CN103588192B - A kind of metal mixes the preparation method of order mesoporous carbon composite - Google Patents
A kind of metal mixes the preparation method of order mesoporous carbon composite Download PDFInfo
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Abstract
The invention discloses the preparation method that a kind of metal mixes order mesoporous carbon composite, comprising: (1) charcoal source presoma modulates to obtain AMP; (2) metal ion is blended: charcoal source precursor A MP adds in deionized water, obtains dark solution A, adds metal-salt presoma MS, obtains dark solution B; (3) self-assembly process: add BP, HCl and EtOH in dark solution B, obtains dark solution C; (4) ageing is dry: by ageing in dark solution C water-bath, make solution C and AMP fully carry out self-assembly; Obtain black precipitate after completing, throw out filters to obtain filter cake, filtration cakes torrefaction, obtains the complex body of AMP/ block polyether/metallic compound; (5) charing reduction: complex body temperature-gradient method in atmosphere charring furnace, insulation; Furnace cooling, obtains the ordered mesoporous carbon that metal mixes.The method employing raw materials cost is low, wide material sources; Carbon yield is high, and mesoporous carbon skeleton is fine and close, Stability Analysis of Structures; Aqua-mesophase can realize effectively mixing of metal oxide or metal ion.
Description
Technical field
The present invention relates to material manufacturing technology field, particularly relate to the preparation method that a kind of novel metal mixes order mesoporous carbon composite.
Background technology
Ordered mesoporous carbon not only has the general advantage of Carbon Materials, and has high-specific surface area, large pore volume, mesoporous orderly feature, if carry out the metals such as Co, Fe, Ni to the skeleton of ordered mesoporous carbon to mix the more excellent mesoporous composite material of availability.Based on above feature, ordered mesoporous carbon is widely used in fields such as catalysis, ultracapacitor, lithium-ion secondary celies.1999, (the Ryoo R such as Ryoo, Joo S H, Jun S.Synthesis of highly ordered carbon molecular sieves via template-mediatedstructural transformation [J] .J Phys Chem B, 1999,103 (37): 7743-7746.) proposing with ordered meso-porous silicon oxide is hard template, and dipping is containing carbon precursor wherein, obtains CMK-1 ordered mesoporous carbon by the method oppositely copied.After this, the ordered mesoporous carbon material such as SNU-1, CMK-3, CMK-5 occurs in succession.But the method is prepared ordered mesoporous carbon and be there is the shortcomings such as operation is many, consuming time, template cannot reclaim, environmental pollution, because the impact of carbon precursor diffusional resistance and the surface adsorption effect of template cause, the yield of ordered mesoporous carbon is low, defect is many simultaneously, is not suitable with suitability for industrialized production.Hard template method metal mixes general employing liquid-phase impregnation process or vapour deposition process, in charcoal source, namely add metallic compound or in advance metal compound solution is carried out liquid phase coating to template, but the method is dispersed to reaching metallic particles.After this, investigator proposes a kind of hard template method of improvement, is about to introduce reaction system containing carbon precursor and silicon source simultaneously, organic-organic, organic and inorganic self-assembly occurs and can obtain silicon oxide/charcoal complex mesoporous material, namely obtain ordered mesoporous carbon after removing silicon oxide.Existing patent by introducing the mesoporous carbon preparation method of a tensio-active agent self-assembling reaction system containing carbon precursor and silicon source simultaneously, without the need to carrying out charcoal source dipping, but the step such as this process still can not omit pickling or alkali is molten.Though the hard template method improved is easy to metal and mixes, the concentration and distribution that the process influence metal of follow-up removal silicon oxide mixes.From 2004, domestic and international multidigit investigator utilized self-assembly soft template method to prepare two dimension, three-dimensional structure ordered mesoporous carbon material.Compare hard template method, the method need not be introduced separately into charcoal source, and without the need to HF acid or NaOH washing, greatly the preparation section of mesoporous carbon has been lacked in letter, reduces manufacturing cost.Chinese patent 201010500123.3 discloses a kind of method being prepared ordered mesoporous carbon material by direct self-assembly; Chinese patent 200710120381.1 discloses a kind of method of preparing ordered mesoporous carbon with organic mould plate method; Chinese patent 200910033053.2 discloses a kind of preparation method of iron-carrying ordered mesoporous charcoal.These achievements in research almost have selected the reaction monomers of oligomeric resol or resol and organic formwork agent bar none and organic-organic self-assembly occurs prepare mesoporous carbon.And this resinoid carbon yield is low, after charing, structure is easily subsided, and causes aperture, pore volume reduction, causes material quality to decline, affect its end-use performance.
Summary of the invention
The object of the invention is to solve current soft template method, to prepare mesoporous carbon presoma range of choice narrow, and there is the problem that carbon yield is low, structural stability is poor, metal mixes difficulty, and propose a kind of presoma product being applicable to soft template method and preparing mesoporous carbon, and this precursor power metal is utilized to mix order mesoporous carbon composite.
Metal mixes a preparation method for order mesoporous carbon composite, and concrete steps are as follows:
(1) modulation of charcoal source presoma
After ground for charcoal source precursor material 100 mesh sieves, through nitration mixture oxidation-alkali cleaning-pickling-filtration process process, be prepared into charcoal source presoma-Aqua-mesophase that metal mixes order mesoporous carbon composite, net result is labeled as AMP;
(2) metal ion is blended
Under the condition of 25-40 DEG C, add in deionized water by step (1) gained charcoal source precursor A MP, even dark solution A to be mixed, under same agitation condition, add metal-salt presoma MS, continuing to stir obtains dark solution B;
(3) self-assembly process
In 25-40 DEG C, in step (2) gained dark solution B, add nonionogenic tenside BP, HCl solution and ethanol EtOH successively under agitation, adjusted to ph, to 2-3, stirs and obtains dark solution C;
(4) ageing is dry
The dark solution C stirred is placed in the water-bath ageing 5-60h that temperature is 70-90 DEG C, makes block polyether fully carry out self-assembly with the AMP mixing metal ion; Obtain black precipitate after completing, obtain filter cake after being filtered by throw out, filter cake is placed in the dry 1-3h of baking oven of 100 DEG C, obtain the complex body of AMP/ block polyether/metallic compound;
(5) charing reduction
Step (4) gained complex body is placed in atmosphere charring furnace, temperature-gradient method, insulation; Furnace cooling after thermal treatment completes, the final ordered mesoporous carbon obtaining metal and mix.
Further, described charcoal source precursor material is one or more mixtures in coal-tar pitch, thermopolymerization mesophase pitch, oil green coke, slag oil asphalt or naphthalene synthetic mesophase asphalt phase.
Further, described in step (2), metal-salt presoma MS is [Ni (H
2o)
6] (NO
3)
2, Fe (NO
3)
39H
2o, FeCl
3or NiCl
2in one.
Further, the quality proportioning adding each reactant in dark solution described in step (3) is: AMP:BP:H
2o:HCl:MS:EtOH=1.5 ~ 2.5:1.8 ~ 3.0:40.0 ~ 50.0:5.0 ~ 10:0.02 ~ 0.3:3.0 ~ 6.0.
Further, described HCl concentration is 37%.
Further, described agitation condition is 150 ~ 500rmp.
Further, block polyether nonionogenic tenside BP described in step (3) is polyethylene oxide (PEO)-poly(propylene oxide) (PPO)-polyethylene oxide (PEO), comprising F127(PEO
106-PPO
70-PEO
106), P123(PEO
20-PPO
70-PEO
20) or F108(PEO
132-PPO
50-PEO
132) in one or more.
Further, be nitrogen or argon gas in atmosphere charring furnace described in step (5).
Further, temperature-gradient method described in step (5), insulation, be first warming up to 180-300 DEG C with 1-3 DEG C/min, insulation 1-4h; Then 450-600 DEG C is warming up to 0.5-3 DEG C/min, insulation 1-3h; Continue to be warming up to 800-1050 DEG C of insulation 1-4h with 1-5 DEG C/min.
Compared with prior art, beneficial effect of the present invention is: (1) material cost is low, wide material sources; (2) starting material carbon yield is high, and the mesoporous carbon skeleton of preparation is fine and close, Stability Analysis of Structures; (3) Aqua-mesophase can realize effectively mixing of metal oxide or metal ion.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
The preparation method that a kind of ordered mesoporous carbon and metal thereof mix matrix material material comprises that the modulation of charcoal source presoma, metal ion are blended, self-assembly process, ageing are dry, charing reduction process.Its concrete steps are as follows:
(1) modulation of charcoal source presoma
After ground 100 mesh sieves of one or more mixtures in coal-tar pitch, thermopolymerization mesophase pitch, oil green coke, slag oil asphalt, naphthalene synthetic mesophase asphalt phase, through main processes such as nitration mixture oxidation-alkali cleaning-pickling-filtrations, be prepared into charcoal source presoma-Aqua-mesophase that metal mixes order mesoporous carbon composite, net result is labeled as AMP.
(2) metal ion is blended
Under the condition of 25-40 DEG C, add in deionized water by step (1) gained charcoal source precursor A MP, even dark solution A to be mixed, adds metal-salt presoma MS under same agitation condition; Stirring velocity: 150 ~ 500rmp, churning time: 0.5-5h, obtains homogeneous black solution B.
The described metal-salt MS of step (2) is [Ni (H
2o)
6] (NO
3)
2, Fe (NO
3)
39H
2o, FeCl
3or NiCl
2in one.
(3) self-assembly process
In 25-40 DEG C, in step (2) gained dark solution B, add nonionogenic tenside BP, 37%HCl, ethanol EtOH, stirring velocity: 150 ~ 500rmp, churning time: 1-5h successively under agitation; PH value: 2-3, obtains homogeneous black solution C;
The quality proportioning of final each reactant is:
AMP:BP:H
2O:HCl:MS:EtOH=1.5～2.5:1.8～3.0:40.0～50.0:5.0～10:0.02～0.3:3.0～6.0。
Block polyether nonionogenic tenside is selected to be structure directing agent in step (3).
Described block polyether nonionogenic tenside BP is polyethylene oxide (PEO)-poly(propylene oxide) (PPO)-polyethylene oxide (PEO), comprising F127(PEO
106-PPO
70-PEO
106) or P123(PEO
20-PPO
70-PEO
20) or F108(PEO
132-PPO
50-PEO
132) in one or more.
(4) ageing is dry
The dark solution C stirred is placed in the water-bath ageing 5-60h that temperature is 70-90 DEG C, makes block polyether fully carry out self-assembly with the AMP mixing metal ion; Obtain black precipitate after completing, obtain filter cake after being filtered by throw out, filter cake is placed in the dry 1-3h of baking oven of 100 DEG C, obtain the complex body of AMP/ block polyether/metallic compound.
(5) charing reduction
Step (4) gained complex body is placed in atmosphere charring furnace, under nitrogen or argon gas condition, 180-300 DEG C is warming up to 1-3 DEG C/min, insulation 1-4h, then be warming up to 450-600 DEG C with 0.5-3 DEG C/min, insulation 1-3h, continue to be warming up to 800-1050 DEG C of insulation 1-4h with 1-5 DEG C/min, tensio-active agent and low molecular weight substance are removed completely, and metal ion is reduced to metallic particles.Furnace cooling after thermal treatment completes, the final ordered mesoporous carbon obtaining metal and mix.
Below to add kind, the quantity of metal-salt, and in the mode of magnetic agitation, the present invention is elaborated.
Embodiment 1:
Coal tar pitch is obtained AMP according to the method for step (1).Take the AMP of 1.5g, be dissolved under 25 DEG C of conditions in the deionized water of 40ml, stir 4 hours to obtain dark solution A with 150rmp; To add 0.02gFe (NO under same agitation condition
3)
39H
2o, continues stirring and obtains dark solution B in 4 hours; In dark solution B, add the hydrochloric acid of 1.8g P123,3.0g ethanol, 5g37% subsequently successively, now the pH value of system should be less than 2, continues stirring 5 hours, obtain homogeneous black solution C with 150rmp; Dark solution C is placed in 90 DEG C of water-baths still aging 5 hours, obtains black precipitate, filter to obtain filter cake; Under 100 DEG C of conditions, dry cake obtains P123/AMP/Fe (NO in 1 hour
3)
3mixture; this mixture is placed in atmosphere charring furnace using nitrogen as shielding gas; rise to 180 DEG C with 3 DEG C/min by room temperature and be incubated 4 hours; then rise to 450 DEG C with 3 DEG C/min and be incubated 3 hours; rise to 800 DEG C with 1 DEG C/min subsequently and be incubated 4 hours, furnace cooling obtains the ordered mesoporous carbon material that Fe mixes.Prepared has following characteristics containing Fe ordered mesoporous carbon, and yield is 70%, and most probable pore size is 3.6nm, and specific surface area is 690m
2/ g.
Embodiment 2:
Coal tar pitch is obtained AMP according to the method for step (1).Take the AMP of 2.0g, be dissolved under 30 DEG C of conditions in the deionized water of 45ml, stir 3 hours to obtain dark solution A with 300rmp; 0.2gFe (NO is added at same temperature and agitation condition
3)
39H
2o, continues stirring and obtains dark solution B in 3 hours; In dark solution B, add the hydrochloric acid of 2.2g P123,4.0g ethanol, 8.0g37% subsequently successively, now the pH value of system should be less than 2, continues stirring 3 hours, obtain homogeneous black solution C with 300rmp; Dark solution C is placed in 80 DEG C of water-baths still aging 48 hours, obtains black precipitate, filter to obtain filter cake; Under 100 DEG C of conditions, dry cake obtains P123/AMP/Fe (NO in 1 hour
3)
3mixture; this mixture is placed in atmosphere charring furnace using nitrogen as shielding gas; rise to 240 DEG C with 3 DEG C/min by room temperature and be incubated 2 hours; then rise to 500 DEG C with 2 DEG C/min and be incubated 2 hours; rise to 900 DEG C with 2 DEG C/min subsequently and be incubated 3 hours, furnace cooling obtains the ordered mesoporous carbon material that Fe mixes.Prepared has following characteristics containing Fe ordered mesoporous carbon, and yield is 75%, and most probable pore size is 3.4nm, and specific surface area is 626m
2/ g.
Embodiment 3:
Coal tar pitch is obtained AMP according to the method for step 1.Take the AMP of 2.5g, be dissolved in the deionized water of 50ml under 30 DEG C of conditions, stir 2 hours to obtain dark solution A with 300rmp; 0.3gFe (NO is added at same temperature and agitation condition
3)
39H
2o, continues stirring and obtains dark solution B in 2 hours; In dark solution B, add the hydrochloric acid of 2.2g P123,6.0g ethanol, 10.0g37% subsequently successively, now the pH value of system should be less than 3, continues stirring 3 hours, obtain homogeneous black solution C with 300rmp; Dark solution C is placed in 70 DEG C of water-baths still aging 60 hours, obtains black precipitate, filter to obtain filter cake; Under 100 DEG C of conditions, dry cake obtains P123/AMP/Fe (NO in 1 hour
3)
3mixture; this mixture is placed in atmosphere charring furnace using nitrogen as shielding gas; rise to 300 DEG C with 2 DEG C/min by room temperature and be incubated 1 hour; then rise to 600 DEG C with 1 DEG C/min and be incubated 2 hours; rise to 1000 DEG C with 3 DEG C/min subsequently and be incubated 2 hours, furnace cooling obtains the ordered mesoporous carbon material that Fe mixes.Prepared has following characteristics containing Fe ordered mesoporous carbon, and yield is 68%, and most probable pore size is 3.3nm, and specific surface area is 610m
2/ g.
Embodiment 4:
Naphthalene synthetic mesophase asphalt phase is obtained AMP according to the method for step 1.Take the AMP of 2.0g, be dissolved under 30 DEG C of conditions in the deionized water of 40ml, stir 1 hour to obtain dark solution A with 400rmp; 0.1g FeCl is added at same temperature and agitation condition
3, continue stirring and obtain dark solution B in 1 hour; In dark solution B, add the hydrochloric acid of 2.5g P123,5.0g ethanol, 8.0g37% subsequently successively, now the pH value of system should be less than 3, continues stirring 1 hour, obtain homogeneous black solution C with 400rmp; Dark solution C is placed in 80 DEG C of water-baths still aging 30 hours, obtains black precipitate, filter to obtain filter cake; Under 100 DEG C of conditions, dry cake obtains P123/AMP/Fe (NO in 1 hour
3)
3mixture; this mixture is placed in atmosphere charring furnace using nitrogen as shielding gas; rise to 240 DEG C with 2 DEG C/min by room temperature and be incubated 2 hours; then rise to 450 DEG C with 1 DEG C/min and be incubated 2 hours; rise to 1050 DEG C with 4 DEG C/min subsequently and be incubated 1 hour, furnace cooling obtains the ordered mesoporous carbon material that Fe mixes.Prepared has following characteristics containing Fe ordered mesoporous carbon, and yield is 86%, and most probable pore size is 4.1nm, and specific surface area is 590m
2/ g.
Embodiment 5:
Naphthalene synthetic mesophase asphalt phase is obtained AMP according to the method for step 1.Take the AMP of 2.5g, be dissolved under 35 DEG C of conditions in the deionized water of 50ml, stir 0.5 hour to obtain dark solution A with 500rmp; 0.3g FeCl is added at same temperature and agitation condition
3, continue stirring and obtain dark solution B in 0.5 hour; In dark solution B, add the hydrochloric acid of 3.0g P123,6.0g ethanol, 10.0g37% subsequently successively, now the pH value of system should be less than 3, continues stirring 1 hour, obtain homogeneous black solution C with 500rmp; Dark solution C is placed in 90 DEG C of water-baths still aging 15 hours, obtains black precipitate, filter to obtain filter cake; Under 100 DEG C of conditions, dry cake obtains P123/AMP/Fe (NO in 1 hour
3)
3mixture; this mixture is placed in atmosphere charring furnace using nitrogen as shielding gas; rise to 300 DEG C with 2 DEG C/min by room temperature and be incubated 1 hour; then rise to 600 DEG C with 0.5 DEG C/min and be incubated 1 hour; rise to 1050 DEG C with 5 DEG C/min subsequently and be incubated 1 hour, furnace cooling obtains the ordered mesoporous carbon material that Fe mixes.Prepared has following characteristics containing Fe ordered mesoporous carbon, and yield is 79%, and most probable pore size is 3.9nm, and specific surface area is 575m
2/ g.
Embodiment 6:
Coal tar pitch is obtained AMP according to the method for step 1.Take the AMP of 2.4g, be dissolved under 25 DEG C of conditions in the deionized water of 50ml, stir 2 hours to obtain dark solution A with 300rmp; 0.08g [Ni (H is added at same temperature and agitation condition
2o)
6] (NO
3)
2, continue stirring and obtain dark solution B in 2 hours; In dark solution B, add the hydrochloric acid of 2.0g F127,4.0g ethanol, 5.0g37% subsequently successively, now the pH value of system should be less than 2, continues stirring 3 hours, obtain homogeneous black solution C with 300rmp; This dark solution is placed in 80 DEG C of water-baths still aging 40 hours, obtains black precipitate, filter to obtain filter cake; Under 100 DEG C of conditions, dry cake obtains F127/AMP/Ni (NO in 1 hour
3)
2mixture; this mixture is placed in atmosphere charring furnace using nitrogen as shielding gas; rise to 200 DEG C with 2 DEG C/min by room temperature and be incubated 3 hours; then rise to 450 DEG C with 3 DEG C/min and be incubated 3 hours; rise to 900 DEG C with 3 DEG C/min subsequently and be incubated 3 hours, furnace cooling obtains the ordered mesoporous carbon material that Ni mixes.Prepared has following characteristics containing Ni ordered mesoporous carbon, and yield is 78%, and most probable pore size is 3.8nm, and specific surface area is 676m
2/ g.
Embodiment 7:
Coal tar pitch is obtained AMP according to the method for step 1.Take the AMP of 2.5g, be dissolved under 30 DEG C of conditions in the deionized water of 50ml, stir 2 hours to obtain dark solution A with 300rmp; 0.2g NiCl is added at same temperature and agitation condition
2, continue stirring and obtain dark solution B in 2 hours; In dark solution B, add the hydrochloric acid of 2.2g F127,5.0g ethanol, 7.0g37% subsequently successively, now the pH value of system should be less than 2, continues stirring 3 hours, obtain homogeneous black solution C with 300rmp; Dark solution C is placed in 80 DEG C of water-baths still aging 36 hours, obtains black precipitate, filter to obtain filter cake; Under 100 DEG C of conditions, dry cake obtains F127/AMP/Ni (NO in 1 hour
3)
2mixture; this mixture is placed in atmosphere charring furnace using nitrogen as shielding gas; rise to 240 DEG C with 2 DEG C/min by room temperature and be incubated 2 hours; then rise to 500 DEG C with 2 DEG C/min and be incubated 2 hours; rise to 1000 DEG C with 3 DEG C/min subsequently and be incubated 2 hours, furnace cooling obtains the ordered mesoporous carbon material that Ni mixes.Prepared has following characteristics containing Ni ordered mesoporous carbon, and yield is 75%, and most probable pore size is 3.5nm, and specific surface area is 650m
2/ g.
Embodiment 8:
Naphthalene synthetic mesophase asphalt phase is obtained AMP according to the method for step 1.Take the AMP of 1.8g, be dissolved under 35 DEG C of conditions in the deionized water of 40ml, stir 1 hour to obtain dark solution A with 400rmp; 0.1g [Ni (H is added at same temperature and agitation condition
2o)
6] (NO
3)
2, continue stirring and obtain dark solution B in 1 hour; In dark solution B, add the hydrochloric acid of 2.0g F127,3.0g ethanol, 5.0g37% subsequently successively, now the pH value of system should be less than 2, continues stirring 2 hours, obtain homogeneous black solution C with 400rmp; Dark solution C liquid is placed in 80 DEG C of water-baths still aging 24 hours, obtains black precipitate, filter to obtain filter cake; Under 100 DEG C of conditions, dry cake obtains F127/AMP/Ni (NO in 1 hour
3)
2mixture; this mixture is placed in atmosphere charring furnace using nitrogen as shielding gas; rise to 300 DEG C with 2 DEG C/min by room temperature and be incubated 1 hour; then rise to 450 DEG C with 3 DEG C/min and be incubated 3 hours; rise to 1050 DEG C with 5 DEG C/min subsequently and be incubated 1 hour, furnace cooling obtains the ordered mesoporous carbon material that Ni mixes.Prepared has following characteristics containing Ni ordered mesoporous carbon, and yield is 84%, and most probable pore size is 3.9nm, and specific surface area is 610m
2/ g.
Embodiment 9:
Naphthalene synthetic mesophase asphalt phase is obtained AMP according to the method for step 1.Take the AMP of 2.0g, be dissolved under 40 DEG C of conditions in the deionized water of 40ml, stir 0.5 hour to obtain dark solution A with 500rmp; 0.3g [Ni (H is added at same temperature and agitation condition
2o)
6] (NO
3)
2, continue stirring and obtain dark solution B in 0.5 hour; In dark solution B, add the hydrochloric acid of 2.0g F127,6.0g ethanol, 5.0g37% subsequently successively, now the pH value of system should be less than 2, continues stirring 1 hour, obtain homogeneous black solution C with 500rmp; Dark solution C is placed in 80 DEG C of water-baths still aging 24 hours, obtains black precipitate, filter to obtain filter cake; Under 100 DEG C of conditions, dry cake obtains F127/AMP/Ni (NO in 3 hours
3)
2mixture; this mixture is placed in atmosphere charring furnace using nitrogen as shielding gas; rise to 300 DEG C with 2 DEG C/min by room temperature and be incubated 2 hours; then rise to 600 DEG C with 1 DEG C/min and be incubated 2 hours; rise to 1050 DEG C with 4 DEG C/min subsequently and be incubated 1 hour, furnace cooling obtains the ordered mesoporous carbon material that Ni mixes.Prepared has following characteristics containing Ni ordered mesoporous carbon, and yield is 80%, and most probable pore size is 3.5nm, and specific surface area is 585m
2/ g.
Embodiment 10:
Naphthalene synthetic mesophase asphalt phase is obtained AMP according to the method for step 1.Take the AMP of 2.5g, be dissolved in the deionized water of 40ml under 40 DEG C of conditions, stir 1 hour to obtain dark solution A with 500rmp; 0.3g NiCl is added at same temperature and agitation condition
2, continue stirring and obtain dark solution B in 1 hour; In dark solution B, add the hydrochloric acid of 2.5g F127,6.0g ethanol, 8.0g37% subsequently successively, now the pH value of system should be less than 2, continues stirring 1 hour, obtain homogeneous black solution C with 500rmp; Dark solution C is placed in 80 DEG C of water-baths still aging 24 hours, obtains black precipitate, filter to obtain filter cake; Under 100 DEG C of conditions, dry cake obtains F127/AMP/Ni (NO in 2 hours
3)
2mixture; this mixture is placed in atmosphere charring furnace using nitrogen as shielding gas; rise to 240 DEG C with 2 DEG C/min by room temperature and be incubated 2 hours; then rise to 600 DEG C with 1 DEG C/min and be incubated 3 hours; rise to 1000 DEG C with 5 DEG C/min subsequently and be incubated 2 hours, furnace cooling obtains the ordered mesoporous carbon material that Ni mixes.Prepared has following characteristics containing Ni ordered mesoporous carbon, and yield is 75%, and most probable pore size is 3.2nm, and specific surface area is 578m
2/ g.
Embodiment 11:
Naphthalene synthetic mesophase asphalt phase is obtained AMP according to the method for step 1.Take the AMP of 2.0g, be dissolved under 40 DEG C of conditions in the deionized water of 40ml, stir 1 hour to obtain dark solution A with 400rmp; 0.2g NiCl is added at same temperature and agitation condition
2, continue stirring and obtain dark solution B in 1 hour; In dark solution B, add the hydrochloric acid of 2.2g F108,5.0g ethanol, 6.0g37% subsequently successively, now the pH value of system should be less than 2, continues stirring 2 hours, obtain homogeneous black solution C with 400rmp; Dark solution C is placed in 80 DEG C of water-baths still aging 24 hours, obtains black precipitate, filter to obtain filter cake; Under 100 DEG C of conditions, dry cake obtains F108/AMP/Ni (NO in 1 hour
3)
2mixture; this mixture is placed in atmosphere charring furnace using nitrogen as shielding gas; rise to 200 DEG C with 3 DEG C/min by room temperature and be incubated 3 hours; then rise to 500 DEG C with 2 DEG C/min and be incubated 2 hours; rise to 900 DEG C with 2 DEG C/min subsequently and be incubated 3 hours, furnace cooling obtains the ordered mesoporous carbon material that Ni mixes.Prepared has following characteristics containing Ni ordered mesoporous carbon, and yield is 78%, and most probable pore size is 3.3nm, and specific surface area is 584m
2/ g.
Embodiment 12:
Naphthalene synthetic mesophase asphalt phase is obtained AMP according to the method for step 1.Take the AMP of 2.4g, be dissolved under 35 DEG C of conditions in the deionized water of 50ml, stir 1 hour to obtain dark solution A with 500rmp; 0.3g [Ni (H is added under same temperature agitation condition
2o)
6] (NO
3)
2, continue stirring and obtain dark solution B in 1 hour; In dark solution B, add the hydrochloric acid of 0.8gP123,1.6g F127,5.0g ethanol, 10.0g37% subsequently successively, now the pH value of system should be less than 2, continues stirring 1 hour, obtain homogeneous black solution C with 500rmp; Dark solution C is placed in 80 DEG C of water-baths still aging 5 hours, obtains black precipitate, filter to obtain filter cake; Under 100 DEG C of conditions, dry cake obtains P123/F127/AMP/Ni (NO in 1 hour
3)
2mixture; this mixture is placed in atmosphere charring furnace using nitrogen as shielding gas; rise to 300 DEG C with 2 DEG C/min by room temperature and be incubated 2 hours; then rise to 600 DEG C with 0.5 DEG C/min and be incubated 3 hours; rise to 1050 DEG C with 4 DEG C/min subsequently and be incubated 1 hour, furnace cooling obtains the ordered mesoporous carbon material that Ni mixes.Prepared has following characteristics containing Ni ordered mesoporous carbon, and yield is 82%, and most probable pore size is 4.0nm, and specific surface area is 638m
2/ g.
Above content is in conjunction with concrete preferred implementation further description made for the present invention; can not assert that the specific embodiment of the present invention is only limitted to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made, all should be considered as belonging to the present invention by submitted to claims determination scope of patent protection.
Claims (4)
1. metal mixes a preparation method for order mesoporous carbon composite, it is characterized in that, concrete steps are as follows:
(1) modulation of charcoal source presoma
By after ground for charcoal source precursor material 100 mesh sieves through nitration mixture oxidation-alkali cleaning-pickling-filtration process process, be prepared into charcoal source presoma-Aqua-mesophase that metal mixes order mesoporous carbon composite, net result is labeled as AMP;
(2) metal ion is blended
Under the condition of 25-40 DEG C, add in deionized water by step (1) gained charcoal source precursor A MP, stir to obtain dark solution A, adds metal-salt presoma MS under same agitation condition, and continuing to stir obtains dark solution B;
(3) self-assembly process
In 25-40 DEG C, in step (2) gained dark solution B, add nonionogenic tenside BP, HCl solution and ethanol EtOH successively under agitation, adjusted to ph, to 2-3, stirs and obtains dark solution C;
(4) ageing is dry
The dark solution C stirred is placed in the water-bath ageing 5-60h that temperature is 70-90 DEG C, makes block polyether fully carry out self-assembly with the AMP mixing metal ion; Obtain black precipitate after completing, obtain filter cake after being filtered by throw out, filter cake is placed in the dry 1-3h of baking oven of 100 DEG C, obtain the complex body of AMP/ block polyether/metallic compound;
(5) charing reduction
Step (4) gained complex body is placed in atmosphere charring furnace, temperature-gradient method, insulation; Furnace cooling after thermal treatment completes, the final ordered mesoporous carbon obtaining metal and mix;
Described charcoal source precursor material is one or more mixtures in coal-tar pitch, thermopolymerization mesophase pitch, oil green coke, slag oil asphalt or naphthalene synthetic mesophase asphalt phase;
Described in step (2), metal-salt presoma MS is [Ni (H
2o)
6] (NO
3)
2, Fe (NO
3)
39H
2o, FeCl
3or NiCl
2in one;
Step (2) with the quality proportioning of each reactant described in (3) is:
AMP:BP:H
2O:HCl:MS:EtOH＝1.5～2.5:1.8～3.0:40.0～50.0:5.0～10:0.02～0.3:3.0～6.0；
Described agitation condition is 150 ~ 500rpm;
Temperature-gradient method described in step (5), insulation, be first warming up to 180-300 DEG C with 1-3 DEG C/min, insulation 1-4h; Then 450-600 DEG C is warming up to 0.5-3 DEG C/min, insulation 1-3h; Continue to be warming up to 800-1050 DEG C of insulation 1-4h with 1-5 DEG C/min.
2. metal according to claim 1 mixes the preparation method of order mesoporous carbon composite, it is characterized in that, described HCl concentration is 37%.
3. metal according to claim 1 mixes the preparation method of order mesoporous carbon composite, it is characterized in that, nonionogenic tenside BP described in step (3) is polyethylene oxide (PEO)-poly(propylene oxide) (PPO)-polyethylene oxide (PEO), comprising F127 (PEO
106-PPO
70-PEO
106), P123 (PEO
20-PPO
70-PEO
20) or F108 (PEO
132-PPO
50-PEO
132) in one or more.
4. metal according to claim 1 mixes the preparation method of order mesoporous carbon composite, it is characterized in that, is nitrogen or argon gas in atmosphere charring furnace described in step (5).
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| CN101585529A (en) * | 2008-05-23 | 2009-11-25 | 北京化工大学 | Method for in-situ preparation of ordered mesoporous carbon/metal composite material by organic template method |
| CN102745677A (en) * | 2012-07-06 | 2012-10-24 | 同济大学 | Collaborative graphitization method for amorphous carbon material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101585529A (en) * | 2008-05-23 | 2009-11-25 | 北京化工大学 | Method for in-situ preparation of ordered mesoporous carbon/metal composite material by organic template method |
| CN102745677A (en) * | 2012-07-06 | 2012-10-24 | 同济大学 | Collaborative graphitization method for amorphous carbon material |
Non-Patent Citations (4)
| Title |
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| A family of ordered mesoporous carbons derived from mesophase pitch using ordered mesoporous silicas as templates;Liang Cao et al.;《Adsorption》;20100731;第16卷;第466页第2栏第1段 * |
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