CN108083242A - The purposes of ternary phosphatization ferronickel nanometer sheet, its preparation method and electrolysis water - Google Patents
The purposes of ternary phosphatization ferronickel nanometer sheet, its preparation method and electrolysis water Download PDFInfo
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Abstract
The present invention provides a kind of ternary phosphatization ferronickel nanometer sheet, is the Ni being grown in substratexFe(1‑x)P2Nanometer sheet, 0 ＜ x ＜ 1, the size of nanometer sheet is 500~1000nm, and thickness is 10~30nm.The present invention also proposes the preparation method and purposes of the ternary phosphatization ferronickel nanometer sheet.The good crystallinity of the phosphatization ferronickel nanometer sheet of the present invention, chemical property are stablized, and electro-chemical activity is high, applied to electrochemistry liberation of hydrogen, is reaching 10mA/cm2Current density when, overpotential is down to 151mV.Applied to Electrochemical oxygen evolution, reaching 10mA/cm2Current density when, overpotential is down to 200mV.Also there is extraordinary performance applied to electrochemistry complete solution water, reaching 10mA/cm2Current density when, required applied voltage is only 1.51V.
Description
Technical field
The invention belongs to non-polar compound field of nanometer material technology, and in particular to a kind of nano material of catalytic electrolysis water and its
It prepares and applies.
Background technology
The relevant environment problem that global energy crisis and fossil fuel generate is more and more serious, and more efficiently utilizing can be again
The raw energy becomes increasingly to be important.It is most promising that the sustainability and environmental protection characteristic of Hydrogen Energy become substitution fossil fuel
One of candidate material.The method of production hydrogen has very much, and most viable method is electrochemical decomposition water, it is by evolving hydrogen reaction
(HER, 2H++2e-→H2) and oxygen evolution reaction (OER, 2H2O→4e-+4H++O2) composition.But evolving hydrogen reaction and oxygen evolution reaction
Process is required for can be only achieved optimal reaction rate under the conditions of sufficiently large overvoltage.Especially for OER, which needs
It shifts four electronics and forms covalent O -- O bond in this process.This can make the dynamic process of the reaction become slow, because
This, which designs suitable elctro-catalyst, has very big challenge.In order to reduce the overpotential during complete solution water, exploitation has height
The bifunctional electrocatalyst of activity is very important.At present, Pt sills are the optimal Electrocatalytic Activity for Hydrogen Evolution Reaction agent of performance, and Ir/
Ru sills are considered as then optimal oxygen-separating catalyst.However, the high cost and low abundance of these precious metal materials are very
Their large-scale application is hampered in big degree.Therefore, the novel electro-catalytic agent that exploitation is cheap and catalytic activity is high is very
Urgent.
In the past few years, transistion metal compound material has been widely used for HER, OER and complete solution water.In these materials
In material, metal phosphide is either all showed in acid solution or alkaline solution except efficient electric Hydrogen Evolution Performance.And layer
Shape double-hydroxide (LDHs) has been widely studied as efficient analysis oxygen elctro-catalyst.However, the electrical conductivity of LDHs it is low and
Active site is extremely limited, this largely hinders their large-scale application.Recently, metal phosphide due to than
LDH has better electric conductivity, therefore also shows high Electrochemical oxygen evolution performance.Simultaneously as in oxygen evolution reaction process
In, metal oxidation/hydroxide with LDH features can be formed on metal phosphide surface.Therefore, in recent years, many binary
Transition metal phosphide is used for as efficient bifunctional catalyst during complete solution water.With binary transition metal phosphide phase
Than ternary transition metal phosphide can further improve its electrocatalysis characteristic by adjusting the electronic structure of catalyst.Cause
And it studies a kind of simple method for preparing ternary transition metal phosphide and is of great significance.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of phosphatization ferronickel nanometer sheet,
Preparation method and the usage.The preparation method step of nanometer sheet proposed by the present invention is simple and convenient to operate and at low cost, is prepared into
The phosphatization ferronickel nanometer sheet good crystallinity arrived, chemical property are stablized, and electro-chemical activity is high, has very applied to electrochemistry complete solution water
Good performance, electrochemistry liberation of hydrogen, the stability for analysing oxygen are good.It has broad application prospects.
The technical solution for realizing above-mentioned purpose of the present invention is：
A kind of ternary phosphatization ferronickel nanometer sheet, is the Ni being grown in substratexFe(1-x)P2Nanometer sheet, 0 ＜ x ＜ 1, nanometer
The size of piece is 500~1000nm, and thickness is 10~30nm.
Further, the substrate is carbon cloth, carbon paper or carbon felt, and the nanometer sheet is with crystalline NixFe(1-x)P2
Nanometer sheet, vertical-growth is in substrate.
The preparation method of the ternary phosphatization ferronickel nanometer sheet, including step：
(1) by hydro-thermal reaction, hydroxide ferronickel nanometer sheet is grown in substrate；
(2) substrate that growth has hydroxide ferronickel nanometer sheet is placed on to the downstream of double temperature-area tubular furnaces, the dual temperature area pipe
The placed upstream phosphorus powder of formula stove prepares ternary phosphatization ferronickel nanometer sheet by the method for chemical vapor deposition (CVD).
Further, the substrate is carbon cloth, before hydro-thermal reaction, first passes through and is cleaned by ultrasonic in deionized water, in second
Ultrasonic cleaning and ultrasonic cleaning in acetone in alcohol, when then drying 6~18 is small at 20~80 DEG C.
Wherein, in step (1), base material is immersed in the mixed solution containing nickel source, source of iron and amine source, in 100
~120 DEG C of progress hydro-thermal reactions, then it is washed and dried, obtain being grown in the hydroxide ferronickel nanometer sheet in substrate；The nickel
Source is one or both of nickel nitrate, nickel chloride, nickel sulfate or nickel acetate, and the source of iron is ferric nitrate, iron chloride, ferric sulfate
Or any one in ferric acetate or two kinds；The amine source is urea or 2- amino terephthalic acid (TPA)s (NH2- BDC), the hydro-thermal
When the time of reaction is 5~10 small.
Preferably, in step (1), the quality volume content of nickel source, source of iron and amine source is respectively 8~20g/ in mixed solution
L, 2~8g/L and 20~30g/L.
Wherein, in step (2), the substrate of hydroxide ferronickel nanometer sheet and phosphorus powder are respectively put into a pair of of quartz sleeve growth
In the large diameter pipe and minor diameter pipe of pipe, large diameter pipe and minor diameter pipe sleeve are put so that quartz socket tube front and back end is respectively placed in
The furnace temperature in downstream after the entire boiler tube of argon purge, is increased to 450~600 DEG C, upstream by the downstream and upstream of dual temperature tube furnace
Furnace temperature be increased to 350~450 DEG C, keep carrier gas 100~120sccm of argon flow amount, grow 60~90 minutes, it is anti-to carry out phosphatization
Should, then natural cooling, obtains being grown in the ternary phosphatization ferronickel nanometer sheet in substrate.
It is highly preferred that the furnace temperature in downstream is 480~550 DEG C, the furnace temperature of upstream is 380~400 DEG C.
Ternary phosphatization ferronickel nanometer sheet of the present invention is in electrochemistry liberation of hydrogen, Electrochemical oxygen evolution and electrochemistry complete solution water
Purposes.
The beneficial effects of the present invention are：
(1) hydroxide ferronickel nanometer sheet has been prepared as raw material using phosphorus powder and by hydro-thermal method in the present invention, passes through chemistry
Vapor deposition method prepares phosphatization ferronickel nanometer sheet, and there is the method preparation process to be simple and convenient to operate and at low cost excellent
Point；
(2) good crystallinity of phosphatization ferronickel nanometer sheet of the invention, chemical property are stablized, and electro-chemical activity is high, is applied to
Electrochemistry liberation of hydrogen is reaching 10mA/cm2Current density when, overpotential is down to 151mV.Applied to Electrochemical oxygen evolution, up to
To 10mA/cm2Current density when, overpotential is down to 200mV.Also there is extraordinary property applied to electrochemistry complete solution water
Can, reaching 10mA/cm2Current density when, required applied voltage is only 1.51V.Above test is in alkaline environment
It is carried out in (1M KOH).
Description of the drawings
Fig. 1 its (a) and Fig. 1 its (b) is the Ni that embodiment 1 is preparedxFe(1-x)P2The scanning of (0 ＜ x ＜ 1) nanometer sheet
Electron microscope (SEM) top view；
Fig. 2 is the Ni that embodiment 1 is preparedxFe(1-x)P2The scanning electron microscope of (0 ＜ x ＜ 1) nanometer sheet is not of the same race
Mapping (SEM-EDX elemental mapping) figure of element；
Fig. 3 its (a) is the NixFe that embodiment 1 is prepared(1-x)P2The transmission electron microscope (TEM) of (0 ＜ x ＜ 1) nanometer sheet
Figure；Fig. 3 its (b) is NixFe(1-x)P2High-resolution-ration transmission electric-lens (HRTEM) figure of (0 ＜ x ＜ 1) nanometer sheet.
Fig. 4 is the Ni that embodiment 1 is preparedxFe(1-x)P2The energy spectrum analysis figure (EDX) of (0 ＜ x ＜ 1) nanometer sheet.
Fig. 5 a, Fig. 5 b and Fig. 5 c are respectively the Ni that embodiment 1 is preparedxFe(1-x)P2(0 ＜ x ＜ 1) and NiP2 nanometer sheets
HER performances compare figure, OER performances compare figure and complete solution is aqueous can compare figure.
Fig. 6 is the Ni that embodiment 1 is preparedxFe(1-x)P2Stereoscan photograph.
Specific embodiment
The present invention is now illustrated with following most preferred embodiment, but is not limited to the scope of the present invention.
Unless otherwise specified, the means used in embodiment are technological means commonly used in the art.
Embodiment 1：
NixFe(1-x)P2The preparation of nanometer sheet
(1) deionized water, ethyl alcohol and acetone ultrasonic clean carbon cloth (CF) are used, when 60 DEG C of dryings 7 are small.Clean CF is soaked
Enter 40mL and contain 0.654g Nickelous nitrate hexahydrates (Ni (NO3)2·6H2), O 0.303g Fe(NO3)39H2Os (Fe (NO3)3·9H2O)
With 0.9g urea (CO (NH2)2) mixed solution in, be placed in the reaction kettle of 50mL and be warming up to 100 DEG C of holding 6h, reaction terminates
Washing is cooled to room temperature, after 60 DEG C of dryings, obtains NixFe(1-x)(OH)2Nanometer sheet.
(2) by P powder and the Ni being grown on carbon clothxFe(1-x)(OH)2Nanometer sheet is respectively put into the minor diameter pipe of quartz socket tube
(inner tube) and large diameter pipe (outer tube), large diameter pipe and minor diameter pipe sleeve are put, are respectively placed in the rear and front end of quartz socket tube
The upstream and downstream center warm area of dual temperature area pipe reaction stove, makes P powder and nanometer sheet be respectively placed in upstream and downstream；Use argon gas
(Ar) after cleaning entire boiler tube repeatedly, upstream furnace temperature is raised to 400 DEG C, downstream furnace temperature is increased to 500 DEG C, keeps carrier gas Ar flows
100sccm grows cooled to room temperature after sixty minutes, NixFe(1-x)(OH)2Nanometer sheet is just converted into NixFe(1-x)P2Nanometer
Piece.
Its performance indicator is briefly illustrated with lower part：
Fig. 1 its (a) and (b) are the Ni that embodiment 1 is preparedxFe(1-x)P2The scanning electron of (0 ＜ x ＜ 1) nanometer sheet is shown
Micro mirror (SEM) top view, the Ni synthesized it can be seen from Fig. 1 (a)xFe(1-x)P2Nanometer sheet is evenly distributed in carbon cloth surfaces,
The Ni it can be seen from Fig. 1 (b)xFe(1-x)P2Nanometer sheet is vertical-growth in carbon cloth substrate.
Fig. 2 is the Ni that embodiment 1 is preparedxFe(1-x)P2The scanning electron microscope of (0 ＜ x ＜ 1) nanometer sheet is not of the same race
Mapping (SEM-EDX elemental mapping) figure of element, as seen from Figure 2, three kinds of nickel, iron, phosphorus elements are in nanometer
It is equally distributed in piece.
Fig. 3 (a) and (b) are respectively the Ni that embodiment 1 is preparedxFe(1-x)P2The transmission electron microscope of (0 ＜ x ＜ 1) nanometer sheet
Scheme (TEM) figure and high-resolution-ration transmission electric-lens (HRTEM) figure.The Ni it can be seen from Fig. 3 (a) and Fig. 6xFe(1-x)P2Nanometer sheet size
About 1 μm, shape is trapezoidal, i.e. the half of hexagon.The Ni it can be seen from Fig. 3 (b)xFe(1-x)P2Nanometer sheet crystallinity is high,
Lattice fringe is very clear.
Fig. 4 is the Ni that embodiment 1 is preparedxFe(1-x)P2The energy spectrum analysis (EDX) of (0 ＜ x ＜ 1) nanometer sheet, by Fig. 4
As can be seen that comprising Ni, Fe and P element in the nanometer sheet that embodiment 1 is prepared, and each atom content respectively is
23.4%th, 8.2% and 68.4%.Comparative example
With NiP2Nanometer sheet is contrast material.NiP2The synthetic method of nanometer sheet is：
(1) deionized water, ethyl alcohol and acetone ultrasonic clean carbon cloth (CF) are used, when 60 DEG C of dryings 7 are small.Clean CF is soaked
Enter 40mL and contain 0.654g Nickelous nitrate hexahydrates (Ni (NO3)2·6H2) and 0.9g urea (CO (NH O2)2) mixed solution in, put
100 DEG C of holding 6h are warming up in the reaction kettle of 50mL, reaction terminates to be cooled to room temperature washing, after 60 DEG C of dryings, obtains Ni
(OH)2Nanometer sheet.
(2) by P powder and the Ni (OH) being grown on carbon cloth2Nanometer sheet is respectively put into quartz socket tube rear and front end, is placed in double
The upstream and downstream center warm area of warm area pipe reaction stove, after cleaning entire boiler tube repeatedly with argon gas (Ar), by upstream furnace temperature 400
DEG C, downstream furnace temperature is increased to 500 DEG C, keeps carrier gas Ar flow 100sccm, grows cooled to room temperature after sixty minutes, Ni
(OH)2Nanometer sheet is just converted into NiP2Nanometer sheet.
Electrochemical test
Electrochemical test, the Ni that embodiment 1 is prepared are carried out in 1M KOH solutionsxFe(1-x)P2Or contrast material is
Working electrode, is the carbon-point that electrochemical properties are stablized to electrode, and reference electrode is (the final current potential conversion of mercury/mercuric oxide electrode
To compared with standard hydrogen electrode).By linear scan method (LSV) record during the test electric current with the variation of current potential and
Than the situation of variation.The test potential window of evolving hydrogen reaction is lied prostrate for 0-0.3 (compared with standard hydrogen electrode), sweeps speed as 5mV/s.Analysis
The potential window of oxygen reaction is lied prostrate for 1.2-1.6 (compared with standard hydrogen electrode), sweeps speed as 5mV/s.It, will during all-hydrolytic reaction test
Reference electrode is connected with auxiliary electrode, respectively to be grown in the Ni of carbon cloth surfacesxFe(1-x)P2Nanometer sheet be anode and cathode,
Pass through the situation of change between linear scan curve record current potential and electric current.
Fig. 5 a, Fig. 5 b and Fig. 5 c are respectively the Ni that embodiment 1 is preparedxFe(1-x)P2(0 ＜ x ＜ 1) nanometer sheet and NiP2
The Hydrogen Evolution Performance of nanometer sheet analyses the comparison of oxygen performance and the aqueous energy of complete solution.It can see by Fig. 5 a, ternary NixFe(1-x)P2Nanometer
The Hydrogen Evolution Performance of piece will be substantially better than corresponding binary NiP2Nanometer sheet is reaching 10mA/cm2Electric current when, NixFe(1-x)P2It receives
The overpotential (151mV) that rice piece needs compares NiP2Nanometer sheet (202mV) is much lower.It can see by Fig. 5 b, ternary NixFe(1-x)P2
The analysis oxygen performance of nanometer sheet will be substantially better than corresponding binary NiP2Nanometer sheet is reaching 10mA/cm2Electric current when, NixFe(1-x)
P2The overpotential (198mV) that nanometer sheet needs compares NiP2Nanometer sheet (271mV) is much lower.It can see by Fig. 5 a, ternary
NixFe(1-x)P2The complete solution of nanometer sheet is aqueous to be equally better than corresponding binary NiP2Nanometer sheet is reaching 10mA/cm2Electric current
When, NixFe(1-x)P2The applied voltage that nanometer sheet needs is 1.51V, and NiP2Nanometer sheet then needs 1.6V.
Embodiment 2
NixFe(1-x)P2The preparation of nanometer sheet
(1) deionized water, ethyl alcohol and acetone ultrasonic clean carbon cloth (CF) are used, in 60 DEG C of dryings.Clean CF is immersed
40mL contains 0.741g Nickelous nitrate hexahydrate Ni (NO3)2·6H2O, 0.182g Fe(NO3)39H2O Fe (NO3)3·9H2O and 0.9g
Urea (CO (NH2)2) mixed solution in, be placed in the reaction kettle of 50mL be warming up to 100 DEG C holding 6h, reaction terminate be cooled to
Room temperature washing after 60 DEG C of dryings, obtains NixFe(1-x)(OH)2Nanometer sheet.
(2) by P powder and Ni obtainedxFe(1-x)(OH)2Nanometer sheet is respectively put into casing both ends, and it is anti-to be placed in dual temperature area tubular type
The upstream and downstream center warm area of stove is answered, after cleaning quartz ampoule repeatedly with argon gas (Ar), by 400 DEG C of upstream furnace temperature, downstream furnace temperature
500 DEG C are increased to, keeps carrier gas Ar flow 100sccm, grows cooled to room temperature after sixty minutes, NixFe(1-x)(OH)2It receives
Rice piece is just converted into NixFe(1-x)P2Nanometer sheet.
Its performance indicator is briefly illustrated with lower part：
The phosphatization ferronickel Ni that the present embodiment is preparedxFe(1-x)P2The nickle atom of (0 ＜ x ＜ 1) nanometer sheet and iron atom it
Between ratio be about 5.6:1.For the diameter of nanometer sheet between 500~1000nm, shape is trapezoidal；Nickel, iron, P elements are equably
It is dispersed in nanometer sheet；Electrochemistry liberation of hydrogen (HER) test display, the liberation of hydrogen ability for the nanometer sheet that the present embodiment is prepared is than real
It is slightly poor to apply the nanometer sheet that example one is prepared, but is still better than binary NiP2Hydrogen Evolution Performance.Correspondingly, Electrochemical oxygen evolution
(OER) and the test of complete solution water show the analysis oxygen performance of nanometer sheet that the present embodiment is prepared and complete solution is aqueous can be equally between reality
Apply nanometer sheet and the binary NiP that example one is prepared2Between nanometer sheet.
Embodiment 3
NixFe(1-x)P2The preparation of nanometer sheet
(1) deionized water, ethyl alcohol and acetone ultrasonic clean carbon cloth (CF) are used, in 60 DEG C of dryings.Clean CF is immersed
40mL contains 0.567g Nickelous nitrate hexahydrate Ni (NO3)2·6H2O, 0.424g Fe(NO3)39H2O Fe (NO3)3·9H2O and 0.9g
Urea (CO (NH2)2) mixed solution in, be placed in the reaction kettle of 50mL be warming up to 100 DEG C holding 6h, reaction terminate be cooled to
Room temperature washing after 60 DEG C of dryings, obtains NixFe(1-x)(OH)2Nanometer sheet.
(2) by P powder and Ni obtainedxFe(1-x)(OH)2Nanometer sheet is respectively put into casing both ends, and it is anti-to be placed in dual temperature area tubular type
The upstream and downstream center warm area of stove is answered, after cleaning quartz ampoule repeatedly with argon gas (Ar), by 400 DEG C of upstream furnace temperature, downstream furnace temperature
500 DEG C are increased to, keeps carrier gas Ar flow 100sccm, grows cooled to room temperature after sixty minutes, NixFe(1-x)(OH)2It receives
Rice piece is just converted into NixFe(1-x)P2Nanometer sheet.
Its performance indicator is briefly illustrated with lower part：
The phosphatization ferronickel Ni that the present embodiment is preparedxFe(1-x)P2The nickle atom of (0 ＜ x ＜ 1) nanometer sheet and iron atom it
Between ratio be about 1.86:1.For the diameter of nanometer sheet between 500~1000nm, shape is trapezoidal；Nickel, iron, P elements are uniform
Ground is dispersed in nanometer sheet；Electrochemistry liberation of hydrogen (HER), Electrochemical oxygen evolution (OER), complete solution water test result show, the present embodiment
The Hydrogen Evolution Performance for the nanometer sheet being prepared analyses oxygen performance, the performance phase of the aqueous nanometer sheet that can be obtained with embodiment 2 of complete solution
Closely.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.
Claims (9)
1. a kind of ternary phosphatization ferronickel nanometer sheet, which is characterized in that be the Ni being grown in substratexFe(1-x)P2Nanometer sheet, 0 ＜ x
＜ 1, the size of nanometer sheet is 500~1000nm, and thickness is 10~30nm.
2. ternary phosphatization ferronickel nanometer sheet according to claim 1, which is characterized in that the substrate for carbon cloth, carbon paper or
Carbon felt, the nanometer sheet are with crystalline NixFe(1-x)P2Nanometer sheet, vertical-growth is in substrate.
3. the preparation method of the ternary phosphatization ferronickel nanometer sheet of claim 1 or 2, which is characterized in that including step：
(1) by hydro-thermal reaction, hydroxide ferronickel nanometer sheet is grown in substrate；
(2) substrate that growth has hydroxide ferronickel nanometer sheet is placed on to the downstream of double temperature-area tubular furnaces, double temperature-area tubular furnaces
Placed upstream phosphorus powder, ternary phosphatization ferronickel nanometer sheet is prepared by the method for chemical vapor deposition.
4. preparation method according to claim 3, which is characterized in that the substrate is carbon cloth, before hydro-thermal reaction, is first passed through
Ultrasonic cleaning in deionized water, in ethanol ultrasonic cleaning and ultrasonic cleaning in acetone are crossed, then at 20~80 DEG C
When drying 6~18 is small.
5. preparation method according to claim 3, which is characterized in that in step (1), base material is immersed in containing nickel
In the mixed solution in source, source of iron and amine source, hydro-thermal reaction is carried out in 100~120 DEG C, then it is washed and dried, it is grown in
Hydroxide ferronickel nanometer sheet in substrate；The nickel source is one kind or two in nickel nitrate, nickel chloride, nickel sulfate or nickel acetate
Kind, the source of iron is any one or two kinds in ferric nitrate, iron chloride, ferric sulfate or ferric acetate；The amine source for urea or
2- amino terephthalic acid (TPA)s, when the time of the hydro-thermal reaction is 5~10 small.
6. preparation method according to claim 5, which is characterized in that in step (1), nickel source in mixed solution, source of iron and
The quality volume content in amine source is respectively 8~20g/L, 2~8g/L and 20~30g/L.
7. according to claim 3~5 any one of them preparation method, which is characterized in that in step (2), growth is had hydrogen-oxygen
The substrate and phosphorus powder for changing ferronickel nanometer sheet are respectively put into the large diameter pipe and minor diameter pipe of a pair of of quartz socket tube, by large diameter pipe
It is put with minor diameter pipe sleeve so that quartz socket tube front and back end is respectively placed in the downstream and upstream of dual temperature tube furnace, with argon purge stove
The furnace temperature in downstream is increased to 450~600 DEG C by Guan Hou, and the furnace temperature of upstream is increased to 350~450 DEG C, keeps carrier gas argon flow amount
100~120sccm is grown 60~90 minutes, carries out phosphating reaction, then natural cooling, obtains being grown in the ternary in substrate
Phosphatization ferronickel nanometer sheet.
8. preparation method according to claim 7, which is characterized in that the furnace temperature in downstream is 480~550 DEG C, the stove of upstream
Temperature is 380~400 DEG C.
9. the ternary phosphatization ferronickel nanometer sheet described in claim 1 or 2 is in electrochemistry liberation of hydrogen, Electrochemical oxygen evolution and electrochemistry complete solution
Purposes in water.
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