CN107641817B - A kind of light anode preparation method and gained light anode structure improving photocatalytic water performance - Google Patents
A kind of light anode preparation method and gained light anode structure improving photocatalytic water performance Download PDFInfo
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- CN107641817B CN107641817B CN201710818779.1A CN201710818779A CN107641817B CN 107641817 B CN107641817 B CN 107641817B CN 201710818779 A CN201710818779 A CN 201710818779A CN 107641817 B CN107641817 B CN 107641817B
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Abstract
The invention discloses a kind of light anode preparation methods and gained light anode structure for improving photocatalytic water performance.Light anode preparation method is the following steps are included: a. uses resistivity for the n-type silicon chip of 0.01~0.05 Ω cm；B. to preparing silicon micron linear array after Wafer Cleaning；C. using silicon micron linear array as substrate, using containing Fe3+Solution, and be mixed into doped source solion wherein, as the precursor liquid of growth iron oxide layer, annealing early period carried out to the silicon micro wire array substrate of precursor liquid absorption in air, obtains silicon/iron oxide micron linear array；D. post annealed processing is carried out in nitrogen or argon atmosphere to silicon/iron oxide micro wire array substrate；E. resulting silicon/iron oxide micro wire array substrate backside deposition conductive layer after post annealed, and draw external conducting wire；F. insulating layer of turning one's coat is coated on the electrically conductive.
Description
Technical field
The present invention relates to a kind of light anode preparation methods and obtained light anode structure for improving photocatalytic water performance, belong to
Photoelectric conversion and energy field.
Background technique
In recent years, the research of sun optical drive water decomposition is received more and more attention, photocatalytic water technology is possible into
The effective way of the problems such as to solve energy crisis and fuel contamination.Currently, photoelectrochemical cell is the one kind for realizing photocatalytic water
Main collocation form, it absorbs sunlight by semiconductor photoelectrode and promotes water that oxidation and reduction reaction occurs, that is, completes to catch
It obtains solar energy and switchs to green fuel (the i.e. H of high-energy2).However, the application of solar hydrogen making but receives many skills
Art is difficult.Wherein, critical issue be solar energy be converted into hydrogen (STH) efficiency it is too low and cost is too high.From technology and economy
Property angle estimator show that make it have competitiveness with fossil energy, the technical bottleneck for needing to solve has: realizing scale
(non-small area, small-scale) reaches 10% with STH efficiency.STH efficiency is limited by many processes, is specifically included: efficiency of light absorption,
Carrier Injection Efficiency, electrode surface carrier transformation efficiency (participate in chemical reaction at carrier separation efficiency, solid-liquid interface
Efficiency) and produced H2From the desorption efficiency of electrode surface.Therefore, to obtain the system of high STH efficiency, need to meet with
Lower key condition: the 1) solar absorption of wide spectrum；2) carrier can effectively extract inside optoelectronic pole to solid-liquid interface；3)
The chemical reaction of photoelectricity pole surface can quickly carry out and overpotential is small；4) optoelectronic pole has excellent stability in aqueous solution.
In addition, the conduction band and valence band location of semiconductor material need to be simultaneously across liberations of hydrogen and analysis oxygen voltage in order to realize complete photocatalytic water.When
It is preceding only to find a few broad stopband (> 3eV) semiconductor material (such as KTaO3And GaN) reach level of energy requirement, but these materials
The constructed all universal deviation of optoelectronic pole stability of material, more undesirable place is that STH efficiency extreme value is only 2%.Therefore, it constructs
More absorbed layer photoelectrochemical cells, so that the oxidation reaction of water and the reduction reaction reality by the photoresponse of different semiconductors respectively
It is existing, to obtain the higher complete photodissociation aqueous systems of performance.
Iron oxide (α-Fe2O3) since (1.9-2.3eV, theoretically STH is imitated for its excellent stability, suitable forbidden bandwidth
Rate is 12.9-16.8%), good environment compatibility and the features such as the earth is rich in mineral resources and be considered as photooxidation water reason
Think anode material.Silicon materials are since its conduction band potential is higher than water reduction potential, and it is with good electric property and excellent
Optical absorption characteristics are widely used as the light absorbing layer of photodissociation aqueous systems.Iron oxide and silicon are stacked up, double absorption layer light is formed
Electrode has following advantage: 1) (iron oxide is absorbed compared with short-wave band, and is inhaled compared with long-wave band by silicon for the subrane absorption of realization incident light
It receives)；2) hole needed for water oxidation reaction comes from iron oxide, and electronics needed for reduction reaction comes from silicon；3) iron oxide and silicon are formed
Hetero-junctions can produce photovoltage, thus the chemical reaction overpotential for promoting the separation of electrode interior carrier, reducing electrode surface.
Van de Krol and Liang grow nothing using spray pyrolysis technologies on N-shaped planar silicon (10-20 Ω cm) and mix
Miscellaneous sull, it was demonstrated that silicon/iron oxide hetero-junctions can produce the photovoltage of 0.3V, and this configuration is thermodynamically
It can be achieved on photocatalytic water (R.van de Krol, and Y.Liang, the An n-Si/n- of no-bias
Fe2O3Heterojunction Tandem Photoanode for Solar Water Splitting,Chimia,2013,
67:168–171).Sull is grown on n-type silicon nano-wire array (5-15 using technique for atomic layer deposition by Wang etc.
Ω cm), the double absorption layer light anode of core-shell structure is made, observes that the unlatching potential of photoelectric current is only 0.6V vs.RHE,
Current density is 0.85mA/cm under 1.23V vs.RHE, a standard solar irradiation2, and sull is grown directly upon
Corresponding current density is only~0.3mA/cm when in bright conductive substrates2(M.T.Mayer,C.Du,and D.Wang,
Hematite/Si Nanowire Dual-Absorber System for Photoelectrochemical Water
Splitting at Low Applied Potentials,J.Am.Chem.Soc.,2012,134:12406–12409).These
Research, which demonstrates silicon/iron oxide double absorption layer structure, may be implemented the photocatalytic water of no-bias auxiliary, and heterojunction structure is relative to list
Absorbed layer system has more preferably performance.However, there are still problems or can improvements for the double absorption layer system: 1) silicon/
Iron oxide Interface composites are serious；2) iron oxide surface is compound more serious；3) silicon/iron oxide double absorption layer internal resistance is excessive；4)
Silicon/iron oxide double absorption layer electrode preparation cost is higher.
In order to realize photolysis water hydrogen technological industrialization application, the STH efficiency for effectively improving photocatalytic water device is developed
With critical performance parameters [such as: cut-in voltage, density of photocurrent (@1.23V vs.RHE)], reduces the scheme of cost or realize skill
Art is crucial and difficult point.
Summary of the invention
It is an object of the invention to propose a kind of light anode preparation method and gained light anode knot for improving photocatalytic water performance
Structure.
In order to achieve the above object, the present invention provides a kind of technical solutions: a kind of light anode improving photocatalytic water performance
Preparation method, it the following steps are included:
A. use resistivity for the n-type silicon chip of 0.01~0.05 Ω cm；
B. silicon is corroded to the laggard row metal assistant chemical of Wafer Cleaning, and prepares silicon micron linear array, silicon micron linear array
Specific preparation process can refer to the patent of invention application No. is 201610183558.7；
C1. using silicon micron linear array as substrate, using containing Fe3+Solution, and be mixed into doped source solion wherein,
As the precursor liquid of growth iron oxide layer, it is adsorbed in precursor liquid in silicon micro wire array substrate by infusion process or spray-on process,
Obtain the silicon micro wire array substrate of precursor liquid absorption；
C2. the silicon micro wire array substrate by precursor liquid absorption carries out annealing early period；
D. post annealed processing is carried out to silicon/iron oxide micro wire array substrate after annealing early period；
E. resulting silicon/iron oxide micro wire array substrate backside deposition conductive layer after post annealed, and draw outer
Set conducting wire；
F. waterproof insulating layer is coated on the electrically conductive.
Further, in step b, silicon micro wire spacing is 1~10 μm, 1~10 μm of diameter, length are 5~100 μm.
Further, in step c1, doped source solion is SnCl4、TiCl4、MnCl4、SiCl4、GeCl4、ZrCl4、
NbCl4The combination of one or more of solution.
Further, in step d, the condition of post annealed processing are as follows: quick anneal oven is used, at 300~600 DEG C
Reason 3~10 minutes, atmosphere are nitrogen or argon gas.
Further, in step c1, Fe3+Solution be Fe (NO3)3Or FeCl3Ethyl alcohol or aqueous solution.
Further, in step c1, precursor liquid is made to be adsorbed in silicon micron linear array by spray-on process method particularly includes: will
Precursor liquid ultrasonic atomizatio, and be pyrolyzed in the silicon micro wire array substrate for being heated to 100~200 DEG C.
Further, in step c1, precursor liquid is made to be adsorbed in silicon micron linear array by infusion process method particularly includes: will
Silicon micro wire array substrate is impregnated in precursor liquid 10~60 minutes.
Further, circulating repetition carries out step c1 and step c2, and circulating repetition number is 1~20 time, works as precursor liquid
Middle Fe3+Concentration is bigger, then circulating repetition number is smaller.
Further, in step c2, early period annealing condition are as follows: in tubular annealing furnace, at 400~600 DEG C
Processing 2~5 hours, atmosphere is air.
Further, in step f, waterproof insulating layer is epoxy resin or 704 silica gel.
Further, in step e, conductive layer is In-Ga or Al layers.
Further, in step b, cleaning uses standard RCA clean technique.
The present invention also provides another technical solutions: a kind of light anode using a kind of above-mentioned raising photocatalytic water performance
The resulting light anode structure of preparation method.
By using above-mentioned technical proposal, a kind of light anode preparation method and gained light for improving photocatalytic water performance of the present invention
Compared with the prior art anode construction has the advantage that
(1) it is base that the prior art, which is all made of resistivity (medium doped) as the silicon nanowires or planar silicon of 1~20 Ω cm,
Bottom, and (heavily doped) the silicon micron linear array for 0.01~0.05 Ω cm of resistivity of the present invention, corresponding electricity
Pole internal resistance (devices in series resistance) is small, the more conducively output of the transmission of carrier and photovoltage；Silicon micron linear array is relative to silicon
Nano-wire array, specific surface area is smaller, the surface defect density of states is much smaller, significantly improves present in silicon/iron oxide interface
The serious problem of Interface composites；And relative to planar silicon, although silicon micron linear array interface defect density is slightly larger, subtract with light
Minus effect, the iron oxide supported are being not planar structures, have electromagnetic wave coupling effect.
(2) doped chemical is introduced during the growth process in iron oxide, so that the electric property of the iron oxide grown is more preferably
(more sons are easier to transport, and minority carrier life time is elongated, increase the conductivity of silicon and iron oxide, reduce silicon/iron oxide double absorption layer light
The internal resistance of electrode improves the collection efficiency of carrier).
(3) after completing iron oxide growth course, Post isothermal treatment technique is carried out under nitrogen or argon atmosphere, so that institute
The Lacking oxygen density of the iron oxide of growth increases, the collection and injection of more conducively few son.
(4) relative atom layer deposition techniques, equipment cost involved in the present invention is low and the iron oxide speed of growth is fast；And it is right
In iron oxide growth technique of the present invention, silicon micro wire/iron oxide heterojunction structure proposed by the invention is relative to silicon
Nano wire/iron oxide (or planar silicon/iron oxide) heterojunction structure has more perfect interface property.The present invention is guaranteeing low cost
Under the premise of, realize iron oxide uniform, conformal, quick, high quality growth in silicon micro wire substrate.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Attached drawing 1 is silicon wafer schematic diagram in a kind of step a for the light anode preparation method for improving photocatalytic water performance of the present invention；
Attached drawing 2 is that obtained product shows in a kind of step b for the light anode preparation method for improving photocatalytic water performance of the present invention
It is intended to；
Attached drawing 3 is that obtained product shows in a kind of step c1 for the light anode preparation method for improving photocatalytic water performance of the present invention
It is intended to；
Attached drawing 4 is that obtained product shows in a kind of step d for the light anode preparation method for improving photocatalytic water performance of the present invention
It is intended to；
Attached drawing 5 is that obtained product shows in a kind of step e for the light anode preparation method for improving photocatalytic water performance of the present invention
It is intended to；
Attached drawing 6 is that obtained product shows in a kind of step f for the light anode preparation method for improving photocatalytic water performance of the present invention
It is intended to；
Attached drawing 7 is a kind of resulting light anode structure of light anode preparation method and its light for improving photocatalytic water performance of the present invention
Hydrolyze schematic diagram.
Attached drawing 8 is silicon/iron oxide hetero-junctions light anode electricity that several different disposal processes obtain in performance test experiment
Stream-potential energy diagram.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
Embodiment one
One of the present embodiment improve photocatalytic water performance light anode preparation method, it the following steps are included:
A. use resistivity for the n-type silicon chip of 0.01~0.05 Ω cm, referring to attached drawing 1.
B1. standard RCA clean technique is carried out to silicon wafer, spin coating photoresist carries out uv-exposure, then develops, obtain light
Photoresist micron column array (diameter is 4 μm, the square arrangement that the period is 8 μm) pattern；
B2. titanium and golden film are deposited using electron beam evaporation plating respectively, thickness is respectively 3nm and 40nm；
B3. corrode 20 in hydrofluoric acid and the mixed aqueous solution of hydrogen peroxide (concentration is respectively 8mol/L and 0.4mol/L)
Hour, corrosion temperature is 5 DEG C, and obtaining silicon micron linear array, (length is 30 μm, and diameter is 4 μm, the square row that the period is 8 μm
Cloth), referring to attached drawing 2.
C1. configuration concentration is the FeCl of 0.05mol/L3Ethanol solution, and be mixed into doped source solion wherein, make
For the precursor liquid for growing iron oxide layer, silicon micro wire array substrate is immersed in precursor liquid, 10~take out after sixty minutes, before obtaining
The silicon micro wire array substrate for driving liquid absorption, referring to attached drawing 3.The above-mentioned immersion time is preferably 30 minutes；Above-mentioned doped source
Solion is preferably SnCl4、TiCl4、MnCl4、SiCl4、GeCl4、ZrCl4、NbCl4One or more of combination, this
The SnCl of 0.005mol/L is used in embodiment4Solution；
C2. silicon/micro wire array substrate that precursor liquid adsorbs is subjected to annealing early period: time in tubular annealing furnace
It is 2~5 hours, preferably 3 hours, temperature is 400~600 DEG C, and preferably 500 DEG C, atmosphere is air.
D. circulating repetition carries out step c1 and step c2, can recycle 1~20 time, Fe in number and precursor liquid3+Concentration phase
It closes, concentration is bigger, and preferably number is smaller, and preferred number is 3 times in the present embodiment.D. the progress later period moves back in quick anneal oven
Fire processing: the time be 3~10 minutes, preferably 5 minutes, temperature be 300~600 DEG C, preferably 400 DEG C, atmosphere N2；
Referring to attached drawing 4.
E. resulting silicon/iron oxide micro wire array substrate backside coating conductive layer after post annealed, and draw outer
Conducting wire is set, referring to attached drawing 5.Conductive layer uses In-Ga or Al conductive layer in the present embodiment.
F. waterproof insulating layer is coated on the electrically conductive, covers back conductive layer completely, obtains light anode, referring to attached drawing 6.Waterproof
Insulating layer is preferably epoxy resin or 704 silica gel.
G. the light anode prepared is immersed in the NaOH aqueous solution of 1mol/L, is to electrode, Ag/AgCl with gauze platinum electrode
Electrode is to connect this three electrode to electrode using electrochemical workstation, be built into three electrode test systems.
The present embodiment additionally provides another technical solution: a kind of light sun using a kind of above-mentioned raising photocatalytic water performance
The resulting light anode structure of pole preparation method.
Embodiment two
One of the present embodiment improve photocatalytic water performance light anode preparation method, it the following steps are included:
A. use resistivity for the n-type silicon chip of 0.01~0.05 Ω cm, referring to attached drawing 1.
B1. standard RCA clean technique is carried out to silicon wafer, spin coating photoresist carries out uv-exposure, then develops, obtain light
Photoresist micron column array (diameter is 3 μm, the square arrangement that the period is 6 μm) pattern；
B2. titanium and golden film are deposited using electron beam evaporation plating respectively, thickness is respectively 3nm and 40nm；
B3. corrode 20 in hydrofluoric acid and the mixed aqueous solution of hydrogen peroxide (concentration is respectively 8mol/L and 0.4mol/L)
Hour, corrosion temperature is 5 DEG C, and obtaining silicon micron linear array, (length is 30 μm, and diameter is 3 μm, the square row that the period is 6 μm
Cloth), referring to attached drawing 2；
B4. using ex vivo treatments silicon micron linear arrays such as oxygen, power 400W, the time is 20 minutes.
C1. Fe (the NO of 0.05mol/L is configured3)3Ethanol solution, and be mixed into doped source solion, aoxidized as growth
Precursor liquid is stored in syringe pump, is sprayed in silicon micro wire array substrate using ultrasonic spray pyrolysis equipment by the precursor liquid of iron layer
Precursor liquid is applied, the silicon micro wire array substrate of precursor liquid absorption is obtained, referring to attached drawing 3.The charge velocity of precursor liquid is 0.1mL/
Min, substrate temperature are 200 DEG C；Above-mentioned doped source solion is preferably SnCl4、TiCl4、MnCl4、SiCl4、GeCl4、
ZrCl4、NbCl4One or more of combination, the SnCl of 0.005mol/L is used in the present embodiment4Solution；
C2. the silicon micro wire array substrate that presoma adsorbs is subjected to annealing early period: time in tubular annealing furnace
It is 2~5 hours, preferably 3 hours, temperature is 400~600 DEG C, and preferably 500 DEG C, atmosphere is air.
D. post annealed processing is carried out in quick anneal oven: the time is 3~10 minutes, and preferably 5 minutes, temperature was
300~600 DEG C, preferably 400 DEG C, atmosphere N2；Referring to attached drawing 4.
E. resulting silicon/iron oxide micro wire array substrate backside coating conductive layer after post annealed, and draw outer
Conducting wire is set, referring to attached drawing 5.Conductive layer uses In-Ga conductive layer in the present embodiment.
F. waterproof insulating layer is coated on the electrically conductive, covers back conductive layer completely, obtains light anode, referring to attached drawing 6.Waterproof
Insulating layer is preferably epoxy resin or 704 silica gel.
G. the light anode prepared is immersed in the NaOH aqueous solution of 1mol/L, is to electrode, Ag/AgCl with gauze platinum electrode
Electrode is to connect this three electrode to electrode using electrochemical workstation, be built into three electrode test systems.
The present embodiment additionally provides another technical solution: a kind of light sun using a kind of above-mentioned raising photocatalytic water performance
The resulting light anode structure of pole preparation method.
Working principle:
Referring to attached drawing 7, under solar irradiation, light anode 1 and cathode 2 are in electrolyte, silicon/iron oxide light anode 1
Incident light is absorbed, electron-hole pair is generated, hole participates in the oxidation reaction of water and give birth to toward light anode/electrolyte interface migration
At oxygen；The back of electronics toward light anode 1 transports and reaches to electrode (i.e. cathode 2), in the reduction for participating in water to electrode surface
It reacts and generates hydrogen.
Performance test:
Linear voltage sweep test is carried out under no light and a standard sunlight intense irradiation respectively.Test result is as schemed
8, in which: 31 be to introduce Sn doping and carried out N2Atmosphere short annealing processing, while giving a standard sunlight irradiation；
32 be to introduce Sn doping and carried out N2Atmosphere short annealing processing, does not give illumination；33 have carried out N to be not introduced into doping2Atmosphere
Short annealing processing is enclosed, while giving a standard sunlight irradiation；34 do not carry out N to introduce Sn doping2Atmosphere is quick
Annealing, while giving a standard sunlight irradiation；35 be to be not introduced into doping and do not carry out N2Atmosphere short annealing processing,
A standard sunlight irradiation is given simultaneously.
As can be seen that of the invention introduces Sn doping and has carried out N2The silicon micron linear array of atmosphere short annealing processing
Column/sull light anode, relative to no introducing adulterate or without short annealing processing or both all no light anode,
Under same potential, corresponding density of photocurrent is above other contrast samples.
A kind of this light anode preparation method and gained light anode structure for improving photocatalytic water performance, silicon/iron oxide biabsorption
The internal resistance very little of layer light anode；Iron oxide has preferable absorbing properties；Silicon/iron oxide boundary defect density of states is small, current-carrying
Sub-interface is compound small；Sull oxygen vacancies density with higher, carrier injection at iron oxide/solution interface and turns
It changes high-efficient；Optical electro-chemistry test result embodies are as follows: photoelectric current cut-in voltage is lower, relative to H2O/O2The short circuit current of potential
Density is larger.
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. it is a kind of improve photocatalytic water performance light anode preparation method, it the following steps are included:
A. use resistivity for the n-type silicon chip of 0.01~0.05 Ω cm；
B. silicon is corroded to the laggard row metal assistant chemical of Wafer Cleaning, and prepares silicon micron linear array；
C1. using silicon micron linear array as substrate, using containing Fe3+Solution, and be mixed into doped source solion wherein, as
The precursor liquid for growing iron oxide layer, makes precursor liquid be adsorbed in silicon micro wire array substrate by spray-on process；
C2. annealing early period is carried out to the silicon micro wire array substrate for having precursor liquid to adsorb, obtains silicon/iron oxide micron linear array
Column；
D. post annealed processing is carried out under nitrogen or argon atmosphere to the silicon/iron oxide micron linear array；
E. resulting silicon/iron oxide micro wire array substrate backside deposition conductive layer after post annealed, and draw external lead
Line；
F. waterproof insulating layer is coated on the conductive layer.
2. a kind of light anode preparation method for improving photocatalytic water performance according to claim 1, it is characterised in that: described
In step b, the silicon micro wire spacing is 1~10 μm, diameter is 1~10 μm, length is 5~100 μm.
3. a kind of light anode preparation method for improving photocatalytic water performance according to claim 1, it is characterised in that: described
In step c1, the doped source solion is SnCl4、TiCl4、MnCl4、SiCl4、GeCl4、ZrCl4、NbCl4In solution
One or more of combinations.
4. a kind of light anode preparation method for improving photocatalytic water performance according to claim 1, it is characterised in that: described
In step d, the condition of post annealed processing are as follows: use quick anneal oven, handled 3~10 minutes at 300~600 DEG C, gas
Atmosphere is nitrogen or argon gas.
5. a kind of light anode preparation method for improving photocatalytic water performance according to claim 1, it is characterised in that: described
In step c1, Fe3+Solution be Fe (NO3)3Or FeCl3Ethyl alcohol or aqueous solution.
6. a kind of light anode preparation method for improving photocatalytic water performance according to claim 1, it is characterised in that: described
In step c1, precursor liquid is set to be adsorbed in silicon micro wire array substrate by spray-on process method particularly includes: to surpass the precursor liquid
Sound atomization, and the silicon micro wire array substrate that will warm up 100~200 DEG C is placed in below atomizer.
7. a kind of light anode preparation method for improving photocatalytic water performance according to claim 6, it is characterised in that: circulation weight
Multiple to carry out the step c1 and step c2, circulating repetition number is 1~20 time, as Fe in precursor liquid3+Concentration is bigger, then recycles
Number of repetition is smaller.
8. a kind of light anode preparation method for improving photocatalytic water performance according to claim 1, it is characterised in that: described
In step c2, early period annealing condition are as follows: in tubular annealing furnace, handled 2~5 hours at 400~600 DEG C, gas
Atmosphere is air.
9. a kind of light anode preparation method for improving photocatalytic water performance using one of any one of claim 1-8 is resulting
Light anode structure.
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| CN108642511A (en) * | 2018-04-12 | 2018-10-12 | 肇庆市华师大光电产业研究院 | A kind of preparation method of silicon nanowires/pucherite complex light anode |
| CN109252179B (en) * | 2018-09-19 | 2020-02-21 | 苏州大学 | Double-absorption-layer photo-anode for photolyzing water and preparation method thereof |
| CN110224033B (en) * | 2019-06-17 | 2020-12-08 | 苏州大学 | Iron oxide photo-anode system embedded with silicon pn junction and preparation method |
| CN111188058B (en) * | 2020-02-10 | 2021-02-19 | 桂林电子科技大学 | System for producing hydrogen by full-film silicon semiconductor double-electrode unbiased photoelectrocatalysis full-decomposition of water and application thereof |
| CN115305498B (en) * | 2021-09-13 | 2024-08-06 | 苏州大学 | Photoelectrode and preparation method thereof, pt-based alloy catalyst and preparation method thereof |
| CN114262911B (en) * | 2021-12-27 | 2023-03-21 | 安阳工学院 | Full-space gradient doped photoelectrode for photolysis of water and preparation method |
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