CN107881524B - Using Ni1-xFexThe method of OOH modified titanic oxide light anode progress photoelectrocatalysis hydrogen production by water decomposition - Google Patents

Using Ni1-xFexThe method of OOH modified titanic oxide light anode progress photoelectrocatalysis hydrogen production by water decomposition Download PDF

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CN107881524B
CN107881524B CN201711372792.5A CN201711372792A CN107881524B CN 107881524 B CN107881524 B CN 107881524B CN 201711372792 A CN201711372792 A CN 201711372792A CN 107881524 B CN107881524 B CN 107881524B
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CN107881524A (en
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张晓凡
张炳雁
孔维倩
杨保成
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Huanghe Science and Technology College
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Abstract

The invention belongs to optoelectronic materials technologies, and in particular to a kind of to use Ni1‑xFexThe method of OOH modified titanic oxide light anode progress photoelectrocatalysis hydrogen production by water decomposition, it is characterised in that: three-electrode system is used, respectively with Ni1‑xFexOOH modified titanic oxide light anode is working electrode, and platinized platinum is to electrode, and saturated calomel electrode is reference electrode, and electrolyte is 1mol L‑1Potassium hydroxide solution, the hydrogen production by water decomposition under light source, applying bias are 0.4V~1.6V vs.RHE.The present invention uses Ni1‑xFexOOH modified titanic oxide light anode is used for photoelectrocatalysis hydrogen production by water decomposition, not only can effectively inhibit TiO2The Carrier recombination of optoelectronic pole, and reaction activity is advantageously reduced, to promote photoelectricity pole surface oxygen evolution reaction, catalytic activity more higher than NiOOH and FeOOH is presented in terms of electrocatalytic oxidation evolution reaction.

Description

Using Ni1-xFexOOH modified titanic oxide light anode carries out photoelectrocatalysis and decomposes water system The method of hydrogen
Technical field
The invention belongs to optoelectronic materials technologies, and in particular to a kind of Ni1-xFexOOH modified titanic oxide optoelectronic pole and Preparation method decomposes the application in water in photoelectrocatalysis.
Background technique
Energy crisis and environmental pollution are the severe challenges that current social development faces, the fuel that people use at present with Based on the fossil energies such as coal, petroleum, natural gas, not only reserves are limited and are all non-renewable energy resources.In face of this two hang-up, when This life circle is being subjected to unprecedented challenge, actively finds abundance, environmentally protective renewable energy with far-reaching Strategic importance.Solar energy is not only resourceful, but also without geographical restrictions, therefore by the concern of researcher.Hydrogen Energy burning Exclusive product is that water not can cause environmental pollution, while have many advantages, such as the energy density of 143kJ/kg, abundance, wide Big researcher is considered most promising efficient, environmentally protective renewable energy.Therefore, using semiconductor photoelectrocatalysielectrode technology Water decomposition is directly generated into hydrogen and oxygen using solar energy, and in the form of this chemical energy of hydrogen then storage utilizes, and is Solve the most promising mode of the above problem.In solar energy electrocatalytic decomposition aqueous systems, optoelectronic pole material is to determine the sun Can absorb and Utilization ability key factor, therefore, select suitable electrode material and it is subject to modification to improve its Performance has highly important influence.
The band gap locations of titanium dioxide are suitable, have good stability, and meet the condition of ideal optoelectronic pole, are current most studies One of semiconductor material.Wherein TiO2Almost meet all conditions of ideal optoelectronic pole, but there is also visible light utilization efficiency is low The problems such as (ultraviolet light can only be absorbed), electron-hole low separation efficiency and interfacial reaction rate slow (~s grades).These defects at It is further increased for its performance and the bottleneck of application.For this purpose, on the one hand researcher goes out from raising photogenerated charge separative efficiency Hair, by itself and other semiconductors couplings, formed Type II type hetero-junctions [X.Zhang, B.Zhang, K.Cao, J.Brillet, J.Chen, M. Wang, Y.RHEn, J.Mater.Chem.A, 2015,3,21630-21636] or p-n junction [X.Zhang, H.Yang, B.Zhang, Y.RHEn, Adv.Mater.Interfaces, 2016,3,1500273], under built-in electric field action Promote electron-hole separation.On the other hand it helps the methods of electro-deposition to help in titanium dioxide surface modification by electro-deposition or light to urge Agent, such as: electro-deposition prepares CoNi LDH/TiO2Nanotube complex light electrode [W.Chen, T.Wang, J.Xue, S.Li, Z.Wang, S.Sun, Small, 2017,1602420], and NiFe LDH/RGO/TiO is prepared by illumination electro-deposition2Nanometer Stick complex light electrode [F.Ning, M.Shao, S.Xu, Y.Fu, R.Zhang, M.Wei, D.Evans, X.Duan, Energy Environ.Sci.,2016,9,2633-2643].Co-catalyst can not only provide more reactivity sites, reduce anti- Required activation energy is answered, photohole can also be captured and then oxidation reaction occurs, while there is the work for inhibiting Carrier recombination With finally improving its light hydrogen transfer efficiency.But for now, for modifying TiO2Co-catalyst type it is also extremely limited, It mainly include metal oxide containing precious metals (RuOx、IrOx), Co based compounds (CoNi LDH), nickel iron based compound (NiFe LDH) Deng this just seeks novel, efficient and cheap co-catalyst for researcher and provides challenge.Research shows that in alkaline environment, Due to the influence in Fe reactivity site, Ni1-xFexOOH present in terms of electrocatalytic oxidation evolution reaction than NiOOH and The higher catalytic activity of FeOOH.
Summary of the invention
In order to promote the oxygen evolution reaction on titanium dioxide photo anode surface, the object of the present invention is to provide a kind of Ni1- xFexThe preparation method of OOH modified titanic oxide optoelectronic pole, passes through Ni1-xFexThe combination of OOH and titanium dioxide photoelectrode promotees Into the separation of carrier, Ni is additionally provided1-xFexOOH modified titanic oxide optoelectronic pole decomposes the application in water in photoelectrocatalysis.
To achieve the goals above, the technical solution adopted by the present invention are as follows:
A kind of Ni1-xFexThe preparation method of OOH modified titanic oxide optoelectronic pole, comprising the following steps:
(1) titanium source compound is added into 5.5~6.5mol/L hydrochloric acid, stirs 8~15 minutes, is mixed at room temperature Liquid；The titanium source compound is isopropyl titanate or tetrabutyl titanate, the volume ratio of hydrochloric acid and titanium source compound be 3:0.06~ 0.07；
(2) by mixed liquor obtained by electro-conductive glass inserting step (1), and in 140~160 DEG C hydro-thermal reaction 6~12 hours, It is cooled to room temperature；Then electro-conductive glass is taken out, washes, dries, then be warming up to 440~460 with 2~5 DEG C/min of speed DEG C, after calcining 2~3 hours, it is cooled to room temperature, obtains TiO2Light anode；
(3) with step (2) resulting TiO2Light anode is working electrode, and platinized platinum is to electrode, and Ag/AgCl is reference electrode Three-electrode system is constituted, to contain 3~7mmol/L ferric trichloride, 1~5mmol/L nickel chloride, 4.5~5.5mmol/L fluorination The aqueous solution of sodium, 0.08~0.12mol/L potassium chloride and 0.98~1.02mol/L hydrogen peroxide is electrolyte, is lied prostrate using circulation The potential region of An Facong -0.5 ± 0.05V to 0.5 ± 0.05V sweeps 1~10 circle with the speed circulation of sweeping of 180~220mV/s, so After take out working electrode, washed, dry to get.
Preferably, electro-conductive glass described in step (2) is fluorine-doped tin oxide (FTO) electro-conductive glass.
Preferably, dry be all made of is dried with nitrogen in dry and step (3) in step (2).
The Ni being prepared using the above method1-xFexOOH modified titanic oxide optoelectronic pole, by Fe in ferric trichloride3+'s Molar concentration is denoted as C1, Ni in nickel chloride2+Molar concentration be denoted as C2, then x=C1/(C1+C2)。
Above-mentioned Ni1-xFexOOH modified titanic oxide optoelectronic pole decomposes the application in water in photoelectrocatalysis.
The FTO electro-conductive glass is ordinary commercial products.
The present invention is by TiO2FTO conducting glass material surface is grown to, then by Ni1-xFexOOH is attached to semiconductor material (TiO2) surface, form co-catalysis layer.Using Ni1-xFexOOH modified titanic oxide light anode decomposes water system for photoelectrocatalysis Hydrogen not only can effectively inhibit TiO2The Carrier recombination of optoelectronic pole, and reaction activity is advantageously reduced, to promote photoelectricity Pole surface oxygen evolution reaction.
Detailed description of the invention
Fig. 1 is 2 gained TiO of embodiment2/Ni0.5Fe0.5OOH complex light anode, FTO/Ni0.5Fe0.5OOH and blank substrate The XRD comparison diagram of FTO；
Fig. 2 is 2 gained TiO of embodiment2Light anode and TiO2/Ni0.5Fe0.5The full spectrogram of the XPS of OOH complex light anode；
Fig. 3 is 2 gained TiO of embodiment2Light anode and TiO2/Ni0.5Fe0.5The linear volt of OOH complex light anode in the dark state Pacify curve；
Fig. 4 is TiO obtained by Examples 1 to 32/Ni1-xFexThe linear sweep voltammetry curve of OOH optoelectronic pole under light illumination；
Fig. 5 is 2 gained TiO of embodiment2Light anode and TiO2/Ni0.5Fe0.5OOH complex light anode is in illumination and open-circuit voltage Under the conditions of electrochemical impedance figure.
Specific embodiment
In order to keep technical purpose of the invention, technical scheme and beneficial effects clearer, combined with specific embodiments below Technical solution of the present invention is further illustrated, but the embodiment is intended to explain the present invention, and should not be understood as pair Limitation of the invention, in the examples where no specific technique or condition is specified, according to the literature in the art described technology or Condition is carried out according to product description.
FTO electro-conductive glass is purchased from Wuhan lattice solar energy Science and Technology Ltd. in following embodiments, with a thickness of 2.2mm, electricity Resistance is 14 Ω, light transmittance 90%.
Embodiment 1
A kind of Ni1-xFexThe preparation method of OOH modified titanic oxide optoelectronic pole, comprising the following steps:
(1) 0.42mL isopropyl titanate is added into 18mL 6mol/L hydrochloric acid, stirs 10 minutes, is mixed at room temperature Liquid；
(2) mixed liquor obtained by step (1) is poured into 25mL reaction kettle, and is inserted into FTO electro-conductive glass, FTO electro-conductive glass Upper end be higher than the liquid level of mixed liquor, so as to certain blank area be stayed above FTO electro-conductive glass, as electrode holder fixed area；It will be anti- Answer kettle to be placed in baking oven, in 150 DEG C hydro-thermal reaction 6 hours, cooled to room temperature；Then electro-conductive glass is taken out, use is high-purity Water cleaning, and with being dried with nitrogen, obtain the FTO electro-conductive glass for being covered with milky film；It will be covered with milky film again FTO electro-conductive glass is placed in Muffle furnace, after being warming up to 450 DEG C, calcining 2 hours with 5 DEG C/min of speed, naturally cools to room Temperature obtains TiO2Light anode；
(3) with step (2) resulting TiO2Light anode is working electrode, and platinized platinum is to electrode, and Ag/AgCl is reference electrode Three-electrode system is constituted, to contain 7mmol/L ferric trichloride, 1mmol/L nickel chloride, 5mmol/L sodium fluoride, 0.1mol/L chlorine The aqueous solution for changing potassium and 1mol/L hydrogen peroxide is electrolyte, using cyclic voltammetry from -0.5 to 0.45V (vs.RHE) electricity Position section sweeps 3 circles with the speed circulation of sweeping of 200mV/s, then takes out working electrode, washed, dried to get TiO is denoted as2/ Ni0.125Fe0.875OOH complex light anode.
Embodiment 2
A kind of Ni1-xFexThe preparation method of OOH modified titanic oxide optoelectronic pole, comprising the following steps:
(1) 0.42mL isopropyl titanate is added into 18mL 6mol/L hydrochloric acid, stirs 10 minutes, is mixed at room temperature Liquid；
(2) mixed liquor obtained by step (1) is poured into 25mL reaction kettle, and is inserted into FTO electro-conductive glass, FTO electro-conductive glass Upper end be higher than the liquid level of mixed liquor, so as to certain blank area be stayed above FTO electro-conductive glass, as electrode holder fixed area；It will be anti- Answer kettle to be placed in baking oven, in 150 DEG C hydro-thermal reaction 6 hours, cooled to room temperature；Then electro-conductive glass is taken out, use is high-purity Water cleaning, and with being dried with nitrogen, obtain the FTO electro-conductive glass for being covered with milky film；It will be covered with milky film again FTO electro-conductive glass is placed in Muffle furnace, after being warming up to 450 DEG C, calcining 2 hours with 5 DEG C/min of speed, naturally cools to room Temperature obtains TiO2Light anode；
(3) with step (2) resulting TiO2Light anode is working electrode, and platinized platinum is to electrode, and Ag/AgCl is reference electrode Three-electrode system is constituted, to contain 4mmol/L ferric trichloride, 4mmol/L nickel chloride, 5mmol/L sodium fluoride, 0.1mol/L chlorine The aqueous solution for changing potassium and 1mol/L hydrogen peroxide is electrolyte, using cyclic voltammetry from -0.5 to 0.45V (vs.RHE) electricity Position section sweeps 3 circles with the speed circulation of sweeping of 200mV/s, then takes out working electrode, washed, dried to get TiO is denoted as2/ Ni0.5Fe0.5OOH complex light anode.
Embodiment 3
A kind of Ni1-xFexThe preparation method of OOH modified titanic oxide optoelectronic pole, comprising the following steps:
(1) 0.42mL isopropyl titanate is added into 18mL 6mol/L hydrochloric acid, stirs 10 minutes, is mixed at room temperature Liquid；
(2) mixed liquor obtained by step (1) is poured into 25mL reaction kettle, and is inserted into FTO electro-conductive glass, FTO electro-conductive glass Upper end be higher than the liquid level of mixed liquor, so as to certain blank area be stayed above FTO electro-conductive glass, as electrode holder fixed area；It will be anti- Answer kettle to be placed in baking oven, in 150 DEG C hydro-thermal reaction 6 hours, cooled to room temperature；Then electro-conductive glass is taken out, use is high-purity Water cleaning, and with being dried with nitrogen, obtain the FTO electro-conductive glass for being covered with milky film；It will be covered with milky film again FTO electro-conductive glass is placed in Muffle furnace, after being warming up to 450 DEG C, calcining 2 hours with 5 DEG C/min of speed, naturally cools to room Temperature obtains TiO2Light anode；
(3) with step (2) resulting TiO2Light anode is working electrode, and platinized platinum is to electrode, and Ag/AgCl is reference electrode Three-electrode system is constituted, to contain 3mmol/L ferric trichloride, 5mmol/L nickel chloride, 5mmol/L sodium fluoride, 0.1mol/L chlorine The aqueous solution for changing potassium and 1mol/L hydrogen peroxide is electrolyte, using cyclic voltammetry from -0.5 to 0.45V (vs.RHE) electricity Position section sweeps 3 circles with the speed circulation of sweeping of 200mV/s, then takes out working electrode, washed, dried to get TiO is denoted as2/ Ni0.625Fe0.375OOH complex light anode.
Embodiment 4
A kind of Ni1-xFexThe preparation method of OOH modified titanic oxide optoelectronic pole, comprising the following steps:
(1) 0.36mL isopropyl titanate is added into 18mL 5.5mol/L hydrochloric acid, stirs 8 minutes, is mixed at room temperature Liquid；
(2) mixed liquor obtained by step (1) is poured into 25mL reaction kettle, and is inserted into FTO electro-conductive glass, FTO electro-conductive glass Upper end be higher than the liquid level of mixed liquor, so as to certain blank area be stayed above FTO electro-conductive glass, as electrode holder fixed area；It will be anti- Answer kettle to be placed in baking oven, in 140 DEG C hydro-thermal reaction 12 hours, cooled to room temperature；Then electro-conductive glass is taken out, use is high-purity Water cleaning, and with being dried with nitrogen, obtain the FTO electro-conductive glass for being covered with milky film；It will be covered with milky film again FTO electro-conductive glass is placed in Muffle furnace, after being warming up to 440 DEG C, calcining 3 hours with 4 DEG C/min of speed, naturally cools to room Temperature obtains TiO2Light anode；
(3) with step (2) resulting TiO2Light anode is working electrode, and platinized platinum is to electrode, and Ag/AgCl is reference electrode Three-electrode system is constituted, to contain 4mmol/L ferric trichloride, 4mmol/L nickel chloride, 4.5mmol/L sodium fluoride, 0.08mol/L The aqueous solution of potassium chloride and 0.98mol/L hydrogen peroxide is electrolyte, using cyclic voltammetry from -0.5 to 0.45V (vs.RHE) Potential region, with 180mV/s sweep speed circulation sweep 1 circle, then take out working electrode, washed, dry to get.
Embodiment 5
A kind of Ni1-xFexThe preparation method of OOH modified titanic oxide optoelectronic pole, comprising the following steps:
(1) 0.4mL isopropyl titanate is added into 18mL 6.5mol/L hydrochloric acid, stirs 15 minutes, is mixed at room temperature Liquid；
(2) mixed liquor obtained by step (1) is poured into 25mL reaction kettle, and is inserted into FTO electro-conductive glass, FTO electro-conductive glass Upper end be higher than the liquid level of mixed liquor, so as to certain blank area be stayed above FTO electro-conductive glass, as electrode holder fixed area；It will be anti- Answer kettle to be placed in baking oven, in 160 DEG C hydro-thermal reaction 9 hours, cooled to room temperature；Then electro-conductive glass is taken out, use is high-purity Water cleaning, and with being dried with nitrogen, obtain the FTO electro-conductive glass for being covered with milky film；It will be covered with milky film again FTO electro-conductive glass is placed in Muffle furnace, after being warming up to 460 DEG C, calcining 2 hours with 4 DEG C/min of speed, naturally cools to room Temperature obtains TiO2Light anode；
(3) with step (2) resulting TiO2Light anode is working electrode, and platinized platinum is to electrode, and Ag/AgCl is reference electrode Three-electrode system is constituted, to contain 4mmol/L ferric trichloride, 4mmol/L nickel chloride, 5.5mmol/L sodium fluoride, 0.12mol/L The aqueous solution of potassium chloride and 1.02mol/L hydrogen peroxide is electrolyte, using cyclic voltammetry from -0.5 to 0.45V (vs.RHE) Potential region, with 220mV/s sweep speed circulation sweep 10 circles, then take out working electrode, washed, dry to get.
By the TiO in embodiment 2 in step (3)2Light anode is changed to FTO electro-conductive glass, according to step (3) experiment parameter into Row electrochemical deposition is to get FTO/Ni0.5Fe0.5OOH.To blank substrate FTO (FTO electro-conductive glass), FTO/Ni0.5Fe0.5OOH And the TiO that embodiment 2 is prepared2/Ni0.5Fe0.5OOH carries out XRD characterization, as a result as shown in Figure 1, arrow is signified as shown in figure 1, It is followed successively by TiO from top to bottom2/Ni0.5Fe0.5OOH、FTO/Ni0.5Fe0.5The XRD diagram of OOH and blank substrate FTO.It can by Fig. 1 Know, compared with blank substrate FTO, FTO/Ni0.5Fe0.5OOH does not have new diffraction maximum to occur, should be the result shows that film obtained by electro-deposition For unformed Ni0.5Fe0.5OOH material.With blank substrate FTO and FTO/Ni0.5Fe0.5OOH is compared, 2 gained TiO of embodiment2/ Ni0.5Fe0.5OOH complex light anode in 36.1 °, 62.8 ° and 69.9 ° appearance, three new diffraction maximums, is sent out respectively by comparison It is existing, these diffraction maximums and standard Rutile Type TiO2Diffraction maximum (JCPDS File no.89-4920) result is consistent, illustrates to implement 2 gained TiO of example2/Ni0.5Fe0.5TiO in OOH2For Rutile Type.
To 2 gained TiO of embodiment2Light anode and TiO2/Ni0.5Fe0.5OOH complex light electrode carries out XPS characterization, as a result such as Shown in Fig. 2.As shown in Figure 2, with TiO2Light anode is compared, and occurs the XPS of two kinds of elements of Ni, Fe after electrochemical deposition Peak has obtained Ni after illustrating electrochemical deposition without other impurity peaks0.5Fe0.5OOH, and will not draw in electrochemical treatment process Enter other external impurity.In conjunction with Fig. 1 and Fig. 2 it is found that available unformed Ni after electro-deposition0.5Fe0.5OOH。
In the test system that photoelectrocatalysis decomposes water, photoelectric current be a kind of intuitive reflection semiconductor to the absorption of photon and The means of testing of Utilization ability.By 2 gained TiO of embodiment2Ni obtained by light anode, Examples 1 to 31-xFexOOH modification two Photocatalytic titanium oxide electrode carries out optical electro-chemistry and decomposes water performance test.Test macro uses three-electrode system, respectively with light sun to be measured Extremely working electrode, platinized platinum are to electrode, and saturated calomel electrode is reference electrode, and electrolyte is that 1mol/L potassium hydroxide is water-soluble Liquid.Electro-chemical test instrument is CHI 760E electrochemical workstation (Shanghai Chen Hua Instrument Ltd.), the use of light source is 500W Xenon source (CEL-S500, middle religion Jin Yuan) makes the spectrum of light source close to simulated solar irradiation light by applying AM 1.5G optical filter Spectrum, optical power are 100mW cm by power meter calibration-2.Test method is linear scan cyclic voltammetry, linear scan curve (LSV) potential test range is 0.4V~1.6V vs.RHE, and sweeping speed is 10mV s-1, electrolyte is 1mol L-1Potassium hydroxide Solution must be passed through high-purity N into electrolyte before test2, to remove the dissolved oxygen in electrolyte, duration of ventilation 40min, test As a result as shown in Figure 3 and Figure 4.
Fig. 3 is the TiO under dark-state (being placed in camera bellows, do not receive light irradiation)2Light anode and TiO2/Ni1-xFexOOH electricity Electrochemical property test of the pole under certain bias.From the figure 3, it may be seen that in the case where light is not added, TiO2And TiO2/Ni1- xFexThe electric current of OOH electrode illustrates that dark current of these electrodes under certain bias can be ignored all close to zero.
Fig. 4 is TiO2Light anode and TiO2/Ni1-xFexOOH optoelectronic pole is under illumination (using xenon source) and certain bias It carries out testing resulting photoelectric current.As shown in Figure 4, TiO2Although narrow gap semiconductor, due to carrier separation low efficiency It is slow with interface reaction kinetics, cause it compared with all very littles of electric current under low potential, pacesetter potential calibration.And modify Ni1- xFexPhotoelectric current is not only increased after OOH, under 1.23V vs.RHE bias, TiO2/Ni0.5Fe0.5The electric current of OOH optoelectronic pole is high Up to 0.58 mA cm-2, it is TiO21.45 times of electric current.In addition, we can further be seen that TiO from figure2/Ni0.5Fe0.5OOH light Electrode it is seen that there is apparent photoelectric current to generate, shows to modify Ni at lower bias (0.3V vs.RHE)1-xFexOOH The carrier separation of optoelectronic pole is effectively improved afterwards.
To 2 gained TiO of embodiment2Light anode and TiO2/Ni0.5Fe0.5OOH complex light anode carries out PhotoelectrocatalytiPerformance Performance survey Examination, in order to test under illumination conditions, TiO deeper into the transfer process for understanding charge on semiconductor/electrolyte interface2With TiO2/Ni1-xFexAc impedance spectroscopy (EIS) of the OOH optoelectronic pole in open-circuit voltage studies interface of the optoelectronic pole before and after modification The variation such as charge transfer resistance, capacitor.Test electrolyte is 1mol L-1Potassium hydroxide aqueous solution, must be into electrolyte before test It is passed through high-purity N2, to remove the dissolved oxygen in electrolyte, duration of ventilation 40min.Test results are shown in figure 5.
As shown in Figure 5, under illumination, TiO2/Ni0.5Fe0.5The semicircle of OOH complex light anode is smaller, illustrates its boundary having Surface charge transfer resistance (Rct) smaller, it means that separation and faster interface of the optoelectronic pole with better photo-generated carrier Charge transfer process.
As stated above, co-catalyst Ni1-xFexOOH can be effectively improved TiO2The interface oxygen evolution reaction dynamics of optoelectronic pole Slow problem, under the irradiation of AM 1.5G simulated solar irradiation and 1.23V vs.RHE voltage, TiO2/Ni1-xFexOOH optoelectronic pole Density of photocurrent increases 1.45 times, and it is seen that there is apparent photoelectricity to miscarry at lower bias (300mV vs.RHE) It is raw, illustrate co-catalyst Ni1-xFexThe modification of OOH effectively inhibits the compound of photo-generated carrier, and then promotes interface Oxygen evolution reaction.
After tested, Ni obtained by embodiment 4 and embodiment 51-xFexOOH modified titanic oxide optoelectronic pole is in lower bias It can also be seen that there is apparent photoelectric current to generate under (300 mV vs.RHE), promote the oxygen evolution reaction of interface.
Finally, it is stated that the parameter of preparation complex light electrode can adjust in respective range in the present invention, it will be apparent that Collector, semiconductor material and co-catalyst dosage can make corresponding replacement or modified.Above embodiments are only to say Bright technical solution of the present invention rather than limit, although having been retouched to the present invention by referring to the preferred embodiment of the present invention It states, it should be appreciated by those of ordinary skill in the art that various changes can be made to it in the form and details, Without departing from the spirit and scope of the present invention defined by the appended claims.

Claims (4)

1. using Ni1-xFexThe method of OOH modified titanic oxide light anode progress photoelectrocatalysis hydrogen production by water decomposition, it is characterised in that: Using three-electrode system, respectively with Ni1-xFexOOH modified titanic oxide light anode is working electrode, and platinized platinum is to electrode, saturation Calomel electrode is reference electrode, and electrolyte is 1mol L-1Potassium hydroxide solution, the hydrogen production by water decomposition under light source, applying bias are 0.4V~1.6V vs.RHE；The Ni1-xFexThe preparation method of OOH modified titanic oxide light anode is the following steps are included: (1) Titanium source compound is added into 5.5~6.5mol/L hydrochloric acid, stirs 8~15 minutes at room temperature, obtains mixed liquor；The titanium source Object is closed as isopropyl titanate or tetrabutyl titanate, the volume ratio of hydrochloric acid and titanium source compound is 3:0.06~0.07；It (2) will be conductive In mixed liquor obtained by glass inserting step (1), and in 140~160 DEG C hydro-thermal reaction 6~12 hours, be cooled to room temperature；Then will Electro-conductive glass takes out, washing, drying, then is warming up to 440~460 DEG C, after calcining 2~3 hours, is cooled to room temperature, obtains TiO2 Light anode；(3) with step (2) resulting TiO2Light anode is working electrode, and platinized platinum is to electrode, and Ag/AgCl is reference electrode Three-electrode system is constituted, to contain 3~7mmol/L ferric trichloride, 1~5mmol/L nickel chloride, 4.5~5.5mmol/L fluorination The aqueous solution of sodium, 0.08~0.12mol/L potassium chloride and 0.98~1.02mol/L hydrogen peroxide is electrolyte, is lied prostrate using circulation The potential region of An Facong -0.5 ± 0.05V to 0.5 ± 0.05V sweeps 1~10 circle with the speed circulation of sweeping of 180~220mV/s, so After take out working electrode, it is washed, dry to get.
2. according to claim 1 use Ni1-xFexOOH modified titanic oxide light anode carries out photoelectrocatalysis and decomposes water system The method of hydrogen, it is characterised in that: electro-conductive glass described in step (2) is fluorine-doped tin oxide electro-conductive glass.
3. according to claim 1 or 2 use Ni1-xFexOOH modified titanic oxide light anode carries out photoelectrocatalysis and decomposes water The method of hydrogen manufacturing, it is characterised in that: dry be all made of is dried with nitrogen in dry and step (3) in step (2).
4. according to claim 1 use Ni1-xFexOOH modified titanic oxide light anode carries out photoelectrocatalysis and decomposes water system The method of hydrogen, it is characterised in that: the light source is sunlight or simulated solar irradiation.
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