CN103952719B - Catalyst used for preparation of hydrogen through water electrolysis, and preparation method thereof - Google Patents
Catalyst used for preparation of hydrogen through water electrolysis, and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a catalyst used for the preparation of hydrogen through water electrolysis. The catalyst is amorphous Ni-B, and an atom ratio of Ni to B is 2.7. The catalyst is a granular material with spherical appearance, the diameter range of small balls ranges from 40 nm to 120 nm, and the interior of the small balls is of a flower-shaped structure, the specific surface is large, the catalytic reaction of hydrogen evolution is facilitated, and the pH value range of the applicable solution of the catalyst is 0 -14. The invention also provides a preparation method for the catalyst. The method is characterized in that Ni-B is loaded on the surface of a carrier through a chemical plating method, and the feeding atom ratio of B to Ni in a chemical plating liquid is 3.0-10.0. The amorphous Ni-B is successfully applied in the catalysis of a hydrogen evolution reaction through water decomposition, and the reaction activity of the amorphous Ni-B can be comparable with that of platinum. The amorphous Ni-B has the advantages of low hydrogen evolution over-potential, high catalytic efficiency, stable performances, low price and simple preparation, and becomes one of the most ideal catalysts for substituting the present noble metal Pt catalyst.
Description
Technical field
The invention belongs to hydrogen production by water decomposition catalytic field, and in particular to by the Ni-B Alloyapplications of amorphous in electrocatalytic decomposition
The cathode material of water hydrogen manufacturing.
Background technology
Hydrogen Energy fuel value height, cleanliness without any pollution, aboundresources, use range are wide, and exploitation Hydrogen Energy is for alleviation today's society
The energy and environmental problem be significant.Decomposition water catalyzing manufacturing of hydrogen is the topmost approach for obtaining hydrogen energy source on a large scale.
For evolving hydrogen reaction, precious metal element platinum (Pt) have excellent electrocatalytic decomposition elutriation hydrogen activity, its overpotential of hydrogen evolution is low, but
Its is expensive, it is difficult to large-scale application, the focus that a kind of non-precious metal catalyst is found for this to replace Pt to be research.
Engel Brewer valence bond theories predict that the alloy of some transition metals has higher electro catalytic activity to evolving hydrogen reaction
(see L.Brewer, Bonding and structures of transition metals, Science, 1968,161：115-
122).For transition metal alloy makees the existing substantial amounts of research of liberation of hydrogen catalyst, wherein the catalyst of Ni systems is used as alkalescence
Liberation of hydrogen catalyst used in solution, receives much concern always.
In the exploratory development of base metal liberation of hydrogen catalyst material, there are following two problems to need to consider：First, how to drop
The overpotential of hydrogen evolution of low liberation of hydrogen catalyst, with reducing energy consumption, improves decomposition water liberation of hydrogen efficiency；2nd, the steady of catalyst how is improved
It is qualitative.In order to solve problem above, we have done following analysis from decomposition water liberation of hydrogen mechanism.Volcano graph model (Volcano
Curves decomposition water catalytic hydrogen evolution performance) is reflected with catalyst surface and the relation of hydrogen energy of adsorption：Energy of adsorption is too small, it is impossible to will
Hydrogen is adsorbed in catalyst surface；Energy of adsorption is too big, can not effectively be desorbed (see S.Trasatti, Work after absorption hydrogen
function,electronegativity,and electrochemical behavior of metals.Ⅲ
.Electrolytic hydrogen evolution in acid solutions.J.Electroanal.Chem.1972,
39:163-184.).Only under suitable energy of adsorption, catalyst can just show optimal decomposition water Hydrogen Evolution Performance.Will for this
Overpotential of hydrogen evolution is reduced, the electronic state structure of catalyst surface must be just adjusted, the energy of adsorption for making hydrogen reaches one appropriate
With value, so as to obtain the catalytic activity of hydrogen evolution of optimum.
Amorphous alloy starts from the 7th world in 1981 and is catalyzed the reported firsts such as progress meeting-Smith as catalyst
The catalytic performance of amorphous alloy is (see G.V.Smith, W.E.Brower, M.S.Matyjaszczyk, et
al.Proceedings of the 7th International Congress on Catalysis,Amsterdam:
Elsevier Press,1981:355.).Since then, amorphous material is increasingly paid close attention to as catalyst by everybody.
For crystalline material, amorphous material has the atomic structure of longrange disorder, shortrange order, causes amorphous alloy each
To the same sex, possesses the homogeneous catalytic center of chemical environment；The surface free energy of amorphous alloy is higher, this in metastable state
Metastable structure can become the avtive spot of reaction, improve reactivity；The composition of amorphous material can with continuously adjustabe, from
And a proper adsorption energy can be obtained with Effective Regulation material surface electronic state structure；Amorphous material is general
Also there is superior decay resistance.
For amorphous Ni-B, we can adjust Ni-B Electronic Structures by adjusting component ratio, obtain
One appropriate adsorption energy, so as to obtain optimal decomposition water catalytic hydrogen evolution performance.In addition, in amorphous Ni-B materials
In, the electrons of B are shifted to Ni so that state of the Ni surfaces in electron rich, this has further activated Ni becomes evolving hydrogen reaction
Activated centre, while also cause Ni it is not oxidized and corrosion, improve its stability.Up to the present, yet there are no will be non-
Brilliant Ni-B is used for the hydrogen manufacturing of electrocatalytic decomposition water and obtains the report of excellent catalytic performance.
The content of the invention
It is an object of the invention to provide a kind of catalyst for electric hydrogen production by water decomposition with good catalytic performance
And preparation method thereof.
In order to solve the above problems, the present invention provides a kind of catalyst for electric hydrogen production by water decomposition, and the catalyst is
Amorphous Ni-B, nickel is 2.7 with the atomic ratio of boron；The catalyst is outward appearance granular material spherical in shape, the diameter model of bead
Enclose to be flower-like structure inside 40-120nm, particle, specific surface greatly, is conducive to decomposition water liberation of hydrogen catalytic reaction；The catalysis
The applicable solution ph scope of agent is 0～14.
The present invention also provides a kind of preparation method of described catalyst, comprises the steps：Will using chemical plating method
Amorphous Ni-B is carried on carrier surface, and B and Ni feeds intake atomic ratio for 3.0-10.0 in chemical plating fluid；The carrier be graphite, three
Dimension Graphene, nickel foam or glass material with carbon element, load capacity is 1mg/cm2。
Further, the step is specifically included：
A) the carrier priority water and ethanol solution are cleaned by ultrasonic clean；
B) carrier surface for cleaning up is carried out into hydroxylating hydrophilic treated；
C) after the carrier hydroxylating is processed, it is placed on oil bath heating in silver nitrate solution so that silver ion is carried on load
The hydrophilic surface of body；
D) oil bath heating in the chemical plating fluid of nickel borides is put into after is dried naturally carrier, till bubble collapse, will
The carrier of supported catalyst takes out, and priority ammoniacal liquor, water, and alcohol and acetone are cleaned, until carrier surface is in neutral pH=7；
E) by cleaned carrier be placed in vacuum environment it is lower 80 DEG C at be dried.
Further, the hydroxylating hydrophilic treated of the carrier surface be that electrochemical oxidation is hydrophilic, oxygen or water etc. from
Daughter is etched.
Further, the reaction temperature of chemical plating oil bath is 45-75 DEG C, and the reaction time is 30-240 minutes.
Further, the Ni-B baking temperatures that chemical plating is obtained are 80-180 DEG C, and it is vacuum or inert gas to be dried atmosphere,
Drying time is 5-10 hour.
Relative to prior art, the present invention has following technique effect：
(1) overpotential of hydrogen evolution of catalyst is low, and the activity of decomposition water liberation of hydrogen is high, we simultaneously by amorphous Ni-B catalyst with
Pt has made contrast, and in different pH value solution, the overpotential of hydrogen evolution for finding amorphous Ni-B is almost close to Pt.
(2) the amorphous Ni-B catalyst that the present invention is provided, its composition is adjustable, so as to obtain an optimal surface electronic knot
Structure so that catalyst surface energy of adsorption is in an optimal value.
(3) the amorphous Ni-B catalyst that the present invention is provided is for crystalline material, and surface free energy is high, metastable
Structure provides the avtive spot of reaction, and activity is higher.
(4) catalyst that the present invention is provided can either be acidproof, it is also possible to alkaline-resisting, applicable solution ph wide ranges, its model
Enclose for pH 0-14.
(5) the catalyst amorphous Ni-B stable performances that the present invention is provided, the tendency of the oriented Ni transfers of electronics of B, this is caused
Ni is difficult to be oxidized and corrode, as avtive spot stable performance, in acid, aqueous slkali can Long-Time Service, it is active not send out
Raw decay.
Amorphous Ni-B is successfully applied to the reaction of decomposition water catalytic hydrogen evolution by the present invention, and its reactivity can be with platinum (Pt)
Match in excellence or beauty.The overpotential of hydrogen evolution of amorphous Ni-B is low, high catalytic efficiency, and stable performance is cheap, prepares simply, becomes current generation
One of ideal catalyst for precious metals pt catalyst.
Description of the drawings
ESEM microscope (SEM) figure of the catalyst that Fig. 1 a are provided for the present invention；
Transmission electron microscope (TEM) figure of the catalyst that Fig. 1 b are provided for the present invention, and its SEAD figure；
Collection of illustrative plates of the x-ray photoelectron power spectrum of the catalyst that Fig. 1 c are provided for the present invention in Ni 2p areas；
Collection of illustrative plates of the x-ray photoelectron power spectrum of the catalyst that Fig. 1 d are provided for the present invention in B 1s areas；
The X-ray diffraction spectrum (XRD) of the catalyst that Fig. 2 is provided for the present invention；
The glass-carbon electrode of the supported catalyst that Fig. 3 a are provided for the present invention, blank glass-carbon electrode, nickel electrode, platinum electrode exist
The HClO of 0.1M/L4Polarization curve in solution (pH=1), sweep speed is 1mV/s；
The glass-carbon electrode of the supported catalyst that Fig. 3 b are provided for the present invention, blank glass-carbon electrode, nickel electrode, platinum electrode exist
The HClO of 0.2M/L4Polarization curve in solution (pH=0.7), sweep speed is 1mV/s；
The glass-carbon electrode of the supported catalyst that Fig. 3 c are provided for the present invention, blank glass-carbon electrode, nickel electrode, platinum electrode exist
Potassium phosphate (the K of 0.1M/L2HPO4/KH2PO4) polarization curve in cushioning liquid (pH=7), sweep speed is 1mV/s；
Fig. 3 d are carried on glass-carbon electrode for the catalyst that the present invention is provided, and blank glass-carbon electrode, nickel electrode, platinum electrode exists
Polarization curve in the KOH solution (pH=13) of 0.1M/L, sweep speed is 1mV/s；
Fig. 4 a are carried on glass-carbon electrode for the catalyst that the present invention is provided, and blank glass-carbon electrode, nickel electrode, platinum electrode exists
The HClO of 1M/L4Polarization curve in solution (pH=0), sweep speed is 1mV/s；
Fig. 4 b are carried on HClO of the glass-carbon electrode in 1M/L for the catalyst that the present invention is provided4In analysis in solution (pH=0)
The potentiostatic deposition i-t curves of continuous 8 hours under hydrogen overpotential η=132mV；
Fig. 5 a are carried on glass-carbon electrode for the catalyst that the present invention is provided, and blank glass-carbon electrode, nickel electrode, platinum electrode exists
Polarization curve in the KOH solution (pH=14) of 1M/L, sweep speed is 1mV/s；
Fig. 5 b are carried on glass-carbon electrode in the KOH solution (pH=14) of 1M/L in liberation of hydrogen for the catalyst that the present invention is provided
The potentiostatic deposition i-t curves of continuous 8 hours under overpotential η=194mV.
Specific embodiment
Embodiments of the invention are described in detail below in conjunction with accompanying drawing.It should be noted that not conflicting
In the case of, the feature in embodiment and embodiment in the application can mutually be combined.
Embodiment one：
It is used in below as a example by loading amorphous Ni-B as electrocatalytic decomposition elutriation hydrogen catalyst on glass-carbon electrode, to this patent
It is described in further detail.
The concrete preparation process that amorphous Ni-B is carried on glass-carbon electrode is as follows：
(1) a diameter of 5mm glass-carbon electrodes (glass carbon, abbreviation GC in accompanying drawing), respectively with 5 and 0.25 μm of Al2O3
The aqueous solution is polishing to bright in mirror surface (remaining the described carrier in addition to glass-carbon electrode need not polish) on chamois leather, and successively uses
Water and ethanol solution are cleaned by ultrasonic clean；
(2) glass-carbon electrode of bright in mirror surface is put in into 0.5M/L, in the phosphate buffer solution of pH=7, with respect to Ag/AgCl ginsengs
Than electrode apply on glass-carbon electrode 2.0V ultor be electrolysed 500s time so that glass carbon surface part of hydroxyl and become
Obtain hydrophilic；
(3) after carrier hydroxylating is processed, the silver nitrate solution that mass fraction is 0.05～0.2% is next placed it in
In, it is placed in 4 hours of reaction in 40 DEG C of oil bath so that silver ion is carried on the hydrophilic surface of carrier；
(4) glass-carbon electrode is taken out from silver nitrate solution, and is dried naturally.Then the chemical plating of nickel borides is put it into
Liquid, be placed in 45 DEG C of heating responses of oil bath, and chemical plating fluid specifically comprises 0.05M/L nickel nitrates, the NaBH of 0.15M/L4Solution,
The ethylenediamine solution of 0.3M/L, the sodium hydroxide solution of 1M/L.The time that glass-carbon electrode reacts in chemical plating fluid is 30 minutes
～60 minutes, till bubble collapse.Reaction terminates to take out the glass-carbon electrode of supported catalyst, and priority ammoniacal liquor, water,
Alcohol and acetone are cleaned, until electrode surface is in neutral pH=7；
(5) by cleaned glass-carbon electrode be placed in vacuum environment it is lower 80 DEG C at be dried 5 hours.
Finally we obtain loading the glass-carbon electrode of amorphous Ni-B, and its load capacity is about 1mg/cm2, it is subsequently used for electricity and urges
The electrochemistry experiment for changing decomposition water Hydrogen Evolution Performance is characterized.
As shown in Figure 1a, amorphous Ni-B is coccoid particulate load in glassy carbon electrode surface, and its average diameter is about
80nm, can see in the TEM image from Fig. 1 b, and amorphous Ni-B beads inside is presented petal-shaped, and this is with Ni-B chemical platings
There are a large amount of hydrogen releases relevant in preparation process.Petal-like internal structure causes the specific surface area of Ni-B to increase, and is conducive to point
Solution water catalytic activity for hydrogen evolution.Diffraction spectra illustration from Fig. 1 b, it can be seen that debye (Debye) ring of some amorphous, illustrates Ni-
B shortrange orders, the internal structure of longrange disorder.As shown in the x-ray photoelectron power spectrum in Fig. 1 c, occur in Ni2P spectrums in Ni-B
Two peaks of 853eV and 870eV be all correspondence zero-valent state nickel, but in Ni 2P3/2Correspondence oxidation state Ni in spectrum
But do not occur obvious peak at 856.75eV.There are 187.8 and 193.3eV two peaks in B 1s spectrums in Fig. 1 d, it is right respectively
Answer the B of the zero-valent state and B (B of oxidation state2O3).This explanation, in amorphous Ni-B B have by electro transfer to Ni trend so that at Ni
It is not interposing in electron rich state and is oxidized and corrodes.Additionally, quantitative analysis obtains atomic ratio Ni/B=2.7 from XPS spectrum:1.
XRD diffraction spectras in Fig. 2 are displayed at θ=45 ° a broad peak, other sharp crystalline substances does not in addition occur
Body peak, this also further illustrates the amorphous structure of Ni-B.
Fig. 3 is glass-carbon electrode, blank glass-carbon electrode (GC), nickel electrode and the platinum electrode for loading amorphous Ni-B respectively in 0.1M
HClO4(pH=1), 0.2M HClO4(pH=0.7), the negative electrode in 0.1M KPi (pH=7), 0.1M KOH (pH=13) solution
Polarization curve, we have seen that in the solution of these four different pH value from figure, and the catalysis activity of nickel is almost similar with platinum,
20mA/cm2Overpotential of hydrogen evolution be also almost close to, thus illustrate the superior decomposition water Hydrogen Evolution Performances of amorphous Ni-B.In addition also may be used
Then relatively low with the activity for seeing blank glass-carbon electrode and nickel electrode, the catalysis activity for illustrating Ni-B is mainly derived from it certainly
Body.
Fig. 4 a are glass-carbon electrode, blank glass-carbon electrode (GC), nickel electrode and the platinum electrode for loading amorphous Ni-B respectively in 1M
HClO4(pH=0) cathodic polarization curve in solution, it can be seen that platinum electrode is in 20mA/cm2Overpotential of hydrogen evolution be 76mV, and
The overpotential of hydrogen evolution of amorphous Ni-B is 132mV, one of this best result in current all of base metal liberation of hydrogen catalyst.
It is the potentiostatic deposition curve under η=132mV in Fig. 4 b, it is seen that liberation of hydrogen electric current does not almost have to decay with the time.This explanation
Amorphous Ni-B can in strongly acidic solution steady operation.
Fig. 5 a are glass-carbon electrode, blank glass-carbon electrode (GC), nickel electrode and the platinum electrode for loading amorphous Ni-B respectively in 1M
Cathodic polarization curve in KOH (pH=14) solution, as seen from the figure amorphous Ni-B is in 20mA/cm2Overpotential of hydrogen evolution be
194mV, its overpotential of hydrogen evolution is close to platinum (Pt).Fig. 5 b also show constant voltage electricity of the amorphous Ni-B under overpotential 194mV
Solution curve, it can be seen that cathodic polarization electric current increases as time went on, this is likely to be in the electrode course of work, its table
Some B that face is present2O3Progressively dissolve during electrolysis water, so as to allow more Ni-B avtive spots to come out, so as to electricity
Current density is increasing, and this phenomenon is the equal of the activation process of a catalyst.Amorphous Ni-B under concentrated base environment, long-time
Catalytic performance is not decayed in electrolytic process.
Specific example by more than, it is seen that it is excellent that amorphous Ni-B shows in electrocatalytic decomposition water hydrogen manufacturing
Performance, this also allows it to become one of best base metal liberation of hydrogen catalyst of replacement Pt.Amorphous Ni-B can acid-fast alkali-proof, it is excessively electric
Low, the stable performance in position, manufacturing process is simple, and cost is relatively low, embodies non-crystalline material as the advantage of catalyst.But it is specific
Liberation of hydrogen mechanism need further theoretical modeling and system research.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to, for the skill of this area
For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (6)
1. a kind of catalyst for electric hydrogen production by water decomposition, it is characterised in that：The catalyst is the original of amorphous Ni-B, nickel and boron
Son is than being 2.7；The catalyst is outward appearance granular material spherical in shape, and the diameter range of bead is 40-120nm, in particle
Portion is flower-like structure, and specific surface greatly, is conducive to decomposition water liberation of hydrogen catalytic reaction；The applicable solution ph scope of the catalyst
For 0～14.
2. a kind of preparation method of catalyst as claimed in claim 1, it is characterised in that comprise the steps：Using chemistry
Amorphous Ni-B is carried on carrier surface by electroplating method, and B and Ni feeds intake atomic ratio for 3.0-10.0 in chemical plating fluid；The carrier is
Graphite, three-dimensional grapheme, nickel foam or glass material with carbon element, load capacity is 1mg/cm2。
3. method as claimed in claim 2, it is characterised in that the step is specifically included：
A) the carrier priority water and ethanol solution are cleaned by ultrasonic clean；
B) carrier surface for cleaning up is carried out into hydroxylating hydrophilic treated；
C) after the carrier hydroxylating is processed, it is placed on oil bath heating in silver nitrate solution so that silver ion is carried on carrier parent
The surface of water；
D) oil bath heating in the chemical plating fluid of nickel borides is put into after is dried naturally carrier, till bubble collapse, will be loaded
The carrier of catalyst takes out, and priority ammoniacal liquor, water, and alcohol and acetone are cleaned, until carrier surface is in neutral pH=7；
E) by cleaned carrier be placed in vacuum environment it is lower 80 DEG C at be dried.
4. method as claimed in claim 3, it is characterised in that：The hydroxylating hydrophilic treated of the carrier surface is electrochemistry oxygen
Change the plasma etching of hydrophilic, oxygen or water.
5. method as claimed in claim 4, it is characterised in that：The reaction temperature of chemical plating oil bath is 45-75 DEG C, the reaction time
For 30-240 minutes.
6. method as claimed in claim 5, it is characterised in that：The Ni-B baking temperatures that chemical plating is obtained are 80-180 DEG C, are done
Pathogenic dryness atmosphere is vacuum or inert gas, and drying time is 5-10 hour.
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