CN108588750A - A kind of double-metal phosphide elctro-catalyst and preparation method thereof and its application - Google Patents
A kind of double-metal phosphide elctro-catalyst and preparation method thereof and its application Download PDFInfo
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Abstract
The invention belongs to elctro-catalyst fields, and in particular to a kind of preparation method of the mesoporous double-metal phosphide elctro-catalyst of high-performance electric chemical breakdown aquatic products hydrogen and application.The hydroxide precursor that will be synthesized by hydro-thermal reaction further obtains Ni under low temperature phosphor reactionxMn1P porous nano chip arrays elctro-catalysts.The series double-metal phosphide has the reaction barrier of lower charge transfer resistance and evolving hydrogen reaction, has superior performance in electrocatalytic hydrogen evolution reaction.The catalyst is of low cost simultaneously, and easy to operate, simple for process, catalytic performance is superior, provides the foundation application study in electro-catalysis field for such material.
Description
Technical field
The invention belongs to elctro-catalyst fields, and in particular to a kind of mesoporous bimetallic of high-performance electric chemical breakdown aquatic products hydrogen
The preparation method of phosphide elctro-catalyst and application.
Technical background
Green energy resource with its cleanliness without any pollution, efficiently, can store and transport the advantages that, be considered as optimal energy carrier
With energy storage mode.Water electrolysis hydrogen production (hydrogen evolution reaction, HER) technology is efficient with its, environment is friendly
Good, the advantages that aerogenesis purity is high and energy fluctuation is adaptable, the great application prospect in the development of chemical energy storage technology.
The noble metals such as Pt, Pd and its oxide etc. have excellent catalytic activity, but its scarcity and height for electrocatalytic decomposition water
Cost limits its extensive use.Exploring efficient, low-cost HER elctro-catalysts becomes the task of top priority.
Transition metal phosphide MxP(CoP、Co2P、Ni2P、Cu3P, MoP etc.) phosphorus atoms enter in the lattice of transition metal
And compound is filled between the one kind formed, because it has similar zero-valent metal characteristic, higher chemical stability and good boundary
Face kinetics is widely used in the manufacture of Li ion batteries, opto-electronic device and HER elctro-catalysts at present.It is basic
Construction unit is isotropic crystal structure, and structure easily exposes more surface-active sites, thus compared with metal nitride,
Sulfide has better catalytic activity.Phosphorus atoms electronegativity is big in transition metal phosphide, can adsorb in the reaction proton from
And promote the reaction rate of evolving hydrogen reaction；Phosphorus atoms are H during the reaction2Desorption provide energy, to prevent reaction by
Cause to inactivate in the high coverage rate of strong bonding hydrogen atom, therefore increase phosphorus atoms percentage, can correspondingly increase electro-catalysis work
Property and stability.Relative to monometallic phosphide, double-metal phosphide can play the synergistic effect of two kinds of different metal ions, change
Become elctro-catalyst electronic structure, more surface reaction activity sites is provided, to improve the catalytic efficiency and stability of catalyst.
There are pertinent literature report, nickel cobalt phosphorus lower compared with nickel phosphide fermi level, this illustrates that in-between state hydrogen adsorption energy is relatively low, and reaction is easy to
It carries out.So relative to monometallic phosphide, double-metal phosphide not only has better electric conductivity, is more advantageous to electronics biography
It is defeated, the interface resistance and Surface reaction kinetics energy barrier of electric charge transfer can be also further decreased, therefore electro catalytic activity is available
It further increases (Nano Lett.2016,16,7718-7725).Domestic and foreign scholars have carried out some Zhuos in this respect to be had
The work of effect.For example, Wang et al. has synthesized NiCoP nano wire elctro-catalysts, elctro-catalyst 10and based on nickel foam
100mA cm-2Overpotential of hydrogen evolution respectively reaches 43and 118mV, and activity is apparently higher than single metal phosphide (ACS
Appl.Mater.Interfaces,2016,8(50),34270-34279).Sung et al. modifies nickel iron hydroxide with MOF and closes
At bifunctional electrocatalyst ferronickel phosphorus nanometer stick array, OER overpotentials are 217mV, and HER overpotentials are 74mV
(J.Mater.Chem.A,2017,5,2496-2503).Research at present about double-metal phosphide elctro-catalyst is also fewer,
The key science and technology problem such as optimization design of structure-activity relationship and structure of composed structure and electrocatalysis characteristic is badly in need of solving.
Invention content
It is an object of the present invention to provide a kind of double-metal phosphide electricity of high-performance electric chemical breakdown aquatic products hydrogen to urge
Agent.Catalyst prepared by the invention can substantially reduce overpotential and Tafel slopes, and have good electric conductivity, can
It increases substantially NiMn-LDH base catalyst and decomposes water catalyzing manufacturing of hydrogen efficiency.Separately using nickel foam as the bimetallic of substrate fabricated in situ
Phosphide can reduce electrode internal resistance, improve its conductive capability, and be remarkably improved the catalytic activity of material.Therefore, with foam
Nickel is base material, and fabricated in situ double-metal phosphide is applied to full decomposition water, has preferable application prospect.
Technical solution of the present invention is as follows：
(1) nickel foam is cleaned, it is spare；
After using acetone, hydrochloric acid, ethyl alcohol and deionized water to be cleaned by ultrasonic successively in commercial foam nickel, dry foam totally
Nickel；
(2) the nickel manganese double-metal hydroxide (Ni that nickel foam (NF) is substrate is preparedxMn1-LDH-NF)；
a：Weigh NiCl2·6H2O、MnCl2·4H2O is added in deionized water and dissolves and be placed in reaction kettle, obtains forerunner
Liquid solution A；
b：Weigh H2O2(30w%), NaCl, hexa (HMT), are sequentially added in solution A under stiring, are formed
Solution B；
c：Nickel foam 2 × 1 (cm) cleaned in step (1) is put into B solution, by reaction kettle be transferred in baking oven into
Row hydro-thermal reaction obtains khaki precipitation after reaction；Nickel foam is taken out, washing alcohol is washed, and Ni is dried to obtainxMn1-LDH-NF；
Wherein x=1~3；
(3) the nickel manganese phosphorus double-metal phosphide (Ni that nickel foam is substrate is preparedxMn1P-NF)；
Weigh NaH2PO2It is positioned over semi-enclosed crucible upstream, by Ni made from above-mentioned (2)xMn1- LDH-NF is positioned over half
Closed crucible downstream, crucible is transferred in the heating tube furnace of auto-programming temperature control, with the heating rate of 2~4 DEG C/min
It is warming up to 300~400 DEG C of 2~4h of calcining；It after room temperature, takes out, washing alcohol is washed for several times, is dried to obtain
NixMn1P-NF。
In step (2) the step a, NiCl2·6H2O and MnCl2·4H2The molar ratio of O is x：1, wherein x=1~3；
In step b, in the solution B, a concentration of 0.015molL of NaCl-1, a concentration of 0.045molL of HMT-1, NiCl2·6H2A concentration of 0.25~the 0.75mmol/L, MnCl of O2·4H2O and H2O2(30w%) amount ratio is：1mmol：
50~60 μ L；
In step c, the temperature of hydro-thermal reaction is 90~110 DEG C, 8~12h of reaction time.
In the step (3), NaH2PO2And NixMn1The usage ratio of-LDH-NF is 5mol：1mol.
In above-mentioned steps (1), (2) and (3), the temperature of the drying is 60 DEG C, drying time 12h.
The Ni-based nickel manganese phosphorus double-metal phosphide of foam of the present invention is for answering in terms of electrocatalytic decomposition aquatic products hydrogen
With.
Using X-ray diffractometer (XRD), transmission electron microscope (TEM), composition morphology analysis is carried out to product.Using
Three electrode reaction devices, platinum filament are used as to electrode, and silver-colored silver chlorate (Ag/AgCI) electrode is as reference electrode, in 0.5M H2SO4Electricity
Solve the test for carrying out chemical property in liquid to product；
Beneficial effects of the present invention are：
(1) preparation method of the invention is made of simple hydro-thermal reaction and low temperature phosphor reaction, and step is simple, when reaction
Between it is short, easy to operate, very friendly to environment, repeatability is strong；
(2) the meso-porous nano chip arrays structure of material of the invention contributes to the release of bubble, the collaboration between bimetallic
Effect reduces charge transfer resistance, improves electron-transport.The P elements of introducing are conducive to the de- of M-OH as proton acceptor
It is attached, reduce the reaction barrier of evolving hydrogen reaction.
(3) it since the presence of the special construction of nickel foam greatly increases the specific surface area of electrode active material, provides more
More active sites, the collaboration of these factors enhance electro-catalysis ability of the material in decomposing water reaction.
Description of the drawings
Fig. 1 is prepared Ni2Mn1The XRD diffraction spectrograms of P-NF elctro-catalysts and nickel foam NF.
Fig. 2 a, 2b are respectively prepared simple Ni2Mn1-LDH-NF、Ni2Mn1The stereoscan photograph of P-NF elctro-catalysts；
Fig. 2 c are the transmission electron microscope photo of NiMnP elctro-catalysts；Fig. 2 d are Ni2Mn1The high resolution electron microscopy photo of P-NF elctro-catalysts.
Fig. 3 is prepared phosphide elctro-catalyst in 0.5M H2SO4Under the conditions of evolving hydrogen reaction polarization curve comparison diagram.
Fig. 4 is prepared phosphide elctro-catalyst in 0.5M H2SO4Under the conditions of evolving hydrogen reaction Tafel curve slope compare
Figure.
Specific implementation mode
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is simultaneously
It is without being limited thereto.
Embodiment 1
Nickel foam (NF) is the nickel manganese phosphorus double-metal phosphide (Ni of substrate2Mn1P-NF preparation)：
After nickel foam to be used to acetone, the hydrochloric acid of a concentration of 3M, ethyl alcohol and the clear 30min of deionized water ultrasound successively, 60 DEG C dry
It is dry.
Weigh 0.118g NiCl2·6H2O, and 0.0495g MnCl2·4H2O is added in 80mL deionized waters, obtains forerunner
Liquid solution A (Ni:Mn=2:1)；Weigh 0.0872g NaCl, 0.6308g HMT, 56.6 μ L H2O2In (30w%) plus solution A,
Stirring 30 minutes, 2 × 1 (cm) nickel foams are put into solution A, are transferred in 100mL reaction kettles, 100 DEG C of hydro-thermal reaction 12h,
Obtain khaki product NiMn-LDH-NF；Nickel foam is taken out, washing alcohol is washed, dry.
Weigh NaH2PO2It is positioned over semi-enclosed crucible upstream, NiMn-LDH-NF obtained above is positioned over semiclosed
Crucible downstream, NaH2PO2Usage ratio with NiMn-LDH-NF is 5mol：Crucible is transferred to auto-programming temperature control by 1mol
Heating tube furnace in, with the heating rate of 2 DEG C/min be warming up to 350 DEG C calcining 2h；After room temperature, take out,
Washing alcohol is washed for several times, 60 DEG C of dry 12h.The material designation is Ni2Mn1P-NF。
Embodiment 2
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, the difference is that:NiCl2·6H2The quality of O
For 0.1783g (Ni:Mn=3:1).The material designation is Ni3Mn1P-NF。
Embodiment 3
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, the difference is that:NiCl2·6H2The quality of O
For 0.0594g (Ni:Mn=1:1).The material designation is Ni1Mn1P-NF。
Embodiment 4
After nickel foam to be used to acetone, the hydrochloric acid of a concentration of 3M, ethyl alcohol and the clear 30min of deionized water ultrasound successively, 60 DEG C dry
It is dry.
Weigh 0.118g NiCl2·6H2O, and 0.0495g MnCl2·4H2O is added in 80mL deionized waters, obtains forerunner
Liquid solution A (Ni:Mn=2:1)；Weigh 0.0872g NaCl, 0.6308g HMT, 56.6 μ L H2O2In (30w%) plus solution A,
Stirring 30 minutes, 2 × 1 (cm) nickel foams are put into solution A, are transferred in 100mL reaction kettles, 90 DEG C of hydro-thermal reaction 8h are obtained
Khaki product NiMn-LDH-NF；Nickel foam is taken out, washing alcohol is washed, dry.
Weigh NaH2PO2It is positioned over semi-enclosed crucible upstream, NiMn-LDH-NF obtained above is positioned over semiclosed
Crucible downstream, NaH2PO2Usage ratio with NiMn-LDH-NF is 5mol：Crucible is transferred to auto-programming temperature control by 1mol
Heating tube furnace in, with the heating rate of 2 DEG C/min be warming up to 400 DEG C calcining 4h；After room temperature, take out,
Washing alcohol is washed for several times, 60 DEG C of dry 12h.The material designation is Ni2Mn1P-NF。
Embodiment 5
After nickel foam to be used to acetone, the hydrochloric acid of a concentration of 3M, ethyl alcohol and the clear 30min of deionized water ultrasound successively, 60 DEG C dry
It is dry.
Weigh 0.118g NiCl2·6H2O, and 0.0495g MnCl2·4H2O is added in 80mL deionized waters, obtains forerunner
Liquid solution A (Ni:Mn=2:1)；Weigh 0.0872g NaCl, 0.6308g HMT, 56.6 μ L H2O2In (30w%) plus solution A,
Stirring 30 minutes, 2 × 1 (cm) nickel foams are put into solution A, are transferred in 100mL reaction kettles, 110 DEG C of hydro-thermal reaction 8h are obtained
Khaki product NiMn-LDH-NF；Nickel foam is taken out, washing alcohol is washed, dry.
Weigh NaH2PO2It is positioned over semi-enclosed crucible upstream, NiMn-LDH-NF obtained above is positioned over semiclosed
Crucible downstream, NaH2PO2Usage ratio with NiMn-LDH-NF is 5mol：Crucible is transferred to auto-programming temperature control by 1mol
Heating tube furnace in, with the heating rate of 2 DEG C/min be warming up to 300 DEG C calcining 3h；After room temperature, take out,
Washing alcohol is washed for several times, 60 DEG C of dry 12h.The material designation is Ni2Mn1P-NF。
Nickel manganese double-metal phosphide electrode material electro catalytic activity is tested
A concentration of 0.5 mole every liter of H2SO4Solution is as electrolyte, using three electrode reaction devices, Pt be to electrode,
Ag/AgCI is reference electrode, and sweep speed is 5mV/s, tests the electro-catalysis in the solution of nickel manganese double-metal phosphide electrode material
Decompose aquatic products hydrogen, production oxygen performance.
The phenetic analysis of embodiment nickel manganese phosphorus double-metal phosphide catalyst
Fig. 1 is prepared Ni2Mn1The XRD diffraction spectrograms of P-NF and nickel foam NF, as can be seen from the figure Ni2Mn1P-
The XRD spectrum of NF is consistent with nickel foam NF's, it may be possible to Ni2Mn1The diffraction maximum of P is too weak, and the diffraction maximum of nickel foam is made by force very much
At.
Fig. 2 a, 2b are respectively prepared simple Ni2Mn1-LDH-NF、Ni2Mn1The stereoscan photograph of P-NF elctro-catalysts,
Ni is can be seen that from Fig. 2 a2Mn1- LDH is nano-chip arrays and nanometer sheet surface is smooth；The Ni that Fig. 2 b are presented2Mn1P scanning electron microscope
Photo shows that array does not change after phosphatization and surface becomes coarse；Fig. 2 c are Ni2Mn1The projection Electronic Speculum of P elctro-catalysts is shone
Piece sees ultra-thin nanometer sheet；From Ni2Mn1On the high resolution electron microscopy photo (Fig. 2 d) of P elctro-catalysts it can be seen that in nanometer sheet
Pore structure.
Fig. 3 is prepared phosphide elctro-catalyst in 0.5M H2SO4Under the conditions of evolving hydrogen reaction polarization curve comparison diagram, from
Electro catalytic activity is promoted after can analyzing phosphatization in figure, wherein Ni2Mn1P-NF double-metal phosphide elctro-catalysts
Electro catalytic activity is better than NiP monometallic phosphides, and current density is 10mA cm-2When corresponding overpotential be 120mV；
Fig. 4 is prepared phosphide elctro-catalyst in 0.5M H2SO4Under the conditions of evolving hydrogen reaction Tafel curve slope compare
Scheme, as can be seen from Figure 4 Ni2Mn1P-NF double-metal phosphides elctro-catalyst has smaller Tafel slope than monometallic phosphide.
Claims (8)
1. a kind of preparation method of double-metal phosphide elctro-catalyst, which is characterized in that include the following steps：
(1) cleaning nickel foam NF, it is spare；
(2) the nickel manganese double-metal hydroxide Ni that nickel foam NF is substrate is preparedxMn1-LDH-NF；
a：Weigh NiCl2·6H2O、MnCl2·4H2O is added in deionized water and dissolves and be placed in reaction kettle, obtains precursor solution
A；
b：Weigh H2O2, NaCl, hexa HMT, be sequentially added in solution A under stiring, formed solution B；
c：Nickel foam 2 × 1 (cm) cleaned in step (1) is put into B solution, reaction kettle is transferred in baking oven and carries out water
Thermal response obtains khaki precipitation after reaction；Nickel foam is taken out, washing alcohol is washed, and Ni is dried to obtainxMn1-LDH-NF；Wherein x
=1~3；
(3) the nickel manganese phosphorus double-metal phosphide Ni that nickel foam NF is substrate is preparedxMn1P-NF；
Weigh NaH2PO2It is positioned over semi-enclosed crucible upstream, by Ni made from above-mentioned (2)xMn1- LDH-NF is positioned over semiclosed
Crucible downstream, crucible is transferred in the heating tube furnace of auto-programming temperature control, is heated up with the heating rate of 2~4 DEG C/min
To calcination temperature, after calcining, after room temperature, take out, washing alcohol is washed for several times, and Ni is dried to obtainxMn1P-NF。
2. a kind of preparation method of double-metal phosphide elctro-catalyst as described in claim 1, it is characterised in that：Step (1)
In, the cleaning nickel foam is：After using acetone, hydrochloric acid, ethyl alcohol and deionized water to be cleaned by ultrasonic successively in commercial foam nickel, 60
DEG C dry 12h, obtains nickel foam totally.
3. a kind of preparation method of double-metal phosphide elctro-catalyst as described in claim 1, it is characterised in that：The step
(2) in a, NiCl2·6H2O and MnCl2·4H2The molar ratio of O is x：1, wherein x=1~3.
4. a kind of preparation method of double-metal phosphide elctro-catalyst as described in claim 1, it is characterised in that：The step
(2) in b, in the solution B, a concentration of 0.015molL of NaCl-1, a concentration of 0.045molL of HMT-1, NiCl2·
6H2A concentration of 0.25~0.75mmol/L of O；MnCl2·4H2O and H2O2Amount ratio is：1mmol:50~60 μ L, H2O2Matter
Amount percentage concentration is 30w%.
5. a kind of preparation method of double-metal phosphide elctro-catalyst as described in claim 1, it is characterised in that：The step
(2) in c, the temperature of hydro-thermal reaction is 90~110 DEG C, 8~12h of reaction time.
6. a kind of preparation method of double-metal phosphide elctro-catalyst as described in claim 1, it is characterised in that：The step
(3) in, NaH2PO2And NixMn1The usage ratio of-LDH-NF is 5mol：1mol.
7. a kind of preparation method of double-metal phosphide elctro-catalyst as described in claim 1, it is characterised in that：Step (3)
In, the calcination temperature is 300~400 DEG C, and calcination time is 2~4h.
8. double-metal phosphide elctro-catalyst prepared by the preparation method as described in claim 1~7 is any is under acid condition
Electrocatalytic decomposition aquatic products hydrogen.
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| CN109433234A (en) * | 2018-12-04 | 2019-03-08 | 浙江理工大学 | Ferronickel phosphide/carbon nano tube compound material and its preparation method and application |
| CN109797404A (en) * | 2019-01-26 | 2019-05-24 | 南开大学 | The binary metal phosphide and preparation method and application of molybdenum trioxide (tungsten) regulation |
| CN109821561A (en) * | 2019-03-22 | 2019-05-31 | 黑龙江大学 | A kind of preparation method of self-supporting phosphatization ferro-cobalt nanosphere elctro-catalyst |
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| CN109999861A (en) * | 2019-03-06 | 2019-07-12 | 江苏大学 | A kind of nickel cobalt double-metal phosphide elctro-catalyst and its synthetic method and application |
| CN110157006A (en) * | 2019-06-03 | 2019-08-23 | 贵阳学院 | The preparation and application of the electrode material of the preparation and material containing double-metal phosphide of double-metal phosphide material |
| CN110257859A (en) * | 2019-06-28 | 2019-09-20 | 青岛科技大学 | A kind of Co2P/Ni2P/Al2O3/ NF multilevel structure combination electrode and preparation method thereof |
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| CN111974429A (en) * | 2019-05-21 | 2020-11-24 | 南京大学 | Preparation method of multilayer pie-shaped NiMn-LDHs catalyst |
| CN112206793A (en) * | 2020-09-28 | 2021-01-12 | 沈阳理工大学 | Method for preparing non-noble metal phosphide catalyst |
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| CN113832494A (en) * | 2021-09-28 | 2021-12-24 | 西安建筑科技大学 | Preparation method and application of transition/rare earth multi-metal co-doped phosphide |
| CN114438542A (en) * | 2022-01-24 | 2022-05-06 | 北京工业大学 | Preparation method of nickel nanowire array electrode loaded nickel manganese phosphide active layer and application of nickel nanowire array electrode loaded nickel manganese phosphide active layer in electrocatalysis of benzyl alcohol |
| CN114574891A (en) * | 2022-03-29 | 2022-06-03 | 宁波大学 | Preparation method and application of bimetallic co-doped nickel phosphide nanosheet |
| CN116199277A (en) * | 2023-04-28 | 2023-06-02 | 江苏正力新能电池技术有限公司 | Manganese-nickel bimetallic compound and preparation and application thereof |
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| CN114574891A (en) * | 2022-03-29 | 2022-06-03 | 宁波大学 | Preparation method and application of bimetallic co-doped nickel phosphide nanosheet |
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