CN107507987B - A kind of Ru modification CoNiP is nanocrystalline and its preparation method and application - Google Patents
A kind of Ru modification CoNiP is nanocrystalline and its preparation method and application Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention disclose a kind of Ru, and to modify CoNiP nanocrystalline and its preparation method and application, belongs to nm regime.Ru modify CoNiP it is nanocrystalline be metal simple-substance modification irregular flake structure, crystalline phase for Ru be face-centered cubic phase, CoNiP nanocrystalline is hexagonal phase.The present invention obtains that Ru modifications CoNiP is nanocrystalline, and prepared Ru modifications CoNiP is nanocrystalline to have excellent HER performances, better than business Pt C catalysts using temperature programmed control pattern using the preparation method of " treating different things alike ".The preparation method has simple for process simultaneously, and reaction temperature is low, and the time is short, is suitable for the industrialization feature of batch production.
Description
Technical field
It is nanocrystalline and its preparation method and application the present invention relates to a kind of Ru modifications CoNiP, belong to nm regime.
Background technology
As world energy sources need the increasingly increase with environmental problem, it is extremely urgent to find clean energy resource.It in recent years, can be again
Raw H2-O2Fuel cell because tool high energy efficiency, noiseless, it is pollution-free, can continuous-stable work the features such as, it is considered to be 21 century is most
Promising new energy technology.And during designing fuel cell, improve evolving hydrogen reaction（HER）Reaction efficiency into
Key for commercial applications.According to Sabatier theories, the reaction rate of HER is by the reactive intermediate H of its reactionadWith
Bonded energy between the activated centre of electrode surface（M-Had）Size directly determine.Only work as HadThe absorption of atom and metal
When can be moderate, comparison high current density that surface can generate, HER activity at this time be optimal.In other words, M-HadEffect between key
Power is too strong or the too weak generation for being all unfavorable for HER.It is found according to literature survey, Pt- base nanometer crystals are considered as to be catalyzed HER most
Effective catalyst.It is also worth noting that Pt- base nanometer crystals are expensive, stable under acidic conditions difference further limits
Its commercial applications is made.For renewable H2-O2Fuel cell effectively operation and large-scale commercial application, development is efficiently, surely
Fixed, cheap and sustainable development elctro-catalyst is imperative.
Transition metal phosphide is widely noticed when having the function of similar hydrogenase and rich content.2013, Lewis
And its partner has found Ni2P's（001）Crystal face has higher HER activity（η10=116 mV）, what nearest Han et al. was obtained
CoNiP/NF HER performances advanced optimize（η10=60 mV）.This is because introducing new metal changes mutual charge structure
Can, new synergistic effect is generated, but also coordination effect and group effect for changing catalyst etc..Shown according to literature research
Although transition metal phosphide has higher catalytic activity, its overpotential and catalytic activity are urged significantly lower than business Pt/C
Agent.Therefore, further to promote commercial applications, it is imperative to develop cheap and efficient HER elctro-catalysts.From quotient
Industry angle considers that the price of Ru is lower than Pt, and with the bonding energy similar to Pt-H（∼65 kcal mol-1）, considering will
Ru modifications to transition metal phosphide it is nanocrystalline in, further improve the catalytic activity of catalyst.
Invention content
Goal of the invention：One of the object of the invention is in view of the deficiencies of the prior art, to provide a kind of applied to fuel cell
Cheap, efficient transition metal phosphide catalyst Ru modifications CoNiP in evolving hydrogen reaction is nanocrystalline.
In order to realize the purpose, the invention discloses Ru modifications CoNiP nanocrystalline receive for metal-semiconductor hetero-junctions
The nanocrystalline crystalline phase of meter Jing, wherein CoNiP is hexagonal phase, and Ru is face-centered cubic phase.
Further, the invention also discloses preparation methods nanocrystalline this Ru modifications CoNiP.
Specific technical solution is as follows：
Preparation method nanocrystalline a kind of Ru modifications CoNiP, by Co (acac)2, Ni (HCO2)2, RuCl3•xH2O is added to
Lauryl amine（DDA）, oleic acid（OA）And tri-n-octyl phosphine（TOP）In solution, 300-340 °C is warming up to, and maintains this temperature,
It is obtained by the reaction containing the nanocrystalline products of Ru modification CoNiP, is dispersed through settling, to be centrifugally separating to obtain Ru modifications CoNiP nanocrystalline.
Preferably, the adding proportion of each component nanocrystalline every part of Ru modifications CoNiP is：Co(acac)2Dosage 0.5-
1 mmol, Ni (HCO2)2Dosage 0.5-1 mmol, RuCl3•xH2The dosage 1-5 of dosage the 0.3-0.8 mmol, DDA of O
The dosage 3-8 mL of dosage the 1-3 mL, TOP of mL, OA.
It is further preferred that nanocrystalline preparation uses secondary gradually temperature-rise period.It is warming up to 300-340 °C first, protects
After temperature reaction a period of time, it is cooled to room temperature；300-340 °C is warming up to again according to identical temperature program, one section of insulation reaction
It after time, is cooled to room temperature, obtains containing product nanocrystalline Ru modifications CoNiP.
It is further preferred that secondary gradually temperature-rise period is according to 4-8oC min-1Heating rate gradually heat up.
Further, it is preferable to the insulation reaction time be 10-60 min.After temperature reaches the temperature that we are expected,
It keeps constant temperature and reacts 10-60 min.For example, after temperature reaches 300-340 °C, 10-60 min are reacted.For two
For the temperature-rise period in stage, after temperature reaches 300-340 °C, all it is control constant temperature and reacts 10-60 respectively
min。
Additionally, it is preferred that the product absolute ethyl alcohol dispersing and settling after reaction.Wherein using absolute ethyl alcohol dispersing and settling, centrifugation
The operation of separation can repeat 3-4 times.
The invention also discloses this Ru simultaneously to modify the nanocrystalline applications as fuel-cell catalyst of CoNiP.Especially
It is that the nanocrystalline catalytic hydrogen evolutions as fuel cell of this Ru modification CoNiP react（HER）The application of catalyst.
Ru modifications CoNiP obtained by the present invention is nanocrystalline to be swept using element line, element mapping and X-ray diffractometer
（XRD）To characterize its component and structure；Use transmission electron microscope（TEM）, high resolution electron microscope（HRTEM）And scanning is saturating
Television electronic microscope（STEM）Analyze its size, pattern and micro-structure etc..
Advantageous effect：（1）Ru modifications CoNiP obtained by the present invention is nanocrystalline with excellent HER performances.After testing its
Performance is better than presently commercially available Pt-C, has important directive significance for renewable energy technologies development.
（2）In the present invention prepared by nanocrystalline chemically reacted by solid liquid phase of involved Ru modifications CoNiP, normal pressure and compared with
It is nanocrystalline that Ru modifications CoNiP has controllably been synthesized at low temperature.Simultaneously because by the way of " treating different things alike ", program control is utilized
Warm pattern is obtained with unique metal-heterojunction semiconductor（Ru modifies CoNiP）Nanocrystalline, simple for process, reaction temperature is low, when
Between it is short, be suitable for producing in batches.
Description of the drawings
Fig. 1 a are that Ru prepared by embodiment 1 modifies the nanocrystalline XRD diagram of CoNiP.
Fig. 1 b are that Ru prepared by embodiment 1 modifies the nanocrystalline low power TEM figures of CoNiP.
Fig. 1 c are that Ru prepared by embodiment 1 modifies the nanocrystalline HRTEM figures of CoNiP.
Fig. 1 d are that Ru prepared by embodiment 1 modifies the nanocrystalline STEM figures of CoNiP.
Fig. 1 e are that Ru prepared by embodiment 1 modifies the nanocrystalline linear sweep graphs of CoNiP.
Fig. 1 f are that Ru prepared by embodiment 1 modifies the nanocrystalline element mapping figures of CoNiP.
Fig. 2 a are that Ru modifications CoNiP prepared by embodiment 1 is nanocrystalline in 0.5 M H2SO4HER polarization curves in solution
Figure.
Fig. 2 b are that Ru prepared by embodiment 1 modifies the nanocrystalline Tafel slope figures of CoNiP.
Difference nanocrystalline for the Ru modifications CoNiP of the preparation of embodiment 1 Fig. 2 c sweeps the cyclic voltammetry curve figure under speed.
Fig. 2 d are that Ru prepared by embodiment 1 modifies the nanocrystalline Cdl active area linear fit curve graphs of CoNiP.
Fig. 2 e are that Ru prepared by embodiment 1 modifies the nanocrystalline i-t curve graphs of CoNiP.
Specific embodiment
Technical solution of the present invention is described in detail below by attached drawing, but protection scope of the present invention is not limited to
The embodiment.
Embodiment 1
At room temperature, 178 mg are weighed（0.7 mmol）Co(acac)2, 112 mg（0.75 mmol）Ni(HCO2)2And 104
mg （0.5 mmol）RuCl3•xH2O powder, and whole raw materials are added to three necks that dry capacity is 250 mL together and are justified
In the flask of bottom, then with graduated cylinder measure DDA 1.5 mL of 3 mL, OA and 5 mL of TOP, be added in round-bottomed flask, ultrasound simultaneously stir
To being completely dissolved, dark solution is obtained.
Round-bottomed flask is transferred in sand-bath, is warming up to 320 °C under temperature programmed control with the rate of 7 °C/min, heat preservation 30
It after min, is cooled to room temperature, continues to be warming up to 320 °C with 7 °C/min, 30 min of heat preservation to reaction terminate.Treat reactor nature
It is cooled to room temperature, adds in ethanol in proper amount dispersion, centrifuge solid.Black product is obtained after solid is washed, is being dried in vacuo
After being dried in vacuum overnight in case, for being analyzed and characterized.
Using XRD, TEM, STEM, line is swept and element mapping tests respectively analyze product, as a result such as Fig. 1 institutes
Show.7 sharp diffraction maximums are shown in Fig. 1 a, these diffraction maximums correspond to cubic phase Ru（JCPDS-88-2333）With six sides
Phase CoNiP（JCPDS-71-2336）, the product illustrated is heterojunction structure.
From the low power TEM figures of Fig. 1 b it is observed that the irregular flake structure of a large amount of monodispersed stain modifications.Into one
Microstructure analysis is walked, can be seen that clearly lattice fringe by Fig. 1 c corresponds to cubic phase Ru（111）With hexagonal phase CoNiP
（111）Crystal face.
The STEM figures of Fig. 1 d can be with it is further seen that there is a large amount of little particles to be distributed around thin slice.Fig. 1 e are that Fig. 1 d are corresponding
Linear sweep graph.It is intermediate there is no Ru substantially it is found that surrounding is rich in a large amount of Ru simple substance from Fig. 1 e.
The element mapping of Fig. 1 f further illustrates that Ru is present in around irregular thin slice.
Therefore, based on above-mentioned analysis it is found that our obtained crystalline products are CoNiP nanometers of the hexagonal phase of Ru modifications
It is brilliant.
Embodiment 2
At room temperature, 127 mg are weighed（0.5 mmol）Co(acac)2, 82 mg（0.55 mmol）Ni(HCO2)2And 83 mg
（0.4 mmol）RuCl3•xH2O powder, and whole raw materials are added to the three neck round bottoms that dry capacity is 250 mL together and are burnt
Bottle in, then with graduated cylinder measure DDA 1.5 mL of 2.5 mL, OA and 3.6 mL of TOP, be added in round-bottomed flask, ultrasound simultaneously stir
To being completely dissolved, dark solution is obtained.
Round-bottomed flask is transferred in sand-bath, is warming up to 320 °C under temperature programmed control with the rate of 7 °C/min, heat preservation 30
It after min, is cooled to room temperature, continues to be warming up to 320 °C with 7 °C/min, 30 min of heat preservation to reaction terminate.Treat reactor nature
It is cooled to room temperature, adds in ethanol in proper amount dispersion, centrifuge solid.Black product is obtained after solid is washed, is being dried in vacuo
It is dried in vacuum overnight in case.
Embodiment 3
At room temperature, 127 mg are weighed（0.5 mmol）Co(acac)2, 75 mg（0.5 mmol）Ni(HCO2)2And 62 mg
（0.3 mmol）RuCl3•xH2O powder, and whole raw materials are added to the three neck round bottoms that dry capacity is 250 mL together and are burnt
In bottle, then with graduated cylinder DDA 1 mL of 1 mL, OA and 3 mL of TOP are measured, be added in round-bottomed flask, ultrasound is simultaneously stirred to complete
Dissolving, obtains dark solution.
Round-bottomed flask is transferred in sand-bath, is warming up to 320 °C under temperature programmed control with the rate of 7 °C/min, heat preservation 30
It after min, is cooled to room temperature, continues to be warming up to 320 °C with 7 °C/min, 30 min of heat preservation to reaction terminate.Treat reactor nature
It is cooled to room temperature, adds in ethanol in proper amount dispersion, centrifuge solid.Black product is obtained after solid is washed, is being dried in vacuo
It is dried in vacuum overnight in case.
Embodiment 4
At room temperature, 127 mg are weighed（0.5 mmol）Co(acac)2, 150 mg（1.0 mmol）Ni(HCO2)2And 166 mg
（0.8 mmol）RuCl3•xH2O powder, and whole raw materials are added to the three neck round bottoms that dry capacity is 250 mL together and are burnt
In bottle, then with graduated cylinder DDA 3 mL of 5 mL, OA and 8 mL of TOP are measured, be added in round-bottomed flask, ultrasound is simultaneously stirred to complete
Dissolving, obtains dark solution.
Round-bottomed flask is transferred in sand-bath, is warming up to 320 °C under temperature programmed control with the rate of 7 °C/min, heat preservation 30
It after min, is cooled to room temperature, continues to be warming up to 320 °C with 7 °C/min, 30 min of heat preservation to reaction terminate.Treat reactor nature
It is cooled to room temperature, adds in ethanol in proper amount dispersion, centrifuge solid.Black product is obtained after solid is washed, is being dried in vacuo
It is dried in vacuum overnight in case.
Embodiment 5
At room temperature, 254 mg are weighed（1.0 mmol）Co(acac)2, 150 mg（1.0 mmol）Ni(HCO2)2And 166 mg
（0.8 mmol）RuCl3•xH2O powder, and whole raw materials are added to the three neck round bottoms that dry capacity is 250 mL together and are burnt
In bottle, then with graduated cylinder DDA 3 mL of 5 mL, OA and 8 mL of TOP are measured, be added in round-bottomed flask, ultrasound is simultaneously stirred to complete
Dissolving, obtains dark solution.
Round-bottomed flask is transferred in sand-bath, is warming up to 320 °C under temperature programmed control with the rate of 7 °C/min, heat preservation 30
It after min, is cooled to room temperature, continues to be warming up to 320 °C with 7 °C/min, 30 min of heat preservation to reaction terminate.Treat reactor nature
It is cooled to room temperature, adds in ethanol in proper amount dispersion, centrifuge solid.Black product is obtained after solid is washed, is being dried in vacuo
It is dried in vacuum overnight in case.
Embodiment 6
At room temperature, 178 mg are weighed（0.7 mmol）Co(acac)2, 112 mg（0.75 mmol）Ni(HCO2)2And 104
mg （0.5 mmol）RuCl3•xH2O powder, and whole raw materials are added to three necks that dry capacity is 250 mL together and are justified
In the flask of bottom, then with graduated cylinder measure DDA 1.5 mL of 3 mL, OA and 5 mL of TOP, be added in round-bottomed flask, ultrasound simultaneously stir
To being completely dissolved, dark solution is obtained.
Round-bottomed flask is transferred in sand-bath, is warming up to 320 °C under temperature programmed control with the rate of 4 °C/min, heat preservation 30
It after min, is cooled to room temperature, continues to be warming up to 320 °C with 4 °C/min, 30 min of heat preservation to reaction terminate.Treat reactor nature
It is cooled to room temperature, adds in ethanol in proper amount dispersion, centrifuge solid.Black product is obtained after solid is washed, is being dried in vacuo
It is dried in vacuum overnight in case.
Embodiment 7
At room temperature, 178 mg are weighed（0.7 mmol）Co(acac)2, 112 mg（0.75 mmol）Ni(HCO2)2And 104
mg （0.5 mmol）RuCl3•xH2O powder, and whole raw materials are added to three necks that dry capacity is 250 mL together and are justified
In the flask of bottom, then with graduated cylinder measure DDA 1.5 mL of 3 mL, OA and 5 mL of TOP, be added in round-bottomed flask, ultrasound simultaneously stir
To being completely dissolved, dark solution is obtained.
Round-bottomed flask is transferred in sand-bath, is warming up to 320 °C under temperature programmed control with the rate of 8 °C/min, heat preservation 30
It after min, is cooled to room temperature, continues to be warming up to 320 °C with 8 °C/min, 30 min of heat preservation to reaction terminate.Treat reactor nature
It is cooled to room temperature, adds in ethanol in proper amount dispersion, centrifuge solid.Black product is obtained after solid is washed, is being dried in vacuo
It is dried in vacuum overnight in case.
Embodiment 8
At room temperature, 178 mg are weighed（0.7 mmol）Co(acac)2, 112 mg（0.75 mmol）Ni(HCO2)2And 104
mg （0.5 mmol）RuCl3•xH2O powder, and whole raw materials are added to three necks that dry capacity is 250 mL together and are justified
In the flask of bottom, then with graduated cylinder measure DDA 1.5 mL of 3 mL, OA and 5 mL of TOP, be added in round-bottomed flask, ultrasound simultaneously stir
To being completely dissolved, dark solution is obtained.
Round-bottomed flask is transferred in sand-bath, is warming up to 320 °C under temperature programmed control with the rate of 7 °C/min, heat preservation 20
It after min, is cooled to room temperature, continues to be warming up to 320 °C with 7 °C/min, 20 min of heat preservation to reaction terminate.Treat reactor nature
It is cooled to room temperature, adds in ethanol in proper amount dispersion, centrifuge solid.Black product is obtained after solid is washed, is being dried in vacuo
It is dried in vacuum overnight in case.
Embodiment 9
At room temperature, 178 mg are weighed（0.7 mmol）Co(acac)2, 112 mg（0.75 mmol）Ni(HCO2)2And 104
mg （0.5 mmol）RuCl3•xH2O powder, and whole raw materials are added to three necks that dry capacity is 250 mL together and are justified
In the flask of bottom, then with graduated cylinder measure DDA 1.5 mL of 3 mL, OA and 5 mL of TOP, be added in round-bottomed flask, ultrasound simultaneously stir
To being completely dissolved, dark solution is obtained.
Round-bottomed flask is transferred in sand-bath, is warming up to 320 °C under temperature programmed control with the rate of 7 °C/min, heat preservation 10
It after min, is cooled to room temperature, continues to be warming up to 320 °C with 7 °C/min, 10 min of heat preservation to reaction terminate.Treat reactor nature
It is cooled to room temperature, adds in ethanol in proper amount dispersion, centrifuge solid.Black product is obtained after solid is washed, is being dried in vacuo
It is dried in vacuum overnight in case.
Embodiment 10
At room temperature, 178 mg are weighed（0.7 mmol）Co(acac)2, 112 mg（0.75 mmol）Ni(HCO2)2And 104
mg （0.5 mmol）RuCl3•xH2O powder, and whole raw materials are added to three necks that dry capacity is 250 mL together and are justified
In the flask of bottom, then with graduated cylinder measure DDA 1.5 mL of 3 mL, OA and 5 mL of TOP, be added in round-bottomed flask, ultrasound simultaneously stir
To being completely dissolved, dark solution is obtained.
Round-bottomed flask is transferred in sand-bath, is warming up to 320 °C under temperature programmed control with the rate of 7 °C/min, heat preservation 60
It after min, is cooled to room temperature, continues to be warming up to 320 °C with 7 °C/min, 60 min of heat preservation to reaction terminate.Treat reactor nature
It is cooled to room temperature, adds in ethanol in proper amount dispersion, centrifuge solid.Black product is obtained after solid is washed, is being dried in vacuo
It is dried in vacuum overnight in case.
Embodiment 11
Pass through cyclic voltammetry and method of polarization curve, the electrochemical properties of test sample, specific mistake in three-electrode system
Journey is as follows：
Electrochemistry experiment carries out on CHI660e type electrochemical workstations, using three electrode test systems of standard, accordingly
Glass-carbon electrode of the working electrode for the sample modification acquired in this paper, be graphite rod to electrode, reference electrode is silver/silver chlorate
（Ag/AgCl）.All potentials are both with respect to RHE herein.Electrolyte is the H of 0.5 M2SO4Solution.All electro-chemical tests
30oIt is carried out under C.Every time during experiment, all modified electrodes are in 0.5 M H2SO4It is tested in solution.
The preparation method of sample modified electrode is as follows：
Every time before experiment, by the rotating disk electrode (r.d.e) of a diameter of 3 mm successively with 1.0 μm, 0.3 μm and 0.05 μm
Al2O3Then grinding is cleaned by ultrasonic to minute surface, finally clean with second distillation water wash, in room temperature N2Dried for standby under atmosphere.
By the Ru of 15 mg modification, CoNiP is nanocrystalline is distributed to 200 μ L ethyl alcohol, 35 μ L, 1% naphthol solutions and 765 μ L H2In O, obtain
5 mg mL-1The nanocrystalline suspension of Ru modification CoNiP.4 this suspension of μ L are dispersed in ripple carbon electrode surface N2Atmosphere
Middle drying obtains the Ru modification nanocrystalline modified electrodes of CoNiP.
Before HER tests, high-purity N is first passed through into solution230 min, and continue logical N during the experiment2To keep solution
N2Atmosphere.Corresponding Electrochemical Scanning rate is 5 mV/s, and scanning range is -0.80 V -0 V.
Testing result is respectively referring to Fig. 2.Ru modifies the hydrogen-evolution overpotential of CoNiP catalyst and business Pt/C catalyst in Fig. 2 a
It is close.It is mapped with overpotential to the logarithm of current density, corresponding Tafel curves can be obtained, slope is about 43 mV/dec（Figure
2b）, it is closer to 31 mV/dec of Tafel slopes of 20% Pt/C.In addition, we are in addition to investigating being urged with higher for catalyst
It is nanocrystalline with larger active area to can be seen that Ru modifications CoNiP from Fig. 2 c and Fig. 2 d for the reason of changing activity（49.44
mF/cm2）, there is more active site, so as to effectively increase catalytic activity.In addition, we have also investigated the steady of catalyst
Qualitative, after recycling 9 h, CoNiP is nanocrystalline does not decay substantially for Ru modifications.As can be seen from the above data, Ru modifies CoNiP
It is nanocrystalline to show excellent electro-catalysis HER activity and stability.
As described above, although the present invention has been represented and described with reference to specific preferred embodiment, must not explain
For to the limitation of itself of the invention.It, can be right under the premise of the spirit and scope of the present invention that appended claims define are not departed from
Various changes can be made in the form and details for it.
Claims (7)
1. a kind of Ru modification CoNiP is nanocrystalline, which is characterized in that it is described nanocrystalline for metal-semiconductor heterojunction structure,
The middle nanocrystalline crystalline phases of CoNiP are hexagonal phase, and Ru is face-centered cubic phase.
2. preparation method nanocrystalline a kind of Ru modifications CoNiP described in claim 1, it is characterised in that include the following steps：
By Co (acac)2, Ni (HCO2)2, RuCl3•xH2O is added to lauryl amine, in oleic acid and tri-n-octyl phosphine solution, stirs to complete
Dissolving, obtains dark solution；Reaction process is divided into two stages, is warming up to 300-340 DEG C first, maintains this temperature anti-
Should, it is cooled to room temperature later；300-340 DEG C is warming up to again according to identical temperature program, insulation reaction is cooled to room later
Temperature obtains modifying CoNiP nanocrystalline products containing Ru, is dispersed through settling, to be centrifugally separating to obtain Ru modifications CoNiP nanocrystalline.
3. preparation method according to claim 2, which is characterized in that each component nanocrystalline every part of Ru modifications CoNiP
Adding proportion is：Co(acac)20.5-1mmol, Ni (HCO2)20.5-1mmol, RuCl3•xH2O 0.3-0.8mmol, 12
Amine 1-5mL, oleic acid 1-3mL, tri-n-octyl phosphine 3-8mL.
4. preparation method according to claim 2, which is characterized in that temperature-rise period is according to 4-8 DEG C of .min-1Heating rate
Gradually heat up.
5. preparation method according to claim 2, which is characterized in that the insulation reaction time is 10-60 min.
6. preparation method according to claim 2, which is characterized in that is obtained after reaction modifies CoNiP nanometers containing Ru
Brilliant product absolute ethyl alcohol dispersing and settling, the operation of centrifugation repeat 3-4 times.
7. the application of the Ru modifications nanocrystalline evolving hydrogen reaction catalyst as fuel cell of CoNiP described in claim 1.
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