CN109797404A - The binary metal phosphide and preparation method and application of molybdenum trioxide (tungsten) regulation - Google Patents

The binary metal phosphide and preparation method and application of molybdenum trioxide (tungsten) regulation Download PDF

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CN109797404A
CN109797404A CN201910076389.0A CN201910076389A CN109797404A CN 109797404 A CN109797404 A CN 109797404A CN 201910076389 A CN201910076389 A CN 201910076389A CN 109797404 A CN109797404 A CN 109797404A
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CN109797404B (en
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杨大驰
郑世政
杜玲玲
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Nankai University
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Abstract

The present invention relates to the binary metal phosphides and preparation method and application of a kind of molybdenum trioxide (tungsten) regulation.It is matrix that adopt the present invention, which be by nickel foam, prepares column presoma by hydro-thermal method first, then passes through the method for low temperature phosphor formation MoO3‑xThe columnar arrays structure of the porous surface of regulation.There are amorphous MoO in the structure3‑xAnd CoP/Ni5P4Hetero-junctions is conducive to the activation of hydrone and the precipitation of hydrogen.In addition, vertical porous cylindrical array structure can speed up the infiltration of electrolyte, exposes more electrochemical surface areas and gas is facilitated to be desorbed from catalyst surface.This structure has very big potential using value in electro-catalysis field.

Description

The binary metal phosphide and preparation method and application of molybdenum trioxide (tungsten) regulation
Technical field
The present invention relates to the binary metal phosphides and preparation method and application of a kind of molybdenum trioxide (tungsten) regulation, specifically Take function as the function nano design of material and modification technique of guiding, grows molybdenum cobalt nickel on nickel foam substrate using hydro-thermal method Column presoma and low temperature phosphor technology prepare porous columnar arrays structure.
Background technique
Because preparation process is simple with equipment, and free of contamination advantage, electrochemistry total moisture solution be considered as prepare it is high-purity The promising approach of hydrogen.Theoretical calculation with the experimental results showed that binary transition metal phosphide have good electrolysis water performance, This is mainly due to the adsorption energy of alloy effect and suitable hydrogen between its good electric conductivity, binary metal.But in alkali Under the conditions of property, due to its poor hydrophily, water activates that form hydrionic process slower.Amorphous metal oxide has Good hydrophily can speed up the activation of water, generate more hydrogen ions.In addition, electrocatalytic reaction also requires material to have The desorption performance of good mass transfer and gas.Porous columnar arrays structure is capable of providing more specific surface areas, Ke Yibao Reveal the active site of more electrochemical reactions.Simultaneously as its porous structure, the process of osmosis of electrolyte are accelerated, It can speed up electrochemical reaction.In addition, porous structure is conducive to desorption of the gas molecule from electrode surface, and then enhances electricity and urge Change performance.Hydro-thermal method prepares CoMoO4/NiMoO4Columnar arrays structure uses the column structure prepared to continue to repair as presoma Porous columnar arrays structure is adornd into not realize also.
Summary of the invention
The object of the present invention is to provide a kind of molybdenum trioxide (tungsten) to regulate and control binary metal phosphide and preparation method and application, Realization uses the column structure prepared to continue to be modified into porous columnar arrays structure as presoma.
A kind of binary metal phosphide of molybdenum trioxide regulation provided by the invention is the porous cylindrical array structure of hydridization, The molybdenum trioxide (tungsten) is generated in-situ amorphous structure, and column volume array is meso-hole structure, pore diameter range 5- 10 nanometers, the length of column is 15-30 microns, and diameter is 3-5 microns;There are amorphous MoO in its structure3-xAnd CoP/Ni5P4Hetero-junctions, wherein x is the quantity of Lacking oxygen, 0 < X < 1;
Preparation method includes the column presoma and low temperature phosphor for growing molybdenum cobalt nickel on nickel foam substrate using hydro-thermal method.
In the binary metal phosphide of the molybdenum trioxide regulation provided by the invention, three oxygen of the molybdenum trioxide Change tungsten to replace;The CoP/Ni5P4Hetero-junctions can use CoP/CuP or Ni5P4/ CuP or CuP/Ni5P4Instead of.
The preparation method of the binary metal phosphide of molybdenum trioxide provided by the invention regulation the following steps are included:
1) foam nickel surface is cleaned;Nickel foam is immersed in 0.01-1 M dilute hydrochloric acid, the ultrasound in ultrasonic cleaning instrument Concussion 5-50 minutes, removes the NiO film of surface compact;Ultrasonic cleaning is clean in deionized water again, then ultrasonic in acetone Cleaning;It is finally cleaned in dehydrated alcohol, the nickel foam cleaned up is placed in 20-80 DEG C of vacuum oven dry 3-20 h;
2) hydro-thermal method grows the column presoma of molybdenum cobalt nickel on nickel foam substrate;By 0.002-0.5 M Ni (NO3)3·5H2O、 0.002-0.5 M Co(NO3)2、0.004-1 M Na2MoO4、0.002-0.8 M NH4F is added in reaction kettle, magnetic agitation 10-60 min obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, is 100-180 DEG C in temperature Baking oven in keep the temperature 5-10 hours;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling;It is placed in 30- Dry 2-10 h in 80 DEG C of vacuum oven;
3) low temperature phosphor prepares porous columnar arrays structure, and obtained molybdenum cobalt nickel column shape presoma is placed in pipe reaction furnace Downstream, sodium hypophosphite are placed in the upstream of pipe reaction furnace, first by pipe reaction stove evacuation, are passed through argon gas, flow velocity 10- 100 cc min-1;Select heating rate for 2-20 DEG C/min, in 200-600 DEG C of heat preservation 1-6 h;After natural cooling, deionized water The impurity for rinsing surface, obtains amorphous state deficiency MoO3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure.
Further, the application of the binary metal phosphide regulated and controled the present invention provides molybdenum trioxide or tungstic acid, including (molybdenum trioxide described in detail below is answered for application in terms of for electrocatalytic hydrogen evolution, Electrochemical oxygen evolution and electrochemistry total moisture solution With).
The binary metal phosphide of molybdenum trioxide regulation for the application in terms of electrocatalytic hydrogen evolution the following steps are included:
1) composition of test macro:
The amorphous state deficiency MoO that will be grown on nickel foam substrate3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure is straight It connecing and is used as working electrode, tested in three-electrode system, be respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode, 1 M KOH is electrolyte, is first carried out processing 30 minutes of logical argon gas to electrolyte before test;
2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., in the potential region of -1.232 V of V to -0.832 The CV circulation for carrying out 100 circles, LSV test is then carried out in the potential region of -1.232 V of V to -0.832, is come with this to non- Crystalline defects type MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The Hydrogen Evolution Performance of array structure is assessed;
3) the iR compensation and conversion of current potential:
In this during, all current potentials all pass through 90% iR compensation, in addition, the current potential in this experiment will be converted into it is reversible Hydrogen potential, specific calculation formula are as follows: ERHE=EHg/HgO+0.098+0.059pH。
It is 10 mA cm that experimental result, which is shown in current density,-2When, overpotential is only 90 mV, shows good electricity Catalytic hydrogen evolution performance.
The binary metal phosphide of molybdenum trioxide regulation for the application in terms of Electrochemical oxygen evolution the following steps are included:
1) composition of test macro:
The amorphous state deficiency MoO that will be grown on nickel foam substrate3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure is straight It connecing and is used as working electrode, tested in three-electrode system, be respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode, 1 M KOH is electrolyte, is first carried out processing 30 minutes of logical argon gas to electrolyte before test;
2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., in the potential region of 0.268 V to 0.768 V into The CV circulation that row 100 encloses, the test of LSV is then carried out in the potential region of 0.268 V to 0.768 V, is come with this to amorphous State deficiency MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The analysis oxygen performance of array structure is assessed;
3) the iR compensation and conversion of current potential:
In this during, all current potentials all pass through 90% iR compensation, in addition, the current potential in this experiment will be converted into it is reversible Hydrogen potential, specific calculation formula are as follows: ERHE=EHg/HgO+0.098+0.059pH。
The experimental results showed that porous cylindrical array has catalytic efficiency more higher than business iridium dioxide, it is in current density 50 mA cm-2When, overpotential has dropped close to 100 mV, it is shown that its higher practical application value.
The binary metal phosphide of molybdenum trioxide regulation includes following for the application in terms of electrochemistry total moisture solution field Step:
1) composition of test macro:
The amorphous state deficiency MoO that will be grown on nickel foam substrate3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure is straight It connecing and is used as working electrode, tested in three-electrode system, be respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode, 1 M KOH is electrolyte.First electrolyte is carried out processing 30 minutes of logical argon gas before test;
2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., carries out 100 circles in the potential region of 0 V to 1.7 V CV circulation.Then LSV test is carried out in the potential region of 0 V to 1.7 V, is come with this to amorphous state deficiency MoO3-xIt adjusts The porous cylindrical CoP/Ni of control5P4The total moisture solution performance of array structure is assessed;
3) the iR compensation of current potential: in this during, all current potentials all pass through 90% iR compensation.
By the hybridization porous columnar arrays assembling of amorphous state oxygen defect molybdenum trioxide (tungsten) in situ regulation binary metal phosphide Complete solution water electrode system show good complete solution it is aqueous can, current density be 10 mA cm-2When, overpotential is only 279 MV shows the electrode system formed than business platinum carbon and iridium dioxide more preferably catalytic performance.
The present invention provides a kind of molybdenum trioxide (tungsten) regulation binary metal phosphide and preparation method and application, realize and use The column structure prepared continues to be modified into porous columnar arrays structure as presoma.The present invention can not only prepare amorphous State deficiency MoO3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure, and the ratio of change cobalt source and nickel source can be passed through To regulate and control the electronic structure of hetero-junctions.This porous orthogonal array structure can increase the contact area with electrolyte, exposure More electrochemical reaction sites, accelerate the gas generated to remove from the surface of material.It is expected to prepare other using this technology Amorphous state MoO3-xThe porous cylindrical array structure of regulation, and it is used as the catalyst of electrocatalytic decomposition water.
The present invention solves the problems, such as that water activates slow in alkaline environment.Meanwhile porous columnar arrays structure can The active site of the more electrochemical reactions of exposure, accelerates the infiltration of electrolyte, is conducive to gas molecule from the de- of electrode surface It is attached, and then accelerate electrocatalysis characteristic.The reason of its performance of high spot reviews increases, long-time stability and method it is pervasive Property.Main difficult point is how to be accurately controlled condition, prepares porous columnar arrays structure.
Detailed description of the invention
Fig. 1 is amorphous state deficiency MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The flow chart of array structure;Wherein (a) The washing of nickel foam, (b) hydro-thermal method prepares molybdenum cobalt nickel column shape presoma, and (c) low temperature phosphor prepares amorphous state deficiency MoO3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure;
Fig. 2 is the stereoscan photograph (a) and power spectrum test result (b-b5) of molybdenum cobalt nickel column shape presoma;(a) and Fig. 2 in Fig. 2 In (b) be molybdenum cobalt nickel column shape presoma stereoscan photograph, (b1-b4) is the energy stave of molybdenum cobalt nickel column shape presoma in Fig. 2 Sign is as a result, column presoma contains tetra- kinds of elements of Mo, Co, Ni and O as we can see from the figure, and is evenly distributed in column forerunner In body;
Fig. 3 is MoO3-xThe porous cylindrical CoP/Ni of regulation5P4Scanning electron microscope (SEM) the observation result and power spectrum of array structure are surveyed Test result: (a) low power large area porous cylindrical CoP/Ni5P4Array structure, (b) the porous knot of the damaged surface of high power small area Structure, (c) single MoO3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure and corresponding power spectrum test result;
Fig. 4 is MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The transmission electron microscope (TEM) of array structure: (a) porous under low power Column structure, (b) high-resolution transmission electron microscope, amorphous substance MoO3-x, two kinds of corresponding substances of obvious crystal structure are respectively CoP(0.245 nm) and Ni5P4(0.197 nm);
Fig. 5 is MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The electrochemistry liberation of hydrogen (a) of array structure (Mo-CoNiP), electrification Learn analysis oxygen (b) and total moisture solution (c) the performance test results.
Specific embodiment
Combined with specific embodiments below, it is further elaborated on the present invention.The experiment of actual conditions is not specified in embodiment Method, usually according to normal condition and condition described in handbook, or according to the normal condition proposed by manufacturer;Used is logical With equipment, material, reagent etc., it is commercially available unless otherwise specified.
Embodiment 1
(1) nickel foam surface clean:
Nickel foam is immersed in 0.1 M dilute hydrochloric acid, ultrasonic vibration 30 minutes, remove surface compact in supersonic cleaning machine NiO film;Ultrasonic cleaning is clean in deionized water again.Then it is cleaned by ultrasonic in acetone;Finally cleaning in dehydrated alcohol will The nickel foam cleaned up is placed in 60 DEG C of vacuum oven dry 6 h.
(2) hydro-thermal method prepares molybdenum cobalt nickel column shape presoma:
By 0.002 M Ni (NO3)3·5H2O、0.002 M Co(NO3)2、0.004 M Na2MoO4、0.1 M NH4F is added to In reaction kettle, 30 min of magnetic agitation obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, in temperature 10 hours are kept the temperature in the baking oven that degree is 160 DEG C;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling; Dry 6 h are placed in 60 DEG C of vacuum oven.
(3) low temperature phosphor prepares porous columar structure:
Obtained molybdenum cobalt nickel column shape presoma is placed in the downstream of pipe reaction furnace, sodium hypophosphite is placed in the upper of pipe reaction furnace Trip is passed through argon gas first by pipe reaction stove evacuation, and flow velocity is 20 cc min-1;Select heating rate for 10 DEG C/min, 450 DEG C of 2 h of heat preservation;After natural cooling, deionized water rinses the impurity on surface, obtains amorphous state deficiency MoO3-xWhat is regulated and controled is more Hole column CoP/Ni5P4Array structure.
Embodiment 2
(1) nickel foam surface clean:
Nickel foam is immersed in 0.1 M dilute hydrochloric acid, ultrasonic vibration 30 minutes, remove surface compact in supersonic cleaning machine NiO film;Ultrasonic cleaning is clean in deionized water again.Then it is cleaned by ultrasonic in acetone;Finally cleaning in dehydrated alcohol will The nickel foam cleaned up is placed in 60 DEG C of vacuum oven dry 6 h.
(2) hydro-thermal method prepares tungsten-cobalt nickel column shape presoma:
By 0.002 M Ni (NO3)3·5H2O、0.002 M Co(NO3)2、0.004 M Na2WO4、0.1 M NH4F is added to instead It answers in kettle, 30 min of magnetic agitation obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, in temperature To keep the temperature 10 hours in 160 DEG C of baking ovens;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling;It sets Dry 6 h in 60 DEG C of vacuum oven.
(3) low temperature phosphor prepares porous columar structure:
Obtained tungsten-cobalt nickel column shape presoma is placed in the downstream of pipe reaction furnace, sodium hypophosphite is placed in the upper of pipe reaction furnace Trip is passed through argon gas first by pipe reaction stove evacuation, and flow velocity is 20 cc min-1;Select heating rate for 10 DEG C/min, 450 DEG C of 2 h of heat preservation;After natural cooling, deionized water rinses the impurity on surface, obtains amorphous state deficiency WO3-xWhat is regulated and controled is porous Column CoP/Ni5P4Array structure.
Embodiment 3
(1) nickel foam surface clean:
Nickel foam is immersed in 0.1 M dilute hydrochloric acid, ultrasonic vibration 30 minutes, remove surface compact in supersonic cleaning machine NiO film;Ultrasonic cleaning is clean in deionized water again.Then it is cleaned by ultrasonic in acetone;Finally cleaning in dehydrated alcohol will The nickel foam cleaned up is placed in 60 DEG C of vacuum oven dry 6 h.
(2) hydro-thermal method prepares molybdenum cupro-nickel column presoma:
By 0.002 M Ni (NO3)3·5H2O、0.002 M Cu(NO3)2、0.004 M Na2MoO4、0.1 M NH4F is added to In reaction kettle, 30 min of magnetic agitation obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, in temperature 10 hours are kept the temperature in the baking oven that degree is 160 DEG C;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling; Dry 6 h are placed in 60 DEG C of vacuum oven.
(3) low temperature phosphor prepares porous columar structure:
Obtained molybdenum cupro-nickel column presoma is placed in the downstream of pipe reaction furnace, sodium hypophosphite is placed in the upper of pipe reaction furnace Trip is passed through argon gas first by pipe reaction stove evacuation, and flow velocity is 20 cc min-1;Select heating rate for 10 DEG C/min, 450 DEG C of 2 h of heat preservation;After natural cooling, deionized water rinses the impurity on surface, obtains amorphous state deficiency MoO3-xWhat is regulated and controled is more Hole column CuP/Ni5P4Array structure.
Embodiment 4
(1) nickel foam surface clean:
Nickel foam is immersed in 0.1 M dilute hydrochloric acid, ultrasonic vibration 30 minutes, remove surface compact in supersonic cleaning machine NiO film;Ultrasonic cleaning is clean in deionized water again.Then it is cleaned by ultrasonic in acetone;Finally cleaning in dehydrated alcohol will The nickel foam cleaned up is placed in 60 DEG C of vacuum oven dry 6 h.
(2) hydro-thermal method prepares molybdenum cobalt copper post shape presoma:
By 0.002 M Cu (NO3)2、0.002 M Co(NO3)2、0.004 M Na2MoO4、0.1 M NH4F is added to reaction kettle In, 30 min of magnetic agitation obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, is in temperature 10 hours are kept the temperature in 160 DEG C of baking oven;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling;It is placed in Dry 6 h in 60 DEG C of vacuum oven.
(3) low temperature phosphor prepares porous columar structure:
Obtained molybdenum cobalt copper post shape presoma is placed in the downstream of pipe reaction furnace, sodium hypophosphite is placed in the upper of pipe reaction furnace Trip is passed through argon gas first by pipe reaction stove evacuation, and flow velocity is 20 cc min-1;Select heating rate for 10 DEG C/min, 450 DEG C of 2 h of heat preservation;After natural cooling, deionized water rinses the impurity on surface, obtains amorphous state deficiency MoO3-xWhat is regulated and controled is more Hole column CoP/CuP array structure.
Embodiment 5
(1) nickel foam surface clean:
Nickel foam is immersed in 0.1 M dilute hydrochloric acid, ultrasonic vibration 30 minutes, remove surface compact in supersonic cleaning machine NiO film;Ultrasonic cleaning is clean in deionized water again.Then it is cleaned by ultrasonic in acetone;Finally cleaning in dehydrated alcohol will The nickel foam cleaned up is placed in 60 DEG C of vacuum oven dry 6 h.
(2) hydro-thermal method prepares tungsten-cobalt copper post shape presoma:
By 0.002 M Cu (NO3)2、0.002 M Co(NO3) 2、0.004 M Na2WO4、0.1 M NH4F is added to reaction kettle In, 30 min of magnetic agitation obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, is in temperature 10 hours are kept the temperature in 160 DEG C of baking oven;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling;It is placed in Dry 6 h in 60 DEG C of vacuum oven.
(3) low temperature phosphor prepares porous columar structure:
Obtained tungsten-cobalt copper post shape presoma is placed in the downstream of pipe reaction furnace, sodium hypophosphite is placed in the upper of pipe reaction furnace Trip is passed through argon gas first by pipe reaction stove evacuation, and flow velocity is 20 cc min-1;Select heating rate for 10 DEG C/min, 450 DEG C of 2 h of heat preservation;After natural cooling, deionized water rinses the impurity on surface, obtains amorphous state deficiency WO3-xWhat is regulated and controled is porous Column CoP/CuP array structure.
Embodiment 6
(1) nickel foam surface clean:
Nickel foam is immersed in 0.1 M dilute hydrochloric acid, ultrasonic vibration 30 minutes in ultrasonic cleaning instrument, removes surface compact NiO film;Ultrasonic cleaning is clean in deionized water again.Then it is cleaned by ultrasonic in acetone;Finally cleaned in dehydrated alcohol, it will The nickel foam cleaned up is placed in 60 DEG C of vacuum oven dry 6 h.
(2) hydro-thermal method prepares tungsten ambrose alloy column presoma:
By 0.002 M Ni (NO3)3·5H2O、0.002 M Cu(NO3)2、0.004 M Na2WO4、0.1 M NH4F is added to instead It answers in kettle, 30 min of magnetic agitation obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, in temperature To keep the temperature 10 hours in 160 DEG C of baking ovens;Surface residue is rinsed out with a large amount of deionized water after natural cooling;It is placed in 60 DEG C vacuum oven in dry 6 h.
(3) low temperature phosphor prepares porous columar structure:
Obtained tungsten ambrose alloy column presoma is placed in the downstream of pipe reaction furnace, sodium hypophosphite is placed in the upper of pipe reaction furnace Trip is passed through argon gas first by pipe reaction stove evacuation, and flow velocity is 20 cc min-1;Select heating rate for 10 DEG C/min, 450 DEG C of 2 h of heat preservation;After natural cooling, deionized water rinses the impurity on surface, obtains amorphous state deficiency WO3-xWhat is regulated and controled is porous Column Ni5P4/ CuP array structure.
Embodiment 7
(1) composition of test macro:
The amorphous MoO that will be grown on nickel foam substrate3-x(WO3-x) regulation binary metal phosphide heterojunction structure it is straight It connects and is used as working electrode, tested in three-electrode system.It is respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode, 1 M KOH is electrolyte.First lead to argon gas to electrolyte before test to handle 30 minutes.
(2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., in the potential region of -1.232 V of V to -0.832 Carry out the CV circulation of 100 circles.Then LSV test is carried out in the potential region of -1.232 V of V to -0.832, is come with this to non- Crystalline defects type MoO3-x(WO3-x) the HER performance of binary metal phosphide heterojunction array structure of regulation assessed.? The test that LSV curve is carried out in the potential region of 0.268 V to 0.768 V, is come with this to amorphous state deficiency MoO3-x (WO3-x) the OER performance of binary metal phosphide heterojunction array structure of regulation assessed.It is tested in two electrode systems Amorphous state deficiency MoO3-x(WO3-x) regulation binary metal phosphide heterojunction array structure total moisture solution performance.
(3) the iR compensation and conversion of current potential:
In this during, all current potentials all pass through 90% iR compensation, in addition, the current potential in this experiment will be converted into it is reversible Hydrogen potential, specific calculation formula are as follows: ERHE=EHg/HgO+0.098+0.059pH。

Claims (8)

1. a kind of binary metal phosphide of molybdenum trioxide regulation, it is characterised in that: the binary metal phosphorus of molybdenum trioxide regulation Compound is the porous cylindrical array structure of hydridization, and the molybdenum trioxide is generated in-situ amorphous structure, columnar arrays For meso-hole structure, pore diameter range is 5-10 nanometers, and the length of column is 15-30 microns, and diameter is 3-5 microns;In its structure There are amorphous MoO3-xAnd CoP/Ni5P4Hetero-junctions, wherein x is the quantity of Lacking oxygen, 0 < X < 1;Preparation method includes The column presoma and low temperature phosphor of molybdenum cobalt nickel are grown on nickel foam substrate using hydro-thermal method.
2. the binary metal phosphide of molybdenum trioxide regulation described in accordance with the claim 1, it is characterised in that: three oxidations Molybdenum is replaced with tungstic acid.
3. the binary metal phosphide of molybdenum trioxide regulation according to claim 1 or 2, it is characterised in that: CoP/Ni5P4 Hetero-junctions CoP/CuP or Ni5P4/ CuP or CuP/Ni5P4Instead of.
4. the preparation method of the binary metal phosphide of molybdenum trioxide described in claim 1 regulation, it is characterised in that including with Lower step:
1) foam nickel surface is cleaned;Nickel foam is immersed in 0.01-1 M dilute hydrochloric acid, the ultrasound in ultrasonic cleaning instrument Concussion 5-50 minutes, removes the NiO film of surface compact;Ultrasonic cleaning is clean in deionized water again, then ultrasonic in acetone Cleaning;It is finally cleaned in dehydrated alcohol, the nickel foam cleaned up is placed in 20-80 DEG C of vacuum oven dry 3-20 h;
2) hydro-thermal method grows the column presoma of molybdenum cobalt nickel on nickel foam substrate;By 0.002-0.5 M Ni (NO3)3·5H2O、 0.002-0.5 M Co(NO3)2、0.004-1 M Na2MoO4、0.002-0.8 M NH4F is added in reaction kettle, magnetic agitation 10-60 min obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, is 100-180 DEG C in temperature Baking oven in keep the temperature 5-10 hours;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling;It is placed in 30- Dry 2-10 h in 80 DEG C of vacuum oven;
3) low temperature phosphor prepares the columnar arrays structure of porous surface, and obtained molybdenum cobalt nickel column shape presoma is placed in pipe reaction The downstream of furnace, sodium hypophosphite are placed in the upstream of pipe reaction furnace, first by pipe reaction stove evacuation, are passed through argon gas, flow velocity For 10-100 cc min-1;Select heating rate for 2-20 DEG C/min, in 200-600 DEG C of heat preservation 1-6 h;After natural cooling, go Ionized water rinses the impurity on surface, obtains amorphous state deficiency MoO3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure.
5. the application of binary metal phosphide described in claim 1,2 or 3, it is characterised in that it is used for electrocatalytic hydrogen evolution, electricity The application of chemistry analysis oxygen and electrochemistry total moisture solution.
6. the application of binary metal phosphide according to claim 5, it is characterised in that described is used for electrocatalytic hydrogen evolution Application the following steps are included:
1) composition of test macro:
The amorphous state deficiency MoO that will be grown on nickel foam substrate3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure is direct It as working electrode, is tested in three-electrode system, is respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode, 1 M KOH is electrolyte, is first carried out processing 30 minutes of logical argon gas to electrolyte before test;
2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., in the potential region of -1.232 V of V to -0.832 The CV circulation for carrying out 100 circles, LSV test is then carried out in the potential region of -1.232 V of V to -0.832, is come with this to non- Crystalline defects type MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The Hydrogen Evolution Performance of array structure is assessed;
3) the iR compensation and conversion of current potential:
In this during, all current potentials all pass through 90% iR compensation, in addition, the current potential in this experiment will be converted into it is reversible Hydrogen potential, specific calculation formula are as follows: ERHE=EHg/HgO+0.098+0.059pH。
7. the application of binary metal phosphide according to claim 5, it is characterised in that described is used for Electrochemical oxygen evolution Application the following steps are included:
1) composition of test macro:
The amorphous state deficiency MoO that will be grown on nickel foam substrate3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure is direct It as working electrode, is tested in three-electrode system, is respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode, 1 M KOH is electrolyte, is first carried out processing 30 minutes of logical argon gas to electrolyte before test;
2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., in the potential region of 0.268 V to 0.768 V into The CV circulation that row 100 encloses, the test of LSV is then carried out in the potential region of 0.268 V to 0.768 V, is come with this to amorphous State deficiency MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The analysis oxygen performance of array structure is assessed;
3) the iR compensation and conversion of current potential:
In this during, all current potentials all pass through 90% iR compensation, in addition, the current potential in this experiment will be converted into it is reversible Hydrogen potential, specific calculation formula are as follows: ERHE=EHg/HgO+0.098+0.059pH。
8. the application of binary metal phosphide according to claim 5, it is characterised in that described is used for the full water of electrochemistry Decomposition application the following steps are included:
1) composition of test macro:
The amorphous state deficiency MoO that will be grown on nickel foam substrate3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure is direct It as working electrode, is tested in three-electrode system, is respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode, 1 M KOH is electrolyte, is first carried out processing 30 minutes of logical argon gas to electrolyte before test;
2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., carries out 100 circles in the potential region of 0 V to 1.7 V CV circulation, then in the potential region of 0 V to 1.7 V carry out LSV test, come with this to amorphous state deficiency MoO3-xIt adjusts The porous cylindrical CoP/Ni of control5P4The total moisture solution performance of array structure is assessed;
3) the iR compensation of current potential: in this during, all current potentials all pass through 90% iR compensation.
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