CN107331873A - A kind of transition metal metaborate nanometer bifunctional catalyst and preparation method - Google Patents
A kind of transition metal metaborate nanometer bifunctional catalyst and preparation method Download PDFInfo
- Publication number
- CN107331873A CN107331873A CN201710451822.5A CN201710451822A CN107331873A CN 107331873 A CN107331873 A CN 107331873A CN 201710451822 A CN201710451822 A CN 201710451822A CN 107331873 A CN107331873 A CN 107331873A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- nanometer
- catalyst
- metaborate
- bifunctional catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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
- Y02E60/50—Fuel cells
Abstract
A kind of transition metal metaborate nanometer bifunctional catalyst, its chemical formula is M (BO2)2(M=Fe, Co, Ni), its chemical composition mass percent is：Transition metal 35~45%, boron 10~20%, oxygen 40~50%；The preparation method of above-mentioned transition metal metaborate nanometer bifunctional catalyst, which is mainly, to be first passed through solvent-thermal method and makes micro-nano boron carbide and transition metal salt formation compound, question response stands washing drying after terminating, the product obtained after reaction is carried out in nitrogen atmosphere to the metaborate nanometer bifunctional catalyst that 500~600 DEG C of heat treatment can obtain transition metal.Present invention process is simple, easily operate, preparation cost is low and is easy to large-scale production; the catalyst of preparation is a kind of new catalyst for the high catalytic activity for having catalytic oxidation-reduction reaction and oxygen evolution reaction concurrently; can and only single catalytic activity expensive with fictitious hosts platinum base and ruthenium/iridium based catalyst, applied to fuel battery negative pole and metal-air electrode anode.
Description
Technical field
The invention belongs to catalyst technical field, more particularly to a kind of cell catalyst and preparation method thereof.
Background technology
Fuel cell is a kind of the chemical energy being stored in fuel and oxidant to be directly translated into electricity by electrode reaction
The electrochemical appliance of energy.Because it has the advantages that energy conversion efficiency is high, environment-friendly, noise is low, startup is fast, it is considered to be
One of clean, efficient generation technology of 21 century first choice, is to be hopeful a large amount of offer electricity after wind-force, waterpower and solar energy
The new energy technology of power.Fuel cell technology is greatly developed to solving " energy shortage " and " environmental pollution " that the current world faces
This two hang-up, realizes that energy variation is significant.By effort for many years, fuel cell electric automobile,
The fields such as family expenses cogeneration system, scattered electric power station system have successfully carried out demonstrating running.But because cost is high, stability and
The problems such as poor durability, seriously hinder its industrialization process.
The elctro-catalyst generally reacted in traditional fuel cell using platinum based catalyst as catalytic oxidation-reduction, ruthenium base and
The catalyst of iridium based catalyst then usually as catalysis oxygen uptake reaction.Platinum, ruthenium and iridium are as noble metal, and its proven reserve is very
It is low, it is expensive, cause holding at high price for elctro-catalyst.In addition, platinum based catalyst is steady in fuel cell operation
It is qualitative poor, particularly easily poisoned in the cathode in the environment of high potential, elevated oxygen level by impurity and methanol, can not still expire
The practical requirement of sufficient fuel cell.Therefore, cheap, high activity, high stability are developed and two kinds of catalytic capabilities are had concurrently
Novel non-noble metal catalyst turn into current fuel-cell catalyst field new focus.
The elctro-catalyst for having double-function catalyzing concurrently common at present is that Ca-Ti ore type elctro-catalyst and spinel-type electricity are urged
Agent etc..As Dai Hongjie seminars have studied using graphene oxide with CNT as base load Co3O4It is double
The catalytic performance of function catalyst.D.U.Lee etc. prepares NiCo using one-step method2O4/ graphene composite material, studies it to ORR
With OER double-function catalyzing activity.Fanliang Lu etc. have studied porous spherical perofskite type oxide La0.8Sr0.2MnO3
Electrocatalysis characteristic in lithium-air battery.Either perovskite type catalyst or spinel-type catalyst are all present because of electric conductivity
The not high problem of catalytic activity caused by difference.Chinese patent CN201110315465.2 using nitrogenous and/or boron organic precursor,
Transition metal salt and nano-sized carbon are raw material, and a kind of fuel cell catalyst is prepared by microwave irradiation and subsequent heat treatment
Agent.The catalyst that this patent is related to boron source and does not include boron carbide and prepare is only limitted to catalytic oxidation-reduction reaction.Chinese patent
201110000141.X is prepared using conductivity ceramics boron carbide as carrier by way of being heated to reflux stirring, supports variety classes
The fuel-cell catalyst of noble metal.The metal species being combined in this patent are noble metal, and at the same time conductive carbonized boron is to gold
Category is that simple machinery is supported, and does not occur recombination reaction with metal, also only have studied the electrocatalysis to oxygen reduction reaction
Energy.
The content of the invention
It is an object of the invention to provide a kind of technique is simple, mild condition, easily operation, to prepare cost low and be easy to rule
Modelling production, catalytic activity height and the transition metal metaborate nanometer bifunctional catalyst and preparation method having good stability.
Transition metal is mainly combined by the present invention by hydro-thermal method with micro-nano boron carbide, and by subsequent heat treatment, preparing should
For fuel cell and the double-function catalyzing for having high catalytic activity concurrently to oxygen reduction reaction and oxygen evolution reaction of metal-air battery
Agent.
The transition metal metaborate nanometer bifunctional catalyst of the present invention, its chemical formula is M (BO2)2(M=Fe, Co,
Ni), its chemical composition mass percent is：(oxygen element is present for transition metal 35~45%, boron 10~20%, oxygen 40~50%
In metaboric acid root, introduced by transition metal salt).
The preparation method of above-mentioned transition metal metaborate nanometer bifunctional catalyst：
1) micro-nano boron carbide powder is added in transition metal salt solution A, is sufficiently mixed both, obtain suspension
B；
The mass ratio of transition metal salt of the boron carbide with being added in transition metal salt solution A is in the suspension B：1:
0.5~100；
The granularity of the micro-nano boron carbide is 50nm~3.5 μm；
The transition metal salt solution A solvent for use is one kind in deionized water, absolute ethyl alcohol or ethylene glycol, transition gold
The concentration for belonging to salting liquid is 0.01~0.5mol/L；The transition metal salt is one kind or two kinds of metallic elements in Fe, Co, Ni
Soluble metallic salt, the mol ratio of two kinds of transition metal is：1:0.2~5, the soluble metallic salt is nitrate, sulfuric acid
One kind in salt, acetate, hydrochloride, oxalates, sulfamate；
2) well mixed suspension B is transferred in the polytetrafluoroethyllining lining of water heating kettle, loadings are liner capacity
60%, water heating kettle is placed in thermostatic drying chamber after assembling, under the conditions of 150~180 DEG C be incubated 5h~12h, it is cold with stove
But mixture C is obtained afterwards；
3) mixture C acetone, deionized water, absolute ethyl alcohol are washed more than three times respectively successively, until after precipitation
Supernatant liquid clear, slowly pour out after supernatant by precipitate solid material fully dry, obtain solid powder D；
4) solid powder D is fitted into after ceramic crucible and be put into vacuum drying oven, be first evacuated to 10-1~10Pa, is then shut off
Vavuum pump, nitrogen is passed through into cavity with 10~30L/min speed, handle in a nitrogen atmosphere at 500~600 DEG C to 2~
3h obtains transition metal metaborate nanometer bifunctional catalyst.
It is of the invention to be had the following advantages that compared with existing catalyst and preparation method thereof：
Compound, transition metal sheet occurs for the characteristics of the 1st, carrying graphite linings using micro-nano carbonization boron surface and transition metal salt
Body can be catalyzed boron carbide carbonization as a kind of catalyst, while the carbon-coating formed can will react generation again at a certain temperature
Transition metal oxide is reduced to metal, and the addition of metal causes the microstructure and edge defect of carbonization boron surface to change
Become, the transition metal metaborate catalyst of generation has very high catalytic activity.
2nd, preparation process uses hydro-thermal method, and reaction condition is gentle, and course of reaction is easy to control, and product grain is uniform after reaction
And granularity is small；Compared with the method such as the used high temperature pyrolysis of similar catalyst preparation and solid-phase sintering, preparation technology is simple, bar
Part is gentle, easily operate, preparation cost is low and is easy to large-scale production.
3. compared with traditional noble metal catalyst, base metal and boron carbide aboundresources and the preparation process letter of use
It is single, and then total production cost is largely reduced, prepared catalyst shows good double-function catalyzing activity
And stability, very there is application prospect in fuel cell and metal-air battery.
Brief description of the drawings
Fig. 1 is the Fe (BO that the embodiment of the present invention 1 is obtained2)2The XRD diffraction patterns of catalyst.
Fig. 2 is the Fe (BO that the embodiment of the present invention 1 is obtained2)2The transmission electron microscope picture of catalyst.
Fig. 3 is the Fe (BO that the embodiment of the present invention 1 is obtained2)2Catalyst is in 0.1mol/L KOH solution under 1600rpm
The LSV curve maps of the reverse scan measured, it is 0.01V/s to sweep speed, and test scope is -1V~1V.
Fig. 4 is the Ni (BO that the embodiment of the present invention 2 is obtained2)2Speed of sweeping to oxygen reduction reaction is 0.01V/s,
The LSV curve maps of reverse scan in 0.1mol/L KOH solution under different rotating speeds.
Fig. 5 is the Ni (BO that the embodiment of the present invention 2 is obtained2)2K-L curve maps.
Fig. 6 is the Ni (BO that the embodiment of the present invention 2 is obtained2)2Speed of sweeping to oxygen evolution reaction is 0.005V/s and 0.01V/s,
The LSV curve maps of forward scan in 0.1mol/L KOH solution at 1600 rpm.
Fig. 7 is the Co (BO that the embodiment of the present invention 3 is obtained2)2The CV curve maps measured in 0.1mol/L KOH solution,
It is 0.05V/s to sweep speed.
Fig. 8 is the Co (BO that the embodiment of the present invention 3 is obtained2)2With commercial Pt/C in 0.1mol/L KOH solution
The LSV curve comparison figures of the reverse scan measured under 1600rpm, it is 0.01V/s to sweep speed.
Embodiment
Embodiment 1
Take 0.0540g ferrous oxalates to be dissolved in 30mL ethylene glycol to be sufficiently stirred for, be configured to the grass that concentration is 0.01mol/L
Sour ferrous iron solution, the micrometer silicon carbide boron powder for taking 108mg granularities to be 3.5 μm is added in above-mentioned ferrous oxalate solution, by super
Sound wave dispersion machine is scattered to make micrometer silicon carbide boron particles evenly spread in solution, forms uniform suspension, suspension is transferred to
Capacity is 50mL polytetrafluoroethylene (PTFE) water heating kettle, and water heating kettle is placed in thermostatic drying chamber after assembling, and is protected under the conditions of 180 DEG C
Black precipitate is obtained after warm 10h, furnace cooling；Above-mentioned precipitation is respectively washed successively with acetone, deionized water, absolute ethyl alcohol respectively
Thing three times, then dries 12 hours at 70 DEG C, obtains black solid powder.
It is put into after above-mentioned solid powder is fitted into ceramic crucible in vacuum drying oven, is first evacuated to 10-1Pa, is then shut off true
Empty pump, nitrogen is passed through into cavity with 10L/min speed, is formed after nitrogen environment, heating, vacuum stove, when temperature is increased to
Start insulation at 600 DEG C, soaking time is 3h, and sample is taken out after vacuum drying oven is cooled to room temperature, obtains metaboric acid ferrous iron nanometer
Bifunctional catalyst.
As shown in Figure 1, it can be seen that the diffractive features peak shape in the catalyst prepared is sharp, peak position and standard
Fe (BO in PDF cards2)2(PDF#03-1086) peak position good agreement, does not have other impurities peak, illustrates that the product of synthesis is true
It is in fact Fe (BO2)2And crystallinity is preferably, product component is purer.
As shown in Fig. 2 Fe (BO2)2Pattern to be spherical, particle size is in 20nm or so and is evenly distributed, and illustrate that use is molten
The hot method of agent can control to generate the appearance and particle size of product well.
Fig. 3 is Fe (BO2)2The LSV of reverse scan that is measured in 0.1mol/L KOH solution under 1600rpm of material it is bent
Line, it is 0.01V/s to sweep speed, and test scope is -1V~1V.It is computed obtaining, current density is 10mA/cm2With -3mA/cm2When pair
The electrical potential difference Δ E answered is 0.84V, and the value is much smaller than the potential difference values of noble metal catalyst, had both shown good catalysis oxygen also
The ability of original reaction, shows the ability of good catalysis oxygen evolution reaction again.Illustrate to invent the material have it is excellent difunctional
Electro catalytic activity.
Embodiment 2
Take 4.84g nickel sulfamic acids to be dissolved in 30mL deionized waters to be sufficiently stirred for, it is 0.5mol/L's to be configured to concentration
Nickel sulfamic acid solution, the nano silicon carbide boron powder for taking 48mg granularities to be 80nm is added in above-mentioned nickel sulfamic acid solution, is led to
Cross ultrasonic dispersing machine to disperse to make micro-nano boron carbide particles evenly spread in solution, form uniform suspension, this is suspended
Liquid is transferred to the polytetrafluoroethylene (PTFE) water heating kettle that capacity is 50mL, water heating kettle is placed in thermostatic drying chamber after assembling, at 150 DEG C
Under the conditions of be incubated 5h, furnace cooling after obtain black precipitate；Respectively washed successively with acetone, deionized water, absolute ethyl alcohol respectively
Above-mentioned sediment three times, then dries 12 hours at 70 DEG C, obtains black solid powder.
It is put into after above-mentioned solid powder is fitted into ceramic crucible in vacuum drying oven, is first evacuated to 5Pa, is then shut off vacuum
Pump, nitrogen is passed through into cavity with 20L/min speed, is formed after nitrogen environment, heating, vacuum stove, when temperature is increased to
Start insulation at 500 DEG C, soaking time is 2h；Sample is taken out after vacuum drying oven is cooled to room temperature, metaboric acid nickel nano double is obtained
Function catalyst.
As shown in figure 4, the LSV curves of the reverse scan in 0.1mol/L KOH solution under different rotating speeds can be seen
Go out, with sweeping, speed is almost equidistant to be changed the carrying current value that oxygen reduction reaction is produced, it is hereby achieved that the K-L curves in Fig. 5
Data.As shown in figure 5, according to K-L equations, under -0.4V, -0.5V, -0.6V, -0.7V and -0.8V potentials, reacting electron number
Respectively 3.72,3.73,3.76,3.76,3.75,3.73 (reacting electron number 4 close to highest), illustrate that the catalyst has very
High oxygen reduction reaction catalytic activity.
As shown in fig. 6, when the electric current that oxygen evolution reaction is produced is 10mA/cm2When, corresponding potential is 0.76V, far above platinum
The activity of base catalyst oxygen evolution reaction, illustrates that the catalyst has higher oxygen evolution reaction catalytic activity.
Embodiment 3
Take the acetate hydrate cobalts of 0.7424g tetra- to be dissolved in 30mL absolute ethyl alcohols to be sufficiently stirred for, be configured to concentration for 0.1mol/
L acetic acid cobalt liquor, the nano silicon carbide boron powder for taking 74.2mg granularities to be 50nm is added in above-mentioned acetic acid cobalt liquor, by super
Sound wave dispersion machine is scattered to make micro-nano boron carbide particles evenly spread in solution, forms uniform suspension, and the suspension is turned
The polytetrafluoroethylene (PTFE) water heating kettle that capacity is 50mL is moved to, water heating kettle is placed in thermostatic drying chamber after assembling, in 165 DEG C of conditions
Lower insulation 12h, black precipitate is obtained after furnace cooling；Respectively wash above-mentioned successively with acetone, deionized water, absolute ethyl alcohol respectively
Sediment three times, then dries 12 hours at 70 DEG C, obtains black solid powder.
It is put into after above-mentioned solid powder is fitted into ceramic crucible in vacuum drying oven, is first evacuated to 10Pa, is then shut off true
Empty pump, nitrogen is passed through into cavity with 30L/min speed, is formed after nitrogen environment, heating, vacuum stove, when temperature is increased to
Start insulation at 550 DEG C, soaking time is 2.5h, and sample is taken out after vacuum drying oven is cooled to room temperature, obtain metaboric acid cobalt nanometer
Bifunctional catalyst.
As shown in fig. 7, in oxygen saturation solution reduction peak clearly, correspondence potential it is low, infer that the catalyst should have
There is excellent oxygen reduction reaction catalytic activity.
Fig. 8 is the Co (BO that the present embodiment is obtained2)2Surveyed with commercial Pt/C in 0.1mol/L KOH solution under 1600rpm
The LSV curve comparison figures for the reverse scan arrived, it is 0.01V/s to sweep speed.As seen from the figure, the obtained catalyst hydrogen reduction is anti-
Take-off potential, half wave potential and carrying current for answering etc. characterize the parameter of catalytic activity compared with traditional platinum based catalyst, closely
It is suitable with commercial Pt/C, and then prove that the catalyst has excellent oxygen reduction reaction catalytic activity.
Embodiment 4
0.0834g ferrous sulfate and 0.4217g cobaltous sulfates (common 0.5051g) is taken to be dissolved in 30mL deionized waters and fully stir
Mix, be configured to ferrous sulfate and cobaltous sulfate mixed solution, transition metal ions total concentration is 0.06mol/L, wherein ferrous sulfate
Mol ratio with cobaltous sulfate is 1:5.Take 101mg granularities be 3.5 μm of nano silicon carbide boron powder be added to above-mentioned ferrous sulfate and
In cobaltous sulfate mixed solution, make nano boron carbide even particulate dispersion into solution by the way that ultrasonic dispersing machine is scattered, form equal
Even suspension, is transferred to the polytetrafluoroethylene (PTFE) water heating kettle that capacity is 50mL, by water after assembling by the well mixed suspension
Hot kettle is placed in thermostatic drying chamber, and black precipitate is obtained after 5h, furnace cooling are incubated under the conditions of 180 DEG C；Respectively with acetone,
Deionized water, absolute ethyl alcohol respectively wash above-mentioned sediment three times successively, are then dried 12 hours at 70 DEG C, obtain black solid
Powder；
It is put into after above-mentioned solid powder is fitted into ceramic crucible in vacuum drying oven, is first evacuated to 1Pa, is then shut off vacuum
Pump, nitrogen is passed through into cavity with 15L/min speed, is formed after nitrogen environment, heating, vacuum stove, when temperature is increased to
Start insulation at 600 DEG C, soaking time is 3h, and sample is taken out after vacuum drying oven is cooled to room temperature, obtain metaboric acid ferrous and inclined
Cobalt borate mixes nanometer bifunctional catalyst.
Embodiment 5
1.3085g nickel nitrates and 0.2620g cobalt nitrates (common 1.5705g) is taken to be dissolved in 30mL absolute ethyl alcohols and fully stir
Mix, be configured to nickel nitrate and cobalt nitrate mixed solution, transition metal ions total concentration is 0.18mol/L, wherein nickel nitrate and nitre
The mol ratio of sour cobalt is 1:0.2.The nano silicon carbide boron powder for taking 62.8mg granularities to be 50nm is added to above-mentioned nickel nitrate and nitric acid
In cobalt mixed solution, make nano boron carbide even particulate dispersion into solution by the way that ultrasonic dispersing machine is scattered, form uniform outstanding
Turbid liquid, is transferred to the polytetrafluoroethylene (PTFE) water heating kettle that capacity is 50mL, by water heating kettle after assembling by the well mixed suspension
It is placed in thermostatic drying chamber, black precipitate is obtained after 12h, furnace cooling are incubated under the conditions of 150 DEG C；Respectively with acetone, go
Ionized water, absolute ethyl alcohol respectively wash above-mentioned sediment three times successively, are then dried 12 hours at 70 DEG C, obtain black solid powder
End；
It is put into after above-mentioned solid powder is fitted into ceramic crucible in vacuum drying oven, is first evacuated to 0.5Pa, is then shut off true
Empty pump, nitrogen is passed through into cavity with 20L/min speed, is formed after nitrogen environment, heating, vacuum stove, when temperature is increased to
Start insulation at 550 DEG C, soaking time is 3h, and sample is taken out after vacuum drying oven is cooled to room temperature, obtains metaboric acid cobalt and inclined boron
Sour nickel mixes nanometer bifunctional catalyst.
Embodiment 6
1.2511g ferrous sulfate and 1.0696g nickel chlorides (common 2.3207g) is taken to be dissolved in 30mL deionized waters and fully stir
Mix, be configured to ferrous sulfate and nickel chloride mixed solution, transition metal ions total concentration is 0.3mol/L, wherein ferrous sulfate with
The mol ratio of nickel chloride is 1:1.The nano silicon carbide boron powder for taking 77.4mg granularities to be 80nm is added to above-mentioned ferrous sulfate and sulphur
In sour cobalt mixed solution, make nano boron carbide even particulate dispersion into solution by the way that ultrasonic dispersing machine is scattered, form uniform
Suspension, is transferred to the polytetrafluoroethylene (PTFE) water heating kettle that capacity is 50mL, by hydro-thermal after assembling by the well mixed suspension
Kettle is placed in thermostatic drying chamber, and black precipitate is obtained after 8h, furnace cooling are incubated under the conditions of 170 DEG C；Respectively with acetone, go
Ionized water, absolute ethyl alcohol respectively wash above-mentioned sediment three times successively, are then dried 12 hours at 70 DEG C, obtain black solid powder
End；
It is put into after above-mentioned solid powder is fitted into ceramic crucible in vacuum drying oven, is first evacuated to 2Pa, is then shut off vacuum
Pump, nitrogen is passed through into cavity with 10L/min speed, is formed after nitrogen environment, heating, vacuum stove, when temperature is increased to
Start insulation at 600 DEG C, soaking time is 2h, and sample is taken out after vacuum drying oven is cooled to room temperature, obtain metaboric acid ferrous and inclined
Nickel borate mixes nanometer bifunctional catalyst.
Claims (4)
1. a kind of transition metal metaborate nanometer bifunctional catalyst, it is characterised in that：Its chemical formula is M (BO2)2(M=
Fe, Co, Ni), its chemical composition mass percent is：Transition metal 35~45%, boron 10~20%, oxygen 40~50%.
2. the preparation method of the transition metal metaborate nanometer bifunctional catalyst of claim 1, it is characterised in that：It includes
Following steps：
1) micro-nano boron carbide powder is added in transition metal salt solution A, is sufficiently mixed both, obtain suspension B；Institute
The mass ratio for stating transition metal salt of the boron carbide with being added in transition metal salt solution A in suspension B is：1:0.5~100；
2) well mixed suspension B is transferred in the polytetrafluoroethyllining lining of water heating kettle, loadings are liner capacity
60%, water heating kettle is placed in thermostatic drying chamber after assembling, 5h~12h, furnace cooling are incubated under the conditions of 150~180 DEG C
After obtain mixture C；
3) mixture C acetone, deionized water, absolute ethyl alcohol are washed more than three times respectively successively, until the upper strata after precipitation
Liquid clear, slowly pour out after supernatant by precipitate solid material fully dry, obtain solid powder D；
4) solid powder D is fitted into after ceramic crucible and be put into vacuum drying oven, be first evacuated to 10-1~10Pa, is then shut off vacuum
Pump, nitrogen is passed through into cavity with 10~30L/min speed, handles to 2~3h at 500~600 DEG C obtain in a nitrogen atmosphere
To transition metal metaborate nanometer bifunctional catalyst.
3. the preparation method of transition metal metaborate nanometer bifunctional catalyst according to claim 2, its feature exists
In：The transition metal salt solution A solvent for use is one kind in deionized water, absolute ethyl alcohol or ethylene glycol, transition metal salt
The concentration of solution is 0.01~0.5mol/L；The transition metal salt be one kind in Fe, Co, Ni or two kinds of metallic elements can
Soluble metal salts, the mol ratio of two kinds of transition metal is：1:0.2~5, the soluble metallic salt is nitrate, sulfate, second
One kind in hydrochlorate, hydrochloride, oxalates, sulfamate.
4. the preparation method of transition metal metaborate nanometer bifunctional catalyst according to claim 2, its feature exists
In：The granularity of the micro-nano boron carbide is 50nm~3.5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710451822.5A CN107331873B (en) | 2017-06-15 | 2017-06-15 | A kind of transition metal metaborate nanometer bifunctional catalyst and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710451822.5A CN107331873B (en) | 2017-06-15 | 2017-06-15 | A kind of transition metal metaborate nanometer bifunctional catalyst and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107331873A true CN107331873A (en) | 2017-11-07 |
| CN107331873B CN107331873B (en) | 2019-07-26 |
Family
ID=60195217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710451822.5A Active CN107331873B (en) | 2017-06-15 | 2017-06-15 | A kind of transition metal metaborate nanometer bifunctional catalyst and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107331873B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110459737A (en) * | 2018-05-07 | 2019-11-15 | 福建师范大学 | A kind of preparation method and applications of the carbon coating boric acid ferrous iron of core-shell structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102088093A (en) * | 2011-01-04 | 2011-06-08 | 武汉理工大学 | Fuel cell catalyst taking conductive ceramic boron carbide as supporter and preparation method thereof |
| CN103050714A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst |
-
2017
- 2017-06-15 CN CN201710451822.5A patent/CN107331873B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102088093A (en) * | 2011-01-04 | 2011-06-08 | 武汉理工大学 | Fuel cell catalyst taking conductive ceramic boron carbide as supporter and preparation method thereof |
| CN103050714A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| G.M.ARZAC: "Boron Compounds as Stabilizers of a Complex Microstructure in a Co-B-based Catalyst for NaBH4 Hydrolysis", 《CHEM. CAT. CHEM》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110459737A (en) * | 2018-05-07 | 2019-11-15 | 福建师范大学 | A kind of preparation method and applications of the carbon coating boric acid ferrous iron of core-shell structure |
| CN110459737B (en) * | 2018-05-07 | 2022-03-18 | 福建师范大学 | Preparation method and application of carbon-coated ferrous borate with core-shell structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107331873B (en) | 2019-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108543545B (en) | A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications | |
| CN109252180B (en) | Ternary MOF nanosheet array material, preparation method and application thereof | |
| CN107051559B (en) | A kind of hydrogen reduction and analysis oxygen phosphatization cobalt@NPC dual-function composite catalyst and its preparation method and application | |
| CN109065897B (en) | Phosphorus-doped porous carbon-coated cobaltosic oxide oxygen reduction catalyst and preparation method and application thereof | |
| CN109248703B (en) | Loaded Ni3Preparation method of Fe nitrogen-doped carbon nanocomposite material, and obtained material and application thereof | |
| CN108754531B (en) | Preparation method of Co-and Ru-containing bimetallic carbon nano composite electro-catalytic material | |
| CN106229521B (en) | A kind of FeCx@NC catalyst with core-casing structure and preparation method thereof | |
| CN106807416A (en) | A kind of self-supporting nickel phosphide nanometer sheet material of electrocatalytic decomposition water hydrogen manufacturing and preparation method thereof | |
| CN105826574A (en) | Nitrogen-doped graphene/ ferrocobalt hydrotalcite-like compound difunctional oxygen-reduction catalyst and preparing method and application thereof | |
| CN110813350B (en) | Carbon-based composite electrocatalyst and preparation method and application thereof | |
| CN109019602A (en) | Be carbonized molybdenum material, molybdenum carbide vulcanization molybdenum composite material and preparation method and application | |
| CN107321373B (en) | Doped carbon carrying transition metal boride multifunctional nano catalyst and preparation method | |
| CN111785977B (en) | Preparation method of iron-cobalt alloy/nitrogen co-doped carbon aerogel electrocatalytic material | |
| CN112058293B (en) | Preparation method of nitrogen-phosphorus-codoped foam carbon nanosheet loaded NiCo nanoparticle composite material, product and application thereof | |
| CN111659439B (en) | Nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction and preparation method and application thereof | |
| CN108704663A (en) | A kind of preparation method of the nano combined electrocatalysis material of bimetallic carbon | |
| CN113512737B (en) | Nickel hydroxide electrocatalyst, preparation method, electrochemical activation method and application thereof | |
| CN109012704A (en) | A kind of two cobaltous selenide of nanometer load carbon nano-fiber composite material and its preparation method and application | |
| CN109755600A (en) | The application of carbon cloth nickel-loaded cobalt oxide nano-sheet composite material and preparation method and electrode | |
| CN110655120B (en) | Preparation method of mesoporous spherical nickel cobaltate nano material | |
| CN113322473A (en) | Loaded Ni-CeO2Preparation method and application of heterojunction nitrogen-doped porous carbon nanofiber material | |
| CN107331873B (en) | A kind of transition metal metaborate nanometer bifunctional catalyst and preparation method | |
| CN108306023A (en) | A kind of BN/CuAg/CNT composite material and preparation methods and purposes | |
| CN115172770A (en) | Gas diffusion electrode and preparation method and application thereof | |
| CN114824331A (en) | Layered double-metal oxide negative electrode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |