CN102931418B - Preparation method of mesoporous carbon nitride loaded precious nano particle - Google Patents
Preparation method of mesoporous carbon nitride loaded precious nano particle Download PDFInfo
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- CN102931418B CN102931418B CN201210416030.1A CN201210416030A CN102931418B CN 102931418 B CN102931418 B CN 102931418B CN 201210416030 A CN201210416030 A CN 201210416030A CN 102931418 B CN102931418 B CN 102931418B
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Abstract
The invention discloses a preparation method of a mesoporous carbon nitride loaded precious nano particle, which comprises the steps of: with mesoporous silica as a hard template, preparing a mesoporous nitrogen-doped carbon material by using a nano pouring method; then carrying out alkylation reaction by using halohydrocarbon to ensure that the nitrogen-doped carbon surface is subjected to quaternization; enabling an anion group with precious metals to replace a halide ion by means of an ion exchange method, binding on the surface of the material; and finally reducing metal ions by using a reducing agent, and preparing the mesoporous carbon nitride loaded precious nano particle. According to the method, a precious metal particle precursor and a mesoporous material are tightly combined by means of an ion bond, and the precious metal particle is well dispersed on the ordered mesoporous material to form a precious metal/nitrogen carbon compound material. The mesoporous carbon nitride loaded precious nano particle has the activity of the precious nano particle and is high in specific area and large in hole volume of a mesoporous molecular sieve. The mesoporous carbon nitride loaded precious nano particle has excellent catalysis activity and catalysis stability for cathode oxygen reduction of a fuel cell, and has a potential commercial application prospect.
Description
Technical field
The present invention relates to the preparation method of material, specifically taking mesopore silicon oxide as hard template, prepare mesoporous carbonization nitrogen material by nanometer casting method, then utilizing halogenated hydrocarbons to carry out alkylated reaction makes carbonization nitrogen surface quaternized, relend and help the mode of ion-exchange to make to replace halogen ion with the anionic group of noble metal, be bundled in material surface, finally used reducing agent reducing metal ion, prepared the method for mesoporous carbonization nitrogen supported precious metal nano-particle material.
Background technology
Metallic is because physics, the chemical property of its uniqueness have caused widely and paid close attention at catalysis, separation, magnetic, photoelectricity and microelectronic.The special nature of these metallics depends on their size, shape, crystal structure and organizational parameter.In the size of numerous noble metal nano particles and the control method of pattern, be a kind of conventional method by the big or small pattern of mesopore orbit load and restriction nano noble metal particles, can prepare dynamical composite mesoporous functional material catalyst.
Ordered mesoporous molecular sieve is because aperture and the high specific area of well-regulated pore passage structure, homogeneous are widely used in the fields such as separation, absorption and catalysis.Mesoporous material can allow between reactant molecule as catalyst carrier and reaction molecular and catalytic active component between contact more fully, and can reduce the high surface energy due to metal nanoparticle, the coacervation occurring in preparation process.By Pt, in the duct of the noble metal introducing molecular sieves such as Au, can be formed with the Subjective and Objective material of dual-use function.Metal nanoparticle is incorporated in mesopore orbit, just need to utilizes organo-functional group guiding or grafting to fix and reducing metal nano particle on mesoporous material surface.But the functionalization of mesoporous substrate relates to multiple steps, need to consume the plenty of time, may make ordered mesoporous material and metallic poisoning and deactivation, even destroy the structure of mesoporous material.Therefore for mesoporous material, finding a kind of stable embedded functional group, to form stable nano particle be very important.Recently, Vinu etc. has reported a kind of preparation method of order mesoporous carbon-nitrogen material.By taking SBA-15 as template, ethylenediamine and carbon tetrachloride simply pour into polymerization reaction and generate the material with carbon element of order mesoporous nitrogen doping.On its duct wall, there is embedded-NH
2can provide a platform for the nano particle that forms metal nanoparticle and metal oxide with-NH functional group.But in synthetic process, just make metallic precursor and the combination of mesoporous carbonization nitrogen material by electrostatic attraction, this active force is very weak, and metallic precursor is easy to come off, and thinks that the mesoporous material of the noble metal nano particles load that synthetic load capacity is higher exists certain difficulty.
Summary of the invention
The object of the invention is to utilize prior art and for the deficiencies in the prior art, a kind of method of New Type of Mesoporous carbonization nitrogen supported precious metal nano-particle material is provided, in this kind of method, between noble metal precursor and mesoporous material, lean on ionic bond combination, compared with electrostatic attraction, can in conjunction with tightr.And noble metal granule is distributed on ordered mesoporous material preferably, form noble metal/nitrogen carbon composite, the activity of the existing noble metal nano particles of this material has again the high-specific surface area of mesopore molecular sieve and large pore volume; This material has presented superior catalytic activity and catalytic stability to the cathodic oxygen reduction of fuel cell, has potential commercial application prospect.
The concrete technical scheme that realizes the object of the invention is:
A preparation method for mesoporous carbonization nitrogen supported precious metal nano-particle, feature is that the method comprises following concrete steps:
Synthesizing of a, order mesoporous carbonization nitrogen material
SBA-15, carbon tetrachloride, ethylenediamine are mixed to 60～120 DEG C of heating reflux reactions 2～4 hours, 60～100 DEG C of dried overnight, then be placed in quartz ampoule, in 40ml/min pure nitrogen gas atmosphere, be heated to 300～600 DEG C, keep within 4 hours, making it carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 3～10h with 25% hydrofluoric acid solution, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material; Wherein: the mass ratio of SBA-15, carbon tetrachloride, ethylenediamine is 1:6:2.7; 25% hydrofluoric acid consumption is every gram of brown-black powder 20mL;
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material that step a obtains, add DMF solution to entirely molten, then add halogenated alkane, at 90～180 DEG C, add hot reflux 1～24h, suction filtration, gained solid is respectively with distilled water, acetone washing; Then dry in baking oven; Obtain alkylation halogen ionic compound; Wherein: the mass ratio of order mesoporous nitrogen-doped carbon quality of materials and halogenated alkane is 1:0.5～3; Described halogenated alkane is iodomethane, iodoethane, n-propyl chloride or 1-chlorobutane;
The preparation of c, noble metal anionic compound
Get precious metal salt and add deionized water to entirely molten, the product then obtaining with step b mixes, and stirs 0.5～5h, and suction filtration, with distilled water washing, obtains noble metal anionic compound; Wherein: precious metal salt is 5:1～100 with the ratio of the amount of substance of halogenated alkane; Described precious metal salt is chloroplatinic acid or gold chloride;
The reduction of d, noble metal
Get the NaBH that product that step c obtains joins 0.1M
4in solution, to entirely molten, stir 0.5～2h, suction filtration, with distilled water washing, obtains described mesoporous carbonization nitrogen supported precious metal nano-particle.
The present invention is taking mesopore silicon oxide as hard template, build the mesoporous carbonization nitrogen material of preparation by nanometer, then utilizing halogenated hydrocarbons to carry out alkylated reaction makes nitrogen-doped carbon surface quaternized, relend and help the mode of ion-exchange to make to replace halogen ion with the anionic group of noble metal, be bundled in material surface, finally use reducing agent reducing metal ion, prepare mesoporous carbonization nitrogen supported precious metal nano-particle material.
The present invention compared with prior art, has following distinguishing feature:
(1) utilize, first precursor and the mesoporous material of ionic bond in conjunction with slaine, what make that slaine precursor is combined with material is tightr.
(2), prepared material noble metal can be uniformly dispersed, the characteristic of composite material concurrent nano metal and the advantage of mesoporous material.
, prepared material is as fuel battery cathod catalyst, and hydrogen reduction is had to good catalytic effect, carry platinum and platinum alloy catalyst with traditional carbon compared with, conservation, economy is easy to get.
Brief description of the drawings
Fig. 1 is the XRD diffraction pattern of resulting materials of the present invention; Wherein: figure A is XRD small-angle diffraction; Figure B is big angle diffraction;
Fig. 2 is the transmission electron microscope picture of resulting materials of the present invention;
Fig. 3 is resulting materials isothermal adsorption desorption curve of the present invention and graph of pore diameter distribution; Wherein: figure A is isothermal adsorption desorption curve chart; Figure B is graph of pore diameter distribution;
Fig. 4 be resulting materials of the present invention in 0.1M KOH electrolyte, the cyclic voltammogram of the glass-carbon electrode under saturated nitrogen, Oxygen Condition.
Embodiment
The invention will be further described by the following examples:
Embodiment 1
Synthesizing of a, order mesoporous carbonization nitrogen material
By 1g SBA-15,6g carbon tetrachloride, 2.7g ethylenediamine mixes with certain proportion, 60 DEG C of heating reflux reaction 4h, dried overnight, is then placed in quartz ampoule, at 600 DEG C and in 40ml/min pure nitrogen gas atmosphere, heat, keep within 2 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 3h with 25% the hydrofluoric acid solution of 50mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.5g, is dissolved in 100mLDMF solution, then adds the iodomethane of 5.6g, adds hot reflux 0.5h at 100 DEG C, suction filtration, and gained solid is used respectively distilled water, and acetone washing is then dry.
Producing of c, noble metal anionic compound
0.26g chloroplatinic acid is joined to wiring solution-forming in 20mL water, and with the dried product mix and blend of step b 0.5h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 50mL
4in solution, stir 0.5h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 2
Synthesizing of a, order mesoporous carbonization nitrogen material
By 1g SBA-15,6g carbon tetrachloride, 2.7g ethylenediamine mixes with certain proportion, 100 DEG C of heating reflux reaction 4h, dried overnight, is then placed in quartz ampoule, at 300 DEG C and in 40ml/min pure nitrogen gas atmosphere, heat, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 4h with 25% the hydrofluoric acid solution of 50mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.5g, is dissolved in 100mLDMF solution, then adds the iodomethane of 14g, at 90 DEG C, adds hot reflux 5 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.8g chloroplatinic acid is joined to wiring solution-forming in 40mL water, and with the dried product mix and blend of step b 0.5h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 100mL
4in solution, stir 1h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 3
Synthesizing of a, order mesoporous carbonization nitrogen material
By 2gSBA-15,12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 100 DEG C of heating reflux reaction 3h, dried overnight, is then placed in quartz ampoule, at 500 DEG C and in 40ml/min pure nitrogen gas atmosphere, heat, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 10h with 25% the hydrofluoric acid solution of 100mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.5g, is dissolved in 100mLDMF solution, then adds the iodomethane of 7g, at 120 DEG C, adds hot reflux 10 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.4g chloroplatinic acid is joined to wiring solution-forming in 20mL water, and with the dried product mix and blend of step b 1h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 50mL
4in solution, stir 2h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 4
Synthesizing of a, order mesoporous carbonization nitrogen material
By 1g SBA-15,6g carbon tetrachloride, 2.7g ethylenediamine mixes with certain proportion, 60 DEG C of heating reflux reaction 3h, dried overnight, is then placed in quartz ampoule, at 300 DEG C and in 40ml/min pure nitrogen gas atmosphere, heat, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 8h with 25% the hydrofluoric acid solution of 50mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.5g, is dissolved in 100mLDMF solution, then adds the iodomethane of 2.8g, at 120 DEG C, adds hot reflux 12 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.13g chloroplatinic acid is joined to wiring solution-forming in 20mL water, and with the dried product mix and blend of step b 2h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 50mL
4in solution, stir 1h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 5
Synthesizing of a, order mesoporous carbonization nitrogen material
By 2g SBA-15,12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 90 DEG C of heating reflux reactions 4 hours, dried overnight, is then placed in quartz ampoule, at 600 DEG C and in 40ml/min pure nitrogen gas atmosphere, heats, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 6h with 25% the hydrofluoric acid solution of 100mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.8g, is dissolved in 150mLDMF solution, then adds the iodoethane of 0.772g, at 150 DEG C, adds hot reflux 4 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.05g chloroplatinic acid is joined to wiring solution-forming in 10mL water, and with the dried product mix and blend of step b 4h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 50mL
4in solution, stir 0.5h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 6
Synthesizing of a, order mesoporous carbonization nitrogen material
By 2g SBA-15,12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 90 DEG C of heating reflux reactions 4 hours, 100 DEG C of dried overnight, are then placed in quartz ampoule, at 600 DEG C and in 40ml/min pure nitrogen gas atmosphere, heat, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 3h with 25% the hydrofluoric acid solution of 100mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.8g, is dissolved in 150mLDMF solution, then adds the iodoethane of 3.088g, at 180 DEG C, adds hot reflux 1 hour, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
1.02g chloroplatinic acid is joined to wiring solution-forming in 20mL water, and with the dried product mix and blend of step b 2h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 200mL
4in solution, stir 1h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 7
Synthesizing of a, order mesoporous carbonization nitrogen material
By 2g SBA-15,12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 90 DEG C of heating reflux reactions 4 hours, dried overnight, is then placed in quartz ampoule, at 600 DEG C and in 40ml/min pure nitrogen gas atmosphere, heats, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 10h with 25% the hydrofluoric acid solution of 100mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.8g, is dissolved in 150mLDMF solution, then adds the n-propyl chloride of 0.4g, at 100 DEG C, adds hot reflux 6 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.01g chloroplatinic acid is joined to wiring solution-forming in 10mL water, and with the dried product mix and blend of step b 0.5h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 50mL
4in solution, stir 1h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 8
Synthesizing of a, order mesoporous carbonization nitrogen material
By 2g SBA-15,12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 90 DEG C of heating reflux reactions 4 hours, dried overnight, is then placed in quartz ampoule, at 400 DEG C and in 40ml/min pure nitrogen gas atmosphere, heats, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 10h with 25% the hydrofluoric acid solution of 100mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.8g, is dissolved in 150mLDMF solution, then adds the n-propyl chloride of 1.78g, at 90 DEG C, adds hot reflux 24 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.02g chloroplatinic acid is joined to wiring solution-forming in 10mL water, and with the dried product mix and blend of step b 4h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 50mL
4in solution, stir 0.5h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 9
Synthesizing of a, order mesoporous carbonization nitrogen material
By 1g SBA-15,6g carbon tetrachloride, 2.7g ethylenediamine mixes with certain proportion, 90 DEG C of heating reflux reactions 4 hours, 100 DEG C of dried overnight, are then placed in quartz ampoule, at 500 DEG C and in 40ml/min pure nitrogen gas atmosphere, heat, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 10h with 25% the hydrofluoric acid solution of 50mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.5g, is dissolved in 100mLDMF solution, then adds the iodomethane of 5.6g, at 90 DEG C, adds hot reflux 20 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.22g gold chloride is joined to wiring solution-forming in 40mL water, and with the dried product mix and blend of step b 2h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 100mL
4in solution, stir 0.5h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 10
Synthesizing of a, order mesoporous carbonization nitrogen material
By 1g SBA-15,6g carbon tetrachloride, 2.7g ethylenediamine mixes with certain proportion, 90 DEG C of heating reflux reactions 4 hours, 100 DEG C of dried overnight, are then placed in quartz ampoule, at 600 DEG C and in 40ml/min pure nitrogen gas atmosphere, heat, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 10h with 25% the hydrofluoric acid solution of 50mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.5g, is dissolved in 100mLDMF solution, then adds the iodomethane of 1.5g, at 120 DEG C, adds hot reflux 5 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.42g gold chloride is joined to wiring solution-forming in 40mL water, and with the dried product mix and blend of step b 4h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 100mL
4in solution, stir 0.5h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle material.
Embodiment 11
Synthesizing of a, order mesoporous carbonization nitrogen material
By 2g SBA-15,12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 90 DEG C of heating reflux reactions 4 hours, 100 DEG C of dried overnight, are then placed in quartz ampoule, at 600 DEG C and in 40ml/min pure nitrogen gas atmosphere, heat, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 8h with 25% the hydrofluoric acid solution of 100mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.8g, is dissolved in 150mLDMF solution, then adds the iodoethane of 7.72g, at 100 DEG C, adds hot reflux 20 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.2g chloroplatinic acid is joined to wiring solution-forming in 20mL water, and with the dried product mix and blend of step b 2h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 100mL
4in solution, stir 1h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle material.
Embodiment 12
Synthesizing of a, order mesoporous carbonization nitrogen material
SBA-15 prepared by 2g150 DEG C of hydro-thermal, 12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 90 DEG C of heating reflux reactions 4 hours, 100 DEG C of dried overnight, are then placed in quartz ampoule, at 600 DEG C and in 40ml/min pure nitrogen gas atmosphere, heat, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 8h with 25% the hydrofluoric acid solution of 100mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.8g, is dissolved in 150mLDMF solution, then adds the iodoethane of 1.544g, at 160 DEG C, adds hot reflux 2 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.03g chloroplatinic acid is joined to wiring solution-forming in 10mL water, and with the dried product mix and blend of step b 1h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 50mL
4in solution, stir 1h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 13
Synthesizing of a, order mesoporous carbonization nitrogen material
SBA-15 prepared by 1g150 DEG C of hydro-thermal, 6g carbon tetrachloride, 2.7g ethylenediamine mixes with certain proportion, 90 DEG C of heating reflux reactions 4 hours, 100 DEG C of dried overnight, are then placed in quartz ampoule, at 600 DEG C and in 40ml/min pure nitrogen gas atmosphere, heat, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 10h with 25% the hydrofluoric acid solution of 50mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.5g, is dissolved in 100mLDMF solution, then adds the n-propyl chloride of 2.225g, at 100 DEG C, adds hot reflux 16 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.11g chloroplatinic acid is joined to wiring solution-forming in 20mL water, and with the dried product mix and blend of step b 3h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 50mL
4in solution, stir 30min, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 14
Synthesizing of a, order mesoporous carbonization nitrogen material with carbon element
SBA-15 prepared by 1g150 DEG C of hydro-thermal, 6g carbon tetrachloride, 2.7g ethylenediamine mixes with certain proportion, 90 DEG C of heating reflux reactions 4 hours, 100 DEG C of dried overnight, are then placed in quartz ampoule, at 600 DEG C and in 40ml/min pure nitrogen gas atmosphere, heat, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 10h with 25% the hydrofluoric acid solution of 50mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.5g, is dissolved in 100mLDMF solution, then adds the n-propyl chloride of 0.356g, at 160 DEG C, adds hot reflux 5 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.01g chloroplatinic acid is joined to wiring solution-forming in 10mL water, and with the dried product mix and blend of step b 0.5h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 100mL
4in solution, stir 1.5h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 15
Synthesizing of a, order mesoporous carbonization nitrogen material
SBA-15 prepared by 1g150 DEG C of hydro-thermal, 6g carbon tetrachloride, 2.7g ethylenediamine mixes with certain proportion, 90 DEG C of heating reflux reactions 4 hours, 100 DEG C of dried overnight, are then placed in quartz ampoule, at 600 DEG C and in 40ml/min pure nitrogen gas atmosphere, heat, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 10h with 25% the hydrofluoric acid solution of 50mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.5g, is dissolved in 100mLDMF solution, then adds the n-propyl chloride of 1.78g, at 110 DEG C, adds hot reflux 10 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.01g chloroplatinic acid is joined to wiring solution-forming in 10mL water, and with the dried product mix and blend of step b 1h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 50mL
4in solution, stir 0.5h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 16
Synthesizing of a, carbonization nitrogen material
SBA-15 prepared by 2g150 DEG C of hydro-thermal, 12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 80 DEG C of heating reflux reactions 4 hours, dried overnight, is then placed in quartz ampoule, at 600 DEG C and in 40ml/min pure nitrogen gas atmosphere, heats, keep within 4 hours, making material carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 10h with 25% the hydrofluoric acid solution of 100mL, and with deionized water, ethanol washing for several times, dry, obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
The order mesoporous carbonization nitrogen material of getting 0.8g, is dissolved in 150mLDMF solution, then adds the 1-chlorobutane of 3.56g, at 100 DEG C, adds hot reflux 8 hours, suction filtration, and gained solid is used respectively distilled water, acetone washing.Then dry.
Producing of c, noble metal anionic compound
0.02g chloroplatinic acid is joined to wiring solution-forming in 10mL water, and with the dried product mix and blend of step b 2h, suction filtration, washs with distilled water.
The reduction of d, noble metal
Step c product is joined to the NaBH of the 0.1M of 50mL
4in solution, stir 0.5h, suction filtration, with distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Claims (1)
1. a preparation method for mesoporous carbonization nitrogen supported precious metal nano-particle, is characterised in that: the method comprises following concrete steps:
Synthesizing of a, mesoporous carbonization nitrogen material
SBA-15, carbon tetrachloride, ethylenediamine are mixed to 60～120 DEG C of heating reflux reactions 2～4 hours, 60～100 DEG C of dried overnight, then be placed in quartz ampoule, in 40ml/min pure nitrogen gas atmosphere, be heated to 300～600 DEG C, keep within 4 hours, making it carbonization, obtain brown-black powder; Gained brown-black powder is stirred to 3～10h with 25% hydrofluoric acid solution, and with deionized water, ethanol washing for several times, dry, obtains described mesoporous carbonization nitrogen material; Wherein: the mass ratio of SBA-15, carbon tetrachloride, ethylenediamine is 1:6:2.7; 25% hydrofluoric acid consumption is every gram of brown-black powder 20mL;
The preparation of b, alkylation halogen ionic compound
Get the mesoporous carbonization nitrogen material that step a obtains, add DMF solution to entirely molten, then add halogenated alkane, at 90～180 DEG C, add hot reflux 1～24h, suction filtration, gained solid is respectively with distilled water, acetone washing; Then dry in baking oven; Obtain alkylation halogen ionic compound; Wherein: the mass ratio of mesoporous carbonization nitrogen material quality and halogenated alkane is 1:0.5～3; Described halogenated alkane is iodomethane, iodoethane, n-propyl chloride or 1-chlorobutane;
The preparation of c, noble metal anionic compound
Get precious metal salt and add deionized water to entirely molten, the product then obtaining with step b mixes, and stirs 0.5～5h, and suction filtration, with distilled water washing, obtains noble metal anionic compound; Wherein: precious metal salt is 5:1～100 with the ratio of the amount of substance of halogenated alkane; Described precious metal salt is chloroplatinic acid or gold chloride;
The reduction of d, noble metal
Get the NaBH that product that step c obtains joins 0.1M
4in solution, to entirely molten, stir 0.5～2h, suction filtration, with distilled water washing, obtains described mesoporous carbonization nitrogen supported precious metal nano-particle.
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