CN110496616A - The boron-doped diamond and preparation method and application of the carried metal of photoelectrocatalysis - Google Patents
The boron-doped diamond and preparation method and application of the carried metal of photoelectrocatalysis Download PDFInfo
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- CN110496616A CN110496616A CN201910817545.4A CN201910817545A CN110496616A CN 110496616 A CN110496616 A CN 110496616A CN 201910817545 A CN201910817545 A CN 201910817545A CN 110496616 A CN110496616 A CN 110496616A
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- boron
- doped diamond
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- 239000010432 diamond Substances 0.000 title claims abstract description 224
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 222
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 93
- 239000002184 metal Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims description 20
- 239000000758 substrate Substances 0.000 claims abstract description 92
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 31
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- 238000006722 reduction reaction Methods 0.000 claims description 33
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 21
- 229910052796 boron Inorganic materials 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 18
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 16
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052737 gold Inorganic materials 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000004544 sputter deposition Methods 0.000 claims description 10
- 239000013077 target material Substances 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 239000011435 rock Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
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- 230000003197 catalytic effect Effects 0.000 abstract description 34
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- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 5
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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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
- B01J35/33—Electric or magnetic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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Abstract
The present invention provides a kind of boron-doped diamonds of the carried metal of photoelectrocatalysis, the boron-doped diamond of the carried metal includes substrate, the boron-doped diamond layer of any side of the substrate is set, the boron-doped diamond layer include planarizing underlayer and perpendicular to the planarizing underlayer pyramidal structure layer and uniform load the tip of the pyramidal structure layer metal nanoparticle catalyst.The selectivity of the boron-doped diamond of the carried metal of photoelectrocatalysis catalytic activity with higher, stability and chemical process greatly improves the selectivity and efficiency of catalytic process.
Description
Technical field
The present invention relates to optical electro-chemistry catalysis electrode field more particularly to the boron doping Buddha's warrior attendants of the carried metal of photoelectrocatalysis
Stone and preparation method and application.
Background technique
As population in the world constantly increases, the increasingly depleted and Global Environmental Problems of fossil fuel are increasingly severe, energy
Conventional fossil fuel is enough substituted, realizes that the exploration of the New-type fuel of the sustainable use of the energy is compeled while mitigating environmental pressure
The eyebrows and eyelashes.Ammonia is mainly used for the production of chemical fertilizer in chemical process, for solving the problems, such as that world food plays an important role, while it
It is the energy carrier of green, is potential energy source fuel.
Nitrogen reduction generates ammonia main function and is Chemical Manufacture, growth of the ammonia to crops is synthesized, for solving the whole world
Food problem has very big significance.Currently, the main method that nitrogen restores ammonia processed in industrial production is using Haber-Bo Shite
Method, the process conditions that Haber-Bo Shitefa needs are more harsh, and reaction temperature needs to be maintained within the scope of 300-500 DEG C, pressure
It needs to be maintained between 150-300atm, hydrogen is also indispensable one of raw material, and the energy that simultaneous reactions need derives from
The burning of fossil fuel, this produces a large amount of carbon dioxide again, increases environmental pressure.Using optical electro-chemistry be catalyzed reaction or
Electrochemical catalysis reaction carries out the reaction of reduction nitrogen, compared with traditional Haber-Bo Shitefa, optical electro-chemistry catalytic reduction of nitrogen
Gas generates ammonia and has the advantage that (1) reduction technique mild condition；(2) it does not need to consume a large amount of energy, reduces carbon foot
Mark；(3) equipment is simple, avoids and builds complicated consersion unit in the factory
It is reduced into whether ammonia reaction can efficiently carry out using photoelectrocatalysis or electro-catalysis nitrogen, largely takes
Certainly in the design of catalysis electrode.Conventional electrode materials lead to reaction speed since the adsorption capacity for nitrogen is poor, stability is lower
Rate is slow, catalytic capability is weak.Meanwhile the intermediate energy for participating in reaction is high, and reaction is caused to be difficult to continue, so that reduction
Low yield limits its use.
Summary of the invention
The purpose of the present invention is to provide boron-doped diamonds of carried metal of a kind of photoelectrocatalysis and preparation method thereof
And application, it is intended to solve the problems, such as that the electrode material stability reacted in the prior art for photoelectrocatalysis is poor, catalytic capability is weak.
For achieving the above object, The technical solution adopted by the invention is as follows:
A kind of boron-doped diamond of the carried metal of photoelectrocatalysis, the boron-doped diamond of the carried metal includes base
Bottom, is arranged in the boron-doped diamond layer of any side of the substrate, and the boron-doped diamond layer includes planarizing underlayer and hangs down
The directly metal nanoparticle in the pyramidal structure layer of the planarizing underlayer and uniform load at the tip of the pyramidal structure layer
Catalyst.
And a kind of preparation method of the boron-doped diamond of the carried metal of photoelectrocatalysis, include the following steps:
Offer boron-doped diamond is carrier, and the boron-doped diamond includes a substrate, and is arranged in the substrate
The boron-doped diamond layer of any side；
Processing is performed etching on the surface of the boron-doped diamond layer of any side of the substrate, obtaining that treated, boron is mixed
Miscellaneous diamond layer, described treated that boron-doped diamond layer includes planarizing underlayer and the taper knot perpendicular to the planarizing underlayer
Structure layer；
Metal targets are provided, metal is carried out on the surface of the boron-doped diamond carrier by the way of magnetron sputtering and splashes
Processing is penetrated, the boron-doped diamond of the carried metal of the photoelectrocatalysis is obtained.
And a kind of photoelectrocatalysis reduction reaction electrode, the material of the reduction reaction electrode are above-mentioned photoelectrocatalysis
Carried metal boron-doped diamond or the photoelectrocatalysis being prepared by above-mentioned method carried metal boron doping gold
Hard rock.
And the boron-doped diamond or prepared by the above method of the carried metal comprising above-mentioned photoelectrocatalysis
Application of the electrode of the boron-doped diamond of the carried metal of photoelectrocatalysis in photoelectrocatalysis reduction reaction.
Compared with prior art, the present invention provides the boron-doped diamond of the carried metal of photoelectrocatalysis, including substrate, if
Set the boron-doped diamond layer in any side of the substrate, the boron-doped diamond layer includes planarizing underlayer and perpendicular to institute
State planarizing underlayer pyramidal structure layer and uniform load the tip of the pyramidal structure layer metal nanoparticle.Wherein,
For the boron-doped diamond layer as carrier, diamond is semiconductor material with wide forbidden band, and the boron doped diamond of high concentration can be with
Excellent electric conductivity is obtained, it can be achieved that semimetal even metallic conductivity, resistivity is low, stability height provides electronics for reaction,
Accelerate reaction to carry out, improves reaction rate；Wherein, the boron-doped diamond layer includes planarizing underlayer and perpendicular to described smooth
The pyramidal structure layer of bottom forms pyramidal structure layer, can make it have bigger specific surface area, can be conducive to more metals
The load of catalyst enhances catalytic activity；Metal nanoparticle catalyst uniform load is in the tip of pyramidal structure layer position
It sets, metal nanoparticle and boron-doped diamond carrier interact, and this interaction is so that metallic atom has low coordination
And maximum atom utilization efficiency, keep the boron-doped diamond of the carried metal for the photoelectrocatalysis being prepared with higher
The selectivity of catalytic activity, stability and chemical process greatly improves the selectivity and efficiency of catalytic process.
The preparation method of the boron-doped diamond of the carried metal of the photoelectrocatalysis provided by the invention, first offer boron
Doped diamond carrier performs etching processing to the surface of the boron-doped diamond layer of any side of the substrate, is handled
Boron-doped diamond layer afterwards, treated boron-doped diamond layer the includes planarizing underlayer and perpendicular to the planarizing underlayer
Pyramidal structure layer；Metal targets are provided again, by the way of magnetron sputtering the surface of the boron-doped diamond carrier into
Row metal sputter process obtains the boron-doped diamond of the carried metal；Used magnetically controlled sputter method is easy, quickly,
It is easily controllable, using the method for magnetron sputtering also can guarantee that metal nanoparticle and boron-doped diamond carrier are biggish attached simultaneously
Put forth effort, stability of material is good, improves catalytic efficiency, is conducive to industrial applications.
Photoelectrocatalysis reduction reaction electrode provided by the invention, the material of the photoelectrocatalysis reduction reaction electrode are above-mentioned
Photoelectrocatalysis carried metal boron-doped diamond or the photoelectrocatalysis being prepared by above-mentioned method carried metal
Boron-doped diamond, using the boron-doped diamond of carried metal as the material of working electrode carry out photoelectrocatalysis reduction reaction
During, the reduction reaction catalytic activity with higher, the catalytic rate of electrode reaches higher level.
The boron-doped diamond of carried metal provided by the invention comprising above-mentioned photoelectrocatalysis or by above method system
The electrode of the boron-doped diamond of the carried metal of standby obtained photoelectrocatalysis includes light in the application of photoelectrocatalysis reduction reaction
The chemical reactions such as electro-catalysis nitrogen reduction.
Detailed description of the invention
Fig. 1 is the boron-doped diamond electrode of the load gold nano grain for the photoelectrocatalysis that the embodiment of the present invention 1 provides
Schematic diagram.
Fig. 2 is the schematic diagram of the boron-doped diamond electrode for the load gold nano grain that comparative example 1 of the present invention provides.
Fig. 3 is the schematic diagram for the boron-doped diamond electrode that comparative example 3 of the present invention provides.
Fig. 4 is the signal of the embodiment of the present invention 2, comparative example 2, the progress photoelectrocatalysis nitrogen reduction reaction of the offer of comparative example 4
Figure.
Specific embodiment
To keep the purpose, technical solution and technical effect of the embodiment of the present invention clearer, the present invention will be implemented below
Technical solution in example is clearly and completely described, it is clear that and described embodiments are some of the embodiments of the present invention, and
The embodiment being not all of.In conjunction with the embodiment in the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
The embodiment of the invention provides a kind of boron-doped diamond of the carried metal of photoelectrocatalysis, the carried metal
Boron-doped diamond includes substrate, and the boron-doped diamond layer of any side of the substrate, the boron-doped diamond is arranged in
Layer include planarizing underlayer and perpendicular to the planarizing underlayer pyramidal structure layer and uniform load in the pyramidal structure layer
The metal nanoparticle catalyst at tip.
Specifically, the boron-doped diamond of the carried metal includes substrate, it is preferred that the material of the substrate is selected from silicon
Piece, chromium piece, titanium net, carbon cloth, molybdenum net any one material.In a preferred embodiment of the invention, select chromium piece as substrate into
Row subsequent processing.
Specifically, the boron-doped diamond layer of any side of the substrate is arranged in, the boron-doped diamond layer includes
Planarizing underlayer and pyramidal structure layer perpendicular to the planarizing underlayer.The boron-doped diamond layer, which is arranged, can be used as subsequent processing
Carrier, using the boron-doped diamond layer as carrier, diamond is semiconductor material with wide forbidden band, and high concentration is boron doped
Diamond can obtain excellent electric conductivity, it can be achieved that semimetal even metallic conductivity, resistivity is low, and it is anti-that stability is high
Electronics should be provided, reaction is accelerated to carry out, improve reaction rate.Further, the boron-doped diamond layer includes planarizing underlayer
With the pyramidal structure layer perpendicular to the planarizing underlayer, pyramidal structure layer is formed, bigger specific surface area, energy can be made it have
Enough be conducive to the load of more multimetal reforming catalyst, enhance catalytic activity.Preferably, the boron-doped diamond layer with a thickness of
500nm-10μm.If obtained boron-doped diamond thickness spend it is thin, will lead to thin diamond membrane stability it is poor, deposition not
Uniformly；If obtained boron-doped diamond thickness spends thickness, more easy to fall off, subsequent use is influenced.It is preferably implemented in the present invention
Example in, the boron-doped diamond layer with a thickness of 10 μm.
Preferably, the planarizing underlayer with a thickness of 500nm~5 μm；The height of the pyramidal structure layer is the μ of 500nm~2
m.It is further preferred that the base diameter of pyramidal structure is 100 μm~1 μm in the pyramidal structure layer；The tip of pyramidal structure
Radius of curvature is no more than 20nm.
Specifically, the metal nanoparticle catalyst uniform load, at the tip of the pyramidal structure layer, catalyst is equal
The even tip for being supported on the pyramidal structure layer makes the exposed achievable catalysis characteristics of most of catalysed particulate, metal nanoparticle
It interacts with boron-doped diamond layer, this interaction is so that there is metallic atom low coordination and maximum atom to utilize
Efficiency, make the metal nanoparticle being prepared load boron-doped diamond catalytic activity with higher, stability and
The selectivity of electrochemical process greatly improves the selectivity and efficiency of catalytic process.Preferably, the metal nanoparticle is selected from
Any one of gold, silver, platinum, ruthenium, palladium, iridium, niobium, molybdenum, the metal nanoparticle are noble metal, and noble metal possesses good urge
Change activity and stability, the service life of electrode can be extended, it can be with stronger absorption nitrogen molecule, so that catalysis reaction can
To go on smoothly on its surface, reaction rate is improved.
Preferably, the partial size of the metal nanoparticle catalyst is 0.1nm~20nm.Wherein, the size of catalyst is
Influence a key factor of catalytic activity.In the presence of catalyst is with bulk form, their catalytic performance depends on them
Exposed surface, catalytic effect are poor；When partial size is reduced to nano-scale range, nonmetallic characteristic will be generated, including
Some new response characteristics and higher catalysis characteristics.Preferably, the partial size of the catalyst is 0.1nm~20nm.If catalysis
The partial size of particle is too small, then be easy to cause a large amount of aggregations, and catalytic effect is poor；If the partial size of catalysed particulate is excessive, does not have and urge
Change effect.
Preferably, the load area of the metal nanoparticle catalyst accounts for the ratio of the boron-doped diamond level product
For 10%-20%.If catalyst load area is excessive, metal nanoparticle is excessive, then in the boron-doped diamond taper
The aggregation of structure tip is excessive, and it is bad that it will cause catalytic effects；If catalyst load area is very few, the metal nanoparticle
Very few, then catalytic efficiency is not high enough, and catalytic effect is poor.
The present invention provides the boron-doped diamond of the carried metal of photoelectrocatalysis, including substrate, and setting is appointed in the substrate
The boron-doped diamond layer of meaning side, the boron-doped diamond layer includes planarizing underlayer and the cone perpendicular to the planarizing underlayer
The metallic catalyst of shape structure sheaf and uniform load at the tip of the pyramidal structure layer.Wherein, the boron-doped diamond
Layer is used as carrier, and diamond is semiconductor material with wide forbidden band, and the boron doped diamond of high concentration can obtain excellent electric conductivity,
Semimetal even metallic conductivity can be achieved, resistivity is low, and stability is high, provides electronics for reaction, reaction is accelerated to carry out, improve
Reaction rate；Wherein, the boron-doped diamond layer includes planarizing underlayer and the pyramidal structure layer perpendicular to the planarizing underlayer,
Pyramidal structure layer is formed, bigger specific surface area can be made it have, the load of more multimetal reforming catalyst can be conducive to, is enhanced
Catalytic activity；Metal nanoparticle catalyst uniform load the pyramidal structure layer tip location, metal nanoparticle with
The interaction of boron-doped diamond carrier, this interaction is so that there is metallic atom low coordination and maximum atom to utilize
Efficiency, make the boron-doped diamond of the carried metal for the photoelectrocatalysis being prepared catalytic activity with higher, stability with
And the selectivity of chemical process, greatly improve the selectivity and efficiency of catalytic process.
Correspondingly, the boron-doped diamond of the carried metal of above-mentioned photoelectrocatalysis is prepared by the following method to obtain.
The embodiment of the invention provides a kind of preparation methods of the boron-doped diamond of the carried metal of photoelectrocatalysis, including
Following steps:
S01. providing boron-doped diamond is carrier, and the boron-doped diamond includes a substrate, and is arranged described
The boron-doped diamond layer of any side of substrate；
S02. processing is performed etching on the surface of the boron-doped diamond layer of any side of the substrate, obtains that treated
Boron-doped diamond layer, described treated that boron-doped diamond layer includes planarizing underlayer and the cone perpendicular to the planarizing underlayer
Shape structure sheaf；
S03., metal targets are provided, carry out gold on the surface of the boron-doped diamond carrier by the way of magnetron sputtering
Belong to sputter process, obtains the boron-doped diamond of the carried metal of the photoelectrocatalysis.
Specifically, providing substrate in step S01, it is preferred that the material of the substrate be selected from silicon wafer, chromium piece, titanium net,
Any one material of carbon cloth, molybdenum net.In a preferred embodiment of the invention, the base material selects chromium piece.Preferably, described
The area of base material is 4 × 4~10 × 10cm2, with a thickness of 0.5mm.
Preferably, the substrate is subjected to pre-treatment, the pre-treatment is that acid solution, organic solvent progress ultrasound is respectively adopted
Processing, then be placed in nano-diamond powder suspension and be ultrasonically treated 1~3 hour.It is further preferred that being carried out using acid solution to substrate
Ultrasonic treatment, in order to clean the impurity of substrate surface, while form defect in substrate surface, facilitate at subsequent deposition
Reason.In a preferred embodiment of the invention, the mixed solution of hydrogen peroxide and the concentrated sulfuric acid is selected to carry out pickling processes, wherein peroxide
The volume ratio for changing hydrogen solution and concentrated sulfuric acid solution is 10:1.Preferably, the time that addition acid solution is ultrasonically treated is 30~40
Minute.
It is further preferred that first being carried out with acetone in the step of being ultrasonically treated using organic solvent to the substrate
Ultrasonic cleaning, handled using acetone, based on acetone have it is good fat-soluble and water-soluble, first handled with acetone,
The organic impurities of substrate material surface can be subjected to dissolution cleaning.Preferably, the additive amount of the acetone is 50mL, and ultrasound is clear
The time washed is 10~20 minutes.
Acetone is cleaned by ultrasonic and then is cleaned by ultrasonic with ethyl alcohol, by further ethyl alcohol being used to clean, can incite somebody to action
The impurity not cleaned up and the removal of remaining acetone soln, guarantee that substrate material surface does not have impurity, meanwhile, in substrate material
Material forms uneven microscopic surface texture；The rough microscopic surface texture is to plant brilliant site, the brilliant site of the plant
Stablize the position of absorption for diamond seeds.Be conducive to the subsequent processing of base material.Preferably, the additive amount of ethyl alcohol is
50mL, the time of ultrasonic cleaning are 10~20 minutes.
It is further preferred that being ultrasonically treated and then being placed in Nano diamond using organic solvent to the substrate
Be ultrasonically treated 1~3 hour in powder suspension, it is preferred that the nano-diamond powder suspension the preparation method is as follows: provide 1-5mL
100-400mL deionized water is added in the diamond solution of purchase.The nano-diamond powder suspension grain diameter being prepared
Size is 1-100nm.Guarantee submergence base material when adding solution.Diamond seeds are implanted on the surface of base material,
It is prepared for subsequent deposition processing.If sonication treatment time is too short, Nano diamond can not equably be implanted into base material
Surface will cause surface diamond crystal seed if ultrasonic time is too long and fall off, influence subsequent deposition processes.
Preferably, the substrate is placed in nano-diamond powder suspension and is ultrasonically treated 1~3 hour and then in room temperature
Under substrate is dried in inert gas flow, guarantee subsequent deposition treatment process in there is no impurity.It is excellent in the present invention
During choosing is implemented, the inert gas flow selects stream of nitrogen gas, is handled in stream of nitrogen gas, avoids introducing it in preparation process
His impurity.
Preferably, boron-doped diamond is prepared on any side of the substrate using heated filament chemical vapor deposition method
Layer.Preferably, the specific operation method is as follows for the heated filament chemical vapor deposition method:
S11. pretreated chromium piece substrate will have been carried out to be placed on the base station of heated filament vapor deposition apparatus, kept chromium piece
It is among heated filament and parallel with heated filament；The spacing on heated filament and chromium piece surface is 20mm.
S12. pressure in furnace is evacuated to 0.1Pa hereinafter, then passing to reaction gas carries out deposition reaction.
Wherein, in above-mentioned steps S11, it is preferred that it is the tantalum wire of 0.5~0.6mm, the heat that the heated filament, which selects diameter,
The quantity of silk is 9~10 heated filaments.It is further preferred that keeping chromium piece among heated filament and parallel with heated filament, wherein the heat
The spacing on silk and chromium piece surface is 6~25mm, and the hot-wire temperature is 2000-2400 DEG C, heater power 5000-
7000W, the temperature of chromium piece substrate are 500-850 DEG C.In a preferred embodiment of the invention, selecting 9 diameters is the tantalum wire of 0.5mm
As heated filament, and keeping the heated filament is 20mm at a distance from chromium piece surface；Keeping hot-wire temperature is 2000 DEG C, and heater power is
6900W, chromium piece base reservoir temperature are 500 DEG C.
In above-mentioned steps S12, it is preferred that the reaction gas total gas pressure being passed through is 1000-5000Pa, general gas flow
For 500sccm.It is further preferred that the reaction gas is inert gas, CH4、H2, trimethyl borine (Trimethyl
Boron, TMB) mixed gas, wherein CH4As the carbon source of diamond deposition, CH4Concentration is 1.5-5%；Trimethyl borine
It is the mixed gas of trimethyl borine and hydrogen, trimethyl borine is dense in mixed gas as the boron dopant source of BDD deposition
Degree is 0.1%~1%.H2Effect is performed etching to the carbon of non-diamond；The effect of inert gas is to maintain general gas flow not
Become, in a preferred embodiment of the invention, the inert gas is argon gas.In a preferred embodiment of the invention, the reaction gas
For Ar, CH4、H2, trimethyl borine (Trimethyl Boron, TMB) mixed gas.In the specific embodiment of the invention, if
Setting be passed through total gas couette is 500sccm, wherein reaction gas guarantees each gas CH4、H2, Ar, TMB flow be
10sccm、100sccm、370sccm、20sccm。
Preferably, it is passed through after gas, adjustment deposition pressure is 1500Pa；Preferred volume is heavy using heated filament gas chemistry
Area method in the step of any side of the substrate prepares boron-doped diamond layer, sink by the heated filament chemical vapor deposition method
The product time is 8~10 hours, diamond thin can be made to start forming core and growth, boron-doped diamond layer is prepared.At this
It in invention preferred embodiment, is passed through after gas, adjustment deposition pressure is 1500Pa, is arranged sedimentation time 10 hours, obtains thickness
About 10 μm of boron-doped diamond layer is spent to get boron-doped diamond carrier is arrived.
Specifically, performing etching place on the surface of the boron-doped diamond layer of any side of the substrate in step S02
Reason, the boron-doped diamond layer that obtains that treated, treated boron-doped diamond layer the includes planarizing underlayer and perpendicular to
The pyramidal structure layer of the planarizing underlayer.By performing etching processing to the boron-doped diamond carrier, planarizing underlayer is obtained
With the pyramidal structure layer perpendicular to the planarizing underlayer, the pyramidal structure layer can increase the ratio table of boron-doped diamond carrier
Area makes in subsequent processes, can increase the quantity of loaded catalysed particulate, can further increase catalytic effect.It is excellent
Choosing, the method for the etching processing are as follows: after above-mentioned deposition processes, the distance between substrate and tantalum wire are reduced into
5cm, CH4Gas flow be adjusted to 10sccm, H2Gas flow be adjusted to 490sccm, other conditions are constant to be carved
Erosion.Etch period is 4 hours.If etch period is too long, nanostructure can be destroyed, influences subsequent further processing processing；If
Etch period is too short, then is unable to get pyramidal structure layer, is unfavorable for improving catalytic effect.
Specifically, metal targets are provided in above-mentioned steps S03, in the boron doping gold by the way of magnetron sputtering
The surface of hard rock carrier carries out metal sputtering processing, obtains the boron-doped diamond of the carried metal of the photoelectrocatalysis.
Preferably, the metal targets are selected from gold target material, silver-colored target, platinum target, ruthenium target, niobium target, palladium target, molybdenum target
Any one of material, iridium target.In the specific embodiment of the invention, gold target material is selected to be reacted.
Preferably, in the step of keeping the surface of the boron-doped diamond carrier in parallel and metal targets described in face,
The spacing of the boron-doped diamond carrier and the metal targets is 5~15cm.If adjusting the boron-doped diamond carrier
With the spacing of the metal targets, if spacing is too long, the metal nanoparticle that will lead to load is very few；If spacing is too short,
It is excessive to will lead to responsible metal nanoparticle, easy to knot groups are unfavorable for playing catalytic action.
Specifically, being carried out at metal sputtering by the way of magnetron sputtering on the surface of the boron-doped diamond carrier
Reason, obtains the boron-doped diamond of the carried metal.Preferably, it provides in a magnetron sputtering apparatus, it will will be obtained
Diamond thin be placed in magnetron sputtering apparatus, keep the surface of boron-doped diamond carrier parallel and face gold target material,
Ensure that the metal nanoparticle obtained by magnetron sputtering can be carried on boron-doped diamond carrier.
Preferably, during sputter process, pressure and time are adjusted, after sputtering, closes mechanical pump, opening is put
Air valve takes out sample, closes vent valve.It is further preferred that pressure is 1~2 × 10 in adjustment equipment cavity-3Pa.Further
Preferably, the time of the sputter process is 2~4 minutes.If sputtering time is too short, metal nanoparticle load capacity is inadequate,
It is unfavorable for the progress of catalysis reaction；If sputtering time is too long, metal nanoparticle load capacity is excessive, and excessive metal nano
Particle easy to knot groups can not play catalytic action.
The preparation method of the boron-doped diamond of the carried metal of the photoelectrocatalysis provided by the invention, first offer boron
Doped diamond carrier performs etching processing to the surface of the boron-doped diamond layer of any side of the substrate, is handled
Boron-doped diamond layer afterwards, treated boron-doped diamond layer the includes planarizing underlayer and perpendicular to the planarizing underlayer
Pyramidal structure layer；Metal targets are provided again, by the way of magnetron sputtering the surface of the boron-doped diamond carrier into
Row metal sputter process obtains the boron-doped diamond of the carried metal；Used magnetically controlled sputter method is easy, quickly,
It is easily controllable, using the method for magnetron sputtering also can guarantee that metal nanoparticle and boron-doped diamond carrier are biggish attached simultaneously
Put forth effort, stability of material is good, improves catalytic efficiency, is conducive to industrial applications.
Correspondingly, the embodiment of the present invention also provides a kind of photoelectrocatalysis reduction reaction electrode, the reduction reaction electrode
Material is the boron-doped diamond of the carried metal of above-mentioned photoelectrocatalysis or the photoelectrocatalysis that is prepared by above-mentioned method
Carried metal boron-doped diamond.Preferably, the photoelectrocatalysis reduction reaction includes that photoelectrocatalysis nitrogen is reduced to ammonia
The reaction of gas.
In a preferred embodiment of the invention, using the boron-doped diamond of the above-mentioned carried metal being prepared as work
Electrode carries out the application of photoelectrocatalysis reduction nitrogen.Concrete operations are as follows: providing a closed double pond reactors, working electrode pole
Room and electrode chamber is isolated with sheet glass, passes through electronics, but solution is prevented to mix.The carried metal that will be prepared
Boron-doped diamond as working electrode, Pt plate electrode is to electrode, working electrode and to electrode spacing 2cm.Working electrode
Deionized water solution is added in room, electrode chamber is added the KI solution of isometric 0.1M.Reaction starts preceding in working electrode room
The N of pre- logical 0.5h2, it is continually fed into N later2.Photoelectrocatalysis, which is carried out, using electric Hg/Xe arc photoelectric light irradiation work pole restores N2Instead
It answers.
Using the boron-doped diamond of the carried metal as the material photoelectrocatalysis reduction reaction of working electrode, with load
During the diamond of metal carries out photoelectrocatalysis reaction as the material of working electrode, the photoelectrocatalysis reduction reaction tool
There is higher catalytic activity, the catalytic rate of electrode reaches higher level.
Correspondingly, in the embodiment of the present invention comprising above-mentioned photoelectrocatalysis carried metal boron-doped diamond or by upper
The electrode of the boron-doped diamond of the carried metal for the photoelectrocatalysis that the method for stating is prepared is answered photoelectrocatalysis reduction reaction
With.
The boron-doped diamond of carried metal provided by the invention comprising above-mentioned photoelectrocatalysis or by above method system
The electrode of the boron-doped diamond of the carried metal of standby obtained photoelectrocatalysis includes light in the application of photoelectrocatalysis reduction reaction
Electro-catalysis nitrogen is reduced to the chemical reaction such as reaction of ammonia.
Now by taking the boron-doped diamond of the carried metal of photoelectrocatalysis and preparation method and application as an example, the present invention is carried out
It is further described.
Embodiment 1
The boron-doped diamond of the gold-supported of photoelectrocatalysis the preparation method is as follows:
Step 1: providing boron-doped diamond carrier, and the boron-doped diamond carrier includes a substrate, and setting exists
The boron-doped diamond layer of any side of substrate；
Firstly, providing the substrate of a chromium sheet material, the substrate is pre-processed: substrate is placed among beaker, and
The hydrogenperoxide steam generator of 100mL and the concentrated sulfuric acid of 10mL, ultrasonic 30min is added；It is washed with water after ultrasound, adds 50mL third
Ketone, ultrasonic 10min；Change acetone into ethyl alcohol again, ultrasonic 10min removes the miscellaneous of substrate chromium piece surface by ultrasonic step twice
Matter, while certain defect is formed on surface, it is formed and plants brilliant site.It then takes out chromium piece and is placed in ultrasound 10min in deionized water
Cleaning.The substrate after cleaning is finally placed in ultrasound 1h in nano-diamond powder suspension, implantation diamond is brilliant on the surface of substrate
Kind.After ultrasound terminates, it is placed in the dry substrate chromium piece in nitrogen stream at room temperature.
Secondly, boron-doped diamond layer is prepared on any side of the substrate using heated filament chemical vapor deposition method,
Concrete operations are as follows: pretreated chromium piece substrate will have been carried out and be placed on base station, keep chromium piece among heated filament and with heat
Silk is parallel, and the spacing on heated filament and chromium piece surface is 20mm.Pressure in furnace is evacuated to 0.1Pa hereinafter, then passing to reaction mixture gas
Body, CH4The boron dopant source deposited as the carbon source of diamond deposition, TMB as boron-doped diamond layer.TMB used in it
For the mixed gas of TMB and hydrogen, TMB concentration is 0.1% in gaseous mixture.Deposition pressure is adjusted, diamond thin forming core is started
And growth.Design parameter is as follows: the tantalum wire that 9 diameters are 0.5mm is as being 20mm, CH at a distance from heated filament, with chromium piece surface4/
H2/ Ar/TMB flow is 10sccm/100sccm/350sccm/30sccm/, total gas couette 500sccm, and deposition pressure is
1500Pa, heater power: carbon cloth base reservoir temperature: 6900W 500 DEG C, sedimentation time: 10 hours, obtains the boron that thickness is about 10 μm
Doped diamond layer.
Step 2: processing is performed etching on the surface of the boron-doped diamond layer of any side of the substrate, is handled
Boron-doped diamond layer afterwards, treated boron-doped diamond layer the includes planarizing underlayer and perpendicular to the planarizing underlayer
Pyramidal structure layer；, specific steps are as follows: after deposition terminates, adjustment test parameter, by between substrate and tantalum wire away from
From being reduced into 5cm, gas flow CH4/H2It is changed to 10sccm/490sccm, etch period 4h.
Step 3: provide metal targets, by the way of magnetron sputtering the surface of the boron-doped diamond carrier into
Row metal sputter process obtains the boron-doped diamond of the carried metal of photoelectrocatalysis.Concrete operations are as follows: will be obtained
Diamond thin is placed in magnetron sputtering apparatus, is kept diamond thin parallel and is faced gold target material, target and substrate surface
Spacing be 5~15cm.Mechanical pump is opened, pressure in cavity is evacuated to 1~2 × 10-3Pa, later be arranged sputtering time 2~
4min starts to sputter, and after sputtering, closes mechanical pump, opens vent valve, take out sample, closes vent valve, obtain the light
The boron-doped diamond of the carried metal of electro-catalysis.
The structure of the boron-doped diamond electrode of the carried metal for the photoelectrocatalysis being prepared is as shown in Figure 1, described negative
The boron-doped diamond electrode for carrying metal includes substrate, and the boron-doped diamond layer of any side of the substrate is arranged in, described
Boron-doped diamond layer include planarizing underlayer and perpendicular to the planarizing underlayer pyramidal structure layer and uniform load described
The metal nanoparticle catalyst at the tip of pyramidal structure layer.
Embodiment 2
The boron-doped diamond of the gold-supported of the preparation-obtained photoelectrocatalysis of embodiment 1 carries out photoelectrocatalysis as electrode
Nitrogen reduction reaction such as Fig. 4, the specific steps are as follows:
Using closed double pond reactors, working electrode pole room and electrode chamber is isolated with sheet glass, leads to electronics
It crosses, but solution is prevented to mix.Using the diamond film electrode of preparation as working electrode, Pt plate electrode is to electrode, work
Electrode and to electrode spacing 2cm.Deionized water solution is added in working electrode room, and the KI for electrode chamber being added isometric 0.1M is molten
Liquid.The N of logical 0.5h pre- in working electrode room before reaction starts2, it is continually fed into N later2.Use Hg/Xe arc photoelectric light irradiation work
It is handled as electrode, later the test of row reducing property, finally by the amount for the ammonia that the measurement nitrogen reduction of indophenol blue method generates.
Comparative example 1
A kind of boron-doped diamond of gold-supported the preparation method is as follows:
Step 1: providing boron-doped diamond carrier, and the boron-doped diamond carrier includes a substrate, and setting exists
The boron-doped diamond layer of any side of substrate；
Firstly, providing the substrate of a chromium sheet material, the substrate is pre-processed: substrate is placed among beaker, and
The hydrogenperoxide steam generator of 100mL and the concentrated sulfuric acid of 10mL, ultrasonic 30min is added；It is washed with water after ultrasound, adds 50mL third
Ketone, ultrasonic 10min；Change acetone into ethyl alcohol again, ultrasonic 10min removes the miscellaneous of substrate chromium piece surface by ultrasonic step twice
Matter, while certain defect is formed on surface, it is formed and plants brilliant site.It then takes out chromium piece and is placed in ultrasound 10min in deionized water
Cleaning.The substrate after cleaning is finally placed in ultrasound 1h in nano-diamond powder suspension, implantation diamond is brilliant on the surface of substrate
Kind.After ultrasound terminates, it is placed in the dry substrate chromium piece in nitrogen stream at room temperature.
Secondly, boron-doped diamond layer is prepared on any side of the substrate using heated filament chemical vapor deposition method,
Concrete operations are as follows: pretreated chromium piece substrate will have been carried out and be placed on base station, keep chromium piece among heated filament and with heat
Silk is parallel, and the spacing on heated filament and chromium piece surface is 20mm.Pressure in furnace is evacuated to 0.1Pa hereinafter, then passing to reaction mixture gas
Body, CH4The boron dopant source deposited as the carbon source of diamond deposition, TMB as boron-doped diamond layer.TMB used in it
For the mixed gas of TMB and hydrogen, TMB concentration is 0.1% in gaseous mixture.Deposition pressure is adjusted, diamond thin forming core is started
And growth.Design parameter is as follows: the tantalum wire that 9 diameters are 0.5mm is as being 20mm, CH at a distance from heated filament, with chromium piece surface4/
H2/ Ar/TMB flow is 10sccm/100sccm/350sccm/30sccm/, total gas couette 500sccm, and deposition pressure is
1500Pa, heater power: carbon cloth base reservoir temperature: 6900W 500 DEG C, sedimentation time: 10 hours, obtains the boron that thickness is about 10 μm
Doped diamond layer.
Step 2: provide metal targets, by the way of magnetron sputtering the surface of the boron-doped diamond carrier into
Row metal sputter process obtains the boron-doped diamond of the carried metal.Concrete operations are as follows: by diamond obtained
Film suspension is placed in magnetron sputtering apparatus, is kept diamond thin parallel and is faced gold target material, target and substrate surface
Spacing is 5~15cm.Open mechanical pump, pressure in cavity is evacuated to 1~2 × 10-3Pa, later be arranged sputtering time 2~
4min starts to sputter, and after sputtering, closes mechanical pump, opens vent valve, take out sample, closes vent valve, obtains described negative
Carry the boron-doped diamond of metal.
The boron-doped diamond electrode structure for the gold-supported being prepared is as shown in Fig. 2, the boron doping of the gold-supported is golden
Hard rock electrode includes substrate, and the boron-doped diamond layer and uniform load that any side of the substrate is arranged in are in the boron
The metal nanoparticle catalyst of doped diamond layer surface.
Comparative example 2
The boron-doped diamond of the preparation-obtained gold-supported of comparative example 1 carries out photoelectrocatalysis nitrogen reduction reaction as electrode
Such as Fig. 4, the specific steps are as follows:
Using closed double pond reactors, working electrode pole room and electrode chamber is isolated with sheet glass, leads to electronics
It crosses, but solution is prevented to mix.Using the diamond film electrode of preparation as working electrode, Pt plate electrode is to electrode, work
Electrode and to electrode spacing 2cm.Deionized water solution is added in working electrode room, and the KI for electrode chamber being added isometric 0.1M is molten
Liquid.The N of logical 0.5h pre- in working electrode room before reaction starts2, it is continually fed into N later2.Use Hg/Xe arc photoelectric light irradiation work
It is handled as electrode, later the test of row reducing property, finally by the amount for the ammonia that the measurement nitrogen reduction of indophenol blue method generates.
Comparative example 3
A kind of boron-doped diamond the preparation method is as follows:
Step 1: providing boron-doped diamond carrier, and the boron-doped diamond carrier includes a substrate, and setting exists
The boron-doped diamond layer of any side of substrate；
Firstly, providing the substrate of a chromium sheet material, the substrate is pre-processed: substrate is placed among beaker, and
The hydrogenperoxide steam generator of 100mL and the concentrated sulfuric acid of 10mL, ultrasonic 30min is added；It is washed with water after ultrasound, adds 50mL third
Ketone, ultrasonic 10min；Change acetone into ethyl alcohol again, ultrasonic 10min removes the miscellaneous of substrate chromium piece surface by ultrasonic step twice
Matter, while certain defect is formed on surface, it is formed and plants brilliant site.It then takes out chromium piece and is placed in ultrasound 10min in deionized water
Cleaning.The substrate after cleaning is finally placed in ultrasound 1h in nano-diamond powder suspension, implantation diamond is brilliant on the surface of substrate
Kind.After ultrasound terminates, it is placed in the dry substrate chromium piece in nitrogen stream at room temperature.
Secondly, boron-doped diamond layer is prepared on any side of the substrate using heated filament chemical vapor deposition method,
Concrete operations are as follows: pretreated chromium piece substrate will have been carried out and be placed on base station, keep chromium piece among heated filament and with heat
Silk is parallel, and the spacing on heated filament and chromium piece surface is 20mm.Pressure in furnace is evacuated to 0.1Pa hereinafter, then passing to reaction mixture gas
Body, CH4The boron dopant source deposited as the carbon source of diamond deposition, TMB as boron-doped diamond layer.TMB used in it
For the mixed gas of TMB and hydrogen, TMB concentration is 0.1% in gaseous mixture.Deposition pressure is adjusted, diamond thin forming core is started
And growth.Design parameter is as follows: the tantalum wire that 9 diameters are 0.5mm is as being 20mm, CH at a distance from heated filament, with chromium piece surface4/
H2/ Ar/TMB flow is 10sccm/100sccm/350sccm/30sccm/, total gas couette 500sccm, and deposition pressure is
1500Pa, heater power: carbon cloth base reservoir temperature: 6900W 500 DEG C, sedimentation time: 10 hours, obtains the boron that thickness is about 10 μm
Doped diamond layer.
Step 2: processing is performed etching on the surface of the boron-doped diamond layer of any side of the substrate, is handled
Boron-doped diamond layer afterwards, treated boron-doped diamond layer the includes planarizing underlayer and perpendicular to the planarizing underlayer
Pyramidal structure layer；Specific steps are as follows: after deposition terminates, adjustment test parameter, by between substrate and tantalum wire away from
From being reduced into 5cm, gas flow CH4/H2It is changed to 10sccm/490sccm, etch period 4h.
The boron-doped diamond electrode structure that is prepared as shown in figure 3, the boron-doped diamond electrode includes substrate,
The boron-doped diamond layer of any side of the substrate is set, the boron-doped diamond layer include planarizing underlayer and perpendicular to
The pyramidal structure layer of the planarizing underlayer.
Comparative example 4
The preparation-obtained boron-doped diamond of comparative example 3 carries out photoelectrocatalysis nitrogen reduction reaction such as Fig. 4, tool as electrode
Steps are as follows for body:
Using closed double pond reactors, working electrode pole room and electrode chamber is isolated with sheet glass, leads to electronics
It crosses, but solution is prevented to mix.Using the diamond film electrode of preparation as working electrode, Pt plate electrode is to electrode, work
Electrode and to electrode spacing 2cm.Deionized water solution is added in working electrode room, and the KI for electrode chamber being added isometric 0.1M is molten
Liquid.The N of logical 0.5h pre- in working electrode room before reaction starts2, it is continually fed into N later2.Use Hg/Xe arc photoelectric light irradiation work
It is handled as electrode, later the test of row reducing property, finally by the amount for the ammonia that the measurement nitrogen reduction of indophenol blue method generates.
The result of photoelectrocatalysis nitrogen reduction reaction described in above-described embodiment 2, comparative example 2 and comparative example 4 is analyzed,
As a result as follows:
For embodiment 2, under conditions of Hg/Xe arc photoelectric light irradiation, the catalytic rate of the electrode and faraday's effect
Rate reaches highest, and production ammonia rate is 5 μ g h-1cm-2, faradic efficiency reached 20%.
For comparative example 2, under conditions of Hg/Xe arc photoelectric light irradiation, the catalytic rate of the electrode and faraday's effect
Rate increases, and production ammonia rate is 2 μ g h-1cm-2, faradic efficiency reached 10%.
For comparative example 4, under conditions of Hg/Xe arc photoelectric light irradiation, the catalytic rate of the electrode and faraday's effect
Rate increases, and production ammonia rate is 1 μ g h-1cm-2, faradic efficiency reached 5%.
Experiments prove that the boron-doped diamond electrode of the carried metal of preparation-obtained photoelectrocatalysis, described negative
The boron-doped diamond for carrying metal includes substrate, the boron-doped diamond layer of any side of the substrate is arranged in, the boron is mixed
Miscellaneous diamond layer include planarizing underlayer and perpendicular to the planarizing underlayer pyramidal structure layer and uniform load in the taper
The metal nanoparticle catalyst at the tip of structure sheaf, the boron-doped diamond electrode of the carried metal of the photoelectrocatalysis is in light
Catalytic activity with higher in the experimentation of electro-catalysis nitrogen reduction.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of boron-doped diamond of the carried metal of photoelectrocatalysis, which is characterized in that the boron doping gold of the carried metal
Hard rock includes substrate, and the boron-doped diamond layer of any side of the substrate is arranged in, and the boron-doped diamond layer includes flat
Whole bottom and perpendicular to the planarizing underlayer pyramidal structure layer and uniform load the tip of the pyramidal structure layer gold
Metal nano-particle catalyst.
2. the boron-doped diamond of the carried metal of photoelectrocatalysis according to claim 1, which is characterized in that described smooth
Bottom with a thickness of 500nm~5 μm；And/or
The height of the pyramidal structure layer is 500nm~2 μm.
3. the boron-doped diamond of the carried metal of photoelectrocatalysis according to claim 1, which is characterized in that the taper
In structure sheaf, the base diameter of pyramidal structure is 100nm~1 μm；And/or
The tip curvature radius of pyramidal structure is no more than 20nm.
4. the boron-doped diamond of the carried metal of any photoelectrocatalysis according to claim 1~3, which is characterized in that
The partial size of the metal nanoparticle catalyst is 0.1nm~20nm.
5. the boron-doped diamond of the carried metal of any photoelectrocatalysis according to claim 1~3, which is characterized in that
The ratio that the load area of the metal nanoparticle catalyst accounts for the boron-doped diamond level product is 10%-20%.
6. a kind of preparation method of the boron-doped diamond of the carried metal of photoelectrocatalysis, which comprises the steps of:
Offer boron-doped diamond is carrier, and the boron-doped diamond includes a substrate, and is arranged any in the substrate
The boron-doped diamond layer of side；
Processing is performed etching on the surface of the boron-doped diamond layer of any side of the substrate, the boron doping gold that obtains that treated
Hard rock layer, described treated that boron-doped diamond layer includes planarizing underlayer and the pyramidal structure perpendicular to the planarizing underlayer
Layer；
Metal targets are provided, are carried out at metal sputtering by the way of magnetron sputtering on the surface of the boron-doped diamond carrier
Reason, obtains the boron-doped diamond of the carried metal of the photoelectrocatalysis.
7. the preparation method of the boron-doped diamond of the carried metal of photoelectrocatalysis according to claim 6, feature exist
Gold target material, silver-colored target, platinum target, ruthenium target, palladium target, iridium target, niobium target, molybdenum target material are selected from, metal targets
Any one.
8. according to the preparation method of the boron-doped diamond of the carried metal of any photoelectrocatalysis of claim 6~7,
It is characterized in that, the time of the sputter process is 2~4 minutes；And/or
The spacing of the pyramidal structure layer and the metal targets is 5~15cm.
9. a kind of photoelectrocatalysis reduction reaction electrode, which is characterized in that the material of the reduction reaction electrode is wanted for aforesaid right
It seeks the boron-doped diamond of the carried metal of 1~5 any photoelectrocatalysis or to be gone by aforesaid right 6~8 any described
The boron-doped diamond of the carried metal of photoelectrocatalysis that is prepared of method.
10. the boron-doped diamond of the carried metal comprising any photoelectrocatalysis of the claims 1~5 or by above-mentioned
The electrode of the boron-doped diamond of the carried metal for the photoelectrocatalysis that any method of claim 6~8 is prepared exists
The application of photoelectrocatalysis reduction reaction.
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| CN111646634A (en) * | 2020-05-11 | 2020-09-11 | 南京岱蒙特科技有限公司 | Ultrasonic coupling photoelectric Fenton activated persulfate water treatment system and water treatment method |
| CN115350295A (en) * | 2022-08-19 | 2022-11-18 | 元旭半导体科技(无锡)有限公司 | Deep ultraviolet LED photocatalyst module and preparation method thereof |
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| CN107988616A (en) * | 2017-12-26 | 2018-05-04 | 深圳先进技术研究院 | A kind of nitrogen co-doped diamond electrode of nickel boron and its preparation and application |
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| CN107988616A (en) * | 2017-12-26 | 2018-05-04 | 深圳先进技术研究院 | A kind of nitrogen co-doped diamond electrode of nickel boron and its preparation and application |
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| JASON A.等: "Photocatalytic reduction of nitrogen to ammonia on diamond thin films grown on metallic substrates", 《DIAMOND & RELATED MATERIALS》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111646634A (en) * | 2020-05-11 | 2020-09-11 | 南京岱蒙特科技有限公司 | Ultrasonic coupling photoelectric Fenton activated persulfate water treatment system and water treatment method |
| CN115350295A (en) * | 2022-08-19 | 2022-11-18 | 元旭半导体科技(无锡)有限公司 | Deep ultraviolet LED photocatalyst module and preparation method thereof |
| CN115350295B (en) * | 2022-08-19 | 2023-11-10 | 元旭半导体科技(无锡)有限公司 | Deep ultraviolet LED photocatalyst module and preparation method thereof |
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