CN106119882A - The preparation of iron titanate/iron sesquioxide complex light electrode and surface modifying method - Google Patents
The preparation of iron titanate/iron sesquioxide complex light electrode and surface modifying method Download PDFInfo
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- CN106119882A CN106119882A CN201610615181.8A CN201610615181A CN106119882A CN 106119882 A CN106119882 A CN 106119882A CN 201610615181 A CN201610615181 A CN 201610615181A CN 106119882 A CN106119882 A CN 106119882A
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Abstract
The invention provides preparation and the surface modifying method of a kind of iron titanate/iron sesquioxide complex light electrode, relate to Material Field.The preparation method of complex light electrode includes: clean FTO electro-conductive glass；FTO electro-conductive glass is inserted in the ventricumbent mode of conduction in the inorganic salt solution of titanium, at 60 80 DEG C, soak 10 60min；FTO electro-conductive glass after cleaning heats 10 30min at 150 200 DEG C；FTO electro-conductive glass after heating is inserted in the reactor of inorganic salt and the mineralizer aqueous solution filling ferrum, and described reactor is heated at 60 100 DEG C 2 5h；Taking out the most reacted described FTO electro-conductive glass, and be carried out, the FTO electro-conductive glass after cleaning is annealed 1 3h, then 10 30min that anneal at 700 800 DEG C at 500 600 DEG C, prepares nano barium titanate ferrum/iron sesquioxide complex light electrode.The complex light electrode preparation method of the application is simple, and experiment condition is easily controllable, and the composite photoelectric prepared has high photoelectrocatalysis decomposition water performance.
Description
Technical field
The present invention relates to Material Field, particularly relate to nano barium titanate ferrum/iron sesquioxide complex light electrode preparation and
Surface modifying method.
Background technology
In recent decades, along with the most exhausted and the most adjoint environmental pollution of the fossil energies such as coal, oil, natural gas
Problem increasingly serious, the sustainable development of human society receives serious threat, and the regenerative resource of exploitation cleaning is
Extremely urgent.As the one in clean energy resource, Hydrogen Energy has high fuel value, high efficiency and eco-friendly feature and quilt because of it
It is believed that it is one of the most preferable alternative energy source solving energy crisis and environmental problem.But, obtaining on a large scale of current hydrogen
Take the reformation mostling come from coal, oil and gas, though this product hydrogen mode technical maturity with high costs, pollute ring
Border, thus seek green, economy, environmental protection product hydrogen methods imperative.Meanwhile, because having cleanliness without any pollution, distribution
Extensively, inexhaustible and nexhaustible advantage, solar energy is increasingly subject to people's attention and starts to tie at the existing energy
Structure is played the part of important role.Therefore, the photoelectrocatalysis with semiconductor nano material as catalyst, with solar energy as energy source
Decomposing Aquatic product hydrogen technology will be one of following mankind's optimal path obtaining Hydrogen Energy on a large scale.
In numerous conductor photocatalysis materials, alpha-phase ferricoxide (α-Fe2O3) energy gap of nano material is narrow
(2.0-2.2eV), the ultraviolet light in sunlight and visible ray are respectively provided with good Optical Electro-Chemistry and respond, and nanometer α-Fe2O3
Also have that PhotoelectrocatalytiPerformance Performance is stable, abundance, environmentally friendly and cheap advantage.Theoretical research show nanometer α-
Fe2O3The maximum photogenerated current density of optoelectronic pole is up to 12.6mA/cm2, the conversion efficiency of corresponding solar energy-Hydrogen Energy up to
15.5%[4].Therefore, α-Fe2O3Nano material, as the most promising visible-light photocatalyst of one, has become as quasiconductor
Photoelectrocatalysis decomposes one of the study hotspot in Aquatic product hydrogen field.
But, although α is-Fe2O3Semi-conducting material has the advantage of numerous uniqueness, but is 1.5 (AM 1.5) in air quality
Simulated solar irradiation irradiation under, the transformation efficiency of the high solar-chemical energy reported now still less than 3%, its photoelectricity
The correlational study of catalytic decomposition water is the most still in the laboratory research stage.
Summary of the invention
By analyzing the main cause finding to cause the problems referred to above it is: α-Fe2O3The poorly conductive of nano material, photoproduction sky
Cave diffusion path short (2-4nm), optoelectronic pole surface moisture oxidation reaction speed are slow, poor to the absorbability of sunlight；Lead
H+/H is compared in band position2Potential low, under the irradiation of sunlight, it is impossible to spontaneous carrying out produces hydrogen reaction, needs additional
The effect of bias just can complete the reaction of whole photodissociation Aquatic product hydrogen.
It is an object of the present invention to provide the preparation side of a kind of nano barium titanate ferrum/iron sesquioxide complex light electrode
Method, complex to solve the preparation method of current complex light electrode, experiment condition is the harshest, prepared nano barium titanate
Ferrum/iron sesquioxide complex light electrode with compound before optoelectronic pole pattern problem that large change can occur.
The present invention one further objective is that the surface providing a kind of nano barium titanate ferrum/iron sesquioxide complex light electrode
Method of modifying, to improve the performance of the photoelectrocatalysis decomposition water of nano barium titanate ferrum/iron sesquioxide complex light electrode.
Especially, the invention provides the preparation method of a kind of nano barium titanate ferrum/iron sesquioxide complex light electrode, including
Following steps:
Clean fluorine-doped tin oxide (fluorine-doped tin oxide, FTO) electro-conductive glass；
FTO electro-conductive glass after cleaning is inserted in the inorganic salt solution of titanium in the ventricumbent mode of conduction, at 60-80
10-60min is soaked at DEG C；
Taking out the described FTO electro-conductive glass after soaking, and be carried out, the FTO electro-conductive glass after cleaning is at 150-200
10-30min is heated at DEG C；
FTO electro-conductive glass after heating is inserted in the reactor of inorganic salt and the mineralizer aqueous solution filling ferrum, and will
Described reactor heats 2-5h at 60-100 DEG C；
Take out the most reacted described FTO electro-conductive glass, and be carried out, the FTO conduction glass after cleaning
Glass is annealed 1-3h at 500-600 DEG C, then the 10-30min that anneals at 700-800 DEG C, prepares nano barium titanate ferrum/tri-oxidation
Two ferrum complex light electrodes.
Further, described being inserted by FTO electro-conductive glass after heating fills the inorganic salt of ferrum and D/W
In reactor, it is that the FTO electro-conductive glass after heating is inserted the reaction of inorganic salt and the D/W filling ferrum obliquely
In still.
Further, the one or many during the inorganic salt of described titanium is titanium tetrachloride, titanous chloride., Titanium Nitrate and titanium sulfate
The combination planted；
The inorganic salt of described ferrum is one or more in iron chloride, ferrous chloride, ferric nitrate, ferrous sulfate and iron sulfate
Combination；
Described mineralizer is the combination of one or more in glucose, sodium nitrate and carbamide.
Further, the molar concentration of the inorganic salt of described titanium is 1-40mmol/l；
The molar concentration of the inorganic salt of described ferrum is 0.1-0.5mol/l；
The molar concentration of described mineralizer is 50-100mmol/l.
Further, described will clean after FTO electro-conductive glass at 150-200 DEG C, heat 10-30min, be to clean
After FTO electro-conductive glass be placed on warm table, at 150-200 DEG C heat 10-30min；
Described described reactor is heated at 60-100 DEG C 2-5h, be that described reactor is placed in drying baker,
2-5h is heated at 60-100 DEG C；
Described will clean after FTO electro-conductive glass anneal at 500-600 DEG C 1-3h, then annealing 10-at 700-800 DEG C
30min, is that the FTO electro-conductive glass after cleaning is placed in Muffle furnace, and anneal at 500-600 DEG C 1-3h, then at 700-800
Anneal at DEG C 10-30min.
Especially, the invention provides the surface modifying method of a kind of nano barium titanate ferrum/iron sesquioxide complex light electrode,
Comprise the steps:
Surface fluorination process step:
Nano barium titanate ferrum/iron sesquioxide complex light electrode is inserted in the solution containing inorganic fluoride, at 40-80 DEG C
Lower immersion 1-10min, takes out the described complex light electrode after soaking, and heats 10-30min at 150-250 DEG C, and heating terminates
After cool the temperature to room temperature, and be carried out；
The load step of rhodium hydroxide promoter:
In the precursor solution containing the inorganic salt of rhodium, use the electrochemical deposition method of light auxiliary, rhodium hydroxide is helped
Catalyst is carried on the nano barium titanate ferrum/iron sesquioxide complex light electrode after surface fluorination processes.
Further, described surface fluorination processes nano barium titanate ferrum/iron sesquioxide complex light electrode described in step
Insert in the solution containing inorganic fluoride, comprise the steps:
Inorganic fluoride is dissolved in the mixed solution of hydrogen peroxide and deionized water, is configured to used by surface fluorination process
Etching solution；
Described nano barium titanate ferrum/iron sesquioxide complex light electrode is inserted in described etching solution.
Further, in the load step of described rhodium hydroxide promoter, the described forerunner at the inorganic salt containing rhodium
Liquid solution uses the electrochemical deposition method of light auxiliary, comprises the steps:
Nano barium titanate ferrum/iron sesquioxide complex light electrode after being processed by surface fluorination is as working electrode, platinum filament electricity
Pole is as to electrode, and saturated Ag/AgCl electrode is as reference electrode；
In 1moll/l sodium hydroxide electrolyte solution, under the irradiation of AM1.5G simulated solar irradiation, at surface fluorination
Nano barium titanate ferrum after reason/iron sesquioxide complex light electrode carries out linear voltammetric scan；
With the inorganic salt solution of the rhodium of 0.2-0.3mmoll/l as electrolyte solution, described multiple after above-mentioned steps is processed
Close optoelectronic pole and carry out identical linear voltammetric scan；
After the end of scan, described complex light electrode is carried out and is dried, prepare rhodium hydroxide and fluorion coexistence
Nano barium titanate ferrum/iron sesquioxide complex light the electrode of reason.
Further, the mass ratio of described inorganic fluoride, hydrogen peroxide and deionized water is 1-2:50-60:45-55；
Described inorganic fluoride is the combination of one or more in sodium fluoride, ammonium fluoride, ammonium acid fluoride and prodan；
The inorganic salt of described rhodium is the combination of one or more in rhodium chloride, rhodium triiodid, rhodium nitrate and rhodium sulfate.
Further, the scanning voltage of described linear voltammetric scan is-0.4-0.8V, and sweep speed is 50mV/s.
Inorganic due to first with titanium of the preparation method of the nano barium titanate ferrum of the present invention/iron sesquioxide complex light electrode
Salt soaks FTO electro-conductive glass, is formed on FTO electro-conductive glass by the compound of titanium, then is combined iron sesquioxide, this kind of method system
The standby nano barium titanate ferrum/iron sesquioxide composite photoelectric obtained has high photoelectrocatalysis decomposition water performance.Additionally, with existing skill
In art, the preparation method of complex light electrode is compared, and the complex light electrode preparation method of the application is simple, and experiment condition is easily controllable,
The complex light electrode prepared before compound be combined after varying topography less, thus, the photoelectricity to complex light electrode
The impact of catalytic decomposition aqueous energy is reduced to minimum.According to the solution of the present invention, the molar concentration of the inorganic salt of described titanium is 1-
During 40mmol/l, the optoelectronic pole prepared is respectively provided with higher photoelectrocatalysis decomposition water performance, but when the inorganic salt of titanium is tetrachloro
Change titanium, and when molar concentration is 4mmol/l, its photoelectrocatalysis decomposition water performance is optimal.
Further, the surface modifying method of the nano barium titanate ferrum of the present invention/iron sesquioxide complex light electrode, step letter
Single controlled, owing to using surface fluorion to process the method with electrochemical deposition rhodium hydroxide promoter to above-mentioned composite photoelectric
Pole has carried out modification and modification, so that the starting voltage of described complex light electrode is effectively reduced, i.e. drops
Low about 230mV, the density of photocurrent at 1.0V vs.RHE is by 0.38mA/cm2Increase to 1.47mA/cm2.Thus,
Process due to surface fluorion and the cooperative effect of electrochemical deposition rhodium hydroxide promoter coprocessing makes above-mentioned complex light
The photoelectrocatalysis decomposition water performance of electrode is significantly improved.
According to below in conjunction with the accompanying drawing detailed description to the specific embodiment of the invention, those skilled in the art will be brighter
Above-mentioned and other purposes, advantage and the feature of the present invention.
Accompanying drawing explanation
Describe some specific embodiments of the present invention the most by way of example, and not by way of limitation in detail.
Reference identical in accompanying drawing denotes same or similar parts or part.It should be appreciated by those skilled in the art that these
Accompanying drawing is not necessarily drawn to scale.In accompanying drawing:
Fig. 1 is the structural representation of nano barium titanate ferrum/iron sesquioxide complex light electrode according to an embodiment of the invention
Figure；
Fig. 2 is the system of the nano barium titanate ferrum according to the one or more embodiment of the present invention/iron sesquioxide complex light electrode
Preparation Method flow chart；
Fig. 3 is the preparation method of nano barium titanate ferrum/iron sesquioxide complex light electrode according to an embodiment of the invention
Schematic flow sheet；
Fig. 4 is that the high-resolution of nano barium titanate ferrum/iron sesquioxide complex light electrode according to an embodiment of the invention is saturating
Penetrate electron microscope picture and distribution diagram of element；
Fig. 5 is nano barium titanate ferrum/iron sesquioxide complex light electrode Ti element L limit according to an embodiment of the invention
X-ray absorption spectrogram；
Fig. 6 is that the nano barium titanate ferrum according to the multiple embodiment of the present invention/iron sesquioxide complex light electrode is at different moles
Density of photocurrent-voltage curve under the immersion of concentration titanium tetrachloride solution；
Fig. 7 is changing of the nano barium titanate ferrum/iron sesquioxide complex light electrode according to the one or more embodiment of the present invention
The flow chart of property method；
Fig. 8 is nano barium titanate ferrum/iron sesquioxide complex light before and after fluorion process according to an embodiment of the invention
The comparison diagram of electrode photoelectric current density-voltage curve；
Fig. 9 is nano barium titanate ferrum/tri-oxidation before and after rhodium hydroxide promoter process according to an embodiment of the invention
The comparison diagram of two ferrum composite photoelectric aurora current density voltage curves；
Figure 10 is nano barium titanate ferrum/tri-after fluorion and rhodium hydroxide coprocessing according to an embodiment of the invention
Aoxidize high resolution transmission electron microscopy figure and the distribution diagram of element of two ferrum complex light electrodes；
Figure 11 is that the X of nano barium titanate ferrum/iron sesquioxide complex light electrode F element according to an embodiment of the invention penetrates
Photoelectron spectra figure；
Figure 12 is nano barium titanate ferrum/tri-oxygen after fluorion and rhodium hydroxide coprocessing according to an embodiment of the invention
Change the x-ray photoelectron energy spectrogram of two ferrum complex light electrode O elements；
Figure 13 is nano barium titanate ferrum/tri-oxygen after fluorion and rhodium hydroxide coprocessing according to an embodiment of the invention
Change the x-ray photoelectron energy spectrogram of two ferrum complex light electrode Rh elements；
Figure 14 is that fluorion and rhodium hydroxide help coprocessing nano barium titanate ferrum/tri-oxidation according to an embodiment of the invention
Density of photocurrent-the voltage curve of two ferrum complex light electrodes；
Figure 15 is that fluorion and rhodium hydroxide help coprocessing nano barium titanate ferrum/tri-oxidation according to an embodiment of the invention
The Photoelectrochemical stabilization test figure of two ferrum complex light electrodes.
Detailed description of the invention
For term defined below, unless provided a difference elsewhere in claims or this specification
Definition, these otherwise should be applied to define.All numerical value, regardless of whether be explicitly indicated, are defined as by term at this
" about " modify.Term " about " generally refers to a numerical range, and this numerical range is considered as by those of ordinary skill in the art
It is equal to character that stated value is substantially the same, function, result etc. with generation.By a low value and the instruction of high level
Include in all numerical value that one numerical range includes in being defined to include this numerical range and this numerical range is all
Subrange.Term " nanoscale " is defined as at least one size less than 100 nanometers.Term " micron order " is defined as
There is at least one size less than 5 microns." mM " that occurred is considered as the abbreviation of " mmol/l "." M " that occurred regards
Abbreviation for " mol/l ".
Principal information about the hydro-thermal reaction in the present invention all can obtain in various science and patent documentation.Letter at this
Singly it is set fourth as hydro-thermal reaction and refers in airtight system, using water as reaction medium, under certain temperature and pressure, in solution
The general name of relevant chemical reaction that carried out of material.When utilizing hydro-thermal reaction to prepare nano material, the size of its synthetic product,
Pattern and structure etc. all can be affected by conditions such as heating rate, reaction temperature, response time and reactant concentrations.Therefore,
Compared with other preparation method, hydro-thermal reaction the nano material prepared has size and morphology controllable, crystal formation is good, flow process is simple
Advantage single, that condition is relatively mild.Hydro-thermal method is to prepare nanometer α-Fe2O3One of common method of optoelectronic pole, from existing document
From the point of view of Bao Dao, its preparation process can be divided into following two part: first with FeCl3Or Fe (NO3)3The hydrolysis of solution
Make FeOOH (FeOOH) nanometer stick array be grown in conductive substrates (generally using FTO electro-conductive glass), pass through the most again
The high temperature anneal in air makes FeOOH change into α-Fe2O3Nano thin-film, reactor is the reaction vessel of hydro-thermal reaction.
One aspect of the present invention covers a kind of nano barium titanate ferrum/iron sesquioxide complex light electrode.The present invention's is another
One aspect covers the method preparing nano barium titanate ferrum/iron sesquioxide complex light electrode.Another aspect of the present invention is contained
The method having covered nano barium titanate ferrum/iron sesquioxide complex light electrode surface reforming.Another aspect of the present invention cover by
Nano barium titanate ferrum after surface modification/iron sesquioxide complex light electrode is applied to the performance evaluation of photoelectrocatalysis decomposition water.
Fig. 1 is that the structure of nano barium titanate ferrum/iron sesquioxide complex light electrode 100 according to an embodiment of the invention is shown
It is intended to.As it is shown in figure 1, the invention provides a kind of nano barium titanate ferrum/iron sesquioxide complex light electrode 100, FTO can be included
Electro-conductive glass 1, the oxide skin(coating) 2 and Fe of ferrotitanium2O3Layer 3.The oxide skin(coating) 2 of described ferrotitanium is formed on FTO electro-conductive glass 1, institute
State Fe2O3Layer 3 is formed on the oxide skin(coating) 2 of ferrotitanium.The oxide skin(coating) 2 of described ferrotitanium be mainly composed of Fe2TiO5, it is thick
Degree is nanoscale or micron order.Described Fe2O3Layer 3 be mainly composed of α-Fe2O3, its thickness is micron order.According to the present invention's
One or more embodiments, described FTO electro-conductive glass 1 can also be other electro-conductive glass.One or more according to the present invention
Embodiment, described conductive substrates can include that substrate and conductive layer, described substrate are silicon chip or glass, and described conductive layer is gold
Belong to or metal-oxide film, and described metal or metal-oxide film are made up of exotic material, described metal-oxide
Thin film is fluorine-doped tin oxide or aluminium-doped zinc oxide, and in described fluorine-doped tin oxide, the mass percent of Fluorin doped is 10-
15%, in described aluminium-doped zinc oxide, the mass percent of aluminum doping is 5-8%, and the thickness of described metal-oxide film is 10
～100nm.Only under this doping ratio, the composite photo-catalyst finally prepared, its performance is optimal.
Fig. 2 is the system of the nano barium titanate ferrum according to the one or more embodiment of the present invention/iron sesquioxide complex light electrode
Preparation Method flow chart.According to one embodiment of the invention, it is provided that a kind of nano barium titanate ferrum/iron sesquioxide complex light electrode
New preparation method and a kind of new method soaking electro-conductive glass of offer.According to the multiple embodiment of the present invention, the method include as
Lower step:
S101, cleaning fluorine-doped tin oxide (fluorine-doped tin oxide, FTO) electro-conductive glass；
S102, will clean after FTO electro-conductive glass insert in the inorganic salt solution of titanium conducting electricity ventricumbent mode,
10-60min is soaked at 60-80 DEG C；
Described FTO electro-conductive glass after S103, taking-up immersion, and be carried out, the FTO electro-conductive glass after cleaning exists
10-30min is heated at 150-200 DEG C；
S104, the FTO electro-conductive glass after heating is inserted in the reactor of inorganic salt and the mineralizer aqueous solution filling ferrum,
And described reactor is heated at 60-100 DEG C 2-5h；
S105, the most reacted described FTO electro-conductive glass of taking-up, and be carried out, the FTO after cleaning leads
Electricity glass anneal 1-3h at 500-600 DEG C, then annealing 10-30min at 700-800 DEG C, prepares nano barium titanate ferrum/tri-
Aoxidize two ferrum complex light electrodes.
Fig. 3 is the preparation method of nano barium titanate ferrum/iron sesquioxide complex light electrode according to an embodiment of the invention
Schematic flow sheet.As it is shown on figure 3, specifically, according to the multiple embodiment of the present invention, the method comprises the steps:
S11, FTO electro-conductive glass is cut into the square of 5cm × 3cm × 0.2cm, the multiple FTO electro-conductive glass after cutting
It is sequentially placed into ultrasonic cleaning in deionized water, ethanol and propanol solution, each self-cleaning in deionized water, ethanol and propanol solution
15min；
S12, will clean after multiple FTO electro-conductive glass with conduct electricity ventricumbent mode insert successively 1.8mM, 4.0mM,
In 9.0mM, 18mM and 36mM titanium tetrachloride aqueous solution, at 75 DEG C, soak 30min；
Described FTO electro-conductive glass after S13, taking-up immersion, and be carried out with deionized water, the FTO that will clean up
Electro-conductive glass is placed on warm table, heats 15min at 180 DEG C；
S14, configuration 80ml molar concentration are respectively the FeCl of 75mM and 0.3M3·6H2O and D/W, and by upper
State solution pour into volume be 100ml containing in teflon-lined stainless steel cauldron, the most again by the FTO after heating
Electro-conductive glass is inserted in aforesaid reaction vessel obliquely；
S15, will seal after reactor be placed in blowing-type drying baker, hydro-thermal reaction 4h at 95 DEG C；
After S16, hydro-thermal reaction terminate, after reactor is cooled to room temperature, takes out FTO electro-conductive glass, and use deionized water
It is carried out；
S17, will clean after FTO electro-conductive glass put in Muffle furnace, at 550 DEG C anneal 5h, then at 750 DEG C anneal
15min, prepares nano barium titanate ferrum/iron sesquioxide complex light electrode.
Fig. 4 shows that the high-resolution of the nano barium titanate ferrum/iron sesquioxide complex light electrode of one embodiment of the invention is saturating
Penetrate electron microscope picture and distribution diagram of element.As shown in Figure 4, the crystal structure of the complex light electrode that the embodiment of the present invention is prepared
Clearly, and elementary composition for Fe, Ti and O, there is no other miscellaneous elements.
Fig. 5 shows the nano barium titanate ferrum/iron sesquioxide complex light electrode Ti element L limit of one embodiment of the invention
X-ray absorption spectrogram.As shown in Figure 5, the X-ray absorption on the Ti element L limit of nano barium titanate ferrum/iron sesquioxide complex light electrode
Spectrum and object of reference iron titanate, i.e. Fe2TiO5, Ti element L limit X-ray absorption spectrum substantially coincide.Therefore, provable receive
The Ti element of rice iron titanate/iron sesquioxide complex light electrode is mainly presented in iron titanate.
Fig. 6 shows that the nano barium titanate ferrum/iron sesquioxide complex light electrode of the multiple embodiment of the present invention is at different moles
Density of photocurrent-voltage curve under the immersion of concentration titanium tetrachloride solution.Molten by the different molar concentration titanium tetrachloride of contrast
Density of photocurrent-the voltage curve of the nano barium titanate ferrum/iron sesquioxide complex light electrode prepared by immersion bubble, it is known that, mole
Concentration is that the composite photoelectric prepared by titanium tetrachloride solution immersion of 4mM has optimal photoelectrocatalysis decomposition water performance.
In another embodiment, the one during described titanium tetrachloride could alternatively be titanous chloride., Titanium Nitrate and titanium sulfate
Or multiple combination in titanium tetrachloride, titanous chloride., Titanium Nitrate and titanium sulfate.The molar concentration of the inorganic salt of titanium can be 1-
Arbitrary molar concentration in 40mmol/l.
In another embodiment, during described iron chloride could alternatively be ferrous chloride, ferric nitrate, ferrous sulfate and iron sulfate
A kind of or iron chloride, ferrous chloride, ferric nitrate, ferrous sulfate and iron sulfate in multiple combination.The inorganic salt of ferrum mole
Concentration is arbitrary molar concentration in 0.1-0.5mol/l.
In another embodiment, described glucose could alternatively be sodium nitrate or carbamide, or glucose, sodium nitrate and carbamide
In multiple combination.The molar concentration of mineralizer is arbitrary molar concentration in 50-100mmol/l.
According to the solution of the present invention, the preparation method of nano barium titanate ferrum/iron sesquioxide complex light electrode is due to first sharp
Soak FTO electro-conductive glass with the inorganic salt of titanium, the compound of titanium be formed on FTO electro-conductive glass, then be combined iron sesquioxide,
Nano barium titanate ferrum/iron sesquioxide composite photoelectric that this kind of method prepares has high photoelectrocatalysis decomposition water performance.This
Outward, compared with the preparation method of complex light electrode in prior art, the complex light electrode preparation method of the application is simple, tests bar
Part is easily controllable, the complex light electrode prepared before compound be combined after varying topography less, thus, to complex light
The impact of the photoelectrocatalysis decomposition water performance of electrode is reduced to minimum.According to the solution of the present invention, the inorganic salt of described titanium mole
When concentration is 1-40mmol/l, the optoelectronic pole prepared is respectively provided with higher photoelectrocatalysis decomposition water performance, but works as the inorganic of titanium
Salt is titanium tetrachloride, and when molar concentration is 4mmol/l, its photoelectrocatalysis decomposition water performance is optimal.
Fig. 7 is changing of the nano barium titanate ferrum/iron sesquioxide complex light electrode according to the one or more embodiment of the present invention
The schematic flow sheet of property method.According to one embodiment of the invention, it is provided that a kind of nano barium titanate ferrum/iron sesquioxide complex light
The new method of electrode modification.
According to one embodiment of present invention, the method for described nano barium titanate ferrum/iron sesquioxide complex light electrode modification
It it is nano barium titanate ferrum/iron sesquioxide complex light electrode of preparing of above-mentioned preparation method based on the present invention.
According to another embodiment of the present invention, the method for described nano barium titanate ferrum/iron sesquioxide complex light electrode modification
It it is the nano barium titanate ferrum/iron sesquioxide complex light electrode prepared based on other preparation methoies.
According to the multiple embodiment of the present invention, the method comprises the steps:
S201, surface fluorination process step:
Nano barium titanate ferrum/iron sesquioxide complex light electrode is inserted in the solution containing inorganic fluoride, at 40-80 DEG C
Lower immersion 1-10min, takes out the described complex light electrode after soaking, and heats 10-30min at 150-250 DEG C, and heating terminates
After cool the temperature to room temperature, and be carried out；
S202, the load step of rhodium hydroxide promoter:
In the precursor solution containing the inorganic salt of rhodium, use the electrochemical deposition method of light auxiliary, rhodium hydroxide is helped
Catalyst is carried on the nano barium titanate ferrum/iron sesquioxide complex light electrode after surface fluorination processes.
Specifically, according to the multiple embodiment of the present invention, the method for modifying of nano barium titanate ferrum/iron sesquioxide complex light electrode
Processing step and the load step of rhodium hydroxide promoter including surface fluorination, wherein, described surface fluorination processes step bag
Include:
S21,0.185g ammonium fluoride is dissolved in 5ml hydrogen peroxide (mass fraction 30%) and the mixed solution of 5ml deionized water
In, it is configured to the etching solution used by surface fluorination process；
S22, described nano barium titanate ferrum/iron sesquioxide complex light electrode is inserted in described etching solution, at 60 DEG C
Soak 5min；
Described complex light electrode after S23, taking-up immersion, and described complex light electrode is placed in heating plate, 200
20min is heated at DEG C；
S24, heating cool the temperature to room temperature, with this complex light electrode surface of deionized water rinsing after terminating.
Fig. 8 is nano barium titanate ferrum/iron sesquioxide complex light electrode before and after fluorion according to embodiments of the present invention processes
The comparison diagram of density of photocurrent-voltage curve, as shown in Figure 8, tests nano barium titanate ferrum/tri-oxidation two before and after fluorion processes
Density of photocurrent-the voltage curve of two kinds of samples of ferrum complex light electrode, as seen from the figure, by the photoelectric current of two kinds of samples of comparison
Density-voltage curve, finds the starting voltage of the nano barium titanate ferrum/iron sesquioxide complex light electrode processed through fluorion,
Its numerical value is down to 0.79Vvs.RHE by 0.95V vs.RHE, i.e. reduces 160mV.It is indicated above surface fluorion process to make
The photoelectrocatalysis decomposition water performance of complex light electrode is improved.
The load step of described rhodium hydroxide promoter includes:
S25, using surface fluorination process after nano barium titanate ferrum/iron sesquioxide complex light electrode as working electrode, platinum
Silk electrode is as to electrode, and saturated Ag/AgCl electrode is as reference electrode；
S26, in 1M sodium hydroxide electrolyte solution, under the irradiation of AM1.5G simulated solar irradiation, at surface fluorination
Nano barium titanate ferrum after reason/iron sesquioxide complex light electrode carries out linear voltammetric scan, relative to saturated Ag/AgCl reference electricity
The electrode potential of pole, i.e. scanning voltage scope are-0.4-0.8V, and sweep speed is 50mV/s, and scanning times is 5 times；
After S27, the end of scan, utilize deionized water rinsing nano barium titanate ferrum/iron sesquioxide complex light electrode；
S28, described complex light electrode with the rhodium chloride solution of 0.25mM as electrolyte solution, after above-mentioned steps is processed
Carrying out identical linear voltammetric scan, scanning voltage scope is-0.4-0.8V, and sweep speed is 50mV/s, and scanning times is 5
Secondary；
After S29, the end of scan, described complex light electrode is spent ionized water to be carried out, and is at room temperature dried,
Prepare the nano barium titanate ferrum/iron sesquioxide complex light electrode of rhodium hydroxide and fluorion coprocessing.
Fig. 9 is nano barium titanate ferrum/tri-oxidation before and after rhodium hydroxide promoter process according to an embodiment of the invention
The comparison diagram of two ferrum composite photoelectric aurora current density voltage curves.As shown in Figure 9, the load of rhodium hydroxide promoter can
Substantially to reduce the starting voltage of nano barium titanate ferrum/iron sesquioxide complex light electrode, its numerical value is down to by 0.95V vs.RHE
0.82V vs.RHE, reduces 130mV.
Figure 10 is nano barium titanate ferrum/tri-oxygen after fluorion and rhodium hydroxide coprocessing according to an embodiment of the invention
Change high resolution transmission electron microscopy figure and the distribution diagram of element of two ferrum complex light electrodes.Figure 10 and Fig. 4 is compared analysis,
Nano barium titanate ferrum/iron sesquioxide complex light electrode is not made from the coprocessing of data in figure, fluorion and rhodium hydroxide
Microscopic appearance change.As shown in Figure 10, to be evenly distributed on nano barium titanate ferrum/iron sesquioxide multiple for fluorine and two kinds of elements of rhodium
Close the surface of optoelectronic pole.
Figure 11 is that the X of nano barium titanate ferrum/iron sesquioxide complex light electrode F element according to an embodiment of the invention penetrates
Photoelectron spectra figure.Nano barium titanate ferrum/tri-oxidation two after fluorion and rhodium hydroxide coprocessing by data validation in figure
The existence of fluorine element in ferrum complex light electrode.
Figure 12 is nano barium titanate ferrum/tri-oxygen after fluorion and rhodium hydroxide coprocessing according to an embodiment of the invention
Change the x-ray photoelectron energy spectrogram of two ferrum complex light electrode O elements.Figure 13 be according to an embodiment of the invention fluorion and
The x-ray photoelectron energy spectrogram of the nano barium titanate ferrum after rhodium hydroxide coprocessing/iron sesquioxide complex light electrode Rh element.By
Nano barium titanate ferrum/iron sesquioxide complex light electrode after data validation fluorion and rhodium hydroxide coprocessing in Figure 12 and 13
Middle rhodium element is mainly presented in rhodium hydroxide.
Figure 14 is that fluorion and rhodium hydroxide help coprocessing nano barium titanate ferrum/tri-oxidation according to an embodiment of the invention
Density of photocurrent-the voltage curve of two ferrum complex light electrodes.As shown in Figure 14, process and rhodium hydroxide through surface fluorion
After the load of promoter, the starting voltage of nano barium titanate ferrum/iron sesquioxide complex light electrode is all produced with density of photocurrent
Having given birth to significant improvement, its starting voltage is down to 0.72V vs.RHE by 0.95V, reduces 230mV；At 1.0V vs.RHE
Density of photocurrent is by 0.38mA/cm2Increase to 1.47mA/cm2, increase more than 3 times, thus rhodium hydroxide and fluorion be described
The performance of coprocessing technical coordination effect improves the photoelectrocatalysis of nano barium titanate ferrum/iron sesquioxide complex light electrode significantly and divides
The performance of Xie Shui.
Figure 15 shows under the irradiation of 1 hour simulated solar irradiation, fluorion and rhodium hydroxide coprocessing nano barium titanate
Ferrum/iron sesquioxide complex light electrode density of photocurrent change curve at 1.0V vs.RHE applying bias, by the number in figure
According to understanding, fluorion and rhodium hydroxide coprocessing nano barium titanate ferrum/iron sesquioxide composite photoelectric have good photoelectrochemical
Learn stability.
In another embodiment, during the mass ratio of inorganic fluoride, hydrogen peroxide and deionized water is 1-2:50-60:45-55
Any proportion.
In another embodiment, the one during described ammonium fluoride could alternatively be sodium fluoride, ammonium acid fluoride and prodan
Or the combination in sodium fluoride, ammonium fluoride, ammonium acid fluoride and prodan.
In another embodiment, the one during described rhodium chloride could alternatively be rhodium triiodid, rhodium nitrate and rhodium sulfate
Or multiple combination in rhodium chloride, rhodium triiodid, rhodium nitrate and rhodium sulfate.
According to the solution of the present invention, the surface modifying method of nano barium titanate ferrum/iron sesquioxide complex light electrode, step letter
Single controlled, owing to using surface fluorion to process the method with electrochemical deposition rhodium hydroxide promoter to above-mentioned composite photoelectric
Pole has carried out modification and modification, so that the starting voltage of described complex light electrode is effectively reduced, i.e. drops
Low about 230mV, the density of photocurrent at 1.0V vs.RHE is by 0.38mA/cm2Increase to 1.47mA/cm2.Thus,
Process due to surface fluorion and the cooperative effect of electrochemical deposition rhodium hydroxide promoter coprocessing makes above-mentioned complex light
The photoelectrocatalysis decomposition water performance of electrode is significantly improved.
So far, although those skilled in the art will appreciate that the multiple of the most detailed present invention of illustrate and describing show
Example embodiment, but, without departing from the spirit and scope of the present invention, still can be direct according to present disclosure
Determine or derive other variations or modifications of many meeting the principle of the invention.Therefore, the scope of the present invention is it is understood that and recognize
It is set to and covers other variations or modifications all these.
Claims (10)
1. a preparation method for nano barium titanate ferrum/iron sesquioxide complex light electrode, comprises the steps:
Clean FTO electro-conductive glass；
FTO electro-conductive glass after cleaning is inserted in the inorganic salt solution of titanium in the ventricumbent mode of conduction, at 60-80 DEG C
Soak 10-60min；
Taking out the described FTO electro-conductive glass after soaking, and be carried out, the FTO electro-conductive glass after cleaning is at 150-200 DEG C
Heating 10-30min；
FTO electro-conductive glass after heating is inserted in the reactor of inorganic salt and the mineralizer aqueous solution filling ferrum, and by described
Reactor heats 2-5h at 60-100 DEG C；
Taking out the most reacted described FTO electro-conductive glass, and be carried out, the FTO electro-conductive glass after cleaning exists
Anneal at 500-600 DEG C 1-3h, then the 10-30min that anneals at 700-800 DEG C, prepares nano barium titanate ferrum/iron sesquioxide
Complex light electrode.
The preparation method of nano barium titanate ferrum the most according to claim 1/iron sesquioxide complex light electrode, wherein, described
FTO electro-conductive glass after heating is inserted in the reactor of inorganic salt and the D/W filling ferrum, after heating
FTO electro-conductive glass is inserted in the reactor of inorganic salt and the D/W filling ferrum obliquely.
The preparation method of nano barium titanate ferrum the most according to claim 2/iron sesquioxide complex light electrode, wherein, described
The inorganic salt of titanium is the combination of one or more in titanium tetrachloride, titanous chloride., Titanium Nitrate and titanium sulfate；
The inorganic salt of described ferrum is the group of one or more in iron chloride, ferrous chloride, ferric nitrate, ferrous sulfate and iron sulfate
Close；
Described mineralizer is the combination of one or more in glucose, sodium nitrate and carbamide.
4. according to the preparation method of the nano barium titanate ferrum described in Claims 2 or 3/iron sesquioxide complex light electrode, wherein,
The molar concentration of the inorganic salt of described titanium is 1-40mmol/l；
The molar concentration of the inorganic salt of described ferrum is 0.1-0.5mol/l；
The molar concentration of described mineralizer is 50-100mmol/l.
5. according to the preparation method of the nano barium titanate ferrum according to any one of claim 2-4/iron sesquioxide complex light electrode,
Wherein,
Described will clean after FTO electro-conductive glass at 150-200 DEG C, heat 10-30min, be will clean after FTO conduction glass
Glass is placed on warm table, heats 10-30min at 150-200 DEG C；
Described described reactor is heated at 60-100 DEG C 2-5h, be that described reactor is placed in drying baker, at 60-
2-5h is heated at 100 DEG C；
Described will clean after FTO electro-conductive glass anneal at 500-600 DEG C 1-3h, then annealing 10-at 700-800 DEG C
30min, is that the FTO electro-conductive glass after cleaning is placed in Muffle furnace, and anneal at 500-600 DEG C 1-3h, then at 700-800
Anneal at DEG C 10-30min.
6. a surface modifying method for nano barium titanate ferrum/iron sesquioxide complex light electrode, comprises the steps:
Surface fluorination processes step: that is inserted by nano barium titanate ferrum/iron sesquioxide complex light electrode containing inorganic fluoride is molten
In liquid, at 40-80 DEG C, soak 1-10min, take out the described complex light electrode after soaking, and at 150-250 DEG C, heat 10-
30min, heating cools the temperature to room temperature after terminating, and is carried out；
The load step of rhodium hydroxide promoter: use the electrification of light auxiliary in the precursor solution containing the inorganic salt of rhodium
Learn deposition process, rhodium hydroxide promoter is carried on the nano barium titanate ferrum/iron sesquioxide after surface fluorination processes and is combined
On optoelectronic pole.
The surface modifying method of nano barium titanate ferrum the most according to claim 6/iron sesquioxide complex light electrode, wherein,
Described surface fluorination processes and described in step inserts nano barium titanate ferrum/iron sesquioxide complex light electrode containing inorganic fluoride
Solution in, comprise the steps:
Inorganic fluoride is dissolved in the mixed solution of hydrogen peroxide and deionized water, is configured to the etching used by surface fluorination process
Solution；
Described nano barium titanate ferrum/iron sesquioxide complex light electrode is inserted in described etching solution.
8. according to the surface modifying method of the nano barium titanate ferrum described in claim 6 or 7/iron sesquioxide complex light electrode, its
In, in the load step of described rhodium hydroxide promoter, described employing light in the precursor solution containing the inorganic salt of rhodium
The electrochemical deposition method of auxiliary, comprises the steps:
Nano barium titanate ferrum/iron sesquioxide complex light electrode after being processed by surface fluorination is made as working electrode, platinum electrode
For to electrode, saturated Ag/AgCl electrode is as reference electrode；
In 1moll/l sodium hydroxide electrolyte solution, under the irradiation of AM1.5G simulated solar irradiation, after surface fluorination is processed
Nano barium titanate ferrum/iron sesquioxide complex light electrode carry out linear voltammetric scan；
Described complex light with the inorganic salt solution of the rhodium of 0.2-0.3mmoll/l as electrolyte solution, after above-mentioned steps is processed
Electrode carries out identical linear voltammetric scan；
After the end of scan, described complex light electrode is carried out and is dried, prepare rhodium hydroxide and fluorion coprocessing
Nano barium titanate ferrum/iron sesquioxide complex light electrode.
9. according to the surface modifying method of the nano barium titanate ferrum described in claim 7 or 8/iron sesquioxide complex light electrode, its
In,
The mass ratio of described inorganic fluoride, hydrogen peroxide and deionized water is 1-2:50-60:45-55；
Described inorganic fluoride is the combination of one or more in sodium fluoride, ammonium fluoride, ammonium acid fluoride and prodan；
The inorganic salt of described rhodium is the combination of one or more in rhodium chloride, rhodium triiodid, rhodium nitrate and rhodium sulfate.
10. according to the surface modification of the nano barium titanate ferrum according to any one of claim 7-9/iron sesquioxide complex light electrode
Method, wherein, the scanning voltage of described linear voltammetric scan is-0.4-0.8V, and sweep speed is 50mV/s.
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| CN106868530B (en) * | 2017-01-18 | 2017-12-26 | 黄河科技学院 | Modified titanic oxide optoelectronic pole and preparation method thereof, application |
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| CN109518206A (en) * | 2018-12-06 | 2019-03-26 | 苏州大学 | A kind of preparation method and surface modifying method of molybdenum modified ferric oxide optoelectronic pole |
| CN109675637A (en) * | 2018-12-19 | 2019-04-26 | 天津理工大学 | A kind of α-ferric oxide film preparation method of ferrous salt modification |
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