CN107188122A - Transition metal phosphide reacts the application of catalyst for preparing hydrogen as borohydride hydrolytic - Google Patents
Transition metal phosphide reacts the application of catalyst for preparing hydrogen as borohydride hydrolytic Download PDFInfo
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- CN107188122A CN107188122A CN201610146184.1A CN201610146184A CN107188122A CN 107188122 A CN107188122 A CN 107188122A CN 201610146184 A CN201610146184 A CN 201610146184A CN 107188122 A CN107188122 A CN 107188122A
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- C01—INORGANIC CHEMISTRY
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- C01B2203/1052—Nickel or cobalt catalysts
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- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- 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
The invention discloses the application that transition metal phosphide reacts catalyst for preparing hydrogen as borohydride hydrolytic.Compared with prior art, transition metal phosphide is applied to the hydrolytic hydrogen production technical field of sodium borohydride and for catalyzing hydrolysis hydrogen manufacturing by the present invention first, and it shows excellent catalytic efficiency and circulation and heat endurance, has broad application prospects.
Description
Technical field
The invention belongs to the technical field of hydrolytic hydrogen production, more particularly, it is related to transition metal phosphide conduct
Borohydride hydrolytic reacts the application of catalyst for preparing hydrogen.
Background technology
Into 21 century, the increase of energy resource consumption and the quick of fossil fuel make the mankind be faced with exploitation
The Tough questions of the High-efficiency Sustainable energy.Therefore, in order to realize the sustainable development of human society, exploitation is clear
Clean regenerative resource is extremely urgent.Hydrogen is a kind of with the replaceable of high fuel value, high efficiency and cleaning
The new energy of conventional fossil.But, the production of current Hydrogen Energy also mainly comes by the reformation of coal, natural gas
Obtain, this will necessarily aggravate the consumption of non-regeneration energy and bring problem of environmental pollution.Pass through hydrolysis one
A little high compounds of hydrogen content efficiently, safe storage and prepare hydrogen to prepare hydrogen be a kind of simple
Mode, such as sodium borohydride (NaBH4), lithium borohydride (LiBH4) and ammonia borine (NH3BH3) etc., especially
It is the hydrolysis of wherein sodium borohydride.Sodium borohydride has hydrogen reserves high, and hydrolysising condition is gentle, raw material
Cost is low, and the advantages of reacting controllable, is optimal hydrogen source.Wherein, the equation of sodium borohydride hydrolysis
Formula is as follows：
NaBH4+H2O→NaBO2+4H2
The hydrolysis of sodium borohydride is very slow under normal circumstances, and when adding a certain amount of catalyst, should
Hydrolysis reaction can substantially be accelerated.Therefore, catalyst is the core for controlling preparing hydrogen by sodium borohydride hydrolysis speed.
At present, the catalytic body based on noble metal (Pt, Ru, Pd etc.) and base metal (Co, Ni, Fe etc.)
System is the catalyst for the preparing hydrogen by sodium borohydride hydrolysis mainly developed in the past few decades.Although lot of documents and patent
It is directed to the raising of such catalyst system and catalyzing catalytic efficiency, and achieves notable results, but for catalyst system and catalyzing
Stability and controllability then study deficiency.It was verified that directly load to catalyst on substrate surface, by
Be limited to the limitation of catalyst and the adhesion of substrate, cause catalyst activity area reduction, it is easy to fall off.Therefore,
Higher activity is kept again while catalyst metals firmly to be loaded to substrate surface by specific process
Area is the emphasis direction of preparing hydrogen by sodium borohydride hydrolysis research in recent years.
It is mainly boronation class, alloy type currently used for the transition metal-type catalyst of catalysis sodium borohydride hydrolysis
Deng, phosphatization class transition metal is used to be catalyzed the unspecial report of sodium borohydride hydrolysis, and in electrochemical catalysis
In terms of hydrogen manufacturing, phosphatization class transition metal has been proved to excellent catalytic performance.Therefore, transition is prepared
Metal phosphide, which is used for sodium borohydride hydrolysis, has important application prospect and meaning.
The content of the invention
In order to solve problems of the prior art, it is an object of the invention to overcome existing catalyst system and catalyzing
There is provided applied to preparing hydrogen by sodium borohydride hydrolysis and more efficient, more reliable catalyst and its can answer for defect
With.
The invention provides a kind of transition metal phosphide catalyst for preparing hydrogen is reacted as borohydride hydrolytic
Using.
It is direct using transition metal phosphide as catalyst according to one embodiment of application of the present invention
It is in contact with the alkaline aqueous solution of boron hydride, realizes quick, the effectively hydrolyzing hydrogen manufacturing of boron hydride.
According to one embodiment of application of the present invention, the boron hydride be alkali metal borohydride or
The content of boron hydride is 0.1~15wt in alkaline-earth metal boron hydride, the alkaline aqueous solution of the boron hydride
%.
According to one embodiment of application of the present invention, in the transition metal phosphide containing a kind of or
A variety of transition metals, the transition metal is iron, cobalt, nickel, copper, molybdenum, tungsten or vanadium.
According to one embodiment of application of the present invention, the transition metal phosphide be nanostructured,
The nanofilmstructures of nano composite structure or growth in situ in substrate.
According to one embodiment of application of the present invention, the nano composite structure is using nanostructured as load
Body and the transition metal phosphide including being supported on the carrier surface.
According to one embodiment of application of the present invention, the carrier be selected from CNT, graphene,
One in carbon nano-fiber, activated carbon, titanium dioxide nano thread and titania nanotube manganese oxide nano wire
Plant or a variety of.
According to one embodiment of application of the present invention, nanometer film knot of the growth in situ in substrate
Transition metal phosphide content in structure for 0.1~1.5wt% and substrate be selected from carbon cloth, nickel screen, nickel foil,
Copper mesh, copper foil, stainless (steel) wire, stainless steel foil, ferronickel net, cobalt paper tinsel, titanium net, titanium sheet, molybdenum foil, tungsten paper tinsel,
One or more in sheet glass, silicon chip, ceramic honey comb and pomelo peel.
According to one embodiment of application of the present invention, nanometer film knot of the growth in situ in substrate
Structure is made up of single/multiple nano-particle or nano-array, wherein, the nano-array by nano wire, receive
Mitron, nanometer sheet or the nano wire, nanotube, the hierarchy of nanometer sheet or core shell structure are constituted.
According to one embodiment of application of the present invention, the nano wire, nanotube, the core of nanometer sheet
The core of shell structure is that the shell of transition metal phosphide or nontransition metal phosphide and the core shell structure is
Transition metal phosphide, wherein, the nontransition metal phosphide is CNT, titanium dioxide or oxidation
Manganese.
Compared with prior art, transition metal phosphide is applied to the hydrolysis system of sodium borohydride by the present invention first
Hydrogen technical field is simultaneously used for catalyzing hydrolysis hydrogen manufacturing, and it shows excellent catalytic efficiency and circulation and thermally-stabilised
Property, have broad application prospects.
Brief description of the drawings
Fig. 1 shows in example 1 scanning electron microscopic picture (a) of the phosphatization cobalt of obtained array structure and urged
Change the catalytic performance (b) of sodium borohydride hydrolysis.
Fig. 2 shows the scanning electron microscopic picture (a) of the nickel phosphide of obtained nano-chip arrays structure in example 2
And the catalytic performance (b) of catalysis sodium borohydride hydrolysis.
Fig. 3 shows the scanning electron microscopic picture (a) of the iron cobalt phosphide of obtained array structure in example 3
And the catalytic performance (b) of catalysis sodium borohydride hydrolysis.
Fig. 4 shows the scanning electron microscopic picture (a) of the iron cobalt phosphide of obtained array structure in example 4
And the catalytic performance (b) of catalysis sodium borohydride hydrolysis.
Fig. 5 shows the scanning electron microscopic picture (a) of the iron cobalt phosphide of obtained array structure in example 5
And the catalytic performance (b) of catalysis sodium borohydride hydrolysis.
Embodiment
All features disclosed in this specification, or disclosed all methods or during the step of, except mutual
Beyond the feature and/or step mutually repelled, it can combine in any way.
Any feature disclosed in this specification, unless specifically stated otherwise, can be equivalent by other or with similar
The alternative features of purpose are replaced.I.e., unless specifically stated otherwise, each feature is a series of equivalent or class
Like an example in feature.
The invention provides the application that transition metal phosphide reacts catalyst for preparing hydrogen as borohydride hydrolytic,
Directly it is in contact transition metal phosphide as catalyst with the alkaline aqueous solution of boron hydride, realizes boron
Quick, the effectively hydrolyzing hydrogen manufacturing of hydride.
According to the exemplary embodiment of the present invention, above-mentioned boron hydride can be alkali metal borohydride or alkaline earth
Metallic boron hydrides, such as sodium borohydride (NaBH4), lithium borohydride (LiBH4) and ammonia borine (NH3BH3)；
In the alkaline aqueous solution of boron hydride the content of boron hydride be 0.1~15wt%, wherein, using NaOH,
The alkaloids such as KOH are adjusted to alkalescence, and control the mass content of alkaline matter for 0.1~15wt%.
Transition metal phosphide is to be filled in transition metal atoms by the larger nonmetalloid phosphorus of atomic radius
The class calking type compound formed in lattice, with covalent compound, ionic crystals and transition metal
Property, such as CoP, NiP2, FeP etc..
Containing one or more transition metals in heretofore described transition metal phosphide, wherein,
Transition metal can be iron, cobalt, nickel, copper, molybdenum, tungsten or vanadium.
It is highly preferred that above-mentioned transition metal phosphide is nanostructured, nano composite structure or growth in situ
Nanofilmstructures in substrate.Borohydride hydrolytic is used as using the transition metal phosphide of nanometer class formation
The catalyst of hydrogen manufacturing, can more effectively improve catalytic effect, promote the hydrolytic hydrogen production and hydrogen of boron hydride
The acquisition of gas.
Specifically, nanostructured is object structures of the size between molecule and micro-meter scale；And the present invention
Nano composite structure is the transition metal phosphorus using nanostructured as carrier and including being supported on the carrier surface
Compound；Nanofilmstructures include substrate and growth in situ the transition metal phosphide in substrate.
According to the present invention, the carrier in above-mentioned nano composite structure can be selected from CNT, graphene, receive
One kind in rice carbon fiber, activated carbon, titanium dioxide nano thread and titania nanotube manganese oxide nano wire
Or it is a variety of.Transition metal phosphide content in nanofilmstructures of the above-mentioned growth in situ in substrate is
0.1~1.5wt% and substrate can selected from carbon cloth, nickel screen, nickel foil, copper mesh, copper foil, stainless (steel) wire,
Stainless steel foil, ferronickel net, cobalt paper tinsel, titanium net, titanium sheet, molybdenum foil, tungsten paper tinsel, sheet glass, silicon chip, honeycomb pottery
One or more in porcelain and pomelo peel.In fact, above-mentioned substrate can also use other any sheets, net
The material of shape structure.
It is highly preferred that nanofilmstructures of the above-mentioned growth in situ in substrate by single/multiple nano-particle or
Nano-array is constituted, wherein, nano-array can be by nano wire, nanotube, nanometer sheet or the nanometer
Line, nanotube, the hierarchy of nanometer sheet or core shell structure are constituted.
Wherein, nano wire, nanotube, the core of the core shell structure of nanometer sheet are transition metal phosphide or non-mistake
The shell for crossing metal phosphide and core shell structure is transition metal phosphide, namely must assure that core shell structure
Shell is made up of transition metal phosphide, so as to ensure its catalytic action.Wherein, the non-transition used
Metal phosphide can be the materials such as CNT, titanium dioxide or manganese oxide.
According to the exemplary embodiment of the present invention, the transition gold of the present invention can be prepared using following steps
Belong to phosphide.
The powder or the array of hydroxide of the metal salt of transition metal are added into tube furnace, while plus
Enter phosphorus source, 2~6h is reacted in argon atmosphere and under conditions of 250~800 DEG C, transition metal phosphatization is obtained
Thing.Obtained transition metal phosphide is directly used in the hydrolytic hydrogen production of boron hydride as catalyst or incited somebody to action
It is fixed in catalyst carrier the hydrolytic hydrogen production for being used further to boron hydride.
Wherein, the metal salt of transition metal can be nitrate, chloride, acetate, sulfuric acid, grass
One or more in acid, citric acid, tartaric acid, carbonate；Phosphorus source can for sodium hypophosphite, phosphorous acid,
Sodium phosphite；Catalyst carrier can for nickel screen, nickel foil, copper mesh, copper foil, stainless (steel) wire, stainless steel foil,
Ferronickel net, cobalt paper tinsel, titanium net, titanium sheet, molybdenum foil or tungsten paper tinsel.
Step made above is only an exemplary embodiment for preparing transition metal phosphide, and for saying
A kind of bright feasible preparation method, the invention is not restricted to this.
The transition metal phosphide of the present invention is reacted as borohydride hydrolytic below in conjunction with specific example
The application of catalyst for preparing hydrogen is described further.
Example 1：
Step one：20mL distilled water is added into polytetrafluoroethyllining lining, control adds in every milliliter of water
Enter the water of 0.0146g six and cobalt nitrate, 0.00046g ammonium fluorides, 0.015g urea, that is, add the water of 0.291g six
With cobalt nitrate, 0.093g ammonium fluorides and 0.30g urea and stirring until solid is completely dissolved, formed transparent molten
Liquid.
Step 2：Catalyst substrate titanium net is put into the inner liner of reaction kettle of step one, and polytetrafluoroethylene (PTFE)
Liner is sealed in stainless steel mould, is placed in thermostatic drying chamber and is heated at 120 DEG C under sealing condition
React 6h.
Step 3：After the completion of reaction, then titanium net is taken out, distilled water is used successively by furnace cooling to room temperature
Washed, and the titanium net after washing is placed in vacuum drying chamber and vacuum is done at 40 DEG C with absolute ethyl alcohol
Dry 24h, obtains being fluorinated the array structure of cobalt hydroxide.
Step 4：Presoma made from step 3 is placed in tube furnace and phosphorus source sodium hypophosphite is added, in argon
During atmosphere is enclosed, 2h is reacted under the conditions of 300 DEG C, the array structure of phosphatization cobalt is obtained, its microstructure is as schemed
Shown in 1 (a).
Step 5：The concentration for selecting sodium borohydride alkaline solution is 1wt% and the concentration of wherein sodium hydroxide is
1wt%, overall solution volume is 3mL.In the case where temperature is 293K environment temperature made from testing procedure four
Hydrolytic hydrogen production catalytic performance of the phosphatization cobalt of array structure in sodium borohydride alkaline solution, specific catalytic performance
As a result as shown in Fig. 1 (b).
Example 2：
Step one：36mL distilled water is added into polytetrafluoroethyllining lining, that is, adds 1.45395g nitre
Sour nickel and 1.4019g hexamethylenetetramine, and stir up to solid is completely dissolved, form clear solution.
Step 2：Catalyst substrate carbon cloth is put into the inner liner of reaction kettle of step one, and polytetrafluoro
Ethene liner is sealed in stainless steel mould, is placed under sealing condition in thermostatic drying chamber and at 100 DEG C
Heating response 10h.
Step 3：After the completion of reaction, then furnace cooling to room temperature takes out carbon cloth, successively with steaming
Distilled water and absolute ethyl alcohol are washed, and the carbon cloth after washing is placed in vacuum drying chamber and 40
24h is dried in vacuo at DEG C, the array structure of nickel hydroxide is obtained.
Step 4：Presoma made from step 3 is placed in tube furnace and phosphorus source sodium hypophosphite is added, in argon
During atmosphere is enclosed, 2h is reacted under the conditions of 300 DEG C, the nano-chip arrays structure of nickel phosphide is obtained, its microcosmic knot
Shown in structure such as Fig. 2 (a).
Step 5：The concentration for selecting sodium borohydride alkaline solution is 1wt% and the concentration of wherein sodium hydroxide is
1wt%, overall solution volume is 3mL.In the case where temperature is 293K environment temperature made from testing procedure four
Hydrolytic hydrogen production catalytic performance of the nickel phosphide of nano-chip arrays structure in sodium borohydride alkaline solution, is specifically urged
Change shown in results of property such as Fig. 2 (b).
Example 3：
Step one：90mL distilled water is added into polytetrafluoroethyllining lining, control adds in every milliliter of water
Enter 1.21g ferric nitrates, 1.873g cobalt nitrates, 10.6g ammonium fluorides and 1.6g urea and stir until solid is complete
Fully dissolved, forms clear solution.
Step 2：Catalyst substrate titanium sheet is put into the inner liner of reaction kettle of step one, and polytetrafluoroethylene (PTFE)
Liner is sealed in stainless steel mould, is placed in thermostatic drying chamber and is heated at 120 DEG C under sealing condition
React 6h.
Step 3：After the completion of reaction, then titanium sheet is taken out, distilled water is used successively by furnace cooling to room temperature
Washed, and the titanium net after washing is placed in vacuum drying chamber and vacuum is done at 40 DEG C with absolute ethyl alcohol
Dry 24h, obtains the array structure of iron cobalt hydroxide.
Step 4：Presoma made from step 3 is placed in tube furnace and phosphorus source sodium hypophosphite is added, in argon
During atmosphere is enclosed, 2h is reacted under the conditions of 300 DEG C, the array structure of iron cobalt phosphide is obtained, its microstructure
As shown in Fig. 3 (a).
Step 5：The concentration for selecting sodium borohydride alkaline solution is 1wt% and the concentration of wherein sodium hydroxide is
1wt%, overall solution volume is 3mL.In the case where temperature is 293K environment temperature made from testing procedure four
Hydrolytic hydrogen production catalytic performance of the iron cobalt phosphide of array structure in sodium borohydride alkaline solution, specific catalysis
Shown in results of property such as Fig. 3 (b).
Example 4：
Step one：30mL distilled water is added into polytetrafluoroethyllining lining, control adds in every milliliter of water
Enter 1.45g cobalt nitrates and 1.4019g hexamethylenetetramines, and stir until solid is completely dissolved, formation is saturating
Bright solution.
Step 2：Catalyst substrate carbon cloth is put into the inner liner of reaction kettle of step one, and polytetrafluoro
Ethene liner is sealed in stainless steel mould, is placed under sealing condition in thermostatic drying chamber and at 105 DEG C
Heating response 10h.
Step 3：After the completion of reaction, then furnace cooling to room temperature takes out carbon cloth, successively with steaming
Distilled water and absolute ethyl alcohol are washed, and the carbon cloth after washing is placed in vacuum drying chamber and 40
24h is dried in vacuo at DEG C, the array structure of the hydroxide of cobalt is obtained.
Step 4：Presoma made from step 3 is placed in tube furnace and phosphorus source sodium hypophosphite is added, in argon
During atmosphere is enclosed, 2h is reacted under the conditions of 300 DEG C, the array structure of phosphatization cobalt is obtained, its microstructure is as schemed
Shown in 4 (a).
Step 5：The concentration for selecting sodium borohydride alkaline solution is 1wt% and the concentration of wherein sodium hydroxide is
1wt%, overall solution volume is 3mL.In the case where temperature is 293K environment temperature made from testing procedure four
Hydrolytic hydrogen production catalytic performance of the phosphatization cobalt of array structure in sodium borohydride alkaline solution, specific catalytic performance
As a result as shown in Fig. 4 (b).
Example 5：
Step one：In 0.05M/L cobalt nitrate electrolyte, titanium net is regard as the electrode body of electrochemical workstation three
The working electrode of system, Ag/AgCl is as reference electrode, and graphite flake is, to electrode, to be existed with cyclic voltammetry
In the range of -1.2V to -0.8V, sweep speed is 0.05V/s, and scan round 50 is enclosed, and obtains sinking in titanium net
Long-pending presoma.
Step 2：Presoma made from step one is placed in tube furnace and phosphorus source sodium hypophosphite is added, in argon
During atmosphere is enclosed, 2h is reacted under the conditions of 300 DEG C, the array structure of phosphatization cobalt is obtained, its microstructure is as schemed
Shown in 5 (a).
Step 3：The concentration for selecting sodium borohydride alkaline solution is 1wt% and the concentration of wherein sodium hydroxide is
1wt%, overall solution volume is 3mL.In the case where temperature is 293K environment temperature made from testing procedure three
Hydrolytic hydrogen production catalytic performance of the array structure of phosphatization cobalt in sodium borohydride alkaline solution, specific catalytic performance
As a result as shown in Fig. 5 (b).
In summary, transition metal phosphide is applied to the hydrolytic hydrogen production technology of sodium borohydride by the present invention first
Domain variability is used for catalyzing hydrolysis hydrogen manufacturing, and it shows excellent catalytic efficiency, had broad application prospects.
The invention is not limited in foregoing embodiment.The present invention expand to it is any in this manual
The new feature of disclosure or any new combination, and disclose any new method or process the step of or it is any
New combination.
Claims (10)
1. transition metal phosphide reacts the application of catalyst for preparing hydrogen as borohydride hydrolytic.
2. application according to claim 1, it is characterised in that using transition metal phosphide as urging
Agent is directly in contact with the alkaline aqueous solution of boron hydride, realizes the quick of boron hydride, effectively hydrolyzing system
Hydrogen.
3. application according to claim 2, it is characterised in that the boron hydride is alkali metal boron
The content of boron hydride is in hydride or alkaline-earth metal boron hydride, the alkaline aqueous solution of the boron hydride
0.1~15wt%.
4. application according to claim 1, it is characterised in that contain in the transition metal phosphide
Have one or more transition metals, the transition metal be iron, cobalt, nickel, copper, molybdenum, tungsten or
Vanadium.
5. application according to claim 1, it is characterised in that the transition metal phosphide is to receive
The nanofilmstructures of rice structure, nano composite structure or growth in situ in substrate.
6. application according to claim 5, it is characterised in that the nano composite structure is with nanometer
Structure is carrier and the transition metal phosphide including being supported on the carrier surface.
7. application according to claim 6, it is characterised in that the carrier be selected from CNT,
Graphene, carbon nano-fiber, activated carbon, titanium dioxide nano thread and titania nanotube manganese oxide nanometer
One or more in line.
8. application according to claim 5, it is characterised in that the growth in situ is in substrate
Transition metal phosphide content in nanofilmstructures is 0.1~1.5wt% and substrate is selected from carbon cloth, nickel
Net, nickel foil, copper mesh, copper foil, stainless (steel) wire, stainless steel foil, ferronickel net, cobalt paper tinsel, titanium net, titanium sheet,
One or more in molybdenum foil, tungsten paper tinsel, sheet glass, silicon chip, ceramic honey comb and pomelo peel.
9. the application according to claim 5 or 8, it is characterised in that the growth in situ is in substrate
On nanofilmstructures be made up of single/multiple nano-particle or nano-array, wherein, the nano-array
By nano wire, nanotube, nanometer sheet or the nano wire, nanotube, nanometer sheet hierarchy or core
Shell structure is constituted.
10. application according to claim 9, it is characterised in that the nano wire, nanotube, receive
The core of the core shell structure of rice piece is transition metal phosphide or nontransition metal phosphide and the nucleocapsid knot
The shell of structure is transition metal phosphide, wherein, the nontransition metal phosphide is CNT, titanium dioxide
Titanium or manganese oxide.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108525685A (en) * | 2017-03-01 | 2018-09-14 | 中国科学院理化技术研究所 | The phosphorous metallic compound of a kind of monodisperse or support type releases hydrogen system as the hydrogen storage material hydrolysis of catalyst |
| CN111501061A (en) * | 2020-04-24 | 2020-08-07 | 唐友莲 | Nano Ni2P-MoS2Electrocatalytic hydrogen production material modified with graphene and preparation method thereof |
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| CN115928120A (en) * | 2021-09-27 | 2023-04-07 | 中国科学院福建物质结构研究所 | Composite catalytic material of carbon element doped tungsten phosphide film and preparation method and application thereof |
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| CN116393151A (en) * | 2023-03-23 | 2023-07-07 | 淮阴师范学院 | Basic chloride catalyst and preparation method thereof |
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| CN108525685B (en) * | 2017-03-01 | 2021-05-14 | 中国科学院理化技术研究所 | Hydrogen storage material hydrolysis hydrogen release system using monodisperse or supported phosphorus-containing metal compound as catalyst |
| CN108525685A (en) * | 2017-03-01 | 2018-09-14 | 中国科学院理化技术研究所 | The phosphorous metallic compound of a kind of monodisperse or support type releases hydrogen system as the hydrogen storage material hydrolysis of catalyst |
| CN111501061A (en) * | 2020-04-24 | 2020-08-07 | 唐友莲 | Nano Ni2P-MoS2Electrocatalytic hydrogen production material modified with graphene and preparation method thereof |
| CN111604072A (en) * | 2020-05-15 | 2020-09-01 | 桂林电子科技大学 | Nano particle-graphene-foam nickel composite material with bionic structure and preparation method thereof |
| CN112044462B (en) * | 2020-09-10 | 2021-11-05 | 中山大学 | Graphene-loaded transition metal nitride nanocomposite and preparation method and application thereof |
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| CN112044459B (en) * | 2020-09-10 | 2022-02-18 | 中山大学 | Punicallyid porous nickel-based phosphide nano-structure material and preparation method and application thereof |
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| CN113368878B (en) * | 2021-05-31 | 2024-01-30 | 江苏师范大学 | MnCoP catalyst, preparation and application |
| CN113385203A (en) * | 2021-06-07 | 2021-09-14 | 北京科技大学 | Preparation method of core-shell structure bimetal phosphide nano-array |
| CN115928120A (en) * | 2021-09-27 | 2023-04-07 | 中国科学院福建物质结构研究所 | Composite catalytic material of carbon element doped tungsten phosphide film and preparation method and application thereof |
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| CN116351445A (en) * | 2023-02-28 | 2023-06-30 | 齐鲁工业大学(山东省科学院) | Core-shell phosphating zero-valent iron material and preparation method and application thereof |
| CN116351445B (en) * | 2023-02-28 | 2024-05-10 | 齐鲁工业大学(山东省科学院) | Core-shell phosphating zero-valent iron material and preparation method and application thereof |
| CN116393151A (en) * | 2023-03-23 | 2023-07-07 | 淮阴师范学院 | Basic chloride catalyst and preparation method thereof |
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