second reaction solution, namely the mercaptopropionic acid coated quantum dot ZnCuInS 2 A solution;
the procedure is as in example 1.
A photoelectrochemical cell, the method of making comprising the steps of: the quantum dot sensitized bismuth vanadate electrode is used as a working electrode, a platinum sheet is used as a counter electrode, ag/AgCl containing 4mol/L potassium chloride is used as a reference electrode, and a 0.5mol/L potassium borate solution with the pH value of 9 is used as an electrolyte, so that the bias three-electrode system photoelectrochemical cell is constructed.
Comparative examples 5 to 8:
the bismuth vanadate electrodes in comparative examples 1 to 4 were replaced with cuprous oxide electrodes, respectively, which were used as working electrodes, platinum sheets as counter electrodes, ag/AgCl containing 4mol/L potassium chloride as reference electrode, and 0.5mol/L potassium borate solution having pH value of 9 as electrolyte, and a bias three-electrode system photoelectrochemical cell was constructed, and the rest were the same.
Comparative example 9:
a photoelectrochemical cell, the method of making comprising the steps of: the bismuth vanadate electrode prepared in comparative example 1 is used as a photo-anode, the cuprous oxide electrode in comparative example 2 is used as a cathode, and a 0.5mol/L potassium borate solution with the pH value of 9 is used as an electrolyte, so that the bias-free photoelectrochemical cell of the two-electrode system is constructed.
Test examples
1. The cut-off surfaces of the quantum dot sensitized oxide electrodes prepared in examples 1 to 2 were subjected to electron microscopic examination, respectively, and a schematic diagram was drawn, and the results are shown in fig. 1 to 4. From FIGS. 1-4, it can be seen that the dodecyl mercaptan coated quantum dot ZnCuInS 2 Into the bismuth vanadate electrode, the thickness is approximately 2.2 μm; dodecyl mercaptan coated quantum dot ZnCuInS 2 Into the cuprous oxide electrode, the thickness is approximately 3.2 μm.
2. The photoelectrochemical cell prepared in example 3 was used with a standard am1.5g solar simulator as a light source, and the result is shown in fig. 5. As can be seen from fig. 5, the electrodes all generate hydrogen.
3. The biased three-electrode system photoelectrochemical cells prepared in example 1 and comparative examples 1 to 4 were subjected to performance testing using a standard AM1.5G solar simulator as a light source, and the results are shown in Table 1. As can be seen from Table 1, the quantum dots ZnCuInS coated with dodecyl mercaptan 2 Sensitized bismuth vanadate electrodeThe solar simulated photo-generated current density is the most excellent, and compared with an unsensitized electrode, the performance is improved by about 2 times.
Table 1 photoelectrochemical cell anode performance biased test data
4. The biased three-electrode system photoelectrochemical cells prepared in example 2 and comparative examples 5 to 8 were subjected to performance testing using a standard AM1.5G solar simulator as a light source, and the results are shown in Table 2. As can be seen from Table 2, the quantum dots ZnCuInS coated with dodecyl mercaptan 2 The sensitized cuprous electrode has the most excellent solar simulated photo-generated current density, and the performance is improved by 4 times compared with an unsensitized electrode.
Table 2 photoelectrochemical cell cathode performance biased test data
5. Performance tests were performed on the bias-free two-electrode system photoelectrochemical cells prepared in example 3 and comparative example 9, using a standard am1.5g solar simulator as a light source, solar conversion hydrogen energy efficiency = bias-free current density x 1.23V/optical power density; two electrode system, continuous light for 2h,2h stability = final current density/initial current density, results are shown in table 3. As can be seen from Table 3, the quantum dots ZnCuInS coated with dodecyl mercaptan 2 The unbiased photoelectrochemical cell constructed by the sensitized bismuth vanadate photoanode and the cuprous oxide cathode has excellent solar energy conversion efficiency and excellent stability.
Table 3 photoelectrochemical cell no bias test data
| Performance parameters | Example 3 | Comparative example 9 |
| The efficiency of converting sunlight into hydrogen energy is% | 0.65 | 0.06 |
| 2h stability% | 99.9 | / |
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the quantum dot sensitized oxide electrode is characterized by comprising the following steps of:
(1) Completely dissolving cuprous iodide, zinc acetate and indium acetate in mixed solution of dodecyl mercaptan and oleylamine, heating at 200-250deg.C for 8-12min, dropwise adding oleylamine solution of sulfur, continuously heating at 180-220deg.C for 18-22min, and quenching to obtain first reaction solution, namely quantum dot ZnCuInS coated with oleylamine and dodecyl mercaptan 2 A solution;
(2) Adding the first reaction solution prepared in the step (1) into a mixed solution of dodecyl mercaptan and octadecene, degassing for 28-32min under the conditions of vacuum and 45-55 ℃, heating to 100-150 ℃, keeping for 10-20min, and then carrying out quenching reaction to obtain a second reaction solution, namely the dodecyl mercaptan coated quantum dot ZnCuInS 2 A solution;
(3) And (3) adding toluene and ethanol into the second reaction solution prepared in the step (2), uniformly mixing, centrifuging, dispersing the precipitate in toluene again to obtain an electrophoretic deposition solution, and carrying out electrophoretic deposition by taking two oxide electrodes as working electrodes to obtain the oxide electrode sensitized by the quantum dots.
2. The method for preparing a quantum dot sensitized oxide electrode according to claim 1, wherein in the step (1), the molar volume ratio of cuprous iodide, zinc acetate, indium acetate, dodecathiol and oleylamine is 0.4 to 0.6mmol:0.4-0.6mmol:0.8-1.2mmol:4-6mL:4-6mL.
3. The method for preparing a quantum dot sensitized oxide electrode according to claim 1, wherein in the step (1), the dissolution process is completed by degassing for 28 to 32 minutes under vacuum at 80 to 100 ℃ and then heating to 130 to 150 ℃ under nitrogen atmosphere for 10 to 20 minutes.
4. The method for preparing a quantum dot sensitized oxide electrode according to claim 1, wherein in the step (2), the volume ratio of the first reaction liquid, dodecathiol and octadecene is 2-4:4-6:8-12.
5. The method of preparing a quantum dot sensitized oxide electrode according to claim 1, wherein in the step (3), the oxide electrode is a bismuth vanadate electrode or a cuprous oxide electrode.
6. The method for preparing a quantum dot sensitized oxide electrode according to claim 1, wherein in the step (3), the volume ratio of the second reaction liquid to toluene and ethanol added is 2-4:5-10:3-8; the volume ratio of the second reaction liquid to the toluene which is dispersed and precipitated is 2-4:5-10.
7. The method of preparing a quantum dot sensitized oxide electrode according to claim 1, wherein in the step (3), the electrophoretic deposition conditions are: the distance between electrodes is 0.8-1.2cm, and the electrode area is 1×1cm 2 The voltage of 180-220V is applied,the deposition time is 1.5-2.5h.
8. A quantum dot sensitized oxide electrode prepared by the method for preparing a quantum dot sensitized oxide electrode according to any one of claims 1 to 7.
9. Use of a quantum dot sensitized oxide electrode according to claim 8 for the preparation of a photoelectrochemical cell.
10. A photoelectrochemical cell comprising a quantum dot sensitized oxide electrode according to claim 8.
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