CN109267095A - A kind of new phosphide Raney nickel and preparation method thereof - Google Patents
A kind of new phosphide Raney nickel and preparation method thereof Download PDFInfo
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- CN109267095A CN109267095A CN201811409939.8A CN201811409939A CN109267095A CN 109267095 A CN109267095 A CN 109267095A CN 201811409939 A CN201811409939 A CN 201811409939A CN 109267095 A CN109267095 A CN 109267095A
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The present invention relates to a kind of new phosphide Raney nickel, the catalyst has biggish specific surface area and pore volume, and in multistage pore size distribution, the catalyst is Ni2P catalytic active center is uniformly dispersed in the composite material in nitrogen-phosphor codoping carbon network skeleton.Preparation method includes the following steps: the preparation of the MOFs presoma of 1) nitrogenous phosphorus atoms: weighing phosphorous, nitrogenous organic ligand and nickel salt respectively and is dissolved in a certain amount of deionized water and is sufficiently stirred to obtain three kinds of solution；Nitrogenous phosphorus atoms MOFs presoma is synthesized followed by microlayer model method；2) the MOFs presoma of a certain amount of nitrogenous phosphorus atoms is placed in corundum porcelain boat, is then placed in tube furnace and calcines, obtain a kind of porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping.Catalyst of the invention has biggish specific surface area and pore volume, is conducive to the progress of electrochemical catalysis, hydrodesulfurization, selective hydrogenation and other hydrogenation reactions, has broad application prospects.
Description
Technical field
The present invention relates to material, energy technology field, in particular to a kind of new phosphide Raney nickels and preparation method thereof.
Background technique
With world population and economic fast development, the energy has been considered as the most basic demand of human social development, so
And the fossils such as coal, petroleum class A fuel A significantly limits society and economy since reserves are limited, non-renewable and increasingly exhausted
Development.Meanwhile fossil fuel equally affects the health of the mankind in a series of environmental problems that development and utilization process generates
With development.Therefore, for sustainable economic development and environmental protection the considerations of, the reproducible clean energy resource of development and utilization green
It is the critical issue urgently to be resolved that energy technology field faces now.Hydrogen Energy is hydrogen and the energy that oxygen reaction generates, and is made
For a kind of secondary energy sources of clean and environmental protection, there is high energy density, from a wealth of sources, zero carbon emission of use process, renewable many
Advantage, therefore favored extensively；In addition, Hydrogen Energy is also used as the intermediate of energy storage, wind energy, solar energy etc. other
Intermittent and unstable clean energy resource is converted into Hydrogen Energy and is stored and transported, and can be added in the form of Hydrogen Energy again when needed
To utilize.Therefore, among these new energy, hydrogen energy source is considered as optimal energy carrier, and people grind exploitation hydrogen energy source
Studying carefully also becomes increasingly frequently, and hydrogen making is the key that then deep exploitation Hydrogen Energy how efficiently, at low cost.Electro-catalysis point
Water hydrogen manufacturing is solved since raw material sources are extensive, the operation is simple and convenient, it is considered to be most have the hydrogen producing technology of application prospect at present
One of.The hydrogen manufacturing of electrocatalytic decomposition water mainly includes the Electrochemical oxygen evolution reaction (OER) on anode and the electrochemistry liberation of hydrogen on cathode
React (HER) two crucial core reactions.However, during electrocatalytic decomposition water, OER and HER generally require higher
Reaction overpotential overcome reaction energy barrier, this can greatly increase the loss of energy in reaction process, therefore, it is necessary to efficient, steady
Fixed and cheap elctro-catalyst accelerates the kinetics of catalysis reaction, reduces energy consumption of reaction.Currently, most effective
HER and OER catalyst is the Pt base catalyst and Ru, Ir base catalyst of noble metal respectively, but noble metal is at high cost, reserves
It is low, seriously hinder the application of electrocatalytic decomposition water in the industry.Therefore, rich reserves, cheap and easy to get, catalysis how to be developed
The catalyst of performance and excellent in stability is the key point for limiting hydrogen utilization.
In recent years, transition metal phosphide is due to its reserves abundant, cheap price and can be with noble metal platinum, iridium phase
The catalytic activity to match in excellence or beauty receives the extensive concern of scientists, especially with nickel phosphide (Ni2It P is) catalyst of representative,
Catalytic performance can be rated as phosphide most, have broad application prospects.In addition, the scientific research of theoretical calculation and early period are demonstrate,proved
Bright, multi-element doping can significantly improve the catalytic activity of catalyst, this mainly has benefited from the synergistic effect between activated centre.Than
If doped chemical can optimize the electronic structure of catalyst body, the energy barrier of catalyst matter lotus transfer is reduced, and then promote
Into the progress of catalysis reaction.But since multi-element doping catalyst is limited to the valence of element during forming composite material
The composition of state and object phase, the uniform compound of controlled syntheses are mutually difficult.Metal-organic framework compound (MOFs) be by
One-dimensional, the two-dimentional or three-dimensional porous network structure that metal ion or metal cluster and organic ligand are formed by self assembly mode,
It is a kind of novel crystal material with wide application prospect.Since its controllable pore structure, big specific surface area, unsaturation are matched
The characteristics such as position key, before the multiple fields such as gas storage, gas separation, biological medicine and photoelectromagnetic all have and are widely applied
Scape becomes one of forward position focus of Material Field.Further, since in MOFs skeleton metal center atom it is horizontal be uniformly distributed with
And higher metal element content, MOFs material are the ideal moulds for preparing the porous metals phosphide composite material of high degree of dispersion
Plate.And have benefited from each element in MOFs skeleton and divide equally the characteristic being distributed, we can be miscellaneous by introducing nitrogen, phosphorus etc. in organic ligand
The synthesis of atom progress multi-element doping material.Relative to other loaded catalysts, MOFs is preferable for different metal center
Compatibility enormously simplifies the process for synthesizing homogeneous monometallic/more metal phosphides.Due to metal in metal-organic framework material
Center and carbon containing organic ligand are uniformly distributed, and composite material derived from metal-organic framework material usually has special inside
Electronic structure and surface composition, and the activated centre of this special composition form and area load differs widely, it can be more
The efficient activity for playing catalytic center.
106475122 A of Chinese patent literature CN discloses a kind of Ni of low temperature preparation three-dimensional step pore structure2P catalysis
The method of agent, this method comprises the following steps: (1) synthesizing nickel based metal organic framework materials using conventional method；It (2) will be Ni-based
Metal-organic framework material and hypophosphites be heat-treated at a temperature of 200-350 DEG C under inert gas shielding 1-500min to get
The Ni of three-dimensional step pore structure2P catalyst.The invention is that presoma passes through the one of additional phosphorus source by nickel based metal organic frame
Step phosphating reaction has obtained the multi-stage porous Ni with high specific surface area2P catalyst.But this method still needs additional phosphorus
Source could react.The porous carbon coating copper phosphide composite catalyst of 107790164 A nitrogen-phosphor codoping of Chinese patent literature CN
And preparation method thereof, this method comprises the following steps: (1) having synthesized Cu-NPMOF using with nitrogenous, phosphorus double organic ligands
Presoma；(2) Cu-NPMOF presoma is calcined under a nitrogen, obtains black powder, and with dilute hydrochloric acid supersound washing, dry
To solid powder；(3) obtained black powder and sodium hypophosphite are mixed, calcines, obtains in a nitrogen atmosphere after being fully ground
Black powder, and be washed with deionized, be centrifuged, dry after obtain target product, and obtained catalyst is used for electro-catalysis
Produce hydrogen.107694581 A of Chinese patent literature CN discloses the porous compound catalysis of carbon coating copper phosphide of Heteroatom doping
The application of agent, this method is similar to the preparation method of 107790164 A of Chinese patent literature CN, and catalyst is applied in electricity
In terms of catalysis reaction and zinc-air battery.Foregoing invention contains polynary heteroatomic ligand, is had by multistep reaction
The composite catalyst of high specific surface area.But although this method introduces nitrogen phosphorus heteroatoms by MOFs presoma, still
Need additional phosphorus source that can just obtain phosphide catalyst.And the reaction process that response path is related to is more, in materials synthesis
The utilization rate and reaction efficiency of atom are more unfavorable, this is because inevitably occurring the loss of energy in actual reaction
And side reaction.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of new phosphide Raney nickel and preparation method thereof.The present invention
Using microlayer model method, quickly continuously synthesis contains the polynary hetero atom MOFs material of nitrogen phosphorus as presoma, and passes through the letter of a step
The porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping has directly been prepared in single heat treatment, has
There is excellent catalytic reaction activity.Preparation method of the invention with it is simple, efficient, inexpensive, be easy to the preparation of industrialized method
The porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping is obtained.Preparation-obtained catalyst
With biggish specific surface area and pore volume, in multistage pore size distribution, Ni2P catalytic active center is uniformly dispersed in nitrogen phosphorus and is co-doped with
In miscellaneous carbon network skeleton, be conducive to the progress of electrochemical catalysis, hydrodesulfurization, selective hydrogenation and other hydrogenation reactions, have
Have broad application prospects.
In order to solve the above technical problems, technical solution provided by the invention are as follows: a kind of new phosphide Raney nickel, it is described to urge
Agent has biggish specific surface area and pore volume, and in multistage pore size distribution, the catalyst is Ni2P catalytic active center is uniform
The composite material being dispersed in nitrogen-phosphor codoping carbon network skeleton.
A kind of preparation method of new phosphide Raney nickel, includes the following steps:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms: phosphorous, nitrogenous organic ligand and nickel salt are weighed respectively and is dissolved in
It is sufficiently stirred to obtain three kinds of solution in a certain amount of deionized water；Nitrogenous phosphorus atoms MOFs forerunner is synthesized followed by microlayer model method
Body；
2) the MOFs presoma of a certain amount of nitrogenous phosphorus atoms is placed in corundum porcelain boat, is then placed in tube furnace, risen
Temperature calcines 0.5-12 hours to 600-1100 DEG C, obtains the porous carbon-coated catalytic center equally distributed one of nitrogen-phosphor codoping
Kind catalyst of phosphatizing nickel.
Further, organic ligand phosphorous described in step 1) includes 2,4,6- trimethylbenzenes -1,3, tri- methylene of 5-
Base tri methylene phosphonic acid ligand, 2,4,6- trimethylbenzene -1,3- dimethylene di 2 ethylhexyl phosphonic acids, 2,5- dimethyl benzenes-Isosorbide-5-Nitrae-dimethylene diphosphine
Acid, terephthalylidene di 2 ethylhexyl phosphonic acid, 2,5- dimethyl benzenes-Isosorbide-5-Nitrae-di 2 ethylhexyl phosphonic acid, 2,4- di 2 ethylhexyl phosphonic acid trimethylbenzenes, methylphosphonic acid, hydroxyl
Base ethylene-diphosphonic acid, AminomethylphosphoniAcid Acid, aminotrimethylenephosphonic acid, zoledronic acid.As an improvement, the phosphorous organic ligand
Including 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 2,4,6- trimethylbenzene -1,3- dimethylene diphosphine
Acid；Highly preferred, the phosphorous organic ligand includes 2,4,6- trimethylbenzenes -1,3, and 5- trimethylene tri methylene phosphonic acid is matched
Body.
Further, the concentration of organic ligand phosphorous described in step 1) is 0.05-0.5mol/L.As an improvement,
The concentration of the phosphorous organic ligand is 0.10mol/L.
Further, organic ligand nitrogenous described in step 1) includes 4,4'- bipyridyl, and 2,2'- bipyridyls are adjacent luxuriant and rich with fragrance
Sieve quinoline, pyrazine.
Further, the concentration of organic ligand nitrogenous described in step 1) is 0.05-0.5mol/L.As an improvement,
The concentration of the nitrogenous organic ligand is 0.15mol/L.
Further, nickel salt described in step 1) includes the hydrate of nickel sulfate, nickel nitrate, nickel chloride, nickel acetate.Make
To improve, the nickel salt is the hydrate of nickel sulfate and nickel nitrate.
Further, the concentration of nickel salt described in step 1) is 0.05-0.5mol/L.As an improvement, the nickel salt
Concentration be 0.15mol/L.
Further, the synthetic method of the MOFs presoma of nitrogenous phosphorus atoms described in step 1) includes microlayer model synthesis
Method and hydrothermal synthesis method.As an improvement, the synthetic method of the MOFs presoma of the nitrogenous phosphorus atoms is microlayer model synthetic method.
Further, the reaction condition of the microlayer model synthetic method of the MOFs presoma of nitrogenous phosphorus atoms described in step 1)
Are as follows: organic ligand solution, nickel salt solution are squeezed into mixer using the syringe pump in the continuous synthesizer of microlayer model, and in 80-
It is reacted in 100 DEG C of reaction zone 20-200 minutes, sample and separation cleaning is then collected by subsequent collection device, contained
The MOFs presoma of nitrogen phosphorus atoms；As an improvement, the temperature of reaction zone is 100 DEG C, the reaction time is 80 minutes.
Further, the reaction condition of the hydrothermal synthesis method of the MOFs presoma of nitrogenous phosphorus atoms described in step 1)
Are as follows: mixed solution is transferred in the reaction kettle of polytetrafluoro liner and is warming up to 120-150 DEG C of reaction 6-72 hours, product is centrifuged
It is cleaned after separation, obtains the MOFs presoma of nitrogenous phosphorus atoms；As an improvement, it is 72 small that reaction temperature, which is 140 DEG C of reaction time,
When.
Further, the quality of the MOFs presoma of nitrogenous phosphorus atoms described in step 2) is 0.05-10g.
Further, inert atmosphere described in step 2) is argon gas, nitrogen or helium；As an improvement, the inertia
Atmosphere is nitrogen.
Further, inert gas flow velocity is 1-500mL/min in step 2)；As an improvement, the inert gas flow velocity
For 20-100mL/min.
Further, in step 2), heating rate is 1-20 DEG C/min；As an improvement, heating rate is 5-10 DEG C/min.
Further, heat treatment temperature described in step 2) is 600-1100 DEG C, and heat treatment time is 0.5-12 hours；
As an improvement, the heat treatment temperature is 800-1000 DEG C, heat treatment time is 0.5-5 hours；It is further improved, it is described
Heat treatment temperature is 900 DEG C, and heat treatment time is 2 hours.
The present invention has quickly continuously synthesized the heteroatomic MOFs material of Nitrogen-and Phosphorus-containing using microlayer model reaction system, and passes through
One step, which is simply heat-treated, has obtained the multi-stage porous Ni of the controllable nitrogen-phosphor codoping carbon-coating cladding of constituent content2P catalyst (Ni2P
NPHPN).In addition, can be synthesized a series of with different specific surface areas by the temperature and time for simply controlling heat treatment
With the Ni of doping ratio2P NPHPN catalyst, since N, P, Ni and C are uniformly distributed in MOFs presoma, obtained Ni2P
Ni in NPHPN catalyst2P is uniformly dispersed in nitrogen-phosphor codoping carbon-coating, and the specific surface area of material can achieve
758.78m2·g-1。
The present invention will not destroy the spy of presoma in the way of the one step pyrolysis of progress of the MOFs presoma of nitrogenous, phosphorus, nickel
Different appearance structure, and additional phosphorus source is not needed, catalyst does not need further to wash purification, and simple process is conducive to scale
Production.
Beneficial effects of the present invention are as follows:
1. the present invention uses the metal-organic framework materials of nitrogenous, phosphorus, nickel as presoma, the letter being heat-treated by a step
Single reaction mode, the multi-stage porous Ni of the available equally distributed nitrogen-phosphor codoping carbon-coating cladding of N, P, Ni and C2P catalyst.Phase
Compared with traditional supported catalysts, the catalyst activity that the present invention obtains is more uniformly spread, with the obvious advantage, and passes through one
The composite catalyst of polynary hetero atom Uniform Doped can be obtained in step reaction.The process requires reaction unit low, no nocuousness
The reactants such as gas, organic solvent participate in, simple process, are suitable for industrialized production.
2. the multi-stage porous Ni that nitrogen-phosphor codoping carbon-coating of the invention coats2It is P catalyst nitrogen and phosphorus content with higher, larger
Specific surface area (572.9-758.8m2/ g) and pore volume (0.32-0.41cm3/ g) and hierarchical porous structure, it can expose more
Ni2P active site, and the available more defect sites of the doping of nitrogen, phosphorus, carbon, with nickel phosphide activated centre
Synergistic effect can be further improved the catalytic effect of catalyst, in addition, carbon network skeleton can also be improved in catalytic process
Matter lotus transfer efficiency, and then improve the catalytic effect of catalyst.
Detailed description of the invention
Fig. 1 is the schematic diagram of the continuous synthesizer of microlayer model of the present invention；
Fig. 2 is the X-ray powder diffraction pattern (PXRD) of the MOFs material of nitrogenous phosphorus atoms prepared by embodiment 1；
Fig. 3 is the multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by embodiment 12The PXRD map of P catalyst；
Fig. 4 is the multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by embodiment 12The scanning electron microscopy of P catalyst
Mirror (SEM) photo；
Fig. 5 is the multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by embodiment 12The transmission electron microscopy of P catalyst
Mirror (TEM) photo；
Fig. 6 is the multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by embodiment 12The high power transmitted electron of P catalyst
Microscope (HRTEM) photo；
Fig. 7 is the multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by embodiment 12The EDS corresponding element of P catalyst
Mapping distribution map；
Fig. 8 is the multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by embodiment 12The nitrogen physisorption of P catalyst
Curve and graph of pore diameter distribution；
Fig. 9 is the multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by embodiment 12P catalyst Electrochemical oxygen evolution
React the linear sweep voltammetry curve graph of (OER).
Figure 10 is the multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by embodiment 12P catalyst electrochemistry liberation of hydrogen
React the linear sweep voltammetry curve graph of (HER).
Figure 11 is the multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by embodiment 12The catalysis of P catalyst is complete to decompose
The linear sweep voltammetry curve graph of water.
Specific embodiment
The present invention is described further combined with specific embodiments below, but not limited to this.Simultaneously in following embodiments
The experimental method is unless otherwise specified conventional method；The reagent and material unless otherwise specified can be from business
Approach obtains.
The multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by the present invention2The object of P catalyst is mutually spread out by x-ray powder
It penetrates figure to determine, using the X'pert PRO powder diffractometer of Dutch Panaco company.
The multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by the present invention2The pattern of P catalyst is scanned by Flied emission
Electron microscope (SEM) photo and corresponding element mapping image are shown, using Japanese JSM-7500F Flied emission scanning electron
Microscope.
The multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by the present invention2The internal morphology and Elemental redistribution of P catalyst
It is shown by transmission electron microscope (TEM) photo, using Japanese JEOL JEM2100F transmission electron microscope.
The multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by the present invention2The specific surface area of P catalyst passes through cryogenic nitrogen
Gas adsorption/desorption curve is shown, using Kang Ta company of U.S. Autosorb-iQ2Full-automatic specific surface and pore-size distribution analyzer.
The multi-stage porous Ni of nitrogen-phosphor codoping carbon-coating cladding prepared by the present invention2The electrocatalysis characteristic of P catalyst passes through Shanghai
Occasion China CHI760E electrochemical workstation measures.
Embodiment 1
A kind of preparation method of the porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping, step
It is rapid as follows:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms:
Nickel sulfate, 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 4,4'- bipyridyl are distributed to
In ionized water, it is configured to concentration and is respectively 0.15 mole every liter, 0.1 mole every liter and 0.15 mole every liter of solution, and utilize
Raw material is driven into mixer by the device of attached drawing 1, and enters reaction zone, and reaction zone temperature is 100 DEG C, and the residence time is 80 points
Clock, the nozzle in tail portion collect product, are centrifuged or filter to isolate product, the MOFs presoma of nitrogenous phosphorus atoms can be obtained.
2) the MOFs presoma for weighing the nitrogenous phosphorus atoms in 0.5g step 1), is placed in corundum porcelain boat, porcelain boat is put into
In tube furnace, under 30 milliliters of nitrogen atmospheres per minute with 5 DEG C of heating rates per minute it is heated to 900 DEG C and in the temperature
It is lower to be kept for 2 hours (persistently being purged using 30 milliliters of nitrogen per minute during this), nitrogen-phosphor codoping porous carbon can be obtained
The equally distributed catalyst of phosphatizing nickel of the catalytic center of cladding.
The X-ray powder diffraction figure of the MOFs presoma of obtained nitrogenous phosphorus atoms is as shown in Fig. 2, as shown in Figure 2, the reality
Example is applied to be successfully prepared to have obtained the MOFs presoma of nitrogenous phosphorus atoms.In the porous carbon-coated catalysis of obtained nitrogen-phosphor codoping
The X-ray powder diffraction figure of the equally distributed catalyst of phosphatizing nickel of the heart is as shown in figure 3, the nickel phosphide that the embodiment is prepared is
The Ni of pure phase2P catalyst.Scanning electron microscope (SEM), transmission electron microscope (TEM) and high power transmission electron microscopy
Mirror (HRTEM) can be seen that resulting catalyst of phosphatizing nickel with porous more as shown in Figure 4, Figure 5 and Figure 6, from Fig. 4, Fig. 5
Face body structure.The HRTEM of Fig. 6 can be seen that nickel phosphide activated centre and be coated by carbon-coating, and this several layers of carbon structure not to the utmost may be used
It to accelerate charge transfer effciency of nickel phosphide during electro-catalysis, can also play a protective role to nickel phosphide, promote material
Catalytic activity and reaction stability.It is available that being uniformly distributed of a element in Fig. 7 has also embodied the synthetic method
The phosphatization nickel composite catalyst of even dispersion.As the nitrogen physisorption curve and graph of pore diameter distribution of Fig. 8 it is found that obtained by catalysis material
Expect specific surface area with higher (758.8 square metres every gram), and there is apparent hierarchical porous structure, it is living to each contribute to catalyst
The performance of property.
Electrocatalysis characteristic test:
More metal phosphide nano tube catalyst catalytic electrochemical evolving hydrogen reactions (HER) that the embodiment is prepared with
Oxygen evolution reaction (OER), concrete operations are as follows: weighing 5 milligrams of catalyst, be distributed to 1 milliliter of (volume ratio, ethyl alcohol: water: nafion
=1:1:0.05) in solvent, ultrasound 30 minutes or more, uniform suspension is obtained, 5 microlitres of working solutions are added drop-wise to diameter 4
It is sufficiently dry at room temperature on the rotating disc electrode of millimeter (load capacity is 0.19 milligram every square centimeter), using three electricity of standard
Electrode systems are analyzed and evaluated by Shanghai Chen Hua CHI760E electrochemical workstation.Test method uses linear sweep voltammetry
Method, analysis carry out in 1.0 moles every liter of potassium hydroxide solution, and test scope is 0.1 to minus 0.4 volt of (HER), 1.0 to 1.8
It lies prostrate (OER), above-mentioned electricity window is the voltage relative to standard hydrogen electrode.Complete solution water performance test use nickel foam as electrode two
Electrode system is tested, and catalyst loadings are 1.0 grams every square centimeter, and the test scope of linear sweep voltammetry is 1.0
To 1.8 volts.The above scanning speed is 5 millivolts per second.
The linear sweep voltammetry curve graph of catalytic electrochemical oxygen evolution reaction, evolving hydrogen reaction and the reaction of complete solution water is obtained as schemed
9, shown in Figure 10 and Figure 11.It can be seen from the figure that gained catalyst current density in analysis oxygen and liberation of hydrogen two reactions reaches
10mAcm-2Required overpotential only has 255mV and 125mV respectively, urges compared to the most of phosphides having disclosed at present
Changing material has obvious gain effect.And two electrode systems of catalyst composition is utilized only to need during decomposing water entirely
1.62 volts of voltage can reach 10mA cm-2Current density, be better than most of non-precious metal catalyst.This be by
The nickel phosphide crystal phase of the high activity possessed by the porous carbon-coated catalyst of phosphatizing nickel of nitrogen-phosphor codoping of preparation, it is higher
Specific surface area and multistage holes mechanism can expose lacking for the carbon structure offer of more active sites and nitrogen-phosphor codoping
Fall into the synergistic effect of position.In addition, the carbon in composite catalyst can also improve electric charge transfer of catalyst during electro-catalysis
Efficiency, these favorable factors are conducive to the promotion of the catalytic performance of catalyst.
Embodiment 2
A kind of preparation method of the porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping, step
It is rapid as follows:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms:
By nickel sulfate, 2,4,6- trimethylbenzene -1,3- dimethylene di 2 ethylhexyl phosphonic acid ligand and 4,4'- bipyridyl be distributed to from
In sub- water, it is configured to the solution that concentration is respectively 0.15 mole every liter, 0.1 mole every liter and 0.15 mole every liter, and utilize attached
Raw material is driven into mixer by the device of Fig. 1, and enters reaction zone, and reaction zone temperature is 100 DEG C, and the residence time is 80 points
Clock, the nozzle in tail portion collect product, are centrifuged or filter to isolate product, the MOFs presoma of nitrogenous phosphorus atoms can be obtained.
2) the MOFs presoma for weighing the nitrogenous phosphorus atoms in 0.5g step 1), is placed in corundum porcelain boat, porcelain boat is put into
In tube furnace, under 30 milliliters of nitrogen atmospheres per minute with 5 DEG C of heating rates per minute it is heated to 900 DEG C and in the temperature
It is lower to be kept for 2 hours (persistently being purged using 30 milliliters of nitrogen per minute during this), nitrogen-phosphor codoping porous carbon can be obtained
The equally distributed catalyst of phosphatizing nickel of the catalytic center of cladding.
Embodiment 3
A kind of preparation method of the porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping, step
It is rapid as follows:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms:
Nickel sulfate, 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 4,4'- bipyridyl are distributed to
In ionized water, it is configured to concentration and is respectively 0.15 mole every liter, 0.2 mole every liter and 0.15 mole every liter of solution, and utilize
Raw material is driven into mixer by the device of attached drawing 1, and enters reaction zone, and reaction zone temperature is 100 DEG C, and the residence time is 80 points
Clock, the nozzle in tail portion collect product, are centrifuged or filter to isolate product, the MOFs presoma of nitrogenous phosphorus atoms can be obtained.
2) the MOFs presoma for weighing the nitrogenous phosphorus atoms in 0.5g step 1), is placed in corundum porcelain boat, porcelain boat is put into
In tube furnace, under 30 milliliters of nitrogen atmospheres per minute with 5 DEG C of heating rates per minute it is heated to 900 DEG C and in the temperature
It is lower to be kept for 2 hours (persistently being purged using 30 milliliters of nitrogen per minute during this), nitrogen-phosphor codoping porous carbon can be obtained
The equally distributed catalyst of phosphatizing nickel of the catalytic center of cladding.
Embodiment 4
A kind of preparation method of the porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping, step
It is rapid as follows:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms:
Nickel sulfate, 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 2,2'- bipyridyl are distributed to
In ionized water, it is configured to concentration and is respectively 0.15 mole every liter, 0.1 mole every liter and 0.15 mole every liter of solution, and utilize
Raw material is driven into mixer by the device of attached drawing 1, and enters reaction zone, and reaction zone temperature is 100 DEG C, and the residence time is 80 points
Clock, the nozzle in tail portion collect product, are centrifuged or filter to isolate product, the MOFs presoma of nitrogenous phosphorus atoms can be obtained.
2) the MOFs presoma for weighing the nitrogenous phosphorus atoms in 0.5g step 1), is placed in corundum porcelain boat, porcelain boat is put into
In tube furnace, under 30 milliliters of nitrogen atmospheres per minute with 5 DEG C of heating rates per minute it is heated to 900 DEG C and in the temperature
It is lower to be kept for 2 hours (persistently being purged using 30 milliliters of nitrogen per minute during this), nitrogen-phosphor codoping porous carbon can be obtained
The equally distributed catalyst of phosphatizing nickel of the catalytic center of cladding.
Embodiment 5
A kind of preparation method of the porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping, step
It is rapid as follows:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms:
Nickel sulfate, 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 4,4'- bipyridyl are distributed to
In ionized water, it is configured to the solution that concentration is respectively 0.15 mole every liter, 0.1 mole every liter and 0.3 mole every liter, and utilize attached
Raw material is driven into mixer by the device of Fig. 1, and enters reaction zone, and reaction zone temperature is 100 DEG C, and the residence time is 80 points
Clock, the nozzle in tail portion collect product, are centrifuged or filter to isolate product, the MOFs presoma of nitrogenous phosphorus atoms can be obtained.
2) the MOFs presoma for weighing the nitrogenous phosphorus atoms in 0.5g step 1), is placed in corundum porcelain boat, porcelain boat is put into
In tube furnace, under 30 milliliters of nitrogen atmospheres per minute with 5 DEG C of heating rates per minute it is heated to 900 DEG C and in the temperature
It is lower to be kept for 2 hours (persistently being purged using 30 milliliters of nitrogen per minute during this), nitrogen-phosphor codoping porous carbon can be obtained
The equally distributed catalyst of phosphatizing nickel of the catalytic center of cladding.
Embodiment 6
A kind of preparation method of the porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping, step
It is rapid as follows:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms:
Nickel sulfate, 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 4,4'- bipyridyl are distributed to
In ionized water, it is configured to concentration and is respectively 0.15 mole every liter, 0.1 mole every liter and 0.15 mole every liter of solution, and utilize
Raw material is driven into mixer by the device of attached drawing 1, and enters reaction zone, and reaction zone temperature is 100 DEG C, the residence time 120
Minute, the nozzle in tail portion collects product, is centrifuged or filters to isolate product, the MOFs forerunner of nitrogenous phosphorus atoms can be obtained
Body.
2) the MOFs presoma for weighing the nitrogenous phosphorus atoms in 0.5g step 1), is placed in corundum porcelain boat, porcelain boat is put into
In tube furnace, under 30 milliliters of nitrogen atmospheres per minute with 5 DEG C of heating rates per minute it is heated to 900 DEG C and in the temperature
It is lower to be kept for 2 hours (persistently being purged using 30 milliliters of nitrogen per minute during this), nitrogen-phosphor codoping porous carbon can be obtained
The equally distributed catalyst of phosphatizing nickel of the catalytic center of cladding.
Embodiment 7
A kind of preparation method of the porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping, step
It is rapid as follows:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms:
Nickel sulfate, 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 4,4'- bipyridyl are distributed to
In ionized water, it is configured to concentration and is respectively 0.15 mole every liter, 0.1 mole every liter and 0.15 mole every liter of solution, and utilize
Raw material is driven into mixer by the device of attached drawing 1, and enters reaction zone, and reaction zone temperature is 90 DEG C, and the residence time is 80 points
Clock, the nozzle in tail portion collect product, are centrifuged or filter to isolate product, the MOFs presoma of nitrogenous phosphorus atoms can be obtained.
2) the MOFs presoma for weighing the nitrogenous phosphorus atoms in 0.5g step 1), is placed in corundum porcelain boat, porcelain boat is put into
In tube furnace, under 30 milliliters of nitrogen atmospheres per minute with 5 DEG C of heating rates per minute it is heated to 900 DEG C and in the temperature
It is lower to be kept for 2 hours (persistently being purged using 30 milliliters of nitrogen per minute during this), nitrogen-phosphor codoping porous carbon can be obtained
The equally distributed catalyst of phosphatizing nickel of the catalytic center of cladding.
Embodiment 8
A kind of preparation method of the porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping, step
It is rapid as follows:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms:
Nickel sulfate, 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 4,4'- bipyridyl are distributed to
In ionized water, it is configured to concentration and is respectively 0.15 mole every liter, 0.1 mole every liter and 0.15 mole every liter of solution, and utilize
Raw material is driven into mixer by the device of attached drawing 1, and enters reaction zone, and reaction zone temperature is 100 DEG C, and the residence time is 80 points
Clock, the nozzle in tail portion collect product, are centrifuged or filter to isolate product, the MOFs presoma of nitrogenous phosphorus atoms can be obtained.
2) the MOFs presoma for weighing the nitrogenous phosphorus atoms in 3.0g step 1), is placed in corundum porcelain boat, porcelain boat is put into
In tube furnace, under 30 milliliters of nitrogen atmospheres per minute with 5 DEG C of heating rates per minute it is heated to 900 DEG C and in the temperature
It is lower to be kept for 2 hours (persistently being purged using 30 milliliters of nitrogen per minute during this), nitrogen-phosphor codoping porous carbon can be obtained
The equally distributed catalyst of phosphatizing nickel of the catalytic center of cladding.
Embodiment 9
A kind of preparation method of the porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping, step
It is rapid as follows:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms:
Nickel sulfate, 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 4,4'- bipyridyl are distributed to
In ionized water, it is configured to concentration and is respectively 0.15 mole every liter, 0.1 mole every liter and 0.15 mole every liter of solution, and utilize
Raw material is driven into mixer by the device of attached drawing 1, and enters reaction zone, and reaction zone temperature is 100 DEG C, and the residence time is 80 points
Clock, the nozzle in tail portion collect product, are centrifuged or filter to isolate product, the MOFs presoma of nitrogenous phosphorus atoms can be obtained.
2) the MOFs presoma for weighing the nitrogenous phosphorus atoms in 0.5g step 1), is placed in corundum porcelain boat, porcelain boat is put into
In tube furnace, under 30 milliliters of argon atmospheres per minute with 5 DEG C of heating rates per minute it is heated to 900 DEG C and in the temperature
It is lower to be kept for 2 hours (persistently being purged using 30 milliliters of argon gas per minute during this), nitrogen-phosphor codoping porous carbon can be obtained
The equally distributed catalyst of phosphatizing nickel of the catalytic center of cladding.
Embodiment 10
A kind of preparation method of the porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping, step
It is rapid as follows:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms:
Nickel sulfate, 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 4,4'- bipyridyl are distributed to
In ionized water, it is configured to concentration and is respectively 0.15 mole every liter, 0.1 mole every liter and 0.15 mole every liter of solution, and utilize
Raw material is driven into mixer by the device of attached drawing 1, and enters reaction zone, and reaction zone temperature is 100 DEG C, and the residence time is 80 points
Clock, the nozzle in tail portion collect product, are centrifuged or filter to isolate product, the MOFs presoma of nitrogenous phosphorus atoms can be obtained.
2) the MOFs presoma for weighing the nitrogenous phosphorus atoms in 0.5g step 1), is placed in corundum porcelain boat, porcelain boat is put into
In tube furnace, under 100 milliliters of nitrogen atmospheres per minute with 5 DEG C of heating rates per minute it is heated to 900 DEG C and in the temperature
Degree is lower to be kept for 2 hours (persistently being purged using 100 milliliters of nitrogen per minute during this), and it is porous that nitrogen-phosphor codoping can be obtained
The carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center.
Embodiment 11
A kind of preparation method of the porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping, step
It is rapid as follows:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms:
Nickel sulfate, 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 4,4'- bipyridyl are distributed to
In ionized water, it is configured to concentration and is respectively 0.15 mole every liter, 0.1 mole every liter and 0.15 mole every liter of solution, and utilize
Raw material is driven into mixer by the device of attached drawing 1, and enters reaction zone, and reaction zone temperature is 100 DEG C, and the residence time is 80 points
Clock, the nozzle in tail portion collect product, are centrifuged or filter to isolate product, the MOFs presoma of nitrogenous phosphorus atoms can be obtained.
2) the MOFs presoma for weighing the nitrogenous phosphorus atoms in 0.5g step 1), is placed in corundum porcelain boat, porcelain boat is put into
In tube furnace, under 30 milliliters of nitrogen atmospheres per minute with 10 DEG C of heating rates per minute it is heated to 900 DEG C and in the temperature
Degree is lower to be kept for 2 hours (persistently being purged using 30 milliliters of nitrogen per minute during this), and it is porous that nitrogen-phosphor codoping can be obtained
The carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center.
Embodiment 12
A kind of preparation method of the porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping, step
It is rapid as follows:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms:
Nickel sulfate, 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 4,4'- bipyridyl are distributed to
In ionized water, it is configured to concentration and is respectively 0.15 mole every liter, 0.1 mole every liter and 0.15 mole every liter of solution, and utilize
Raw material is driven into mixer by the device of attached drawing 1, and enters reaction zone, and reaction zone temperature is 100 DEG C, and the residence time is 80 points
Clock, the nozzle in tail portion collect product, are centrifuged or filter to isolate product, the MOFs presoma of nitrogenous phosphorus atoms can be obtained.
2) the MOFs presoma for weighing the nitrogenous phosphorus atoms in 0.5g step 1), is placed in corundum porcelain boat, porcelain boat is put into
In tube furnace, under 30 milliliters of nitrogen atmospheres per minute with 5 DEG C of heating rates per minute it is heated to 1000 DEG C and in the temperature
Degree is lower to be kept for 2 hours (persistently being purged using 30 milliliters of nitrogen per minute during this), and it is porous that nitrogen-phosphor codoping can be obtained
The carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center.
Embodiment 13
A kind of preparation method of the porous carbon-coated equally distributed catalyst of phosphatizing nickel of catalytic center of nitrogen-phosphor codoping, step
It is rapid as follows:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms:
Nickel sulfate, 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 4,4'- bipyridyl are distributed to
In ionized water, it is configured to concentration and is respectively 0.15 mole every liter, 0.1 mole every liter and 0.15 mole every liter of solution, and utilize
Raw material is driven into mixer by the device of attached drawing 1, and enters reaction zone, and reaction zone temperature is 100 DEG C, and the residence time is 80 points
Clock, the nozzle in tail portion collect product, are centrifuged or filter to isolate product, the MOFs presoma of nitrogenous phosphorus atoms can be obtained.
2) the MOFs presoma for weighing the nitrogenous phosphorus atoms in 0.5g step 1), is placed in corundum porcelain boat, porcelain boat is put into
In tube furnace, under 30 milliliters of nitrogen atmospheres per minute with 5 DEG C of heating rates per minute it is heated to 900 DEG C and in the temperature
It is lower to be kept for 5 hours (persistently being purged using 30 milliliters of nitrogen per minute during this), nitrogen-phosphor codoping porous carbon can be obtained
The equally distributed catalyst of phosphatizing nickel of the catalytic center of cladding.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of new phosphide Raney nickel, it is characterised in that: the catalyst has biggish specific surface area and pore volume, is in
Multistage pore size distribution, the catalyst are Ni2P catalytic active center is uniformly dispersed in answering in nitrogen-phosphor codoping carbon network skeleton
Condensation material.
2. a kind of preparation method of new phosphide Raney nickel according to claim 1, includes the following steps:
1) preparation of the MOFs presoma of nitrogenous phosphorus atoms: phosphorous, nitrogenous organic ligand and nickel salt are weighed respectively and is dissolved in centainly
It is sufficiently stirred to obtain three kinds of solution in the deionized water of amount；Nitrogenous phosphorus atoms MOFs presoma is synthesized followed by microlayer model method；
2) the MOFs presoma of a certain amount of nitrogenous phosphorus atoms is placed in corundum porcelain boat, is then placed in tube furnace, is warming up to
It 600-1100 DEG C, calcines 0.5-12 hours, obtains a kind of porous carbon-coated equally distributed phosphorus of catalytic center of nitrogen-phosphor codoping
Change Raney nickel.
3. a kind of preparation method of new phosphide Raney nickel according to claim 2, which is characterized in that institute in step 1)
The phosphorous organic ligand stated includes 2,4,6- trimethylbenzenes -1,3,5- trimethylene tri methylene phosphonic acid ligand, 2,4,6- trimethylbenzenes -
1,3- dimethylene di 2 ethylhexyl phosphonic acid, 2,5- dimethyl benzenes-Isosorbide-5-Nitrae-dimethylene di 2 ethylhexyl phosphonic acid, terephthalylidene di 2 ethylhexyl phosphonic acid, 2,5- bis-
Methylbenzene-Isosorbide-5-Nitrae-di 2 ethylhexyl phosphonic acid, 2,4- di 2 ethylhexyl phosphonic acid trimethylbenzenes, methylphosphonic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid, AminomethylphosphoniAcid Acid, amino
Three methylenephosphonic acids, zoledronic acid, and the concentration of the phosphorous organic ligand are 0.05-0.5mol/L；
Nitrogenous organic ligand described in step 1) include 4,4'- bipyridyl, 2,2'- bipyridyls, Phen, pyrazine, and
The concentration of the nitrogenous organic ligand is 0.05-0.5mol/L；
Nickel salt described in step 1) includes the hydrate of nickel sulfate, nickel nitrate, nickel chloride, nickel acetate, and the nickel salt
Concentration is 0.05-0.5mol/L.
4. a kind of preparation method of new phosphide Raney nickel according to claim 3, which is characterized in that institute in step 1)
The phosphorous organic ligand stated includes 2,4,6- trimethylbenzene -1,3,5- trimethylene tri methylene phosphonic acid ligand and 2,4,6- trimethyl
Benzene -1,3- dimethylene di 2 ethylhexyl phosphonic acid, and the concentration of the phosphorous organic ligand is 0.10mol/L；
The concentration of nitrogenous organic ligand described in step 1) is 0.15mol/L；
Nickel salt described in step 1) is the hydrate of nickel sulfate and nickel nitrate, and the concentration of the nickel salt is 0.15mol/L.
5. a kind of preparation method of new phosphide Raney nickel according to claim 2, which is characterized in that institute in step 1)
The synthetic method of the MOFs presoma for the nitrogenous phosphorus atoms stated includes microlayer model synthetic method and hydrothermal synthesis method；
The reaction condition of the microlayer model synthetic method of the MOFs presoma of nitrogenous phosphorus atoms described in step 1) are as follows: utilize microlayer model
Organic ligand solution, nickel salt solution are squeezed into mixer by the syringe pump in continuous synthesizer, and in 80-100 DEG C of reaction zone
Middle reaction 20-200 minutes then collects sample and separation cleaning by subsequent collection device, obtains nitrogenous phosphorus atoms
MOFs presoma；
The reaction condition of the hydrothermal synthesis method of the MOFs presoma of nitrogenous phosphorus atoms described in step 1) are as follows: turn mixed solution
It moves on in the reaction kettle of polytetrafluoro liner and is warming up to 120-150 DEG C of reaction 6-72 hours, clean, obtain after product is centrifugated
The MOFs presoma of nitrogenous phosphorus atoms.
6. a kind of preparation method of new phosphide Raney nickel according to claim 5, which is characterized in that institute in step 1)
In the reaction condition of the microlayer model synthetic method of the MOFs presoma for the nitrogenous phosphorus atoms stated, the temperature of reaction zone is 100 DEG C, reaction
Time is 80 minutes；
During the reaction condition of the hydrothermal synthesis method of the MOFs presoma of nitrogenous phosphorus atoms described in step 1) is, reaction temperature is
140 DEG C of reaction time are 72 hours.
7. a kind of preparation method of new phosphide Raney nickel according to claim 2, which is characterized in that institute in step 2)
The quality of the MOFs presoma for the nitrogenous phosphorus atoms stated is 0.05-10g.
8. a kind of preparation method of new phosphide Raney nickel according to claim 2, which is characterized in that institute in step 2)
The inert atmosphere stated is argon gas, nitrogen or helium, and inert gas flow velocity is 1-500mL/min in step 2)；It is risen in step 2)
Warm rate is 1-20 DEG C/min；Heat treatment temperature described in step 2) is 600-1100 DEG C, and heat treatment time is that 0.5-12 is small
When.
9. a kind of preparation method of new phosphide Raney nickel according to claim 8, which is characterized in that institute in step 2)
The inert atmosphere stated is nitrogen, and inert gas flow velocity described in step 2) is 20-100mL/min；Heating rate in step 2)
For 5-10 DEG C/min；Heat treatment temperature described in step 2) is 800-1000 DEG C, and heat treatment time is 0.5-5 hours.
10. a kind of preparation method of new phosphide Raney nickel according to claim 9, which is characterized in that in step 2)
The heat treatment temperature is 900 DEG C, and heat treatment time is 2 hours.
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| CN110013871A (en) * | 2019-04-18 | 2019-07-16 | 常州大学 | Support type nickel phosphide-nickel/composite catalyst containing nitrogen nano-material and its preparation method and application |
| CN111672527A (en) * | 2020-06-22 | 2020-09-18 | 齐鲁工业大学 | Molybdenum phosphide catalyst and preparation method thereof |
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| CN109569683A (en) * | 2018-10-19 | 2019-04-05 | 郑州大学 | A kind of preparation method and application of the porous carbon sheet of nitrogen-phosphor codoping/transition metal phosphide composite material |
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| CN109569683A (en) * | 2018-10-19 | 2019-04-05 | 郑州大学 | A kind of preparation method and application of the porous carbon sheet of nitrogen-phosphor codoping/transition metal phosphide composite material |
Non-Patent Citations (1)
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| SHANSHANSHI等: ""A covalent heterostructure of monodisperse Ni2P immobilized on N, P-codoped carbon nanosheets for high performance sodium/lithium storage"", 《NANO ENERGY》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110013871A (en) * | 2019-04-18 | 2019-07-16 | 常州大学 | Support type nickel phosphide-nickel/composite catalyst containing nitrogen nano-material and its preparation method and application |
| CN110013871B (en) * | 2019-04-18 | 2021-10-01 | 常州大学 | Supported nickel phosphide-nickel/nitrogen-containing nano material composite catalyst and preparation method and application thereof |
| CN111672527A (en) * | 2020-06-22 | 2020-09-18 | 齐鲁工业大学 | Molybdenum phosphide catalyst and preparation method thereof |
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