CN106563432B - The method that carbon-supported transition metal silicide is prepared by rice husk - Google Patents
The method that carbon-supported transition metal silicide is prepared by rice husk Download PDFInfo
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- CN106563432B CN106563432B CN201610997357.0A CN201610997357A CN106563432B CN 106563432 B CN106563432 B CN 106563432B CN 201610997357 A CN201610997357 A CN 201610997357A CN 106563432 B CN106563432 B CN 106563432B
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- rice husk
- transition metal
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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Abstract
The invention discloses the methods for preparing carbon-supported transition metal silicide by rice husk, are related to catalysis material preparation method.The invention solves it is existing prepare transition metal silicide method exist to equipment requirement it is higher, accuracy controlling is also required to response parameter, low output, is unfavorable for the technical issues of fairly large production.The method of the present invention：One, rice husk is crushed to obtain rice husk fragment, by it is negatively charged or positively charged it is surfactant modified arrive rice husk fractal surfaces, washed successively with distilled water and ethyl alcohol, drying；Two, preparing metal deionized water solution, is added pore creating material, stirs after supersound process, adds through step 1 treated rice husk fragment, stirring wash with distilled water and ethyl alcohol successively, and drying obtains reacting precursor；Three, presoma is carbonized under an inert atmosphere and obtains carbon-supported transition metal silicide.Product of the present invention is used for electrochemical catalysis liberation of hydrogen.
Description
Technical field
The invention belongs to utilize agriculture waste biomass, simple and prepare with scale catalysis material.More particularly to rice husk
Surface modification is carried out, the silicon of homogeneous distribution is as silicon source using in rice husk, using the lignin of rice husk itself, cellulose as in situ
Carbon source introduces the ion for containing Fe, Co, Ni, W, Mo, V as source metal, and carburizing reagent under an inert atmosphere synchronizes to obtain silication
Object/carbon composite.
Background technology
Transition metal silicide due to its with high-melting-point, low-resistivity, preferable conductivity of heat and excellent high temperature resistant,
Have been widely used for the fields such as heating element, integrated circuit and high-temperature oxidation resistant coating.It is prepared by traditional transition metal silicide
Method includes dissolved salt reaction technology, chemical vapour deposition technique, chemical vapor transport method, temperature programming ihrigising etc..These technologies
Method preparation condition is harsh, process is complicated, control difficult (such as chemical vapour deposition technique, chemical vapor transport method, temperature programming
Ihrigising is required for being passed through SiH4And H2Mixed gas, the proportioning of gas, flow velocity, duration of ventilation have a direct impact product),
And products obtained therefrom specific surface area is small, specific surface area is small<5m2/ g, low output, yield are generally less than 20%, limit transition gold
Belong to research and application of the silicide as catalysis material.On the other hand, transition metal silicide belongs to metal gap compound,
It is applied to catalytic hydrogenation reaction in chemical catalysis industry, however its application in electrocatalytic hydrogen evolution field is less.
Invention content
The preparation condition of existing method is harsh, such as fused salt reaction technology needs autoclave, lava stove.
The control of existing method is difficult, such as chemical vapour deposition technique, chemical vapor transport method, temperature programming ihrigising are all
It needs to be passed through SiH4And H2Mixed gas, the proportioning of gas, flow velocity, duration of ventilation have a direct impact product.
The invention solves it is existing prepare transition metal silicide method exist to equipment requirement it is higher, to response parameter
The technical issues of needing accurately to regulate and control, low output, being unfavorable for fairly large production；And provide prepared by rice husk it is carbon-supported
The method of transition metal silicide.
For the present invention using rice husk as carbon source in situ, silicon source introduces transition metal sun thereto by surface modification treatment
Ion, anion obtain presoma, and further it is carbonized under an inert atmosphere obtains carbon-supported transition metal silicide.
In order to solve the above technical problems, the method that the present invention prepares carbon-supported transition metal silicide by rice husk, special
Sign is that this method carries out in the steps below：
Step 1: rice husk crushes to obtain rice husk fragment, surfactant modified rice husk is arrived by negatively charged or positively charged
Fractal surfaces are washed with distilled water and ethyl alcohol successively, drying；
Step 2: preparing metal deionized water solution, is added pore creating material, stirs, added through at step 1 after supersound process
Rice husk fragment after reason, stirring, is washed with distilled water and ethyl alcohol successively, is dried, and reaction precursor is obtained；
Step 3: then carbonization obtains carbon-supported transition metal silicide under inert atmosphere；
When step 1 rice husk fractal surfaces modify electronegative surface activating agent, aqueous metallic ions described in step 2 be iron from
The aqueous metallic ions of son, cobalt ions or nickel ion, when step 1 rice husk fractal surfaces modify positive surface activating agent, step
Two aqueous metallic ions are the aqueous metallic ions of tungstate radicle, vanadic acid root or molybdate.
Pore creating material described in step 2 is ZnCl2。
The method of modification of surfaces activating agent is as follows in step 1：Rice husk fragment is added at solution in surfactant formulatory,
Ultrasonic power is ultrasonically treated 15min under conditions of being 100W, is 25 DEG C~30 DEG C in rotating speed 400r/min~500r/min, temperature
Under the conditions of stir 2h~5h, stand 2h；Mixing speed is easy very much to blend on rice husk soon.
Electronegative surfactant described in step 1 is lauryl sodium sulfate (SDS), neopelex
(SDBS) or stearic acid.
Positively charged surfactant described in step 1 is polyethyleneimine (PEI), cetyl trimethylammonium bromide
(CTAB), dioctadecyl dimethyl ammonium chloride (DODMAC) or quaternary ammonium compound.
Drying temperature described in step 1 is 60~80 DEG C, and drying time is 24 hours.
Step 2 ultrasonic power be 100W under conditions of be ultrasonically treated 15min, rotating speed 400r/min~500r/min,
Temperature stirs 5h or more under the conditions of being 25 DEG C~30 DEG C.Drying temperature described in step 2 is 60~80 DEG C, and drying time is
24 hours.
The reaction precursor that step 2 obtains is placed in tube furnace in step 3, with the speed of 100ml~180ml/min
It is passed through inert gas, is raised to 1000 DEG C~1200 DEG C, constant temperature 3h from room temperature with the heating rate of 5 DEG C/min, furnace cooling.It is described
Inert gas is argon gas or nitrogen.
The carbon-supported silicide yield that method using the present invention obtains is high, and response parameter can be reached without stringent regulation and control
To 37%, be conducive to mass produce.
Rice husk is rich in cellulose, lignin and silica, can be as natural carbon source and silicon source.The method of the present invention pair
Rice husk surface carries out specified substituent (such as sulfonic group, amino) modification, will produce special surface group, so that
It has variability and Modulatory character on the Nomenclature Composition and Structure of Complexes.
China is the first in the world Chan Dao big countries, accounts for 1/3 or more of world's paddy total output, will generate tens million of tons of rice every year
Shell waste, because its density is small, volume is big, and pollution is caused to environment.The present invention, which realizes, carries out enormous amount rice husk
It recycles, is translated into the higher new material of added value, to handling Grain Industry waste, Sustainable Development environment warp
Ji plays an important role.
The present invention is not high to equipment requirement, can be carried out reacting using the common tubular type furnace apparatus in laboratory；The present invention's
Response parameter is easily controllable, argon gas or nitrogen is passed through in reaction process as protective gas, protective gas is not involved in chemical anti-
It answers, is passed through the flow velocity of protection gas, flow does not influence reaction；The yield of the present invention is high, and yield is conducive to solve up to 46.5%
Certainly the technical issues of fairly large production.
Products application of the present invention is in electrochemical catalysis liberation of hydrogen.
Description of the drawings
Fig. 1 is the x-ray powder that one method of specific implementation mode prepares carbon-supported transition metal iron suicide (FeSi/C)
Diffraction spectra；Fig. 2 is business 20%Pt/C and FeSi/C in 0.1mol/l sulfuric acid (H2SO4) electrocatalytic hydrogen evolution reacts in electrolyte
Linear scan (LSV) curve.
Specific implementation mode
Specific implementation mode one：The method that carbon-supported transition metal silicide is prepared by rice husk in present embodiment,
It is characterized in that this method carries out in the steps below：
Step 1: rice husk crushes to obtain rice husk fragment, lauryl sodium sulfate takes after being configured to 0.05mol/l aqueous solutions
3g rice husk fragments are added in 50mL, 15min are ultrasonically treated under conditions of ultrasonic power is 100W, in rotating speed 500r/min, room temperature
Under the conditions of stir 2h, stand 2h, washed with distilled water and ethyl alcohol, dried 24 hours under the conditions of 60 DEG C successively；
Step 2: compound concentration is the FeCl of 2mol/l39g ZnCl are added in aqueous solution 150ml2As pore creating material, super
Acoustical power be 100W under conditions of be ultrasonically treated 15min, then in rotating speed 500r/min, stir 10h under room temperature, add
Through step 1 treated rice husk fragment, in rotating speed 500r/min, 10h is stirred under room temperature, uses distilled water and ethyl alcohol successively
Washing, is dried 24 hours under the conditions of 80 DEG C, obtains reaction precursor；
Step 3: the reaction precursor that step 2 obtains is placed in ceramic boat, then it is placed in tube furnace, with 100ml/
The speed of min is passed through nitrogen, is raised to 1000 DEG C from room temperature under an inert atmosphere with the heating rate of 5 DEG C/min, constant temperature 3h, with stove
It is cooling；Obtain carbon-supported transition metal silicide (FeSi/C).Carbon in product comes from rice husk itself lignin, fiber
The carbonization of element, since metal precursor Fe3+ has the function of at high temperature by carbon catalyzed graphitization, the C in FeSi/C
For graphitized carbon, this point is conducive to improve electron transfer rate in electrocatalytic reaction.
As shown in Figure 1, product contains iron suicide and graphitic carbon.
Platinum is generally acknowledged at present to the optimal catalyst of electrochemistry evolving hydrogen reaction, but its resource scarcity, expensive.By scheming
2 it is found that graphitic carbon prepared by present embodiment method loads the starting of iron suicide (FeSi/C) evolving hydrogen reaction under acid system
Current potential (36mV) is close to the hydrogen-evolution overpotential of noble metal platinum, and the current density of catalytic hydrogen evolution can be with business 20%Pt/C phases
It carries and mentioning in the same breath.
Yield is 46.5% in present embodiment.
Specific implementation mode two：The method that carbon-supported transition metal silicide is prepared by rice husk in present embodiment,
It is characterized in that this method carries out in the steps below：
Step 1: rice husk crushes to obtain rice husk fragment, polyethyleneimine takes 50mL after being configured to 0.05mol/l aqueous solutions,
3g rice husk fragments are added, 15min are ultrasonically treated under conditions of ultrasonic power is 100W, in rotating speed 400r/min, room temperature condition
Lower stirring 2h stands 2h, is washed with distilled water and ethyl alcohol, dried 24 hours under the conditions of 60 DEG C successively；
Step 2: sodium tungstate (the Na of configuration 2mol/l2WO4) aqueous solution 150ml, 9g ZnCl are added2(pore creating material), super
Acoustical power be 100W under conditions of be ultrasonically treated 15min, then in rotating speed 400r/min, stir 10h under room temperature, add
Through step 1 treated rice husk fragment, in rotating speed 400r/min, 10h is stirred under room temperature, uses distilled water and ethyl alcohol successively
Washing, is dried 24 hours under the conditions of 80 DEG C, obtains reaction precursor；
Step 3: the reaction precursor that step 2 obtains is placed in ceramic boat, then it is placed in tube furnace, with 180ml/
The speed of min is passed through nitrogen, is raised to 1000 DEG C from room temperature under an inert atmosphere with the heating rate of 5 DEG C/min, constant temperature 3h, with stove
It is cooling；Obtain carbon-supported transition metal silicide.
Yield is 45.8% in present embodiment.
Claims (10)
1. the method for preparing carbon-supported transition metal silicide by rice husk, it is characterised in that this method is to carry out in the steps below
's：
Step 1: rice husk crushes to obtain rice husk fragment, surfactant modified rice husk fragment is arrived by negatively charged or positively charged
Surface is washed with distilled water and ethyl alcohol successively, drying；
Step 2: preparing metal deionized water solution, is added pore creating material, stirs, added after step 1 is handled after supersound process
Rice husk fragment, stirring, washed successively with distilled water and ethyl alcohol, drying, obtain precursors；
Step 3: the precursors that step 2 obtains are carbonized under argon gas or nitrogen obtains carbon-supported transition metal silicon
Compound；
When step 1 rice husk fractal surfaces modify electronegative surface activating agent, aqueous metallic ions described in step 2 be iron ion,
The aqueous metallic ions of cobalt ions or nickel ion, when step 1 rice husk fractal surfaces modify positive surface activating agent, step 2
The aqueous metallic ions are tungstate radicle, molybdate or vanadic acid root.
2. the method for preparing carbon-supported transition metal silicide by rice husk according to claim 1, it is characterised in that step
Pore creating material described in two is ZnCl2。
3. the method for preparing carbon-supported transition metal silicide by rice husk according to claim 1, it is characterised in that step
The method of modification of surfaces activating agent is as follows in one：Surfactant formulatory is added rice husk fragment, is in ultrasonic power at solution
It is ultrasonically treated 15min under conditions of 100W, is stirred under the conditions of rotating speed 400r/min~500r/min, temperature are 25 DEG C~30 DEG C
2h~5h stands 2h.
4. the method for preparing carbon-supported transition metal silicide by rice husk according to claim 1, it is characterised in that step
Electronegative surfactant described in one is lauryl sodium sulfate (SDS), neopelex (SDBS) or tristearin
Acid.
5. the method for preparing carbon-supported transition metal silicide by rice husk according to claim 1, it is characterised in that step
Positively charged surfactant described in one is polyethyleneimine (PEI), cetyl trimethylammonium bromide (CTAB) or double ten
Eight alkyl dimethyl ammonium chlorides (DODMAC).
6. the method for preparing carbon-supported transition metal silicide by rice husk according to claim 1, it is characterised in that step
Drying temperature described in one and two is 60~80 DEG C, and drying time is 24 hours.
7. the method for preparing carbon-supported transition metal silicide by rice husk according to claim 1, it is characterised in that step
Two ultrasonic power be 100W under conditions of be ultrasonically treated 15min, rotating speed 400r/min~500r/min, temperature be 25 DEG C~
5h or more is stirred under the conditions of 30 DEG C.
8. the method for preparing carbon-supported transition metal silicide by rice husk according to claim 1, it is characterised in that step
The reaction precursor that step 2 obtains is placed in tube furnace in three, indifferent gas is passed through with the speed of 100ml~180ml/min
Body is raised to 1000 DEG C~1200 DEG C, constant temperature 3h, furnace cooling with the heating rate of 5 DEG C/min from room temperature.
9. the method for preparing carbon-supported transition metal silicide by rice husk according to claim 1, it is characterised in that step
The negatively charged or positively charged aqueous surfactant solution of a concentration of 0.05mol/l of 50ml is added in one in every 3g rice husk fragments
In.
10. the method for preparing carbon-supported transition metal silicide by rice husk according to claim 1, it is characterised in that with 3g
Rice husk fragment calculates, and the aqueous metallic ions of a concentration of 2mol/l of 150ml are added in step 2, and pore creating material addition is 9g.
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Patent Citations (5)
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| CN101456552A (en) * | 2009-01-06 | 2009-06-17 | 黑龙江大学 | In-situ synchronous synthesizing method of tungsten carbide/graphitic carbon nano complexes |
| CN102784621A (en) * | 2012-08-29 | 2012-11-21 | 西南科技大学 | Method for preparing biomass adsorption material based on modified rice husks |
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Non-Patent Citations (1)
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| Silicon-Based Materials from Rice Husks and Their Applications;Luyi Sun,et.al.;《Ind. Eng. Chem. Res.》;20011031;第5861-5877页 * |
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