CN114622206B - NH (NH) 2 -MIL-101(Cr)/TiO 2 Composite photo-anode and preparation method and application thereof - Google Patents

NH (NH) 2 -MIL-101(Cr)/TiO 2 Composite photo-anode and preparation method and application thereof Download PDF

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CN114622206B
CN114622206B CN202210141185.2A CN202210141185A CN114622206B CN 114622206 B CN114622206 B CN 114622206B CN 202210141185 A CN202210141185 A CN 202210141185A CN 114622206 B CN114622206 B CN 114622206B
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CN114622206A (en
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王秀通
池丽凤
牛建民
杨黎晖
南有博
吴沿
孙欣
王丽菲
黄彦良
段继周
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Qingdao Marine Science And Technology Center
Institute of Oceanology of CAS
Shipbuilding Technology Research Institute of CSSC No 11 Research Institute
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Institute of Oceanology of CAS
Shipbuilding Technology Research Institute of CSSC No 11 Research Institute
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Abstract

The invention provides an NH 2 ‑MIL‑101(Cr)/TiO 2 A composite photo-anode and a preparation method and application thereof. The invention includes a titanium substrate; a composite film is arranged on the surface of the titanium matrix and comprises TiO growing on the surface of the titanium matrix 2 Nanotube film and hydrothermal synthesis of TiO 2 NH on nanotube film surface 2 MILs-101 (Cr) nanoparticle porous membranes. The invention also provides a preparation method of the composite photo-anode, and the composite photo-anode is combined with a metal cathode and is used for inhibiting corrosion of the metal cathode. NH of the invention 2 The MIL-101 (Cr) nanoparticle porous membrane has good visible light responsiveness, and can widen TiO 2 The absorption of visible light is favorable for light to be scattered for multiple times, the light absorption intensity is improved, the utilization rate of sunlight is increased, the light conversion efficiency is high, the corrosion potential is reduced, the corrosion of a metal cathode is inhibited, and the cathode protection efficiency is high.

Description

NH (NH) 2 -MIL-101(Cr)/TiO 2 Composite photo-anode and preparation method and application thereof
Technical Field
The invention relates to the technical field of photoelectrode materials, in particular to a NH (NH) 2 -MIL-101(Cr)/TiO 2 A composite photo-anode and a preparation method and application thereof.
Background
Metals are important functional and structural materials, known as "industrial bones". However, under the action of a plurality of factors such as salt content, oxygen concentration, temperature, marine organisms, microorganisms and the like, the metallic materials and structures in ocean platforms and equipment are extremely easy to corrode and destroy, so that the development of the national 'blue economy' is seriously hindered and the life safety of people is threatened. It has been estimated that taking reasonable corrosion protection measures can save about 15-35% of global corrosion costs. The current marine corrosion protection technology of metals mainly has the problems of resource, energy, environmental pollution and the like. Therefore, clean and environment-friendly and energy-saving sustainable photo-generated cathode protection technology attracts wide attention.
The principle of the photo-generated cathode protection technology is as follows: by absorbing sunlight, the semiconductor material having photoelectric conversion property generates photoelectrons, which are transferred to the metal in time and effectively to cause cathodic polarization, and the metal electrode potential is lowered, whereby the corrosion behavior of the metal is suppressed.
Titanium dioxide (TiO) 2 ) Has good photoelectrochemical property, low preparation cost, safety and stability. However, when it is used as a photoanode, it has low photoprotection efficiency against metal. This is because the forbidden bandwidth is wide, the separation and transfer efficiency of the photogenerated carriers is low, and the photoelectric conversion efficiency is low only in response to ultraviolet light accounting for 5% of sunlight. Therefore, it is necessary to treat TiO 2 The photoanode is modified.
Disclosure of Invention
The invention aims to provide an NH 2 -MIL-101(Cr)/TiO 2 Composite photo-anode and preparation method and application thereof, aiming at solving the problem of TiO in the prior art 2 The photo anode has lower photo cathode protection efficiency to metal.
In order to solve the technical problems, the technical scheme of the invention is realized as follows:
in one aspect, an NH of the present invention 2 -MIL-101(Cr)/TiO 2 A composite photoanode comprising a titanium matrix; the surface of the titanium matrix is provided with a composite film, and the composite film comprises TiO (titanium dioxide) growing on the surface of the titanium matrix 2 Nanotube film and hydrothermal synthesis of TiO 2 NH on nanotube film surface 2 MILs-101 (Cr) nanoparticle porous membranes.
NH of the invention 2 -MIL-101(Cr)/TiO 2 The composite photo-anode is prepared by growing TiO on titanium matrix 2 Nanotube film, then, hydrothermal method is used for TiO 2 Synthesis of NH on nanotube film surface 2 -MILs-101 (Cr) nanoparticle porous membranes forming a porous membrane with NH 2 -MIL-101(Cr)/TiO 2 A composite structured photoanode; NH (NH) 2 The MIL-101 (Cr) nanoparticle porous membrane has good visible light responsiveness and is compatible with TiO 2 After the nanotube film is compounded, the TiO can be widened 2 Absorption of visible light; at the same time NH 2 MIL-101 (Cr) nanoparticles and TiO 2 After the nano tubes are combined, a porous ordered film is formed, and the porous ordered film structure is favorable for multiple scattering of light in the nano tubes, so that the light absorption intensity is effectively improved; under the irradiation of visible light, electrons are excited by light, transition from the valence band to the conduction band of the composite photo-anode, and then NH 2 Electrons in the MIL-101 (Cr) conduction band transfer to TiO 2 The conduction band is transferred to the metal cathode through the lead, so that cathode polarization occurs to the metal cathode, and the corrosion potential is reduced, thereby inhibiting the corrosion of the metal cathode; such NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode not only has higher photo-response performance, but also provides a channel for efficient transfer of electrons, thereby providing more stable and efficient photo-generated cathode protection for the metal cathode.
As a preferred embodiment, in the composite membrane, NH 2 The thickness of the porous membrane of MIL-101 (Cr) nano particles is 30-70nm, and the TiO is 2 The thickness of the nanotube film is 0.6-3.0 μm. NH in the present invention 2 The MIL-101 (Cr) nanoparticle porous membrane not only has good visible light response and narrow forbidden bandwidth, but also has a porous structure, large specific surface area, weak reducing capability and TiO 2 The nano tube film is compounded, so that the TiO can be remarkably widened 2 Absorption of visible light.
As a preferred embodiment, the TiO 2 TiO in the nanotube film 2 The pore size of the nano tube is 60-160nm. TiO of the invention 2 The nanotube film is grown on the surface of the titanium matrix in situ, and the TiO is 2 The surfaces of the nano tubes are clean and tidy, and uniform TiO is formed 2 A nanotube array; such TiO 2 The nanotubes are anatase TiO 2 A nanotube.
As a preferred embodiment, the NH is 2 NH in MIL-101 (Cr) nanoparticle porous film 2 The size of the MIL-101 (Cr) nanoparticle is 30-60nm. NH of the invention 2 MIL-101 (Cr) nanoparticles in TiO 2 A loose porous ordered film is formed on the surface of the nanotube array, and the loose porous film structure is high in electronsThe efficient transfer provides a channel, thereby improving photoelectric conversion efficiency.
In another aspect, an NH of the present invention 2 -MIL-101(Cr)/TiO 2 The preparation method of the composite photo-anode comprises the following steps: 1) Pre-treating a titanium substrate, cutting, polishing, cleaning and reserving; 2) TiO (titanium dioxide) 2 Preparing a nanotube film, namely taking the pretreated titanium substrate obtained in the step 1) as an anode, taking a platinum sheet as a cathode, placing the anode in an electrolyte, oxidizing for 1-2 hours under the voltage of 20-60V, wherein the electrolyte consists of ethylene glycol and an ammonium fluoride aqueous solution, the molar concentration of the ammonium fluoride aqueous solution is 1.4-1.6M, the volume ratio of the ammonium fluoride aqueous solution to the ethylene glycol is 1:9-11, cleaning, airing, calcining for 1-3 hours at the temperature of 400-500 ℃, and cooling to obtain the nano-tube film with TiO (titanium dioxide) 2 A titanium matrix of the nanotube film; 3) NH (NH) 2 Preparing an MIL-101 (Cr) nanoparticle porous membrane, namely adding sodium hydroxide, chromium nitrate and 2-amino terephthalic acid into deionized water, and mixing to obtain a synthetic solution, wherein the molar concentration of the sodium hydroxide is 0.08-0.18M, the molar concentration of the chromium nitrate is 0.05-0.10M, and the molar concentration of the 2-amino terephthalic acid is 0.03-0.07M; the TiO-bearing material obtained in the step 2) is treated 2 Titanium matrix and synthesis solution for nanotube films with TiO 2 The mass ratio of the titanium matrix of the nanotube film to the synthetic solution is 7:500-3:200, the nanotube film is placed in a high-pressure reaction kettle, reacted for 12-24 hours at 140-160 ℃ in a blast drying box, cooled, washed and dried to obtain NH 2 -MIL-101(Cr)/TiO 2 And (3) a composite photo-anode.
NH of the invention 2 -MIL-101(Cr)/TiO 2 The preparation method of the composite photo-anode comprises the steps of pre-treating a titanium matrix, and then utilizing an anodic oxidation method to grow TiO on the surface of the titanium matrix in situ 2 Nanotube film, finally, tiO is prepared by hydrothermal method 2 Synthesis of NH on nanotube film surface 2 -MILs-101 (Cr) nanoparticle porous membranes; such NH 2 -MIL-101(Cr)/TiO 2 The preparation method of the composite photo-anode is that NH with high-efficiency photo-generated cathode protection performance is obtained by a one-step anodic oxidation method and a one-step hydrothermal method 2 -MIL-101(Cr)/TiO 2 The composite photo-anode has simple operation, short process flow and mild condition,low energy consumption, energy conservation and environmental protection, and is easy to realize industrialization.
As a preferred embodiment, in the step 3), the synthesis solution is mixed under stirring or ultrasonic conditions for a period of 15 to 30 minutes. The chromium nitrate is usually chromium nitrate nonahydrate, and under the condition of stirring or ultrasonic, sodium hydroxide, the chromium nitrate nonahydrate and 2-amino terephthalic acid are fully dissolved and uniformly mixed to form uniform NH 2 -MILs-101 (Cr) reaction solution, i.e. synthesis solution; through the control of the mixing time, the operation is convenient and the control is easy.
As a preferred embodiment, in the step 3), the drying is vacuum drying, the drying temperature is 60-100 ℃, and the drying time is 12-24 hours. The sample synthesized by the hydrothermal method is placed in a vacuum drying oven for vacuum drying, the temperature of vacuum drying is low, the drying effect is quick, and NH can not be carried out 2 -MIL-101(Cr)/TiO 2 The structure of the composite photo-anode is damaged.
As a preferred embodiment, in the step 3), the washing is performed by using deionized water, then N, N-dimethylformamide and finally methanol. The sample synthesized by the hydrothermal method is naturally cooled to room temperature, and then taken out for washing; washing with deionized water to remove residual sodium hydroxide; n, N-Dimethylformamide (DMF) washing to remove 2-amino terephthalic acid (H) remaining after the reaction 2 ATA); methanol washing to exchange residual DMF; when flushing, the flushing is usually carried out for a plurality of times; the residue may be sufficiently removed by soaking for several hours with the corresponding solutions in sequence as necessary.
As a preferred embodiment, in the step 1), the titanium substrate is soaked in a polishing solution for 20-30s, wherein the polishing solution is a mixed solution consisting of 15-16% ammonium fluoride deionized water solution, 68% concentrated nitric acid and 30% hydrogen peroxide; in the polishing solution, the volume ratio of the ammonium fluoride deionized water solution, the concentrated nitric acid and the hydrogen peroxide is 9-11:23-25:23-25. The titanium substrate is firstly cleaned alternately by deionized water and ethanol to remove surface stains and is dried for later use; the invention adopts special polishing solution to polish, so that the surface of the titanium substrate forms a uniform white fog surface; after polishing, deionized water and ethanol are alternately used for cleaning for a plurality of times, and the mixture is put into absolute ethanol for sealing and preservation for standby.
In yet another aspect, an NH of the present invention 2 -MIL-101(Cr)/TiO 2 Application of composite photo-anode, NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode is used in combination with the metal cathode for inhibiting corrosion of the metal cathode.
NH of the invention 2 -MIL-101(Cr)/TiO 2 When the composite photo-anode is combined with the metal cathode, NH is carried out under the illumination condition 2 -MIL-101(Cr)/TiO 2 Photoelectrons generated by the photoelectric effect of the composite photo-anode can cause cathode polarization of a metal cathode connected with the composite photo-anode, and the metal cathode is in a thermodynamic state, so that corrosion of the metal cathode is inhibited; even in the dark state, NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode can also provide electrons for the metal cathode, so that the potential of the metal cathode is still obviously lower than the self-corrosion potential of the metal cathode; thus NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode can provide high-efficiency stable photo-generated cathode protection for the metal cathode.
Compared with the prior art, the invention has the beneficial effects that: NH of the invention 2 The MIL-101 (Cr) nanoparticle porous membrane has good visible light responsiveness and is compatible with TiO 2 After the nanotube film is compounded, the TiO can be widened 2 Absorption of visible light; at the same time NH 2 MIL-101 (Cr) nanoparticles and TiO 2 After the nano tubes are combined, a porous ordered film is formed, and the porous ordered film structure is favorable for multiple scattering of light in the nano tubes, so that the light absorption intensity is effectively improved; under the irradiation of visible light, electrons are excited by light, transition from the valence band to the conduction band of the composite photo-anode, and then NH 2 Electrons in the MIL-101 (Cr) conduction band transfer to TiO 2 The conduction band is transferred to the metal cathode through the lead, so that cathode polarization occurs to the metal cathode, and the corrosion potential is reduced, thereby inhibiting the corrosion of the metal cathode; such NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode not only has higher photo-response performance, but also provides a channel for efficient transfer of electrons, thereby providing more stable and efficient photo-generated cathode protection for the metal cathode. NH of the invention 2 -MIL-101(Cr)/TiO 2 The preparation method of the composite photo-anode is obtained through a one-step anodic oxidation method and a one-step hydrothermal method, and is simple to operate, short in process flow, mild in condition, low in energy consumption, energy-saving, environment-friendly and easy to realize industrialization. NH of the invention 2 -MIL-101(Cr)/TiO 2 When the composite photo-anode is combined with the metal cathode, NH is carried out under the illumination condition 2 -MIL-101(Cr)/TiO 2 Photoelectrons generated by the photoelectric effect of the composite photo-anode can cause cathode polarization of a metal cathode connected with the composite photo-anode, and the metal cathode is in a thermodynamic state, so that corrosion of the metal cathode is inhibited; even in the dark state, NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode can also provide electrons for the metal cathode, so that the potential of the metal cathode is still obviously lower than the self-corrosion potential of the metal cathode; thus NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode can provide high-efficiency stable photo-generated cathode protection for the metal cathode.
Drawings
FIG. 1 shows a TiO-bearing composition according to an embodiment of the present invention 2 Scanning electron microscope photo of the nanotube film titanium sheet;
FIG. 2 is a diagram of NH according to an embodiment of the present invention 2 -MIL-101(Cr)/TiO 2 Scanning electron microscope photo pictures of the composite photo anode;
FIG. 3 is a diagram of NH according to an embodiment of the present invention 2 -MIL-101(Cr)/TiO 2 An ultraviolet visible diffuse reflection graph of the composite photo-anode;
FIG. 4 shows NH according to an embodiment of the present invention 2 -MIL-101(Cr)/TiO 2 Composite photoanode and TiO alone 2 Open circuit potential diagrams of the titanium sheets of the nanotube film coupled with 304 stainless steel, respectively;
FIG. 5 shows NH according to an embodiment of the present invention 2 -MIL-101(Cr)/TiO 2 Composite photoanode and TiO alone 2 The titanium sheets of the nanotube film are respectively coupled with 304 stainless steelTransient photoelectric spectrum;
FIG. 6 is a diagram of NH according to a second embodiment of the present invention 2 -MIL-101(Cr)/TiO 2 Composite photoanode and TiO alone 2 Open circuit potential diagrams of the titanium sheets of the nanotube film coupled with 304 stainless steel, respectively;
FIG. 7 is a diagram of NH according to a second embodiment of the present invention 2 -MIL-101(Cr)/TiO 2 Composite photoanode and TiO alone 2 Transient state photoelectric spectrum of titanium sheet of nanotube film coupled with 304 stainless steel separately;
FIG. 8 is a NH group obtained in accordance with a third embodiment of the present invention 2 -MIL-101(Cr)/TiO 2 Composite photoanode and TiO alone 2 Open circuit potential diagrams of the titanium sheets of the nanotube film coupled with 304 stainless steel, respectively;
FIG. 9 is a diagram of NH according to a third embodiment of the present invention 2 -MIL-101(Cr)/TiO 2 Composite photoanode and TiO alone 2 Transient state photoelectric spectrum of titanium sheet of nanotube film coupled with 304 stainless steel separately;
in the figure: ON-turn ON the light source; OFF-turn OFF the light source; a-with TiO only 2 Titanium sheets of nanotube film; B-NH 2 -MIL-101(Cr)/TiO 2 A composite photo-anode; c-304SS electrode.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with specific embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
NH of the invention 2 -MIL-101(Cr)/TiO 2 A composite photoanode comprising a titanium matrix; the surface of the titanium matrix is provided with a composite film, and the composite film comprises TiO (titanium dioxide) growing on the surface of the titanium matrix 2 Nanotube film and hydrothermal synthesis of TiO 2 NH on nanotube film surface 2 MILs-101 (Cr) nanoparticle porous membranes.
Preferably, the saidIn the composite film, NH 2 The thickness of the porous membrane of MIL-101 (Cr) nano particles is 30-70nm, and the TiO is 2 The thickness of the nanotube film is 0.6-3.0 μm.
Preferably, the TiO 2 TiO in the nanotube film 2 The pore size of the nano tube is 60-160nm.
Preferably, the NH 2 NH in MIL-101 (Cr) nanoparticle porous film 2 The size of the MIL-101 (Cr) nanoparticle is 30-60nm.
NH of the invention 2 -MIL-101(Cr)/TiO 2 The preparation method of the composite photo-anode comprises the following steps:
1) Pretreatment of
Taking a titanium substrate, cutting, polishing, cleaning and reserving;
2)TiO 2 preparation of nanotube films
Taking the pretreated titanium matrix obtained in the step 1) as an anode, taking a platinum sheet as a cathode, placing the anode in an electrolyte, oxidizing for 1-2h under the voltage of 20-60V, wherein the electrolyte consists of glycol and ammonium fluoride aqueous solution, the molar concentration of the ammonium fluoride aqueous solution is 1.4-1.6M, the volume ratio of the ammonium fluoride aqueous solution to the glycol is 1:9-11, cleaning, airing, calcining for 1-3h at 400-500 ℃, and cooling to obtain the product with TiO 2 A titanium matrix of the nanotube film;
3)NH 2 preparation of MIL-101 (Cr) nanoparticle porous films
Adding sodium hydroxide, chromium nitrate and 2-amino terephthalic acid into deionized water, and mixing to obtain a synthetic solution, wherein the molar concentration of the sodium hydroxide is 0.08-0.18M, the molar concentration of the chromium nitrate is 0.05-0.10M, and the molar concentration of the 2-amino terephthalic acid is 0.03-0.07M;
the TiO-bearing material obtained in the step 2) is treated 2 Titanium matrix and synthesis solution for nanotube films with TiO 2 The mass ratio of the titanium matrix of the nanotube film to the synthetic solution is 7:500-3:200, the nanotube film is placed in a high-pressure reaction kettle, reacted for 12-24 hours at 140-160 ℃ in a blast drying box, cooled, washed and dried to obtain NH 2 -MIL-101(Cr)/TiO 2 And (3) a composite photo-anode.
Preferably, in the step 3), the synthesis solution is mixed under stirring or ultrasonic conditions for 15-30min.
Preferably, in the step 3), the drying is vacuum drying, the drying temperature is 60-100 ℃, and the drying time is 12-24 hours.
Preferably, in the step 3), the washing is performed by deionized water, then N, N-dimethylformamide, and finally methanol.
Preferably, in the step 1), the titanium substrate is soaked in a polishing solution for 20-30s, wherein the polishing solution is a mixed solution composed of 15-16% ammonium fluoride deionized water solution, 68% concentrated nitric acid and 30% hydrogen peroxide; in the polishing solution, the volume ratio of the ammonium fluoride deionized water solution, the concentrated nitric acid and the hydrogen peroxide is 9-11:23-25:23-25.
NH of the invention 2 -MIL-101(Cr)/TiO 2 Application of composite photo-anode, NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode is used in combination with the metal cathode for inhibiting corrosion of the metal cathode.
Example 1
NH of the invention 2 -MIL-101(Cr)/TiO 2 The preparation method of the composite photo-anode comprises the following steps:
1) Pretreatment of
Taking titanium matrix with purity of 99.9%, thickness of 0.03cm, cutting into 1×4cm 2 The titanium sheet is kept flat and has no scratch, deionized water and ethanol are adopted to alternately clean the titanium sheet to remove surface stains, and the titanium sheet is dried for later use;
ammonium fluoride (NH) was prepared at a mass concentration of 15.3% 4 F) Adding 68% concentrated nitric acid and 30% hydrogen peroxide (H) 2 O 2 ) Ammonium fluoride (NH) 4 F) The volume ratio of the aqueous solution to the concentrated nitric acid to the hydrogen peroxide is 5:12:12, so as to form polishing solution;
placing the titanium sheet into polishing solution, soaking for 25 seconds, taking out the titanium sheet after the surface of the titanium sheet forms uniform white fog, alternately cleaning the titanium sheet for a plurality of times by adopting deionized water and ethanol, and placing the titanium sheet into absolute ethanol for sealing and preserving for later use;
2)TiO 2 preparation of nanotube films
Preparation of 50mL of NH with molar concentration of 1.5M 4 F, adding 500mL of ethylene glycol into the aqueous solution, and stirring for 1h to obtain uniformly mixed anodic oxidation electrolyte;
taking 60mL of the electrolyte, placing in a 100mL beaker, respectively taking the titanium sheet and the platinum electrode as an anode and a cathode, setting an anodic oxidation voltage of 60V in a high-voltage direct-current power supply, and obtaining TiO on a titanium substrate after the anodic oxidation reaction is finished, wherein the oxidation time is 1h 2 Washing the nano tube with ethanol and water for several times, and naturally airing;
the above-mentioned material with TiO 2 Placing the titanium sheet of the nanotube in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours, cooling to room temperature along with the furnace, and growing TiO on the surface of the titanium sheet in situ 2 A nanotube film;
3)NH 2 preparation of MIL-101 (Cr) nanoparticle porous films
Adding 0.2g of sodium hydroxide, 0.8g of chromium nitrate nonahydrate and 0.36g of 2-amino terephthalic acid into 30mL of deionized water, and mixing for 30min under the stirring action to obtain a synthetic solution;
the TiO-bearing material obtained in the step 2) is treated 2 The titanium substrate of the nanotube film is erected in a polytetrafluoroethylene lining of a 50mL stainless steel high-pressure reaction kettle, then the synthetic solution is poured into the reaction kettle, the reaction kettle is screwed up, the reaction kettle is placed in a blast drying box, the reaction temperature is set to be 150 ℃, the reaction time is 12 hours, the reaction kettle is naturally cooled to room temperature, the reaction kettle is taken out, deionized water, anhydrous DMF and anhydrous methanol are sequentially adopted to wash a sample wafer, and residual NaOH and H are removed 2 ATA and DMF, placing the washed sample in a vacuum drying oven at 100deg.C, vacuum drying for 12 hr to obtain NH 2 -MIL-101(Cr)/TiO 2 And (3) a composite photo-anode.
The TiO-bearing material obtained in the step 2) is treated 2 The titanium sheet of the nanotube film was subjected to a test on a scanning electron microscope model S-8200, manufactured by Hitachi, japan, and as can be seen from FIG. 1, the surface of the titanium substrate was allUniformly grow a layer of TiO 2 Nanotube film, tiO 2 The pore size of the nano tube is 110nm, and TiO 2 The nanotube length is about 2 μm, tiO 2 The surface of the nano tube is clean and the nano tube is orderly arranged.
NH obtained in step 3) 2 -MIL-101(Cr)/TiO 2 The composite photoanode was also tested on the scanning electron microscope described above, as can be seen in FIG. 2, the newly synthesized NH 2 MIL-101 (Cr) nanoparticles in TiO 2 A loose porous film is formed on the surface of the nanotube film, the thickness of the film is 70nm, and NH 2 MIL-101 (Cr) nanoparticles with a particle size of 50nm, NH 2 MIL-101 (Cr) in TiO 2 The surface of the porous film is aggregated into a network, which is favorable for light absorption and scattering, so that the light response performance of the photo-anode is enhanced, and the photoelectric conversion efficiency is improved.
NH obtained in step 3) 2 -MIL-101(Cr)/TiO 2 The composite photoanode was placed on Hitachi U-3900H type ultraviolet visible Diffuse Reflectometer (DRS) manufactured by Hitachi, japan, as BaSO 4 As a reference sample, testing the light absorption intensity and the light response range of the photo-anode in a wave band of 200-800 nm; as can be seen from FIG. 3, NH 2 Modification of the MIL-101 (Cr) nanoparticle layer not only improves TiO 2 The absorption intensity of the nanotube film on ultraviolet light also widens the absorption in the visible light region, which is beneficial to improving the photo-generated cathode protection performance of the composite photo-anode.
NH obtained in step 3) 2 -MIL-101(Cr)/TiO 2 The composite photo-anode is used for photo-generated cathode protection test, an electrochemical workstation and an H-shaped double-solution cell are used for testing open circuit potential, and the composite photo-anode is obtained in the step 2) and is provided with TiO only 2 The titanium sheet of the nanotube film is used as a control sample; the H-type double-solution tank comprises a photolysis tank and a corrosion tank which are connected by a proton membrane, wherein NaCl solution with the mass concentration of 3.5% is filled in the corrosion tank so as to simulate seawater, and NH is used for treating the seawater 2 -MIL-101(Cr)/TiO 2 Composite photoanode and TiO alone 2 The titanium sheet of the nanotube film is used as a photo-anode, and the working electrode, the reference electrode and the counter electrode are respectively 304 stainless steel (304 SS), a Saturated Calomel Electrode (SCE) and a Pt electrode; is provided with stoneOne end of the quartz glass window is a photolysis tank, chi Zhongzhuang has 0.1M Na 2 S and 0.2M NaOH solution are used as hole capturing agents, the photo anode is fixed in a photolysis tank by adopting an electrode clamp and is coupled with 304SS by adopting a lead, thus electrons in the photo anode can be transferred to 304SS, and the photo anode is immersed in the solution and has an illuminated area of 2cm 2 The visible light source is provided by a xenon lamp with a visible light filter, and the irradiation intensity is 100mW cm -2 . As can be seen from fig. 4, under irradiation with visible light, 304SS and the TiO alone 2 The potential of the nanotube film after the titanium sheet is coupled is 460mV (corresponding to the saturated calomel electrode, the same applies below), and the potential drop amplitude is about 310mV;304SS and NH 2 -MIL-101(Cr)/TiO 2 The potential of the composite photo-anode after coupling is-718 mV, and the potential drop amplitude is about 490mV. Thus NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode can obviously promote TiO 2 The nano-tube photo-anode has the protection performance on the photo-generated cathode and has good protection effect on 304 SS; and, under the condition of no light, NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode can still make 304SS in a better polarization state.
NH obtained in step 3) 2 -MIL-101(Cr)/TiO 2 The photo-generated cathode protection test is carried out on the composite photo-anode, the photo-current density is tested by adopting an electrochemical workstation and an H-shaped double-solution cell, and the photo-current density is tested by adopting the method obtained in the step 2) and only has TiO 2 The titanium sheet of the nanotube film is used as a control sample; the H-type double-solution tank comprises a photolysis tank and a corrosion tank which are connected by a proton membrane, wherein NaCl solution with the mass concentration of 3.5% is filled in the corrosion tank so as to simulate seawater, and NH is used for treating the seawater 2 -MIL-101(Cr)/TiO 2 Composite photoanode and TiO alone 2 The titanium sheet of the nanotube film is used as a working electrode, the reference electrode and the counter electrode are respectively a Saturated Calomel Electrode (SCE) and a Pt electrode, the counter electrode and the reference electrode are in short circuit, and 304SS is grounded; the end provided with the quartz glass window is a photolysis tank, chi Zhongzhuang has 0.1M Na 2 S and 0.2M NaOH solution are used as hole capturing agents, a photo-anode is fixed in a photolysis tank by adopting an electrode clamp and is coupled with 304SS by adopting a lead, and the photo-anode is immersed in the solution and is illuminated with 2cm in area 2 The visible light source is lifted by a xenon lamp with a visible light filterFor the irradiation, the irradiation intensity was 100 mW.cm -2 The illumination interval time is 100s; as can be seen from FIG. 5, NH is irradiated intermittently with visible light 2 -MIL-101(Cr)/TiO 2 The photocurrent stability value generated by the composite photo-anode can reach 20 mu A cm -2 This is with TiO only 2 About 4 times of the nanotube film titanium sheet; the photocurrent reflects to some extent the electron separation and transfer efficiency of the photoanode under illumination. Thus, tiO 2 Nanotubes and NH 2 After MIL-101 (Cr) nano particles are compounded, the electron separation and transfer efficiency is obviously improved, and more efficient photo-generated cathode protection can be provided for 304 SS.
Example two
NH of the invention 2 -MIL-101(Cr)/TiO 2 The preparation method of the composite photo-anode comprises the following steps:
1) Pretreatment of
Taking titanium matrix with purity of 99.9%, thickness of 0.03cm, cutting into 1×4cm 2 The titanium sheet is kept flat and has no scratch, deionized water and ethanol are adopted to alternately clean the titanium sheet to remove surface stains, and the titanium sheet is dried for later use;
ammonium fluoride (NH) was prepared at a mass concentration of 15.3% 4 F) Adding 68% concentrated nitric acid and 30% hydrogen peroxide (H) 2 O 2 ) Ammonium fluoride (NH) 4 F) The volume ratio of the aqueous solution to the concentrated nitric acid to the hydrogen peroxide is 5:12:12, so as to form polishing solution;
placing the titanium sheet into polishing solution, soaking for 30s, taking out, alternately cleaning the titanium sheet with deionized water and ethanol for several times, and placing into absolute ethanol for sealing and preserving for later use;
2)TiO 2 preparation of nanotube films
Preparation of 50mL of NH with molar concentration of 1.5M 4 F, adding 500mL of ethylene glycol into the aqueous solution, and stirring for 1h to obtain uniformly mixed anodic oxidation electrolyte;
60mL of the electrolyte is taken and placed in a 100mL beaker, and the titanium sheet and the platinum electrode are respectively taken as positive electrode and negative electrodeSetting anode oxidation voltage of 60V in high voltage DC power supply for 2h, and obtaining TiO on titanium substrate after anode oxidation reaction 2 Washing the nano tube with ethanol and water for several times, and naturally airing;
the above-mentioned material with TiO 2 The titanium sheet of the nanotube is placed in a muffle furnace, the temperature is raised to 450 ℃ at the heating rate of 5 ℃/min, the calcination is carried out for 2 hours, the furnace is cooled to room temperature, and anatase type TiO grows on the surface of the titanium sheet in situ 2 A nanotube film;
3)NH 2 preparation of MIL-101 (Cr) nanoparticle porous films
Adding 0.1g of sodium hydroxide, 0.4g of chromium nitrate nonahydrate and 0.18g of 2-amino terephthalic acid into 30mL of deionized water, and mixing for 15min under the stirring action to obtain a synthetic solution;
the TiO-bearing material obtained in the step 2) is treated 2 The titanium substrate of the nanotube film is erected in a polytetrafluoroethylene lining of a 50mL stainless steel high-pressure reaction kettle, then the synthetic solution is poured into the reaction kettle, the reaction kettle is screwed up, the reaction kettle is placed in a blast drying box, the reaction temperature is set to be 150 ℃, the reaction time is 24 hours, the reaction kettle is naturally cooled to room temperature, the reaction kettle is taken out, deionized water, anhydrous DMF and anhydrous methanol are sequentially adopted to wash a sample wafer, and residual NaOH and H are removed 2 ATA and DMF, placing the washed sample in a vacuum drying oven at 100deg.C, vacuum drying for 12 hr to obtain NH 2 -MIL-101(Cr)/TiO 2 And (3) a composite photo-anode.
NH obtained in step 3) 2 -MIL-101(Cr)/TiO 2 The composite photo-anode is used for photo-generated cathode protection test, an electrochemical workstation and an H-shaped double-solution cell are used for testing open circuit potential, and the composite photo-anode is obtained in the step 2) and is provided with TiO only 2 The titanium sheet of the nanotube film is used as a control sample; the H-type double-solution tank comprises a photolysis tank and a corrosion tank which are connected by a proton membrane, wherein NaCl solution with the mass concentration of 3.5% is filled in the corrosion tank so as to simulate seawater, and NH is used for treating the seawater 2 -MIL-101(Cr)/TiO 2 Composite photoanode and TiO alone 2 The titanium sheet of the nanotube film is used as a photo-anode, and the working electrode, the reference electrode and the counter electrode are respectively 304SS, saturated Calomel Electrode (SCE) and Pt electrode; with quartz glass windowOne end is a photolytic cell, chi Zhongzhuang has 0.1M Na 2 S and 0.2M NaOH solution are used as hole capturing agents, the photo anode is fixed in a photolysis tank by adopting an electrode clamp and is coupled with 304SS by adopting a lead, thus electrons in the photo anode can be transferred to 304SS, and the photo anode is immersed in the solution and has an illuminated area of 2cm 2 The visible light source is provided by a xenon lamp with a visible light filter, and the irradiation intensity is 100mW cm -2 . As can be seen from fig. 6, under irradiation with visible light, 304SS and the TiO alone 2 The potential of the nanotube film after the titanium sheet is coupled is 460mV below zero, and the potential drop is about 200mV;304SS and NH 2 -MIL-101(Cr)/TiO 2 The potential after the coupling of the composite photoanode is-659 mV, and the potential drop amplitude is about 359mV. Thus NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode can obviously promote TiO 2 The nano-tube photo-anode has the protection performance on the photo-generated cathode and has good protection effect on 304 SS; and, under the condition of no light, NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode can still make 304SS in a better polarization state.
NH obtained in step 3) 2 -MIL-101(Cr)/TiO 2 The photo-generated cathode protection test is carried out on the composite photo-anode, the photo-current density is tested by adopting an electrochemical workstation and an H-shaped double-solution cell, and the photo-current density is tested by adopting the method obtained in the step 2) and only has TiO 2 The titanium sheet of the nanotube film is used as a control sample; the H-type double-solution tank comprises a photolysis tank and a corrosion tank which are connected by a proton membrane, wherein NaCl solution with the mass concentration of 3.5% is filled in the corrosion tank so as to simulate seawater, and NH is used for treating the seawater 2 -MIL-101(Cr)/TiO 2 Composite photoanode and TiO alone 2 The titanium sheet of the nanotube film is used as a working electrode, the reference electrode and the counter electrode are respectively a Saturated Calomel Electrode (SCE) and a Pt electrode, the counter electrode and the reference electrode are in short circuit, and 304SS is grounded; the end provided with the quartz glass window is a photolysis tank, chi Zhongzhuang has 0.1M Na 2 S and 0.2M NaOH solution are used as hole capturing agents, a photo-anode is fixed in a photolysis tank by adopting an electrode clamp and is coupled with 304SS by adopting a lead, and the photo-anode is immersed in the solution and is illuminated with 2cm in area 2 The visible light source is provided by a xenon lamp with a visible light filter, and the irradiation intensity is 100mW cm -2 Illumination roomThe interval time is 100s; as can be seen from FIG. 7, NH is irradiated intermittently with visible light 2 -MIL-101(Cr)/TiO 2 The stable value of the photocurrent generated by the composite photo-anode can reach 35.4 mu A cm -2 This is with TiO only 2 About 4 times of the nanotube film titanium sheet; the photocurrent reflects to some extent the electron separation and transfer efficiency of the photoanode under illumination. Thus, tiO 2 Nanotubes and NH 2 After MIL-101 (Cr) nano particles are compounded, the electron separation and transfer efficiency is obviously improved, and more efficient photo-generated cathode protection can be provided for 304 SS. In addition, in the dark state, NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode still releases a larger photocurrent, which enables the composite photo-anode to provide effective protection for 304SS from corrosion of metals even in the dark state.
Example III
NH of the invention 2 -MIL-101(Cr)/TiO 2 The preparation method of the composite photo-anode comprises the following steps:
1) Pretreatment of
Taking titanium matrix with purity of 99.9%, thickness of 0.03cm, cutting into 1×4cm 2 The titanium sheet is kept flat and has no scratch, deionized water and ethanol are adopted to alternately clean the titanium sheet to remove surface stains, and the titanium sheet is dried for later use;
ammonium fluoride (NH) was prepared at a mass concentration of 15.3% 4 F) Adding 68% concentrated nitric acid and 30% hydrogen peroxide (H) 2 O 2 ) Ammonium fluoride (NH) 4 F) The volume ratio of the aqueous solution to the concentrated nitric acid to the hydrogen peroxide is 5:12:12, so as to form polishing solution;
placing the titanium sheet into polishing solution, soaking for 20s, taking out, alternately cleaning the titanium sheet with deionized water and ethanol for several times, and placing into absolute ethanol for sealing and preserving for later use;
2)TiO 2 preparation of nanotube films
Preparation of 50mL of NH with molar concentration of 1.5M 4 F, adding 500mL of ethylene glycol into the aqueous solution, and stirring for 1h to obtain a mixtureUniformly anodizing electrolyte;
taking 60mL of the electrolyte, placing in a 100mL beaker, respectively taking the titanium sheet and the platinum electrode as an anode and a cathode, setting an anodic oxidation voltage of 20V in a high-voltage direct-current power supply, and obtaining TiO on a titanium substrate after the anodic oxidation reaction is finished, wherein the oxidation time is 1h 2 Washing the nano tube with ethanol and water for several times, and naturally airing;
the above-mentioned material with TiO 2 Placing the titanium sheet of the nanotube in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours, cooling to room temperature along with the furnace, and growing TiO on the surface of the titanium sheet in situ 2 A nanotube film;
3)NH 2 preparation of MIL-101 (Cr) nanoparticle porous films
Adding 0.2g of sodium hydroxide, 0.8g of chromium nitrate nonahydrate and 0.36g of 2-amino terephthalic acid into 30mL of deionized water, and mixing for 20min under the ultrasonic action to obtain a synthetic solution;
the TiO-bearing material obtained in the step 2) is treated 2 The titanium substrate of the nanotube film is erected in a polytetrafluoroethylene lining of a 50mL stainless steel high-pressure reaction kettle, then the synthetic solution is poured into the reaction kettle, the reaction kettle is screwed up, the reaction kettle is placed in a blast drying box, the reaction temperature is set to be 150 ℃, the reaction time is 18H, the reaction kettle is naturally cooled to room temperature, the reaction kettle is taken out, deionized water, anhydrous DMF and anhydrous methanol are sequentially adopted to wash a sample wafer, and residual NaOH and H are removed 2 ATA and DMF, placing the washed sample in a vacuum drying oven at 100deg.C, vacuum drying for 12 hr to obtain NH 2 -MIL-101(Cr)/TiO 2 And (3) a composite photo-anode.
NH obtained in step 3) 2 -MIL-101(Cr)/TiO 2 The composite photo-anode is used for photo-generated cathode protection test, an electrochemical workstation and an H-shaped double-solution cell are used for testing open circuit potential, and the composite photo-anode is obtained in the step 2) and is provided with TiO only 2 The titanium sheet of the nanotube film is used as a control sample; the H-type double-solution tank comprises a photolysis tank and a corrosion tank which are connected by a proton membrane, wherein NaCl solution with the mass concentration of 3.5% is filled in the corrosion tank so as to simulate seawater, and NH is used for treating the seawater 2 -MIL-101(Cr)/TiO 2 Composite photoanode and TiO alone 2 Nanometer scaleThe titanium sheet of the tube film is used as a photo-anode, and the working electrode, the reference electrode and the counter electrode are respectively 304SS, saturated Calomel Electrode (SCE) and Pt electrode; the end provided with the quartz glass window is a photolysis tank, chi Zhongzhuang has 0.1M Na 2 S and 0.2M NaOH solution are used as hole capturing agents, the photo anode is fixed in a photolysis tank by adopting an electrode clamp and is coupled with 304SS by adopting a lead, thus electrons in the photo anode can be transferred to 304SS, and the photo anode is immersed in the solution and has an illuminated area of 2cm 2 The visible light source is provided by a xenon lamp with a visible light filter, and the irradiation intensity is 100mW cm -2 . As can be seen from fig. 8, under irradiation of visible light, 304SS and TiO 2 The potential after coupling is stabilized at-380 mV and is combined with NH 2 -MIL-101(Cr)/TiO 2 The potential after coupling is stabilized at-620 mV, which is higher than that of pure TiO 2 The potential at the time of coupling was lowered by 240mV; in the dark state, NH 2 -MIL-101(Cr)/TiO 2 The photoanode can still provide adequate cathodic protection for 304 SS. Thus NH 2 MIL-101 (Cr) and TiO 2 After recombination, the separation efficiency and transfer rate of the photo-generated electron-hole pairs are obviously improved, more electrons are transferred to the surface of 304SS, and 304SS is protected by a photo-generated cathode with high efficiency and stability.
NH obtained in step 3) 2 -MIL-101(Cr)/TiO 2 The photo-generated cathode protection test is carried out on the composite photo-anode, the photo-current density is tested by adopting an electrochemical workstation and an H-shaped double-solution cell, and the photo-current density is tested by adopting the method obtained in the step 2) and only has TiO 2 The titanium sheet of the nanotube film is used as a control sample; the H-type double-solution tank comprises a photolysis tank and a corrosion tank which are connected by a proton membrane, wherein NaCl solution with the mass concentration of 3.5% is filled in the corrosion tank so as to simulate seawater, and NH is used for treating the seawater 2 -MIL-101(Cr)/TiO 2 Composite photoanode and TiO alone 2 The titanium sheet of the nanotube film is used as a working electrode, the reference electrode and the counter electrode are respectively a Saturated Calomel Electrode (SCE) and a Pt electrode, the counter electrode and the reference electrode are in short circuit, and 304SS is grounded; the end provided with the quartz glass window is a photolysis tank, chi Zhongzhuang has 0.1M Na 2 S and 0.2M NaOH solution are used as hole capturing agents, a photo-anode is fixed in a photolysis tank by adopting an electrode clamp and is coupled with 304SS by adopting a lead, and the photo-anode is immersed in the solution and is illuminated by lightIs 2cm 2 The visible light source is provided by a xenon lamp with a visible light filter, and the irradiation intensity is 100mW cm -2 The illumination interval time is 100s; as can be seen from fig. 9, under irradiation of visible light, tiO 2 The photo-generated current density of (C) is 7 mu A cm-1, NH 2 -MIL-101(Cr)/TiO 2 The photo-generated current density of (C) is 25 mu A cm -1 This is pure TiO 2 3.5 times of (C), obviously NH 2 MIL-101 (Cr) and TiO 2 The recombination can obviously accelerate the separation and transfer efficiency of photogenerated carriers and obviously promote the pure TiO 2 The composite photo-anode can provide more photo-generated electrons for 304SS, which means better photo-generated cathode protection.
Therefore, compared with the prior art, the invention has the beneficial effects that: NH of the invention 2 The MIL-101 (Cr) nanoparticle porous membrane has good visible light responsiveness and is compatible with TiO 2 After the nanotube film is compounded, the TiO can be widened 2 Absorption of visible light; at the same time NH 2 MIL-101 (Cr) nanoparticles and TiO 2 After the nano tubes are combined, a porous ordered film is formed, and the porous ordered film structure is favorable for multiple scattering of light in the nano tubes, so that the light absorption intensity is effectively improved; under the irradiation of visible light, electrons are excited by light, transition from the valence band to the conduction band of the composite photo-anode, and then NH 2 Electrons in the MIL-101 (Cr) conduction band transfer to TiO 2 The conduction band is transferred to the metal cathode through the lead, so that cathode polarization occurs to the metal cathode, and the corrosion potential is reduced, thereby inhibiting the corrosion of the metal cathode; such NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode not only has higher photo-response performance, but also provides a channel for efficient transfer of electrons, thereby providing more stable and efficient photo-generated cathode protection for the metal cathode. NH of the invention 2 -MIL-101(Cr)/TiO 2 The preparation method of the composite photo-anode is obtained through a one-step anodic oxidation method and a one-step hydrothermal method, and is simple to operate, short in process flow, mild in condition, low in energy consumption, energy-saving, environment-friendly and easy to realize industrialization. NH of the invention 2 -MIL-101(Cr)/TiO 2 Composite photo-anode and metal cathodeWhen combined, under the illumination condition, NH 2 -MIL-101(Cr)/TiO 2 Photoelectrons generated by the photoelectric effect of the composite photo-anode can cause cathode polarization of a metal cathode connected with the composite photo-anode, and the metal cathode is in a thermodynamic state, so that corrosion of the metal cathode is inhibited; even in the dark state, NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode can also provide electrons for the metal cathode, so that the potential of the metal cathode is still obviously lower than the self-corrosion potential of the metal cathode; thus NH 2 -MIL-101(Cr)/TiO 2 The composite photo-anode can provide high-efficiency stable photo-generated cathode protection for the metal cathode.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (4)

1. NH for inhibiting metal cathode corrosion 2 -MIL-101(Cr)/TiO 2 The preparation method of the composite photo-anode is characterized by comprising the following steps:
1) Pretreatment of
Taking a titanium substrate, cutting, polishing, cleaning and reserving;
2）TiO 2 preparation of nanotube films
Taking the pretreated titanium substrate obtained in the step 1) as an anode, taking a platinum sheet as a cathode, placing the anode in an electrolyte, oxidizing 1-2h under the voltage of 20-60V, wherein the electrolyte consists of ethylene glycol and an ammonium fluoride aqueous solution, the molar concentration of the ammonium fluoride aqueous solution is 1.4-1.6M, the volume ratio of the ammonium fluoride aqueous solution to the ethylene glycol is 1:9-11, cleaning, airing, calcining 1-3h at 400-500 ℃, and cooling to obtain the titanium-containing titanium oxide film with TiO (TiO) 2 A titanium matrix of the nanotube film;
3）NH 2 preparation of MIL-101 (Cr) nanoparticle porous films
Adding sodium hydroxide, chromium nitrate and 2-amino terephthalic acid into deionized water, and mixing to obtain a synthetic solution, wherein the molar concentration of the sodium hydroxide is 0.08-0.18M, the molar concentration of the chromium nitrate is 0.05-0.10M, and the molar concentration of the 2-amino terephthalic acid is 0.03-0.07M;
the TiO-bearing material obtained in the step 2) is treated 2 Titanium matrix and synthesis solution for nanotube films with TiO 2 The mass ratio of the titanium matrix of the nanotube film to the synthetic solution is 7:500-3:200, the nanotube film is placed in a high-pressure reaction kettle, and is reacted at the temperature of 140-160 ℃ in a blast drying box for 12-24h, and is cooled, and is firstly washed by deionized water, then is washed by N, N-dimethylformamide, finally is washed by methanol, and is dried to obtain NH 2 -MIL-101(Cr)/TiO 2 A composite photo-anode;
the NH is 2 -MIL-101(Cr)/TiO 2 The composite photoanode comprises a titanium matrix, wherein a composite film is arranged on the surface of the titanium matrix, and comprises TiO (titanium oxide) growing on the surface of the titanium matrix 2 Nanotube film and hydrothermal synthesis of TiO 2 NH on nanotube film surface 2 MIL-101 (Cr) nanoparticle porous membrane, NH 2 The thickness of the porous membrane of MIL-101 (Cr) nano-particles is 30-70nm, and the TiO is 2 The thickness of the nanotube film is 0.6-3.0 μm, and TiO 2 The pore size of the nano tube is 60-160nm, NH 2 The size of the MIL-101 (Cr) nanoparticle is 30-60nm.
2. The NH for inhibiting metal cathodic corrosion of claim 1 2 -MIL-101(Cr)/TiO 2 The preparation method of the composite photo-anode is characterized by comprising the following steps:
in the step 3), the synthetic solution is mixed under stirring or ultrasonic condition, and the mixing time is 15-30min.
3. The NH for inhibiting metal cathodic corrosion of claim 2 2 -MIL-101(Cr)/TiO 2 The preparation method of the composite photo-anode is characterized by comprising the following steps:
in the step 3), the drying is vacuum drying, the drying temperature is 60-100 ℃, and the drying time is 12-24h.
4. The NH for inhibiting metal cathodic corrosion according to any one of claims 1 to 3 2 -MIL-101(Cr)/TiO 2 The preparation method of the composite photo-anode is characterized by comprising the following steps:
in the step 1), a titanium substrate is placed in a polishing solution for soaking 20-30s, wherein the polishing solution is a mixed solution consisting of 15-16% ammonium fluoride deionized water solution, 68% concentrated nitric acid and 30% hydrogen peroxide; in the polishing solution, the volume ratio of the ammonium fluoride deionized water solution, the concentrated nitric acid and the hydrogen peroxide is 9-11:23-25:23-25.
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