CN101143330B - Nanocrystalline WC-Co-Ni catalyst - Google Patents
Nanocrystalline WC-Co-Ni catalyst Download PDFInfo
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- CN101143330B CN101143330B CN2007101560867A CN200710156086A CN101143330B CN 101143330 B CN101143330 B CN 101143330B CN 2007101560867 A CN2007101560867 A CN 2007101560867A CN 200710156086 A CN200710156086 A CN 200710156086A CN 101143330 B CN101143330 B CN 101143330B
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Abstract
The invention discloses a nano-crystalline WC-Co-Ni catalyst, consisting of tungsten carbide, cobalt and nickel. The catalyst is prepared in the following procedures: the tungsten, the cobalt and the nickel soluble salt is mixed according to the mass ratio 100:1 to 20: 1 to 20 and is mixed in distilled water to produce mixed aqueous solution with a concentration of 5 to 30 percent; the mixed aqueous solution is introduced into a spray dryer for spray drying to yield oxide granule precursor; the oxide granule precursor is sintered, reduced and carbonized in the reaction furnace; after that the free carbon is removed in hydrogen atmosphere; and at last the product is cooled to room temperature under the protection of inert gas to yield nano-crystalline WC-Co-Ni catalyst. The process and the devices are simple, the cost is low and the nano-crystalline WC-Co-Ni catalyst yielded has high catalytic performance. Used as electrochemical hydrogen evolution and fuel cell, the electrocatalyst has wide practical prospects.
Description
(1) technical field
The present invention relates to a kind of nanocrystalline WC-Co-Ni catalyst.
(2) technical background
Tungsten carbide (WC) and composite thereof have a wide range of applications in the carbide alloy field always, because Co has good wetability and caking property to hard phase WC, and C, the W dissolving in Co makes the WC-Co series hard metal have high rigidity, high strength and high-wearing feature, therefore from CEMENTED CARBIDE PRODUCTION and use angle, Co is undoubtedly the best bond agent of WC base cemented carbide.Yet Co is as a kind of costliness and rare metal, and global reserves are extremely limited, and price goes up year by year.Modal Co substitute is the alloy of Ni and Fe or these metals and Co.Ni and Fe and Co belong to the iron group metal together in the periodic table of elements, its density, fusing point, atomic radius and physics, chemical property are close, can both wetting well WC hard phase.But because the easy oxidation of iron powder is generally very low as the carbide alloy mechanical strength of binding agent with iron powder; Ni also shows good wetability to WC, and has than better non-oxidizability of Co and corrosion stability, especially after alloying, can make the carbide alloy performance excellent more, and also have non-magnetic advantage under low carbon content.The global reserves of Ni are 70 times of Co, and resource is abundanter, are the more cheap metals of a kind of relative Co price.Therefore, Ni is counted as the first-selected substitute of Co.If can produce production and use cost that " Ni is for the Co carbide alloy " will reduce carbide alloy greatly with the part or all of replaced C o of Ni as the carbide alloy binding agent, have vast market prospect and significant social and economic benefit.
On the other hand, the WC based composites can be widely used in catalytic field, has particularly added Co or Ni in WC, and material self physical property is improved, and more can bring into play cooperative effect in catalystic converter system.For example such material can be applicable to the chemical catalysis field, as hydrogenation, dehydrogenation, isomerization and the hydrocarbon conversion with catalyst for reaction such as synthesize; In electrochemical field, the WC based composites is having also aspect the electro-catalysis such as evolving hydrogen reaction and will have a wide range of applications.The preparation of special construction WC based composites has important theoretical Research Significance and actual application value.Nanocrystalline WC-Co-Ni catalyst proposed by the invention and preparation method thereof is not seen document and application report as yet.
(3) summary of the invention
The technical problem to be solved in the present invention provides a kind of nanocrystalline WC-Co-Ni catalyst, and the nanocrystalline WC-Co-Ni catalyst that obtains has good catalytic performance, and preparation technology is simple, and technology controlling and process is simple and direct, is suitable for large-scale industrialization production.
Nanocrystalline WC-Co-Ni catalyst of the present invention is made up of WC, Co and Ni, and its preparation comprises the steps:
(1) water soluble salt of tungsten, cobalt, nickel is mixed by the proportioning of mass ratio 100: 1～20: 1～20 and be dissolved in distilled water to be mixed with mass concentration be 5～30% mixed aqueous solution;
(2) mixed aqueous solution that step (1) is obtained stirs down and carries out spray-drying in the importing spray dryer, obtains the oxide particle presoma;
(3) the oxide particle presoma that step (2) is obtained carries out calcination under hydrogen atmosphere; be that reduction and carbonization atmosphere is carried out the reduction and carbonization reaction with methane and hydrogen mixed gas again; question response finishes; under hydrogen atmosphere, remove free carbon; at last under the protection of inert gas, product is cooled to room temperature, obtains the Dark grey sample and be nanocrystalline WC-Co-Ni catalyst.
The impurity of bringing into by raw material that may contain trace in the above-mentioned preparation catalyst, but the existence of these trace impurities does not influence the performance of catalyst.
The mass ratio of WC, Co and Ni is 100: 3～62: 3～62 in the above-mentioned nanocrystalline WC-Co-Ni catalyst for preparing.Can observe from SEM, nanocrystalline WC-Co-Ni catalyst is the meso-hole structure hollow ball-shape, and spherome surface is made of short cylinder nanocrystal granule not of uniform size.
Further, the described water-soluble tungsten salt mixing that is following one or more arbitrary proportions: ammonium metatungstate, ammonium paratungstate, sulfo-ammonium tungstate, six carboxyl tungsten;
Described water soluble cobaltous salt is the mixing of following one or more arbitrary proportions: cobalt nitrate, cobalt oxalate, cobalt acetate, cobalt chloride;
Described water soluble nickel salt is the mixing of following one or more arbitrary proportions: nickel acetate, nickel chloride, nickel nitrate.
The described mixed aqueous solution of above-mentioned steps (1) can at room temperature carry out step (2) with supersonic oscillations again after 10～60 minutes.
Particularly, the described calcination temperature of step (3) is 400～550 ℃, is preferably 500 ℃; The calcination time is 0.5～3 hour, preferred 0.5～2 hour, most preferably is 1 hour.
The volume ratio of methane described in the step (3) and hydrogen is 1: 5～15, preferred 1: 5～10, most preferably be 1: 8, and the gaseous mixture flow velocity is 0.25～0.55m/S.
Described reduction and carbonization reaction temperature is 600～900 ℃, is preferably 600～800 ℃, most preferably is 750 ℃; The reduction and carbonization reaction time is 0.5～4 hour, preferred 2～3 hours.
The treatment temperature that removes free carbon under the described hydrogen atmosphere is 900～1000 ℃, and the processing time is 60～120 minutes.
The spray-drying process of recommendation step (2) carries out in following condition: tungsten, cobalt, nickel water soluble salt mixture aqueous solution inlet flow velocity are 5～40mL/min, the air intake flow velocity is 400～800L/h, the inlet nozzle temperature of hot air nozzle is 160～250 ℃, and tail gas exit temperature is 80～120 ℃.More preferably: tungsten, cobalt, nickel water soluble salt mixture aqueous solution inlet flow velocity are 20mL/min, and the air intake flow velocity is 600L/h, and the inlet nozzle temperature of hot air nozzle is 200 ℃, and tail gas exit temperature is 100 ℃.
Spray-dired purpose is with tungsten, cobalt, the dry formation of nickel water soluble salt mixed aqueous solution oxide particle presoma, and finishes the control of granulation, structure and the pattern of oxide precursor.
Concrete recommendation nanocrystalline WC-Co-Ni catalyst of the present invention carries out according to following steps:
(1) tungsten, cobalt, nickel water soluble salt raw material fully being hybridly prepared into mass concentration by 100: 10: 10 proportioning of mass ratio in distilled water is 10% mixed aqueous solution, and at room temperature with mixed aqueous solution with supersonic oscillations 10～60 minutes;
(2) mixed aqueous solution that step (1) is got stirs down and carries out spray-drying in the importing spray dryer, obtains the oxide particle presoma; Mixture aqueous solution inlet flow velocity is 20mL/min in the described spray-drying process, and the air intake flow velocity is 600L/h, and the inlet nozzle temperature of hot air nozzle is 200 ℃, and tail gas exit temperature is 100 ℃;
(3) with the resultant oxide particle presoma of step (2) under hydrogen atmosphere in 450 ℃ carry out calcination 1 hour, be that 1: 8 gaseous mixture is that reduction and carbonization atmosphere was carried out reduction and carbonization 2～3 hours at 750 ℃ with methane and hydrogen volume ratio again; after finishing, reaction under 950 ℃ of hydrogen atmospheres, carried out carbonization treatment 90 minutes; at last under the protection of inert gas, product is cooled to room temperature, obtains nanocrystalline WC-Co-Ni catalyst.
The innovative point of nanocrystalline WC-Co-Ni catalyst of the present invention and preparation method thereof is mainly reflected in:
(1) Co not only as the catalyst of presoma reduction and carbonization, and as the binding agent of WC and Ni, makes the WC-Co-Ni catalyst can give full play to the cooperative effect of WC and Ni in reaction, significantly improves the catalytic efficiency of catalyst.
(2) utilize the method and the technology of spray-drying-gas-solid reaction, and prepare nanocrystalline WC-Co-Ni catalyst in conjunction with the heat treatment decarburization technique, technology is simple, and technology controlling and process is simple and direct, but provides a kind of large-scale industrialization to produce the new technology of nanocrystalline WC-Co-Ni catalyst on production technology.
(3) utilize the advantage of spray drying technology,, and realize control final product pattern and structure mainly to the control of mixing, drying, granulation, pattern and the structure of presoma.
To sum up, the nanocrystalline WC-Co-Ni catalyst that the present invention prepares has demonstrated higher catalytic performance, is with a wide range of applications as the eelctro-catalyst of electrochemistry liberation of hydrogen and fuel cell.
(4) description of drawings
Fig. 1 is the XRD figure of the WC-Co-Ni sample of embodiment 1 preparation.
Fig. 2 is the scanning electron microscope diagram of the WC-Co-Ni sample of embodiment 1 preparation, and wherein a amplifies 5000 times, and b amplifies 50000 times.
Fig. 3 is the linear scan curve of electrode in 1mol/LKOH solution of embodiment 5 and comparative example 1 preparation.Wherein a is the WC electrode, and b is the WC-Co-Ni electrode.
(5) specific embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
16.25g ammonium metatungstate, 1.63g cobalt nitrate and 1.63g nickel nitrate fully are hybridly prepared into mass concentration in distilled water be 10% mixed aqueous solution, at room temperature used supersonic oscillations 30 minutes, under magnetic stirrer, will carry out spray-drying in this solution importing spray-drying instrument then, obtain the oxide particle presoma, mixture aqueous solution inlet flow velocity is 20mL/min in the described spray-drying process, the air intake flow velocity is 600L/h, the inlet nozzle temperature of hot air nozzle is 200 ℃, and tail gas exit temperature is 100 ℃; The dried presoma quartz boat of packing into is positioned in the tube type resistance furnace, feed hydrogen down at 450 ℃, after carrying out 2 hours calcination heat treatment, be warming up to 750 ℃ again, feeding methane, hydrogen gas mixture carry out reduction and carbonization, the mass ratio that methane and hydrogen mix is 1: 8, and gas flow rate is 0.45m/S, and the reduction and carbonization time is 3 hours.Reaction finishes and carried out carbonization treatment 90 minutes after afterreaction finishes under 950 ℃ of hydrogen atmospheres, cools to product with the furnace room temperature at last, obtains nanocrystalline WC-Co-Ni catalyst.The sample that obtains detects (as shown in Figure 1) through XRD, and sample is made up of WC, Co and Ni.The SEM figure of WC-Co-Ni sample as shown in Figure 2, can find from Fig. 2, sample is a hollow ball-shape, this hollow ball diameter is about 10 μ m, ball wall thickness is less than 1 μ m, and spherome surface is made of short cylinder nanocrystal granule not of uniform size, makes whole sample form the pattern of meso-hole structure hollow ball-shape.
Embodiment 2
20.20g ammonium paratungstate, 0.20g cobalt oxalate and 0.20g nickel chloride fully are hybridly prepared into mass concentration in distilled water be 5% mixed aqueous solution, at room temperature used supersonic oscillations 10 minutes, under magnetic stirrer, will carry out spray-drying in this solution importing spray-drying instrument then, obtain the oxide particle presoma, mixture aqueous solution inlet flow velocity is 5mL/min in the described spray-drying process, the air intake flow velocity is 400L/h, the inlet nozzle temperature of hot air nozzle is 160 ℃, and tail gas exit temperature is 80 ℃; The dried presoma quartz boat of packing into is positioned in the tube type resistance furnace, feed hydrogen down at 400 ℃, after carrying out 0.5 hour calcination heat treatment, be warming up to 900 ℃ again, feeding methane, hydrogen gas mixture carry out reduction and carbonization, the mass ratio that methane and hydrogen mix is 1: 15, and gas flow rate is 0.25m/S, and the reduction and carbonization time is 4 hours.Reaction finishes and carried out carbonization treatment 120 minutes after afterreaction finishes under 1000 ℃ of hydrogen atmospheres, cools to product with the furnace room temperature at last, obtains nanocrystalline WC-Co-Ni catalyst.
Embodiment 3
22.10g six carboxyl tungsten, 0.22g cobalt acetate and 4.42g nickel acetate fully are hybridly prepared into mass concentration in distilled water be 30% mixed aqueous solution, at room temperature used supersonic oscillations 60 minutes, under magnetic stirrer, will carry out spray-drying in this solution importing spray-drying instrument then, obtain the oxide particle presoma, mixture aqueous solution inlet flow velocity is 40mL/min in the described spray-drying process, the air intake flow velocity is 800L/h, the inlet nozzle temperature of hot air nozzle is 250 ℃, and tail gas exit temperature is 120 ℃; The dried presoma quartz boat of packing into is positioned in the tube type resistance furnace, feed hydrogen down at 500 ℃, after carrying out 1 hour calcination heat treatment, be warming up to 600 ℃ again, feeding methane, hydrogen gas mixture carry out reduction and carbonization, the mass ratio that methane and hydrogen mix is 1: 5, and gas flow rate is 0.55m/S, and the reduction and carbonization time is 2 hours.Reaction finishes and carried out carbonization treatment 60 minutes after afterreaction finishes under 900 ℃ of hydrogen atmospheres, cools to product with the furnace room temperature at last, obtains nanocrystalline WC-Co-Ni catalyst.
15.52g sulfo-ammonium tungstate, 3.11g cobalt oxalate and 3.11g nickel nitrate fully are hybridly prepared into mass concentration in distilled water be 10% mixed aqueous solution, at room temperature used supersonic oscillations 30 minutes, under magnetic stirrer, will carry out spray-drying in this solution importing spray-drying instrument then, obtain the oxide particle presoma, mixture aqueous solution inlet flow velocity is 20mL/min in the described spray-drying process, the air intake flow velocity is 600L/h, the inlet nozzle temperature of hot air nozzle is 200 ℃, and tail gas exit temperature is 100 ℃; The dried presoma quartz boat of packing into is positioned in the tube type resistance furnace, feed hydrogen down at 550 ℃, after carrying out 3 hours calcination heat treatment, be warming up to 800 ℃ again, feeding methane, hydrogen gas mixture carry out reduction and carbonization, the mass ratio that methane and hydrogen mix is 1: 10, and gas flow rate is 0.45m/S, and the reduction and carbonization time is 0.5 hour.Reaction finishes and carried out carbonization treatment 90 minutes after afterreaction finishes under 900 ℃ of hydrogen atmospheres, cools to product with the furnace room temperature at last, obtains nanocrystalline WC-Co-Ni catalyst.
Embodiment 5
Take by weighing 0.8g embodiment 1 preparation WC-Co-Ni powder, 0.05g acetylene black and 0.15g60%PTFE emulsion (production of Shanghai three Ai Fu companies), add an amount of absolute ethyl alcohol, after 5 minutes, in 85 ℃ of water-baths, add thermal agitation again through ultrasonic dispersion treatment until PTFE, acetylene black and WC-Co-Ni conglomerate; Condensation product is put into roll repeatedly on two roller rollers of 50～60 ℃ of temperature and makes the PTFE fibrillatable, make the film of thick 0.2mm, WC-Co-Ni film and graphite paper (making conductive carrier) are superimposed together, cold moudling under the pressure of 10MPa, opposite side with graphite paper seals with epoxy resin then, promptly makes the WC-Co-Ni electrode.
Adopt the linear scan method that WC-Co-Ni is carried out the catalytic activity for hydrogen evolution test, the results are shown in Figure the 3b curve.Used instrument is a microcomputer control CHI660B electrochemical analyser, and three electrode test systems are adopted in experiment, and electrolyte is KOH (1mol/L), and working electrode is the WC-Co-Ni electrode, and area is 0.25cm
2, reference electrode is the Hg/HgO electrode, is the Pt sheet to electrode, and experimental temperature is 25 ℃, and sweep speed is 0.5mV/S.
Comparative Examples 1
The 20g ammonium metatungstate is water-soluble, be mixed with the solution of 5wt%, the chamber is surely down with supersonic oscillations 30 minutes; In magnetic stirrer,, obtain H with carrying out spray-drying in this solution importing spray-drying instrument
2WO
3The particle presoma, mixture aqueous solution inlet flow velocity is 20mL/min in the described spray-drying process, and the air intake flow velocity is 600L/h, and the inlet nozzle temperature of hot air nozzle is 200 ℃, and tail gas exit temperature is 100 ℃; The dried presoma quartz boat of packing into is positioned in the tube type resistance furnace, feed hydrogen down at 400 ℃, after carrying out 2 hours calcination heat treatment, be warming up to 900 ℃ again, feeding methane, hydrogen gas mixture carry out reduction and carbonization, the mass ratio that methane and hydrogen mix is 20: 1, and gas flow rate is 0.45m/S, and the reduction and carbonization time is 12 hours.Cool to product with the furnace room temperature after reaction finishes, obtain the WC powder sample.
The method for preparing electrode according to embodiment 5 is made the WC membrane electrode, repeats embodiment 5 described electro-chemical test steps, the results are shown in Figure the 3a curve.
As seen from Figure 3, in alkaline solution, the prepared WC-Co-Ni catalyst of the present invention has higher electro catalytic activity to evolving hydrogen reaction.Under identical reaction condition, compare the current potential of WC-Co-Ni electrode about 0.1V that shuffles with the WC electrode.This explanation WC by Co be binding agent in conjunction with Ni after, can bring into play the cooperative effect of WC and Ni, the catalytic performance of raising catalyst.
Claims (6)
1. nanocrystalline WC-Co-Ni catalyst is characterized in that described catalyst is made up of WC, Co and Ni, and described Preparation of catalysts comprises the steps:
(1) water soluble salt of tungsten, cobalt, nickel is mixed by the proportioning of mass ratio 100: 1～20: 1～20 and be dissolved in distilled water to be mixed with mass concentration be 5～30% mixed aqueous solution;
(2) mixed aqueous solution that step (1) is obtained stirs down and carries out spray-drying in the importing spray dryer, obtains the oxide particle presoma; The water soluble salt mixed aqueous solution of tungsten, cobalt, nickel inlet flow velocity is 5～40mL/min in the described spray-drying process, the air intake flow velocity is 400～800L/h, the inlet nozzle temperature of hot air nozzle is 160～250 ℃, and tail gas exit temperature is 80～120 ℃;
(3) the oxide particle presoma that step (2) is obtained carries out calcination, is that reduction and carbonization atmosphere is carried out reduction and carbonization reaction with methane and hydrogen mixed gas again under hydrogen atmosphere, question response finishes, under hydrogen atmosphere, remove free carbon, at last under the protection of inert gas, product is cooled to room temperature, obtains described nanocrystalline WC-Co-Ni catalyst; Described calcination is to carry out under 400～550 ℃ calcination temperature, and the calcination time is 0.5～3 hour; The volume ratio of methane and hydrogen is 1: 5～15 in the gaseous mixture of described methane and hydrogen, and the gaseous mixture flow velocity is 0.25～0.55m/S; Described reduction and carbonization is to carry out under 600～900 ℃ reaction temperature, and the reaction time is 0.5～4 hour; The treatment temperature that removes free carbon under the described hydrogen atmosphere is 900～1000 ℃, and the processing time is 60～120 minutes.
2. nanocrystalline WC-Co-Ni catalyst as claimed in claim 1, the water soluble salt that it is characterized in that described tungsten is the mixing of following one or more arbitrary proportions: ammonium metatungstate, ammonium paratungstate, sulfo-ammonium tungstate, six carboxyl tungsten.
3. nanocrystalline WC-Co-Ni catalyst as claimed in claim 1, the water soluble salt that it is characterized in that described cobalt is the mixing of following one or more arbitrary proportions: cobalt nitrate, cobalt oxalate, cobalt acetate, cobalt chloride.
4. nanocrystalline WC-Co-Ni catalyst as claimed in claim 1, the water soluble salt that it is characterized in that described nickel is the mixing of following one or more arbitrary proportions: nickel acetate, nickel chloride, nickel nitrate.
5. nanocrystalline WC-Co-Ni catalyst as claimed in claim 1 is characterized in that the described mixed aqueous solution of step (1) at room temperature carries out step (2) again with supersonic oscillations after 10～60 minutes.
6. nanocrystalline WC-Co-Ni catalyst as claimed in claim 1 is characterized in that described preparation method carries out according to following:
(1) the water soluble salt raw material of tungsten, cobalt, nickel fully being hybridly prepared into mass concentration by 100: 10: 10 proportioning of mass ratio in distilled water is 10% mixed aqueous solution, and at room temperature with mixed aqueous solution with supersonic oscillations 10～60 minutes;
(2) mixed aqueous solution that step (1) is got stirs down and carries out spray-drying in the importing spray dryer, obtains the oxide particle presoma; Mixed aqueous solution inlet flow velocity is 20mL/min in the described spray-drying process, and the air intake flow velocity is 600L/h, and the inlet nozzle temperature of hot air nozzle is 200 ℃, and tail gas exit temperature is 100 ℃;
(3) with the resultant oxide particle presoma of step (2) under hydrogen atmosphere in 450 ℃ carry out calcination 1 hour, be that 1: 8 gaseous mixture is a reduction and carbonization atmosphere with the volume ratio of methane and hydrogen again; carried out reduction and carbonization 2～3 hours at 750 ℃; after finishing, reaction under 950 ℃ of hydrogen atmospheres, carried out carbonization treatment 90 minutes; at last under the protection of inert gas, product is cooled to room temperature, obtains nanocrystalline WC-Co-Ni catalyst.
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| CN102357308A (en) * | 2011-10-19 | 2012-02-22 | 江西稀有稀土金属钨业集团有限公司 | Method for directly preparing anhydrous cobalt chloride powder from cobalt chloride solution |
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| CN101648140B (en) * | 2008-08-14 | 2011-09-07 | 中国科学院大连化学物理研究所 | Tungsten carbide catalyst, preparation thereof and application thereof in reaction for preparing glycol from cellulose |
| CN102172527B (en) * | 2011-01-28 | 2013-04-10 | 华南理工大学 | Method for preparing volatile organic compound oxidation catalyst by ultrasound-hydrogen reduction |
| CN102145386B (en) * | 2011-05-06 | 2013-07-17 | 河南煤业化工集团研究院有限责任公司 | Method for preparing metal with surface coated with nano nickel |
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| CN109675598B (en) * | 2019-03-04 | 2022-03-11 | 合肥工业大学 | Preparation method of nickel tungsten carbide nano composite powder used as electrocatalyst |
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