CN101347736A - Catalyst for hydrogen production by catalyzing and hydrolyzing borohydride and preparation method thereof - Google Patents
Catalyst for hydrogen production by catalyzing and hydrolyzing borohydride and preparation method thereof Download PDFInfo
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- CN101347736A CN101347736A CNA2007100122032A CN200710012203A CN101347736A CN 101347736 A CN101347736 A CN 101347736A CN A2007100122032 A CNA2007100122032 A CN A2007100122032A CN 200710012203 A CN200710012203 A CN 200710012203A CN 101347736 A CN101347736 A CN 101347736A
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Abstract
The invention relates to hydrogen production and hydrogen storage technologies and materials, in particular to a catalyst for catalytic hydrolysis of borane for the hydrogen production and a preparation method thereof, thereby solving the problems that the direct application of powder catalyst in a catalytic hydrolysis solid-liquid reaction system can cause the loss of the catalyst, the catalytic hydrolysis reaction is difficult to control and the hydrolysis by-products are difficult to be recovered, etc. The catalyst is composed of an active component and a carrier; the active component is a binary, ternary or multinary alloy or a single precious metal or the combination thereof which is composed of one or more transition metals, rare earth metals or precious metals and metalloids; the active component is deposited on the carrier through the improved chemical plating technology, the surface thereof is rough and porous, and the structure of the prepared catalyst is the amorphous or the nanocrystalline structure. The preparation method has simple preparation process, high preparation efficiency and convenient large-scale preparation; the sources of the used raw materials are rich; the catalytic activity of the prepared supported catalyst is high, the real-time control of the catalytic hydrolysis reaction of the borane can be realized, the catalytic performance is stable, and the catalyst can be repeatedly used for a plurality of times.
Description
Technical field
The present invention relates to hydrogen manufacturing, hydrogen storage technology and material, be specially a kind of supported catalyst that is used for hydrogen production by catalyzing and hydrolyzing borohydride and preparation method thereof.
Background technology
Hydrogen is acknowledged as optimal clean energy resource carrier, has weight energy storage density height, wide material sources, reusable edible and energy and utilizes remarkable advantage such as no environment negative effect in the process.Adopt hydrogen fuel driving traffic to transport instrument and can realize " zero-emission ", be regarded as advancing the significant progress in the Hydrogen Energy application process.But owing to lack efficient, safe vehicle-mounted hydrogen storage technology at present, the commercialization process of hydrogen-burning automobile is subjected to serious restriction.
Hydrogen storage method can be divided into physics and chemical method two big classes.The former comprises: liquid hydrogen, compressed hydrogen tank, absorption storage, glass microsphere storage etc.; The latter comprises: metal hydride, coordination metal hydride, chemical hydride etc.Wherein, chemical hydride (example: alkali metal or alkaline-earth metal boron hydride etc.) is acknowledged as the hydrogen manufacturing/hydrogen-storing integrated technology of current tool application prospect.Be different from reversible hydrogen storage material such as metal hydride, chemical hydride will be put hydrogen and fill two sport technique segments of hydrogen and separate, and greatly reduce the technical difficulty of exploitation practicability hydrogen storage system.
Sodium borohydride (NaBH
4) be the most representative chemical hydride.Introducing under the catalyst situation, sodium borohydride can make hydrogen in the quick hydrolysis of room temperature, and it reacts as the formula (1):
NaBH
4+4H
2O→NaBO
2+4H
2↑+300kJ (1)
And NaBH
4Safe storage can add a small amount of alkali lye stabilizing agent and realize by simple.NaBH
4The advantage of hydrolytic hydrogen production is: (1) high storage hydrogen efficiency, and its theoretical weight hydrogen-storage density reaches 10.8wt.%; (2) can introduce realization by the control catalyst and produce hydrogen as required, reaction rate is controlled; (3) can be in room temperature even more hydrogen manufacturing under the low temperature; (4) make hydrogen and only contain steam, can directly use for Proton Exchange Membrane Fuel Cells; (5) safety non-pollution, NaBH
4Basic materials liquid is stable under air, can adopt conventional plastic containers accumulating.Its hydrolytic hydrogen production accessory substance kodalk (NaBO
2) nontoxic, environmental sound.
NaBH
4The hydrogen manufacturing performance of hydrolysis system depends on the catalysis efficiency of catalyst to a great extent.At present, be used for NaBH
4The catalyst of catalyzing hydrolysis hydrogen manufacturing mostly is the powder form, as transition metal or noble metal and salt (Ni, Co, Ru, Rh, Pt etc.), transition metal boride (Ni-B and Co-B etc.) etc.The powder catalyst has characteristics such as the little and specific area of particle diameter is big, but if directly application can cause catalyst loss in catalyzing hydrolysis solid-liquid reaction system, catalytic hydrolysis reaction is restive and hydrolysising by-product is difficult to problems such as recovery.Develop supported catalyst efficiently thereby constitute key problem in technology in the hydrolytic hydrogen production system practicalization.
Summary of the invention
The object of the present invention is to provide a kind of borohydride hydrolytic hydrogen production Catalysts and its preparation method of practicality, directly application can cause catalyst loss in catalyzing hydrolysis solid-liquid reaction system, catalytic hydrolysis reaction is restive and hydrolysising by-product is difficult to problems such as recovery to solve the powder catalyst.
Technical scheme of the present invention is:
The invention provides the effective catalyst that is applicable to hydrogen production by catalyzing and hydrolyzing borohydride, catalyst is made up of active component and carrier, and the weight loading of active component is 1～100%, and preferable range is 5～80%.The activity of such catalysts component is a kind of or binary, ternary or the multicomponent alloy of several transition metal, noble metal or rare earth metal and metalloid composition, or precious metal simple substance or its combination, for example, bianry alloys such as Fe-P, Fe-B, Co-B, Co-P, Ni-B, Ni-P, Ru-B, Ru-P, ternary alloy three-partalloys such as Ni-Co-B, Ni-Co-P, Fe-Co-B, Fe-Co-P, Ni-W-B, Ni-W-P, Co-W-B, Co-W-P, Co-Mo-B, Co-Mo-P, Co-La-B, Co-La-P, Ni-B-P, Co-B-P, multicomponent alloys such as Ni-Co-B-P, Ni-Co-La-B-P; Perhaps, precious metal simple substance or its combinations such as Ru, Pt, Rh.Active component is to be deposited on the carrier by a kind of improved electroless plating technology, and its outward appearance is black, rough surface, porous, and pore size is in 1～10 mu m range.Carrier is a metal or nonmetal, comprising: metal oxide, nonmetal oxide, foam metal, wire netting, sheet metal, ion exchange resin, molecular sieve or various material with carbon element, carrier preferred foams metal, wire netting, sheet metal or material with carbon element.
Design Mechanism of the present invention is as follows:
With the nickel foam is carrier, and preparing the agent of Co-B/ foamed nickel catalyst by the improvement electroless plating technology is example, and operation principle of the present invention is described.Chemical plating is under the reducing agent effect, the solution metal ion, has the process that is reduced into metal or alloy on the matrix of catalytic action.Electroless plating technology since the nineteen forty-six invention, just has been widely used in various matrixes and has prepared multiple functional coating.But the catalyst that the traditional chemical coating technology is used to prepare hydrogen production by catalyzing and hydrolyzing borohydride meets with some difficulties, and this mainly is because characteristics such as traditional chemical plating gained coating has continuously, homogeneous and densifications.The coating densification causes the surface area of catalyst to reduce, and this has just reduced contacting of reactant liquor and catalyst; Therefore, relatively low with traditional chemical coating technology gained coating catalytic activity.The feature of the used chemical plating process of the present invention is: plating bath is made up of the main salt and the reducing agent of high concentration, and does not use stabilizing agent; During chemical plating Co-B, the forming core speed and the sedimentation rate of metal Co are very fast, and produce a large amount of H
2, cause coarse, the porous of gained coating.This is the high main cause of catalyst activity of the used modified chemical coating technology preparation of the present invention just.
Following three reactions [(2), (3) and (4)] mainly take place in chemical plating Co-B:
BH
4 -+4Co
2++8OH
-→4Co↓+BO
2 -+6H
2O (2)
2BH
4 -+2H
2O→2B+2OH
-+5H
2↑ (3)
BH
4 -+2H
2O→BO
2 -+4H
2↑ (4)
Among the present invention, boron hydride is alkali metal or alkaline-earth metal boron hydride.
Among the present invention, by weight percentage, metallic element is preferably 70～95% in binary, ternary or the multicomponent alloy; Metalloid element is preferably 5～30%;
The invention provides a kind of improvement electroless plating technology that is applicable to preparation borohydride hydrolytic hydrogen production effective catalyst.Active component is deposited on the carrier by improved electroless plating technology, and the structure that makes catalyst is amorphous or nanocrystalline structure.Chemical plating bath is made up of main salt, compounding ingredient and reducing agent.Main salt be halide, nitrate, sulfate, sulfamate, the acetate of transition metal, rare earth metal or noble metal and contain oxygen or the oxygen-free hydrochlorate in a kind of or several combination, transition metal and rare earth metal comprise: Fe, Co, Ni, Cu, Mn, La, Ce; Noble metal comprises: Ag, Au, Ru, Rh, Pd, Pt, Ir.Main salt concentration is 0.01～5M; Compounding ingredient is by a kind of in ammoniacal liquor, sodium potassium tartrate tetrahydrate, ethylenediamine or the natrium citricum or several combination, and compounding ingredient concentration is 0.01～10M; Reducing agent is sodium borohydride (NaBH
4), potassium borohydride (KBH
4) or inferior sodium phosphate (NaH
2PO
2) in a kind of or two kinds combination, reductant concentration is 0.02～8M.At first, carrier material is carried out oil removing and acid activation pre-treatment; Then, it is immersed in the mixed solution of being made up of main salt and compounding ingredient dip time 5 seconds～10 minutes; Add reducing agent again, react, till plating bath does not produce bubble, finish chemical plating one time.According to the catalytic activity requirement, plating 1～20 time.Prepared catalyst can use after dry 2～10 hours under 30～80 ℃ of conditions, also can carry out subsequent heat treatment.By to catalyst heat treatment, the adhesion of activity of such catalysts and active component and carrier can further improve heat treatment temperature: 200～600 ℃, and heat treatment time: 1～4 hour; Heat treatment can be carried out under argon gas, nitrogen, hydrogen atmosphere or vacuum condition.
Among the present invention, main salt concentration is preferably 0.1～2M.
Among the present invention, compounding ingredient concentration is preferably 0.2～8M.
Among the present invention, reductant concentration is preferably 0.5～3.0M.
Among the present invention, carrier material immerses that dip time is preferably 30 seconds in main salt and the compounding ingredient mixed solution～and 1 minute.
Among the present invention, the catalyst heat treatment temperature is preferably 300～400 ℃.
Among the present invention, the acid activation pre-treatment specifically refers to 0.5～15wt.% hydrochloric acid or sulfuric acid treatment.
The effective catalyst of hydrogen production by catalyzing and hydrolyzing borohydride that is applicable to provided by the invention has adopted following advanced method and technology in catalyst formation and preparation process:
1. be different from the powder catalyst of current common employing, the invention provides efficient supported catalyst;
2. be different from the traditional chemical electroplating method, the invention provides a kind of improved electroless plating technology, active component is deposited on the carrier, by improving main salt and reductant concentration and removing stabilizing agent, improve the forming core and the sedimentation rate of catalyst, made catalyst coat coarse, porous.This electroless plating technology sedimentation rate is fast, and the structure that makes catalyst is amorphous or nanocrystalline structure.
Improvement electroless plating technology provided by the invention has overcome continuous, the fine and close shortcoming of traditional chemical electroplating method prepared catalyst coating by adjusting bath composition and concentration thereof, has increased substantially the specific area of catalyst coating, thereby the catalysis efficiency excellence.Adopt the supported catalyst of this technology preparation to efficiently solve the restive and hydrolysising by-product of catalyst loss, catalytic hydrolysis reaction that the powder catalyst exists and be difficult to problems such as recovery, the chemical hydride hydrolytic hydrogen production system that possesses application prospect for development provides the catalyst of highly effective.
The advantage that is used for the hydrogen production by catalyzing and hydrolyzing borohydride Catalysts and its preparation method provided by the invention is: this preparation technology is simple, and the preparation efficiency height is convenient to scale preparation; Raw materials used source is abundant; Prepared supported catalyst catalytic activity height can be realized the instant control to the boron hydride catalytic hydrolysis reaction, and catalysis efficiency is stable, can be repeatedly used.
Description of drawings
Fig. 1 is the outward appearance with the agent of improvement chemical plating Co-B/ foamed nickel catalyst;
Fig. 2 for the conventional chemical depositing process (a, c) and improve chemical plating process (b is d) at the microstructure of the Co-B/ foamed nickel catalyst agent of nickel foam substrate preparation;
Fig. 3 is for conventional chemical depositing process (a) with improve specific activity that chemical plating process (b) prepares the agent of Co-B/ foamed nickel catalyst, and used reaction solution is 20wt.%NaBH
4+ 10wt.%NaOH, temperature is 30 ℃;
Fig. 4 is the influence of plating number of times to Co-B alloy load capacity and hydrogen-producing speed, and used reaction solution is 20wt.%NaBH
4+ 10wt.%NaOH, temperature is 30 ℃;
Fig. 5 is the influence of sintering temperature to Co-B/ foamed nickel catalyst agent hydrogen-producing speed;
Fig. 6 is the X ray diffracting spectrum (XRD) of freshly prepd Co-B/ foamed nickel catalyst agent;
Fig. 7 is the product hydrogen kinetic curve of Co-B/ foamed nickel catalyst agent in different temperatures (25～45 ℃), and used reaction solution is 20wt.%NaBH
4+ 10wt.%NaOH;
Fig. 8 is the influence of plating number of times to Co-Mn-B alloy load capacity and hydrogen-producing speed, and used reaction solution is 20wt.%NaBH
4+ 10wt.%NaOH, temperature is 30 ℃;
Fig. 9 is the influence of sintering temperature to Co-Mn-B/ foamed nickel catalyst agent hydrogen-producing speed.
The specific embodiment
Need according to hydrolysis raw material and hydrogen production efficiency, choose main salt, compounding ingredient, reducing agent and carrier material.Carrier material is carried out oil removing and acid activation pre-treatment, then it is immersed in the mixed solution of being made up of main salt and compounding ingredient dip time 5 seconds～10 minutes, add an amount of reducing agent again, react, till plating bath does not produce bubble, finish chemical plating one time.According to the catalytic activity requirement, plating 1～20 time.Prepared catalyst can use after under 30～80 ℃ of conditions dry 2～10 hours, also can carry out the adhesion of subsequent heat treatment with further raising activity of such catalysts and active component and carrier.
With the nickel foam is carrier, its Main physical performance: thickness is 1.80mm, and surface density is 575g/m
2, having the pore structure that runs through continuously, the aperture is 0.20～0.50mm.Before chemical plating, nickel foam is cleaned oil removing 10 minutes through ultrasonic oscillation in ethanol, immerses then in the 10wt.% hydrochloric acid solution to activate 1 minute.It is pure that used chemical reagent is analysis, without any processing.
Improve chemical plating and prepare amorphous Co-B alloy as catalyst agent prescription:
Solution A: cobalt chloride (CoCl
26H
2O) 50g/l, ammonium chloride (NH
4Cl) 80g/l, ammoniacal liquor [NH
3H
2O (25wt.%)] 45ml/l.
Solution B: sodium borohydride (NaBH
4) 40g/l, NaOH (NaOH) 10g/l.
Operating condition: pH value 14,25 ℃ of reacting initial temperatures.
The preparation of Co-B/ foamed nickel catalyst agent:
To place solution A 20 seconds through the nickel foam carrier of pre-treatment, more isopyknic solution B be poured into, react, till solution does not produce bubble, finish chemical plating one time, repeat this operation 4 times.Prepared catalyst was heated to 300 ℃ of constant temperature heat treatments 2 hours under argon shield after under 60 ℃ dry 8 hours.Prepared Co-B base binary alloy plating, through ICP (inductive coupling plasma emission spectrograph) chemical analysis, the content of B is 8wt.% in the coating, and the coating outward appearance is the black (see figure 1), and rough surface, porous, and mean pore size is 5 μ m.In the present embodiment, the weight loading of active component is 80%.
For comparing purpose, will be through the nickel foam carrier of pre-treatment, chemical plating prescription and operating condition are carried out chemical plating routinely.
Fig. 2 provided adopt respectively traditional chemical plating (a, c) and improve chemical plating process (b, d) microstructure of Zhi Bei Co-B/ foamed nickel catalyst agent contrasts.The coating that adopts the preparation of conventional chemical depositing process continuously, homogeneous, densification; Improve coarse, the porous of catalyst coating that chemical plating process prepares and adopt.
Fig. 3 has provided the catalytic activity contrast and experiment of the Co-B/ foamed nickel catalyst agent of adopting two kinds of chemical plating process preparations.Obviously, improvement electroless plating technology provided by the invention significantly is better than the traditional chemical plating.
Fig. 4 has provided the influence of plating number of times to Co-B catalyst loadings and hydrogen-producing speed.
Fig. 5 has provided the catalytic performance test result of Co-B/ foamed nickel catalyst agent after different temperatures (100～500 ℃) heat treatment.Test reaction solution is 20wt.%NaBH
4+ 10wt.%NaOH, the solution initial temperature is 30 ℃.
Fig. 6 has provided X-ray diffraction (XRD) collection of illustrative plates of the Co-B/ foamed nickel catalyst agent that makes.Test result shows: adopting the catalyst coating that improves the chemical plating process preparation is non crystalline structure.
Fig. 7 has provided and has adopted the product hydrogen kinetic curve of Co-B/ foamed nickel catalyst agent when different temperatures (25～45 ℃) that improves the chemical plating process preparation.Test reaction solution is 20wt.%NaBH
4+ 10wt.%NaOH.
Used nickel foam carrier and pre-treating technology are identical with embodiment 1.
Improve the prescription of chemical plating Co-Mn-B:
Solution A: cobalt chloride (CoCl
26H
2O) 60g/l, manganese chloride (MnCl
24H
2O) 60g/l, ammonium chloride (NH
4Cl) 80g/l, ethylenediamine (H
2NCH
2CH
2NH
2) 15ml/l.
Solution B: sodium borohydride (NaBH
4) 40g/l, NaOH (NaOH) 10g/l.
The preparation of Co-Mn-B/ foamed nickel catalyst agent:
The preparation process of Co-Mn-B/ foamed nickel catalyst agent is identical with embodiment 1, and prepared Co-Mn-B ternary alloy coating is through the ICP chemical analysis, the content of Mn is 25wt.% in the coating, and the content of B is 9wt.%, and the coating outward appearance is a black, and rough surface, porous, mean pore size are 2 μ m.In the present embodiment, the weight loading of active component is 40%; Adopt XRD to characterize freshly prepd Co-Mn-B catalyst, coating is non crystalline structure.Under 30 ℃ in 20wt.%NaBH
4Test Co-Mn-B/ foamed nickel catalyst agent among the+10wt.%NaOH, hydrogen-producing speed is 670ml/mincm
2(nickel foam) is equivalent to 22L/ming (Co-Mn-B).
Fig. 8 has provided the influence of plating number of times to Co-Mn-B load capacity and hydrogen-producing speed.
Fig. 9 has provided the influence of sintering temperature to Co-Mn-B/ foamed nickel catalyst agent hydrogen-producing speed.
Used nickel foam carrier and pre-treating technology are identical with embodiment 1.
Improve the prescription of chemical plating Co-P:
Solution A: cobalt acetate (Co (AC)
24H
2O) 70g/l, natrium citricum (Na
3C
6H
5O
72H
2O) 60g/l, ammonium chloride (NH
4Cl) 80g/l, ammoniacal liquor [NH
3H
2O (25wt.%)] 45ml/l.
Solution B: inferior sodium phosphate (NaH
2PO
2H
2O) 70g/l, NaOH (NaOH) 10g/l.
The preparation of Co-P/ foamed nickel catalyst agent:
Nickel foam carrier through pre-treatment under 85 ℃ of temperature, places the solution A of isopyknic improvement chemical plating Co-P and the mixed liquor of solution B, after 1 minute, drips 1ml 1M NaBH again
4Or 1ml 0.02M PdCl
2Solution is induced, carry out chemical plating Co-P, till not producing bubble, finish chemical plating one time, requirement according to catalytic activity, plating 6 times, prepared Co-P base binary alloy plating is through the ICP chemical analysis, the content of P is 12wt.% in the coating, the coating outward appearance is a black, and rough surface, porous, and mean pore size is 4 μ m.In the present embodiment, the weight loading of active component is 45%; Characterize freshly prepd Co-P catalyst with XRD, the structure of coating is an amorphous.After 4 hours, heat treatment is 2 hours under 250 ℃ of argon atmosphers through 80 ℃ of dryings for prepared catalyst.Under 30 ℃ in 20wt.%NaBH
4Test Co-P/ foamed nickel catalyst agent among the+10wt.%NaOH, hydrogen-producing speed is 350ml/mincm
2(nickel foam) is equivalent to 4L/ming (Co-P).
Embodiment 4Co-B-P alloy/stainless (steel) wire catalyst is used for Mg (BH
4)
2Catalyzing hydrolysis hydrogen manufacturing
With the stainless (steel) wire is carrier, average pore size 150 μ m, and before chemical plating Co-B-P alloy, stainless (steel) wire need carry out pre-treatment, and pre-treating technology is same as embodiment 1.
Improve the prescription of chemical plating Co-B-P:
Solution A: cobalt chloride (CoCl
26H
2O) 50g/l, ammonium chloride (NH
4Cl) 80g/l, ammoniacal liquor [NH
3H
2O (25wt.%)] 45ml/l.
Solution B: sodium borohydride (NaBH
4) 20g/l, inferior sodium phosphate (NaH
2PO
2H
2O) 40g/l, NaOH (NaOH) 10g/l.
Co-B-P/ stainless (steel) wire Preparation of catalysts:
Co-B-P/ stainless (steel) wire Preparation of catalysts process is identical with embodiment 1, and prepared Co-B-P ternary alloy coating is through the ICP chemical analysis, the content of B is 5wt.% in the coating, and the content of P is 8wt.%, and the coating outward appearance is a black, and rough surface, porous, mean pore size are 8 μ m; In the present embodiment, the weight loading of active component is 60%.XRD analysis shows: prepared Co-B-P catalyst is a non crystalline structure.Co-B-P/ stainless (steel) wire catalyst is in heat treatment under 350 ℃ of argon atmosphers after 2 hours, through 15wt.%Mg (BH
4)
2+ 10wt.%NaOH solution testing, 30 ℃ of following hydrogen-producing speeds are 630ml/mincm
2(stainless (steel) wire) is equivalent to 15L/ming (Co-B-P).
The graphite that with thickness is 1mm is carrier, and its density is 2.23g/cm
3Before chemical plating noble metal Ru, graphite need carry out pre-treatment, and pre-treating technology is same as embodiment 1.
Improve the prescription of chemical plating Ru:
Solution A: ruthenic chloride (RuCl
33H
2O) 2g/l, ammonium chloride (NH
4Cl) 30g/l, ammoniacal liquor [NH
3H
2O (25wt.%)] 20ml/l.
Solution B: sodium borohydride (NaBH
4) 1.5g/l, NaOH (NaOH) 5g/l.
The preparation of Ru/ graphite catalyst:
In immersing by the solution A of improving chemical plating Ru through the graphite of pre-treatment 20 seconds, again the equal-volume solution B is poured into, carry out chemical plating Ru, till not producing bubble, finish chemical plating one time, according to the requirement of catalytic activity, plating 2 times, prepared catalyst, at 30 ℃, dry 10 hours.Prepared coating outward appearance is a black, and rough surface, porous, and mean pore size is 2 μ m.In the present embodiment, the weight loading of active component is 15%; XRD analysis shows: the Ru/ graphite catalyst of preparation, coating Ru are structure of hexagonal crystal, are calculated by Scherrer (Scherrer) equation, and the Ru average grain size is about 35nm.Under 30 ℃ in 10wt.%LiBH
4+ 2wt.%NaOH solution testing Ru/ graphite catalyst, hydrogen-producing speed is 254ml/mincm
2(graphite) is equivalent to 23L/ming (Ru).
The model of used molecular sieve is 3A, and molecular formula is 0.4K
2O 0.6Na
2O Al
2O
32.0SiO
24.5H
2O, its aperture is 3A, and particle diameter is 3.0～5.0mm, and before chemical plating noble metal Ru-Pt, pre-treating technology is identical with embodiment 1.
Improve the prescription of chemical plating Ru-Pt:
Solution A: ruthenic chloride (RuCl
33H
2O) 2g/l, chloroplatinic acid (H
2PtCl
66H
2O) 1.5g/l, ammonium chloride (NH
4Cl) 30g/l, ammoniacal liquor [NH
3H
2O (25wt.%)] 20ml/l.
Solution B: sodium borohydride (NaBH
4) 2.5g/l, NaOH (NaOH) 8g/l.
The preparation of Ru-Pt/ molecular sieve catalyst:
In immersing by the solution A of improving chemical plating Ru-Pt through the molecular sieve of pre-treatment 20 seconds, again the equal-volume solution B is poured into, carry out chemical plating Ru-Pt, till not producing bubble, finish chemical plating one time, according to the requirement of catalytic activity, plating 2 times, prepared catalyst, at 30 ℃, dry 10 hours.Prepared Ru-Pt base binary alloy plating, through the ICP chemical analysis, the content of Pt is 35wt.% in the coating, and the coating outward appearance is a black, and rough surface, porous, and mean pore size is 1 μ m.In the present embodiment, the weight loading of active component is 12%; XRD analysis shows: coating is to be the alloy layer of matrix with Ru, and wherein Pt is calculated by Scherrer (Scherrer) equation for the displacement solid solution, and the average grain size of Ru-Pt is about 20nm.Under 30 ℃ in 10wt.%NaBH
4+ 5wt.%NaOH solution testing Ru-Pt/ molecular sieve catalyst, hydrogen-producing speed are 35L/ming (Ru-Pt).
With the Copper Foil is carrier, and thickness is 0.2mm, and before chemical plating Co-La-B alloy, Copper Foil need carry out pre-treatment, and pre-treating technology is same as embodiment 1.
Improve the prescription of chemical plating Co-La-B:
Solution A: cobalt nitrate (Co (NO
3)
26H
2O) 50g/l, lanthanum chloride (LaCl
33H
2O) 10g/l, ammonium sulfate ((NH
4)
2SO
4) 80g/l, sodium potassium tartrate tetrahydrate (KNaC
4H
4O
44H
2O) 60g/l.
Solution B: potassium borohydride (KBH
4) 35g/l, NaOH (NaOH) 10g/l.
Co-La-B/ Copper Foil Preparation of catalysts:
Co-La-B/ Copper Foil Preparation of catalysts process is identical with embodiment 1, and prepared Co-La-B ternary alloy coating is through the ICP chemical analysis, the content of La is 4wt.% in the coating, and the content of B is 8wt.%, and the coating outward appearance is a black, and rough surface, porous, mean pore size are 6 μ m.In the present embodiment, the weight loading of active component is 35%.XRD analysis shows: prepared coating is non crystalline structure.Co-La-B/ Copper Foil catalyst is in heat treatment under 350 ℃ of argon atmosphers after 2 hours, through 20wt.%NaBH
4+ 10wt.%NaOH solution testing, 30 ℃ of following hydrogen-producing speeds are 690ml/mincm
2(Copper Foil) is equivalent to 25L/ming (Co-La-B).
With the aluminium foil is carrier, and thickness is 0.1mm, and before Electroless Plating Ni-W-B alloy, aluminium foil need carry out pre-treatment, and pre-treating technology is same as embodiment 1.
Improve the prescription of Electroless Plating Ni-W-B:
Solution A: nickelous sulfate (NiSO
46H
2O) 80g/l, sodium tungstate (NaWO
42H
2O) 20g/l, ammonium sulfate ((NH
4)
2SO
4) 95g/l, ethylenediamine (H
2NCH
2CH
2NH
2) 45ml/l.
Solution B: potassium borohydride (KBH
4) 50g/l, NaOH (KOH) 15g/l.
Ni-W-B/ aluminium foil Preparation of catalysts:
Ni-W-B/ aluminium foil Preparation of catalysts process is identical with embodiment 1, and prepared Ni-W-B ternary alloy coating is through the ICP chemical analysis, the content of W is 3wt.% in the coating, and the content of B is 7wt.%, and the coating outward appearance is a black, and rough surface, porous, mean pore size are 5 μ m.In the present embodiment, the weight loading of active component is 30%; Adopt XRD to characterize freshly prepd Ni-W-B catalyst, coating is non crystalline structure.Ni-W-B/ aluminium foil catalyst is in heat treatment under 400 ℃ of argon atmosphers after 2 hours, through 20wt.%NaBH
4+ 10wt.%NaOH solution testing, 30 ℃ of following hydrogen-producing speeds are 430ml/mincm
2(aluminium foil) is equivalent to 6L/ming (Ni-W-B).
Embodiment 9Ni-Co-B-P alloy/foamed nickel catalyst agent is used for NaBH
4Catalyzing hydrolysis hydrogen manufacturing
Used nickel foam carrier and pre-treating technology are identical with embodiment 1.
Improve the prescription of Electroless Plating Ni-Co-B-P:
Solution A: nickel chloride (CoCl
26H
2O) 40g/l, cobalt chloride (CoCl
26H
2O) 30g/l, ammonium chloride (NH
4Cl) 80g/l, ammoniacal liquor [NH
3H
2O (25wt.%)] 45ml/l.
Solution B: sodium borohydride (NaBH
4) 20g/l, inferior sodium phosphate (NaH
2PO
2H
2O) 40g/l, NaOH (NaOH) 10g/l.
The preparation of Ni-Co-B-P/ foamed nickel catalyst agent:
The preparation process of Ni-Co-B-P/ foamed nickel catalyst agent is identical with embodiment 1, prepared Ni-Co-B-P quaternary alloy coating, through the ICP chemical analysis, the content of Co is 25wt.% in the coating, the content of B is 5wt.% in the coating, and the content of P is 10wt.% in the coating, and the coating outward appearance is a black, and rough surface, porous, mean pore size are 8 μ m.In the present embodiment, the weight loading of active component is 60%.XRD analysis shows: prepared coating is non crystalline structure.The agent of Ni-Co-B-P/ foamed nickel catalyst is in heat treatment under 350 ℃ of argon atmosphers after 2 hours, through 20wt.%NaBH
4+ 10wt.%NaOH solution testing, 30 ℃ of following hydrogen-producing speeds are 640ml/mincm
2(nickel foam) is equivalent to 18L/ming (Ni-Co-B-P).
Claims (10)
1, a kind of hydrogen production by catalyzing and hydrolyzing borohydride catalyst that is used for, it is characterized in that: catalyst is made up of active component and carrier, the activity of such catalysts component is a kind of or binary, ternary or the multicomponent alloy of several transition metal, rare earth metal or noble metal and metalloid composition, or precious metal simple substance and combination thereof; The weight loading of active component is 1～100%.
2, according to the described hydrogen production by catalyzing and hydrolyzing borohydride catalyst that is used for of claim 1, it is characterized in that: described boron hydride is alkali metal or alkaline-earth metal boron hydride.
3, according to the described hydrogen production by catalyzing and hydrolyzing borohydride catalyst that is used for of claim 1, it is characterized in that: described activity of such catalysts component is preferably: Fe-P, Fe-B, Co-B, Co-P, Ni-B, Ni-P, Ru-B or Ru-P bianry alloy; Perhaps, Ni-Co-B, Ni-Co-P, Fe-Co-B, Fe-Co-P, Ni-W-B, Ni-W-P, Co-W-B, Co-W-P, Co-Mo-B, Co-Mo-P, Co-La-B, Co-La-P, Ni-B-P or Co-B-P ternary alloy three-partalloy; Perhaps, Ni-Co-B-P or Ni-Co-La-B-P multicomponent alloy; Perhaps, Ru, Pt or Rh precious metal simple substance or its combination.
4, according to the described hydrogen production by catalyzing and hydrolyzing borohydride catalyst that is used for of claim 1, it is characterized in that: by weight percentage, the metallic element preferred content is 70～95% in binary, ternary or the multicomponent alloy; The metalloid element preferred content is 5～30%.
5, according to the described hydrogen production by catalyzing and hydrolyzing borohydride catalyst that is used for of claim 1, it is characterized in that: carrier is a metal or nonmetal, comprising: metal oxide, nonmetal oxide, foam metal, wire netting, sheet metal, ion exchange resin, molecular sieve or various material with carbon element.
6, according to the described hydrogen production by catalyzing and hydrolyzing borohydride Preparation of catalysts method that is used for of claim 1, it is characterized in that: active component is deposited on the carrier by electroless plating technology, and the structure that makes catalyst is amorphous or nanocrystalline structure.
7, according to the described hydrogen production by catalyzing and hydrolyzing borohydride Preparation of catalysts method that is used for of claim 6, it is characterized in that: the plating bath of described electroless plating technology is made up of main salt, compounding ingredient and reducing agent, main salt be halide, nitrate, sulfate, sulfamate, the acetate of transition metal, rare earth metal or noble metal and contain oxygen or the oxygen-free hydrochlorate in a kind of or several combination, main salt concentration is 0.01～5M; Compounding ingredient is by a kind of in ammoniacal liquor, sodium potassium tartrate tetrahydrate, ethylenediamine or the natrium citricum or several combination, and compounding ingredient concentration is 0.01～10M; Reducing agent is a kind of or two kinds combination in sodium borohydride or potassium borohydride or the inferior sodium phosphate, and reductant concentration is 0.02～8M.
8, according to the described hydrogen production by catalyzing and hydrolyzing borohydride Preparation of catalysts method that is used for of claim 7, it is characterized in that: in the described main salt, transition metal and rare earth metal comprise: Fe, Co, Ni, Cu, Mn, La or Ce; Noble metal comprises: Ag, Au, Ru, Rh, Pd, Pt or Ir.
9, according to the described hydrogen production by catalyzing and hydrolyzing borohydride Preparation of catalysts method that is used for of claim 6, it is characterized in that: at first, carrier material is carried out oil removing and acid activation pre-treatment; Then, it is immersed in the mixed solution of being made up of main salt and compounding ingredient dip time 5 seconds～10 minutes; Add reducing agent again, react, till plating bath does not produce bubble, finish chemical plating one time; According to the catalytic activity requirement, plating 1～20 time; Prepared catalyst can use after dry 2～10 hours under 30～80 ℃ of conditions; Perhaps, carry out subsequent heat treatment.
10, according to the described hydrogen production by catalyzing and hydrolyzing borohydride Preparation of catalysts method that is used for of claim 9, it is characterized in that: the adhesion that further improves activity of such catalysts and active component and carrier by heat treatment, heat treatment temperature: 200～600 ℃, heat treatment time: 1～4 hour; Heat treatment is carried out under argon gas, nitrogen, hydrogen atmosphere or vacuum condition.
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