CN110252308A - A kind of active metal is in the loaded catalyst and its preparation method and application of atom level dispersion in the carrier - Google Patents
A kind of active metal is in the loaded catalyst and its preparation method and application of atom level dispersion in the carrier Download PDFInfo
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Abstract
The invention discloses the loaded catalysts that a kind of active metal is in atom level dispersion in the carrier comprising: active metal species；Carrier metal oxide；Wherein the active metal includes one of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au or a variety of, and the carrier metal includes one of Ti, Zr, Nb, Ce, Al, Ga, In, Si, Ge, Sn or a variety of.The invention also discloses the preparation method of above-mentioned catalyst and purposes.The method that the present invention is generated by carrier situ, preparing active metal in the carrier is in the loaded catalyst of atom level dispersion, wherein the state of aggregation particle of the active metal species of the granularity greater than 1nm is not present.The cost of raw material is cheap, operation is simple, highly-safe, does not need post-processing step, is conducive to industry's enlarging production.Its is widely applicable simultaneously, is conducive to carry out scientific research and expanding production for different catalyst systems.
Description
Technical field
It is in the carrier in what atom level was dispersed the invention belongs to new material preparation field more particularly to a kind of active metal
Loaded catalyst and its preparation method and application.
Background technique
It is generally believed that sub-nanometer cluster has better catalytic activity or selectivity than nano particle, block materials, because
When particle dispersion degree reaches monatomic size, cause many new characteristics, the surface free energy that such as increased dramatically, quantum size
Effect, unsaturated coordination environment and the interaction of Metal-Support etc..Theoretically, the load type metal of perfect condition is urged
Agent dispersion is that metal is evenly distributed on carrier in the form of monoatomic.Compared to the supported catalyst of Nano grade, atom
Each metallic atom of rank catalyst is used as active sites to use, and is greatly improved on catalytic efficiency.Especially for valence
For the more expensive metal of lattice, by active catalytic components atomization, the usage amount of catalyst can be substantially reduced, reduce catalyst at
This, promotes the potentiality of catalyst scale application in the industrial production.
Currently, the supported catalyst of atomic level is in CO oxidation and selective oxidation plus hydrogen and selective hydrogenation, NO
The neck such as reduction and oxidation, Water gas shift/WGS, organic synthesis, methanol steam reforming, fuel cell, photoelectrocatalysis, oxidation of formaldehyde
Domain shows greater advantage.However, equally there is also obvious deficiencies for monatomic or cluster rank catalyst.When metallic is reduced to
When atomic level, specific surface area be increased dramatically, and metal surface free energy is caused to sharply increase, and easily be occurred in preparation and reaction
Coupling of reuniting forms larger particles, is greatly reduced so as to cause catalyst activity, therefore, prepares the stable atom level of physico-chemical property
Supported catalyst is faced with larger challenge.
Current atom grade dispersion supported catalyst preparation method be broadly divided into it is following several: coprecipitation, infusion process,
Atomic layer deposition method, anti-Ostward curing method, solid phase fusion method etc..Generally speaking, the above method can effectively prepare atom
The supported catalyst of grade dispersion, but most methods are related to the post-processing of harsh synthesis condition, expensive drug and raw material, complexity
Process strongly limits application of the atom level dispersion supported catalyst in production in practice.
The invention from cost control, using the Metal Source materials and formamide of price economy, by setting
Count easy reaction synthesis path, realize low cost, can the preparation of scale magnanimity atom level dispersed metal supported catalyst
Universality preparation.
Summary of the invention
First aspect present invention provides the loaded catalyst that a kind of active metal is in atom level dispersion in the carrier, packet
It includes:
Active metal species；
Carrier metal oxide；
Wherein the active metal includes in Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au
It is one or more, the carrier metal includes one of Ti, Zr, Nb, Ce, Al, Ga, In, Si, Ge, Sn or a variety of.
Preferably, the oxygen atoms bond on the active metal and carrier metal oxide surface.
Preferably, the active metal species and/or the carrier metal oxide at least partly vulcanized, nitrogenized,
Phosphatization or boronation, correspondingly, the sulphur, nitrogen, phosphorus or boron on at least partly described active metal and carrier metal oxide surface are former
Sub-key is closed.
Preferably, wherein the state of aggregation particle of the active metal species there is no granularity greater than 1nm.
Second aspect of the present invention provides the support type that active metal described in first aspect is in atom level dispersion in the carrier
The preparation method of catalyst, comprising the following steps:
1) at least one first kind metal salt and at least one second metalloid salt are dissolved in formamide, the first eka-gold
Belong to salt and complex reaction occurs for formamide, obtains the formamide solution of mixed metal salt；Wherein, in the first kind metal salt
Metallic element is one of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au；Second eka-gold
Belonging to the metallic element in salt is one of Ti, Zr, Nb, Ce, Al, Ga, In, Si, Ge, Sn；
2) formamide solution for the mixed metal salt for obtaining step 1) reacts 1 to 99 hours at 100-300 DEG C, so that
Formamide polymerize, and with wherein the second metalloid salt hydrolysis occurs for the by-product water of formamide polymerization reaction；
3) mixture after step 2) reaction is separated by solid-liquid separation, by obtained solid matter in air atmosphere, temperature
1 to 99 hours are roasted at 300-900 DEG C to get the loaded catalyst is arrived.
Preferably, in step 1), total concentration of the first kind metal salt in formamide be 0.001-0.1mol/L, second
Total concentration of the metalloid salt in formamide are as follows: 0.009-1.0mol/L.
Preferably, further include step 4): the loaded catalyst that step 3) is obtained at least partly nitrogenized,
Vulcanization, phosphatization or boronation.
Wherein, " at least partly nitridation, vulcanization, phosphatization or boronation " is referred to through control nitridation, vulcanization, phosphatization
Or the degree that boronation reaction carries out, the carrier metal oxide in the loaded catalyst that step 3) obtains is by extremely
Partially replace with carrier metal nitride, carrier metal sulfide, carrier metal phosphide, in carrier metal boride
One kind, correspondingly, at least partly described active metal are bonded with sulphur, nitrogen, phosphorus or the boron atom on carrier metal oxide surface.
Preferably, the nitridation is to be reacted using nitrogen source with the loaded catalyst that step 3) obtains, wherein nitrogen source packet
Include ammonia, ammonium hydroxide, Sodamide, sodium azide；
The vulcanization be reacted using sulphur source with the loaded catalyst that step 3) obtains, wherein sulphur source include sulphur powder,
Vulcanized sodium, hydrogen sulfide, thioacetamide, thiocarbamide；
The phosphatization be reacted using phosphorus source with the loaded catalyst that step 3) obtains, wherein phosphorus source include phosphorus powder,
Phosphoric acid, alkali metal phosphate, triphenylphosphine；
The boronation be reacted using boron source with the loaded catalyst that step 3) obtains, wherein boron source include boron powder,
Boric acid, alkali borate.
Preferably, the liquid phase means include flask heating, hydrothermal reaction kettle heating, and the gas phase means include pipe
Formula stove heating.
Preferably, the mixed method includes manual oscillation, mechanical oscillation, ultrasound, stirring.
Preferably, the reaction vessel of the step 1) and step 2) is the preferable safety container of heat resistance, including flask, poly-
Tetrafluoroethene reaction kettle.
Preferably, the method for the separation of solid and liquid includes centrifugation, filtering, standing sedimentation.
Above-mentioned steps 2) in, formamide autohemagglutination, carbonization forms nitrogen carbon material, and nitrogen therein can orientation chelating the
A kind of metal cation is distributed in first kind metal ion on the nitrogen carbon material with the state that atom level is dispersed, and forms activity
Metal nitrogen carbon material.The by-product water generated in formamide polymerization, carbonisation forms phase with the second metalloid ionic reaction
Answer support oxide or hydroxide.
Both the above is reacted while being occurred, and active metal nitrogen carbon material and carrier metal oxide or hydrogen-oxygen abundant are formed
Compound interface.Therefore, carrier metal oxide or hydroxide that the active metal nitrogen carbon material of atom level dispersion generates in situ
It is formed on object base material and uniformly, is closely loaded, the as described loaded catalyst presoma.
Above-mentioned steps 3) in, the loaded catalyst presoma is roasted in air atmosphere, and metal hydroxides generates gold
Belong to oxide, while removing nitrogen carbon material, the active force of stationary atom grade active metal component is transferred to support oxide circle
Face, in roasting process, the strong anchoring effect that nitrogen carbon material has the active metal atom of surrounding has largely delayed work
Property metal component reunion obtain activity gold after oxygen atoms bond on active metal and carrier metal oxide surface
Belong in the carrier in the loaded catalyst of atom level dispersion.
Third aspect present invention provides the support type that active metal described in first aspect is in atom level dispersion in the carrier
The purposes of catalyst, including: it is suitable for all non-electrical and reacts, such as hydrogenation reaction, dehydrogenation reaction, isomerization reaction, desulfurization
Reaction, catalytic polymerization etc..
The difference of preparation method and infusion process of the invention is as follows:
The present invention realizes atom level high-dispersion load of the extensive metallic element in a variety of substrates by two-step method, first
The carrier metal oxide or hydroxide substrate material that the active metal nitrogen carbon material of step, first atom level dispersion generates in situ
It is formed on material and uniformly, is closely loaded；
Second step, during nitrogen carbon is removed in roasting, nitrogen carbon material plays Anchoring Effect to active metal atom, in active gold
Before category component is stablized by support oxide, the reunion of active metal component is largely delayed, has continued to maintain active gold
Belong to atom level dispersity, is scattered in active metal on carrier metal oxide in atom level.
And traditional infusion process, the absorption of atom level is realized mostly under low temperature, and active metal trip is often resulted in after heating roasting
It moves seriously, because not having active force to delay the aggregation of active metal component in roasting process, active metal is in carrier metal
It can not be in atom level dispersity on oxide, final active metal is even millimetre-sized in nanoscale, the micron order of state of aggregation
Particle form.
Beneficial effects of the present invention are as follows:
(1) method that the present invention is generated by carrier situ, preparing active metal in the carrier is in what atom level was dispersed
Loaded catalyst, wherein the state of aggregation particle of the active metal species there is no granularity greater than 1nm.Raw material cost is low
It is honest and clean, operation is simple, highly-safe, do not need post-processing step, be conducive to industry's enlarging production.Its is widely applicable simultaneously, benefit
In for the progress scientific research of different catalyst systems and expanding production.
(2) catalytic mechanical intensity of the invention is high, active component dispersion degree is high, catalytic activity is high, selectivity is high, compares
In the catalyst of similar non-atomic grade dispersion, it is easier to be reduced.
Detailed description of the invention
Fig. 1 is Ni/Al prepared by the embodiment of the present invention 12O3Transmission electron microscope photo.
Fig. 2 is Ni/CeO prepared by the embodiment of the present invention 22Transmission electron microscope photo.
Fig. 3 is Ni/Al prepared by the embodiment of the present invention 32O3Transmission electron microscope photo.
Fig. 4 is Ni/Al prepared by the embodiment of the present invention 42O3Transmission electron microscope photo.
Fig. 5 is Ni/Al prepared by the embodiment of the present invention 52O3Transmission electron microscope photo.
Fig. 6 is Co/Al prepared by the embodiment of the present invention 62O3Transmission electron microscope photo.
Fig. 7 is Cu/Al prepared by the embodiment of the present invention 72O3Transmission electron microscope photo
Fig. 8 is Au/Al prepared by the embodiment of the present invention 82O3Transmission electron microscope photo.
Fig. 9 is Pd/Al prepared by the embodiment of the present invention 92O3Transmission electron microscope photo.
Figure 10 is CuZrO prepared by the embodiment of the present invention 102Transmission electron microscope photo.
Figure 11 is Ni-W/Al prepared by the embodiment of the present invention 112O3Transmission electron microscope photo.
Figure 12 is Ni-W/Al prepared by the embodiment of the present invention 112O3Element Surface scan photo.
Figure 13 is the embodiment of the present invention 1,3-9,11 Al prepared2O3The X-ray diffractogram of the monatomic catalyst of load
Spectrum.
Figure 14 is Ni/Al prepared by the embodiment of the present invention 12O3Nitrogen adsorption desorption curve, wherein De. indicate desorption curve,
Ab. adsorption curve is indicated.
Figure 15 is Ni/Al prepared by the embodiment of the present invention 12O3XPS Ni2p swarming curve.
Figure 16 is Co/MoO prepared by the embodiment of the present invention 123X ray diffracting spectrum.
Figure 17 is Co/MoS prepared by the embodiment of the present invention 122X ray diffracting spectrum.
Figure 18 is Ni/Al prepared by the embodiment of the present invention 12O3In CO2Add the performance evaluation in hydrogen methane reaction.
Figure 19 is Ni/CeO prepared by the embodiment of the present invention 22In CO2Add the performance evaluation in hydrogen methane reaction.
Figure 20 is Ni/CeO prepared by the embodiment of the present invention 22Hydrogen temperature programmed reduction curve.
Specific embodiment
The contents of the present invention are further illustrated below by specific embodiment.
Embodiment 1
By 60.0mL dissolved with the anhydrous NiCl of 0.009mol/L2With the anhydrous AlCl of 0.091mol/L3Formamide solution be placed in body
Product is to react 12 hours in the ptfe autoclave of 100.0mL in 180 DEG C.After reaction time cut-off, Temperature fall is taken
Solidliquid mixture out makes to be separated by solid-liquid separation using centrifugation, and solid is placed in drying in 80 DEG C of baking ovens, dried powder is collected, makes
With Muffle furnace 450 DEG C roast 3 hours to get arrive target product Ni/Al2O3, transmission electron microscope photo is shown in Fig. 1, and nitrogen adsorption desorption is bent
Line is shown in that Figure 14, XPS Ni2p swarming curve are shown in Figure 15.
Embodiment 2
Except by the anhydrous AlCl of B class salt3Replace with Ce (NO3)2·6H2O, other are with embodiment 1 with to get arriving target product
Ni/CeO2, transmission electron microscope photo is shown in Fig. 2.
Embodiment 3
Except by anhydrous NiCl2Concentration be promoted to 0.018mol/L, AlCl3Concentration is promoted to 0.182mol/L, other and reality
Example 1 is applied with to get to target product Ni/Al2O3, transmission electron microscope photo is shown in Fig. 3.
Embodiment 4
Except by anhydrous NiCl2Concentration be promoted to 0.027mol/L, AlCl3Concentration is promoted to 0.273mol/L, other and reality
Example 1 is applied with to get to target product Ni/Al2O3, transmission electron microscope photo is shown in Fig. 4.
Embodiment 5
Except the temperature and time for roasting Muffle furnace adjusts separately as 550 DEG C, 3 hours, other with embodiment 1 with to get
To target product Ni/Al2O3, transmission electron microscope photo is shown in Fig. 5.
Embodiment 6
Except by the anhydrous NiCl of A metalloid salt2Replace with anhydrous CoCl2, other arrive target product Co/ with embodiment 1
Al2O3, Fig. 6 is seen with transmission electron microscope photo.
Embodiment 7
Except by the anhydrous NiCl of A metalloid salt2Replace with anhydrous Cu (NO3)2, other are produced with embodiment 1 with to get to target
Object Cu/Al2O3, transmission electron microscope photo is shown in Fig. 7.
Embodiment 8
Except by the anhydrous NiCl of A metalloid salt2Replace with anhydrous AuCl3, other are with embodiment 1 with to get arriving target product
Au/Al2O3, transmission electron microscope photo is shown in Fig. 8.
Embodiment 9
Except by the anhydrous NiCl of A metalloid salt2Replace with anhydrous PdCl3, other are with embodiment 1 with to get arriving target product
Pd/Al2O3, transmission electron microscope photo is shown in Fig. 9.
Embodiment 10
Except by the anhydrous NiCl of A metalloid salt2Replace with anhydrous Cu (NO3)2, the anhydrous AlCl of B class salt3Replace with Zr (SO4)2,
Other are with embodiment 1 with to get arriving target product Cu/ZrO2, transmission electron microscope photo is shown in Figure 10.
Embodiment 11
A metalloid salt is extended to double activated metal system, except the NiCl that will be used as A metalloid salt2A half strength replace
It is changed to the anhydrous WCl of equimolar concentration3, other are with embodiment 1 with to get arriving target product Ni-W/Al2O3, transmission electron microscope photo
See that Figure 11, element Surface scan photo are shown in Figure 12.
The obtained product of embodiment 1-12 is characterized and is analyzed:
Wherein MAThe first metalloid is represented, wherein MBRepresent the second metalloid.
Transmission electron microscope photo (attached drawing 1,3-10,11) display: formamide, AlCl are used3It is synthesized with different transition metal salts
MA/Al2O3The pattern of supported catalyst is graininess, Al2O3Average particle size transmits in 5-10nm in common high-resolution
Under, have no the state of aggregation particle of active metal species of the granularity greater than 1nm.
Transmission electron microscope photo (attached drawing 2) display: formamide, NiCl are used2It is synthesized with the precursor metal salts of different carriers
Ni/MBOxThe pattern of supported catalyst is graininess, MBOxAverage particle size is in 5-10nm, under the transmission of common high-resolution, not
See the state of aggregation particle of Ni of the granularity greater than 1nm.
Transmission electron microscope element Surface scan photo (attached drawing 12) display: formamide, NiCl are used2、WCl3And AlCl3Synthesis
Ni-W/Al2O3In supported catalyst particles, Ni and W active metal component is uniformly distributed and is formed without particle.
X-ray powder diffraction pattern (attached drawing 13) display: load is only detected in the embodiment 1-12 for including in the present invention
The diffraction maximum of body material has no the diffraction maximum of active metal component, it was demonstrated that active metal species are deposited in the form of sub-nanometer or cluster
That is, it is indicating to be in atom level dispersity.
Specific surface area tests (14 nitrogen adsorption desorption curve of attached drawing) display and uses formamide, NiCl2And AlCl3The Ni/ of synthesis
Al2O3The specific surface area of supported catalyst is 407m2/ g, aperture form is based on wedged hole.
XPS Ni2p swarming curve (attached drawing 15) display uses formamide, NiCl2And AlCl3The Ni/Al of synthesis2O3Load
With the oxygen atoms bond on carrier metal oxide surface, no zero-valent metal state of aggregation exists the Ni component of catalyst.
Embodiment 12
By 60.0mL dissolved with the anhydrous CoCl of 0.009mol/L2(MAMetalloid salt) and the anhydrous MoCl of 0.091mol/L3(MBClass
Salt) formamide solution be placed in volume be 100.0mL ptfe autoclave in, in 180 DEG C react 12 hours.When reaction
Between end after, Temperature fall, take out solidliquid mixture, make to be separated by solid-liquid separation using centrifugation, solid be placed in 80 DEG C of baking ovens
It is dry, dried powder is collected, is roasted 3 hours using Muffle furnace at 450 DEG C, is obtained active metal and carrier metal is in oxide
The loaded catalyst Co/MoO of form3.After this product is stirred 0.5h in 30mL thiourea solution, being placed in volume is
In the reaction kettle of 50.0mL, in 220 DEG C of reaction 18h.Reaction time cut-off after, Temperature fall, take out solidliquid mixture, using from
Heart mode makes to be separated by solid-liquid separation, and solid is placed in 60 DEG C of baking ovens and is dried in vacuo, and collects dried powder to get target product Co/ is arrived
MoS2Supported catalyst, i.e., the described carrier metal oxide are replaced all with carrier metal sulfide, the active metal with
Sulfur atom linkage in carrier metal sulfide surface.Figure 16 is Co/MoO manufactured in the present embodiment3X ray diffracting spectrum.
Figure 17 is Co/MoS manufactured in the present embodiment2X ray diffracting spectrum.
Embodiment 13
The Ni/Al that Examples 1 and 2 are synthesized2O3And Ni/CeO2Supported catalyst is for being catalyzed CO2Hydrogenation reaction is being surveyed
Strip part are as follows: the grinding of gained catalyst, tabletting are made to the particle of 20~60 mesh, the loading of adsorbent is 0.5g, prereduction
Temperature is 450 DEG C, pressure 0.1MPa, hydrogen flowing quantity 30mL/min, and the recovery time is half an hour.CO2Add hydrogen evaluation condition:
200-350 DEG C of temperature, normal pressure reacts 1 hour after temperature is stablized, and a product is taken every 10 minutes and with gas-chromatography pair
Product is analyzed.Reaction gas is CO2With H2Mixed gas, mixed proportion CO2:H2=1:4.
Conclusion is as follows:
Under 200 DEG C, 230 DEG C, 260 DEG C, 290 DEG C, 320 DEG C, 350 DEG C of reaction temperature, Ni/Al2O3Catalytic selectivity
Respectively 85.86%, 84.48%, 85%, 90.56%, 100%, 100%, are shown in attached drawing 18.It is 200 DEG C, 230 in test temperature
DEG C, 260 DEG C, Ni/CeO2Catalytic selectivity be respectively 96.85%, 99.99%, 100%, see attached drawing 19.Therefore, it urges for two kinds
Agent all shows good catalytic selectivity.
Embodiment 14
The Ni/CeO that characterization embodiment 2 synthesizes is tested using hydrogen temperature programmed reduction2Supported catalyst, in characterization result
Three groups of reduction peaks (attached drawing 20) occur: they are respectively at 270 DEG C, 326 DEG C and 434 DEG C, wherein 326 DEG C aoxidize for carrier surface
The reduction peak of nickel.Documents, Ni particulate load is in CeO2The Ni/CeO of upper preparation2The hydrogen temperature programming of loaded catalyst
Occur five groups of reduction peaks in restoring data result, they are respectively at 210 DEG C, 265 DEG C, 360 DEG C, 500 DEG C and 582 DEG C
(Morphology dependence of catalytic properties of Ni/CeO2 for CO2 methanation:
A kinetic and mechanism study[J].Catalysis Today,2018,DOI:10.1016/
j.cattod.2018.04.067.).Wherein 360 DEG C of reduction peaks for carrier surface nickel oxide.Show reality with the COMPARATIVE CATALYST
Apply the Ni/CeO of the atom level dispersion of the synthesis of example 22Supported catalyst is easier to be activated reduction.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be subject to the protection scope in claims.
Claims (9)
1. the loaded catalyst that a kind of active metal is in atom level dispersion in the carrier, characterized in that it comprises:
Active metal species；
Carrier metal oxide；
Wherein the active metal includes one in Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au
Kind or it is a variety of, the carrier metal includes one of Ti, Zr, Nb, Ce, Al, Ga, In, Si, Ge, Sn or a variety of.
2. loaded catalyst according to claim 1, which is characterized in that the active metal and carrier metal oxide
Oxygen atoms bond on surface.
3. loaded catalyst according to claim 1, which is characterized in that the active metal species and/or the load
Body metal oxide is by least partly vulcanization, nitridation, phosphatization or boronation, correspondingly, at least partly described active metal and load
Sulphur, nitrogen, phosphorus or boron atom bonding on body metal oxide surface.
4. loaded catalyst according to claim 1 or 2, which is characterized in that wherein there is no the institutes that granularity is greater than 1nm
State the state of aggregation particle of active metal species.
5. the preparation side that active metal according to claim 1 is in the loaded catalyst of atom level dispersion in the carrier
Method, which comprises the following steps:
1) at least one first kind metal salt and at least one second metalloid salt are dissolved in formamide, first kind metal salt
Complex reaction occurs with formamide, obtains the formamide solution of mixed metal salt；Wherein, the metal in the first kind metal salt
Element is one of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au；The second metalloid salt
In metallic element be one of Ti, Zr, Nb, Ce, Al, Ga, In, Si, Ge, Sn；
2) formamide solution for the mixed metal salt for obtaining step 1) reacts 1 to 99 hours at 100-300 DEG C, so that formyl
Amine polymerize, and with wherein the second metalloid salt hydrolysis occurs for the by-product water of formamide polymerization reaction；
3) mixture after step 2) reaction is separated by solid-liquid separation, by obtained solid matter in air atmosphere, temperature 300-900
1 to 99 hours are roasted at DEG C to get the loaded catalyst is arrived.
6. the preparation method of loaded catalyst according to claim 5, which is characterized in that in step 1), the first eka-gold
Belonging to total concentration of the salt in formamide is 0.001-0.1mol/L, total concentration of the second metalloid salt in formamide are as follows:
0.009—1.0mol/L。
7. the preparation method of loaded catalyst according to claim 5, which is characterized in that further include step 4): will walk
The rapid loaded catalyst 3) obtained at least partly nitrogenized, vulcanized, phosphatization or boronation.
8. preparation method according to claim 7, which is characterized in that the nitridation is to be obtained using nitrogen source and step 3)
Loaded catalyst reaction, wherein nitrogen source includes ammonia, ammonium hydroxide, Sodamide, sodium azide；
The vulcanization is to be reacted using sulphur source with the loaded catalyst that step 3) obtains, and wherein sulphur source includes sulphur powder, vulcanization
Sodium, hydrogen sulfide, thioacetamide, thiocarbamide；
The phosphatization be reacted using phosphorus source with the loaded catalyst that step 3) obtains, wherein phosphorus source include phosphorus powder, phosphoric acid,
Alkali metal phosphate, triphenylphosphine；
The boronation be reacted using boron source with the loaded catalyst that step 3) obtains, wherein boron source include boron powder, boric acid,
Alkali borate.
9. loaded catalyst according to claim 1 is in catalysis CO2Purposes in hydrogenation reaction.
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