CN107354480A - A kind of metal oxide/NiPi light anodes material and its preparation - Google Patents

A kind of metal oxide/NiPi light anodes material and its preparation Download PDF

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CN107354480A
CN107354480A CN201710465279.4A CN201710465279A CN107354480A CN 107354480 A CN107354480 A CN 107354480A CN 201710465279 A CN201710465279 A CN 201710465279A CN 107354480 A CN107354480 A CN 107354480A
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nipi
metal oxide
film
electrode
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CN107354480B (en
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高文华
王建
陈耀文
鲁福身
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Shantou University
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Abstract

The present invention relates to a kind of metal oxide/NiPi light anode materials, including metal oxide light anode and NiPi thin film passivation layers；The NiPi films are wrapped on the outside of the metal oxide light anode.Preparation method is：(1) preparation of metal oxide photo-anode film；(2) drop coating Ni salt and neutral phosphate buffer solution on metal oxide photo-anode film, deposition prepare NaNiPO4Film；(3) to metal oxide light anode/NaNiPO4Film performs optical electro-chemistry regulation and control.The Ti of the present invention is entrained in pure Fe2O3Surface is introduced than more rich oxygen vacancies, and helpful for electric conductivity raising, NiPi integuments inhibit pure Fe2O3Surface state, NiPi integuments have the performance for suppressing conduction band electron and oxygen reaction, so as to comprehensive raising Fe2O3The transfer of electrode surface electric charge, has lower overpotential for oxygen evolution, and NiPi films are a CoPi good substitute in terms of water decomposition is catalyzed.And the present invention is simple to operate, the catalyst containing Ni is prepared at room temperature, and power consumption is low, and the operating time is short.

Description

A kind of metal oxide/NiPi light anodes material and its preparation
Technical field
The invention belongs to optical electro-chemistry anode field, more particularly to a kind of metal oxide/NiPi light anodes material and its Prepare.
Background technology
Photoelectrolysis water is considered as a kind of hydrogen and oxygen production method of cleaning.For optical electro-chemistry anode, basic requirement has 2 points, first is to have relatively low production oxygen take-off potential, and second point is the need for preferable job stability, is reduced in work Oxidation and dissolving.Wherein, α-Fe2O3(it is abbreviated as Fe2O3) theoretical maximum photogenerated current density reaches 12.6mA/cm2, can meet Needs (the 10mA/cm of industry2).However, Fe2O3Electrode body phase charge low separation efficiency, surface voids injection (catalytic water oxidation) Efficiency is low.CoPi and IrO2Integument is most commonly used reduction Fe2O3Water oxygen take-off potential (Angew.Chem.Int.Ed., 49 (2010) 6405- 6408.), the material of raising surface voids injection efficiency.Also, CoPi and IrO2Have very high steady It is qualitative.But Co, Ir earth's crust content are relatively low, their applications in the industry are seriously constrained.By contrast, Ni Earth's crust content be about higher by ten times of Co.In order to solve this problem, catalyst film containing Ni is improving Fe2O3Surface voids are injected Greatly success (J.Catal., 340 (2016) 261-269.), and there is higher stability is obtained in terms of efficiency.
The phosphate radical of catalyst surface is advantageous to catalytic water oxidation, the phosphate (LiNiPO of crystalline state4And LiCoPO4) in water Surface Creation layer of Ni OOH and CoOOH (J.Am.Chem.Soc., 134 (2012) 16959-16962.), makes in oxidizing process It is lost in into phosphate radical.
The content of the invention
It is an object of the invention to provide a kind of metal oxide/NiPi light anodes material and its prepare existing to solve Problem.
In order to realize above-mentioned purpose, adopt the following technical scheme that：
A kind of metal oxide/NiPi light anode materials, including metal oxide light anode and NiPi thin film passivation layers；Institute NiPi films are stated to be wrapped on the outside of the metal oxide light anode.
Further, the metal oxide light anode is Fe2O3, 0~5%Ti:Fe2O3Nanometer stick array, TiO2、ZnO Or BiVO4In one kind.
Further, the metal oxide light anode is 0.05%Ti:Fe2O3Nanometer stick array.Performance is optimal.
Further, the pattern of the metal oxide light anode is nano-porous film, nanometer flower pattern film, nanotrees One kind in prominent shape, nanometer coral polyp shape or nanometer sea urchin shape.
Further, the NiPi film thicknesses are 2~10nm, and integument macroscopic view load capacity is 8~12 μ g/cm2。
Further, the Fe2O3With 0~5%Ti:Fe2O3Nanometer stick array load capacity is 0.8~1mg/cm2, nanometer rods A diameter of 40~100nm.
The preparation method of above-mentioned metal oxide/NiPi light anode materials, is mainly included the following steps that：
(1) preparation of metal oxide photo-anode film；
(2) drop coating Ni salt and neutral phosphate buffer solution on metal oxide photo-anode film, deposition prepare NaNiPO4 Film；
(3) to metal oxide light anode/NaNiPO4Film performs optical electro-chemistry regulation and control.
In theory, Ni3(PO4)2Class compound stability is poor：
Sour environment：
Ni3(PO4)2+nH+→Ni2++HnPO4 (n-3) (1)
Alkaline environment：
Ni3(PO4)2+2OH-→3Ni(OH)2+PO4 3- (2)
Much document reports are shown, the LiNiPO for the highly crystalline that high-temperature calcination is formed4And LiCoPO4In strong basicity environment Down easily in Surface Creation NiOOH and CoOxAnd form NiOOH/LiNiPO4And CoOx/LiCoPO4Hetero-junctions,
Further, step (3) optical electro-chemistry is regulated in 0.25~0.5M Na3PO4In solution, metal oxide light sun Pole film/NaNiPO4As working electrode, platinum electrode is used as to electrode membrane electrode, Ag/AgCl electrodes as reference electrode, Receive AM 1.5G simulated solars light radiation 30~60 minutes under 1~1.3V vs RHE voltages, rinse.
Further, the metal oxide light anode is Fe2O3Or 0~5%Ti:Fe2O3Nanometer stick array, prepare Mainly include the following steps that：
(a) FeOOH or 0~5%Ti on FTO:The preparation of FeOOH nano-rod films：It is by formula： 0.15M FeCl3:0~1M NaNO3, hydro-thermal reaction solution or formula that pH is 1.3~2 are 0.15M FeCl3:0~1M NaNO3：0 ~7.5mM Ti (such as K2TiF6、TiCl3、TiCl4、TiCN、TiF4Deng) (regulation pH is 1.3~2), pH is 1.3~2 hydro-thermal Reaction solution is placed in the inner bag equipped with FTO, and inner bag is sealed in autoclave, in 70~110 DEG C of 3~10h of hydro-thermal reaction, clearly Wash, dry；Increase the hydro-thermal reaction time can obtain larger sized FeOOH nanometer rods；
(b)Fe2O3Or 0~5%Ti:Fe2O3The preparation of film：(a) obtained film is placed on tube furnace and is warming up to 500 Calcined 20~120 minutes at~750 DEG C, be cooled to room temperature.Higher temperature calcining can cause the increase of FTO electro-conductive glass resistance.
Further, step (2) NaNiPO4The preparation of film mainly includes：On metal oxide photo-anode film The μ L of drop coating 10~100 0.01~0.1M Ni salt, alcohol flushing after 10~60 minutes, dry the 0.1 of the rear μ L of drop coating 10~100 ~0.2M neutrality phosphate buffer solutions, alcohol flushing after 10~60 minutes, dry, repeatedly.
NiPi provided by the present invention not only includes Ni2+And Ni3+Two kinds of valence states, surface and inside may all contain phosphoric acid Root, so as to form amorphous state, show to improve 0~5%Ti in low potential scope:Fe2O3The density of photocurrent of electrode.
Compared with prior art, Ti of the invention is entrained in pure Fe2O3Surface is introduced than more rich oxygen vacancies, for Electric conductivity raising is helpful, and NiPi integuments inhibit pure Fe2O3Surface state, NiPi integuments have suppress conduction band electron with The performance of oxygen reaction, so as to comprehensive raising Fe2O3The transfer of electrode surface electric charge, there is lower overpotential for oxygen evolution, NiPi Film is a CoPi good substitute in terms of water decomposition is catalyzed.And simple to operate, the catalyst containing Ni of the invention Prepare at room temperature, power consumption is low, and the operating time is short.Although there is a small amount of Ni in optical electro-chemistry regulation process3+Generation, but surface Phosphate radical in modification, phosphate radical are advantageous to improve Ni3+Proton and electron transmission in catalytic water oxidizing process, it is thin to improve NiPi The stability of film catalyst.Compared with the CoPi films of the electro-deposition of classics, NiPi film catalysts can improve Fe2O3With 0.05%Ti:Fe2O3Electrode is in the density of photocurrent and hole injection efficiency of low potential scope, suppression Fe2O3Electrode surface state.
Brief description of the drawings
Fig. 1 is the Fe that (B) is adulterated undoped with (A) and 0.05%Ti2O3The pattern of the FESEM tests of electrode；
Fig. 2 is Fe2O3, 0.05%Ti:Fe2O3Fe 2p and O 1s high-resolution power spectrum test；
Fig. 3 (A) is 0.05%Ti:Fe2O3/NaNiPO4, (B) be 0.05%Ti:Fe2O3/ NiPi (FESEM (Flied emissions ESEM) test pattern, (C), (D) are 0.05%Ti:Fe2O3/ NiPi TEM (transmission electron microscope), (E) is 0.05% Ti:Fe2O3/ NiPi HRTEM (high-resolution-ration transmission electric-lens) tests, (F) is 0.05%Ti:Fe2O3The element of/NiPi electrodes point Cloth (electron scattering power spectrum Elemental redistribution), the element such as including Fe, Ti, O, Ni and P；
Fig. 4 is to Fe2O3/NaNiPO4Electrode carries out density of photocurrent-time graph of optical electro-chemistry regulation and control；
Fig. 5 (A) and (B) are respectively 0.05%Ti:Fe2O3/NaNiPO4And 0.05%Ti:Fe2O3/ NiPi O 1s high scores Power spectrum is distinguished, (C) and (D) is respectively 0.05%Ti:Fe2O3/NaNiPO4With 0.05% Ti:Fe2O3/ NiPi P 2p3/ power spectrums and The comparison of Ni 2p3/2 power spectrums, (E) are 0.05% Ti:Fe2O3/NaNiPO4And 0.05%Ti:Fe2O3/ NiPi Na 1s power spectrums Compare；
Fig. 6 (A) is Fe2O3、Fe2O3/ NiPi, 0.05%Ti:Fe2O3, 0.05%Ti:Fe2O3/ NiPi, 0.05% Ti: Fe2O3/ CoPi analysis oxygen curves (density of photocurrent-application voltage), condition：Sweep speed：0.01V/s, electrolyte：1M NaOH、AM Under 1.5G simulated solar irradiations.(B) it is Fe2O3, 0.05%Ti:Fe2O3Body phase separation of charge efficiency-application voltage curve.(C) it is Fe2O3、Fe2O3/ NiPi, 0.05%Ti:Fe2O3, 0.05% Ti:Fe2O3/ NiPi, 0.05%Ti:Fe2O3/ CoPi surface voids Injection efficiency-application voltage curve；
Fig. 7 (A) is Fe2O3, 0.05%Ti:Fe2O3, 0.05%Ti:Fe2O3/ NiPi, 0.05%Ti:Fe2O3/ CoPi is each Electrode transient photocurrents density-time graph, (B) are their photoelectric current kinetic curve；
Fig. 8 is that surface state suppresses research, and (A) is respectively Fe2O3, 0.05%Ti:Fe2O3, 0.05%Ti:Fe2O3/NiPi And 0.05%Ti:Fe2O3The model of/CoPi electrodes-Schottky test.(B), (C), (D), (E) are respectively under dark conditions Fe2O3, 0.05%Ti:Fe2O3, 0.05%Ti:Fe2O3/ NiPi and 0.05% Ti:Fe2O3The cyclic voltammetric of each electrodes of/CoPi Test.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with accompanying drawing It is described in detail on step ground.
Embodiment 1
A kind of preparation method of Fe2O3/NiPi light anodes is as follows：
(1) on FTO FeOOH nano-rod films preparation：It is by formula：0.15M FeCl3:0~1M NaNO3 (regulations PH is 1.3~2) hydro-thermal reaction solution is placed in the inner bag equipped with FTO, inner bag is sealed in autoclave, in 70~110 DEG C of water 3~10h of thermal response, cleaning, dries, and generates one layer of flaxen transparent FeOOH nano-rod film.Increase the hydro-thermal reaction time meeting Obtain larger sized FeOOH nanometer rods.
(2)Fe2O3The preparation of film：Above-mentioned FeOOH films be placed on calcining 20 when tube furnace is warming up to 500~750 DEG C~ 120 minutes, it is cooled to room temperature and takes out, obtains the Fe2O3 and electrode of crimson color, pattern is as shown in Figure 1A.
Fe as can be seen from Figure 2A2O3The Fe 2p3/2 and 2p1/2 of film are located at 710.4eV and 723.7 eV respectively, are Fe2O3Feature.
(3)Fe2O3/NaNiPO4The preparation of film：In Fe2O3The upper μ L of drop coating 10~100 0.01~0.1M Ni salt (NiCl2、Ni(OAc)2、Ni(NO3)2、NiSO4Deng), alcohol flushing after 10~60 minutes, dry the 0.1 of the rear μ L of drop coating 10~100 ~0.2M neutrality phosphate buffer solutions, alcohol flushing after 10~60 minutes, dry.The technique repeats 2~5 times, and deposition prepares white The transparent NaNiPO of color4Film.
(4)Fe2O3The preparation of/NiPi electrodes：In 0.25~0.5M Na3PO4In solution, Fe2O3/NaNiPO4Membrane electrode As working electrode, platinum electrode to electrode, Ag/AgCl electrodes as reference electrode as immersing in the solution, to work electricity Pole applies 1-1.3V vs RHE voltages, while receives AM 1.5G simulated solar irradiations (100mW/cm2) radiation 30~60 minutes it is right Fe2O3/NaNiPO4Film performs optical electro-chemistry and regulates and controls Fe processed2O3/ NiPi films.The inventive method is simple, saved energy and Time.
In general Fe2O3/NaNiPO4Electrode is all unstable in strong basicity and neutral solution, Fe2O3/NaNiPO4Electrode In 1M NaOH electrolyte, carry out water oxygen 1800s under the conditions of 1.23V vs RHE voltages and AM 1.5G simulated solar irradiations after P 2p3/2Energy spectrum signal, Fe2O3/NaNiPO4Electrode electrode surface after 1M NaOH electrolyte reclaimed water aoxidizes a period of time There is no PO4 3-In the presence of.The electrode strong basicity environment ratio under neutral environment it is more unstable, it is unstable under strong basicity environment to be Because OH-With PO4 3-Generation ion exchange, and unstable under neutral environment is because part NaNiPO4Film comes off, therefore Fe2O3/NaNiPO4Contact surface is insecure, and the present embodiment becomes stable after being made using optical electro-chemistry regulation and control.
To Fe2O3/NaNiPO4Electrode photoelectric chemical regulation process current versus time curve (i-t) is divided into three phases, such as schemes Shown in 4：
(1) stage 1 (current density decay)：Fe2O3/NaNiPO4After electrode receives illumination, electron-hole is excited, production Raw higher photoelectric current, but due to surface electronic-hole-recombination, Fe2O3/NaNiPO4The Primary photocurrent density of electrode declines Subtract, this is the universal phenomenon of many semiconductors.Unlike, in structure TiO2Under conditions of nanotube, the densification that is initially formed TiO2Film induced current density decay.
(2) stage 2 (current spike)：Current density sharply increases, and this is different from the behavior that many semiconductors are universal, many Followed by there is stable density of photocurrent what current density decayed in semiconductor.But with building TiO2The I-t curves of nanotube Similar, current spike therein shows TiO2The formation of nanotube and F-Corrosion dissolution under assisting mutually competes.This phenomenon discloses The redeposition of electrode surface new species and NaNiPO4The competition that comes off of thick film.
(3) stage 3 (steady-state current)：Stable water oxygen galvanic current state reaches, this reveals that a new stable species Formed.One stable electric current platform, show that NiPi films stably catalytic water can aoxidize.
Embodiment 2
A kind of Fe2O3The preparation method of/NiPi light anodes is as follows：
(1) 0~5%Ti on FTO:The preparation of FeOOH nano-rod films：It is by formula：0.15M FeCl3:0~1M NaNO3：0~7.5mM Ti solution (such as K2TiF6、TiCl3、TiCl4、TiCN、TiF4Deng) water of (regulation pH be 1.3~2) Thermal response solution is placed in the inner bag equipped with FTO, and inner bag is sealed in autoclave, in 70~110 DEG C of 3~10h of hydro-thermal reaction, Cleaning, dries, and generates one layer of flaxen transparent 0~5%Ti:FeOOH nano-rod films.Increase the hydro-thermal reaction time can obtain To larger sized 0~5%Ti:FeOOH nanometer rods.
(2) 0~5%Ti:Fe2O3The preparation of film：Above-mentioned 0~5%Ti:FeOOH films are placed on tube furnace and are warming up to 500 Calcined 20~120 minutes at~750 DEG C, be cooled to room temperature and take out, obtain 0~5%Ti of crimson color:Fe2O3Electrode, pattern is such as Shown in Figure 1B.As shown in Figure 2 A and 2B, after 0~5%Ti doping, Fe 2p and O 1s peak are shuffled, and show that Ti mixes It is miscellaneous to be diffused into Fe2O3Intracell, Fe sites are instead of, attract Fe and O electron cloud, play a part of electron donor.
(3) 0~5%Ti:Fe2O3/NaNiPO4The preparation of film：In 0.05%Ti:Fe2O3The upper μ L's of drop coating 10~100 0.01~0.1M Ni salt (NiCl2、Ni(OAc)2、Ni(NO3)2、NiSO4Deng), alcohol flushing after 10~60 minutes, dripped after drying 10~100 μ L 0.1~0.2M neutrality phosphate buffer solutions are applied, alcohol flushing after 10~60 minutes, are dried.The technique repeats 2 ~5 times, deposition prepares the NaNiPO of white clear4Film such as Fig. 5 A, C, D, E show 0.05%Ti:Fe2O3/NaNiPO4Film table Bread contains Na+, Ni2+, P5+, O2-, it is designated as NaNiPO4).Due to substantial amounts of NaNiPO4In the presence of, electrode surface cover one layer it is visible Thick film, as shown in Figure 3A.Tested and found by field emission scanning electron microscope (FESEM), NaNiPO4Wrap up 0.05%Ti： Fe2O3 There is the thick film of big sheet in surface after electrode, probably due to the distinctive skeleton structure of nickel phosphate species (Ni-O-P-O-Ni) causes It forms larger and thick film, and zero kinetic energy spectroscopy is displayed without Fe and Ti signal, because XPS detections depth is Within 10nm, so it is more than 10nm without signal instruction thickness.Electrode pattern and 0.05%Ti after optical electro-chemistry regulation and control：Fe2O3Electricity Extremely without parcel NaNiPO4No great changes are compared before film, conjecture NiPi films are very thin.Transmission electron microscope picture shows NiPi only Only 4-6nm, it was demonstrated that form one layer of superfine film after optical electro-chemistry regulation and control.Zero kinetic energy spectroscopy (High resolution XPS spectrum) electrode surface has Fe and Ti signal after display optical electro-chemistry regulation and control, and this also illustrates that film is thinning.
(4) 0~5%Ti:Fe2O3The preparation of/NiPi electrodes：In 0.25~0.5M Na3PO4In solution, 0.05%Ti: Fe2O3/NaNiPO4Membrane electrode is used as to electrode as working electrode, platinum electrode, and Ag/AgCl electrodes are as reference electrode Immerse in the solution, 1-1.3V vs RHE voltages are applied to working electrode, while receive AM 1.5G simulated solar irradiations (100mW/ cm2) 30~60 minutes are radiated to 0.05%Ti:Fe2O3/NaNiPO4Film performs optical electro-chemistry regulation and control and prepares Fe2O3/ NiPi and 0 ~5%Ti:Fe2O3/ NiPi films.The inventive method is simple, has saved energy and time.
It is well known that because electron-hole separation driving force is poor under low potential, the Fe of Ti doping2O3Electrode is in low potential model The density of photocurrent and Fe enclosed2O3Electrode compared to more it is low as shown in Figure 6A.Ti doping improves Fe2O3The electron-hole of electrode Separative efficiency is as shown in Figure 6B.
The Fe of NiPi films parcel as can be seen from Figure 6A2O3And 0.05%Ti:Fe2O3Light of the electrode in low potential scope Current density is improved, density of photocurrent take-off potential (current density 0.02mA/cm2The current potential at place) negative sense migration 200mV.In order to contrast, by using electrodeposition process in 0.05%Ti:Fe2O3Electrode surface wraps up one layer of CoPi film, and CoPi is thin Film integument also improves 0.05%Ti:Fe2O3The density of photocurrent of electrode, but only negative sense moves density of photocurrent take-off potential Move 100mV.
Ti doping as shown in Figure 6 C improves Fe2O3Electrode is in the hole injection efficiency of high potential scope, NiPi films Integument improves Fe2O3Electrode has synergy, CoPi film integuments in the hole injection efficiency of low potential scope Effect does not have NiPi good.
As shown in figures 7 a andb, transient photocurrents test and photoelectric current dynamics simulation show that NiPi films integument improves 0.05%Ti:Fe2O3Electrode shows hole life, and Ti doping and CoPi film integuments reduce hole life.
Mo Te-schottky junction is tested as shown in Figure 8 A, pure Fe2O3The 1/C of sample2Slope after-V curves are first linearly increasing Reduce (in the range of 1.0-1.2V vs RHE).Continue to test 0.05%Ti:Fe2O3, 0.05%Ti:Fe2O3/ NiPi and 0.05%Ti:Fe2O3The 1/C of/CoPi electrodes2- V curves, these curve substantially linears increase, therefore adulterated by 0.05%Ti, NiPi and CoPi films wrap up, Fe2O3The surface state of sample surfaces may be suppressed.
This 4 electrodes of Fig. 8 B follow volt-ampere test to verify that can 0.05%Ti doping, NiPi and CoPi films parcel press down Fe processed2O3Surface state.Pure Fe2O3Electrode has reduction peak at 1.17V vs RHE, is Fe2O3The mark of surface state be present in surface. The Fe of 0.05%Ti doping2O3Electrode forms 0.05% there is also a slightly larger reduction peak (Fig. 8 C), therefore in high-temperature calcination Ti adulterates Fe2O3In electrode process, the increase of electrode surface oxygen defect concentration.The oxygen defect that document report discloses low concentration forms table Face state, the oxygen defect increase carrier concentration of high concentration, improves electric conductivity.It is conductive that the effect of so Ti doping should be attributed to raising Property, it, which eliminates Ti doping, can suppress Fe2O3The conjecture of electrode surface state.0.05%Ti：Fe2O3/ NiPi (Fig. 8 D) and 0.05%Ti： Fe2O3The cyclic voltammetry of/CoPi (Fig. 8 E) electrode shows that the former is in bigger potential range without also Parent peak, and there is reduction peak in the latter, shows that NiPi films integument can suppress Fe2O3Electrode surface state.CoPi films wrap up Layer does not possess this function.
The Fe that embodiment 1 and embodiment 2 respectively obtain2O3/ NiPi and 0~5%Ti:Fe2O3/ NiPi light anodes, including parent Water-based good Fe2O3With 0~5%Ti:Fe2O3Nanometer rods substrate and precursor water solution drop coating deposition-optical electro-chemistry regulation and control The NiPi films of preparation.Fe is wherein obtained by high-temperature calcination2O3With 0~5%Ti:Fe2O3Nanometer stick array, high-temperature calcination carry High Fe2O3With 0~5%Ti:Fe2O3The wellability of nanometer stick array, the Ni salt (NiCl of drop coating2、Ni(OAc)2、Ni(NO3)2、 NiSO4Deng) and neutral phosphate buffer solution come in the uniform drawout of its surface energy, be advantageous to the NaNiPO of depositing homogeneous4Film, And then uniform NiPi films are formed after optical electro-chemistry regulation and control, more comprehensively cover Fe2O3With 0~5%Ti:Fe2O3Nanometer The avtive spot of rod array surface and surface state site.In Fe2O3The Ni (OH) of drop coating-deposition of thick on electrode2Film is in analysis oxygen process The middle Ni for forming more expensive state3+Or Ni4+, cause Ni2+Consumption, so Ni (OH)2The bad stability of catalyst, analysis oxygen move Mechanics is gradually decayed, and thin Ni (OH)2Modified membrane contributes to Ni3+Or Ni4+Rapid oxidation water, is converted into Ni2+, so as to improve The stability of catalyst.As can be seen here, NiPi films relatively thin in the present invention are beneficial to improve oxygen evolution kinetic.On the other hand, electrode The phosphate radical of surface NiPi films is also beneficial to four protons of water oxidizing process and effective transmission of four electronic processes, so this hair The NiPi films of bright exploitation are a kind of efficient water oxidation catalysts.0.05%Ti is further identified in micro ft-ir spectroscopy test： Fe2O3/ NiP and Ni3(PO4)2Two samples are in 806-1297cm-1There is peak at place, belongs to PO4 3-, wherein 0.05%Ti： Fe2O3/ There are fingerprint peakses in NiPi samples, and it is amorphous state to illustrate NiPi.Two samples are in 3400cm-1Also there is peak at place, belongs to OH-, 0.05% Ti：Fe2O3/ NiPi samples spectrogram wideization is relevant with adsorbing a small amount of water.This is consistent with the result of XPS identifications, also illustrate that Phosphate radical be present in NiPi surfaces.
Fe2O3/NaNiPO4With 0~5%Ti：Fe2O3/NaNiPO4As working electrode, Ag/AgCl as reference electrode, Platinum filament as being immersed in electrode, each electrode in 0~1M NaOH, working electrode is applied under 1~1.3V vs RHE voltages, Simulated solar irradiation (the 100mW/cm of AM 1.52) under receive radiation 30~60 minutes, find electrode surface PO is not present4 3-, only have Ni(OH)2In the presence of being unfavorable for Ni (OH)2Steadily in the long term.
Various concentration Ti doping improve Fe to some extent2O3Electrode photoelectric current density, 0.05%Ti doping effect is most It is good.Effect is deteriorated on the contrary for Ti (~5%) doping of high concentration, because an excess amount of Ti doping causes Fe2O3Body phase carrier Compound change is more, and efficient carrier concentration declines.
0.05%Ti after Ti doping：Fe2O3Fe 2p and O 1s the energy spectral peaks of sample shuffle 0.2-0.3eV, illustrate Ti It is doped to Fe2O3Inside, as electron donor, attraction Fe and O electron cloud, so as to improve Fe2O3Electric conductivity.In order to investigate Ti Doping is to Fe2O3The influence of electric conductivity, we are to pure Fe2O3With the Fe of three kinds of concentration Ti doping2O3Electrode Operation impedance-current potential Test.We have found Fe after Ti doping also by the electric conductivity of Mo Te-each electrode of schottky junction formula qualitative assessment2O3Electrode is led Electrically raising to some extent, so as to improve Fe2O3Electrode is in the density of photocurrent of electrode high potential scope, this and document report Road is much like.0.05%Ti doping concentrations are than relatively low therefore no change Fe2O3Crystalline phase, NiPi is unformed state, is not also had There is change Fe2O3Crystalline phase, but equably it is covered in Fe2O3The avtive spot and nonactive site on surface, so as to improve Fe2O3 The density of photocurrent of low potential scope.
According to analyses of Fig. 1-Fig. 8 to principle：
With field emission scanning electron microscope (FESEM) observe undoped with (Figure 1A) and 0.05% concentration Ti doping (Figure 1B) α- Fe2O3Pattern, find 0.05% concentration Ti doping after α-Fe2O3Pattern does not change substantially.In order to analyze Ti doping to α- Fe2O3Fe and O chemical bond influence, to Fe2O3And 0.05%Ti： Fe2O3Electrode test zero kinetic energy spectroscopy (High resolution XPS spectrum) (Fig. 2A, B), find 0.05%Ti：Fe2O3The Ti 2p3/2 and 2p1/ of sample Positioned at 458.2,463.6eV, (place, is Ti respectively at 2 peaks4+Signal.Pure α-Fe2O3The Fe 2p3/2 and 2p1/2 peaks difference of sample Positioned at 710.3,723.7 eV, and 0.05%Ti after Ti doping：Fe2O3The Fe 2p3/2 and 2p1/2 peaks of sample are located at respectively 710.6、 710.9eV.Pure α-Fe2O3The O 1s peaks of sample are located at 530eV, and 0.05%Ti：Fe2O3Sample O 1s peaks are located at Fe 2p and O 1s peak are shuffled after 530.3eV, Ti doping, show that Ti doping is diffused into Fe2O3Intracell, take For Fe sites, attract Fe and O electron cloud, play a part of electron donor.
Each electrode pattern and lattice structure are investigated.Tested and found by field emission scanning electron microscope (FESEM), NaNiPO4 Wrap up 0.05%Ti：Fe2O3There is the thick film (Fig. 3 A) of big sheet in surface after electrode, probably due to the distinctive bone of nickel phosphate species Frame structure (Ni-O-P-O-Ni) causes it to form larger and thick film, zero kinetic energy spectroscopy (High resolution XPS spectrum) Fe and Ti signal are displayed without, because XPS detection depth is within 10nm, so without signal instruction Thickness is more than 10nm.Electrode pattern (Fig. 3 B) and 0.05%Ti after optical electro-chemistry regulation and control：Fe2O3Electrode does not wrap up NaNiPO4Film No great changes are compared before, and conjecture NiPi films are very thin.Transmission electron microscope picture (TEM) shows that NiPi only only has 4-6nm (figures 3D), it was demonstrated that form one layer of superfine film after optical electro-chemistry regulation and control.Zero kinetic energy spectroscopy (High resolution XPS Spectrum) electrode surface has Fe and Ti signal after the regulation and control of display optical electro-chemistry, and this also illustrates that film is thinning.Relatively thin NiPi films Beneficial to raising oxygen evolution kinetic.High-resolution-ration transmission electric-lens (HRTEM) show that inner crystalline core spacing of lattice is d=0.27nm, belong to α-Fe2O3(104) interplanar distance (Fig. 3 E), it was demonstrated that α-Fe2O3Crystalline phase is present, and outside NiPi integuments do not have lattice to deposit In signal, it was demonstrated that NiPi films are amorphous states.Distribution diagram of element (EDS element Mapping) Fig. 3 C and 3F (including Fe, O, Ti, Ni, P scheme) display 0.05%Ti：Fe2O3/ NiPi nanostructured surfaces form NiPi films.
The formation of NiPi films is new species redeposition and NaNiPO4The result of the competition that comes off of thick film, in order to analyze The microcosmic formation of NiPi films, compound state, we are to 0.05%Ti：Fe2O3/NaNiPO4With 0.05% Ti：Fe2O3/ NiPi electricity It is as shown in Figure 5 that pole performs zero kinetic energy spectroscopy (High resolution XPS spectrum) test：0.05%Ti： Fe2O3/NaNiPO4O 1s power spectrums be fitted to three peaks, first fitting peak be located at 536.2eV at, is the transmitting of Na KLL Augers Peak (Na KLL Auger emission), second fitting peak, which is located at 531.1eV, is mainly classified as PO4 3-.3rd fitting peak Organic species are belonged at 532.6eV, such as C-O and O=C-O.0.05%Ti：Fe2O3/ NiPi O1s spectrums are also fitted to three Fig. 5 B are shown at individual peak, and first fitting peak is located at 529.6eV, meets metal-oxygen key (Fe/Ni-O) feature.Second fitting peak At 531eV, represent to there may be OH in NiPi films-And PO4 3-.3rd fitting peak is located at 532.5eV, is absorption The feature of water.
0.05%Ti：Fe2O3/NaNiPO4See Fig. 5 C and 0.05%Ti：Fe2O3/ NiPi see Fig. 5 C electrodes in 133.5eV and Peak at 133eV belongs to P 2p3/2 signals, it was demonstrated that 0.05%Ti：Fe2O3/NaNiPO4Electrode photoelectric chemistry (PEC) regulation and control produce Cell membrane in still have PO4 3-.In pure alkaline electrolyte (1M NaOH) after optical electro-chemistry (PEC) regulation and control, electrode surface does not have There is PO4 3-, it was demonstrated that 0.05%Ti： Fe2O3/NaNiPO4OH only occurs for surface-And PO4 3-Exchange, only PO4 3-Abjection, no PO4 3- Insertion occurs.And in rich PO4 3-Alkaline electrolyte (0.25M Na3PO4) in optical electro-chemistry (PEC) regulation and control after electrode surface have PO4 3-, it was demonstrated that 0.05%Ti：Fe2O3/NaNiPO4OH is occurring for surface-And PO4 3-During exchange, it is allowed to the PO of part4 3-Retain, produce Nickel-hydroxy-phosphate species (NiPi).0.05%Ti：Fe2O3/NaNiPO4Ni 2p3/2 and Ni 2p1/2 the fittings peak of electrode Positioned in 856.4eV and 874.3eV, belong to Ni2+Compound range.0.05%Ti：Fe2O3/NaNiPO4The Ni 2p's of electrode defends (satellite peaks) is very sharp at star peak, represents NaNiPO4The most nickel of film belongs to Ni2+, in addition, 0.05%Ti：Fe2O3/ NaNiPO4The Ni 2p3/2 peaks of electrode, which are located at high combination, to be located, and show that no nickel metal and its oxide are present, disclose the change Compound is subordinate to Ni-O-P series.0.05%Ti：Fe2O3Ni 2p3/2 and Ni 2p1/2 the fittings peak of/NiPi electrodes are located at 856.1eV and 873.0eV (Fig. 5 D), with 0.05%Ti：Fe2O3/NaNiPO4Ni 2p3/2 and Ni 2p1/2 the fittings peak of electrode (Fig. 5 D) is compared, and is moved with reference to that can occur to bear.For surface modification FeOOH NiPi, Ni 2p3/2 and Ni 2p3/2 peaks are tied to height Conjunction can locate migration, be due to the result that electronics shifts between FeOOH and NiPi.Ni 2p3/2 and the Ni 2p1/2 of nickel based compound Bear shifting and have proven to be Ni in peak3+Formation.
In fact, the Ni 2p signals of the NiPi species after optical electro-chemistry (PEC) regulation and control are stable, in X radiation exposures Under there is no Ni reduction and oxidation, the Ni 2p3/2 and Ni 2p1/2 peaks of the species, which move to relatively low combination, can locate (to bear Move), show a small amount of Ni3+Accumulation.In general, the Ni on nickel-base catalyst surface3+The more expression catalyst of accumulation are used for oxygen It is fewer to change the effective charge of water, causes transient photocurrents drastically to decline.In contrast, Fe2O3/NaNiPO4Electrode photoelectric chemistry (PEC) in regulation process, the current density in stage 3 not decay pattern, it should have benefited from PO4 3-Embedded or modification is in Fe2O3/NiPi Surface, it promotes Fe2O3Proton transfer between/NiPi surfaces and electrolyte, therefore Fe2O3/ NiPi electrode catalyst water oxygens Four protons and four electronic processes effectively carried out.
Ti doping is investigated to Fe2O3The influence of electric conductivity, pure Fe is marked and drawed2O3And 0.05%Ti:Fe2O3Electrode body phase charge Separative efficiency ηsepSee Fig. 6 B.It was found that 0.05%Ti under low pressure:Fe2O3Body phase separation of charge efficiency is worse, represents more under low pressure Carrier recombination.And high hold-down weight phase charge separative efficiency uprises, this shows Ti doped with point beneficial to body phase carrier From improving carrier concentration.
With pure Fe2O3Electrode Fig. 6 A are compared, 0.05%Ti:Fe2O3Hole injection efficiency (Fig. 6 A) is worse under electrode low pressure, Hole injection efficiency increases under high pressure, and the trend of this and body phase separation of charge efficiency is consistent.
In order to improve 0.05%Ti:Fe2O3Electrode surface voids injection efficiency under low pressure, in 0.05%Ti:Fe2O3With Fe2O3Electrode surface deposited by drop coating-and the method that regulates and controls of optical electro-chemistry (DPEC) wraps up one layer of layer of Ni Pi and electro-deposition CoPi films.
In order to the pure Fe before parcel2O3(Fig. 6 C) and 0.05%Ti:Fe2O3(Fig. 6 C) electrode compares, and we are to Fe2O3/ NiPi (Fig. 6 C), 0.05%Ti:Fe2O3/ NiPi (Fig. 6 C), 0.05%Ti:Fe2O3/ CoPi (Fig. 6 C) sample has been carried out linearly Voltammetric scan is tested, the influence after investigation parcel NiPi and CoPi to density of photocurrent.It was found that Fe2O3Electrode is after NiPi parcels (E under low-voltage<0.9V vs RHE) density of photocurrent be improved (Fig. 6 C), and with pure Fe2O3Electrode is compared to starting electricity Position (0.02mA/cm2The current potential at place) bear and move 200mV, 0.05%Ti:Fe2O3(Fig. 6 C) take-off potential is negative after sample NiPi parcels moves 200 mV, represent that NiPi parcels improve the photolytic activity at low potential, 0.05%Ti:Fe2O3Sample is after CoPi parcels (Fig. 6 C) Take-off potential is only born and moves 100mV, and this shows that NiPi parcels can more improve 0.05%Ti than CoPi parcels:Fe2O3Electrode light is lived Property.
With pure Fe2O3Electrode is compared, and NiPi integuments only improve only Fe2O3The hole injection effect of electrode low potential scope Rate.With 0.05%Ti:Fe2O3Electrode is compared, and is also enhanced in low voltage range hole injection efficiency after NiPi parcels, in high electricity Hole injection efficiency is deteriorated at pressure, but still than pure Fe2O3Electrode is good.CoPi is wrapped up to 0.05%Ti:Fe2O3Note in electrode hole The no NiPi parcels effect of raising for entering efficiency is good.This explanation is for Fe2O3For semiconductor, NiPi films are in low potential scope It is a good hole extract layer, therefore Ti doping and NiPi parcels have synergy, improve pure Fe jointly2O3Electrode Hole injection efficiency in whole potential range.
Transient photocurrents (transient photocurrent) analysis is a kind of assessment electrode surface carrier lifetime Effective method.Such as Fig. 7 A, a relatively low voltage 0.9V vs RHE is selected to perform Fe2O3, 0.05% Ti:Fe2O3、 0.05%Ti:Fe2O3/ NiPi, 0.05%Ti:Fe2O3/ CoPi electrode transient photocurrents density measurements.With the J-V of each electrode The trend that curve is presented is the same, the 0.05%Ti under low potential:Fe2O3Sample current density minimum (Fig. 7 A), 0.05%Ti: Fe2O3/ NiPi (7A) electrode current density is more than 0.05%Ti:Fe2O3/ CoPi (7A) electrode.
Wherein, Ii、IfPhotoelectric current when representative simulation sunshine light just opens and closes respectively, I are transient photocurrents, and τ is The time value during time, numerically equal to lnD=-1 that electrode surface Carrier recombination needs.
The time τ (Fig. 7 B) that each electrode surface Carrier recombination needs according to formula analysis, it was confirmed that electronics-hole In pure Fe2O3Surface recombination needs 0.18s (Fig. 7 B).And with pure Fe2O3Compare, in 0.05%Ti:Fe2O3Surface is easier multiple Close, it is necessary to 0.15s (Fig. 7 B).Electron-hole is in 0.05%Ti:Fe2O3/ NiPi surface recombinations need the time most long, are 1.1s (Fig. 7 B).Electron-hole is in 0.05%Ti:Fe2O3The time that/CoPi surface recombinations need is most short, is 0.1s (Fig. 7 B), so The effect of NiPi integuments is to improve the surface voids life-span, and CoPi integuments do not possess this effect.
Ti is adulterated and NiPi parcel collaborations improve Fe2O3Hole injection efficiency of the electrode in whole test scope. Fe2O3With Fe2O3/ NiPi or 0.05%Ti：Fe2O3And 0.05%Ti：Fe2O3/ NiPi electrodes high potential scope density of photocurrent with it is low Potential range is compared, and difference is smaller, therefore we guess that NiPi integuments may suppress Fe2O3Surface state.In order to verify, carry out A series of electro-chemical test.First, Mo Te-schottky junction test (Fig. 8 A) is operated, finds pure Fe2O3The 1/C of sample2-V Curve is first linearly increasing and speedup slows down (in the range of 1.0-1.2V vs RHE) (Fig. 8 A).Document report is disclosed in surface state Area space electric capacity does not change substantially, and conjecture Fig. 8 A situation may be relevant with surface state.Continue to test 0.05%Ti：Fe2O3(figure 8A), 0.05%Ti：Fe2O3/ NiPi (Fig. 8 A) and 0.05%Ti：Fe2O3The 1/C of/CoPi (Fig. 8 A) electrode2- V curves, find The increase of these curve substantially linears, therefore guess and wrapped up by 0.05%Ti doping, NiPi and CoPi films, Fe2O3Sample table The surface state in face is suppressed.Then, operate this 4 electrodes follow volt-ampere test come verify 0.05%Ti doping, NiPi and Can CoPi films parcel suppress Fe2O3Surface state (Fig. 8 B, C, D, E).We have found that pure Fe2O3Electrode is in 1.17V vs There is reduction peak (Fig. 8 B) at RHE, be Fe2O3The mark of surface state be present in surface.The Fe of 0.05%Ti doping2O3Electrode there is also One slightly larger reduction peak (Fig. 8 C), it is believed that form 0.05%Ti doping Fe in high-temperature calcination2O3In electrode process, electrode The increase of Surface Oxygen defect density.The oxygen defect that past report discloses low concentration forms surface state, the oxygen defect increase of high concentration Carrier concentration, improve electric conductivity.The effect of so Ti doping should be attributed to raising electric conductivity, and it at least eliminates Ti doping energy Enough suppress Fe2O3The conjecture of electrode surface state.We operate 0.05%Ti：Fe2O3/ NiPi (Fig. 8 D) and 0.05%Ti： Fe2O3The cyclic voltammetry of/CoPi (Fig. 8 E) electrode, it is found that the former does not have a reduction peak in bigger potential range, and the latter There is reduction peak, show that NiPi films integument can suppress Fe2O3Electrode surface state.CoPi film integuments do not possess this Function.
Explained above is only present pre-ferred embodiments, it is impossible to the interest field of the present invention is limited with this.Therefore The equivalent variations made according to the claims in the present invention, still belong to the scope that the present invention is covered.

Claims (10)

1. a kind of metal oxide/NiPi light anode materials, it is characterised in that including metal oxide light anode and NiPi films Passivation layer；The NiPi films are wrapped on the outside of the metal oxide light anode.
2. metal oxide/NiPi light anode materials according to claim 1, it is characterised in that the metal oxide light Anode is Fe2O3, 0~5%Ti:Fe2O3Nanometer stick array, TiO2, ZnO or BiVO4In one kind.
3. metal oxide/NiPi light anode materials according to claim 2, it is characterised in that the metal oxide light Anode is 0.05%Ti:Fe2O3Nanometer stick array.
4. metal oxide/NiPi light anode materials according to claim 1, it is characterised in that the metal oxide light The pattern of anode is in nano-porous film, nanometer flower pattern film, nanometer dendron shape, nanometer coral polyp shape or nanometer sea urchin shape One kind.
5. metal oxide/NiPi light anode materials according to claim 1, it is characterised in that the NiPi film thicknesses For 2~10nm, integument macroscopic view load capacity is 8~12 μ g/cm2。
6. metal oxide/NiPi light anode materials according to claim 2, it is characterised in that the Fe2O3With 0~5% Ti:Fe2O3Nanometer stick array load capacity is 0.8~1mg/cm2, nanorod diameter is 40~100nm.
7. according to the preparation method of any one of the claim 1-6 metal oxides/NiPi light anode materials, its feature exists In mainly including the following steps that：
(1) preparation of metal oxide photo-anode film；
(2) drop coating Ni salt and neutral phosphate buffer solution on metal oxide photo-anode film, deposition prepare NaNiPO4Film；
(3) to metal oxide light anode/NaNiPO4Film performs optical electro-chemistry regulation and control.
8. preparation method according to claim 7, it is characterised in that step (3) optical electro-chemistry is regulated in 0.25~0.5M Na3PO4In solution, metal oxide photo-anode film/NaNiPO4Membrane electrode is used as to electricity as working electrode, platinum electrode Pole, Ag/AgCl electrodes receive AM 1.5G simulated solars light radiation 30 as reference electrode under 1~1.3V vs RHE voltages ~60 minutes, rinse.
9. preparation method according to claim 8, it is characterised in that the metal oxide light anode is Fe2O3Or 0~ 5%Ti:Fe2O3Nanometer stick array, preparation mainly include the following steps that：
(a) FeOOH or 0~5%Ti on FTO:The preparation of FeOOH nano-rod films：It is by formula：0.15M FeCl3:0~ 1M NaNO3, hydro-thermal reaction solution or formula that pH is 1.3~2 are 0.15M FeCl3:0~1M NaNO3：0~7.5mM The hydro-thermal reaction solution that Ti, pH are 1.3~2 is placed in the inner bag equipped with FTO, inner bag is sealed in autoclave, 70~110 DEG C 3~10h of hydro-thermal reaction, cleaning, dries；
(b)Fe2O3Or 0~5%Ti:Fe2O3The preparation of film：(a) obtained film is placed on tube furnace and is warming up to 500~750 DEG C when calcine 20~120 minutes, be cooled to room temperature.
10. preparation method according to claim 8, it is characterised in that step (2) described NaNiPO4The preparation of film is mainly wrapped Include：The μ L of drop coating 10~100 0.01~0.1M Ni salt on metal oxide photo-anode film, alcohol flushing after 10~60 minutes, The rear μ L of drop coating 10~100 0.1~0.2M neutrality phosphate buffer solutions are dried, alcohol flushing after 10~60 minutes, are dried, are repeated Repeatedly.
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