CN104762634B - Optical electro-chemistry decomposes aquatic products hydrogen, the optoelectronic pole for producing oxygen and its preparation and application - Google Patents
Optical electro-chemistry decomposes aquatic products hydrogen, the optoelectronic pole for producing oxygen and its preparation and application Download PDFInfo
- Publication number
- CN104762634B CN104762634B CN201510119013.5A CN201510119013A CN104762634B CN 104762634 B CN104762634 B CN 104762634B CN 201510119013 A CN201510119013 A CN 201510119013A CN 104762634 B CN104762634 B CN 104762634B
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- optoelectronic pole
- photocathode
- production
- production hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
A kind of optical electro-chemistry decomposes aquatic products hydrogen, produces the optoelectronic pole of oxygen, it is characterised in that the optoelectronic pole includes photocathode and light anode, and the photocathode and light anode have the quantum dot that assembling is aided in by bifunctional molecule.The invention realizes the optical electro-chemistry based on semiconductor, quantum dot and catalyst and decomposes aquatic products hydrogen, produces the foundation and application of oxygen optoelectronic pole；With stability it is high, without sacrifice agent, simple to operate, reproducible, universality it is strong and to the utilization ratio of visible ray it is high the characteristics of, and catalyst does not need noble metal, cheap and easy to get.
Description
Technical field
The present invention relates to photoelectrocatalysis decomposition water field.More particularly, to one kind based on p-type and n-type semiconductor substrate,
The optical electro-chemistry of quantum dot and catalyst decomposes aquatic products hydrogen, production oxygen optoelectronic pole, and its prepares and apply.
Background technology
With the rapid development of economy, the mankind increasingly increase for the demand of the energy.Fossil energy disappears as the world today
The main energy of consumption, the contribution of brilliance was once made on the road of human industryization development.However, continue with the mankind
Exploitation, the exhaustion of fossil energy are inevitable.Related data shows that most fossil energy will be produced nearly within the centuries
To the greatest extent；On the other hand, the adjoint environmental problem of the consumption of fossil energy also receives the mankind and more and more paid attention to.Therefore, open
Send out and using green, sustainable novel energy (such as solar energy, biomass energy, nuclear energy, wind energy), improve it in the whole energy
Ratio in structure is extremely urgent.In numerous novel energies, solar energy not only can be used freely but also need not with its aboundresources
Transport, and do not produce the advantages such as any environmental pollution and attracted increasing concern.Although the total resources of solar energy is suitable
Utilize more than 10,000 times of the energy in current mankind, but its exist energy density it is very low, because when become, vary in different localities the shortcomings that,
Therefore the utilization to solar energy cause very big challenge.In view of above-mentioned limiting factor, people are more likely to find one kind
Effective approach converts solar energy into chemical energy, electric energy etc., and is concentrated storage to utilize.Turn in numerous solar energy
In change approach, the photocatalytic water approach directly converted solar energy into using hydrogen and oxygen as the chemical energy of carrier is of greatest concern
One of mode.In the reaction of photocatalytic water, oxidizing process can produce oxygen, and it is the root of current species diversity；Reduction
Process can produce hydrogen, and it is considered as the clean energy resource of the great potential of high-energy-density.For China, solar energy and
Water resource is all relatively abundanter, therefore solar energy photocatalytic water method has very vast potential for future development.
Semiconductor nano (quantum dot) has the advantages that absorptivity is big, band gap is adjustable, matched with solar spectrum, in recent years
Come the research of the Photocatalyzed Hydrogen Production system using it as light absorbent and achieve huge progress.However, it is currently based on quantum
It is required to add substantial amounts of electronics sacrificial body in the Photocatalyzed Hydrogen Production system of point, should which greatly limits its further reality
With.Photoelectrocatalysis decomposition water provides a kind of method avoided using sacrificial reagent.Compared to the photocatalysis Decomposition in solution
Aqueous systems, photoelectricity system can realize the full decomposition of water, and the generation of hydrogen and oxygen is to betide negative electrode and anode respectively, and nothing
Accessory substance produces, and is had a good application prospect for industrialized production.But current photoelectrocatalytioxidation oxidation system still suffers from a lot
Problem, for example its energy conversion efficiency is still very low, system cost is higher, therefore it is difficult to use in actual production.Therefore photoelectricity is urged
Change decompose aqueous systems carry out deeper into research there is very major and immediate significance.
In photoelectricity system, light anode typically uses n-type semiconductor, wherein it is most widely TiO to study2.Since
Honda and Fujishima utilizes TiO within 19722Electrode, since realizing the decomposition of water under the irradiation of ultraviolet light, various countries
Researcher utilizes TiO2The research of a large amount of optical electro-chemistry hydrogen production by water decomposition is done.But TiO2It is a kind of wide bandgap material
(3.2eV), it is only capable of absorbing contained seldom ultraviolet light in sunshine.This property causes single TiO2Electrode light conversion effect
Rate is very low, it is necessary to expand TiO by suitable method2Light absorption range, such as adulterate, be sensitized.Quantum dot is a kind of excellent
Sensitized material, professor Kamat have been a large amount of quantum dot sensitized TiO2Research, quantum dot is connected to by bifunctional molecule
TiO2On, light induced electron is determined on quantum dot to TiO2Charge velocity, by adjusting quantum dot TiO2The electric charge transfer of interface
And the ligand modified function of quantum point, improve device performance (J.Phys.Chem.C 2013,117,14418-14426；
J.Am.Chem.Soc.2006,128,2385-2393；J.Phys.Chem.Lett.2012,3,663-672；
Proc.Nat.Acad.Sci.U.S.A.2011,108,29-34).But concern is primarily with quantum dot for the work of Kamat professors
It is sensitized TiO2The solar cell of type, the research of decomposition water is not carried out.2013, professor Bisquert etc.
CdSe quantum dot is deposited to TiO by (Adv.Energy Mater.2013,3,176-182) by the way of chemical thought2
On, the light anode of production hydrogen is constructed, theoretical hydrogen-producing speed reaches 20ml/ (cm2day1).At present, the light anode body based on quantum dot
System is so to construct mode (ACS Appl.Mat.Interfaces2013,5,1113-1121 mostly；
Chem.Mater.2010,22,922-927；J.Phys.Chem.C 2011,115,25429-25436；
J.Mater.Chem.2011,21,8749-8755 etc.), but this kind of system is that sacrifice examination is there are in electrolyte solution
Hydrogen is produced under conditions of agent, therefore the half-reaction of the substantially decomposition water carried out.In the case of no sacrifice reagent, quantum
Point is as light anode oxidation water, and there is perishable, the problem of stability difference, the progress of this respect is slower.2010
Year, CdTe quantum is adsorbed onto by Liu etc. (Angew.Chem.Int.Ed.2010,49,5966-5969) by TGA
On ZnO nano-wire, the light anode of decomposition water is prepared for, but hydrogen and oxygen are not detected really in their system.
Therefore, develop efficiently, stably, inexpensively, and the real light sun for decomposing aquatic products oxygen is realized in the system that reagent is sacrificed without adding
Pole is still a difficult task.
On the other hand, photocathode typically uses p-type semiconductor material, because the species of p-type semiconductor material is very limited, because
This is a significant and challenging job for the research of photocathode.At present, the work of photocathode is mainly p-type silicon
And Cu2O systems.Not rarely seen (the Energy Environ.Sci.2011,4,1690-1694 of p-type silicon photocathode；Nano
Lett.2012,12,298-302；Nat.Mater.2011,10,434-438；ACS Appl.Mat.Interfaces 2014,
6,12111-12118 etc.), wherein most representative be, and Ib Chorkendorff etc. (Nat.Mater.2011,10,434-
438) Mo is modified on p-type silicon3S4The solar energy that the photocathode that cluster is constructed is realized more than 10% goes to the transformation efficiency of Hydrogen Energy,
But the manufacturing cost of p-type silicon is very high, the prospect of its large-scale application have impact on.Cu2The problem of O photocathodes be stability too
Difference, maximum is made progress in the research of enhancing stability is SwitzerlandTeach seminar.They
(Nat.Mater.2011,10,456-461；Angew.Chem.Int.Ed.2014,54,664-667 a kind of Cu) is proposed2O is protected
Shield strategy, i.e., in Cu by way of ald2The ZnO and TiO of the Al doping of nanometer grade thickness are deposited on O2, successfully carry
High Cu2O stability.Although protective layer inhibits Cu2O photoetch, but it, which is prepared, needs higher instrument condition,
Operation is also more complicated.Quantum dot is applied to the work that photocathode starts from the professors of Pickett in 2010 et al.
(Angew.Chem.Int.Ed.2010,49,1574-1577), they are by the use of double thiol molecules as connection molecule by InP quantum
Point modification is to having constructed quantum dot light cathode systems on gold electrode, but the cathode photo current of the system (na) and photoelectrocatalysis
Hydrogen output (nanomole) is very low, while sensitising agent InP synthesis condition is harsh, toxicity is larger, and these deficiencies all limit it and entered
One step is applied and development.Henceforth, quantum dot light negative electrode is rarely reported.Until 2013, professor Domen etc.
(J.Am.Chem.Soc.2013,135,3733-3735) use chemical bath deposition by CdS nanoparticle depositions in p-type CuGaSe2
On semiconductor, further modify Pt and constructed photocathode as production hydrogen co-catalyst, this photocathode shows very high stabilization
Property (more than 10 days)；2014, they organized and report Pt/TiO2/CdS/CuInS2Photocathode
(Angew.Chem.Int.Ed.2014,53,11808-11812).But such system the problem of existing is CuGaSe2Or
CuInS2Semiconductor needs to prepare by the way of atomic layer is deposited, complex operation high to equipment requirement, and by the use of Pt as urging
Agent, cost are high.
In recent years, be gradually subject to the people's attention as a kind of cheap p-type semiconductor, NiO, due to NiO band gap compared with
Wide (Eg=3.5eV) is, it is necessary to use suitable dyestuff to be sensitized it to expand its utilization to sunshine.2011, grandson
Stand into and wait (Chem.Commun.2012,48,988-990) that organic dyestuff (P1) is connected on NiO first, and matched somebody with somebody using cobalt oxime
Compound has constructed NiO photocathode of the first case based on molecular photoactive agent and molecular catalyst, but it is catalyzed as co-catalyst
Agent and NiO connection function are weaker, in operation, are easily come off from electrode, influence electrode performance.2013, Wu
Yiying etc. (J.Am.Chem.Soc.135,32,11696-11699) makees sensitising agent using difunctional Ru complexs, realizes
With being connected chemically for NiO electrodes and Co composition catalysts, avoid coming off for catalyst, thus electrode show it is higher
Stability.Organic dye molecule be NiO photocathodes frequently with sensitizer, but organic dyestuff synthesis is complicated, with high costs, and
And less stable.(the ACS Catalysis 2015, DOI such as Richard professors Eisenberg:10.1021/
Cs5021035) CdSe quantum dot is chemically adsorbed on NiO, is prepared for CdSe/NiO electrodes, and in cobalt or the cooperation produce of nickel
Hydrogen catalyst carries out photoelectricity production hydrogen reaction, but obvious problem existing for this system is electricity of the operation needs in organic solvent acetonitrile
In electrolyte solution.2014, Liu etc. (ACS Nano 2014,8,10403-10413) was by IrOX nH2O/CdS/TiO2Light anode
It is together in series with NiS/CdSe/NiO photocathodes, is prepared for the decomposition water battery of double light absorbing layers, but the load of its quantum dot
Respectively by electrochemical deposition and chemical bath deposition mode, it is difficult to control quantum dot size and load capacity on the semiconductor and
Distribution.Simultaneously in the case where being not added with passivation layer and catalyst, the efficiency and less stable of system；In addition, prepared by the system
It is cumbersome, IrOXCatalyst price is high.Therefore, development prepares simple, cheap, stable material to strengthen nickel oxide or other
The light absorbs of p-type semiconductor, the photoelectricity H2-producing capacity for improving photocathode also have many work to do.Preferable optical electro-chemistry is decomposed
Aquatic products hydrogen, the optoelectronic pole of production oxygen should possess simple preparation, efficiency high, reproducible, stability is high, catalyst is cheap, universality
The advantages of strong.
The content of the invention
The invention solves first technical problem be to provide a kind of optoelectronic pole, it eases up without sacrifice agent, protective layer
Photoelectric decomposition aquatic products hydrogen, production oxygen can efficiently and stably be realized by rushing solution, realize conversion of the luminous energy to chemical energy, and with preparation
Simply, efficiency high, it is reproducible, to the high conversion rate of visible ray, stability is high, catalyst is cheap, universality is strong the advantages of.
To solve first technical problem, the present invention provides following technical scheme：
A kind of optical electro-chemistry decomposes aquatic products hydrogen, produces the optoelectronic pole of oxygen, it is characterised in that the optoelectronic pole include photocathode and
Light anode, and the photocathode and light anode have the quantum dot that assembling is aided in by bifunctional molecule.
Preferably, the bifunctional molecule is selected from sulfydryl phosphoric acid, mercaptan carboxylic acid, the amino acid containing sulfydryl, the height containing sulfydryl
One or more in molecule, the polypeptide containing sulfydryl, double carboxyl molecules, pyridine carboxylic acid and thiophene acetic acid.The bifunctional molecule
Connection molecule can be used as, some is alternatively arranged as electronics or hole transport relaying body.The bifunctional molecule conduct in the light anode
Connection molecule, some are alternatively arranged as electric transmission relaying body.Bifunctional molecule has as connection molecule in the photocathode
It is alternatively arranged as hole transport relaying body.
Preferably, the type of the auxiliary assembling is chemisorbed, and the chemisorbed is realized by bifunctional molecule.
Preferably, there is production hydrogen catalyst or production hydrogen catalyst precursor, wherein the production on the quantum dot of the photocathode
Hydrogen catalyst or production hydrogen catalyst precursor are that other non-quantum point of the quantum dot or in load in itself produces hydrogen catalyst or production
Hydrogen catalyst precursor.
Preferably, the quantum dot in the light anode is loaded with producing VPO catalysts or produces VPO catalysts precursor.
Preferably, the quantum dot is water-soluble quantum dot or oil-soluble quantum dot, it is preferable that the quantum dot is selected from
CdS、CdSe、CdTe、CdSe/ZnS、CdSe/ZnSe、CdSe/CdS、ZnSe/CdS、CdTe/CdSe、CdS/ZnSe、CdS/
One or more in ZnS, CdSe/CdS/ZnS and CdTe/CdSe/CdS.
Preferably, production hydrogen catalyst or production the hydrogen catalyst precursor is selected from the metal of iron, cobalt, nickel, copper, molybdenum, zinc or cadmium
One or more in salt, metal oxide, sulfide, hydroxide and metal complex；Preferably, the production hydrogen catalyst
Or catalyst precarsor is selected from Ni (OH)2、CoCl2、FeCl3、NiCl2、CuCl2、Ni(NO3)2、MoS2, hydrogenase and hydrogenation enzyme simulation
One or more in compound；Wherein described hydrogenase simulated compound is iron hydrogenase simulated compound.
Preferably, the production VPO catalysts or produce VPO catalysts precursors be selected from iron, cobalt, nickel, manganese, copper metal oxide,
The one or more of sulfide, hydroxide and metal complex.Preferably, the production VPO catalysts or catalyst precarsor are selected from
Fe(OH)3、Ni(OH)2、FeOOH、NiOOH、CoOOH、Fe2O3、Co2O3With the one or more in NiO.
The material of the photocathode is p-type metal oxide semiconductor, and it is selected from NiO, CuMO2(M=Cr, Al, Fe, Ga,
) and CuBi In2O4In one or more.
The material of the light anode is n-type metal oxide semiconductor, and it is selected from TiO2、ZnO、Fe2O3And WO3In one
Kind is several.
The electrode is that the optical electro-chemistry based on semiconductor, quantum dot and catalyst decomposes aquatic products hydrogen, production oxygen, and can be very
Realize optical electro-chemistry decomposition water in the range of wide pH, while can be with by regulating and controlling the size of quantum dot, the species of bifunctional molecule
It is conveniently adjusted the performance of optoelectronic pole decomposition water.
The invention solves second technical problem be to provide a kind of optical electro-chemistry and decompose aquatic products hydrogen, production oxygen optoelectronic pole
Preparation method.
To solve above-mentioned second technical problem, the present invention uses following technical proposals：
A kind of above-mentioned production hydrogen, the preparation method for producing oxygen optoelectronic pole, including the preparation of photocathode and the preparation of light anode, wherein
The preparation method of the photocathode is：One layer of p-type semiconductor film is prepared first, secondly under the auxiliary of bifunctional molecule, in p
Type semiconductive thin film over-assemble one or more quantum dot, photocathode is made；The preparation method of wherein light anode is as follows：First
Prepare the film of one layer of n-type semiconductor, secondly under the auxiliary of bifunctional molecule n-type semiconductor film over-assemble it is a kind of or
A variety of quantum dots, finally VPO catalysts or production VPO catalysts precursor are produced in load over the qds, and light anode is made.
Preferably, the quantum dot wherein on photocathode has production hydrogen catalyst in itself or produces the function of hydrogen catalyst precursor.
A kind of above-mentioned production hydrogen, the preparation method for producing oxygen optoelectronic pole, including the preparation of photocathode and the preparation of light anode, wherein
The preparation method of the photocathode is：One layer of p-type semiconductor film is prepared first, secondly under the auxiliary of bifunctional molecule, in p
Type semiconductive thin film over-assemble one or more quantum dot, finally hydrogen catalyst or production hydrogen catalyst are produced in load over the qds
Precursor, prepare photocathode；The preparation method of wherein light anode is as follows：The film of one layer of n-type semiconductor is prepared first, is secondly existed
In n-type semiconductor film over-assemble one or more quantum dot under the auxiliary of bifunctional molecule, finally load over the qds
VPO catalysts or production VPO catalysts precursor are produced, light anode is made.
The preparation method of the film of the p-type semiconductor and the film of n-type semiconductor includes silk-screen printing, doctor blade method, molten
Sol-gel, spin-coating method, preferably silk-screen printing；The thickness of the semiconductive thin film is 200nm~10 μm；Preferably, it is described
The carrying method for producing hydrogen catalyst, production hydrogen catalyst precursor, production VPO catalysts and production VPO catalysts precursor is drop coating, dipping, change
Learn the one or more in water-bath deposition, continuous ionic layer absorption deposition, electrochemical deposition and chemisorbed.
A kind of application using above-mentioned production hydrogen, production oxygen optoelectronic pole hydrogen production by water decomposition, oxygen processed, comprise the following steps that：Group first
Packed battery；Secondly, the battery is placed in the electrolyte solution of certain pH；Apply certain bias to the battery, be used in combination
Light source is irradiated to it；Finally, the generation of electric current and gas is detected.
The battery is by single photocathode or single light anode combination reference electrode, to electrode, three electrodes of composition
System；Or photocathode and light anode are composed in series two electrode systems；The scope that preferably three-electrode system is biased is 0
~-0.8V (vs. reference electrodes)；The scope that preferably two electrode systems are biased is 0.8~-0.8V (vs. is to electrode)；It is excellent
Electrolyte solution described in selection of land is selected from Na2SO4、K2SO4、KNO3、NaNO3、Na3PO4、K3PO4、K2CO3、Na2CO3、K2HPO4、
Na2HPO4、KH2PO4And NaH2PO4In one or more of aqueous solution；The scope of the pH is 1~14；Preferably, the light
Source is selected from sunshine, incandescent lamp, xenon lamp, LEDs, laser, solar simulator or high-pressure sodium lamp.
Beneficial effects of the present invention are as follows：
1) invention realize based on p-type and n-type semiconductor, the optical electro-chemistry of quantum dot and catalyst decompose aquatic products hydrogen,
Produce the foundation of oxygen optoelectronic pole；
2) optoelectronic pole can efficiently and stably decomposition water without electronics sacrificial body, cushioning liquid；
3) optoelectronic pole obtains the water-based energy of very high photoelectric decomposition under conditions of not additional production hydrogen catalyst；
4) relaying body in the optoelectronic pole hole has fabulous separation and laser propagation effect for quantum dot photohole；
5) optoelectronic pole is simple to operate, reproducible, stability is good, universality is strong, the utilization ratio height to visible ray；Urge
Agent does not need noble metal, cheap and easy to get.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows the uv-visible absorption spectra and emission spectrum spectrogram of CdS quantum dot.
Fig. 2 shows the uv-visible absorption spectra spectrogram of CdSe quantum dot and CdSe/ZnS quantum dots.
Fig. 3 shows the emission spectrum spectrogram of CdSe quantum dot and CdSe/ZnS quantum dots.
Fig. 4 shows the shape appearance figure that CdS quantum dot is observed under high-resolution-ration transmission electric-lens (HRTEM).
Fig. 5 shows the shape appearance figure that CdSe/ZnS quantum dots are observed under high-resolution-ration transmission electric-lens (HRTEM).
Fig. 6 shows the electrode decomposition water schematic diagram of nickel oxide/quantum dot/production hydrogen catalyst in embodiment 1.
Fig. 7 shows the cathode current versus time curve of embodiment 2.
Fig. 8 shows cathode current versus time curve in embodiment 3.
Fig. 9 shows anode current versus time curve caused by photocathode in example 4.
Figure 10 shows the electric current versus time curve of the electrode of embodiment 5.
Figure 11 is the electric current versus time curve of the electrode of embodiment 6.
Figure 12 shows the electric current versus time curve of embodiment 7.
Figure 13 shows the cathode current versus time curve in embodiment 9.
Figure 14 shows the electric current versus time curve in embodiment 11.
Figure 15 is the electric current versus time curve of embodiment 12.
Figure 16 shows the Monitoring Data that gas is composed in embodiment 13.
Figure 17 shows the structural formula of cobalt complex in embodiment 14.
Figure 18 shows oxygen detection curve in embodiment 15.
Figure 19 shows the electric current versus time curve in embodiment 17.
Figure 20 shows the light anode decomposition water schematic diagram in embodiment 18.
Figure 21 shows the electric current versus time curve in embodiment 18.
Figure 22 shows double optoelectronic pole decomposition water schematic diagrames in embodiment 19.
Figure 23 shows the electric current versus time curve of the electrode in embodiment 19.
Figure 24 shows X-ray diffraction (XRD) collection of illustrative plates of the ZnO/CdS in embodiment 20.
Figure 25 shows the structural formula of the cobalt complex of embodiment 22.
Figure 26 shows the scanning electron microscope (SEM) photograph of the ZnO nanorod in embodiment 23.
Figure 27 shows the scanning electron microscope (SEM) photograph of the FeOOH nanotubes in embodiment 24.
Figure 28 shows TiO in embodiment 252The scanning electron microscope (SEM) photograph of nanometer rods.
Embodiment
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar part is indicated with identical reference in accompanying drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
The preparation of quantum dot：
Quantum dot bibliography is made.The present invention is exemplified below：Exemplified by synthesizing CdS quantum dot, experimental procedure includes：
1. accurately weigh 0.2284g CdCl2·5/2H2O in 500ml round-bottomed flasks, add 190ml deionized waters by its
Dissolving.
2. 1ml mercaptopropionic acids are added, stirring, degasification 30min.
3. 10M sodium hydroxide solutions are added dropwise under fast stirring, it is observed that solution is changed into blue and white from clarifying
Turbid solution, then become clarification.Then pH value is adjusted to 7 or so with 1M sodium hydroxide solutions.
4. add 10ml 0.1M Na2S solution (weighs 0.24018g Na2S·9H2O, with 10.0ml deionized water dissolvings
Both).
5. stirring at normal temperature reacts 3.5h.
Other quantum dots synthesis reference literature (APL Materials 2014,2 (1), 012104；J.Phys.Chem.C
2008,112,8587-8593)。
Fig. 1,2,3 are the uv-visible absorption spectra of CdS quantum dot, CdSe quantum dot and CdSe/ZnS quantum dots respectively
With emission spectrum spectrogram, excitation wavelength is all 400nm.It can be seen that the first absworption peak of CdSe quantum dot is located at
430nm or so；First absworption peak of CdS quantum dot is located at 390nm or so；First absworption peak of CdSe/ZnS quantum dots is located at
450nm or so.In the case where 400nm light excites, emission peak of the CdSe quantum dot at 470nm is its band-edge emission, the hair at 600nm
Peak is penetrated for its defect to launch；Emission peak at 490nm and 600nm two be present in CdSe/ZnS quantum dots.
Fig. 4,5 are CdS quantum dot and CdSe/ZnS quantum dots respectively with being dropped in after water ultrasonic disperse in ultrathin carbon films,
The shape appearance figure observed under HRTEM (high-resolution-ration transmission electric-lens).It can be seen that the average-size of CdS quantum dot is 3.0
±0.3nm；CdSe/ZnS quantum dots are unbodied club shaped structure.Can by control synthesize reaction time of quantum dot, temperature,
The species and proportioning of stabilizer synthesize to obtain different-shape and the quantum dot of structure.
Embodiment 1
A kind of method for the hydrogen production by water decomposition oxygen that aquatic products hydrogen production oxygen optoelectronic pole is decomposed based on optical electro-chemistry, including following step
Suddenly：
Nickel oxide nanoparticle is carried on tin dope conductive glass surface first with screen printing technique and is prepared into
To nickel oxide film；Then the CdSe quantum dot prepared is adsorbed onto nickel oxide film surface using the means of chemisorbed,
Bifunctional molecule is TGA；The method that deposition is finally adsorbed using continuous ionic layer is prepared into quantum dot by hydrogen catalyst is produced
Surface, production hydrogen catalyst are Ni (OH)2, photocathode is made with this.
The negative electrode prepared is connected in photoelectrochemistrpool pool, adds Na2SO4Electrolyte (pH=7), platinized platinum are used as to electricity
Pole, Ag/AgCl electrodes build optical electro-chemistry as reference electrode and decompose water battery.Light source (p=100mW/cm is used as by the use of xenon lamp2)
Irradiate photocathode (working electrode) and apply certain bias (- 0.3V vs. reference electrodes), with gas-chromatography (TCD thermal conductivities
Detector) detect the hydrogen generated in reaction.The electrode decomposition water signal of nickel oxide/quantum dot/production hydrogen catalyst made from Fig. 6
Figure.
Embodiment 2
A kind of method for the hydrogen production by water decomposition oxygen that aquatic products hydrogen production oxygen optoelectronic pole is decomposed based on optical electro-chemistry, including following step
Suddenly：
Nickel oxide nanoparticle is carried on tin dope conductive glass surface using screen printing technique and oxygen is prepared
Change nickel film；Then the CdSe quantum dot prepared is adsorbed onto nickel oxide film surface using the means of chemisorbed, connected
Molecule is mercaptopropionic acid；Photocathode is made with this.
The photocathode prepared is connected in photoelectrochemistrpool pool, adds Na2SO4Electrolyte (pH=7), platinized platinum conduct pair
Electrode, Ag/AgCl electrodes build photoelectrochemical cell as reference electrode.Light source (p=100mW/cm is used as by the use of xenon lamp2) irradiation
Photocathode (working electrode) and apply certain bias (- 0.3V vs. reference electrodes), with gas-chromatography (TCD Thermal Conductivities
Device) detect the hydrogen generated in reaction.Fig. 7 is nickel oxide/cathode current versus time curve caused by quantum point electrode.
As we can see from the figure under the same conditions, this life of nickel oxide can only produce extremely faint cathode current；QDs is sensitized it
Afterwards, cathode current is sharply increased to close -60 μ A/cm2；This result can surmount the photocathode document report based on nickel oxide
Peak.
Embodiment 3
A kind of method for the hydrogen production by water decomposition oxygen that aquatic products hydrogen production oxygen optoelectronic pole is decomposed based on optical electro-chemistry, including following step
Suddenly：
Nickel oxide nanoparticle is carried on tin dope conductive glass surface using screen printing technique and oxygen is prepared
Change nickel film；Then the CdSe quantum dot prepared is adsorbed onto nickel oxide film surface using the means of chemisorbed, connected
Molecule is mercaptopropionic acid, and photocathode is made with this.
The photocathode prepared is connected in photoelectrochemistrpool pool, (pH=9), platinized platinum conduct pair in sodium sulphate electrolyte
Electrode, Ag/AgCl electrodes build photoelectrochemical cell as reference electrode.Light source (p=100mW/cm is used as by the use of xenon lamp2) irradiation
Photocathode (working electrode) and apply certain bias (- 0.3V vs. reference electrodes), with gas-chromatography (TCD Thermal Conductivities
Device) detect the hydrogen generated in reaction.Fig. 8 is nickel oxide/cathode current versus time curve caused by quantum point electrode.
Embodiment 4
A kind of method for the hydrogen production by water decomposition oxygen that aquatic products hydrogen production oxygen optoelectronic pole is decomposed based on optical electro-chemistry, including following step
Suddenly：
Nickel oxide nanoparticle is carried on tin dope conductive glass surface using screen printing technique and oxygen is prepared
Change nickel film；Then the CdS quantum dot prepared is adsorbed onto nickel oxide film surface, connection point using the means of chemisorbed
Son is mercaptohexanoic acid, finally loads to quantum dot surface by hydrogen catalyst is produced using the method for dipping, production hydrogen catalyst is Co
(NO3)2, photocathode is made with this.
The photocathode prepared is connected in photoelectrochemistrpool pool, in Na2SO4(pH=12), platinized platinum conduct pair in electrolyte
Electrode, Ag/AgCl electrodes build photocathode system as reference electrode.Light source (p=100mW/cm is used as by the use of xenon lamp2) irradiation light
Negative electrode (working electrode) and apply certain bias (- 0.3V vs. reference electrodes).Fig. 9 is caused by photocathode in example 4
Cathode current versus time curve.The cathode current of photocathode is about -22 μ A/cm as we can see from the figure2。
Embodiment 5
A kind of method for the hydrogen production by water decomposition oxygen that aquatic products hydrogen production oxygen optoelectronic pole is decomposed based on optical electro-chemistry, including following step
Suddenly：
Nickel oxide nanoparticle is carried on tin dope conductive glass surface using screen printing technique and oxygen is prepared
Change nickel film；Then the CdSe quantum dot prepared is adsorbed onto nickel oxide film surface using the means of chemisorbed, connected
Molecule is mercaptopropionic acid；Finally hydrogen catalyst being produced using the method for dipping and being prepared into quantum dot surface, production hydrogen catalyst is
CoCl2, photocathode is made with this,
(pH=5), platinized platinum are used as in sodium sulphate electrolyte builds light to electrode, Ag/AgCl electrodes as reference electrode
Cathode systems.Light source (p=100mW/cm is used as by the use of xenon lamp2) irradiation photocathode (working electrode) and apply certain bias (-
0.3V vs. reference electrodes).Figure 10 is cathode current versus time curve caused by photocathode in example 5.Can from figure
To see that photoelectric current is about -7 μ A/cm2。
Embodiment 6
A kind of method for the hydrogen production by water decomposition oxygen that aquatic products hydrogen production oxygen optoelectronic pole is decomposed based on optical electro-chemistry, including following step
Suddenly：
Nickel oxide nanoparticle is carried on tin dope conductive glass surface using screen printing technique and oxygen is prepared
Change nickel film, the CdS quantum dot prepared is then adsorbed onto nickel oxide film surface, connection point using the means of chemisorbed
Son is TGA；Finally hydrogen catalyst being produced using the mode of chemical drop coating and being prepared into quantum dot surface, production hydrogen catalyst is
NiCl2, photocathode is made with this.
In Na2SO4(pH=7), platinized platinum are used as in electrolyte builds time to electrode, Ag/AgCl electrodes as reference electrode
Polar body system.Light source (p=100mW/cm is used as by the use of xenon lamp2) irradiation photocathode (working electrode) and apply certain bias (-
0.1V vs. reference electrodes).Figure 11 is cathode current versus time curve caused by photocathode in example 6.Can from figure
To see that photoelectric current is about -48 μ A/cm2。
Embodiment 7
A kind of method for the hydrogen production by water decomposition oxygen that aquatic products hydrogen production oxygen optoelectronic pole is decomposed based on optical electro-chemistry, including following step
Suddenly：
Titania nanoparticles are carried on tin dope conductive glass surface using screen printing technique and are prepared
Titanium deoxid film；Then the CdS quantum dot prepared is adsorbed onto titanium deoxid film surface using the means of chemisorbed,
Bifunctional molecule is mercaptohexanoic acid, finally loads to quantum dot surface by VPO catalysts are produced using the method for chemical thought,
Production VPO catalysts are Co2O3Nano particle.Figure 12 is the material object for the titanium dioxide/quantum dot/catalyst film electrode being prepared
Figure.
Embodiment 8
With embodiment 1, change is that quantum dot is CdSe/ZnS, and bifunctional molecule is mercaptohexanoic acid.
Embodiment 9
With embodiment 6, change is that application voltage is 0V.Changes of the Figure 13 for electric current caused by photocell in example 9 with the time
Change curve.Photoelectric current is about -40 μ A/cm as can see from Figure 132。
Embodiment 10
With embodiment 1, change is that semiconductor is CdS, and bifunctional molecule is glutathione.
Embodiment 11
With embodiment 3, composition is CuBi in metal oxide layer2O4, production hydrogen catalyst is the mixing of nickel chloride and cobalt chloride
(the amount ratio of material is 2 to thing:1).Change curves of the Figure 14 for cathode current caused by photocathode in example 11 with illumination, from figure
It can be seen that cathode current is about -11 μ A/cm under the conditions of being somebody's turn to do2。
Embodiment 12
With embodiment 3, composition is CuCrO in metal oxide layer2, quantum dot CdS, CdSe and CdS/ZnSe (dosage
1:1:1).Figure 15 be example 12 in cathode current caused by photocathode with illumination change curve, as we can see from the figure this
Cathode current is about -16 μ A/cm under part2。
Embodiment 13
With embodiment 6, change is that production hydrogen catalyst is molybdenum disulfide.Figure 16 is the Monitoring Data that gas is composed in example 13.
Embodiment 14
With embodiment 6, change is that production hydrogen catalyst is cobalt complex.Figure 17 is the structural formula of cobalt complex in example 14.
Embodiment 15
With embodiment 5, change is that composition is CuAlO in semiconductor layer2, production hydrogen catalyst is the complex of cobalt.Figure 18 is
Oxygen detection curve in example 15.
Embodiment 16
With embodiment 3, composition is CuCrO in metal oxide layer2, quantum dot CdSe/ZnS.
Embodiment 17
Nickel oxide nanoparticle is carried on tin dope conductive glass surface using screen printing technique and oxygen is prepared
Change nickel film, the CdTe quantum prepared is then adsorbed onto nickel oxide film surface using the means of chemisorbed, connect
Molecule is TGA；Finally hydrogen catalyst being produced using the method for dipping and being prepared into quantum dot surface, production hydrogen catalyst is
NiCl2, photocathode is made with this.
Photocathode and light anode are together in series, light anode is the TiO prepared by embodiment 72/ CdS electrodes, are made with xenon lamp
For light source (p=100mW/cm2) while irradiate photocathode and light anode, it is biased as 0V.Figure 19 is photocell in example 17
Caused electric current versus time curve.Photoelectric current is about -6 μ A/cm as we can see from the figure2。
Embodiment 18
A kind of method for the hydrogen production by water decomposition oxygen that aquatic products hydrogen production oxygen optoelectronic pole is decomposed based on optical electro-chemistry, including following step
Suddenly：
Titania nanoparticles are carried on tin dope conductive glass surface using screen printing technique and are prepared
Titanium deoxid film；Then the CdS quantum dot prepared is adsorbed onto titanium deoxid film surface using the means of chemisorbed,
Bifunctional molecule is mercaptohexanoic acid, finally loads to quantum dot surface by VPO catalysts are produced using the method for chemical thought,
Production VPO catalysts are Co2O3Nano particle, light anode is made.
The light anode prepared is connected in photoelectrochemistrpool pool, using pure water as solvent, platinized platinum is as to electrode, Ag/
AgCl electrodes build photocathode system as reference electrode.Light source (p=100mW/cm is used as by the use of xenon lamp2) irradiation photocathode (work
Make electrode) and apply certain bias (0.5V vs. reference electrodes).Figure 20 is light anode decomposition water schematic diagram in example 18,
Figure 21 is anode current versus time curve caused by light anode.The sun of CdS quantum dot light anode as we can see from the figure
Electrode current is about 100 μ A/cm2。
Embodiment 19
A kind of method for the hydrogen production by water decomposition oxygen that aquatic products hydrogen production oxygen optoelectronic pole is decomposed based on optical electro-chemistry, including following step
Suddenly：
Nickel oxide nanoparticle is carried on tin dope conductive glass surface using screen printing technique and oxygen is prepared
Change nickel film；Then the CdSe quantum dot prepared is adsorbed onto nickel oxide film surface, double work(using the means of chemisorbed
Energy molecule is mercaptopropionic acid；The method that deposition is finally adsorbed using continuous ionic layer is prepared into quantum dot table by hydrogen catalyst is produced
Face, production hydrogen catalyst are Ni (OH)2, photocathode is made with this；
Titania nanoparticles are carried on into tin dope using screen printing technique to lead glass surface and be prepared two
Thin film of titanium oxide；Then the CdS quantum dot prepared is adsorbed onto titanium deoxid film surface using the means of chemisorbed, it is double
Functional molecular is mercaptohexanoic acid, finally loads to quantum dot surface by VPO catalysts are produced using the method for drop coating, produces VPO catalysts
For Co2O3Nano particle, light anode is made with this；
Photocathode and light anode are together in series, light source (p=100mW/cm is used as by the use of xenon lamp2) while irradiate photocathode and
Light anode, it is biased as 0V (vs. is to electrode).Figure 22 is double optoelectronic pole decomposition water schematic diagrames in example 19, and Figure 23 is implementation
Caused electric current versus time curve in example 19.Photoelectric current is about -10 μ A/cm as we can see from the figure2。
Embodiment 20
With embodiment 18, change is that semiconductor is ZnO, and Figure 24 is the XRD spectra of ZnO-CdS electrodes.
Embodiment 21
With embodiment 19, production VPO catalysts are cobalt complex.Figure 25 is the structural formula of cobalt complex in example 21.
Embodiment 22
With embodiment 5, change is that electrolyte solution is K2HPO4 solution.
Embodiment 23
With embodiment 18, change is that semiconductor is ZnO.ZnO pattern is nanometer rods.Figure 26 is the scanning of ZnO nanorod
Electron microscope.As can be seen from the figure TiO2The length of nanometer rods is about 4.5 μm, and diameter is about 350nm.
Embodiment 24
With embodiment 7, change is to load to quantum dot surface by VPO catalysts are produced using the method for electrochemical deposition, produces oxygen
Catalyst is FeOOH nanotube.Figure 27 is the scanning electron microscope (SEM) photograph of FeOOH nanotube.As can be seen from the figure
FeOOH nanometer tube walls are about 30nm, and external diameter is about 150nm, and internal diameter is about 90nm.
Embodiment 25
With embodiment 7, change is that collosol and gel mode prepares TiO2Nanometer rods light anode.Figure 28 is TiO2Nanometer rods are swept
Electron microscope is retouched, as can be seen from the figure TiO2The length of nanometer rods is about 5 μm, and diameter is about 200nm.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical scheme is extended out still in protection scope of the present invention.
Claims (10)
1. a kind of optical electro-chemistry decomposes aquatic products hydrogen, produces the optoelectronic pole of oxygen, it is characterised in that the optoelectronic pole includes photocathode and light
Anode, and the photocathode and light anode have the quantum dot that assembling is aided in by bifunctional molecule；
There is production hydrogen catalyst or production hydrogen catalyst precursor on the quantum dot of the photocathode；It is described production hydrogen catalyst be selected from iron,
One or more in cobalt, nickel, the metal oxide of copper, sulfide, hydroxide and metal complex；The production hydrogen catalyst
Precursor selected from iron, cobalt, nickel, copper, molybdenum, zinc, cadmium metal salt in one or more；
Quantum dot in the light anode is loaded with producing VPO catalysts；The production VPO catalysts are selected from iron, cobalt, nickel, manganese, the gold of copper
Belong to the one or more of oxide, hydroxide and metal complex.
2. production hydrogen according to claim 1, the optoelectronic pole for producing oxygen, it is characterised in that the bifunctional molecule is selected from sulfydryl
One or more in phosphoric acid, mercaptan carboxylic acid, the amino acid containing sulfydryl, double carboxyl molecules, pyridine carboxylic acid and thiophene acetic acid.
3. production hydrogen according to claim 1, the optoelectronic pole for producing oxygen, it is characterised in that the material of the photocathode is p-type gold
Belong to oxide semiconductor, it is selected from NiO, CuCrO2、CuAlO2、CuFeO2、 CuGaO2、CuInO2And CuBi2O4In one kind or
It is several.
4. production hydrogen according to claim 1, the optoelectronic pole for producing oxygen, it is characterised in that the material of the light anode is n-type gold
Belong to oxide semiconductor, it is selected from TiO2、ZnO、Fe2O3And WO3In one or more.
5. production hydrogen according to claim 1, the optoelectronic pole for producing oxygen, it is characterised in that the quantum dot is water-soluble quantum
Point or oil-soluble quantum dot.
6. it is according to claim 5 production hydrogen, produce oxygen optoelectronic pole, it is characterised in that the quantum dot be selected from CdS, CdSe,
CdTe、CdSe/ZnS、CdSe/ZnSe、CdSe/CdS、ZnSe/CdS、CdTe/CdSe、CdS/ZnSe、CdS/ZnS、CdSe/
One or more in CdS/ZnS and CdTe/CdSe/CdS.
7. production hydrogen according to claim 1, the optoelectronic pole for producing oxygen, it is characterised in that
The production hydrogen catalyst is selected from Ni (OH)2、MoS2, one or more in hydrogenase and hydrogenase simulated compound；
The production hydrogen catalyst precursor is selected from CoCl2、FeCl3、NiCl2、CuCl2、Ni(NO3)2In one or more.
8. production hydrogen according to claim 1, the optoelectronic pole for producing oxygen, it is characterised in that the production VPO catalysts are selected from Fe
(OH)3、Ni(OH)2、FeOOH、NiOOH、CoOOH、Fe2O3、Co2O3With the one or more in NiO.
9. a kind of any described production hydrogen of claim 1-7, the preparation method for producing oxygen optoelectronic pole, include preparation and the light of photocathode
The preparation of anode, wherein the preparation method of the photocathode is：First using silk-screen printing, doctor blade method, sol-gal process, spin coating
One kind in method prepares one layer of p-type semiconductor film, secondly under the auxiliary of bifunctional molecule, the group on p-type semiconductor film
One or more kinds of quantum dots are filled, finally hydrogen catalyst or production hydrogen catalyst precursor are produced in load over the qds, prepare time
Pole；The preparation method of wherein light anode is as follows：First using one kind in silk-screen printing, doctor blade method, sol-gal process, spin-coating method
Prepare the film of one layer of n-type semiconductor, secondly under the auxiliary of bifunctional molecule n-type semiconductor film over-assemble it is a kind of or
A variety of quantum dots, finally using drop coating, dipping, chemical thought, continuous ionic layer absorption deposition, electrochemical deposition and chemistry
One or more of production VPO catalysts of load over the qds in absorption, are made light anode.
10. a kind of production hydrogen as claimed in claim 9, the preparation method for producing oxygen optoelectronic pole, it is characterised in that the p-type is partly led
The preparation method of the film of body and the film of n-type semiconductor is silk-screen printing；The thickness of the semiconductive thin film is 200 nm ~ 10
μm。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510119013.5A CN104762634B (en) | 2015-03-18 | 2015-03-18 | Optical electro-chemistry decomposes aquatic products hydrogen, the optoelectronic pole for producing oxygen and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510119013.5A CN104762634B (en) | 2015-03-18 | 2015-03-18 | Optical electro-chemistry decomposes aquatic products hydrogen, the optoelectronic pole for producing oxygen and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104762634A CN104762634A (en) | 2015-07-08 |
| CN104762634B true CN104762634B (en) | 2018-03-16 |
Family
ID=53644715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510119013.5A Active CN104762634B (en) | 2015-03-18 | 2015-03-18 | Optical electro-chemistry decomposes aquatic products hydrogen, the optoelectronic pole for producing oxygen and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104762634B (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238081A (en) * | 2015-12-29 | 2016-12-21 | 中国特种飞行器研究所 | Preparation has the WO of high activity photoelectrocatalysis decomposition water performance3the method of nanometer thorn/CoPi complex light anode |
| CN105986292B (en) * | 2016-01-20 | 2020-10-09 | 安徽大学 | Preparation method of cobalt-nickel double-layer hydroxide modified titanium dioxide nanotube array and application of photoelectrochemical hydrolysis hydrogen production |
| CN107017424A (en) * | 2016-01-28 | 2017-08-04 | 中国科学院大连化学物理研究所 | The lamination generating battery that a kind of photoelectrocatalysis reducing molecular oxygen reaction and fuel cell are coupled |
| CN105727998B (en) * | 2016-02-01 | 2018-04-27 | 浙江工商大学 | A kind of composite titanium dioxide nano flower photoelectrocatalysimaterial material and its preparation and application |
| CN107201226A (en) * | 2016-03-17 | 2017-09-26 | 上海科技大学 | CuInS2Quantum dot, CuInS2/ ZnS quantum dot and its preparation and application |
| CN105797752A (en) * | 2016-04-01 | 2016-07-27 | 上海师范大学 | Fullerene modified graphene/cadmium sulfide catalyst as well as preparation method and application thereof |
| CN107464881B (en) * | 2016-06-02 | 2019-06-18 | 华中科技大学 | A kind of integrated device and preparation method thereof towards photolysis water hydrogen |
| CN107541747B (en) * | 2016-06-27 | 2019-02-19 | 中国科学院金属研究所 | A kind of energy storage device integrating optical electro-chemical water decomposes the design method of battery |
| CN106449149B (en) * | 2016-11-23 | 2018-07-06 | 吉林大学 | A kind of preparation method of self-supporting light anode |
| CN106868530B (en) * | 2017-01-18 | 2017-12-26 | 黄河科技学院 | Modified titanic oxide optoelectronic pole and preparation method thereof, application |
| CN107460513A (en) * | 2017-09-08 | 2017-12-12 | 华南师范大学 | MoS2The preparation method and application of/CdS film electrode |
| CN107829108B (en) * | 2017-09-30 | 2020-04-28 | 华南理工大学 | FeOOH/CdS/Ti: Fe2O3Composite photoelectrode and preparation method thereof |
| JP6783815B2 (en) * | 2018-03-22 | 2020-11-11 | 株式会社東芝 | Oxidation electrode and electrochemical reactor using it |
| CN108654666B (en) * | 2018-04-19 | 2020-10-02 | 南京师范大学 | Preparation method of N, P-codoped three-dimensional Co nanoflower, obtained material and application |
| CN109308982B (en) * | 2018-10-18 | 2020-11-06 | 温州大学 | Preparation method of co-modified copper bismuthate nanorod photocathode |
| CN110331416B (en) * | 2019-08-09 | 2020-07-24 | 河南大学 | CoOOH nanosheet modified Fe2O3Preparation method and application of composite photo-anode |
| CN111007128B (en) * | 2019-12-27 | 2022-03-11 | 郑州轻工业大学 | Iron oxyhydroxide-MoS2Nanometer hybrid material and preparation method thereof, electrode for aptamer sensor and aptamer sensor |
| CN111151305B (en) * | 2020-02-20 | 2022-06-14 | 辽宁大学 | Copper doped ultra-thin TiO2Application of nanosheet-loaded cobalt oxime complex in photocatalytic water decomposition hydrogen production |
| CN111482150B (en) * | 2020-04-22 | 2022-07-19 | 上海市普陀区人民医院(上海纺织第一医院) | Visible light response all-copper-based series photoelectric catalytic device and preparation method thereof |
| CN111468138B (en) * | 2020-05-27 | 2021-11-30 | 辽宁大学 | One-dimensional rod-shaped CuBi2O4@CuBi2S4Visible light catalyst and preparation method and application thereof |
| CN111905736B (en) * | 2020-07-23 | 2021-10-26 | 安徽工业大学 | Cysteine functionalized modified iron oxyhydroxide, electrocatalyst, preparation methods and applications |
| CN113968602B (en) * | 2021-10-25 | 2023-11-24 | 中国科学院合肥物质科学研究院 | Method for removing nitrified nitrogen in water by electrocatalytic treatment |
| CN115318307B (en) * | 2022-08-29 | 2023-07-25 | 四川启睿克科技有限公司 | Method for designing high-performance hydrogen-producing promoter by introducing electric coupling layer and constructing snowflake CuNi@EDL/CdS catalyst |
| CN115679371A (en) * | 2022-11-22 | 2023-02-03 | 电子科技大学长三角研究院(湖州) | Double-cathode parallel light-driven water decomposition hydrogen production electrode system |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101026199A (en) * | 2007-03-26 | 2007-08-29 | 浙江大学 | Method for for preparing cadmiumsulfide quantum dot sensitized porous titanium dioxide photoelectrode |
| CN101393938A (en) * | 2007-12-28 | 2009-03-25 | 北京大学 | Wide forbidden region semi-conductor nano tube/linear array film, preparation and photoelectric pole thereof |
| CN101894689A (en) * | 2010-07-26 | 2010-11-24 | 东南大学 | Quantum dot composite sensitization solar battery and preparation method of electrode thereof |
| CN102024572A (en) * | 2010-12-09 | 2011-04-20 | 华中科技大学 | Method for preparing sulfide quantum dot co-sensitization porous titanium dioxide photoelectrode |
| CN102097214A (en) * | 2010-11-21 | 2011-06-15 | 沈阳工业大学 | Preparation method of zinc oxide-based solar cell electrode |
| CN102226284A (en) * | 2011-06-02 | 2011-10-26 | 厦门大学 | Method for performing photoelectrolysis of water and preparing hydrogen by using palladium quantum dot modified titanium dioxide nanotube array |
| CN102364648A (en) * | 2011-10-18 | 2012-02-29 | 西安交通大学 | Method for manufacturing sulfydryl bridge molecular bonded quantum dot and TiO2 nano compound light anode |
| CN102760581A (en) * | 2011-04-25 | 2012-10-31 | 北京大学 | Titanium dioxide photoelectrode and preparation method thereof |
-
2015
- 2015-03-18 CN CN201510119013.5A patent/CN104762634B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101026199A (en) * | 2007-03-26 | 2007-08-29 | 浙江大学 | Method for for preparing cadmiumsulfide quantum dot sensitized porous titanium dioxide photoelectrode |
| CN101393938A (en) * | 2007-12-28 | 2009-03-25 | 北京大学 | Wide forbidden region semi-conductor nano tube/linear array film, preparation and photoelectric pole thereof |
| CN101894689A (en) * | 2010-07-26 | 2010-11-24 | 东南大学 | Quantum dot composite sensitization solar battery and preparation method of electrode thereof |
| CN102097214A (en) * | 2010-11-21 | 2011-06-15 | 沈阳工业大学 | Preparation method of zinc oxide-based solar cell electrode |
| CN102024572A (en) * | 2010-12-09 | 2011-04-20 | 华中科技大学 | Method for preparing sulfide quantum dot co-sensitization porous titanium dioxide photoelectrode |
| CN102760581A (en) * | 2011-04-25 | 2012-10-31 | 北京大学 | Titanium dioxide photoelectrode and preparation method thereof |
| CN102226284A (en) * | 2011-06-02 | 2011-10-26 | 厦门大学 | Method for performing photoelectrolysis of water and preparing hydrogen by using palladium quantum dot modified titanium dioxide nanotube array |
| CN102364648A (en) * | 2011-10-18 | 2012-02-29 | 西安交通大学 | Method for manufacturing sulfydryl bridge molecular bonded quantum dot and TiO2 nano compound light anode |
Non-Patent Citations (1)
| Title |
|---|
| A stable quantum dot photoelectrolysis cell for unassisted visible light solar water splitting;Hong bin Yang et al.;《ACS Nano》;20140930;第8卷;第10404页右栏第2段至第10405页右栏第2段、第10410页左栏第1段、图1a、1b、8a、8b * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104762634A (en) | 2015-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104762634B (en) | Optical electro-chemistry decomposes aquatic products hydrogen, the optoelectronic pole for producing oxygen and its preparation and application | |
| CN105239091B (en) | It is a kind of based on metal oxide, quantum dot and produce hydrogen catalyst photocathode and its preparation and application | |
| Wang et al. | Recent advances in bismuth vanadate-based photocatalysts for photoelectrochemical water splitting | |
| Sahai et al. | Quantum dots sensitization for photoelectrochemical generation of hydrogen: a review | |
| Jia et al. | 1D alignment of ZnO@ ZIF-8/67 nanorod arrays for visible-light-driven photoelectrochemical water splitting | |
| Hsieh et al. | Near infrared-driven photoelectrochemical water splitting: Review and future prospects | |
| Liu et al. | Aqueous synthesis of core/shell/shell CdSe/CdS/ZnS quantum dots for photocatalytic hydrogen generation | |
| Zeng et al. | ZnxCd1-xSe nanoparticles decorated ordered mesoporous ZnO inverse opal with binder-free heterojunction interfaces for highly efficient photoelectrochemical water splitting | |
| Reddy et al. | An efficient g-C3N4-decorated CdS-nanoparticle-doped Fe3O4 hybrid catalyst for an enhanced H2 evolution through photoelectrochemical water splitting | |
| Long et al. | Layered double hydroxide onto perovskite oxide-decorated ZnO nanorods for modulation of carrier transfer behavior in photoelectrochemical water oxidation | |
| Elemike et al. | Noble metal–semiconductor nanocomposites for optical, energy and electronics applications | |
| Mohamed et al. | Controlled synthesis of CdS nanoflowers thin films for H2 electro-generation | |
| Feng et al. | Fabrication of layered (CdS-Mn/MoS2/CdTe)-promoted TiO2 nanotube arrays with superior photocatalytic properties | |
| CN108806989A (en) | Nuclear shell structure quantum point, preparation method and application and light anode, solar energy electrochemical device with transition zone and application | |
| Shi et al. | Nanoscale heterostructures for photoelectrochemical water splitting and photodegradation of pollutants | |
| Zhang et al. | An anti-photocorrosive photoanode based on a CdS/NixSy@ NF heterostructure for visible-light-driven water splitting | |
| Abdelkarim et al. | Constructing quantum dots sensitized TiO2 nanotube pn heterojunction for photoelectrochemical hydrogen generation | |
| Hu et al. | Simple solid-state synthesis and improved performance of Ni (OH) 2-TiO2 nanocomposites for photocatalytic H2 production | |
| Liu et al. | Facile construction of a molybdenum disulphide/zinc oxide nanosheet hybrid for an advanced photocatalyst | |
| Hassan et al. | Photo-electrochemical water splitting through graphene-based ZnS composites for H2 production | |
| Wang et al. | Functionalized ZnO@ TiO 2 nanorod array film loaded with ZnIn 0.25 Cu 0.02 S 1.395 solid-solution: synthesis, characterization and enhanced visible light driven water splitting | |
| Sadhasivam et al. | CdS and CdSe nanoparticles activated 1D TiO2 heterostructure nanoarray photoelectrodes for enhanced photoelectrocatalytic water splitting | |
| Ikram et al. | Role and prospects of green quantum dots in photoelectrochemical hydrogen generation: A review | |
| Wannapop et al. | Enhanced visible light absorption of TiO2 nanorod photoanode by NiTiO3 decoration for high-performance photoelectrochemical cells | |
| Zhao et al. | Ultra-small colloidal heavy-metal-free nanoplatelets for efficient hydrogen generation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |