Extra small multicomponent alloy composite material, preparation method and its application
Technical field
The present invention relates to technical field of nano material more particularly to extra small multicomponent alloy composite material, preparation method and
It is applied.
Background technique
In recent years, alloy is a kind of important industrial multiphase catalyst, and compared with single metal component, catalysis is stablized
Property, activity and selectivity are all greatly improved.The partial size of metal nanoparticle, composition, surface texture and with carrier
The parameters such as interfacial interaction have very high influence to the catalytic performance of metal supported catalyst.With the reduction of particle size,
Alloy shows some special performances.
Up to the present, it has therefore already been proposed that various methods form microminiature bimetallic cluster, such as dendrimer
Template, polymer protection and liquid phase reduction are directly heat-treated molecular metal organic precursor method, Co-SEA method and surface
Inorganic metal chemical method.All there are many drawbacks in the above method, the catalyst of first method and second method is all liquid phase
Reduction, it is limited with reactant mass transfer in catalytic process by polymer wrapped, while Macroscopic single crystal is comparatively laborious;Third
What kind synthetic method obtained is non-uniform particle size, cannot be mass produced;4th kind of synthetic method, synthetic method by
PH limitation, carrying capacity are relatively low;5th kind of synthetic method is confined to bianry alloy, and particle size is inhomogenous.
In order to obtain the high quality support type alloy catalyst of uniform-dimension, homogeneous component, it is being converted to alloy nanoparticle
Before son, it is necessary to first by metal precursor uniform deposition carrier surface without assemble.There is provided as a result, it is a kind of it is uniform, stablize and
The alloy nano composite material of super-small is of great significance.
Summary of the invention
Present invention solves the technical problem that be to provide it is a kind of it is uniform, stablize and the alloy nano-material of super-small and its
Preparation method.
In view of this, this application provides a kind of extra small multicomponent alloy composite materials, the mesoporous carbon including sulfur doping and negative
It is loaded in the extra small alloying pellet of the mesoporous carbon surface of the sulfur doping;The average-size of the extra small alloying pellet is 2nm.
Preferably, the load capacity of the extra small alloying pellet is 1wt%~20wt%.
Preferably, the metallic element of the extra small alloying pellet be selected from Pt, Rh, Pd, Ir, Ru, Al, Sc, Ti, V, Cr,
Two kinds in Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Cd, In, Sn, Sb, Bi, Pb, Re, W, Ta and Hf or with
On.
Present invention also provides the preparation methods of the extra small multicomponent alloy composite material, comprising the following steps:
The mesoporous carbon of sulfur doping, metal salt presoma and solvent are mixed, obtain original mixture after dry;The metal
Salt precursor body is the metal salt presoma of two or more different metal element;
The original mixture is heat-treated under reducing atmosphere, obtains extra small multicomponent alloy composite material;It is described
400~800 DEG C of the temperature of heat treatment.
Preferably, the preparation method of the mesoporous carbon of the sulfur doping specifically:
By sulfur-bearing small organic molecule, SiO2Bead and transition metal salt are mixed in solvent, and high-temperature calcination after drying obtains
Carbon material;
It is sequentially etched the carbon material using sodium hydroxide and sulfuric acid, obtains the mesoporous carbon of sulfur doping.
Preferably, the sulfur-bearing small organic molecule is 2,2 '-bithiophenes, and transition metal salt is selected from cabaltous nitrate hexahydrate;Institute
State sulfur-bearing small molecule, SiO2The molar ratio of bead and transition metal salt is 2:2:1;The temperature of the calcining is 600~1200
℃。
Preferably, two kinds or more in precious metal salt and base metal salt of the metal salt presoma;It is described expensive
Precious metal element in metal salt is selected from one of Pt, Rh, Pd, Ir and Ru or a variety of, your non-gold in the base metal salt
Belong to element be selected from Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Cd, In, Sn, Sb, Bi,
One of Pb, Re, W, Ta and Hf or a variety of.
Preferably, the reducing atmosphere is hydrogen atmosphere or hydrogen mixed gas atmosphere;The hydrogen mixed gas atmosphere is selected from
The gaseous mixture of the gaseous mixture of hydrogen and nitrogen, the gaseous mixture of hydrogen and argon gas or hydrogen and carbon monoxide.
Preferably, the heating rate of the heat treatment is 2~20 DEG C/min, and the time is 0.5~12h.
Present invention also provides extra small multicomponent alloy composite material described above or extra small multicomponent alloys described above
The preparation method of composite material is applied in heterocatalysis.
This application provides a kind of extra small multicomponent alloy composite materials comprising the mesoporous carbon of sulfur doping and is carried on described
The extra small alloying pellet of the mesoporous carbon surface of sulfur doping, the composite material is uniform, stablizes, and the alloying pellet of super-small is carrying
The mesoporous carbon surface of body sulfur doping is distributed.
It is first that sulfur doping is mesoporous present invention also provides a kind of preparation method of extra small multicomponent alloy composite material
Carbon, metal salt presoma and solvent mixing obtain original mixture, then original mixture are heat-treated to get arriving after dry
Extra small multicomponent alloy composite material;The application use sulfur doping mesoporous carbon have the function of fixing metal well, can be
Alloying pellet provides enough anchor points, to improve the stability of extra small multicomponent alloy composite material, it is suppressed that extra small more
The sintering and reunion of first alloy;Simultaneously by adjusting the temperature of heat treatment, so that it is 2nm's that multicomponent alloy, which forms average-size,
Extra small alloying pellet, stable is carried on the mesoporous carbon surface of sulfur doping.
On the other hand, the preparation method of extra small multicomponent alloy composite material provided by the present application has most of metal general
Adaptive, and can be used as the catalyst of heterocatalysis, there is unique activity and stability.
Detailed description of the invention
Fig. 1 is 5wt%Pt-Co in the embodiment of the present invention 1, in embodiment 6 the extra small alloy of 5wt%Pt-Ir X-ray photoelectricity
The datagram of S element in sub- power spectrum (XPS);
Fig. 2 is that the x-ray powder of 5wt%Pt-Co and the extra small alloy of other parts binary that the embodiment of the present invention 1 provides spread out
Firing table levies map;
The HAADF-mapping that Fig. 3 is the 5wt%Pt-Co that the embodiment of the present invention 1 provides characterizes map;
Fig. 4 is that the line for the 5wt%Pt-Co that the embodiment of the present invention 1 provides sweeps characterization map;
The TPR table that Fig. 5 is the 5wt%Pt-Co that the embodiment of the present invention 1 provides levies map;
Fig. 6 is the X-ray powder diffraction for the extra small alloy of 5wt%Pt-Pb-Ru-Rh quaternary that the embodiment of the present invention 8 provides
Characterization;
Fig. 7 is the 5wt%Pt-Co that provides of the embodiment of the present invention 1 in parachloronitrobenzene selective hydrogenation dynamics number
According to figure;
Fig. 8 is the 5wt%Pt-Co that provides of the embodiment of the present invention 1 in parachloronitrobenzene selective hydrogenation stability column diagram;
Fig. 9 is the 5wt%Pt-Bi that provides of the embodiment of the present invention 9 in benzyl alcohol selective oxidation reaction kinetics datagram.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
In view of the status of the extra small alloying pellet composite material of support type, this application provides a kind of extra small multicomponent alloy is compound
Material and preparation method thereof, multi-nary alloy particles in extra small multicomponent alloy composite material provided by the present application are stable to be carried on
The mesoporous carbon surface of sulfur doping, and due to the high forces of S and metal, so that alloying pellet size is extra small, and stable uniform.
Specifically, the embodiment of the invention discloses a kind of extra small multicomponent alloy composite materials, the mesoporous carbon including sulfur doping and it is carried on
The extra small alloying pellet of the mesoporous carbon surface of the sulfur doping;The average-size of the extra small alloying pellet is 2nm.
For extra small multicomponent alloy composite material provided by the present application comprising the mesoporous carbon of sulfur doping and extra small alloy
Grain, wherein carrier of the mesoporous carbon of sulfur doping as extra small alloying pellet, extra small alloying pellet are by least two metallic elements
The alloying pellet of formation, size are smaller.
The mesoporous carbon of sulfur doping described herein is prepared according to method well known to those skilled in the art, right
This application is not particularly limited.According to the present invention, the alloy in above-mentioned extra small alloying pellet can be those skilled in the art
Member known to any two kinds or more alloying element formed alloying pellet, it is exemplary, the extra small alloying pellet be selected from Pt,
Rh、Pd、 Ir、Ru、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Y、Zr、Nb、Mo、Cd、In、Sn、Sb、Bi、
Two kinds or more in Pb, Re, W, Ta and Hf;More specifically, the extra small alloying pellet can for Pt-Co alloying pellet,
Pt-Ir alloying pellet, Pt-Ir-Sn alloying pellet or Pt-Rh-Ru-Pb alloying pellet.The average ruler of the extra small alloying pellet
Very little is 2nm.The load capacity of the extra small alloying pellet is 1wt%~20wt%;In a particular embodiment, the extra small alloy
The load capacity of particle is 5wt%~10wt%.Extra small alloy in the application, the extra small multicomponent alloy composite material
Grain is the mesoporous carbon surface for being carried on the sulfur doping.
Present invention also provides the preparation methods of above-mentioned extra small multicomponent alloy composite material, comprising the following steps:
The mesoporous carbon of sulfur doping, metal salt presoma and solvent are mixed, obtain original mixture after dry;The metal
Salt precursor body is the metal salt presoma of two or more different metal element;
The original mixture is heat-treated under reducing atmosphere, obtains extra small multicomponent alloy composite material;It is described
400~800 DEG C of the temperature of heat treatment.
Extra small multicomponent alloy composite material provided by the present application can be prepared by the way of dipping, heat treatment, should
Method has universality to various metals, and technological operation is simple and easy.
Specifically, during preparing extra small multicomponent alloy composite material, the application first by the mesoporous carbon of sulfur doping,
Metal salt presoma and solvent mixing, obtain original mixture after dry;Before this process is the mesoporous carbon and metal salt of sulfur doping
Drive a mixed process of body;For the mesoporous carbon of raw material sulfur doping, preparation method is according to well known to those skilled in the art
Method preparation, more specifically, the preparation method of the mesoporous carbon of the sulfur doping specifically:
By sulfur-bearing small organic molecule, SiO2Bead and transition metal salt are mixed in solvent, and high-temperature calcination after drying obtains
Carbon material;
It is sequentially etched the carbon material using sodium hydroxide and sulfuric acid, obtains the mesoporous carbon of sulfur doping.
During the above-mentioned mesoporous carbon for preparing sulfur doping, the sulfur-bearing small organic molecule is selected from those skilled in the art
Well known sulfur-bearing small molecule, in this application, the sulfur-bearing small molecule are selected from 2,2 '-bithiophenes;The transition metal salt also selects
Exemplary from transition metal salt well known to those skilled in the art, the transition metal salt is selected from six hydration nitre in this application
Sour cobalt, solvent can be selected from tetrahydrofuran.The sulfur-bearing small molecule, SiO2The molar ratio of bead and transition metal salt is 2:2:1;Institute
The temperature for stating calcining is 600~1200 DEG C.The preparation method of the mesoporous carbon of above-mentioned sulfur doping can be ripe according to those skilled in the art
The method preparation known, to this application without particularly limiting.During subsequent etching, sodium hydroxide is to etch away carbon
Silica in material, sulfuric acid is to etch away the metallic particles in carbon material, and two processes successively carry out, to realize two respectively
The etching of silica and metallic particles finally obtains the mesoporous carbon of sulfur doping.
It is metallic element well known to those skilled in the art for the metallic element in another raw metal salt precursor body,
Herein described metal salt presoma may include the salt of noble metal, may also comprise base metal salt, can also be the salt of noble metal
With non-noble metal salt;Wherein the precious metal element of the salt of noble metal be selected from can be selected from one of Pt, Rh, Pd, Ir and Ru or
It is a variety of, the non-noble metal j element of the non-noble metal salt can be selected from Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga,
One of Ge, Y, Zr, Nb, Mo, Cd, In, Sn, Sb, Bi, Pb, Re, W, Ta and Hf or a variety of.The metal salt presoma is
The metal salt presoma of two or more different metal element, can be the salt of two kinds or more noble metals, can also be with
It is two kinds or more non-noble metal salt, can also be the mixing of the salt and non-noble metal salt of noble metal;I.e. metallic element it
Between be random combine;Such as: bianry alloy Pt-Al/Pd/Ir/Rh/Fe/Co/Ni/Ga/Ge/Sn/In ...;Ternary is extra small
Alloy PtIrSn/PtIrRu/PtIrZn PtCoCu/PtCoGa/RhCoGa/RhIrRu ...;The extra small alloy of quaternary
PtRuIrSn/PdRuIrSn/RhRuIrSn/PtRuIrCo/PtRuIrCu/PtFeCoNi…….The application is to metal salt precursor
The form of the salt of body is also not particularly limited, and is the form of salt well known to those skilled in the art;By taking Pt as an example, Pt's
Salt can be H2PtCl6、Pt(acac)2、 Pt(NH3)4Cl2…….It is no proportionate relationship for different metal salt presomas
, it is rationally added according to its carrying capacity in the mesoporous carbon of sulfur doping.
During obtaining original mixture, it is suitable that the solvent can be selected according to the addition type of metal salt presoma
Solvent be added, such as metal precursor be inorganic metal salt (CoCl6·6H2O) usually water is solvent, and organic metal salt is usual
It the use of ethyl alcohol is solvent, inorganic metal salt is easy hydrolysis (TiCl4) need that organic solvent is selected to dissolve;In the process, solvent
Main purpose be sufficiently it is miscible, do not chemically react.
According to the present invention, after obtaining original mixture, then it is heat-treated under reducing atmosphere, to be surpassed
Small multicomponent alloy composite material;This process is the reduction process of metal salt presoma, and metal salt presoma removing ligand is reduced,
Metal salt is converted into metal phase.Detailed process are as follows:
The original mixture is transferred in silica crucible or corundum crucible, is put into tube furnace, then with hydrogen or
Hydrogen mixed gas is warming up to 400~800 DEG C as reducing atmosphere, with the rate of 2~20 DEG C/min, keeps the temperature 0.5~12h, then certainly
So it is down to room temperature;In this process, normal pressure is kept in tube furnace.Above-mentioned hydrogen mixed gas be selected from hydrogen and nitrogen gaseous mixture,
The gaseous mixture or hydrogen of hydrogen and argon gas and the gaseous mixture of carbon monoxide.In above process, the rate is in specific embodiment
In be 5~10 DEG C/min, temperature is more specifically 500~700 DEG C.The heating rate is too fast, and alloying pellet can be made excessive;Institute
The temperature for stating heat treatment will determine the homogenization degree of alloy, and temperature is too low to keep alloying level lower, and temperature is excessively high to make alloy
Particle is excessive.During above-mentioned heat treatment, under high temperature and reducing atmosphere, it is ripe that metallic particles is easy to happen your moral of Oswald
Change, little particle causes particle size to increase to migrating above bulky grain;Temperature is raised simultaneously, is conducive to two kinds of alloy inside not
With metal phase counterdiffusion (especially to incompatible metal phase), more uniform composition is formed.So being needed to different metal
Regulate and control suitable temperature and time to guarantee to obtain extra small alloying pellet and there is a phenomenon where reunite.
The application by dipping, heat treatment in the way of be prepared for extra small multicomponent alloy composite material, the composite material metal
There is strong interaction between sulphur, the anti-caking power of metallic particles can be promoted;And metal nanoparticle is under the high temperature conditions
Do not reunite, forms the multicomponent alloy composite material of super-small.
Extra small multicomponent alloy composite material provided by the present application can be used as the catalyst of heterocatalysis, specifically can be used as to chlorine
The catalyst of nitrobenzene hydrogenation, levulic acid hydrogenation reaction or benzyl alcohol selective oxidation;The catalyst is shown solely
Special activity and high stability.The extra small multicomponent alloy composite material is in the catalyst as heterocatalysis, conjunction therein
The ratio of alloying element has larger impact to catalytic effect in gold particle;On this basis, to prepare extra small multicomponent alloy compound
During material, need further to regulate and control the proportionate relationship of metallic element in metal salt presoma.
For a further understanding of the present invention, below with reference to embodiment to extra small multicomponent alloy composite wood provided by the invention
Material, preparation method and its application are described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
A. by 0.5g union II thiophene, 0.5g SiO2Aeroge and 0.25g Co (NO3)2·6H2O is dispersed in tetrahydrofuran
It stirs evenly, revolving removal solvent obtains uniform mixture;Gained homogeneous mixture is transferred to silica crucible or corundum
It in crucible, is put into tube furnace, then passes to nitrogen as protection gas, tube furnace is warming up to 800 with the rate of 5 DEG C/min
DEG C, keep 2h;It is down to room temperature naturally again, keeps normal pressure in tube furnace;Then gained is transferred in flask, addition is about
2mol/L NaOH solution 40mL or so, stirring 36h carry out first time alkaline etching;Then by solution in centrifuge, 8000r item
5min is centrifuged under part;Then the supernatant liquor of centrifugation is outwelled again, the solid of lower layer is transferred again into flask, then plus about
2mol/L NaOH solution 40mL or so stirs 36h, carries out second of alkaline etching;Last centrifuge washing is to neutrality, then by gained
It is placed in 25ml round-bottomed flask, oil bath is carried out in the sulfuric acid solution of 0.5mol/L, oil bath temperature is 90 DEG C, and flow back 6h, then
Centrifuge washing is carried out, neutrality is washed till, is dried, the mesoporous carbon nanomaterial of the sulfur doping of acquisition;
B. by the mesoporous carbon nanomaterial S-C of the above-mentioned sulfur doping of 47.5mg and the H containing 1.5585mg Pt2PtCl6With
The CoCl of 0.9415mgCo2(guaranteeing atomic ratio=0.5 Pt/Co) is placed in 100mL round-bottomed flask, is diluted with water (total volume guarantor
Hold in~50mL) obtain mixture;After said mixture ultrasound 2h, 12h is stirred, revolving obtains catalyst -1;
C. above-mentioned gained catalyst -1 is put into quartz boat, is passed through 5%vol H2/ Ar gas, by tube furnace with 5 DEG C/
The rate of min is warming up to 700 DEG C, keeps 2.0h;Naturally being down to room temperature can be obtained 5wt%Pt-Co/SC.
Fig. 1 is the number of S element in the x-ray photoelectron spectroscopy (XPS) of 5wt%Pt-Co/SC in the embodiment of the present invention 1
According to;As shown in Figure 1, the position at all peaks extra small alloy S is deviated relative to sulphur carbon, this show sulphur carbon carrier and metal it
Between have strong interaction.
Fig. 2 is that the x-ray powder of 5wt%Pt-Co/SC and the extra small alloy of other parts binary spreads out in the embodiment of the present invention 1
Firing table sign;The peak for not seeing any metal illustrates that alloy size is especially small, lower than the detectable limit of X-ray.
The HAADF-mapping characterization that Fig. 3 is the 5wt%Pt-Co/SC that the embodiment of the present invention 1 provides, as seen from the figure, Pt
Mapping and Co mapping it is completely overlapped, illustrate that alloying level is especially good.
Fig. 4 is that the line for the 5wt%Pt-Co/SC that the embodiment of the present invention 1 provides sweeps phenogram;By
Fig. 4 illustrates that alloying level is good it is found that individual particle contains the signal of Pt, Co.
The TPR table sign that Fig. 5 is the 5wt%Pt-Co/SC that the embodiment of the present invention 1 provides;The reduction temperature of PtCo compared with Co to
Low temperature offset, illustrates that H extraction effect has occurred, it was demonstrated that form alloy.
5wt%Pt-Co/SC manufactured in the present embodiment is used for the hydrogenation reaction of parachloronitrobenzene, specifically: to chlorine nitro
In benzene selective hydrogenation process, 7.804mg5wt% is added using 5ml methanol as solvent in 315mg parachloronitrobenzene (2mmol)
Pt-Co/SC is as catalyst (Pt of 0.1% mole), at 40 DEG C, 2.0bar H2Under the conditions of react;Other comparative catalysts
And it is carried out under equal conditions.
Fig. 7 is the 5wt%Pt-Co/SC that provides of the embodiment of the present invention 1 in parachloronitrobenzene selective hydrogenation dynamics
Data;Illustrate that extra small alloy has activity, selectivity well.
Fig. 8 is 5wt%Pt-Co/SC in the embodiment of the present invention 1 in parachloronitrobenzene selective hydrogenation stability column diagram;
Thus illustrate that Pt-Co/SC has preferable stability as chloronitrobenzene hydrogenation catalyst.
Embodiment 2
A. by 0.5g union II thiophene, 0.5g SiO2Aeroge and 0.25g Co (NO3)2·6H2O is dispersed in tetrahydrofuran
It stirs evenly, revolving removal solvent obtains uniform mixture;Gained homogeneous mixture is transferred to silica crucible or corundum
It in crucible, is put into tube furnace, then passes to nitrogen as protection gas, tube furnace is warming up to 800 with the rate of 5 DEG C/min
DEG C, 2h is kept, then be down to room temperature naturally, normal pressure is kept in tube furnace;Then gained is transferred in flask, addition is about
2mol/L NaOH solution 40mL or so stirs 36h, carries out first time alkaline etching;Then by solution in centrifuge, 8000r item
It is centrifuged 5min under part, then the supernatant liquor of centrifugation is outwelled, the solid of lower layer is transferred again into flask, then plus about
2mol/L NaOH solution 40mL or so stirs 36h, carries out second of alkaline etching;Last centrifuge washing is to neutrality, then by gained
It is placed in 25ml round-bottomed flask, in the sulfuric acid solution of 0.5mol/L, carries out oil bath, oil bath temperature is 90 DEG C, and flow back 6h, then
Centrifuge washing is carried out, neutrality is washed till, is dried, the mesoporous carbon nanomaterial of the sulfur doping of acquisition;
B. by the mesoporous carbon nanomaterial S-C of above-mentioned gained 47.5mg sulfur doping and the H containing 1.5585mg Pt2PtCl6With
The Co (acac) of 0.9415mgCo2(guaranteeing atomic ratio=2 Pt/Co) is placed in 100mL round-bottomed flask, adds acetone dilution (overall
Product is maintained at~50mL) mixture is obtained, after said mixture ultrasound 2h, 12h is stirred, revolving obtains catalyst -1;
C. above-mentioned gained catalyst -1 is put into quartz boat, is passed through 5%vol H2/ Ar gas, by tube furnace with 5 DEG C/
The rate of min is warming up to 700 DEG C, keeps 2.0h;Naturally being down to room temperature can be obtained 5wt%Pt-Co/SC.
Embodiment 3
A. by 0.5g union II thiophene, 0.5g SiO2Aeroge and 0.25g Co (NO3)2·6H2O is dispersed in tetrahydrofuran
It stirs evenly, revolving removal solvent obtains uniform mixture;Gained homogeneous mixture is transferred to silica crucible or corundum
It in crucible, is put into tube furnace, then passes to nitrogen as protection gas, tube furnace is warming up to 800 with the rate of 5 DEG C/min
DEG C, 2h is kept, then be down to room temperature naturally, normal pressure is kept in tube furnace;Then gained is transferred in flask, addition is about
2mol/L NaOH solution 40mL or so stirs 36h, carries out first time alkaline etching;Then by solution in centrifuge, 8000r item
It is centrifuged 5min under part, then the supernatant liquor of centrifugation is outwelled, the solid of lower layer is transferred again into flask, then plus about
2mol/L NaOH solution 40mL or so stirs 36h, carries out second of alkaline etching;Washing is then centrifuged for neutrality, then by gained
It is placed in 25ml round-bottomed flask, in the sulfuric acid solution of 0.5mol/L, carries out oil bath, oil bath temperature is 90 DEG C, and flow back 6h, then
Centrifuge washing is carried out, neutrality is washed till, is dried, the mesoporous carbon nanomaterial of the sulfur doping of acquisition;
B. by the mesoporous carbon nanomaterial S-C of above-mentioned gained 47.5mg sulfur doping and the H containing 2.357 mg Pt2PtCl6With
The CoCl of 0.1424mgCo2(guaranteeing atomic ratio=5 Pt/Co) is placed in 100mL round-bottomed flask, is diluted with water (total volume holding
In~50mL) mixture is obtained, after said mixture ultrasound 2h, 12h is stirred, revolving obtains catalyst -1;
C. above-mentioned gained catalyst -1 is put into quartz boat, is passed through 5%vol H2/ Ar gas, by tube furnace with 5 DEG C/
The rate of min is warming up to 700 DEG C, keeps 2.0h;Naturally being down to room temperature can be obtained 5wt%Pt-Co/SC.
Embodiment 4
A. by 0.5g union II thiophene, 0.5g SiO2Aeroge and 0.25g Co (NO3)2·6H2O is dispersed in tetrahydrofuran
It stirs evenly, revolving removal solvent obtains uniform mixture;Gained homogeneous mixture is transferred to silica crucible or corundum
It in crucible, is put into tube furnace, then passes to nitrogen as protection gas, tube furnace is warming up to 800 with the rate of 5 DEG C/min
DEG C, 2h is kept, then be down to room temperature naturally, normal pressure is kept in tube furnace;Then gained is transferred in flask, addition is about
2mol/L NaOH solution 40mL or so stirs 36h, carries out first time alkaline etching;Then by solution in centrifuge, 8000r item
It is centrifuged 5min under part, then the supernatant liquor of centrifugation is outwelled, the solid of lower layer is transferred again into flask, then plus about
2mol/L NaOH solution 40mL or so stirs 36h, carries out second of alkaline etching;Washing is then centrifuged for neutrality, then by gained
It is placed in 25ml round-bottomed flask, in the sulfuric acid solution of 0.5mol/L, carries out oil bath, oil bath temperature is 90 DEG C, and flow back 6h, then
Centrifuge washing is carried out, neutrality is washed till, is dried, the mesoporous carbon nanomaterial of the sulfur doping of acquisition;
B. by the mesoporous carbon nanomaterial S-C of above-mentioned gained 40mg sulfur doping and the H containing 9.4304mg Pt2PtCl6With
The CoCl of 0.5696mgCo2(guaranteeing atomic ratio=5 Pt/Co) is placed in 100mL round-bottomed flask, is diluted with water (total volume holding
In~50mL) mixture is obtained, after said mixture ultrasound 2h, 12h is stirred, revolving obtains catalyst -1;
C. above-mentioned gained catalyst -1 is put into quartz boat, is passed through 5%vol H2/ Ar gas, by tube furnace with 5 DEG C/
The rate of min is warming up to 700 DEG C, keeps 2.0h;Naturally being down to room temperature can be obtained 20wt%Pt-Co/SC.
Embodiment 5
A. by 0.5g union II thiophene, 0.5g SiO2Aeroge and 0.25g Co (NO3)2·6H2O is dispersed in tetrahydrofuran
It stirs evenly, revolving removal solvent obtains uniform mixture;Gained homogeneous mixture is transferred to silica crucible or corundum
It in crucible, is put into tube furnace, then passes to nitrogen as protection gas, tube furnace is warming up to 800 with the rate of 5 DEG C/min
DEG C, keep 2h;It is down to room temperature naturally again, keeps normal pressure in tube furnace;Then gained is transferred in flask, addition is about
2mol/L NaOH solution 40mL or so stirs 36h, carries out first time alkaline etching;Then by solution in centrifuge, 8000r item
It is centrifuged 5min under part, then the supernatant liquor of centrifugation is outwelled, the solid of lower layer is transferred again into flask, then plus about
2mol/L NaOH solution 40mL or so stirs 36h, carries out second of alkaline etching;Washing is then centrifuged for neutrality, then by gained
It is placed in 25ml round-bottomed flask, in the sulfuric acid solution of 0.5mol/L, carries out oil bath, oil bath temperature is 90 DEG C, and flow back 6h, then
Centrifuge washing is carried out, neutrality is washed till, is dried, the mesoporous carbon nanomaterial of the sulfur doping of acquisition;
B. by the mesoporous carbon nanomaterial S-C of above-mentioned gained 47.5mg sulfur doping and the H containing 1.25mg Pt2PtCl6With
1.25mgIr IrCl3(guarantee atomic ratio=1 Pt/Ir) is placed in 100mL round-bottomed flask, is diluted with water that (total volume is maintained at
~50mL) mixture is obtained, after said mixture ultrasound 2h, 12h is stirred, revolving obtains catalyst -1.
C. above-mentioned gained catalyst -1 is put into quartz boat, is passed through 5%vol H2/ Ar gas, by tube furnace with 5 DEG C/
The rate of min is warming up to 700 DEG C, keeps 2.0h;Naturally being down to room temperature can be obtained 5wt%Pt-Ir/SC.
Embodiment 6
A. by 0.5g union II thiophene, 0.5g SiO2Aeroge and 0.25g Co (NO3)2·6H2O is dispersed in tetrahydrofuran
It stirs evenly, revolving removal solvent obtains uniform mixture;Gained homogeneous mixture is transferred to silica crucible or corundum
It in crucible, is put into tube furnace, then passes to nitrogen as protection gas, tube furnace is warming up to 800 with the rate of 5 DEG C/min
DEG C, 2h is kept, then be down to room temperature naturally, normal pressure is kept in tube furnace;Then gained is transferred in flask, addition is about
2mol/L NaOH solution 40mL or so stirs 36h, carries out first time alkaline etching;Then by solution in centrifuge, 8000r item
It is centrifuged 5min under part, then the supernatant liquor of centrifugation is outwelled, the solid of lower layer is transferred again into flask, then plus about
2mol/L NaOH solution 40mL or so stirs 36h, carries out second of alkaline etching;Washing is then centrifuged for neutrality, then by gained
It is placed in 25ml round-bottomed flask, in the sulfuric acid solution of 0.5mol/L, carries out oil bath, oil bath temperature is 90 DEG C, and flow back 6h, then
Centrifuge washing is carried out, neutrality is washed till, is dried, the mesoporous carbon nanomaterial of the sulfur doping of acquisition;
B. by the mesoporous carbon nanomaterial S-C of above-mentioned gained 47.5mg sulfur doping and the H containing 1.25mg Pt2PtCl6With
1.25mgIr IrCl3(guarantee atomic ratio=1 Pt/Ir) is placed in 100mL round-bottomed flask, is diluted with water that (total volume is maintained at
~50mL) mixture is obtained, after said mixture ultrasound 2h, 12h is stirred, revolving obtains catalyst -1;
C. above-mentioned gained catalyst -1 is put into quartz boat, is passed through 5%vol H2/ Ar gas, by tube furnace with 5 DEG C/
The rate of min is warming up to 400 DEG C, keeps 8.0h;Naturally being down to room temperature can be obtained 5wt%Pt-Ir/SC.
Add the catalyst of hydrogen using 5wt%Pt-Ir/SC manufactured in the present embodiment as levulic acid, specifically: levulic acid
In hydrogenation process, 1ml n-butanol is added as solvent, in 4.0MPaH2, under the conditions of 200 DEG C, 60min, 50ul
(0.5mmol) levulic acid, 2.0mg 5wt% Pt-Ir/SC (0.1% mole Pt).
Table 1 has listed different catalysts for the tables of data of levulic acid hydrogenation reaction;As shown in table 1:
Tables of data of 1 different catalysts of table to levulic acid hydrogenation reaction
Catalyst |
Conversion ratio % |
Selective % |
5wt%Pt-Ir/SC |
100 |
>99 |
20wt%Pt-Ir/SC |
89 |
84.36 |
Pt/SC |
87.5 |
76.27 |
Ir/SC |
46.08 |
33 |
C/Pt |
82.06 |
82.46 |
C/Ir |
74.07 |
100 |
V-72-PtIr |
84.96 |
42.0 |
K-300J-PtIr |
89.56 |
>99 |
As shown in Table 1,5wt%Pt-Ir/SC and the 20wt%Pt-Ir/SC catalyst of different carrying capacity are in same metal molar
Under the conditions of amount is added, 5wt%Pt-Ir/SC activity is more preferable, illustrates the advantage (5wt%Pt-Ir/SC of the particle size of extra small alloy
It is smaller than 20wt%Pt-Ir/SC particle size);5wt%Pt-Ir/SC is than monometallic Ir/SC and Pt/SC catalytic activity and choosing simultaneously
Selecting property will be got well;Than commercial catalysts performance also than get well, present bimetallic coordinating effect;Pass through what is loaded with common carbon carrier
Catalyst V-72-PtIr, K-300J-PtIr comparison, it can be seen that the present embodiment carrier S-C has the carrier effect improved to catalysis
It answers, since carrier and extra small alloy have interaction, improves conversion ratio and selectivity.
Embodiment 7
A. by 0.5g union II thiophene, 0.5g SiO2Aeroge and 0.25g Co (NO3)2·6H2O is dispersed in tetrahydrofuran
It stirs evenly, revolving removal solvent obtains uniform mixture;Gained homogeneous mixture is transferred to silica crucible or corundum
It in crucible, is put into tube furnace, then passes to nitrogen as protection gas, tube furnace is warming up to 800 with the rate of 5 DEG C/min
DEG C, 2h is kept, room temperature is down to naturally, keeps normal pressure in tube furnace;Then gained is transferred in flask, being added is about 2mol/L
NaOH solution 40mL or so, stir 36h, carry out first time alkaline etching, then by solution in centrifuge, under the conditions of 8000r from
Heart 5min, then the supernatant liquor of centrifugation is outwelled, the solid of lower layer is transferred again into flask, then plus about 2mol/L
NaOH solution 40mL or so stirs 36h, carries out second of alkaline etching;It is then centrifuged for washing to neutrality, then gained is placed in
In 25ml round-bottomed flask, in the sulfuric acid solution of 0.5mol/L, oil bath is carried out, oil bath temperature is 90 DEG C, and flow back 6h, is then carried out
Centrifuge washing is washed till neutrality, drying, the mesoporous carbon nanomaterial of the sulfur doping of acquisition;
B. by above-mentioned gained 47.5mg S-C and the H containing 0.9639mg Pt2PtCl6, the SnCl of 0.5865mgSn2With
The IrCl of 0.9496mgIr3(guaranteeing atomic ratio=1/1/1 Pt/Ir/Sn) is placed in 100mL round-bottomed flask, is diluted with water (total
Volume is maintained at~50mL) mixture is obtained, after said mixture ultrasound 2h, 12h is stirred, revolving obtains catalyst -1;
C. above-mentioned gained catalyst -1 is put into quartz boat, is passed through 5%vol H2/ Ar gas, by tube furnace with 5 DEG C/
The rate of min is warming up to 400 DEG C, keeps 2.0h;Naturally being down to room temperature can be obtained 5wt%Pt-Ir-Sn/SC (the extra small conjunction of ternary
Gold).
Embodiment 8
A. by 0.5g union II thiophene, 0.5g SiO2Aeroge and 0.25g Co (NO3)2·6H2O is dispersed in tetrahydrofuran
It stirs evenly, revolving removal solvent obtains uniform mixture;Gained homogeneous mixture is transferred to silica crucible or corundum
It in crucible, is put into tube furnace, then passes to nitrogen as protection gas, tube furnace is warming up to 800 with the rate of 5 DEG C/min
DEG C, 2h is kept, room temperature is down to naturally, keeps normal pressure in tube furnace;Then gained is transferred in flask, being added is about 2mol/L
NaOH solution 40mL or so stirs 36h, carries out first time alkaline etching;Then by solution in centrifuge, under the conditions of 8000r from
Heart 5min, then the supernatant liquor of centrifugation is outwelled, the solid of lower layer is transferred again into flask, then plus about 2mol/L
NaOH solution 40mL or so stirs 36h, carries out second of alkaline etching;It is then centrifuged for washing to neutrality, then gained is placed in
In 25ml round-bottomed flask, in the sulfuric acid solution of 0.5mol/L, oil bath is carried out, oil bath temperature is 90 DEG C, and flow back 6h, is then carried out
Centrifuge washing is washed till neutrality, drying, the mesoporous carbon nanomaterial of the sulfur doping of acquisition;
B. by the mesoporous carbon nanomaterial S-C of above-mentioned gained 47.5mg sulfur doping and the H containing 0.0625mg Pt2PtCl6,
The RuCl of 0.0625mgRu3, the Pb (NO of 0.0625mgPb3) 2 and 0.0625mgRh RhCl3(guarantee Pt/Rh/Ru/Pb mass
Than=1/1/1/1) it is placed in 100mL round-bottomed flask, it is diluted with water (total volume is maintained at~50mL) and obtains mixture, it will be upper
After stating mixture ultrasound 2h, 12h is stirred, revolving obtains catalyst -1;
C. above-mentioned gained catalyst -1 is put into quartz boat, is passed through 5%vol H2/ Ar gas, by tube furnace with 5 DEG C/
The rate of min is warming up to 400 DEG C, keeps 2.0h;Naturally being down to room temperature can be obtained 5wt%Pt-Rh-Ru-Pb/SC (quaternary is super
Primary alloy).
Fig. 6 is that the x-ray powder for the extra small alloy of 5wt%Pt-Pb-Ru-Rh/SC quaternary that the embodiment of the present invention 8 provides spreads out
Firing table sign;Illustrate that quaternary alloy size is smaller.
Embodiment 9
It is prepared for Pt-Bi/SC composite material according to the method described above, as the catalyst of benzyl alcohol oxidation, specifically:
It is solvent-free during benzyl alcohol oxidation, it is added 1ml benzyl alcohol (9.6mmol), is added (0.1% mole of 37.45mg catalyst
The Pt of amount) 5wt%Pt-Bi/SC, 1500r, the O of 0.2MPa at 100 DEG C2Reaction.
Fig. 9 is the kinetic curve that benzyl alcohol selective is oxidized to benzaldehyde.
Table 2 has listed benzyl alcohol oxidation reactivity tables of data under different catalysts, as shown in table 2:
Benzyl alcohol oxidation reactivity tables of data under 2 different catalysts of table
As shown in Table 2, the activity of the extra small alloy of PtBi is substantially better than monometallic Pt, Bi in PtBi/SC catalyst, and physics is mixed
The Pt+Bi and commercial catalysts Pt/C of conjunction;Simultaneous selection is better than monometallic and commercial catalysts.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.