Summary of the invention
The object of the present invention is to provide a kind of simple titanium dioxide (TiO
2)/redox graphene (RGO)/Red copper oxide (Cu
2o) synthetic method of combined electrode.
The present invention adopts liquid phase method under low temperature on FTO substrate, first prepare the titanium dioxide (TiO of the relatively homogeneous Detitanium-ore-type of pattern through hydro-thermal reaction
2) nano wire, then prepared the titanium dioxide (TiO of brilliant red stone-type again through calcining by sol-gel method
2) nano wire, then spin-coating method is at titanium dioxide (TiO
2) nanowire surface synthesizes one deck redox graphene (RGO) film, finally by chemical deposition at redox graphene surface deposition Red copper oxide (Cu
2o).
The preparation method of this combined electrode carries out according to the following step:
The concentrated hydrochloric acid of 15mL and the deionized water of 15mL are put into jar agitation by A.
B dropwise adds 0.35mL ~ 0.7mL tetra-n-butyl titanate, stirs to clarification.
The solution that step B obtains by C is transferred in the reactor of tetrafluoroethylene liner, puts into cleaned FTO substrate wherein, and be warming up to constant temperature 6h at 180 DEG C of temperature, naturally cooling, obtains anatase crystal TiO
2nano wire.
FTO substrate taking-up deionized water wash after the hydro-thermal that step C obtains by D is clean.
1mL acetic acid and 50mL ethanol are put into jar agitation by E.
F dropwise adds 0.75mL tetra-n-butyl titanate wherein, stirs to clarification.
The FTO substrate that step D obtains by G steeps the solution 1h in step F.
The FTO substrate seasoning that step G obtains by H, puts into retort furnace and is warming up to 450 DEG C of constant temperature 2h with the temperature rise rate of 2 DEG C/min, can obtain the homogeneous double-deck anatase octahedrite of pattern/brilliant red stone titanium dioxide (TiO
2) nano wire.
The clean seasoning of FTO substrate taking-up deionized water wash that step H obtains by J.
K obtains graphene oxide colloidal sol by graphene oxide powder ultrasonic dispersion deionized water.
Surface preparation has the FTO substrate of two-layer titanium dioxide to be positioned on spin coating instrument by L, graphene oxide colloidal sol is added drop-wise to the on-chip two-layer titanium dioxide of FTO on the surface, spin coating 3 ~ 5 times.
Tube furnace 400 DEG C of calcining 2h in a nitrogen atmosphere put into by FTO substrate after spin coating by M.
O step M is obtained FTO substrate immerse copper sulfate and Sulfothiorine mixing solutions, deionized water, sodium hydroxide solution and deionized water successively; Each immersion time 10 ~ 20s, circulates after 30 ~ 90 times and takes out seasoning; Titanium dioxide (the TiO that pattern is homogeneous can be obtained
2)/redox graphene (RGO)/Red copper oxide (Cu
2o) complex light electrode.
Further, the concentration of graphene oxide colloidal sol is 1g/L.
Further, in copper sulfate and Sulfothiorine mixing solutions, the concentration of copper sulfate and Sulfothiorine is 1mol/L; The concentration of sodium hydroxide solution is also 1mol/L.
Combined electrode in the present invention thing phase, structure and performance characterization by x-ray diffractometer, field emission scanning electron microscope (SEM) measure.
Another object of the present invention, is to provide prepared titanium dioxide (TiO
2)/redox graphene (RGO)/Red copper oxide (Cu
2o) combined electrode is for the application of photoelectric current.
Titanium dioxide (TiO
2)/redox graphene (RGO)/Red copper oxide (Cu
2o) combined electrode photoelectric current test procedure under xenon source irradiates is as follows: carry out under CHI 852C type electrochemical workstation, add the sodium sulfate (Na of 0.5mol/L in electrolyzer
2sO
4) as electrolytic solution, add silver chloride electrode as reference electrode, add platinum electrode as to electrode, titanium dioxide (TiO
2)/redox graphene (RGO)/Red copper oxide (Cu
2o) combined electrode is as working electrode, carries out cyclic voltammetry scan.
beneficial effect
Utilize simple Hydrothermal Synthesis, sol-gel method and the titanium dioxide (TiO prepared by chemical deposition
2)/redox graphene (RGO)/Red copper oxide (Cu
2o) for compound 3 ties up optoelectronic pole, it is good that this material has good chemical stability, the advantage that photoelectrochemical behaviour is good, and present invention process is simple, reproducible, and material therefor is cheap and easy to get, meets environmental friendliness requirement.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail, and to make those skilled in the art understand the present invention better, but the present invention is not limited to following examples.
embodiment 1
A kind of titanium dioxide (TiO
2)/redox graphene (RGO)/Red copper oxide (Cu
2o) preparation method of combined electrode carries out according to following step:
The concentrated hydrochloric acid of 15mL and the deionized water of 15mL are put into jar agitation by A.
B dropwise adds 0.35mL tetra-n-butyl titanate, stirs to clarification.
The solution that step B obtains by C is transferred in the reactor of tetrafluoroethylene liner, puts into cleaned FTO substrate wherein, and be warming up to constant temperature 6h at 180 DEG C of temperature, naturally cooling, obtains anatase crystal TiO
2nano wire.
FTO substrate taking-up deionized water wash after the hydro-thermal that step C obtains by D is clean.
1mL acetic acid and 50mL ethanol are put into jar agitation by E.
F dropwise adds 0.75mL tetra-n-butyl titanate wherein, stirs to clarification.
The FTO substrate that step D obtains by G steeps the solution 1h in step F.
The FTO substrate seasoning that step G obtains by H, puts into retort furnace and is warming up to 450 DEG C of constant temperature 2h with the temperature rise rate of 2 DEG C/min, can obtain the homogeneous double-deck anatase octahedrite of pattern/brilliant red stone titanium dioxide (TiO
2) nano wire.
The clean seasoning of FTO substrate taking-up deionized water wash that step H obtains by J.
K obtains graphene oxide colloidal sol by graphene oxide powder ultrasonic dispersion deionized water.
Surface preparation has the FTO substrate of two-layer titanium dioxide to be positioned on spin coating instrument by L, graphene oxide colloidal sol is added drop-wise to the on-chip two-layer titanium dioxide of FTO on the surface, spin coating 3 times.
Tube furnace 400 DEG C of calcining 2h in a nitrogen atmosphere put into by FTO substrate after spin coating by M.
O step M is obtained FTO substrate immerse copper sulfate and Sulfothiorine mixing solutions, deionized water, sodium hydroxide solution and deionized water successively; Each immersion time 10s, circulates after 30 times and takes out seasoning; Titanium dioxide (the TiO that pattern is homogeneous can be obtained
2)/redox graphene (RGO)/Red copper oxide (Cu
2o) complex light electrode; The concentration of graphene oxide colloidal sol is 1g/L, and in copper sulfate and Sulfothiorine mixing solutions, the concentration of copper sulfate and Sulfothiorine is 1mol/L; The concentration of sodium hydroxide solution is also 1mol/L.
Addition through changing tetrabutyl titanate can regulate TiO
2content, regulate TiO with this
2the diameter of nano wire.
embodiment 2
A kind of titanium dioxide (TiO
2)/redox graphene (RGO)/Red copper oxide (Cu
2o) preparation method of combined electrode carries out according to following step:
The concentrated hydrochloric acid of 15mL and the deionized water of 15mL are put into jar agitation by A.
B dropwise adds 0.35mL tetra-n-butyl titanate, stirs to clarification.
The solution that step B obtains by C is transferred in the reactor of tetrafluoroethylene liner, puts into cleaned FTO substrate wherein, and be warming up to constant temperature 6h at 180 DEG C of temperature, naturally cooling, obtains anatase crystal TiO
2nano wire.
FTO substrate taking-up deionized water wash after the hydro-thermal that step C obtains by D is clean.
1mL acetic acid and 50mL ethanol are put into jar agitation by E.
F dropwise adds 0.75mL tetra-n-butyl titanate wherein, stirs to clarification.
The FTO substrate that step D obtains by G steeps the solution 1h in step F.
The FTO substrate seasoning that step G obtains by H, puts into retort furnace and is warming up to 450 DEG C of constant temperature 2h with the temperature rise rate of 2 DEG C/min, can obtain the homogeneous double-deck anatase octahedrite of pattern/brilliant red stone titanium dioxide (TiO
2) nano wire.
The clean seasoning of FTO substrate taking-up deionized water wash that step H obtains by J.
K obtains graphene oxide colloidal sol by graphene oxide powder ultrasonic dispersion deionized water.
Surface preparation has the FTO substrate of two-layer titanium dioxide to be positioned on spin coating instrument by L, graphene oxide colloidal sol is added drop-wise to the on-chip two-layer titanium dioxide of FTO on the surface, spin coating 5 times.
Tube furnace 400 DEG C of calcining 2h in a nitrogen atmosphere put into by FTO substrate after spin coating by M.
O step M is obtained FTO substrate immerse copper sulfate and Sulfothiorine mixing solutions, deionized water, sodium hydroxide solution and deionized water successively; Each immersion time 10s, circulates after 30 times and takes out seasoning; Titanium dioxide (the TiO that pattern is homogeneous can be obtained
2)/redox graphene (RGO)/Red copper oxide (Cu
2o) complex light electrode.
By the thickness regulating the spin coating number of times of graphite oxide can regulate RGO nanometer sheet.
embodiment 3
The concentrated hydrochloric acid of 15mL and the deionized water of 15mL are put into jar agitation by A.
B dropwise adds 0.35mL tetra-n-butyl titanate, stirs to clarification.
The solution that step B obtains by C is transferred in the reactor of tetrafluoroethylene liner, puts into cleaned FTO substrate wherein, and be warming up to constant temperature 6h at 180 DEG C of temperature, naturally cooling, obtains anatase crystal TiO
2nano wire.
FTO substrate taking-up deionized water wash after the hydro-thermal that step C obtains by D is clean.
1mL acetic acid and 50mL ethanol are put into jar agitation by E.
F dropwise adds 0.75mL tetra-n-butyl titanate wherein, stirs to clarification.
The FTO substrate that step D obtains by G steeps the solution 1h in step F.
The FTO substrate seasoning that step G obtains by H, puts into retort furnace and is warming up to 450 DEG C of constant temperature 2h with the temperature rise rate of 2 DEG C/min, can obtain the homogeneous double-deck anatase octahedrite of pattern/brilliant red stone titanium dioxide (TiO
2) nano wire.
The clean seasoning of FTO substrate taking-up deionized water wash that step H obtains by J.
K obtains graphene oxide colloidal sol by graphene oxide powder ultrasonic dispersion deionized water.
Surface preparation has the FTO substrate of two-layer titanium dioxide to be positioned on spin coating instrument by L, graphene oxide colloidal sol is added drop-wise to the on-chip two-layer titanium dioxide of FTO on the surface, spin coating 3 times.
Tube furnace 400 DEG C of calcining 2h in a nitrogen atmosphere put into by FTO substrate after spin coating by M.
O step M is obtained FTO substrate immerse copper sulfate and Sulfothiorine mixing solutions, deionized water, sodium hydroxide solution and deionized water successively; Each immersion time 20s, circulates after 30 times and takes out seasoning; Titanium dioxide (the TiO that pattern is homogeneous can be obtained
2)/redox graphene (RGO)/Red copper oxide (Cu
2o) complex light electrode.
By regulating the immersion time to regulate and control Cu
2the content of O.
embodiment 4
A kind of titanium dioxide (TiO
2)/redox graphene (RGO)/Red copper oxide (Cu
2o) preparation method of combined electrode carries out according to following step:
The concentrated hydrochloric acid of 15mL and the deionized water of 15mL are put into jar agitation by A.
B dropwise adds 0.35mL tetra-n-butyl titanate, stirs to clarification.
The solution that step B obtains by C is transferred in the reactor of tetrafluoroethylene liner, puts into cleaned FTO substrate wherein, and be warming up to constant temperature 6h at 180 DEG C of temperature, naturally cooling, obtains anatase crystal TiO
2nano wire.
FTO substrate taking-up deionized water wash after the hydro-thermal that step C obtains by D is clean.
1mL acetic acid and 50mL ethanol are put into jar agitation by E.
F dropwise adds 0.75mL tetra-n-butyl titanate wherein, stirs to clarification.
The FTO substrate that step D obtains by G steeps the solution 1h in step F.
The FTO substrate seasoning that step G obtains by H, puts into retort furnace and is warming up to 450 DEG C of constant temperature 2h with the temperature rise rate of 2 DEG C/min, can obtain the homogeneous double-deck anatase octahedrite of pattern/brilliant red stone titanium dioxide (TiO
2) nano wire.
The clean seasoning of FTO substrate taking-up deionized water wash that step H obtains by J.
K obtains graphene oxide colloidal sol by graphene oxide powder ultrasonic dispersion deionized water.
Surface preparation has the FTO substrate of two-layer titanium dioxide to be positioned on spin coating instrument by L, graphene oxide colloidal sol is added drop-wise to the on-chip two-layer titanium dioxide of FTO on the surface, spin coating 5 times.
Tube furnace 400 DEG C of calcining 2h in a nitrogen atmosphere put into by FTO substrate after spin coating by M.
O step M is obtained FTO substrate immerse copper sulfate and Sulfothiorine mixing solutions, deionized water, sodium hydroxide solution and deionized water successively; Each immersion time 10s, circulates after 60 times and takes out seasoning; Titanium dioxide (the TiO that pattern is homogeneous can be obtained
2)/redox graphene (RGO)/Red copper oxide (Cu
2o) complex light electrode.
By regulating Cu
2the circulation time (respectively soaking at four beakers is once a cycle number) of O can regulate and control Cu
2the content of O.