CN108671918A - Regulate and control the method for improving catalyst activity and selectivity based on atomic layer deposition product orientation - Google Patents

Regulate and control the method for improving catalyst activity and selectivity based on atomic layer deposition product orientation Download PDF

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CN108671918A
CN108671918A CN201810326090.1A CN201810326090A CN108671918A CN 108671918 A CN108671918 A CN 108671918A CN 201810326090 A CN201810326090 A CN 201810326090A CN 108671918 A CN108671918 A CN 108671918A
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atomic layer
layer deposition
noble metal
catalyst
reaction
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陈蓉
曹坤
龚渺
单斌
蔡佳明
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6562—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
    • C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof

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Abstract

The invention belongs to metal oxide catalysts to prepare correlative technology field, and disclose a kind of method for regulating and controlling based on atomic layer deposition product orientation and improving catalyst activity and selectivity, including：Noble metal nano particles are distributed in the surface homoepitaxial of reaction carriers, noble metal carrier catalyst sample is thus made；By atomic layer deposition reaction method depositing metal oxide auxiliary agent to obtain required catalyst prod on the surface of noble metal carrier catalyst sample, while targeted design is carried out to the specific process parameter of atomic layer deposition reaction.Through the invention, oxides additive can be allowed to execute the deposition of selectivity in multiple crystal faces of active metal surface, realize discontinuous specific position cladding, the activity and selectivity for effectively improving catalyst simultaneously, are therefore particularly suitable for the catalyst preparation application scenario that synthesis gas prepares C2+ oxygenatedchemicals.

Description

Regulate and control the method for improving catalyst activity and selectivity based on atomic layer deposition product orientation
Technical field
The invention belongs to metal oxide catalysts to prepare correlative technology field, and atom is based on more particularly, to one kind The method that layer deposition orientation regulation and control improve catalyst activity and selectivity.
Background technology
With global warming, fossil fuel exhaustion and oil price rise, people are about alternative fossil fuel It is current most important industrial production side that the exploitation pay attention to day by day of clean energy resource, wherein gas phase catalytic reaction, which prepare clean fuel, To, such as by synthesis gas (CO+H2) C2+ oxygenatedchemicals can be directly catalyzed and synthesized, it is not only a kind of clean fuel, is alternatively arranged as Gasoline additive etc., thus obtained the extensive concern of people.
It is catalyzed the reaction of controlled syntheses clean fuel for this gas-like phase, is faced with most important problem at present and researches and develops A kind of catalytic activity and the excellent associated catalysts of target product selectivity.In catalytic process, catalytic selectivity is catalysis One of critical nature of agent industrially then makes raw material be converted to specified direction using catalytic selectivity, reduces side reaction；This Show that catalyst improves the incidence of main reaction in the process, inhibit the generation of side reaction, is to improve target product yield Important method.For the improvement problem of catalytic selectivity, the solution route proposed in the prior art be concentrated mainly on screening auxiliary agent, Or the chemical state etc. that auxiliary agent content changes active metal is adjusted, the product choosing of catalyst is accordingly improved to a certain extent Selecting property.For the improvement problem of catalytic activity, the solution route proposed in the prior art includes mainly changing catalyst preparation side Method, which improves the dispersion degree of active metal nano particle or is modified to catalyst carrier, carrys out anchoring activity metal etc..
However, further investigations have shown that, the above-mentioned prior art often can not be simultaneously in catalyst activity and selectivity two It makes and being effectively improved in terms of a index, exist simultaneously cumbersome, poor controllability, and be difficult to adapt to needed for catalysis controlled syntheses The technical problems such as the particular demands of target product.Although also proposed some in the prior art using active metal and auxiliary agent to make Standby catalyst (such as the Rh-Mn/SiO used in synthesis C2+ oxygenatedchemicals2Catalyst) scheme, wherein pass through add auxiliary agent The dispersion degree and chemical property that active metal can further be improved with carrier improve the yield of target product, but are found in putting into practice There are still active site lazy weight and discrete specific package is cannot achieve in active metal-auxiliary agent interface etc. no Foot.Correspondingly, this field is there is an urgent need for making this further Improvement, to conform better to the height of modernization catalysis reaction The efficient demand of matter.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides one kind being based on atomic layer deposition product orientation tune The method that control improves catalyst activity and selectivity, wherein the catalytic process by preparing C2+ oxygenatedchemicals in conjunction with synthesis gas Response characteristic and mechanism study, introduce atomic layer deposition method simultaneously the critical craft etc. of its reaction route is re-started Targetedly Curve guide impeller accordingly not only may make active metal to realize the deposition of high dispersive in carrier, but also metal allowed to aoxidize Object auxiliary agent executes the deposition of selectivity in multiple crystal faces of active metal surface, realizes discontinuous specific position cladding, especially It is that can also be significantly expanded the interfacial area formed between active metal-auxiliary agent, thus be conducive to effectively improve catalyst simultaneously Activity and selectivity, and it is particularly suitable for the catalyst preparation application scenario that similar synthesis gas prepares C2+ oxygenatedchemicals.
Correspondingly, it is proposed, according to the invention, provide a kind of based on atomic layer deposition product orientation regulation and control raising catalyst activity and choosing The method of selecting property, the catalyst are suitable for the catalytic reaction process that similar synthesis gas prepares C2+ oxygenatedchemicals, and feature exists In this method includes the following steps：
(a) silica, aluminium oxide or other analogs are chosen as reaction carriers, pass through atomic layer deposition reaction method or leaching Stain method is distributed noble metal nano particles in its surface homoepitaxial, and noble metal carrier catalyst sample is thus made；
(b) on the surface of the noble metal carrier catalyst sample obtained by step (a), atomic layer deposition is continued through Method deposition oxide auxiliary agent obtains required catalyst prod, in the process, the technique ginseng of the atomic layer deposition reaction Number is set as follows：
Using ozone or oxygen and organometallic complex as presoma, nitrogen or helium as carrier gas, atom Layer deposition reaction temperature be 100 DEG C~300 DEG C, the presoma burst length be 30s~120s, carrier gas scavenging period be 30~ 120s, finally the oxides additive deposited 2~10 cycles on the surface of noble metal carrier catalyst sample, thus make Obtain multiple crystal faces of the metal onidiges auxiliary agent on the noble metal nano particles surface of the noble metal carrier catalyst sample It realizes the deposition of selectivity, and then realizes discontinuous network-like growth.
By conceiving above, since atomic layer deposition method is that one kind passing through cycle alternation based on vaporous precursors in substrate The half-reaction after substrate surface chemisorption saturation of the film preparing technology of reaction, wherein presoma stops, and before two kinds Drive body and constitute a cycle preparation process through two half-reactions, this mode can ensure that each reaction only deposit one layer (or less than One layer of atom), thus reach effective control that atomic scale is accurate to deposited material.By this method, by introducing atomic layer For sedimentation to having made targeted design to its critical craft, the present invention can be on the larger carrier of specific surface area with original Sub- form membrane growth activity metal layer by layer is conducive to the height that active metal nano particle is realized on high surface area carrier Dispersion；In addition importantly, prepared by being aoxidized using low activity Atomic layer deposition precursor auxiliary agent is in follow-up atomic layer deposition During product, not only it can realize that auxiliary agent selectively wraps up in multiple and different crystal faces on active metal nano grain surface, but also The interfacial area formed between metal-auxiliary agent can also be noticeably greater than existing preparation method；Such as catalyzing and synthesizing C2+ containing oxidation The reaction for closing object, between metal-auxiliary agent generations at interface provide new active site, improve CO absorption or activation mode, rush It dissociates and its is inserted into CO, therefore can be conducive to improve the activity and selectivity of catalyst simultaneously using the technical process.
As it is further preferred that for step (b), the metal oxide auxiliary agent is matched using low activity, that is, organic The big Atomic layer deposition precursor of position group (such as THD=2,2,6,6- tetramethyl -3,5- heptadione) is obtained to aoxidize, and In this atomic layer deposition reaction process, cooling regulation and control are carried out to depositing temperature so that real reaction temperature is less than well-defined reaction temp About 50 degrees Celsius or more.
Why design in this way, on the one hand, pyroreaction can improve the growth activity of Atomic layer deposition precursor, and reduction helps The table of bonding bonded energy difference, lattice surface matching difference, metallic particles different parts between agent oxide and precious metal surface Face energy difference, cannot achieve selective deposition；Therefore, on the other hand, also specially to the technical process of deposition aid in the present invention Middle specific aim takes Low temperature regulation processing, and the purpose done so is that improve presoma grows work in active metal different loci Property difference, to reach site selectivity growth.
As it is further preferred that the Atomic layer deposition precursor of the low activity preferably selects one kind in following substance Or combination：Mn (thd) 3, Fe (thd) 3, Ce (thd) 4, Co (acac) 2, Mn (acac) 3 and Cu (acac) 2.
As it is further preferred that in step (b), the cooling regulation process carried out for depositing temperature uses journey Sequence cooling monitors the mode of deposition rate to execute, and further preferably regulates and controls to 130-160 degrees Celsius of temperature range.
It is equal on reaction carriers surface by atomic layer deposition reaction method as it is further preferred that for step (a) The further preferably setting of the technological parameter of even growth distribution noble metal nano particles is as follows：Use ozone and noble metal organic coordination Compound is as presoma, nitrogen or helium as carrier gas, and atomic layer deposition reaction temperature is 150 DEG C~300 DEG C, presoma arteries and veins It is 30s~120s to rush the time, and carrier gas scavenging period is 30~120s, finally deposits 2~10 cycles on the surface of the carrier, thus Obtain noble metal carrier catalyst sample.
As it is further preferred that for step (a), the noble metal nano particles preferably use Rh, Pt or its His analog, and its average particle diameter size is preferably controlled to 2nm~6nm.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, pass through introduce atomic layer Sedimentation has simultaneously re-started targetedly Curve guide impeller to the critical craft etc. of its reaction route, especially combines synthesis Gas prepares the catalysis response feature of C2+ oxygenatedchemicals and is made that research to the specific mechanism of particular deposition orientation regulation and control, and shows There are all kinds of catalyst preparation modes of technology to compare, significant technical characterstic is metal oxide auxiliary agent can be allowed in active metal Multiple crystal faces on surface execute the deposition of selectivity, realize discontinuous specific position cladding, can also especially be significantly expanded The interfacial area formed between active metal-auxiliary agent, therefore be conducive to effectively improve the activity and selectivity of catalyst simultaneously, in turn It is more suitable for the catalyst preparation application scenario that synthesis gas prepares C2+ oxygenatedchemicals.
Description of the drawings
Fig. 1 is to be shown as regulating and controlling to improve catalyst based on atomic layer deposition product orientation constructed by the present invention for demonstration The process method flow chart of activity and selectivity；
Fig. 2 be for coating the infrared figure with the noble metal catalyst of uncoated oxides additive, comparison show by According to the correlated characteristic for the auxiliary agent selective coated catalyst that the preparation method of the present invention is obtained；
Fig. 3 is to be shown as the system of the present invention by taking the transmission electron microscope picture of noble metal platinum grain surface deposited oxide cerium as an example The correlated characteristic for the auxiliary agent selective coated catalyst that Preparation Method is obtained.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below It does not constitute a conflict with each other and can be combined with each other.
Fig. 1 is to be shown as regulating and controlling to improve catalyst based on atomic layer deposition product orientation constructed by the present invention for demonstration The process method flow chart of activity and selectivity.As shown in Figure 1, the present invention is mainly by its reaction route and its crucial work Factors such as skill condition, the mechanism of action etc. are studied and have been designed, and are accordingly desirable to realize simultaneously highly selective, high activity Catalysis reaction.Specific explanations explanation will be carried out to it below.
It is possible, firstly, to choose silica, aluminium oxide or other analogs as reaction carriers, pass through atomic layer deposition method (can also take infusion process or other modes) is distributed noble metal nano particles in its surface homoepitaxial, and noble metal is thus made Loaded catalyst sample；
Then, on the surface of obtained noble metal carrier catalyst sample, it is heavy to continue through atomic layer deposition method Oxides additive is accumulated to obtain required catalyst prod, metal oxide auxiliary agent is in atomic layer deposition reaction process, in institute The deposition that multiple crystal faces on the noble metal nano particles surface of noble metal carrier catalyst sample realize selectivity is stated, in turn Realize discontinuous network-like growth.
As the above specific explanations are conducive to because of the self-limiting characteristics of atomic layer deposition itself in high surface area carrier The upper high dispersive for realizing active metal nano particle, while in active metal nano grain surface selective deposition auxiliary agent clad When, the interfacial area for being conducive to generate target product between metal-auxiliary agent is much larger than traditional preparation method, therefore uses this method Be conducive to improve the activity and selectivity of catalyst synthesis C2+ oxygenatedchemicals simultaneously.
A preferred embodiment according to the invention, the metal oxide auxiliary agent preferably use low activity, that is, organic to match The big Atomic layer deposition precursor of position group (such as THD=2,2,6,6- tetramethyl -3,5- heptadione) is obtained to aoxidize, and In this atomic layer deposition reaction process, cooling regulation and control are carried out to depositing temperature so that real reaction temperature is less than well-defined reaction temp About 50 degrees Celsius or more.
In addition, the cooling regulation process carried out for depositing temperature preferably uses program cooling monitoring deposition rate Mode executes, and further preferably regulates and controls to 130-160 degrees Celsius of temperature range.
Another preferred embodiment according to the invention, for being distributed noble metal nano in reaction carriers surface homoepitaxial For the atomic layer deposition process of particle, key process parameter further preferably setting is as follows：It is organic using ozone and noble metal Complex is as presoma, nitrogen or helium as carrier gas, and atomic layer deposition reaction temperature is 150 DEG C~300 DEG C, forerunner The body burst length is 30s~120s, and carrier gas scavenging period is 30~120s, finally deposits 2~10 cycles on the surface of the carrier.
A preferred embodiment according to the invention, the noble metal nano particles preferably use Rh, Pt or other classes Like object, and its average particle diameter size is preferably controlled to 2nm~6nm.The Atomic layer deposition precursor of the low activity is preferably selected Select one kind in following substance or combination：Mn (thd) 3, Fe (thd) 3, Ce (thd) 4, Co (acac) 2, Mn (acac) 3 and Cu (acac)2。
Embodiment 1
Take 0.2g SiO2, 600 DEG C of roasting 2h, are put into atomic layer deposition apparatus in Muffle furnace, and 10 are deposited on its surface The Rh nano particles of secondary cycle, using acetylacetone,2,4-pentanedione rhodium and oxygen as presoma.The reaction temperature of atomic layer deposition is 200 DEG C, is carried Gas is nitrogen, and the presoma burst length is 30s, and nitrogen scavenging period is 60s.Finally high degree of dispersion has been obtained in carrier surface RhOxNano particle.
The RhO of preparationx/SiO2Catalyst is in 10%H2/N2Under atmosphere in Muffle furnace reductase 12 h under the conditions of 400 DEG C, obtain Rh/SiO2Catalyst；It is put into atomic layer deposition apparatus, deposits the oxides additive of 2/4/6 cycle on its surface, use three (DPM dpm,dipivalomethane acid) manganese and ozone are presoma.The reaction temperature of atomic layer deposition is 150 DEG C, is carried Gas is nitrogen, and the presoma burst length is 60s, and nitrogen scavenging period is 60s.Finally selected in active metal Rh nano grain surfaces Selecting property grows manganese oxide nanometer layer, obtains Rh-Mn/SiO2Catalyst.
It can be applied to catalyze and synthesize the reaction of gas C2+ oxygenatedchemicals by the sample obtained by above example 1, be adopted Reaction condition is：P=3MPa, T=300 DEG C, GHSV=10000h-1, CO/H2=1:2.Reaction process test shows this Catalyst sample has higher catalytic activity compared to catalyst prepared by traditional infusion process, and C2+ oxygenatedchemicals is special It is that the selectivity of product of ethyl alcohol greatly improves.
Embodiment 2
It takes rhodium nitrate to be dissolved in deionized water, rhodium nitrate solution is added in silica using equi-volume impregnating, room temperature Lower dry 12h, 120 DEG C of dry 12h, 350 DEG C of roasting 4h in air, finally in 10% hydrogen atmosphere 400 DEG C of reductase 12 h to get To Rh/SiO2Catalyst.
By the Rh/SiO of preparation2Catalyst is put into atomic layer deposition apparatus, and the oxygen of 2/4/6 cycle is deposited on its surface Compound auxiliary agent is presoma using three (2,2,6,6- tetramethyl -3,5- heptadione acid) manganese and ozone.The reaction of atomic layer deposition Temperature is 150 DEG C, and carrier gas is nitrogen, and the presoma burst length is 60s, and nitrogen scavenging period is 60s.Finally in active metal Rh Nano grain surface selective growth manganese oxide nanometer layer, obtains Rh-Mn/SiO2Catalyst.
Embodiment 3
Take 0.2g Al2O3, 650 DEG C of roasting 5h, are put into atomic layer deposition apparatus in Muffle furnace, and 2 are deposited on its surface The Pt nano particles of secondary cycle, using trimethyl (methyl cyclopentadienyl) platinum (IV) and ozone as presoma.Atomic layer deposition Reaction temperature is 150 DEG C, and carrier gas is nitrogen, and the presoma burst length is 60s, and nitrogen scavenging period is 60s.Finally in carrier table Face has obtained the Pt nano particles of high degree of dispersion.
The Pt/Al of preparation2O3Catalyst is put into atomic layer deposition apparatus, and the oxidation of 2/5/8 cycle is deposited on its surface Object auxiliary agent, is cobalt source using two (acetylacetone,2,4-pentanedione) cobalts, and another presoma is ozone.The reaction temperature of atomic layer deposition is 150 DEG C, Carrier gas is nitrogen, and the presoma burst length is 60s, and nitrogen scavenging period is 60s.Finally in active metal Pt nano grain surfaces Selective growth cobalt oxide nanometer layer, obtains Pt-Co/Al2O3Catalyst.
As shown in Fig. 2, Pt/Al when comparison shows uncoated oxides additive2O3It catalyst and oxide coated helps Pt-Co/SiO when agent2Catalyst original position carbon monoxide adsorbs infared spectrum, after the comparison diagram can be seen that cobalt oxide cladding Catalyst in the infrared absorption peak of Pt (211) be remarkably decreased, show that it is selection that cobalt auxiliary agent is aoxidized in atomic layer deposition process Property be grown in Pt (211) surface, it was demonstrated that by the present invention preparation method can get metal oxide auxiliary agent in noble metal nano The catalyst that particle surface selectively wraps up.
Embodiment 4
Take 0.2g Al2O3, 650 DEG C of roasting 5h, are put into atomic layer deposition apparatus in Muffle furnace, and 2 are deposited on its surface The Pt nano particles of secondary cycle, using trimethyl (methyl cyclopentadienyl) platinum (IV) and ozone as presoma.Atomic layer deposition Reaction temperature is 150 DEG C, and carrier gas is nitrogen, and the presoma burst length is 60s, and nitrogen scavenging period is 60s.Finally in carrier table Face has obtained the Pt nano particles of high degree of dispersion.
The Pt/Al of preparation2O3Catalyst is put into atomic layer deposition apparatus, and the oxidation of 2/5/8 cycle is deposited on its surface Object auxiliary agent is presoma using three (2,2,6,6,-tetramethyl -3,5- heptadione acid) manganese and ozone.The reaction of atomic layer deposition Temperature is 150 DEG C, and carrier gas is nitrogen, and the presoma burst length is 60s, and nitrogen scavenging period is 60s.Finally in active metal Pt Nano grain surface selective growth manganese oxide nanometer layer, obtains Pt-Mn/Al2O3Catalyst.
As shown in Figure 3, comparison shows the noble metal platinum grain of noble metal platinum grain and surface deposited oxide manganese Transmission electron microscope picture.(111) crystalline substance that manganese oxide auxiliary agent clad is only grown in Pt nanoparticle surface is can be seen that from the comparison diagram Face shows that the preparation method by the present invention can get metal oxide auxiliary agent and selectively be wrapped up on noble metal nano particles surface Catalyst.
To sum up, designed reaction route and technological parameter can obtain Rh-Mn/SiO through overtesting through the invention2 Equal multiple catalysts are conducive to realize the high score of active metal nano particle on high surface area carrier using atomic layer deposition method It dissipates, while in active metal nano grain surface deposition aid clad, metal-auxiliary agent interfacial characteristics are controllable, therefore adopt Be conducive to improve the activity and selectivity of catalyst synthesis C2+ oxygenatedchemicals simultaneously with this method.Demonstrate the present invention Validity, feasibility and controllability.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include Within protection scope of the present invention.

Claims (5)

1. a kind of regulating and controlling the method for improving catalyst activity and selectivity based on atomic layer deposition product orientation, which is suitable for class The catalytic reaction process of C2+ oxygenatedchemicals is prepared like synthesis gas, which is characterized in that this method includes the following steps：
(a) silica, aluminium oxide or other analogs are chosen as reaction carriers, by atomic layer deposition method or infusion process at it Thus noble metal carrier catalyst sample is made in surface homoepitaxial noble metal nano particles；
(b) on the surface of the noble metal carrier catalyst sample obtained by step (a), it is heavy to continue through atomic layer deposition method Metal oxide auxiliary agent is accumulated to obtain required catalyst prod, in the process, the technique of the atomic layer deposition reaction is joined Number is set as follows：
Using ozone or oxygen and organometallic complex as presoma, nitrogen or helium as carrier gas, atomic layer deposition Product reaction temperature is 100 DEG C~300 DEG C, and the presoma burst length is 30s~120s, and carrier gas scavenging period is 30~120s, most The oxides additive is deposited 2~10 cycles on the surface of noble metal carrier catalyst sample afterwards, so that oxidation Multiple crystal faces of the agent aid on the noble metal nano particles surface of the noble metal carrier catalyst sample realize selectivity Deposition, and then realize discontinuous network-like growth.
2. the method as described in claim 1, which is characterized in that for step (b), the metal oxide auxiliary agent is preferred It is made using the big Atomic layer deposition precursor of low activity namely organic coordination group, and in this atomic layer deposition reaction process In, cooling regulation and control are carried out to depositing temperature so that real reaction temperature is less than about 50 degrees Celsius of well-defined reaction temp or more.
3. method as claimed in claim 1 or 2, which is characterized in that the Atomic layer deposition precursor of the low activity is preferably selected Select one kind in following substance or combination：Mn (thd) 3, Fe (thd) 3, Ce (thd) 4, Co (acac) 2, Mn (acac) 3 and Cu (acac)2。
4. the method as described in claim 1-3 any one, which is characterized in that in step (b), carried out for depositing temperature The cooling regulation process preferably executed in such a way that program cools down monitoring deposition rate, and further preferably regulate and control to 130-160 degrees Celsius of temperature range.
5. the method as described in claim 1-4 any one, which is characterized in that the noble metal nano particles preferably use Rh, Pt or other analogs, and its average particle diameter size is preferably controlled to 2nm~6nm.
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