CN109706364A - Intermetallic compound composite material, preparation method and its application - Google Patents
Intermetallic compound composite material, preparation method and its application Download PDFInfo
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Abstract
The present invention provides a kind of intermetallic compound composite materials, the intermetallic compound of the mesoporous carbon including sulfur doping and the mesoporous carbon surface for being carried on the sulfur doping；The intermetallic compound is the intermetallic compound formed by base of Pt, Rh or Ir.Present invention also provides the preparation methods of intermetallic compound composite material.The application that present invention also provides intermetallic compound composite materials in hydrogenation catalyst.The application has synthesized intermetallic compound composite material by the type and temperature of regulation metal salt presoma, and the size < 5nm of the intermetallic compound in the composite material, size is small, has high usage；And this method has universality, it is easy to operate, low in cost and easy to industrialized production.
Description
Technical field
The present invention relates to technical field of nano material more particularly to intermetallic compound composite material, preparation method and
It is applied.
Background technique
Intermetallic compound is also referred to as atomic ordered alloy, has the metering of specific chemical atomic and crystal structure, with it
Unordered alloy (i.e. solid solution) is compared, and due to strong internal order, mixed metal and covalently/ion are shown apparent
Magnetic, superconduction and chemical bonding effect.The basic role of intermetallic phase can be divided into four classes: electronic effect, geometric effect, space effect
Should and effect of order.The special surface structure of intermetallic compound determines unprecedented three-dimensional effect, shows unique
Performance.Intermetallic compound has the advantage that the design of finely divided catalytic the control of electronic structure, specific orderly original
The uniformity of sub- level structure, geometry and electronic structure.Therefore, intermetallic compound is a kind of up-and-coming inorganic catalysis
Agent material can create the good reaction environment of design, be suitble to the efficient catalyst system of exploitation.
Currently, the synthetic method of compound is mainly the metallurgical method by high temperature equilibrium between conventional metals, tool is only generated
Material between the bulk metal of limited catalytic surface product, improves catalytic active area and makes use of momentum and necessarily reduce intermetallic compound
Particle size meets the requirement of high catalytic activity with this.However, intermetallic compound needs high annealing to realize that atom is arranged
Column ordering, but high annealing frequently results in the sintering curing of particle, and this inevitably leads to of large scale (> 5nm) again
Grain and the distribution of broader size.Therefore the harm for needing to overcome the latter, realizes the atomic ordering in the former.
Scientific research at present is dedicated to compound nano-particle between preparation small sized metallic, while also obtaining good achievement；
Such as carbon coating or metal oxide protective shell, KCl Matrix-assisted are annealed before the anneal, metal-organic framework-limitation is gone back altogether
Former and Organometallic precursor chemical vapor deposition etc..However these methods some excessively very complicateds, it is not easy to operate；Some are former
Material is expensive, is not easy to obtain；The additional addition of some adjuvants, causes waste of resource etc., it is seen that above method pole is unfavorable for
Large-scale industrial production and manufacturing, application prospect cause anxiety.
Summary of the invention
Present invention solves the technical problem that being to provide a kind of intermetallic compound composite material and preparation method thereof, this Shen
The size for the intermetallic compound composite material that please be provided is less than 5nm.
In view of this, this application provides a kind of intermetallic compound composite material, mesoporous carbon including sulfur doping and negative
It is loaded in the intermetallic compound of the mesoporous carbon surface of the sulfur doping；The intermetallic compound is using Pt, Rh or Ir as base shape
At intermetallic compound.
Preferably, the size < 5nm of the intermetallic compound.
Preferably, another metallic element of the intermetallic compound formed using Pt as base be selected from Al, Sc, Ti, V, Cr,
One of Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, In and Sn or a variety of；The intermetallic compound formed using Rh as base
Another metallic element is selected from one of Ti, V, Cr, Fe, Ga, Ge, In and Sb or a variety of；Between the metal formed using Ir as base
Compound is Ir3V。
Present invention also provides the preparation methods of the intermetallic compound 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 one of Pt base salt, Rh base salt and Ir base salt and other metal salts；
The original mixture is heat-treated under reducing atmosphere, obtains intermetallic compound composite material；It is described
800~1100 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 DEG C.
Preferably, when the metal salt presoma is Pt base salt and other metal salts, other gold of other metal salts
Belong to element and is selected from one of Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, In and Sn or a variety of；It is described
Metal salt presoma is Rh base salt and when other metal salts, other metallic elements of other metal salts be selected from Ti, V, Cr,
One of Fe, Ga, Ge, In and Sb or a variety of；The metal salt presoma is Ir base salt and V salt.
Preferably, the reducing atmosphere is the gaseous mixture of hydrogen and argon gas, and the volume fraction of the hydrogen is 5%, described
The volume fraction of argon gas is 95%.
Preferably, the heating rate of the heat treatment is 1~10 DEG C/min, and the time is 0.5~12h.
Present invention also provides the intermetallic compound composite material or the intermetallic compound composite materials
Preparation method applied in hydrogenation catalyst.
This application provides a kind of intermetallic compound composite materials comprising the mesoporous carbon of sulfur doping and is carried on described
The intermetallic compound of the mesoporous carbon surface of sulfur doping；The intermetallic compound is the metal formed by base of Pt, Rh or Ir
Between compound.The distribution of intermetallic compound highly effectiveization and size in the composite material are less than 5nm.
It is first that sulfur doping is mesoporous present invention also provides a kind of preparation method of intermetallic compound composite material
Carbon, metal salt presoma and solvent mixing obtain original mixture, then original mixture are heat-treated to get arriving after dry
Intermetallic compound composite material；The application is using sulfur doping mesoporous carbon as carrier, sulphur therein and metal strong interaction
And the confinement of carrier duct realizes the controlledly synthesis of small size nanocrystalline intermetallics；Simultaneously by adjusting the temperature of heat treatment
Degree, further ensures the size and ordering of intermetallic compound.
On the other hand, the preparation method of intermetallic compound composite material provided by the present application has most of metal general
Adaptive, and can be used as the catalyst of hydrogenation catalyst, there is unique activity and selectivity.
Detailed description of the invention
Fig. 1 is Pt in the composite material of the preparation of the embodiment of the present invention 13Between Co metal XRD, HADDF-STEM of object phase and
Particle size distribution photo；
Fig. 2 be in composite material prepared by the embodiment of the present invention 2 between PtFe metal XRD, HADDF-STEM of object phase and
Particle size distribution photo；
Fig. 3 is PtCu in the composite material of the preparation of the embodiment of the present invention 33Between metal XRD, HADDF-STEM of object phase and
Particle size distribution photo；
Fig. 4 is Pt in the composite material of the preparation of the embodiment of the present invention 42Between FeNi metal XRD, HADDF-STEM of object phase with
And particle size distribution photo；
Fig. 5 is Pt in the composite material of the preparation of the embodiment of the present invention 53XRD, HADDF-STEM of object phase between FeCoNi metal
And particle size distribution photo；
Fig. 6 is Pt in the composite material of the preparation of the embodiment of the present invention 64XRD, HADDF- of object phase between FeCoNiCu metal
STEM and particle size distribution photo；
Fig. 7 is Pt in the composite material of the preparation of the embodiment of the present invention 75XRD, HADDF- of object phase between FeCoNiCuMn metal
STEM and particle size distribution photo；
Fig. 8 is Rh in the composite material of the preparation of the embodiment of the present invention 83Between V metal XRD, HADDF-STEM of object phase and
Particle size distribution photo；
Fig. 9 be in composite material prepared by the embodiment of the present invention 9 between RhSb metal XRD, HADDF-STEM of object phase and
Particle size distribution photo；
Figure 10 be XRD, HADDF-STEM of object phase between RhGe metal in composite material prepared by the embodiment of the present invention 10 with
And particle size distribution photo；
Figure 11 be XRD, HADDF-STEM of object phase between RhGa metal in composite material prepared by the embodiment of the present invention 11 with
And particle size distribution photo；
Figure 12 is Ir in the composite material of the preparation of the embodiment of the present invention 123Between V metal XRD, HADDF-STEM of object phase with
And particle size distribution photo；
Figure 13 is Catalytic data column diagram of the intermetallic compound of the preparation of the embodiment of the present invention 9 as catalyst.
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.
This application provides a kind of intermetallic compound composite material and preparation method thereof, change between metal provided by the present application
Intermetallic compound size in compound composite material is small and high-sequential.Specifically, the embodiment of the invention discloses a kind of gold
Compound composite material between category comprising between the mesoporous carbon of sulfur doping and the metal of mesoporous carbon surface for being carried on the sulfur doping
Compound；The intermetallic compound is the intermetallic compound formed by base of Pt, Rh or Ir.
Well known to those skilled in the art, inter-metallic compound material is High ordering alloy, maximum feature
Be it is High ordering, atom is arranged according to specific structure.
For intermetallic compound composite material provided by the present application comprising the mesoporous carbon and intermetallic of sulfur doping
Object, wherein carrier of the mesoporous carbon of sulfur doping as intermetallic compound, the strong phase of sulphur and metal in the mesoporous carbon of sulfur doping
Interaction and duct confinement limit the size of intermetallic compound, its size is made to be less than 5nm.
The mesoporous carbon of sulfur doping described herein is prepared according to method well known to those skilled in the art, to this
Application is not particularly limited.According to the present invention, above-mentioned intermetallic compound is changed between the metal formed using Pt, Rh or Ir as base
Close object；Specifically, another metallic element of the intermetallic compound formed using Pt as base be selected from Al, Sc, Ti, V, Cr, Mn,
One of Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, In and Sn or a variety of；The intermetallic compound formed using Rh as base it is another
Kind metallic element is selected from one of Ti, V, Cr, Fe, Ga, Ge, In and Sb or a variety of；The intermetallic formed using Ir as base
Object is Ir3V；Above-mentioned metallic element forms intermetallic compound with Pt, Rh or Ir respectively can the small sized intermetallic of shape
Object.
Present invention also provides the preparation methods of above-mentioned intermetallic compound 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 one of Pt base salt, Rh base salt and Ir base salt and other metal salts；
The original mixture is heat-treated under reducing atmosphere, obtains intermetallic compound composite material；It is described
800~1100 DEG C of the temperature of heat treatment.
Intermetallic compound 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 intermetallic compound 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 in Pt base salt, Rh base salt and Ir base salt for metal salt presoma described in another raw metal salt precursor body
A kind of and other metal salts；Pt base salt, Rh base salt and Ir base salt are respectively salt well known to those skilled in the art, to this application
Without particularly limiting；In a particular embodiment, the Pt base salt is H2PtCl6·6H2O, the Rh base salt are RhCl3·
nH2O, the Ir base salt are IrCl3.In this application, different Pt base salt, Rh base salt and Ir base salt correspond to other different gold
Belong to salt, to guarantee the small sized intermetallic compound of shape；Specifically, the metal salt presoma is Pt base salt and other metals
When salt, other metallic elements of other metal salts be selected from Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge,
One of Zr, In and Sn or a variety of；When the metal salt presoma is Rh base salt and other metal salts, other described metal salts
Other metallic elements be selected from one of Ti, V, Cr, Fe, Ga, Ge, In and Sb or a variety of；The metal salt presoma is Ir
Base salt and V salt.Other above-mentioned metal salts can be according to the specific salt of formal character well known to those skilled in the art, to this application
Without particularly limiting；Here, the application lists part metals salt, specifically: ScCl3、TiCl4、VCl3、CrCl3·
6H2O、MnCl2·4H2O、FeCl3·6H2O、CoCl2·6H2O、NiCl2·6H2O、CuCl2·2H2O、Zn(NO3)2·6H2O、Ga
(NO3)2·nH2O、GeCl4、Zr(NO3)2·5H2O、InCl3、SnCl2·2H2O or SbCl3。
The content of intermetallic compound is 5~40wt% in the intermetallic compound composite material of the application preparation；If containing
It measures too low, is then unfavorable for characterizing；If too high levels, particle can be made to become larger；In a particular embodiment, the content is 20wt%
Or 25wt%.Therefore the mass ratio of the mesoporous carbon of sulfur doping and metal in metal salt presoma is (2.5~20): 1, to avoid shadow
Ring the size and ordering of intermetallic compound.Since the intermetallic compound in intermetallic compound composite material is that have to define
Metal ratio relationship, therefore one of Pt base salt, Rh base salt and Ir base salt and the metal quality ratio in other metal salts
Proportionate relationship need to be determined according to final intermetallic compound；If not following the proportionate relationship, the target of pure phase cannot be obtained
Intermetallic compound has impurity generation.
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 it is solvent that metal precursor, which is the usual water of inorganic metal salt, and organic metal salt is molten usually using ethyl alcohol
Agent, inorganic metal salt are easy hydrolysis and need that organic solvent is selected to dissolve；In the process, solvent main purpose is sufficiently miscible,
It does not chemically react.
According to the present invention, after obtaining original mixture, then it is heat-treated under reducing atmosphere, to obtain gold
Compound composite material between category；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, it is then mixed with hydrogen
Gas is closed as reducing atmosphere, 800~1100 DEG C is warming up to the rate of 1~10 DEG C/min, keeps the temperature 0.5~12h, then be down to naturally
Room temperature；In this process, normal pressure is kept in tube furnace.Above-mentioned hydrogen mixed gas is selected from the gaseous mixture of hydrogen and argon gas.Above-mentioned
In the process, the rate is 5~10 DEG C/min in a particular embodiment, and temperature is more specifically 900~1000 DEG C.Above process master
If the reduction of Pt base, Rh base salt or Ir base salt first occurs, then the reduction of other metal salts occurs, then the gold restored at high temperature
It is mobile to obtain ordered structure to belong to atom, finally obtains intermetallic compound；If temperature is excessively high, intermetallic compound will lead to
Grain becomes larger；The destruction of intermetallic compound order is also resulted in, disordered alloy is become；If temperature is too low, can only obtain unordered
Alloy.
The application by dipping, heat treatment in the way of be prepared for intermetallic compound composite material, the composite material metal
There is strong interaction, the small sized intermetallic compound composite material of shape between sulphur.
Intermetallic compound composite material provided by the present application can be used as the catalyst of hydrogenation catalyst, specifically can be used as to chlorine
The catalyst of nitrobenzene hydrogenation；The catalyst shows unique activity and selectivity.
For a further understanding of the present invention, below with reference to embodiment to intermetallic compound 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 mixture is transferred to silica crucible or corundum crucible
In, it is put into tube furnace, then passes to nitrogen as protection gas, tube furnace is warming up to 800 DEG C with the rate of 5 DEG C/min, is protected
Hold 2h；It is down to room temperature naturally again, keeps normal pressure in tube furnace；Then gained is transferred in flask, being added is about 2mol/L
30~50mL of NaOH solution or so stirs 36h~48h, carries out first time alkaline etching；Then by solution in centrifuge with
5min~10min is centrifuged under the conditions of 8000r~10000r；Then the supernatant liquor of centrifugation is outwelled again, again by the solid of lower layer
It is secondary to be transferred in flask, then plus about 30~50mL of 2mol/L NaOH solution or so, stir 12h~36h, carry out second of alkali
Etching；It is then centrifuged for washing to neutrality, then gained is placed in 25ml round-bottomed flask, carried out in the sulfuric acid solution of 0.5mol/L
Oil bath, oil bath temperature are 90 DEG C, and flow back 6h, then carries out centrifuge washing, is washed till neutrality, are dried, the sulfur doping mesoporous carbon of acquisition
Nano material；
B. the mesoporous carbon nanomaterial 50mg of resulting sulfur doping and 10mg metal salt (are guaranteed into H2PtCl6·6H2O and
CoCl2·6H2Pt:Co=3:1 in O) it is placed in 100ml round-bottomed flask, aqueous solvent is added, 6~10h is stirred, rotates drying
Afterwards, uniformly mixed presoma is obtained；
C. presoma is put into tube furnace, argon hydrogen (volume fraction 95%Ar+5%H is passed through into tube furnace2) as guarantor
Gas is protected, tube furnace is warming up to 1000 DEG C with the rate of 5 DEG C/min, keeps 2h；It is finally down to room temperature naturally again, is protected in tube furnace
Normal pressure is held, Pt is obtained3Co intermetallic compound composite material.
Fig. 1 is the Pt that the embodiment of the present invention 1 provides3Pt in Co intermetallic compound composite material3Object phase between Co metal
XRD, HADDF-STEM and particle size distribution photo；
The Pt from XRD it can be seen that object matches3Co standard PDF card；HADDF-STEM shows particle mean size
4.45nm (< 5nm), distribution are presented narrow ditribution and show even particle size.
Embodiment 2
A. step and embodiment 1 are identical；
B. the mesoporous carbon nanomaterial 50mg of resulting sulfur doping and 10mg metal salt (are guaranteed into H2PtCl6·6H2O and
FeCl3·6H2Pt:Fe=1:1 in O) it is placed in 100ml round-bottomed flask, aqueous solvent is added, 6~10h is stirred, rotates drying
Afterwards, uniformly mixed presoma is obtained；
C. presoma is put into tube furnace, argon hydrogen (volume fraction 95%Ar+5%H is passed through into tube furnace2) as guarantor
Gas is protected, tube furnace is warming up to 900 DEG C with the rate of 5 DEG C/min, keeps 2h；Finally room temperature, tube furnace are down in annealing naturally again
Interior holding normal pressure, obtains PtFe intermetallic compound composite material.
Object phase between PtFe metal in the PtFe intermetallic compound composite material that Fig. 2 provides for the embodiment of the present invention 2
XRD, HADDF-STEM and particle size distribution photo；
The PtFe standard PDF card from XRD it can be seen that object matches；HADDF-STEM shows particle mean size 2.62nm
(< 5nm), distribution are presented narrow ditribution and show even particle size.
Embodiment 3
A. step and embodiment 1 are identical；
B. the mesoporous carbon nanomaterial 50mg of resulting sulfur doping and 10mg metal salt (are guaranteed into H2PtCl6·6H2O and
CuCl2·2H2Pt:Cu=1:3 in O) it is placed in 100ml round-bottomed flask, aqueous solvent is added, 6-10h is stirred, after revolving is dry,
Obtain uniformly mixed presoma；
C. presoma is put into tube furnace, argon hydrogen (mass fraction 95%Ar+5%H is passed through into tube furnace2) as guarantor
Gas is protected, tube furnace is warming up to 1100 DEG C with the rate of 5 DEG C/min, keeps 2h；Finally room temperature, tube furnace are down in annealing naturally again
Interior holding normal pressure, obtains PtCu3Intermetallic compound composite material.
Fig. 3 is the PtCu that the embodiment of the present invention 3 provides3PtCu in intermetallic compound composite material3Object phase between metal
XRD, HADDF-STEM and particle size distribution photo；
The PtCu from XRD it can be seen that object matches3Standard PDF card；HADDF-STEM shows particle mean size
4.58nm (< 5nm), distribution are presented narrow ditribution and show even particle size.
Embodiment 4
A. step and embodiment 1 are identical；
B. the mesoporous carbon nanomaterial 50mg of resulting sulfur doping and 10mg metal salt (are guaranteed into H2PtCl6·6H2O、
FeCl3·6H2O and NiCl2·6H2O guarantees Pt:Fe:Ni=2:1:1) it is placed in 100ml round-bottomed flask, aqueous solvent is added, is stirred
It mixes 6-10h and obtains uniformly mixed presoma after revolving is dry；
C. presoma is put into tube furnace, argon hydrogen (mass fraction 95%Ar+5%H is passed through into tube furnace2) as guarantor
Gas is protected, tube furnace is warming up to 1000 DEG C with the rate of 5 DEG C/min, keeps 2h；Finally room temperature, tube furnace are down in annealing naturally again
Interior holding normal pressure, obtains Pt2FeNi intermetallic compound composite material.
Fig. 4 is the Pt that the embodiment of the present invention 4 provides2Pt in FeNi intermetallic compound composite material2Object phase between FeNi metal
XRD, HADDF-STEM and particle size distribution photo；
The Pt from XRD it can be seen that object matches2FeNi standard PDF card；HADDF-STEM shows particle mean size
3.15nm (< 5nm), distribution are presented narrow ditribution and show even particle size.
Embodiment 5
A. step and embodiment 1 are identical；
B. the mesoporous carbon nanomaterial 50mg of resulting sulfur doping and 10mg metal salt (are guaranteed into H2PtCl6·6H2O、
FeCl3·6H2O、CoCl2·6H2O and NiCl2·6H2O guarantees Pt:Fe:Co:Ni=3:1:1:1) it is placed in 100ml round-bottomed flask
In, aqueous solvent is added, 6-10h is stirred and obtains uniformly mixed presoma after revolving is dry；
C. presoma is put into tube furnace, argon hydrogen (mass fraction 95%Ar+5%H is passed through into tube furnace2) as guarantor
Gas is protected, tube furnace is warming up to 1000 DEG C with the rate of 5 DEG C/min, keeps 2h；Finally room temperature, tube furnace are down in annealing naturally again
Interior holding normal pressure, obtains.
Fig. 5 is the Pt that the embodiment of the present invention 5 provides3Pt in FeCoNi intermetallic compound composite material3Between FeCoNi metal
XRD, HADDF-STEM and particle size distribution photo of object phase；
The Pt from XRD it can be seen that object matches2FeNi standard PDF card is (since at present there is no Pt3The standard card of FeCoNi
Piece, and Pt2FeNi crystal structure having the same therewith, only because the part that the Co element added may result in peak is inclined
It moves, but standard card difference should be few, therefore with Pt2FeNi standard PDF card is as reference)；HADDF-STEM shows particle
Mean size 3.21nm (< 5nm), distribution are presented narrow ditribution and show even particle size.
Embodiment 6
A. step and embodiment 1 are identical；
B. the mesoporous carbon nanomaterial 50mg of resulting sulfur doping and 10mg metal salt (are guaranteed into H2PtCl6·6H2O、
FeCl3·6H2O、CoCl2·6H2O、NiCl2·6H2O and CuCl2·2H2O guarantees Pt:Fe:Co:Ni:Cu=4:1:1:1:1) it sets
In 100ml round-bottomed flask, aqueous solvent is added, 6-10h is stirred and obtains uniformly mixed presoma after revolving is dry；
C. presoma is put into tube furnace, argon hydrogen (mass fraction 95%Ar+5%H is passed through into tube furnace2) as guarantor
Gas is protected, tube furnace is warming up to 1000 DEG C with the rate of 5 DEG C/min, keeps 2h；Finally room temperature, tube furnace are down in annealing naturally again
Interior holding normal pressure, obtains Pt4FeCoNiCu intermetallic compound composite material.
Fig. 6 is the Pt that the embodiment of the present invention 6 provides4Pt in FeCoNiCu intermetallic compound composite material4FeCoNiCu gold
XRD, HADDF-STEM of object phase and particle size distribution photo between category；
The Pt from XRD it can be seen that object matches4Fe2NiCu standard PDF card is (since at present there is no Pt4The mark of FeCoNiCu
Quasi- card, and Pt4Fe2NiCu crystal structure having the same therewith, only because the Co element added may result in the portion at peak
Divide offset, but standard card difference should be few, therefore with Pt4Fe2NiCu standard PDF card is as reference)；HADDF-STEM is aobvious
Show particle mean size 3.32nm (< 5nm), distribution is presented narrow ditribution and shows even particle size.
Embodiment 7
A. step and embodiment 1 are identical；
B. the mesoporous carbon nanomaterial 50mg of resulting sulfur doping and 10mg metal salt (are guaranteed into H2PtCl6·6H2O、
FeCl3·6H2O、CoCl2·6H2O、NiCl2·6H2O、CuCl2·2H2O and MnCl2·2H2O guarantees Pt:Fe:Co:Ni:Cu:
Mn=5:1:1:1:1:1 it) is placed in 100ml round-bottomed flask, adds aqueous solvent, stir 6-10h and mixed after revolving is dry
Uniform presoma；
C. presoma is put into tube furnace, argon hydrogen (mass fraction 95%Ar+5%H is passed through into tube furnace2) as guarantor
Gas is protected, tube furnace is warming up to 1000 DEG C with the rate of 5 DEG C/min, keeps 2h；Finally room temperature, tube furnace are down in annealing naturally again
Interior holding normal pressure, obtains Pt5FeCoNiCuMn intermetallic compound composite material.
Fig. 7 is the Pt that the embodiment of the present invention 7 provides5In FeCoNiCuMn intermetallic compound composite material
Pt5XRD, HADDF-STEM of object phase and particle size distribution photo between FeCoNiCuMn metal；
The Pt from XRD it can be seen that object matches4Fe2NiCu standard PDF card is (since at present there is no Pt5FeCoNiCuMn's
Standard card, and Pt4Fe2NiCu crystal structure having the same therewith, only because Co the and Mn element added may result in
The partial offset at peak, but standard card difference should be few, therefore with Pt4Fe2NiCu standard PDF card is as reference)；HADDF-
STEM shows particle mean size 3.86nm (< 5nm), and distribution is presented narrow ditribution and shows even particle size.
Embodiment 8
A. step and embodiment 1 are identical；
B. the mesoporous carbon nanomaterial 40mg of resulting sulfur doping and 10mg metal salt (are guaranteed into RhCl3·nH2O and VCl3In
Rh:V=3:1 it) is placed in 100ml round-bottomed flask, adds etoh solvent (VCl3Facile hydrolysis thus with ethyl alcohol), stir 6-10h, revolving
After drying, uniformly mixed presoma is obtained；
C. presoma is put into tube furnace, argon hydrogen (mass fraction 95%Ar+5%H is passed through into tube furnace2) as guarantor
Gas is protected, tube furnace is warming up to 900 DEG C with the rate of 2-10 DEG C/min, keeps 2h；Finally room temperature, tubular type are down in annealing naturally again
Normal pressure is kept in furnace, obtains Rh3V intermetallic compound composite material.
Fig. 8 is the Rh that the embodiment of the present invention 8 provides3Rh in V intermetallic compound composite material3The XRD of object phase between V metal,
HADDF-STEM and particle size distribution photo；
The Rh from XRD it can be seen that object matches3V standard PDF card；HADDF-STEM shows particle mean size 2.05nm
(< 5nm), distribution are presented narrow ditribution and show even particle size.
Embodiment 9
A. step and embodiment 1 are identical；
B. the mesoporous carbon nanomaterial 40mg of resulting sulfur doping and 10mg metal salt (are guaranteed into RhCl3·nH2O and SbCl3
Middle Rh:Sb=1:1) it is placed in 100ml round-bottomed flask, add etoh solvent (SbCl3Facile hydrolysis thus with ethyl alcohol), stir 6-10h,
After revolving is dry, uniformly mixed presoma is obtained；
C. presoma is put into tube furnace, argon hydrogen (mass fraction 95%Ar+5%H is passed through into tube furnace2) as guarantor
Gas is protected, tube furnace is warming up to 900 DEG C with the rate of 2-10 DEG C/min, keeps 2h；Finally room temperature, tubular type are down in annealing naturally again
Normal pressure is kept in furnace, obtains RhSb intermetallic compound composite material.
Object phase between RhSb metal in the RhSb intermetallic compound composite material that Fig. 9 provides for the embodiment of the present invention 9
XRD, HADDF-STEM and particle size distribution photo；
The RhSb standard PDF card from XRD it can be seen that object matches；HADDF-STEM shows particle mean size 2.42nm
(< 5nm), distribution are presented narrow ditribution and show even particle size.
Embodiment 10
A. step and embodiment 1 are identical；
B. the mesoporous carbon nanomaterial 40mg of resulting sulfur doping and 10mg metal salt (are guaranteed into RhCl3·nH2O and GeCl4
Middle Rh:Ge=1:1) it is placed in 100ml round-bottomed flask, add etoh solvent (GeCl4Facile hydrolysis thus with ethyl alcohol), stir 6-10h,
After revolving is dry, uniformly mixed presoma is obtained；
C. presoma is put into tube furnace；Argon hydrogen (mass fraction 95%Ar+5%H is passed through into tube furnace2) as guarantor
Gas is protected, tube furnace is warming up to 800 DEG C with the rate of 2-10 DEG C/min, keeps 2h；Finally room temperature, tubular type are down in annealing naturally again
Normal pressure is kept in furnace, obtains RhGe intermetallic compound composite material.
Object phase between RhGe metal in the RhGe intermetallic compound composite material that Figure 10 provides for the embodiment of the present invention 10
XRD, HADDF-STEM and particle size distribution photo；
The RhGe standard PDF card from XRD it can be seen that object matches；HADDF-STEM shows particle mean size 1.98nm
(< 5nm), distribution are presented narrow ditribution and show even particle size.
Embodiment 11
A. step and embodiment 1 are identical；
B. the mesoporous carbon nanomaterial 40mg of resulting sulfur doping and 10mg metal salt (are guaranteed into RhCl3·nH2O and Ga
(NO3)3·nH2Rh:Ga=1:1 in O) it is placed in 100ml round-bottomed flask, etoh solvent or water are added, stir 6-10h, revolving
After drying, uniformly mixed presoma is obtained；
C. presoma is put into tube furnace；Argon hydrogen (mass fraction 95%Ar+5%H is passed through into tube furnace2) as guarantor
Gas is protected, tube furnace is warming up to 800 DEG C with the rate of 2-10 DEG C/min, keeps 2h；Finally room temperature, tubular type are down in annealing naturally again
Normal pressure is kept in furnace, obtains Rh3V intermetallic compound composite material.
Figure 11 is the Rh that the embodiment of the present invention 11 provides3Rh in V intermetallic compound composite material3Object phase between V metal
XRD, HADDF-STEM and particle size distribution photo；
The Rh from XRD it can be seen that object matches3V standard PDF card；HADDF-STEM shows particle mean size 1.95nm
(< 5nm), distribution are presented narrow ditribution and show even particle size.
Embodiment 12
A. step and embodiment 1 are identical；
B. the mesoporous carbon nanomaterial 40mg of resulting sulfur doping and 10mg metal salt (are guaranteed into IrCl3And VCl3Middle Ir:V=
It 3:1) is placed in 100ml round-bottomed flask, adds etoh solvent (VCl3Facile hydrolysis thus with ethyl alcohol), stir 6-10h, rotate drying
Afterwards, uniformly mixed presoma is obtained；
C. presoma is put into tube furnace；Argon hydrogen (mass fraction 95%Ar+5%H is passed through into tube furnace2) as guarantor
Gas is protected, tube furnace is warming up to 1000 DEG C with the rate of 2-10 DEG C/min, keeps 4h；Finally room temperature is down in annealing naturally again, is managed
Normal pressure is kept in formula furnace, obtains Ir3V intermetallic compound composite material.
Figure 12 is the Ir that the embodiment of the present invention 12 provides3Ir in V intermetallic compound composite material3Object phase between V metal
XRD, HRTEM and particle size distribution photo；
The Ir from XRD it can be seen that object matches3V standard PDF card；HRTEM shows particle mean size 4.95nm (<
5nm), distribution is presented narrow ditribution and shows even particle size.
Embodiment 13
Using the RhSb intermetallic compound composite material in embodiment 9 as catalyst, it is real to carry out selective hydrogenation catalysis
It tests, substrate is parachloronitrobenzene, and condition is 40 DEG C of temperature, pressure 1Mpa, time 1h, recycles 5 times, records each catalytic performance.
Figure 13 is the activity and selectivity recycled every time.
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.
Claims (10)
1. a kind of intermetallic compound composite material, mesoporous carbon including sulfur doping and the mesoporous carbon table for being carried on the sulfur doping
The intermetallic compound in face；The intermetallic compound is the intermetallic compound formed by base of Pt, Rh or Ir.
2. intermetallic compound composite material according to claim 1, which is characterized in that the ruler of the intermetallic compound
Very little < 5nm.
3. intermetallic compound composite material according to claim 1, which is characterized in that between the metal formed using Pt as base
Another metallic element of compound is in Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, In and Sn
It is one or more；Another metallic element of the intermetallic compound formed using Rh as base is selected from Ti, V, Cr, Fe, Ga, Ge, In
With one of Sb or a variety of；The intermetallic compound formed by base of Ir is Ir3V。
4. the preparation method of intermetallic compound composite material described in claim 1, comprising the following steps:
The mesoporous carbon of sulfur doping, metal salt presoma and solvent are mixed, obtain original mixture after dry；Before the metal salt
Drive body is one of Pt base salt, Rh base salt and Ir base salt and other metal salts；
The original mixture is heat-treated under reducing atmosphere, obtains intermetallic compound composite material；At the heat
800~1100 DEG C of the temperature of reason.
5. the preparation method according to claim 4, which is characterized in that the preparation method of the mesoporous carbon of the sulfur doping is specific
Are as follows:
By sulfur-bearing small organic molecule, SiO2Bead and transition metal salt are mixed in solvent, and high-temperature calcination after drying obtains carbon materials
Material；
It is sequentially etched the carbon material using sodium hydroxide and sulfuric acid, obtains the mesoporous carbon of sulfur doping.
6. preparation method according to claim 5, which is characterized in that the sulfur-bearing small organic molecule is 2,2 '-bithiophenes,
Transition metal salt is selected from cabaltous nitrate hexahydrate；The 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 DEG C.
7. the preparation method according to claim 4, which is characterized in that the metal salt presoma is Pt base salt and other gold
When belonging to salt, other metallic elements of other metal salts be selected from Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge,
One of Zr, In and Sn or a variety of；When the metal salt presoma is Rh base salt and other metal salts, other described metal salts
Other metallic elements be selected from one of Ti, V, Cr, Fe, Ga, Ge, In and Sb or a variety of；The metal salt presoma is Ir
Base salt and V salt.
8. the preparation method according to claim 4, which is characterized in that the reducing atmosphere is the mixing of hydrogen and argon gas
Gas, the volume fraction of the hydrogen are 5%, and the volume fraction of the argon gas is 95%.
9. the preparation method according to claim 4, which is characterized in that the heating rate of the heat treatment be 1~10 DEG C/
Min, time are 0.5~12h.
10. the described in any item intermetallic compound composite materials of claims 1 to 3 or claim 4~9 are described in any item
The preparation method of intermetallic compound composite material is applied in hydrogenation catalyst.
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Effective date of registration: 20221026 Address after: 230000 96 Jinzhai Road, Hefei City, Anhui Province Patentee after: Liang Haiwei Patentee after: Tong Lei Address before: 230026 Jinzhai Road, Baohe District, Hefei, Anhui Province, No. 96 Patentee before: University of Science and Technology of China Effective date of registration: 20221026 Address after: 230000 China (Anhui) Pilot Free Trade Zone, Hefei, Anhui Province 2899 Kongquetai Road, High tech Zone, Hefei, Liandong U Valley, Building 4, Hefei Hi tech International Enterprise Port Patentee after: Anhui Weishui New Energy Technology Co.,Ltd. Address before: 230000 96 Jinzhai Road, Hefei City, Anhui Province Patentee before: Liang Haiwei Patentee before: Tong Lei |