CN110776064A - Self-driven photocatalytic triphibian system with full visible light response - Google Patents

Self-driven photocatalytic triphibian system with full visible light response Download PDF

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CN110776064A
CN110776064A CN201911010346.9A CN201911010346A CN110776064A CN 110776064 A CN110776064 A CN 110776064A CN 201911010346 A CN201911010346 A CN 201911010346A CN 110776064 A CN110776064 A CN 110776064A
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anode
light
cathode
triphibian
photo
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曾庆意
常晟
胡春
王铭麒
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Guangzhou University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses a full-visible-light-response self-driven photocatalytic triphibian system, which comprises an integrated photo-anode, a cathode, an electrolyte solution, refractory organic pollutants, a light source and a quartz reaction tank, wherein the integrated photo-anode is Si-doped TiO 2The nanorod array film electrode and the positive electrode of the photovoltaic cell are connected and superposed to form a composite light anode, and the cathode is a platinum electrode; the integrated photo-anode and cathode are inserted into an electrolyte solution containing refractory organic pollutants in the quartz reaction cell and are communicated through an external circuit; the light source is started to irradiate the integrated photo-anode, and the film electrode absorbs the short-wavelength lightAnd the transmission part of light excites the photovoltaic cell to generate voltage to drive photo-generated electrons to migrate to the cathode through an external circuit, electrode reactions are respectively generated on the surface of the thin film electrode and the cathode, and a loop is formed through the external circuit. The invention has response to all-band visible light, can degrade organic pollutants difficult to degrade in water, and has excellent hydrogen production and power generation efficiency, good stability and low cost.

Description

Self-driven photocatalytic triphibian system with full visible light response
Technical Field
The invention relates to a self-driven photocatalytic triphibian system with full visible light response, belonging to the field of photocatalysis.
Background
With the large-scale growth of human social population, the continuous growth of industrial volume, and the development of life style towards high demand, human beings face more and more serious energy problems and environmental problems. The photocatalysis technology takes light as a driving force, can realize hydrogen production by water decomposition and organic matter degradation, and has great potential in the fields of new energy and water pollution control. The photoelectrocatalysis system based on double electrodes is the earliest electrode type photocatalysis reaction system [ Electrocatalysis 6(2015)415-441], and under the action of external bias voltage, the photoelectrode is driven to transfer photogenerated electrons or holes to a counter electrode, so that photogenerated charge separation is promoted, and hydrogen production by water decomposition or organic matter degradation is realized. However, the addition of an external bias voltage accounts for the consumption of additional energy, reducing the energy utilization efficiency.
In the absence of an applied bias, a two-electrode system, which is commonly referred to as a photocatalytic fuel cell system [ Sci. Total environ.668(2019)966-]. The system does not need external bias voltage, can realize photocatalytic water decomposition or organic matter degradation, and simultaneously realizes power generation by an external circuit, thereby having higher energy utilization efficiency than a photoelectric catalytic system. However, the Fermi level difference between the electrodes is usually small, below 0.6V [ Environ. Sci. Technol.53(2019)3697-]Thus, it is difficult to achieve efficient photo-generated charge transfer, and its application in the field of photolytic water (potential greater than 1.23V) is limited. In addition, a single semiconductor photoelectrode material typically absorbs only a small portion of light having a short wavelength less than its absorption band edge, such as the most widely studied TiO 2The photoelectrode material can only absorb ultraviolet light below 385nm, so that the full utilization of the system to sunlight is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a full visible light response photocatalysis triphibian system with high efficiency and self-driving so as to realize the purpose of converting solar energy into hydrogen energy and electric energy and simultaneously removing organic pollutants in water.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a full-visible-light-response self-driven photocatalytic triphibian system comprises an integrated photo-anode, a cathode, an electrolyte solution, a non-degradable organic pollutant, a light source and a quartz reaction tank, wherein the integrated photo-anode is Si-doped TiO 2The nanorod array film electrode and the positive electrode of the photovoltaic cell are connected and superposed to form a composite light anode, and the cathode is a platinum electrode; the integrated photo-anode and the cathode are inserted into an electrolyte solution containing refractory organic pollutants in the quartz reaction cell and are communicated through an external circuit; and starting a light source to irradiate the integrated photo-anode, wherein a film electrode in the integrated photo-anode absorbs short-wavelength light to generate photo-generated charges, the transmission part of light excites the photovoltaic cell to generate voltage to drive photo-generated electrons to migrate to the cathode through an external circuit, electrode reactions are respectively generated on the surface of the film electrode and the cathode, and a loop is formed through the external circuit, so that organic pollutants in water are removed while self-driven photocatalytic hydrogen production and power generation are realized.
The photovoltaic cell in the invention can adopt a commercial photovoltaic cell, and the platinum electrode can adopt a commercial platinum electrode.
Preferably, the light source is simulated sunlight, and the light intensity is 80-150 mW cm -2。
Preferably, the electrolyte solution is K 2SO 4Solution, Na 2SO 4The concentration of the solution or the phosphate buffer solution is 0.01-1M.
Preferably, the refractory organic pollutant is at least one of tetracycline hydrochloride, methyl orange, acid orange, methylene blue, bisphenol A, rhodamine B and 2 chlorophenol.
Preferably, the electrolyte solution contains 5-20 mg/L of refractory organic pollutants.
The invention also provides a preparation method of the full visible light response self-driven photocatalytic triphibian system, which comprises the following steps:
1) preparation of Si-doped TiO 2Nanorod array thin-film electrode: firstly, clean fluorine-doped transparent conductive glass is used as a substrate material, a mixed solution containing tetrabutyl titanate and absolute ethyl alcohol is dripped on a conductive surface of the clean fluorine-doped transparent conductive glass in a spin coating mode, and the mixture is dried and then is subjected to heat treatment at the temperature of 450-550 ℃ for 2-7 hours to obtain TiO 2Seed crystals; then placing the crystal seed with the front surface facing downwards at 45-75 ℃ in a polytetrafluoroethylene lining containing a precursor solution, then transferring the crystal seed into a high-pressure kettle, carrying out hydrothermal treatment for 4-8 h at 170 ℃, respectively washing the crystal seed with ethanol and deionized water for multiple times after natural cooling, carrying out thermal treatment for 2-6 h at 500 ℃, wherein the heating rate and the cooling rate are both 5 ℃/min, and thus obtaining the Si-doped TiO 2A nanorod array thin film electrode;
2) assembling an integrated photo-anode: welding a copper wire on the back of the cleaned photovoltaic cell, and bonding the copper wire on the Si-doped TiO prepared in the step 1) by using conductive silver adhesive 2The front surface of the nanorod array film electrode is connected with the positive electrode of the photovoltaic cell, and then the back surface and the periphery of the nanorod array film electrode are respectively sealed by insulating epoxy resin and dried in the air to obtain the integrated photo-anode;
3) respectively inserting the integrated photo-anode and cathode prepared in the step 2) into electrolyte solution containing refractory organic pollutants in the quartz reaction cell, wherein the integrated photo-anode and cathode are communicated through an external circuit and are irradiated by a light source to generate photo-generated charges.
Preferably, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol in the mixed solution is 1: 10-100.
Preferably, the volume ratio of the deionized water, 37% by mass of HCl, ethyl orthosilicate and tetrabutyl titanate in the precursor solution is 30:30: 0.01-0.05: 0.72.
The invention also provides application of the self-driven photocatalytic triphibian system with full visible light response in the fields of photocatalytic wastewater treatment, photocatalytic water decomposition, photocatalytic hydrogen production and power generation.
The full visible light response self-driven photocatalytic triphibian system has good stability, can fully utilize sunlight to well degrade organic pollutants, can recover clean energy and generate electricity externally, and is specifically represented as follows:
(1) the invention adopts Si-doped TiO prepared by a simple hydrothermal method 2The nanorod array film electrode has good light absorption performance, mechanical stability and service life, and simultaneously, the doping of Si can effectively promote the separation of current carriers and inhibit the recombination of surface electrons and holes;
(2) the photovoltaic cell adopted by the invention can well absorb the Si-doped TiO 2The long-wave light of the nanorod array film electrode spontaneously generates voltage to accelerate the separation and transfer of charges and promote the electron transfer of an external circuit;
(3) the full visible light response self-driven photocatalytic triphibian system can degrade organic pollution and simultaneously recover clean energy and generate electricity externally, and compared with the traditional photocatalytic fuel cell, the degradation and power generation capacity of organic pollutants is obviously improved;
(4) the full visible light response self-driven photocatalytic triphibian system has good stability, simple operation and low cost, and does not produce secondary pollution.
Drawings
FIG. 1 is a schematic diagram of the structure and operation of the fully visible light responsive self-driven photocatalytic triphibian system of the present invention;
in the figure, 1 is Si-doped TiO 2The nano-rod array thin-film electrode is 2 a photovoltaic cell and 3 a platinum electrode.
FIG. 2 shows Si-doped TiO obtained in example 1 2A surface electron microscope image of the nanorod array film;
in the figure, 1 is the Si-doped TiO 2A surface electron microscope image of the nanorod array film material under a macroscopic condition; 2 is the Si-doped TiO 2Surface electron microscope image and section view of the nano-rod array film material under high power condition.
FIG. 3 shows Si-doped TiO obtained in example 1 2XPS plot of nanorod array films.
FIG. 4 is a block diagramExample 1A total visible light responsive self-driven photocatalytic triphibian system simulating sunlight AM1.5(100 mW/cm) 2) Degradation effect curve of 20mg/L tetracycline hydrochloride under irradiation condition.
FIG. 5 shows the simulation of the full visible light response driving photoelectrocatalysis triphibian system of example 1 in the sunlight AM1.5(100 mW/cm) 2) Under irradiation conditions, at 0.1M K 2SO 4Hydrogen production performance in electrolyte solution and 20mg/L tetracycline hydrochloride and a current density curve in the hydrogen production process;
in the figure, 1 is a current density curve with time; 2 is the hydrogen production over time.
FIG. 6 shows the simulation of the full visible light response self-driven photoelectrocatalysis triphibian system of example 1 in the sunlight AM1.5(100 mW/cm) 2) Under irradiation conditions, at 0.1M K 2SO 4Cell performance curves in electrolyte solution and 20mg/L tetracycline hydrochloride, the short circuit current value, open circuit voltage value, maximum power and fill factor are also indicated.
FIG. 7 shows the full visible light response self-driven photocatalytic triphibian system of example 1 under simulated sunlight AM1.5(100 mW/cm) 2) Under irradiation conditions, at 0.1M K 2SO 4The stability test of degrading organic matters and simultaneously recovering energy in the electrolyte solution and 20mg/L tetracycline hydrochloride;
in the figure, 1 is the removal rate of tetracycline hydrochloride; 2 is hydrogen production.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
A self-driven photocatalytic triphibian system with full visible light response, as shown in figure 1, comprises an integrated photo-anode,The integrated light anode is a composite light anode formed by connecting a film electrode 1 and the positive electrode of a photovoltaic cell 2 and superposing the film electrode 1 and the positive electrode in front and back, and the film electrode 1 is Si-doped TiO 2The nano-rod array thin film electrode is characterized in that the thin film electrode 1 is a visible light response type semiconductor material and can respond to visible light irradiation and generate photo-generated charges; the cathode 3 is a platinum electrode; the integrated photo-anode and the cathode are inserted into an electrolyte solution containing refractory organic pollutants in the quartz reaction cell and are communicated through an external circuit; and starting a light source to irradiate the integrated photo-anode, wherein the film electrode 1 in the integrated photo-anode absorbs short-wavelength light to generate photo-generated charges, the transmission part of light excites the photovoltaic cell 2 to generate voltage to drive photo-generated electrons to migrate to the cathode through an external circuit, electrode reactions are respectively generated on the surface of the film electrode 1 and the cathode 3, and a loop is formed through the external circuit, so that the self-driven photocatalytic hydrogen production and power generation are realized, and organic pollutants in water are removed at the same time.
The photovoltaic cell 2 in the present invention may be a commercial photovoltaic cell, and the platinum electrode 3 may be a commercial platinum electrode.
In the invention, the light source is simulated sunlight, and the light intensity is 8-150 mW cm -2。
In the present invention, the electrolyte solution is K 2SO 4Solution, Na 2SO 4The concentration of the solution or the phosphate buffer solution is 0.01-1M.
In the invention, the refractory organic pollutant is at least one of tetracycline hydrochloride, methyl orange, acid orange, methylene blue, bisphenol A, rhodamine B and 2 chlorophenol.
In the invention, the electrolyte solution contains 5-20 mg/L of refractory organic pollutants.
The invention also provides a preparation method of the full visible light response self-driven photocatalytic triphibian system, which comprises the following steps:
1) preparation of Si-doped TiO 2Nanorod array thin-film electrode: firstly, clean fluorine-doped transparent conductive glass is used as a substrate materialDripping a mixed solution containing tetrabutyl titanate and absolute ethyl alcohol on a conductive surface of the conductive material in a rotary coating mode, drying, and carrying out heat treatment at 450-550 ℃ for 2-7 h to obtain TiO 2Seed crystals; then placing the crystal seed with the front surface facing downwards at 45-75 ℃ in a polytetrafluoroethylene lining containing a precursor solution, then transferring the crystal seed into a high-pressure kettle, carrying out hydrothermal treatment for 4-8 h at 170 ℃, respectively washing the crystal seed with ethanol and deionized water for multiple times after natural cooling, carrying out thermal treatment for 2-6 h at 500 ℃, wherein the heating rate and the cooling rate are both 5 ℃/min, and thus obtaining the Si-doped TiO 2A nanorod array thin film electrode;
2) assembling an integrated photo-anode: welding a copper wire on the back of the cleaned photovoltaic cell, and bonding the copper wire on the Si-doped TiO prepared in the step 1) by using conductive silver adhesive 2The front surface of the nanorod array film electrode is connected with the positive electrode of the photovoltaic cell, and then the back surface and the periphery of the nanorod array film electrode are respectively sealed by insulating epoxy resin and dried in the air to obtain the integrated photo-anode;
3) respectively inserting the integrated photo-anode and cathode prepared in the step 2) into electrolyte solution containing refractory organic pollutants in the quartz reaction cell, wherein the integrated photo-anode and cathode are communicated through an external circuit and are irradiated by a light source to generate photo-generated charges.
In the invention, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol in the mixed solution is 1: 10-100; the volume ratio of deionized water, 37% by mass of HCl, ethyl orthosilicate and tetrabutyl titanate in the precursor solution is 30:30: 0.01-0.05: 0.72.
The full visible light response self-driven photocatalytic triphibian system has good stability, can fully utilize sunlight, well degrade organic pollutants, simultaneously can recover clean energy and generate electricity externally, and can be applied to the fields of photocatalytic wastewater treatment, photocatalytic water decomposition, photocatalytic hydrogen production and power generation.
Example 1
The preparation method of the full visible light response self-driven photocatalytic triphibian system comprises the following steps:
1) first, clean fluorine-doped transparent conductorElectric glass (FTO, 2cm x 4cm) as a substrate, a mixed solution containing 0.1mL of tetrabutyl titanate and 10mL of absolute ethyl alcohol was dropped on the conductive surface by spin coating, dried, and heat-treated at 450 ℃ for 2 hours in a muffle furnace to obtain TiO 2Seed crystals; then putting the crystal seeds of the crystal seeds in a polytetrafluoroethylene lining with the front surface facing downwards and 60 degrees in 100mL, and then transferring the crystal seeds into a stainless steel autoclave for hydrothermal treatment at 170 ℃ for 6h, wherein the precursor solution comprises 30mL of deionized water, 30mLHCl (37%), 20 mu L of ethyl orthosilicate and 0.72mL of tetrabutyl titanate; after natural cooling, respectively washing with ethanol and deionized water for multiple times, and then carrying out heat treatment in a muffle furnace at 500 ℃ for 4h, wherein the heating rate and the cooling rate of the muffle furnace are both 5 ℃/min, namely the Si-doped TiO 2A nanorod array thin film electrode;
the Si-doped TiO is given in FIG. 2 2The surface electron microscope picture and the cross-sectional view of the nanorod array film show that the Si-doped TiO can be seen from the picture 2The nanorod arrays were grown uniformly on the FTO with high order, while it can be seen from fig. 3 that the film consisted primarily of Si, Ti, O, C elements, indicating that Si was successfully doped into TiO 2In the nano-rod;
2) welding copper wires on the back electrode of commercial photovoltaic cells, and bonding the copper wires with conductive silver paste to obtain Si-doped TiO 2Connecting the nanorod array film electrode with the positive electrode of the photovoltaic cell, and sealing the back and the periphery with epoxy resin respectively to obtain the integrated photo-anode;
3) the prepared integrated photoanode was used as an anode, a commercial platinum electrode was used as a cathode, and a solution containing 20mg/L tetracycline hydrochloride (TC) and 0.1M K was inserted 2SO 4In the quartz reaction tank of the electrolyte solution, the anode and the cathode are connected through an external lead; starting the simulated solar light source (the light intensity is 100mW cm) -2) Irradiating said integrated photo-anode while doping Si with TiO 2The nanotube array thin film electrode generates photo-generated charges under the excitation of light, the thin film electrode in the integrated photo-anode absorbs shorter wavelength light to generate the photo-generated charges, and the transmission part of the light excites the photovoltaic cell to generate voltage to drive the photovoltaic cell efficientlyThe dynamic photo-generated electrons migrate to the cathode through the external circuit, respectively carry out electrode reaction on the surface of the membrane electrode and the cathode and form a loop through the external circuit, so that the self-driven photocatalytic hydrogen production and power generation can be realized, and organic pollutants in water can be removed;
FIG. 4 shows the tetracycline hydrochloride removal rate under the above conditions, and it can be seen from the figure that the tetracycline hydrochloride removal rate can reach more than 94% after the system is operated for 1.5 h; FIG. 5 shows the hydrogen production performance under these conditions and the current density curve during the hydrogen production process, and the graph shows that the hydrogen production rate of the present invention is 30.3 mu mol h -1cm -2The current value in the external circuit is 1.78mAcm -2The current value is not obviously reduced or fluctuated in the hydrogen production process; FIG. 6 shows the cell performance curve under the conditions, and the open-circuit voltage is 2.17V and the short-circuit current is 1.82mAcm -2Maximum power of 1.46mWcm -2The fill factor is 37%; FIG. 7 shows a repeated test curve of hydrogen production while degrading tetracycline hydrochloride under the conditions, and it can be seen from the graph that the hydrogen production amount is hardly attenuated while still having good removal ability for tetracycline hydrochloride after 5 continuous operations. The results show that the system has good performances of degrading organic pollutants, producing hydrogen and generating electricity under visible light, and has good stability.
The effects of example 1 are described below with 2 comparative examples.
Comparative example 1
As a control, the Si-doped TiO prepared in example 1 was used without changing the other conditions of example 1 2The nanotube array film electrode is used as a photoanode, a commercial platinum electrode is used as a cathode, and experimental results show that the removal rate of tetracycline hydrochloride is only 11%, and the hydrogen production rate is 0.87 mu mol h -1cm -2Open circuit voltage of 0.5V and short circuit current of 0.006mA cm -2Maximum power of 13 μ W cm -2。
Comparative example 2
As a control, the same as that described in example 1 was used without changing the other conditions of example 1The commercial photovoltaic cell is used as a photoanode, a commercial platinum electrode is used as a cathode, and experimental results show that the removal rate of tetracycline hydrochloride is only 8%, and the hydrogen production rate is 9.87 mu mol h -1cm -2Open circuit voltage of 1.5V and short circuit current of 0.06mA cm -2Maximum power of 0.96mWcm -2。
Example 2
The preparation method of the all visible light responsive self-driven photocatalytic triphibian system of this example is substantially the same as that of example 1, except that in step 3) of this example, the prepared integrated photoanode is used as an anode, a commercial platinum electrode is used as a cathode, and a solution containing 10mg/L tetracycline hydrochloride (TC) and 0.1M K is inserted 2SO 4In the quartz reaction cell of the electrolyte solution, the anode and the cathode are connected through an external lead. Starting the simulated solar light source (the light intensity is 100mW cm) -2) Irradiating said integrated photo-anode while doping Si with TiO 2The nanotube array film electrode generates photo-generated charges under the excitation of light, at the moment, the film electrode in the integrated photo-anode absorbs light with shorter wavelength to generate the photo-generated charges, the light of the transmission part excites the photovoltaic cell to generate voltage to efficiently drive photo-generated electrons to migrate to the cathode through an external circuit, electrode reactions are respectively generated on the surface of the film electrode and the cathode, and a loop is formed through the external circuit, so that the self-driven photocatalytic hydrogen production and power generation can be realized, and organic pollutants in water can be removed at the same time.
The visible light response self-driven photoelectrocatalysis triphibian system of the embodiment has the removal rate of the tetracycline hydrochloride of 95 percent and the hydrogen generation rate of 29.8 mu mol h -1cm -2The current value in the external circuit is tested by an electrochemical workstation to obtain the result of 1.69mAcm -2The current value is not obviously reduced and fluctuated in the hydrogen production process, the open-circuit voltage of the system is 2.16V, and the short-circuit current is 1.79mAcm -2And the filling factor is 36.5%, and the results show that the system has good hydrogen production and power generation performances and good stability while effectively removing organic pollutants under visible light.
Example 3
The preparation method of the all visible light responsive self-driven photocatalytic triphibian system of this example is substantially the same as that of example 1, except that in step 3) of this example, the prepared integrated photoanode is used as an anode, a commercial platinum electrode is used as a cathode, and a solution containing 5mg/L tetracycline hydrochloride (TC) and 0.1M K is inserted 2SO 4In the quartz reaction cell of the electrolyte solution, the anode and the cathode are connected through an external lead. Starting the simulated solar light source (the light intensity is 100mW cm) -2) Irradiating said integrated photo-anode while doping Si with TiO 2The nanotube array film electrode generates photo-generated charges under the excitation of light, at the moment, the film electrode in the integrated photo-anode absorbs light with shorter wavelength to generate the photo-generated charges, the light of the transmission part excites the photovoltaic cell to generate voltage to efficiently drive photo-generated electrons to migrate to the cathode through an external circuit, electrode reactions are respectively generated on the surface of the film electrode and the cathode, and a loop is formed through the external circuit, so that the self-driven photocatalytic hydrogen production and power generation can be realized, and organic pollutants in water can be removed at the same time.
The visible light response self-driven photoelectrocatalysis triphibian system of the embodiment has the removal rate of 99 percent on tetracycline hydrochloride and the hydrogen generation rate of 28.3 mu mol h -1cm -2The current value in the external circuit is tested by an electrochemical workstation to obtain the result of 1.65mAcm -2The current value is not obviously reduced and fluctuated in the hydrogen production process, the open-circuit voltage of the system is 2.06V, and the short-circuit current is 1.69mAcm -2The filling factor is 36.3%, and the results show that the system has good hydrogen production and power generation performances and good stability while effectively removing organic pollutants under visible light.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (9)

1. The all-visible-light-responsive self-driven photocatalytic triphibian system is characterized by comprising an integrated photo-anode, a cathode, an electrolyte solution, refractory organic pollutants, a light source and a quartz reaction tank, wherein the integrated photo-anode is Si-doped TiO 2The nanorod array film electrode and the positive electrode of the photovoltaic cell are connected and superposed to form a composite light anode, and the cathode is a platinum electrode; the integrated photo-anode and the cathode are inserted into an electrolyte solution containing refractory organic pollutants in the quartz reaction cell and are communicated through an external circuit; and starting a light source to irradiate the integrated photo-anode, wherein a film electrode in the integrated photo-anode absorbs short-wavelength light to generate photo-generated charges, the transmission part of light excites the photovoltaic cell to generate voltage to drive photo-generated electrons to migrate to the cathode through an external circuit, electrode reactions are respectively generated on the surface of the film electrode and the cathode, and a loop is formed through the external circuit, so that organic pollutants in water are removed while self-driven photocatalytic hydrogen production and power generation are realized.
2. The full visible light response self-driven photocatalytic triphibian system as claimed in claim 1, wherein the light source is simulated sunlight with light intensity of 80-150 mW cm -2。
3. The all visible light responsive self-driven photocatalytic triphibian system of claim 1, wherein the electrolyte solution is K 2SO 4Solution, Na 2SO 4The concentration of the solution or the phosphate buffer solution is 0.01-1M.
4. The all visible light responsive self-driven photocatalytic triphibian system of claim 1 or 3, wherein the refractory organic contaminant is at least one of tetracycline hydrochloride, methyl orange, acid orange, methylene blue, bisphenol A, rhodamine B, 2 chlorophenol.
5. The full visible light response self-driven photocatalytic triphibian system as claimed in claim 4, wherein the electrolyte solution contains 5-20 mg/L of refractory organic pollutants.
6. A method for preparing a fully visible light responsive self-driven photocatalytic triphibian system according to any one of claims 1 to 5, comprising the steps of:
1) preparation of Si-doped TiO 2Nanorod array thin-film electrode: firstly, clean fluorine-doped transparent conductive glass is used as a substrate material, a mixed solution containing tetrabutyl titanate and absolute ethyl alcohol is dripped on a conductive surface of the clean fluorine-doped transparent conductive glass in a spin coating mode, and the mixture is dried and then is subjected to heat treatment at the temperature of 450-550 ℃ for 2-7 hours to obtain TiO 2Seed crystals; then placing the crystal seed with the front surface facing downwards at 45-75 ℃ in a polytetrafluoroethylene lining containing a precursor solution, then transferring the crystal seed into a high-pressure kettle, carrying out hydrothermal treatment for 4-8 h at 170 ℃, respectively washing the crystal seed with ethanol and deionized water for multiple times after natural cooling, carrying out thermal treatment for 2-6 h at 500 ℃, wherein the heating rate and the cooling rate are both 5 ℃/min, and thus obtaining the Si-doped TiO 2A nanorod array thin film electrode;
2) assembling an integrated photo-anode: welding a copper wire on the back of the cleaned photovoltaic cell, and bonding the copper wire on the Si-doped TiO prepared in the step 1) by using conductive silver adhesive 2The front side of the nanorod array film electrode is connected with the positive electrode of the photovoltaic cell, and then the back side and the periphery of the nanorod array film electrode are respectively sealed by insulating epoxy resin and dried in the air to obtain the integrated photo-anode;
3) respectively inserting the integrated photo-anode and cathode prepared in the step 2) into electrolyte solution containing refractory organic pollutants in the quartz reaction cell, wherein the integrated photo-anode and cathode are communicated through an external circuit and are irradiated by a light source to generate photo-generated charges.
7. The preparation method of the all visible-light-responsive self-driven photocatalytic triphibian system as claimed in claim 6, wherein the volume ratio of tetrabutyl titanate to absolute ethyl alcohol in the mixed solution is 1: 10-100.
8. The preparation method of the all visible-light-responsive self-driven photocatalytic triphibian system as claimed in claim 6, wherein the volume ratio of deionized water, 37% by mass of HCl, ethyl orthosilicate and tetrabutyl titanate in the precursor solution is 30:30: 0.01-0.05: 0.72.
9. The use of the fully visible-light-responsive self-driven photocatalytic triphibian system as claimed in any one of claims 1 to 6 in the fields of photocatalytic wastewater treatment, photocatalytic water splitting, photocatalytic hydrogen production and power generation.
CN201911010346.9A 2019-10-22 2019-10-22 Self-driven photocatalytic triphibian system with full visible light response Pending CN110776064A (en)

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