CN103952719A - 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
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- 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 1.0-5.0. 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, be specifically related to the Ni-B Alloyapplication of amorphous in the cathode material of electrocatalysis hydrogen production by water decomposition.
Background technology
Hydrogen Energy fuel value is high, cleanliness without any pollution, aboundresources, use range are wide, and exploitation Hydrogen Energy is significant for the energy and the environmental problem of alleviating society.Water of decomposition catalyzing manufacturing of hydrogen is the topmost approach that obtains on a large scale hydrogen energy source.For evolving hydrogen reaction, precious metal element platinum (Pt) has excellent electrocatalysis water of decomposition hydrogen evolution activity, and its overpotential of hydrogen evolution is low, but it is expensive, is difficult to large-scale application, find for this reason a kind of non-precious metal catalyst replace Pt be research focus.Engel Brewer valence bond theory predicts that the alloy of some transition metals has higher electro catalytic activity to evolving hydrogen reaction and (sees L.Brewer, Bonding and structures of transition metals, Science, 1968,161:115-122).Do the existing a large amount of research of liberation of hydrogen catalyzer for transition metal alloy, wherein the catalyzer of Ni system, as the liberation of hydrogen catalyzer using in basic solution, receives much concern always.
In the exploratory development of base metal liberation of hydrogen catalystic material, there are following two problems to need to consider: one, how to reduce the overpotential of hydrogen evolution of liberation of hydrogen catalyzer, to reduce energy consumption, to improve water of decomposition liberation of hydrogen efficiency; Two, how to improve the stability of catalyzer.In order to overcome the above problems, we have done following analysis from water of decomposition liberation of hydrogen mechanism.Volcano graph model (Volcano Curves) has reflected the relation of water of decomposition catalytic hydrogen evolution performance and catalyst surface and hydrogen adsorption energy: sorptive power is too small, can not be by hydrogen adsorption in catalyst surface; Sorptive power is too large, after absorption hydrogen, effectively desorption (is shown in S.Trasatti, Work function, electronegativity, and electrochemical behavior of metals. III .Electrolytic hydrogen evolution in acid solutions.J.Electroanal.Chem.1972,39:163-184.).Only, under suitable sorptive power, catalyzer just can show best water of decomposition Hydrogen Evolution Performance.To reduce overpotential of hydrogen evolution for this reason, just must regulate the electronic state structure of catalyst surface, make the sorptive power of hydrogen reach a suitable matching value, thereby obtain optimum catalytic activity of hydrogen evolution.
Amorphous alloy starts from the catalytic performance of the reported first amorphous alloys such as the international catalysis progress of Qi Jie meeting-Smith in 1981 and (sees G.V.Smith as catalyzer, W.E.Brower, M.S.Matyjaszczyk, et al.Proceedings of the7th International Congress on Catalysis, Amsterdam:Elsevier Press, 1981:355.).Since then, amorphous material more and more receives everybody concern as catalyzer.For crystalline material, amorphous material has that long-range is unordered, the atomic structure of short range order, causes amorphous alloy isotropy, possesses the catalytic center of chemical environment homogeneous; The surface free energy of amorphous alloy is higher, and in metastable state, this metastable structure can become the avtive spot of reaction, improves reactive behavior; The composition of amorphous material can be adjustable continuously, thereby can Effective Regulation material surface electronic state structure, obtains a proper surface adsorption energy; Amorphous material generally also has superior corrosion resistance nature.
For amorphous Ni-B, we can, by regulating composition ratio to regulate Ni-B Electronic Structure, obtain a suitable surface adsorption energy, thereby obtain best water of decomposition catalytic hydrogen evolution performance.In addition, in amorphous Ni-B material, the electrons of B shifts to Ni, make the state of Ni surface in electron rich, and this has further activated Ni becomes the active centre of evolving hydrogen reaction, also makes the not oxidized and corrosion of Ni simultaneously, has improved its stability.Up to the present, yet there are no amorphous Ni-B for electrocatalysis hydrogen production by water decomposition and obtain the report of excellent catalytic performance.
Summary of the invention
The object of the present invention is to provide a kind of Catalysts and its preparation method for electric hydrogen production by water decomposition with good catalytic performance.
In order to address the above problem, the invention provides a kind of catalyzer for electric hydrogen production by water decomposition, described catalyzer is amorphous Ni-B, the atomic ratio of nickel and boron is 1.0-5.0.
Further, described catalyzer is outward appearance granulate material spherical in shape, and the diameter range of bead is 40-120nm, and granule interior is flower-like structure, and specific surface is very big, is conducive to water of decomposition liberation of hydrogen catalyzed reaction; The applicable pH scope of described catalyzer is 0～14.
The present invention also provides a kind of preparation method of described catalyzer, comprises the steps: to adopt chemical plating method that amorphous Ni-B is carried on to carrier surface, and in chemical plating fluid, B and the Ni atomic ratio that feeds intake is 3.0-10.0.
Further, described carrier is graphite, three-dimensional grapheme, nickel foam or glass carbon material, and charge capacity is 1mg/cm
2.
Further, described step specifically comprises:
A) by clean to described carrier successively water and ethanolic soln ultrasonic cleaning;
B) the described carrier surface cleaning up is carried out to hydroxylation hydrophilic treatment;
C) after described carrier hydroxylation is processed, be placed on oil bath heating in silver nitrate solution, make silver ions be carried on the hydrophilic surface of carrier;
D) after being dried naturally, puts in carrier the chemical plating fluid oil bath heating of nickel borides, until bubble collapse takes out the carrier of supported catalyst, and priority ammoniacal liquor, water, alcohol and acetone cleaning, until carrier surface is neutral pH=7;
E) cleaned carrier is placed at lower 80 DEG C of vacuum environment dry.
Further, the hydroxylation hydrophilic treatment of described carrier surface be that electrochemical oxidation is hydrophilic, the plasma etching of oxygen or water.
Further, the temperature of reaction of electroless plating oil bath is 45-75 DEG C, and the reaction times is 30-240 minute.
Further, the Ni-B drying temperature that electroless plating obtains is 80-180 DEG C, and dry atmosphere is vacuum or rare gas element, and be 5-10 hour time of drying.
With respect to prior art, the present invention has following technique effect:
(1) overpotential of hydrogen evolution of catalyzer is low, and the activity of water of decomposition liberation of hydrogen is high, and we have done contrast by amorphous Ni-B catalyzer and Pt simultaneously, in different pH value solution, finds that the overpotential of hydrogen evolution of amorphous Ni-B almost approaches with Pt.
(2) amorphous Ni-B catalyzer provided by the invention, its composition is adjustable, thereby obtains a best Electronic Structure, makes catalyst surface sorptive power in an optimal value.
(3) amorphous Ni-B catalyzer provided by the invention is for crystalline material, and surface free energy is high, and metastable structure provides the avtive spot of reaction, and activity is higher.
(4) catalyzer provided by the invention can either be acidproof, also can be alkaline-resisting, and applicable pH wide ranges, its scope is pH0-14.
(5) catalyzer amorphous Ni-B provided by the invention stable performance, the tendency that the oriented Ni of the electronics of B shifts, this makes Ni be difficult for oxidized and corrodes, as avtive spot stable performance, can both life-time service in acid, alkaline solution, activity does not decay.
The present invention is successfully applied to amorphous Ni-B the reaction of water of decomposition catalytic hydrogen evolution, and its reactive behavior can match in excellence or beauty with platinum (Pt).The overpotential of hydrogen evolution of amorphous Ni-B is low, and catalytic efficiency is high, and stable performance is cheap, and preparation is simple, becomes one of ideal catalyzer of current replacement precious metals pt catalyzer.
Brief description of the drawings
Fig. 1 a is scanning electron microscope microscope (SEM) figure of catalyzer provided by the invention;
Fig. 1 b is transmission electron microscope (TEM) figure of catalyzer provided by the invention, and selected area electron diffraction figure;
Fig. 1 c is that the x-ray photoelectron power spectrum of catalyzer provided by the invention is at the collection of illustrative plates in Ni2p district;
Fig. 1 d is the collection of illustrative plates in the x-ray photoelectron power spectrum B1s district of catalyzer provided by the invention;
Fig. 2 is the X-ray diffraction spectrum (XRD) of catalyzer provided by the invention;
Fig. 3 a is the glass-carbon electrode of supported catalyst provided by the invention, blank glass-carbon electrode, nickel electrode, the platinum electrode HClO at 0.1M/L
4polarization curve in solution (pH=1), scanning speed is 1mV/s;
Fig. 3 b is the glass-carbon electrode of supported catalyst provided by the invention, blank glass-carbon electrode, nickel electrode, the platinum electrode HClO at 0.2M/L
4polarization curve in solution (pH=0.7), scanning speed is 1mV/s;
Fig. 3 c is the glass-carbon electrode of supported catalyst provided by the invention, blank glass-carbon electrode, nickel electrode, the platinum electrode potassiumphosphate (K at 0.1M/L
2hPO
4/ KH
2pO
4) polarization curve in buffered soln (pH=7), scanning speed is 1mV/s;
Fig. 3 d be catalyst cupport provided by the invention in glass-carbon electrode, blank glass-carbon electrode, nickel electrode, the polarization curve of platinum electrode in the KOH of 0.1M/L solution (pH=13), scanning speed is 1mV/s;
Fig. 4 a be catalyst cupport provided by the invention in glass-carbon electrode, blank glass-carbon electrode, nickel electrode, platinum electrode is at the HClO of 1M/L
4polarization curve in solution (pH=0), scanning speed is 1mV/s;
Fig. 4 b be catalyst cupport provided by the invention in glass-carbon electrode the HClO at 1M/L
4in solution (pH=0) under overpotential of hydrogen evolution η=132mV the potentiostatic deposition i-t curve of continuous 8 hours;
Fig. 5 a be catalyst cupport provided by the invention in glass-carbon electrode, blank glass-carbon electrode, nickel electrode, the polarization curve of platinum electrode in the KOH of 1M/L solution (pH=14), scanning speed is 1mV/s;
Fig. 5 b be catalyst cupport provided by the invention in glass-carbon electrode in the KOH of 1M/L solution (pH=14) under overpotential of hydrogen evolution η=194mV the potentiostatic deposition i-t curve of continuous 8 hours.
Embodiment
Hereinafter in connection with accompanying drawing, embodiments of the invention are elaborated.It should be noted that, in the situation that not conflicting, the arbitrary combination mutually of the feature in embodiment and embodiment in the application.
Embodiment mono-:
Being used in load amorphous Ni-B on glass-carbon electrode is below example as electrocatalysis water of decomposition liberation of hydrogen catalyzer, and this patent is described in further detail.
The concrete preparation process that amorphous Ni-B is carried on glass-carbon electrode is as follows:
(1) diameter is 5mm glass-carbon electrode (glass carbon is called for short GC in accompanying drawing), uses respectively the Al of 5 and 0.25 μ m
2o
3the aqueous solution is polished to minute surface light (described in all the other except glass-carbon electrode carrier do not need polishing) on chamois leather, and successively water and ethanolic soln ultrasonic cleaning clean;
(2) glass-carbon electrode of minute surface light is put in to 0.5M/L, in the phosphate buffer solution of pH=7, relatively Ag/AgCl reference electrode applies the time of the voltage anode electrolysis 500s of 2.0V on glass-carbon electrode, makes glass carbon surface part of hydroxyl and becomes hydrophilic;
(3) after carrier hydroxylation is processed, next place it in massfraction and be in 0.05～0.2% silver nitrate solution, the oil bath that is placed in 40 DEG C is reacted 4 hours, makes silver ions be carried on the hydrophilic surface of carrier;
(4) glass-carbon electrode is taken out from silver nitrate solution, and naturally dry.Then put it into the chemical plating fluid of nickel borides, be placed in 45 DEG C of reacting by heating of oil bath, chemical plating fluid specifically consist of 0.05M/L nickelous nitrate, the NaBH of 0.15M/L
4solution, 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, until bubble collapse.Reaction finishes the glass-carbon electrode of supported catalyst to take out, and priority ammoniacal liquor, water, and alcohol and acetone clean, until electrode surface is neutral pH=7;
(5) cleaned glass-carbon electrode is placed at lower 80 DEG C of vacuum environment to dry 5 hours.Finally we obtain the glass-carbon electrode of load amorphous Ni-B, and its charge capacity is about 1mg/cm
2, next characterize for the electrochemistry experiment of electrocatalysis water of decomposition Hydrogen Evolution Performance.
As shown in Figure 1a, amorphous Ni-B be coccoid particulate load in glass-carbon electrode surface, its average diameter is about 80nm, in the TEM image from Fig. 1 b, can see, amorphous Ni-B bead inside presents petal-shaped, and this is relevant with there being a large amount of hydrogen to discharge in Ni-B electroless plating preparation process.Petal-like internal structure increases the specific surface area of Ni-B, is conducive to water of decomposition catalytic activity for hydrogen evolution.Diffraction spectra illustration from Fig. 1 b, can see that the debye (Debye) of some amorphous is encircled, and Ni-B short range order has been described, the internal structure that long-range is unordered.As shown in the x-ray photoelectron power spectrum in Fig. 1 c, the nickel that the 853eV occurring in Ni2P spectrum in Ni-B and two peaks of 870eV are all corresponding zero-valent states, but at Ni2P
3/2in spectrum but there is not obvious peak in the 856.75eV place of corresponding oxidation state Ni.In Fig. 1 d, in B1s spectrum, occur 187.8 and two peaks of 193.3eV, the respectively B of corresponding zero-valent state and the B(B of oxidation state
2o
3).This explanation, in amorphous Ni-B, B has the trend to Ni by transfer transport, makes Ni be not interposing at oxidized and corrosion in electron rich state.In addition, from XPS spectrum, quantitative analysis obtains atomic ratio Ni/B=2.7:1.
XRD diffraction spectra in Fig. 2 is presented at θ=45 ° and has located a broad peak, does not in addition occur the crystal peak that other are sharp-pointed, and this also further illustrates the amorphous structure of Ni-B.
Fig. 3 is that the glass-carbon electrode of load amorphous Ni-B, blank glass-carbon electrode (GC), nickel electrode and platinum electrode are respectively at 0.1M HClO
4(pH=1), 0.2M HClO
4(pH=0.7), 0.1M KPi(pH=7), 0.1M KOH(pH=13) cathodic polarization curve in solution, from figure, we see in the solution of these four kinds of different pH values, the catalytic activity of nickel is almost similar with platinum, at 20mA/cm
2overpotential of hydrogen evolution also almost approach, the water of decomposition Hydrogen Evolution Performance that amorphous Ni-B is superior is described thus.In addition the activity that also can see blank glass-carbon electrode and nickel electrode is relatively low, illustrates that the catalytic activity of Ni-B is mainly derived from himself.
Fig. 4 a is that the glass-carbon electrode of load amorphous Ni-B, blank glass-carbon electrode (GC), nickel electrode and platinum electrode are respectively at 1M HClO
4(pH=0) cathodic polarization curve in solution, can see that platinum electrode is at 20mA/cm
2overpotential of hydrogen evolution be 76mV, and the overpotential of hydrogen evolution of amorphous Ni-B is 132mV, one of result that this is best at present all base metal liberation of hydrogen catalyzer.Be potentiostatic deposition curve under η=132mV at Fig. 4 b, we see the almost not decay in time of liberation of hydrogen electric current.This explanation amorphous Ni-B can be in strongly acidic solution steady operation.
Fig. 5 a is that the glass-carbon electrode of load amorphous Ni-B, blank glass-carbon electrode (GC), nickel electrode and platinum electrode are respectively at 1M KOH(pH=14) cathodic polarization curve in solution, amorphous Ni-B is at 20mA/cm as seen from the figure
2overpotential of hydrogen evolution be 194mV, its overpotential of hydrogen evolution and platinum (Pt) approach.Fig. 5 b has also shown the constant potential electrolysis curve of amorphous Ni-B under overpotential 194mV, can see that cathodic polarization electric current increases along with time lengthening, and this is likely in electrode working process, some B that its surface exists
2o
3in brine electrolysis process, progressively dissolve, thereby allow more Ni-B avtive spot come out, thereby current density is increasing, this phenomenon is the equal of the reactivation process of a catalyzer.Amorphous Ni-B is under concentrated base environment, and in long-time electrolytic process, catalytic performance is not decayed.
By above object lesson, we see the excellent properties that amorphous Ni-B shows on electrocatalysis hydrogen production by water decomposition, and this also allows it become one of best base metal liberation of hydrogen catalyzer of replacement Pt.Amorphous Ni-B can acid-fast alkali-proof, and overpotential is low, stable performance, and making processes is simple, and cost is lower, has embodied the advantage of non-crystalline material as catalyzer.But concrete liberation of hydrogen mechanism need further theoretical modeling and systematic study.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. for a catalyzer for electric hydrogen production by water decomposition, it is characterized in that: described catalyzer is amorphous Ni-B, the atomic ratio of nickel and boron is 1.0-5.0.
2. catalyzer as claimed in claim 1, is characterized in that: described catalyzer is outward appearance granulate material spherical in shape, and the diameter range of bead is 40-120nm, and granule interior is flower-like structure, and specific surface is very big, is conducive to water of decomposition liberation of hydrogen catalyzed reaction; The applicable pH scope of described catalyzer is 0～14.
3. a preparation method for catalyzer as claimed in claim 1, is characterized in that, comprises the steps: to adopt chemical plating method that amorphous Ni-B is carried on to carrier surface, and in chemical plating fluid, B and the Ni atomic ratio that feeds intake is 3.0-10.0.
4. method as claimed in claim 3, is characterized in that: described carrier is graphite, three-dimensional grapheme, nickel foam or glass carbon material, and charge capacity is 1mg/cm
2.
5. method as claimed in claim 4, is characterized in that, described step specifically comprises:
A) by clean to described carrier successively water and ethanolic soln ultrasonic cleaning;
B) the described carrier surface cleaning up is carried out to hydroxylation hydrophilic treatment;
C) after described carrier hydroxylation is processed, be placed on oil bath heating in silver nitrate solution, make silver ions be carried on the hydrophilic surface of carrier;
D) after being dried naturally, puts in carrier the chemical plating fluid oil bath heating of nickel borides, until bubble collapse takes out the carrier of supported catalyst, and priority ammoniacal liquor, water, alcohol and acetone cleaning, until carrier surface is neutral pH=7;
E) cleaned carrier is placed at lower 80 DEG C of vacuum environment dry.
6. method as claimed in claim 5, is characterized in that: the hydroxylation hydrophilic treatment of described carrier surface is that electrochemical oxidation is hydrophilic, the plasma etching of oxygen or water.
7. method as claimed in claim 6, is characterized in that: the temperature of reaction of electroless plating oil bath is 45-75 DEG C, and the reaction times is 30-240 minute.
8. method as claimed in claim 7, is characterized in that: the Ni-B drying temperature that electroless plating obtains is 80-180 DEG C, and dry atmosphere is vacuum or rare gas element, and be 5-10 hour time of drying.
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