CN109482218A - It is a kind of to use Ni2The nanocrystalline light-catalysed method of enhancing of P - Google Patents
It is a kind of to use Ni2The nanocrystalline light-catalysed method of enhancing of P Download PDFInfo
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- CN109482218A CN109482218A CN201811469698.6A CN201811469698A CN109482218A CN 109482218 A CN109482218 A CN 109482218A CN 201811469698 A CN201811469698 A CN 201811469698A CN 109482218 A CN109482218 A CN 109482218A
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- water
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000005416 organic matter Substances 0.000 claims abstract description 5
- 238000004528 spin coating Methods 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004793 Polystyrene Substances 0.000 claims description 14
- 229920002223 polystyrene Polymers 0.000 claims description 12
- 239000002077 nanosphere Substances 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000011022 opal Substances 0.000 abstract description 28
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 7
- 238000005286 illumination Methods 0.000 description 6
- 230000005693 optoelectronics Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 229920002620 polyvinyl fluoride Polymers 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011805 ball Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910015335 Ni2In Inorganic materials 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- 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
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Abstract
Ni is used the present invention relates to a kind of2The nanocrystalline light-catalysed method of enhancing of P, it is the following steps are included: (a) loads TiO in substrate surface using hydro-thermal method2Array；(b) in the TiO2Array surface loads an at least strata styrene nanometer film；(c) product of step (b) is immersed in TiO 2 sol precursor solution, takes out dry be placed in oxygen atmosphere and calcines；Then on its surface, spin coating contains Ni2P nanocrystalline hexane solution, baking removes organic matter in glove box.Opal antistructure can not only be made sufficiently to carry out catalysis reaction, and Ni in this way2P also can be to TiO2Play extraordinary co-catalysis effect.
Description
Technical field
The invention belongs to field of nanometer material technology, are related to a kind of photochemical catalyst, and in particular to a kind of to use Ni2The nanocrystalline increasing of P
Strong light-catalysed method.
Background technique
The use of fossil energy not only brings the convenient prosperity with life to us, and following there are also the dirts of environment
Dye, and fossil energy belongs to the not renewable sources of energy, us is thus forced to seek the more clean energy.Combustion of hydrogen releases greatly
The energy of amount generates water, cleanliness without any pollution after burning.Currently, being respectively as follows: fossil energy there are mainly three types of the modes of hydrogen manufacturing
Recombination regeneration, electro-catalysis and photocatalysis.But the recombination of fossil energy regeneration still can generate CO2Equal gases, do not solve sky
Gas problem, electro-catalysis can consume a large amount of energy, and photocatalysis is due to being attracted attention using sunlight.
Using Photocatalyzed Hydrogen Production, there are mainly two types of systems: powder systems and optical electro-chemistry system at present
(Photoelectrochemical, that is, PEC system).Powder systems be by catalyst into the water, under the irradiation of sunlight just
Hydrogen and oxygen can be generated, but is carried out in a kind of catalyst simultaneously due to producing hydrogen and producing oxygen, to the separation of hydrogen and oxygen
Bring difficulty.And PEC system is the form using electrode, cathode can generate oxygen during reaction, and anode can generate hydrogen
Gas, convenient for efficiently separating for hydrogen and oxygen.Therefore efficiency of selection is high, low energy consumption, photochemical catalyst simple to operate then at
For people's urgent problem to be solved.
The position of energy band of photochemical catalyst should be greater than 1.8eV or more, therefore most photochemical catalyst is concentrated mainly on metal
Oxide.Due to TiO2It is nontoxic, the properties such as chemical stability is good and corrosion-resistant and become most classic metal oxide
Photochemical catalyst.But due to TiO2Forbidden bandwidth be 3.2eV, need biggish energy just its electrons and holes can be made to be divided
From.Therefore how TiO is improved2Photocatalysis performance also become all the time people research the problem of.
Summary of the invention
It provides the invention aims to overcome the deficiencies in the prior art using Ni2The nanocrystalline light-catalysed side of enhancing of P
Method.
In order to achieve the above objectives, the technical solution adopted by the present invention is that: it is a kind of use Ni2The nanocrystalline enhancing of P is light-catalysed
Method, it the following steps are included:
(a) TiO is loaded in substrate surface using hydro-thermal method2Array；
(b) in the TiO2Array surface loads an at least strata styrene nanometer film；
(c) product of step (b) is immersed in TiO 2 sol precursor solution, takes out drying and is placed on oxygen atmosphere
Middle calcining；Then on its surface, spin coating contains Ni2P nanocrystalline hexane solution, baking removing organic matter is in glove box
It can.
Optimally, step (a) the following steps are included:
(a1) stirring in aqueous hydrochloric acid solution is added in butyl titanate and extremely obtains the first precursor solution in colourless；
(a2) substrate is immersed in first precursor solution, is heated in baking oven to carry out hydro-thermal reaction, after cooling
Cleaning；
(a3) product of step (a2) is placed in Muffle furnace and is calcined.
Further, step (b) the following steps are included:
(b1) boiling will be carried out in the mixed solution for immersing water, hydrogen peroxide and ammonium hydroxide after Wafer Cleaning obtain hydrophilic table
Face, it is then with deionized water flushing and dry under stream of nitrogen gas；
(b2) step (b1) treated wafer sections are immersed in the water containing surfactant, makes pipe/polyhenylethylene nano
Ball solution is transferred to formation polystyrene nanospheres film on the water surface through the water-wetted surface；
(b3) with load TiO2The substrate of array extracts the polystyrene nanospheres film, dry.
Optimally, in step (c), the TiO 2 sol precursor solution is by being dissolved in ethyl alcohol and dense for isopropyl titanate
It is made in the mixed solution of hydrochloric acid.
Further, in step (c), the temperature of the calcining is 400~650 DEG C, and the temperature of baking is 250~350 DEG C.
Due to the above technical solutions, the present invention has the following advantages over the prior art: the present invention uses Ni2P
The nanocrystalline light-catalysed method of enhancing, by TiO2Array surface loads an at least strata styrene nanometer film, thus with this
Film is that template constructs titanium dioxide nanostructure (i.e. opal antistructure), then in TiO2Array and titanium dioxide nanostructure
Upper load Ni2P is nanocrystalline, and opal antistructure can not only be made sufficiently to carry out catalysis reaction, and Ni in this way2P also can be right
TiO2Play extraordinary co-catalysis effect.
Detailed description of the invention
Fig. 1 is that the present invention uses Ni2The flow diagram of the nanocrystalline light-catalysed method of enhancing of P；
Fig. 2 is the SEM figure of sample in embodiment 2: (a) TiO2The front elevation of opal antistructure；(b)TiO2Opal is anti-
The sectional view of structure；(c)TiO2/Ni2The front elevation of P opal antistructure；(d)TiO2/Ni2The section of P opal antistructure
Figure；
Fig. 3 is the linear voltammetric scan curve graph of sample in embodiment 2；
Fig. 4 is that time dependent current density figure of the sample under the irradiation of intermittent simulated solar irradiation is (outer inclined in embodiment 2
Pressure is 1.23V relative to RHE)；
Fig. 5 is the phototransformation efficiency curve graph that sample changes with applying bias in embodiment 2；
Fig. 6 is incident photon-current conversion efficiency figure of sample in embodiment 2；
Fig. 7 is hydrogen and oxygen evolution datagram of the sample under simulated solar irradiation irradiation in embodiment 2；
Fig. 8 is for sample in embodiment 2 in 24 hours internal stability figures under simulated solar irradiation irradiation.
Specific embodiment
The present invention uses Ni2The nanocrystalline light-catalysed method of enhancing of P, it is the following steps are included: (a) uses hydro-thermal method in base
Bottom surface loads TiO2Array；(b) in the TiO2Array surface loads an at least strata styrene nanometer film；(c) by step
(b) product immerses in TiO 2 sol precursor solution, takes out dry be placed in oxygen atmosphere and calcines；Then in its table
Face spin coating contains Ni2P nanocrystalline hexane solution, baking removes organic matter in glove box.By in TiO2Array table
Face loads an at least strata styrene nanometer film, to construct titanium dioxide nanostructure using the film as template, (i.e. opal is anti-
Structure), then in TiO2Ni is loaded on array and titanium dioxide nanostructure2P is nanocrystalline, can not only make opal in this way
Antistructure sufficiently carries out catalysis reaction, and Ni2P also can be to TiO2Play extraordinary co-catalysis effect.
Step (a) preferably includes following steps: it is extremely in colourless that stirring in aqueous hydrochloric acid solution, which is added, in butyl titanate by (a1)
Obtain the first precursor solution；(a2) substrate is immersed in first precursor solution, is heated in baking oven anti-to carry out hydro-thermal
It answers, is cleaned after cooling；(a3) product of step (a2) is placed in Muffle furnace and is calcined.Step (b) preferably includes following step
Rapid: (b1) will carry out boiling in the mixed solution for immersing water, hydrogen peroxide and ammonium hydroxide after Wafer Cleaning and obtain water-wetted surface, then
It is rinsed with deionized water and dry under stream of nitrogen gas；(b2) step (b1) treated wafer sections are immersed living containing surface
In the water of property agent, it is transferred to polystyrene nanospheres solution on the water surface through the water-wetted surface and forms polystyrene nanospheres
Film；(b3) with load TiO2The substrate of array extracts the polystyrene nanospheres film, dry.In step (c), described two
Titanium oxide sol precursor solution is made by being dissolved in isopropyl titanate in the mixed solution of ethyl alcohol and concentrated hydrochloric acid.In step (c),
The temperature of the calcining is 400~650 DEG C, and the temperature of baking is 250~350 DEG C.
Below in conjunction with embodiment, invention is further explained.
Embodiment 1
Ni is used the present embodiment provides a kind of2The nanocrystalline light-catalysed method of enhancing of P, as shown in Figure 1, it includes following step
It is rapid:
(a) using hydro-thermal method in substrate (FTO) area load TiO2Array；Specifically:
(a1) 50mL water is added in the beaker of 150ml and the concentrated hydrochloric acid (concentration 30wt%) of 50mL stirs
Hydrochloric acid solution is obtained, then addition 2mL butyl titanate stirs to colourless and obtains the first precursor solution；
(a2) by the tin oxide of Fluorin doped (FTO) electro-conductive glass (having a size of 1.0 × 4.0cm) successively in acetone, ethyl alcohol, go
It is cleaned by ultrasonic 10 minutes in ionized water, then dries under nitrogen flowing；It then leans against in the polyvinyl fluoride bottle of 25mL and (just faces
Under), the first precursor solution for taking 10ml above-mentioned is added in polyvinyl fluoride bottle, so that the first predecessor is immersed in electro-conductive glass part
In solution；Polyvinyl fluoride bottle is put into reaction kettle, in 160 DEG C of heat preservation 1h in baking oven, is cooled to room temperature；
(a3) FTO is taken out, with a large amount of deionized water and ethyl alcohol repeated flushing, is then spontaneously dried；After drying
FTO is placed in Muffle furnace 450 DEG C of calcining 2h (heating and cooling rate are each about 5 DEG C/min), is remembered after being cooled to room temperature
Load TiO2The FTO of array；
(b) in above-mentioned TiO2Array surface loads an at least strata styrene nanometer film；Specifically:
(b1) silicon wafer for cutting 6cm × 3cm, with acetone, ethyl alcohol and deionized water successively ultrasound 5min, then with water, peroxidating
The mixed solution of hydrogen and ammonium hydroxide 1:1:4 (volume is respectively 20mL, 20mL, 80mL) by volume boil half under conditions of 150 DEG C
A hour, silicon chip surface is made to reach hydrophilic effect；Finally rinsed with a large amount of deionized water and it is dry under stream of nitrogen gas in case
With；
(b2) water of 300mL or so is added in the clean surface ware that diameter is 14cm, is added with the syringe of 50mL
The aqueous solution about 10 of 2wt% lauryl sodium sulfate (SDS, surfactant) drips；Step (b1) treated silicon wafer is leaned on
Surface plate edge is leaned against, is immersed in the water its part, other parts are exposed in air；Drawing diameter with microsyringe is
Polystyrene (PS) the nanosphere solution (concentration 7.5%, commercially available, Sigma) of 200nm, is slowly added into through silicon chip surface, from
And enters the water surface and form the closelypacked polystyrene nanospheres single layer of hexagonal；Added again after being added dropwise with the syringe of 50mL
The aqueous solution for entering 2wt%SDS stablizes monofilm；
(b3) with load TiO2The FTO of array extracts polystyrene nanospheres film, places to moisture and sufficiently scatters and disappears；
(c) product of step (b) (i.e. sample) is dipped vertically into TiO 2 sol precursor solution (in the burning of 30mL
20mL ethyl alcohol, the commercially available concentrated hydrochloric acid of 0.1mL and 0.4mL isopropyl titanate are added in cup, ultrasound mixes) 1min, take out room temperature from
It is so dry；Above-mentioned sample is placed in Muffle furnace and obtains TiO in 550 DEG C of calcining 3h (heating and rate of temperature fall all about 3/min)2-
Opal antistructure；50 μ L Ni are pipetted using the liquid-transfering gun of 100 μ L2P nanocrystalline hexane solution (concentration 2g/L) is put into
TiO2The middle of opal antistructure carries out spin coating with the speed of 3000r/s；It repeats five times, which is put into glove box
320 DEG C of bakings are carried out with can be to get TiO by organic matter removal2/Ni2P opal antistructure electrode.
Embodiment 2
Ni is used the present embodiment provides a kind of2The light-catalysed method of the nanocrystalline enhancing of P, basic one in it and embodiment 1
It causes, unlike: step (b2) and step (b3) are repeated once, in this way in TiO2Two layers of styrene of the surface appendix of array is received
Rice ball film；Obtained TiO2Shown in opal antistructure such as Fig. 2 (a)-Fig. 2 (b)；Finally obtained TiO2/Ni2P opal reef knot
Shown in structure such as Fig. 2 (c)-Fig. 2 (d).It can be seen that the bilevel structure using PS bead as template is mutual from Fig. 2 (a)
It is staggered, this structure is conducive to Ni2P is nanocrystalline to be smoothly supported on TiO2On to reach better catalytic effect；It can from Fig. 2 (b)
To find out TiO2It is vertically long in FTO substrate, and in TiO2Top exactly prepares resulting opal reef knot by template of PS bead
The structure of structure；From Fig. 2 (c) into Fig. 2 (d) it can be seen that Ni2P is nanocrystalline both to have been loaded in opal antistructure or in TiO2On
Load, this is conducive to that opal antistructure is not only made sufficiently to carry out catalysis reaction, while Ni in catalytic process2P is to TiO2Also can
Play extraordinary co-catalysis effect.
Embodiment 3
Ni is used the present embodiment provides a kind of2The light-catalysed method of the nanocrystalline enhancing of P, basic one in it and embodiment 1
It causes, unlike: step (b2) and step (b3) are repeated twice, in this way in TiO2Three layers of styrene of the surface appendix of array are received
Rice ball film.
Comparative example 1
This example only provides a kind of TiO2The preparation method of array, it is consistent with the step (a) in embodiment 1.
By TiO obtained in embodiment 22Opal antistructure, TiO2/Ni2In P opal antistructure and comparative example 1
TiO2Array is tested for the property, and the result is shown in shown in Fig. 3 to Fig. 8.It is shown in Fig. 3 to be, TiO2、TiO2Opal antistructure with
TiO2/Ni2One group volt-ampere linear scanning data of these three the optoelectronic pole of P opal antistructure under illumination condition, can from figure
To find out that starting potential of the optoelectronic pole of these three under illumination condition is about 0.3V (relative to RHE)；When additional potential is super
When crossing 0.3V, current density increases sharply and quickly reaches saturation, this illustrates that these optoelectronic poles have extraordinary photoproduction
Carrier separation and absorption.Shown in Fig. 4 is the photoelectricity density changed over time under intermittent illumination condition, this, which tests, to be used
Indicate the photoelectric respone behavior under continuous visible light exposure, it is with incident photon-current conversion efficiency in Fig. 6 consistent.
The TiO in Fig. 62、TiO2Opal antistructure electrode does not show considerable photoelectric respone under continuous radiation of visible light,
And TiO2/Ni2P opal antistructure electrode but shows transient state and the photoelectric respone behavior of significant ground.This may be because of Ni2P
It is nanocrystalline to capture TiO rapidly2In the hole that illumination condition generates.Fig. 5 is photoelectric conversion efficiency, as can be seen from the figure this
TiO2、TiO2Opal antistructure and TiO2/Ni2The maximum photoelectric conversion efficiency of three kinds of electrodes of P opal antistructure is respectively
0.2%, 0.3% and 0.86%.Shown in Fig. 7 is that aquatic products is decomposed in the crystal form optical electro-chemistry collaboration under illumination condition of four kinds of optoelectronic poles
The precipitation data of raw hydrogen and oxygen.For all electrodes, hydrogen and oxygen are existed respectively with the stoichiometry of 2:1
Platinum on electrode and working electrode to being precipitated.It can be seen that hydrogen is precipitated in the optical electro-chemistry of these three optoelectronic poles from the precipitation data in figure
The amount of gas to big sequence successively are as follows: TiO2(3.1μmol)<TiO2Opal antistructure (5.9 μm of ol) < TiO2/Ni2P albumen
Stone antistructure (27.6 μm of ol).Fig. 8 is this TiO in 24 hours2、TiO2Opal antistructure and TiO2/Ni2P opal reef knot
Three kinds of electrodes of structure are in illumination condition stability inferior, it can be seen that three kinds of electrodes before the reaction with reaction 24 hours after its current density
Variation less, illustrates that these three electrodes have good stability.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (5)
1. a kind of use Ni2The light-catalysed method of the nanocrystalline enhancing of P, which is characterized in that it the following steps are included:
(a) TiO is loaded in substrate surface using hydro-thermal method2Array；
(b) in the TiO2Array surface loads an at least strata styrene nanometer film；
(c) product of step (b) is immersed in TiO 2 sol precursor solution, takes out dry be placed in oxygen atmosphere and forges
It burns；Then on its surface, spin coating contains Ni2P nanocrystalline hexane solution, baking removes organic matter in glove box.
2. according to claim 1 use Ni2The light-catalysed method of the nanocrystalline enhancing of P, which is characterized in that step (a) includes
Following steps:
(a1) stirring in aqueous hydrochloric acid solution is added in butyl titanate and extremely obtains the first precursor solution in colourless；
(a2) substrate is immersed in first precursor solution, is heated in baking oven to carry out hydro-thermal reaction, is cleaned after cooling；
(a3) product of step (a2) is placed in Muffle furnace and is calcined.
3. according to claim 1 or 2 use Ni2The nanocrystalline light-catalysed method of enhancing of P, which is characterized in that step (b)
The following steps are included:
(b1) boiling will be carried out in the mixed solution for immersing water, hydrogen peroxide and ammonium hydroxide after Wafer Cleaning obtain water-wetted surface, with
It is afterwards with deionized water flushing and dry under stream of nitrogen gas；
(b2) step (b1) treated wafer sections are immersed in the water containing surfactant, keeps polystyrene nanospheres molten
Liquid (PS) is transferred to formation polystyrene nanospheres film on the water surface through the water-wetted surface；
(b3) with load TiO2The substrate of array extracts the polystyrene nanospheres film, dry.
4. according to claim 1 use Ni2The nanocrystalline light-catalysed method of enhancing of P, it is characterised in that: in step (c),
The TiO 2 sol precursor solution is made by being dissolved in isopropyl titanate in the mixed solution of ethyl alcohol and concentrated hydrochloric acid.
5. according to claim 4 use Ni2The nanocrystalline light-catalysed method of enhancing of P, it is characterised in that: in step (c),
The temperature of the calcining is 400~650 DEG C, and the temperature of baking is 250~350 DEG C.
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| CN110681403A (en) * | 2019-10-24 | 2020-01-14 | 吉林师范大学 | Preparation method of defective titanium dioxide/nickel phosphide heterojunction visible-light-induced photocatalyst |
| CN115613037A (en) * | 2022-09-28 | 2023-01-17 | 中国科学院海洋研究所 | Ni 2 P/TiO 2 S-type heterojunction photo-anode material and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110681403A (en) * | 2019-10-24 | 2020-01-14 | 吉林师范大学 | Preparation method of defective titanium dioxide/nickel phosphide heterojunction visible-light-induced photocatalyst |
| CN115613037A (en) * | 2022-09-28 | 2023-01-17 | 中国科学院海洋研究所 | Ni 2 P/TiO 2 S-type heterojunction photo-anode material and application thereof |
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