CN104264123A - Atomic layer deposition preparation method of CuNi alloy film for catalytic methanol synthesis reaction - Google Patents
Atomic layer deposition preparation method of CuNi alloy film for catalytic methanol synthesis reaction Download PDFInfo
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses an atomic layer deposition preparation method of a CuNi alloy film for catalytic methanol synthesis reaction, which comprises the following steps: cleaning a substrate; applying a film; putting in a reaction cavity, and introducing a Cu-containing precursor; introducing nitrogen to remove non-adsorbed Cu precursor residues; introducing a reducer to react the reducer with the Cu-containing product; introducing nitrogen to remove the reaction residues of the reducer and Cu-containing product; introducing a Ni-containing precursor; introducing nitrogen to remove the reaction residues and excess reducer; introducing a reducer to react the reducer with the Ni-containing product; introducing nitrogen to remove the reaction residues of the reducer and Ni-containing product; forming a CuNi film on the substrate; and repeating the operation many times to form a plurality of CuNi films on the substrate, thereby completing the preparation of the CuNi alloy. The Ni-containing precursor can be introduced before the Cu-containing precursor. The material has favorable reactivity for catalytic methanol synthesis.
Description
Technical field
The present invention relates to the deposition method technical field of alloy firm, particularly relate to a kind of ald preparation method of the CuNi alloy firm for catalysis methanol building-up reactions.
Background technology
Methyl alcohol is a kind of important Organic Chemicals, is again a kind of desirable substitute clean fuel.Especially along with the change of energy structure, the proportion of prevailing petroleum resources in whole energy structure will progressively reduce, and Sweet natural gas and coal will be given prominence to further as the importance of chemical industry and energy and raw material.As the critical process of C1 chemical industry, synthesizing methanol is by one of optimal path of Sweet natural gas or other Chemicals of coal production or synthol.At present, industrial widely used low pressure methanol synthesis catalyzer is copper-based catalysts.This catalyzer still also exists the problems such as poor heat stability, easy-sintering and work-ing life is short.
CuNi alloy has well active and stability to methanol-fueled CLC, but different alloy surface compositions but has different selectivity of product, except principal product methyl alcohol, also generates the mixture of a small amount of methane and ethane etc.Relation between the particular surface composition of CuNi alloy and methyl alcohol selectivity, is still not clear at present.Therefore, synthesis has the CuNi alloy of different surfaces composition, studies the relation of its surface composition and methanol-fueled CLC performance, for industrial applications possible from now on provides theory support, has important scientific meaning.
The maximum feature of Atomic layer deposition method is that its surface reaction has self limiting, every secondary response only deposits one deck atom, can realize on an atomic scale body phase and surface composition, particle size, surface tissue and the pattern of accurately control CuNi alloy by controlling the sets of conditions such as the circulating cycle issue of presoma pulse.The catalyst based upper methanol-fueled CLC reaction of Cu is structure sensitive reaction, the surface composition of catalyzer and structures shape reactivity worth, therefore, and the methanol synthesis catalyst utilizing Atomic layer deposition method can obtain high reactivity and highly selective to have both.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of Atomic layer deposition method of CuNi alloy firm, and use it for the catalyzer of methanol-fueled CLC reaction, thering is provided theoretical foundation for solving the problem such as poor heat stability, easy-sintering of existing catalyzer to reaction, laying a good foundation for preparing similar alloy material.
Technical scheme of the present invention is to provide a kind of ald preparation method of CuNi alloy firm, and its step is as follows:
(1) cleaning of the substrate of alloy growth: first clean by the NaOH solution of 4mol/L, then cleans with the HCl solution of 1mol/L, finally uses deionized water, alcohol flushing successively, to surface cleaning light, dries.
Described substrate can select FeCrAl alloy.
(2) in substrate, apply one deck SBA-15 film: according to the Viability colloid of proportional arrangement of every 0.5g SBA-15 and 35mL Alumina gel, substrate is put into take out after active colloidal leaves standstill 5min and dry, namely form one deck SBA-15 film at substrate surface.
(3) setting of atomic layer deposition system parameter: reaction chamber temperature is 300-350 DEG C, reaction chamber pressure is 10hPa;
Reaction chamber is put in the substrate having applied SBA-15 film.
(4) presoma two (hexafluoroacetylacetone) imported containing Cu closes copper (II), is called for short Cu (hfac)
2.
Wherein, the Heating temperature containing the presoma of Cu is 85 DEG C, and pulse is 2s, and the dwell time is 8.5s.
(5) in reaction chamber, nitrogen is passed into, cleaning reaction by product and the unnecessary presoma containing Cu.
(6) reductive agent H is imported to reaction chamber
2, reductive agent is reacted with the resultant containing Cu.
Described reductive agent H
2purity be 99.999%, flow 100sccm, H
2burst length 3s, the dwell time is 10s.
(7) pass into nitrogen to reaction chamber, remove reductive agent with containing the byproduct of reaction of resultant of Cu and unnecessary reductive agent.
(8) repeating step (4)-(7) 50-100 time.
(9) the presoma nickelocene containing Ni is imported to reaction chamber;
Wherein, the pulse containing the presoma of Ni is 120s, and Heating temperature is 100 DEG C.Dwell time is 8s.
(10) nitrogen is passed into reaction chamber, cleaning reaction by product and the unnecessary presoma containing Ni.
(11) reductive agent H is imported to reaction chamber
2, reductive agent is reacted with the resultant containing Ni;
Described reductive agent H
2purity be 99.999%, flow 100sccm, H
2burst length 60s, the dwell time is 10s.
(12) reaction chamber passes into nitrogen, remove reductive agent with containing the reaction residue of resultant of Ni and unnecessary reductive agent;
(13) repeating step (9)-(12) 50-100 time, substrate is formed one deck CuNi alloy firm;
(14) repeating step (4)-(13) repeatedly, substrate form multi-layer C uNi alloy firm, namely complete the preparation of CuNi alloy.
Or, the ald preparation method of described CuNi alloy firm, its step is as follows:
(1) cleaning of the substrate of alloy growth: first clean by the NaOH solution of 4mol/L, then cleans with the HCl solution of 1mol/L, finally uses deionized water, alcohol flushing successively, to surface cleaning light, dries.
Described substrate can select FeCrAl alloy.
(2) in substrate, apply one deck SBA-15 film: according to the Viability colloid of proportional arrangement of every 0.5g SBA-15 and 35mL Alumina gel, substrate is put into take out after active colloidal leaves standstill 5min and dry, namely form one deck SBA-15 film at substrate surface.
(3) setting of atomic layer deposition system parameter: reaction chamber temperature is 300-350 DEG C, reaction chamber pressure is 10hPa;
Reaction chamber is put in the substrate having applied SBA-15 film.
(4) the presoma nickelocene containing Ni is imported to reaction chamber;
Wherein, the pulse containing the presoma of Ni is 120s, and Heating temperature is 100 DEG C.Dwell time is 8s.
(5) nitrogen is passed into reaction chamber, cleaning reaction by product and the unnecessary presoma containing Ni.
(6) reductive agent H is imported to reaction chamber
2, reductive agent is reacted with the resultant containing Ni;
Described reductive agent H
2purity be 99.999%, flow 100sccm, H
2burst length 60s, the dwell time is 10s.
(7) reaction chamber passes into nitrogen, removes reductive agent and contains the reaction residue of Ni resultant and unnecessary reductive agent.
(8) repeating step (4)-(7) 50-100 time.
(9) presoma two (hexafluoroacetylacetone) imported containing Cu closes copper (II), is called for short Cu (hfac)
2.
Wherein, the Heating temperature containing the presoma of Cu is 85 DEG C, and pulse is 2s, and the dwell time is 8.5s.
(10) in reaction chamber, nitrogen is passed into, cleaning reaction by product and the unnecessary presoma containing Cu.
(11) reductive agent H is imported to reaction chamber
2, reductive agent is reacted with the resultant containing Cu.
Described reductive agent H
2purity be 99.999%, flow 100sccm, H
2burst length 3s, the dwell time is 10s.
(12) pass into nitrogen to reaction chamber, remove reductive agent with containing the reaction residue of resultant of Cu and unnecessary reductive agent.
(13) repeating step (9)-(12) 50-100 time, substrate is formed one deck CuNi alloy firm;
(14) repeating step (4)-(13) repeatedly, substrate form multi-layer C uNi alloy firm, namely complete the preparation of CuNi alloy.
Compared with prior art, advantage of the present invention and beneficial effect are:
1, utilize Atomic layer deposition method to prepare CuNi alloy first, in view of Atomic layer deposition method prepares the high controllability of alloy material, simply accurately can control thickness and the composition of prepared film.
2, the film in the present invention coated by deposition CuNi alloy is not limited only to SBA-15, also can use SiO
2, ZrO
2powder etc., applied range.
3, the reactivity worth of the CuNi alloy obtained in the present invention in methanol-fueled CLC is obviously better than utilizing the catalyzer prepared by traditional pickling process, being studied by the catalyticing mechanism of methanol-fueled CLC reaction on alloy catalyzer, being expected to provide theoretical foundation for designing catalyzer on atomic level.
Embodiment
For making object of the present invention, technical scheme, advantage and beneficial effect clearly understand, below in conjunction with specific embodiment, the inventive method is described in further details.
In following examples, FeCrAl substrate is provided by Shanghai dodar electrical alloy Materials Co., Ltd, sheet, 0.05 × 25 × 50mm, and it consists of Cr 19-22wt%, and Al 5-7wt%, Re are appropriate, Fe surplus;
SBA-15 synthesizes voluntarily for applicant, and its specific surface area is 599m2/g, most probable pore size is 8.8nm, pore volume is 0.99cm
3/ g;
Alumina gel be applicant according to following Ph.D. Dissertation: Shi Xuejun, Ji Shengfu. low-carbon alkanes CO
2the preparation of oxy-dehydrogenation catalyst and the research of catalytic performance thereof, 2009, the record of the 17th page was synthesized voluntarily.Its process is summarized as follows: adopt SB powder (commercial, Germany Condea Chemic Products, composition is pseudo-boehmite) prepare colloidal sol for main raw material, its preparation process is: the SB powder taking 17.5g puts into there-necked flask, then adds the HNO of 321mL deionized water and 1mol/L
329mL, stirs 5-6h at 84 DEG C, can obtain required colloidal sol.
Embodiment 1
An ald preparation method for CuNi alloy firm, its step is as follows:
(1) cleaning of the FeCrAl substrate of alloy growth: first clean by the NaOH solution of 4mol/L, then cleans with the HCl solution of 1mol/L, finally uses deionized water, alcohol flushing successively, to surface cleaning light, dries.
(2) in substrate, one deck SBA-15 film is applied: according to the Viability colloid of proportional arrangement of every 0.5g SBA-15 and 35ml Alumina gel, take out after the standing 5min of active colloidal is put in FeCrAl substrate and dry, namely form one deck SBA-15 film on FeCrAl surface.
(3) setting of atomic layer deposition system parameter, tests and carries out on Finland PICOSUN company ALD atomic layer deposition system, and its ald parameter is reaction chamber temperature is 300 DEG C, and reaction chamber pressure is 10hPa.
Reaction chamber is put in the substrate having applied SBA-15 film.
(4) presoma two (hexafluoroacetylacetone) imported containing Cu closes copper (II), and the Heating temperature containing the presoma of Cu is 85 DEG C, and pulse is 2s, and the dwell time is 8.5s.
(5) in reaction chamber, nitrogen is passed into, cleaning reaction by product and the unnecessary presoma containing Cu.The purity of nitrogen is 99.999%, and flow is 100sccm, and scavenging period is 14s.
(6) reductive agent H is imported to reaction chamber
2, make H
2react with the resultant containing Cu.H
2purity is 99.999%, flow 100sccm, H
2burst length 3s, the dwell time is 10s.
(7) pass into nitrogen to reaction chamber, remove reductive agent with containing the reaction residue of resultant of Cu and unnecessary reductive agent.
The purity of nitrogen is 99.999%, and the flow of high pure nitrogen is 100sccm, and scavenging period is 10s.
(8) repeating step (4)-(7) 50 times, generates layer of metal Cu.
(9) import the presoma nickelocene containing Ni to reaction chamber, the pulse wherein containing the presoma of Ni is 120s, and Heating temperature is 100 DEG C.Dwell time is 8s.
(10) nitrogen is passed into reaction chamber, cleaning reaction by product and the unnecessary presoma containing Ni.The purity of nitrogen is 99.999%, and flow is 100sccm, and scavenging period is 60s.
(11) reductive agent H is imported to reaction chamber
2, reductive agent is reacted with the resultant containing Ni.H
2pulse purity is 99.999%, flow 100sccm, H
2burst length 60s, the dwell time is 10s.
(12) pass into nitrogen to reaction chamber, remove reductive agent and contain the reaction residue of Ni resultant and unnecessary reductive agent;
The purity of nitrogen is 99.999%, and flow is 100sccm, and scavenging period is 60s.
(13) repeating step (9)-(12) 50 times, substrate is formed one deck CuNi alloy firm.
(14) repeating step (4)-(13) 3 times, substrate is formed multi-layer C uNi alloy firm, completes the preparation of CuNi alloy.
Embodiment 2
An ald preparation method for CuNi alloy firm, its step is as follows:
(1) cleaning of the FeCrAl substrate of alloy growth: first clean by the NaOH solution of 4mol/L, then cleans with the HCl solution of 1mol/L, finally uses deionized water, alcohol flushing successively, to surface cleaning light, dries.
(2) in substrate, one deck SBA-15 film is applied: according to the Viability colloid of proportional arrangement of every 0.5g SBA-15 and 35ml Alumina gel, take out after the standing 5min of active colloidal is put in FeCrAl substrate and dry, namely form one deck SBA-15 film at FeCrAl substrate surface.
(3) setting of atomic layer deposition system parameter, tests and carries out on Finland PICOSUN company ALD atomic layer deposition system, and its ald parameter is reaction chamber temperature is 300 DEG C, and reaction chamber pressure is 10hPa.
Reaction chamber is put in the substrate having applied SBA-15 film.
(4) import the presoma nickelocene containing Ni, wherein the pulse of presoma nickelocene is 120s, and Heating temperature is 100 DEG C.Dwell time is 8s.
(5) nitrogen is passed into reaction chamber, cleaning reaction by product and the unnecessary presoma containing Ni;
The purity of nitrogen is 99.999%, and flow is 100sccm, and scavenging period is 60s.
(6) reductive agent H is imported to reaction chamber
2, reductive agent is reacted with the resultant containing Ni;
H
2purity be 99.999%, flow 100sccm, H
2burst length 60s, the dwell time is 10s.
(7) in reaction chamber, pass into nitrogen, remove reductive agent and contain the reaction residue of Ni resultant and unnecessary reductive agent;
The purity of nitrogen is 99.999%, and flow is 100sccm, and scavenging period is 60s.
(8) repeating step (4)-(7) 100 times, substrate is formed layer of Ni metallic film.
(9) presoma two (hexafluoroacetylacetone) imported containing Cu to reaction chamber closes copper (II);
Wherein, the Heating temperature containing the presoma of Cu is 85 DEG C, and pulse is 2s, and the dwell time is 8.5s.
(10) in reaction chamber, nitrogen is passed into, cleaning reaction by product and the unnecessary presoma containing Cu.The purity of nitrogen is 99.999%, and flow is 100sccm, and scavenging period is 14s.
(11) reductive agent H is imported to reaction chamber
2, make H
2react with the resultant containing Cu.H
2purity is 99.999%, flow 100sccm, H
2burst length 3s, the dwell time is 10s.
(12) pass into nitrogen to reaction chamber, remove reductive agent with containing the reaction residue of resultant of Cu and unnecessary reductive agent.The purity of nitrogen is 99.999%, and flow is 100sccm, and scavenging period is 10s.
(13) repeating step (9)-(12) 100 times, substrate generates one deck CuNi alloy firm.
(14) repeating step (4)-(13) 5 times, substrate is formed multi-layer C uNi alloy firm, namely completes the preparation of CuNi alloy.
(its preparation process is: get and embodiment 1,2 identical raw material SBA-15 for CuNi/SBA-15 that the CuNi alloy firm prepared by above two embodiment Atomic layer deposition methods is identical with alloy composition prepared by equal-volume co-impregnation and content respectively, in the cupric nitrate being added to calculated amount and nickelous nitrate mixing solutions, dry at room temperature over night, 120 DEG C of dry 3h, 400 DEG C of roasting 4h in air, the last 1h that reduces in 300 DEG C of hydrogen atmospheres, obtains CuNi/SBA-15 catalyzer.Wherein, mol ratio is Cu:Ni=1:1, it is identical with alloy mass per-cent prepared by the atomic layer deposition method of embodiment 1 or 2 that Cu and Ni accounts for the total mass percent of SBA-15), be applied to catalysis methanol building-up reactions simultaneously, can see, contrast the transformation efficiency (X of the CO of heat-resisting front and back
co) and the space-time yield of methyl alcohol, the catalyzer utilizing Atomic layer deposition method to obtain all is better than the catalyzer (see table 1 and table 2) utilizing traditional pickling process to obtain.Wherein, the reaction conditions adopted is: P=3.0MPa, GHSV=10000h
-1, CO/H
2/ CO
2/ N
2(volume ratio)=15:70:5:10.After resistance to Thermal test, data refer to that fresh sample keeps 6h then to cool to temperature in table and records at 400 DEG C.
The activity of table 1 catalyzer compares with thermotolerance
The activity of table 2 catalyzer compares with thermotolerance
Above-described each specific embodiment, further describes object of the present invention, technical scheme and beneficial effect.Institute it should be understood that and the foregoing is only specific embodiments of the invention, is not limited to the present invention, within the spirit and principles in the present invention all, and any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. an ald preparation method for CuNi alloy firm, its step is as follows:
(1) cleaning of the substrate of alloy growth: first clean by the NaOH solution of 4mol/L, then cleans with the HCl solution of 1mol/L, finally uses deionized water, alcohol flushing successively, to surface cleaning light, dries;
(2) in substrate, apply one deck SBA-15 film: according to the Viability colloid of proportional arrangement of every 0.5g SBA-15 and 35mL Alumina gel, substrate is put into take out after active colloidal leaves standstill 5min and dry, namely form one deck SBA-15 film at substrate surface;
(3) setting of atomic layer deposition system parameter: reaction chamber temperature is 300-350 DEG C, reaction chamber pressure is 10hPa;
Reaction chamber is put in the substrate having applied SBA-15 film;
(4) presoma two (hexafluoroacetylacetone) imported containing Cu closes copper (II);
Wherein, the Heating temperature containing the presoma of Cu is 85 DEG C, and pulse is 2s, and the dwell time is 8.5s;
(5) in reaction chamber, nitrogen is passed into, cleaning reaction by product and the unnecessary presoma containing Cu;
(6) reductive agent H is imported to reaction chamber
2, reductive agent is reacted with the resultant containing Cu;
Described reductive agent H
2purity be 99.999%, flow 100sccm, H
2burst length 3s, the dwell time is 10s;
(7) pass into nitrogen to reaction chamber, remove reductive agent with containing the byproduct of reaction of resultant of Cu and unnecessary reductive agent;
(8) repeating step (4)-(7) 50-100 time;
(9) the presoma nickelocene containing Ni is imported to reaction chamber;
Wherein, the pulse containing the presoma of Ni is 120s, and Heating temperature is 100 DEG C, and the dwell time is 8s;
(10) nitrogen is passed into reaction chamber, cleaning reaction by product and the unnecessary presoma containing Ni;
(11) reductive agent H is imported to reaction chamber
2, reductive agent is reacted with the resultant containing Ni;
Described reductive agent H
2purity be 99.999%, flow 100sccm, H
2burst length 60s, the dwell time is 10s;
(12) reaction chamber passes into nitrogen, remove reductive agent with containing the reaction residue of resultant of Ni and unnecessary reductive agent;
(13) repeating step (9)-(12) 50-100 time, substrate is formed one deck CuNi alloy firm;
(14) repeating step (4)-(13) repeatedly, substrate form multi-layer C uNi alloy firm, complete the preparation of CuNi alloy firm;
Or, the ald preparation method of described CuNi alloy firm, its step is as follows:
(1) cleaning of the substrate of alloy growth: first clean by the NaOH solution of 4mol/L, then cleans with the HCl solution of 1mol/L, finally uses deionized water, alcohol flushing successively, to surface cleaning light, dries;
(2) in substrate, apply one deck SBA-15 film: according to the Viability colloid of proportional arrangement of every 0.5g SBA-15 and 35mL Alumina gel, substrate is put into take out after active colloidal leaves standstill 5min and dry, namely form one deck SBA-15 film at substrate surface;
(3) setting of atomic layer deposition system parameter: reaction chamber temperature is 300-350 DEG C, reaction chamber pressure is 10hPa;
Reaction chamber is put in the substrate having applied SBA-15 film;
(4) the presoma nickelocene containing Ni is imported to reaction chamber;
Wherein, the pulse containing the presoma of Ni is 120s, and Heating temperature is 100 DEG C, and the dwell time is 8s;
(5) nitrogen is passed into reaction chamber, cleaning reaction by product and the unnecessary presoma containing Ni;
(6) reductive agent H is imported to reaction chamber
2, reductive agent is reacted with the resultant containing Ni;
Described reductive agent H
2purity be 99.999%, flow 100sccm, H
2burst length 60s, the dwell time is 10s;
(7) reaction chamber passes into nitrogen, removes reductive agent and contains the reaction residue of Ni resultant and unnecessary reductive agent;
(8) repeating step (4)-(7) 50-100 time;
(9) presoma two (hexafluoroacetylacetone) imported containing Cu closes copper (II);
Wherein, the Heating temperature containing the presoma of Cu is 85 DEG C, and pulse is 2s, and the dwell time is 8.5s;
(10) in reaction chamber, nitrogen is passed into, cleaning reaction by product and the unnecessary presoma containing Cu;
(11) reductive agent H is imported to reaction chamber
2, reductive agent is reacted with the resultant containing Cu;
Described reductive agent H
2purity be 99.999%, flow 100sccm, H
2burst length 3s, the dwell time is 10s;
(12) pass into nitrogen to reaction chamber, remove reductive agent with containing the reaction residue of resultant of Cu and unnecessary reductive agent;
(13) repeating step (9)-(12) 50-100 time, substrate is formed one deck CuNi alloy firm;
(14) repeating step (4)-(13) repeatedly, substrate form multi-layer C uNi alloy firm, complete the preparation of CuNi alloy firm.
2. preparation method according to claim 1, is characterized in that: FeCrAl alloy is selected in described substrate.
3. preparation method according to claim 1, is characterized in that: in described step (14), repeating step (4)-(13) 3-5 time.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106423171A (en) * | 2016-08-01 | 2017-02-22 | 中南民族大学 | Ni/Cu/M catalyst for catalytic methanol synthesis reaction and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060145142A1 (en) * | 2004-12-30 | 2006-07-06 | Norman John Anthony T | Volatile metal beta-ketoiminate and metal beta-diiminate complexes |
| CN1826426A (en) * | 2004-03-01 | 2006-08-30 | 东京毅力科创株式会社 | Method for forming copper film |
| CN101069847A (en) * | 2007-05-25 | 2007-11-14 | 上海师范大学 | Mesoporous-structure metal nickel catalyst and its preparing method and use |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1826426A (en) * | 2004-03-01 | 2006-08-30 | 东京毅力科创株式会社 | Method for forming copper film |
| US20060145142A1 (en) * | 2004-12-30 | 2006-07-06 | Norman John Anthony T | Volatile metal beta-ketoiminate and metal beta-diiminate complexes |
| CN101069847A (en) * | 2007-05-25 | 2007-11-14 | 上海师范大学 | Mesoporous-structure metal nickel catalyst and its preparing method and use |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106423171A (en) * | 2016-08-01 | 2017-02-22 | 中南民族大学 | Ni/Cu/M catalyst for catalytic methanol synthesis reaction and preparation method thereof |
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