CN102931418A - 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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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 material preparation method, specifically take mesopore silicon oxide as hard template, prepare mesoporous carbonization nitrogen material by the nanometer casting method, then utilizing halogenated hydrocarbons to carry out alkylated reaction makes carbonization nitrogen surface quaternized, relending the mode that helps ion-exchange makes the anionic group with noble metal replace the halogen ion, it is bundled in material surface, uses at last reducing agent reducing metal ion, prepare the method for mesoporous carbonization nitrogen supported precious metal nano-particle material.
Background technology
Metallic is owing to physics, the chemical property of its uniqueness have caused widely concern 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 control method of the size of numerous noble metal nano particles and pattern, the big or small pattern by mesopore orbit load and restriction nano noble metal particles is a kind of method commonly used, can prepare dynamical composite mesoporous functional material catalyst.
Ordered mesoporous molecular sieve is owing to 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 because the high surface energy of metal nanoparticle the coacervation that in preparation process, occurs.With Pt, can be formed with the Subjective and Objective material of dual-use function in the duct of the noble metals such as Au introducing molecular sieve.Metal nanoparticle is incorporated in the mesopore orbit, just need to utilizes organo-functional group guiding or grafting to fix and the reducing metal nano particle on the mesoporous material surface.But the functionalization of mesoporous substrate relates to a plurality of steps, needs to consume the plenty of time, may make ordered mesoporous material and metallic poisoning and deactivation, even destroys the structure of mesoporous material.Therefore for mesoporous material, seeking 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 take SBA-15 as template, ethylenediamine and carbon tetrachloride simply pour into polymerization reaction and generate the material with carbon element that order mesoporous nitrogen mixes.Embedded-NH is arranged on its duct wall
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 there is certain difficulty in the mesoporous material of the noble metal nano particles load that synthetic load capacity is higher.
Summary of the invention
The objective of the invention is to utilize prior art to reach 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 method, lean on the ionic bond combination between noble metal precursor and the mesoporous material, compare with electrostatic attraction, can in conjunction with tightr.And noble metal granule is distributed on the ordered mesoporous material preferably, forms noble metal/nitrogen carbon composite, and 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 kind of preparation method of mesoporous carbonization nitrogen supported precious metal nano-particle, characteristics are that the method comprises following concrete steps:
Synthesizing of a, order mesoporous carbonization nitrogen material
SBA-15, carbon tetrachloride, ethylenediamine are mixed 60～120 ℃ of heating reflux reactions 2～4 hours, 60～100 ℃ of dried overnight, then be placed in the quartz ampoule, in 40ml/min pure nitrogen gas atmosphere, be heated to 300～600 ℃, keep making it carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 3～10h with 25% hydrofluoric acid solution, use deionized water, ethanol washing several, drying 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 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, add hot reflux 1～24h under 90～180 ℃, suction filtration, gained solid are 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, then mix with the product that step b obtains, stir 0.5～5h, suction filtration with the distilled water washing, obtains the 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
4To entirely molten, stir 0.5～2h in the solution, suction filtration with the distilled water washing, obtains described mesoporous carbonization nitrogen supported precious metal nano-particle.
The present invention is take 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 the nitrogen-doped carbon surface quaternized, relending the mode that helps ion-exchange makes the anionic group with noble metal replace the halogen ion, it is bundled in material surface, use at last 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:
⑴, utilize ionic bond in conjunction with precursor and the mesoporous material of slaine first, make tightr that the slaine precursor is combined with material.
⑵, prepared material noble metal can Uniform Dispersion, the characteristic of composite material concurrent nano metal and the advantages of mesoporous material.
⑶, the prepared material cell cathode catalyst that acts as a fuel has good catalytic effect to hydrogen reduction, carries platinum with traditional carbon and platinum alloy catalyst is compared, conservation, and economy is easy to get.
Description of drawings
Fig. 1 is the XRD diffraction pattern of resulting materials of the present invention; Wherein: figure A is the XRD small-angle diffraction; Figure B is the 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, the Oxygen Condition.
Embodiment
The invention will be further described by the following examples:
Embodiment 1
Synthesizing of a, order mesoporous carbonization nitrogen material
With 1g SBA-15, the 6g carbon tetrachloride, the 2.7g ethylenediamine mixes with certain proportion, 60 ℃ of heating reflux reaction 4h, then dried overnight is placed in the quartz ampoule, heat 600 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making in 2 hours the material carbonization, obtain brown-black powder; The gained brown-black powder is stirred 3h with 25% the hydrofluoric acid solution of 50mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.5g, be dissolved in the 100mLDMF solution, then add the iodomethane of 5.6g, under 100 ℃, add hot reflux 0.5h, suction filtration, the gained solid is used respectively distilled water, and the acetone washing is then dry.
Producing of c, noble metal anionic compound
The 0.26g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 50mL
4In the solution, stir 0.5h, suction filtration, with the distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Synthesizing of a, order mesoporous carbonization nitrogen material
With 1g SBA-15, the 6g carbon tetrachloride, the 2.7g ethylenediamine mixes with certain proportion, 100 ℃ of heating reflux reaction 4h, then dried overnight is placed in the quartz ampoule, heat 300 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making in 4 hours the material carbonization, obtain brown-black powder; The gained brown-black powder is stirred 4h with 25% the hydrofluoric acid solution of 50mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.5g, be dissolved in the 100mLDMF solution, then add the iodomethane of 14g, under 90 ℃, added hot reflux 5 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.8g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 100mL
4In the solution, stir 1h, suction filtration, with the distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Synthesizing of a, order mesoporous carbonization nitrogen material
With 2gSBA-15, the 12g carbon tetrachloride, the 5.4g ethylenediamine mixes with certain proportion, 100 ℃ of heating reflux reaction 3h, then dried overnight is placed in the quartz ampoule, heat 500 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making in 4 hours the material carbonization, obtain brown-black powder; The gained brown-black powder is stirred 10h with 25% the hydrofluoric acid solution of 100mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.5g, be dissolved in the 100mLDMF solution, then add the iodomethane of 7g, under 120 ℃, added hot reflux 10 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.4g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 50mL
4In the solution, stir 2h, suction filtration, with the distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 4
Synthesizing of a, order mesoporous carbonization nitrogen material
With 1g SBA-15, the 6g carbon tetrachloride, the 2.7g ethylenediamine mixes with certain proportion, 60 ℃ of heating reflux reaction 3h, then dried overnight is placed in the quartz ampoule, heat 300 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making in 4 hours the material carbonization, obtain brown-black powder; The gained brown-black powder is stirred 8h with 25% the hydrofluoric acid solution of 50mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.5g, be dissolved in the 100mLDMF solution, then add the iodomethane of 2.8g, under 120 ℃, added hot reflux 12 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.13g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 50mL
4In the solution, stir 1h, suction filtration, with the distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 5
Synthesizing of a, order mesoporous carbonization nitrogen material
With 2g SBA-15, the 12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 90 ℃ of heating reflux reactions 4 hours, then dried overnight is placed in the quartz ampoule, heats 600 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making the material carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 6h with 25% the hydrofluoric acid solution of 100mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.8g, be dissolved in the 150mLDMF solution, then add the iodoethane of 0.772g, under 150 ℃, added hot reflux 4 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.05g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 50mL
4In the solution, stir 0.5h, suction filtration, with the distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 6
Synthesizing of a, order mesoporous carbonization nitrogen material
With 2g SBA-15, the 12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 90 ℃ of heating reflux reactions 4 hours, then 100 ℃ of dried overnight are placed in the quartz ampoule, heat 600 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making the material carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 3h with 25% the hydrofluoric acid solution of 100mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.8g, be dissolved in the 150mLDMF solution, then add the iodoethane of 3.088g, under 180 ℃, added hot reflux 1 hour, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 1.02g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 200mL
4In the solution, stir 1h, suction filtration, with the distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 7
Synthesizing of a, order mesoporous carbonization nitrogen material
With 2g SBA-15, the 12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 90 ℃ of heating reflux reactions 4 hours, then dried overnight is placed in the quartz ampoule, heats 600 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making the material carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 10h with 25% the hydrofluoric acid solution of 100mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.8g, be dissolved in the 150mLDMF solution, then add the n-propyl chloride of 0.4g, under 100 ℃, added hot reflux 6 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.01g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 50mL
4In the solution, stir 1h, suction filtration, with the distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 8
Synthesizing of a, order mesoporous carbonization nitrogen material
With 2g SBA-15, the 12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 90 ℃ of heating reflux reactions 4 hours, then dried overnight is placed in the quartz ampoule, heats 400 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making the material carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 10h with 25% the hydrofluoric acid solution of 100mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.8g, be dissolved in the 150mLDMF solution, then add the n-propyl chloride of 1.78g, under 90 ℃, added hot reflux 24 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.02g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 50mL
4In the solution, stir 0.5h, suction filtration, with the distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 9
Synthesizing of a, order mesoporous carbonization nitrogen material
With 1g SBA-15, the 6g carbon tetrachloride, 2.7g ethylenediamine mixes with certain proportion, 90 ℃ of heating reflux reactions 4 hours, then 100 ℃ of dried overnight are placed in the quartz ampoule, heat 500 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making the material carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 10h with 25% the hydrofluoric acid solution of 50mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.5g, be dissolved in the 100mLDMF solution, then add the iodomethane of 5.6g, under 90 ℃, added hot reflux 20 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.22g gold chloride is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 100mL
4In the solution, stir 0.5h, suction filtration, with the distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Synthesizing of a, order mesoporous carbonization nitrogen material
With 1g SBA-15, the 6g carbon tetrachloride, 2.7g ethylenediamine mixes with certain proportion, 90 ℃ of heating reflux reactions 4 hours, then 100 ℃ of dried overnight are placed in the quartz ampoule, heat 600 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making the material carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 10h with 25% the hydrofluoric acid solution of 50mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.5g, be dissolved in the 100mLDMF solution, then add the iodomethane of 1.5g, under 120 ℃, added hot reflux 5 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.42g gold chloride is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 100mL
4In the solution, stir 0.5h, suction filtration, with the 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
With 2g SBA-15, the 12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 90 ℃ of heating reflux reactions 4 hours, then 100 ℃ of dried overnight are placed in the quartz ampoule, heat 600 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making the material carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 8h with 25% the hydrofluoric acid solution of 100mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.8g, be dissolved in the 150mLDMF solution, then add the iodoethane of 7.72g, under 100 ℃, added hot reflux 20 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.2g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 100mL
4In the solution, stir 1h, suction filtration, with the 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 with 2g150 ℃ of hydro-thermal preparation, the 12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 90 ℃ of heating reflux reactions 4 hours, then 100 ℃ of dried overnight are placed in the quartz ampoule, heat 600 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making the material carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 8h with 25% the hydrofluoric acid solution of 100mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.8g, be dissolved in the 150mLDMF solution, then add the iodoethane of 1.544g, under 160 ℃, added hot reflux 2 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.03g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 50mL
4In the solution, stir 1h, suction filtration, with the 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 with 1g150 ℃ of hydro-thermal preparation, the 6g carbon tetrachloride, 2.7g ethylenediamine mixes with certain proportion, 90 ℃ of heating reflux reactions 4 hours, then 100 ℃ of dried overnight are placed in the quartz ampoule, heat 600 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making the material carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 10h with 25% the hydrofluoric acid solution of 50mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.5g, be dissolved in the 100mLDMF solution, then add the n-propyl chloride of 2.225g, under 100 ℃, added hot reflux 16 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.11g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 50mL
4In the solution, stir 30min, suction filtration, with the 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 with 1g150 ℃ of hydro-thermal preparation, the 6g carbon tetrachloride, 2.7g ethylenediamine mixes with certain proportion, 90 ℃ of heating reflux reactions 4 hours, then 100 ℃ of dried overnight are placed in the quartz ampoule, heat 600 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making the material carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 10h with 25% the hydrofluoric acid solution of 50mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.5g, be dissolved in the 100mLDMF solution, then add the n-propyl chloride of 0.356g, under 160 ℃, added hot reflux 5 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.01g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 100mL
4In the solution, stir 1.5h, suction filtration, with the 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 with 1g150 ℃ of hydro-thermal preparation, the 6g carbon tetrachloride, 2.7g ethylenediamine mixes with certain proportion, 90 ℃ of heating reflux reactions 4 hours, then 100 ℃ of dried overnight are placed in the quartz ampoule, heat 600 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making the material carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 10h with 25% the hydrofluoric acid solution of 50mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.5g, be dissolved in the 100mLDMF solution, then add the n-propyl chloride of 1.78g, under 110 ℃, added hot reflux 10 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.01g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 50mL
4In the solution, stir 0.5h, suction filtration, with the distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Embodiment 16
Synthesizing of a, carbonization nitrogen material
SBA-15 with 2g150 ℃ of hydro-thermal preparation, the 12g carbon tetrachloride, 5.4g ethylenediamine mixes with certain proportion, 80 ℃ of heating reflux reactions 4 hours, then dried overnight is placed in the quartz ampoule, heats 600 ℃ of lower reaching in the 40ml/min pure nitrogen gas atmosphere, keep making the material carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 10h with 25% the hydrofluoric acid solution of 100mL, use deionized water, ethanol washing several, drying obtains described order mesoporous carbonization nitrogen material.
The preparation of b, alkylation halogen ionic compound
Get the order mesoporous carbonization nitrogen material of 0.8g, be dissolved in the 150mLDMF solution, then add the 1-chlorobutane of 3.56g, under 100 ℃, added hot reflux 8 hours, suction filtration, the gained solid is used respectively distilled water, the acetone washing.Then dry.
Producing of c, noble metal anionic compound
The 0.02g chloroplatinic acid is joined wiring solution-forming in the 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 the NaBH of the 0.1M of 50mL
4In the solution, stir 0.5h, suction filtration, with the distilled water washing, products therefrom is mesoporous carbonization nitrogen supported precious metal nano-particle.
Claims (1)
1. the preparation method of a mesoporous carbonization nitrogen supported precious metal nano-particle, be characterised in that: the method comprises following concrete steps:
Synthesizing of a, order mesoporous carbonization nitrogen material
SBA-15, carbon tetrachloride, ethylenediamine are mixed 60～120 ℃ of heating reflux reactions 2～4 hours, 60～100 ℃ of dried overnight, then be placed in the quartz ampoule, in 40ml/min pure nitrogen gas atmosphere, be heated to 300～600 ℃, keep making it carbonization in 4 hours, obtain brown-black powder; The gained brown-black powder is stirred 3～10h with 25% hydrofluoric acid solution, use deionized water, ethanol washing several, drying 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 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, add hot reflux 1～24h under 90～180 ℃, suction filtration, gained solid are 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, then mix with the product that step b obtains, stir 0.5～5h, suction filtration with the distilled water washing, obtains the 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
4To entirely molten, stir 0.5～2h in the solution, suction filtration with the distilled water washing, obtains described mesoporous carbonization nitrogen supported precious metal nano-particle.
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