CN103406129B - Preparation method of wire mesh monolithic catalyst based on surface porous structure - Google Patents
Preparation method of wire mesh monolithic catalyst based on surface porous structure Download PDFInfo
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- CN103406129B CN103406129B CN201310362348.0A CN201310362348A CN103406129B CN 103406129 B CN103406129 B CN 103406129B CN 201310362348 A CN201310362348 A CN 201310362348A CN 103406129 B CN103406129 B CN 103406129B
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Abstract
The invention relates to a preparation method of a wire mesh monolithic catalyst based on surface porous structure. The method comprises the following steps: (1) preparing a discoid Cu wire mesh substrate from a Cu wire, and carrying out ultrasonic cleaning; (2) preparing an electrodeposition solution, wherein the electrodeposition solution is a copper sulfate, auric chloride acid and sulfuric acid mixed solution; (3) carrying out electrodeposition on an electrochemical work station by using a tri-electrode system, wherein the tri-electrode system uses the discoid Cu wire mesh substrate as a working electrode, a platinum sheet electrode as a counter electrode and a saturated calomel electrode as a reference electrode; and respectively preparing a Cu monometallic, Au monometallic or Au/Cu bimetallic wire mesh monolithic catalyst with a three-dimensional porous surface. The catalyst provided by the invention is an Au or/and Cu metal porous film formed by the Cu wire mesh and a hydrogen bubble template on the surface layer under high cathode potential; and the catalyst is a macroscopic monolithic catalyst with a nano porous structure, can be used in multiple catalytic reaction systems. The preparation method is simple and has favorable repetitiveness.
Description
Technical field
The present invention relates to the preparation method of the silk screen integer catalyzer with porous surface double structure, belong to chemical catalyst technical field.
Background technology
In recent years, nano porous metal is widely used in catalytic field.Such as calendar year 2001, J.Erlebacher etc. adopt red fuming nitric acid (RFNA) acid gilding silver alloy to prepare nano-porous gold, see Nature2001410:450 ~ 453;
seminar and Ding seminar find that nano-porous gold has good activity, see Angew.Chem., Int.Ed.2006 to CO catalytic oxidation at normal temperatures respectively, 45 (48), 8241-8244. and J.Am.Chem.Soc.2006,129 (1), 42-43..
Usually the method preparing porous material is removal alloying method and hard template method, and removal alloying method can obtain the catalyst compared with Large ratio surface, but the nano grade pore that the method obtains is unfavorable for the transmission of reactant and product.Although hard template method can the parameter such as control hole gauge structure size well, the removal of template is usually more difficult, and the method process is complicated, and easily pollutes catalyst.The most important thing is, the porous metal catalyst prepared in existing report lacks effective carrier in catalytic reaction process, causes the decentralization of catalyst bad, mass transfer and heat-transfer capability poor, reduce catalytic efficiency.
CN102688756A (201210162612.1) discloses a kind of monolithic porous rhotanium catalyst, it deposits one deck copper in the surface electrical of golden palladium-silver silk, copper coating and inside gold palladium-silver is made to realize alloying through high annealing, then strong electrolytic solution is utilized to carry out freely corroding or electrochemical corrosion, obtained catalyst comprises golden palladium-silver core and porous rhotanium film, and porous rhotanium film uniform fold is in the extexine of golden palladium-silver core.The preparation method of this catalyst is comparatively complicated, time consumption and energy consumption and require higher and bullion content is very high to original material, and cost is high, is not suitable for large-scale production.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of silk screen integer catalyzer of surface porosity.Particularly a kind of preparation method of Au/Cu bimetal structure silk screen integer catalyzer of porous surface.
Summary of the invention:
The present invention adopts Cu silk screen to be substrate, utilizes bubble hydrogen as dynamic template, containing mantoquita Cu (SO
4)
2or gold chloride HAuCl
4solution in, or containing in the solution of mantoquita and gold chloride, prepare porous metals Au/Cu catalyst by constant potential cathodic deposition method.The active component of this catalyst is attached to the porous layer on surface equably, has higher utilization rate.
Detailed Description Of The Invention:
A preparation method for the silk screen integer catalyzer of surface porosity, comprises step as follows:
(1) prepare the substrate of plate-like Cu silk screen with Cu line or directly adopt that to be purchased plate-like Cu silk screen be substrate, ultrasonic cleaning;
(2) electric depositing solution is prepared:
Electric depositing solution is the mixed solution of copper sulphate, gold chloride and sulfuric acid, the Cu (SO containing 0 ~ 20mmol/L in solution
4)
2, 0 ~ 20mmol/L HAuCl
4be 0 ~ 20mmol/L and 0.5 ~ 2mol/L H
2sO
4; Wherein Cu (SO
4)
2and HAuCl
4be asynchronously 0.
(3) adopt three-electrode system to carry out electro-deposition on electrochemical workstation, described three-electrode system adopts the plate-like Cu silk screen substrate described in step (1) to be working electrode, and platinum plate electrode is to electrode, and saturated calomel electrode is reference electrode; Obtain the Cu monometallic of surface three dimension loose structure, Au monometallic or Au/Cu bimetallic silk screen integer catalyzer respectively.
Collect obtained porous C u monometallic, Au monometallic or Au/Cu bimetallic silk screen integer catalyzer, with ultra-pure water cyclic washing 8 ~ 10 times, be neutrality to detecting the water rinsed, then putting into vacuum drying chamber for subsequent use.
According to the present invention, preferably, in step (1), the method preparing the substrate of Cu silk screen with Cu line is: be that the substrate of plate-like Cu silk screen become by the Cu drum of 50 ~ 500 μm by diameter, and carry out ultrasonic cleaning 5 ~ 8min in absolute ethyl alcohol, 1M HCl and ultra-pure water.Preferred further, forming diameter with the Cu drum that diameter is 100 ~ 300 μm is the substrate of 4 ~ 20mm plate-like Cu silk screen.
According to the present invention, preferably, step (2) described electric depositing solution is one of following:
A. Cu (the SO of 0.05 ~ 5mmol/L is contained in solution
4)
2, the H of 1 ~ 2mol/L
2sO
4, for the preparation of the Cu monometallic silk screen integer catalyzer of porous; Further preferably, the Cu (SO of 2.67mM is contained in solution
4)
2with 2M H
2sO
4.
B. the HAuCl of 0.05 ~ 5mmol/L is contained in solution
4, the H of 1 ~ 2mol/L
2sO
4, for the preparation of the Au monometallic silk screen integer catalyzer of porous; Further preferably, the Cu (SO of 1.38mM is contained in solution
4)
2, the HAuCl of 1.38mM
4, 2M H
2sO
4.
C. Cu (the SO of 0.05 ~ 5mmol/L is contained in solution
4)
2, the HAuCl of 0.05 ~ 5mmol/L
4with the H of 1 ~ 2mol/L
2sO
4, for the preparation of the Au/Cu bimetal structure silk screen integer catalyzer of porous; Further preferably, the HAuCl of 2.67mM is contained in solution
4and 2MH
2sO
4.
According to the present invention, preferably, step (3) electrodeposition condition is: deposit 10 ~ 500s under the current potential of-1 ~-5V.Further preferably, electrodeposition condition is: under the current potential of-1.5V, deposit 100s.
According to the present invention, preferably, step (3) electrochemical workstation is CHI1130A electrochemical workstation, CHI440A electrochemical workstation or CHI660D electrochemical workstation.
The most preferred product of the present invention is porous Au/Cu bimetal structure silk screen integer catalyzer prepared by embodiment 2; The main component of this catalyst is Cu and is loaded with the noble metal Au of minute quantity, is about 1.3:1.8 at suprabasil Au and the Cu atomic ratio of Cu silk screen, and therefore the catalytic activity of catalyst is high and cost is low.
The present invention controls the Au/Cu atomic ratio in product on porous membrane by the ratio controlling Au and Cu in electroplating solution, realizes catalyst surface composition controlled.
Catalyst of the present invention is formed by the substrate of Cu silk screen and at its surperficial porous membrane formed, the thickness of porous membrane is 0.5 ~ 40 μm, film spreads all over the micron order macropore of 10 ~ 15 μm, and its macroporous structure is conducive to the transmission of reactant, hole wall is made up of the particle packing of 5 ~ 300nm, the nano grade pore structure of hole wall is conducive to the specific activity surface increasing catalyst, thus improves its catalytic performance.
The present invention, by making this catalyst can be used for multiple catalytic reaction to the regulation and control of its surface composition and structure, comprises the catalytic gas phase oxidation of phenmethylol, ethanol etc. and the catalytic oxidation of methyl alcohol, ethanol, glucose etc.Preferably, the catalyst of preparation is specially adapted to catalytic gas phase oxidation phenmethylol.
Compared with the prior art, advantage applies of the present invention exists:
1, the invention provides a kind of Au, Cu or Au/Cu woven wire integer catalyzer based on surface porosity; described catalyst is formed by the substrate of Cu silk screen and at its surperficial porous membrane formed, and solves the problem that traditional porous metal catalyst lacks effective carrier in catalytic reaction process; Such catalyst has excellent heat conduction, electric conductivity, and high catalytic activity.In addition, the main component of this catalyst is Cu, or surface is loaded with the noble metal Au of minute quantity, and therefore the cost of catalyst is very low, and preparation method is green, simple, quick, is applicable to large-scale production.
2, the present invention uses Cu, Au and Au/Cu bimetallic catalyst of bubble hydrogen template synthesis three-dimensional porous structure, and the catalyst of preparation is macroscopical integer catalyzer with nano-porous structure, and therefore this integer catalyzer is easy to reclaim and recycling; Bubble hydrogen template is a kind of green, easy, prepares the method for porous membrane fast, and under comparatively negative cathode potential (higher cathode potential), form bubble hydrogen at electrode surface, metal deposits between bubble hydrogen, thus forms loose structure.Importantly, the method can realize several intermetallic codeposition easily, can control the thickness of porous membrane, pore structure and composition easily by the composition controlling deposition parameter and electroplate liquid.
3, the present invention uses bubble hydrogen template can simply by controlling the parameter of electro-deposition and effectively control the thickness of porous membrane, pore structure and surface composition; The catalyst prepared by the method is applicable to multiple catalytic reaction.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of porous C u catalyst prepared by embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of porous Au/Cu bimetallic catalyst prepared by embodiment 2.
Fig. 3 is the scanning electron microscope (SEM) photograph of porous Au catalyst prepared by embodiment 3 electro-deposition.
Fig. 4 be the embodiment of the present invention prepare the substrate of Cu silk screen, the catalytic activity of silk screen integer catalyzer catalytic gas phase oxidation phenmethylol of porous surface Cu, porous surface Au and porous surface Au/Cu structure and selectivity curve.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is further described.But be not limited thereto.Electrochemical workstation in embodiment is CHI1130A electrochemical workstation.
Embodiment 1: the preparation of porous C u catalyst
(1) select diameter to be that the plate-like Cu silk screen substrate that diameter is 6mm prepared by the Cu line of 200 μm, then the substrate of Cu silk screen is put into absolute ethyl alcohol successively, in 1M HCl and ultra-pure water, carry out ultrasonic cleaning.
(2) electric depositing solution is prepared: containing the Cu (SO of 2.67mM in solution
4)
2with 2M H
2sO
4.
(3) on electrochemical workstation, carry out electro-deposition with three-electrode system and obtain three-dimensional porous Cu, actual conditions is deposit 100s under the current potential of-1.5V.Collecting the porous C u that electroplate, with ultra-pure water cyclic washing 10 times, is neutrality with the water that wide pH value detection paper is rinsed, then to put into vacuum drying chamber for subsequent use.
Fig. 1 is shown in by the SEM photo of the Porous Cu integral catalyzer that said method obtains.Obtained catalyst carries out the test of gas phase selective catalytic oxidation phenmethylol, and catalytic gas phase oxidation curve as shown in Figure 3.Result is described as follows:
As can be seen from Fig. 1 a, the Cu catalyst with loose structure is obtained by this simple method, it is 10 ~ 15 μm that this catalyst has regular micrometer grade hole pore size, and hole wall is formed by particle packing, particle and see and form nano level aperture between particle.This micron order macropore is conducive to the transmission of reactant, reduces diffusion effect; Wherein, hole wall is made up of particle packing, and the size of particle is at 150 ~ 200nm (Fig. 1 b); The thickness that Fig. 1 c indicates film is 7 ~ 8 μm.
As can be seen from the porous C u of Fig. 4 to the catalytic gas phase oxidation curve of phenmethylol, the substrate of Cu silk screen compared by the porous C u catalyst obtained by bubble hydrogen template, is greatly improved to the catalytic gas phase oxidation activity of phenmethylol.As seen from Figure 4, the activity of porous C u catalyst is about 5 times of the substrate of Cu silk screen.
Embodiment 2: the preparation of porous aurum-copper bimetallic catalyst
(1) plate-like Cu silk screen substrate, preparation method is with embodiment 1.
(2) prepare electric depositing solution, solution comprises the Cu (SO of 1.38mM
4)
2, the HAuCl of 1.38mM
4with 2M H
2sO
4.
(3) on electrochemical workstation, carry out electro-deposition with three-electrode system and obtain three-dimensional porous Au/Cu, actual conditions is deposit 100s under the current potential of-1.5V.Collecting the porous Au/Cu catalyst electroplate, with ultra-pure water cyclic washing 10 times, is neutrality with the water that wide pH value detection paper is rinsed, then to put into vacuum drying chamber for subsequent use.
Fig. 2 is shown in by the SEM photo of above-mentioned porous aurum-copper bimetallic integral catalyzer.
The each 2ml of electroplate liquid before and after power taking deposition carries out ICP test respectively, and the results are shown in Table 1.
Obtained catalyst is carried out the test of gas-phase benzene methyl alcohol selective oxidation, as Fig. 4.Result illustrates:
As can be seen from Fig. 2 a, by this simple method, obtain porous surface Au/Cu film bimetallic catalyst and have regular micrometer grade hole, compared with porous C u catalyst (embodiment 1), the size of micron openings does not have significant change, at 10 ~ 15 μm.Fig. 2 b shows the structure of micron openings hole wall, can find out that hole wall is formed by particle packing, but compare with porous Au film with porous C u film from Fig. 2 b, and composition hole wall particle size obviously diminishes, and is about about 50nm.
Table 1 shows test I CP result, and result display is deposited on suprabasil Au and the Cu atomic ratio of Cu silk screen and is approximately 1.3:1.8, and the atomic ratio of Au and Cu in this and electroplate liquid is closely.This shows to be controlled the Au/Cu ratio on porous membrane by the atomic ratio controlling Au and Cu in electroplate liquid, realizes catalyst surface composition controlled.
Porous Au/Cu bimetallic catalyst ICP test result prepared by table 1. electro-deposition
Fig. 4 shows the catalytic result of the silk screen integer catalyzer gas phase selective catalytic oxidation phenmethylol of porous surface Au/Cu bimetal structure, and generating benzaldehyde to benzyl alcohol selective catalytic gas phase oxidation has good catalytic effect.Within reaction 7h, conversion ratio all remains on more than 54%, selectively all remains on more than 99%, illustrates that porous Au/Cu Catalyzed by Pt/M Bimetallic Nano activity is high, good stability.It should be noted that in addition and compare and porous Au, porous C u catalyst, porous Au/Cu catalyst has better catalytic activity, and this perhaps can sum up in the point that the synergy between Au/Cu.
Embodiment 3: the preparation of porous Au catalyst
(1) plate-like Cu silk screen substrate, preparation method is with embodiment 1.
(2) electric depositing solution is prepared, containing the HAuCl of 2.67mM in solution
4with 2M H
2sO
4.
(3) on electrochemical workstation, carry out electro-deposition with three-electrode system and obtain three-dimensional porous Au film, actual conditions is deposit 100s under the current potential of-1.5V.Collecting the porous Au catalyst electroplate, with ultra-pure water cyclic washing 10 times, is neutrality with the water that wide pH value detection paper is rinsed, then to put into vacuum drying chamber for subsequent use.
Fig. 3 is shown in by the SEM photo of above-mentioned porous gold integral catalyzer.Obtained catalyst carries out the test of gas-phase benzene methyl alcohol selective oxidation, as shown in Figure 4.Result is described as follows:
As can be seen from Fig. 3 a ~ b, by this simple method, we obtain the Au catalyst with loose structure, Fig. 3 a shows catalyst and has regular micrometer grade hole, compared with the porous C u of embodiment 1,2 and porous Au/Cu film, the size of micron openings does not have significant change to be 10 ~ 15 μm; Fig. 3 b shows the structure of micron openings hole wall, can find out that hole wall is formed by particle packing from Fig. 3 b, but compared with porous C u catalyst, composition hole wall particle size obviously diminishes, and is about about 70nm.
Fig. 4 shows the catalytic result of Integrate porous Au catalyst 240 DEG C of gas phase selective catalytic oxidation phenmethylols of preparation, and generating benzaldehyde to benzyl alcohol selective catalytic gas phase oxidation has good catalytic effect.After reaction 7h, conversion ratio still remains on more than 40%, selectively still remains on more than 99%, illustrates that Integrate porous Au metallic catalyst catalytic activity is high, good stability.
Catalytic performance is tested
By porous Au prepared by embodiment 1,2 and 3 and the substrate of Cu silk screen, Cu or Au/Cu integer catalyzer sample is fixed in the middle part of vertical quartz pipe reactor.The gas phase selective catalytic oxidation reaction of phenmethylol is carried out in compact catalytic reaction evaluating device.Experiment is carried out under normal pressure temperature-controllable.In course of reaction, total gas flow rate is controlled by mass flowmenter; Phenmethylol utilizes syringe pump without interruption.Phenmethylol needs to vaporize through preheater preheats before entering the reactor.Reacted gas (product and unreacted phenmethylol) uses cold-trap condensation to reclaim, end product gas chromatographic detection.Catalytic result as shown in Figure 4.Three kinds of catalyst are at 240 DEG C, and at the mist of AIR Proportional, (total gas speed is 44mLmin
~ 1) to phenmethylol, (flow velocity is 0.18mmol min under condition
~ 1) selective oxidation generation benzaldehyde.Different catalysts catalytic oxidation phenmethylol the results are shown in Figure 4.
Claims (7)
1. a preparation method for the silk screen integer catalyzer of surface porosity, comprises step as follows:
(1) prepare the substrate of plate-like Cu silk screen with Cu line or directly adopt that to be purchased plate-like Cu silk screen be substrate, ultrasonic cleaning;
The method that the substrate of Cu silk screen prepared by described Cu line is: be that the substrate of plate-like Cu silk screen become by the Cu drum of 50 ~ 500 μm by diameter, and carry out ultrasonic cleaning 5 ~ 8 min in absolute ethyl alcohol, 1 M HCl and ultra-pure water;
(2) electric depositing solution is prepared: electric depositing solution is the mixed solution of copper sulphate, gold chloride and sulfuric acid, the Cu (SO containing 0 ~ 20 mmol/L in solution
4)
2, 0 ~ 20 mmol/L HAuCl
4with 0.5 ~ 2 mol/L H
2sO
4; Wherein Cu (SO
4)
2and HAuCl
4be asynchronously 0;
(3) adopt three-electrode system to carry out electro-deposition on electrochemical workstation, described three-electrode system adopts the plate-like Cu silk screen substrate described in step (1) to be working electrode, and platinum plate electrode is to electrode, and saturated calomel electrode is reference electrode; Obtain the Cu monometallic of surface three dimension porous, Au monometallic or Au/Cu bimetallic silk screen integer catalyzer respectively.
2.2
.the preparation method of the silk screen integer catalyzer of surface porosity as claimed in claim 1, it is characterized in that obtained porous C u monometallic, Au monometallic or Au/Cu bimetallic silk screen integer catalyzer, with ultra-pure water cyclic washing 8 ~ 10 times, the water rinsed to detection is neutral, then puts into vacuum drying chamber for subsequent use.
3.3
.the preparation method of the silk screen integer catalyzer of surface porosity as claimed in claim 1, is characterized in that forming diameter with the Cu drum that diameter is 100 ~ 300 μm is 4 ~ 20 mm plate-like Cu silk screen substrates.
4.4
.the preparation method of the silk screen integer catalyzer of surface porosity as claimed in claim 1, is characterized in that, step (2) described electric depositing solution is one of following:
A. Cu (the SO of 0.05 ~ 5 mmol/L is contained in solution
4)
2, the H of 1 ~ 2 mol/L
2sO
4, for the preparation of the Cu monometallic silk screen integer catalyzer of porous;
B. the HAuCl of 0.05 ~ 5 mmol/L is contained in solution
4, the H of 1 ~ 2 mol/L
2sO
4, for the preparation of the Au monometallic silk screen integer catalyzer of porous;
C. Cu (the SO of 0.05 ~ 5 mmol/L is contained in solution
4)
2, the HAuCl of 0.05 ~ 5 mmol/L
4with the H of 1 ~ 2 mol/L
2sO
4, for the preparation of the Au/Cu bimetal structure silk screen integer catalyzer of porous.
5.5
.the preparation method of the silk screen integer catalyzer of surface porosity as claimed in claim 4, is characterized in that, step (2) described electric depositing solution is one of following:
A. Cu (the SO of 2.67 mM is contained in solution
4)
2with 2 M H
2sO
4;
B. the HAuCl of 2.67 mM is contained in solution
4with 2 M H
2sO
4;
C. Cu (the SO of 1.38 mM is contained in solution
4)
2, the HAuCl of 1.38 mM
4with 2 M H
2sO
4.
8.6
.the preparation method of the silk screen integer catalyzer of surface porosity as claimed in claim 1, is characterized in that step (3) electrodeposition condition is: deposit 10 ~ 500 s under the current potential of-1 ~-5 V.
7.7
.the preparation method of the silk screen integer catalyzer of surface porosity as claimed in claim 1, is characterized in that step (3) electrodeposition condition is: under the current potential of-1.5 V, deposit 100 s.
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| CN108118360A (en) * | 2017-12-26 | 2018-06-05 | 东华大学 | A kind of efficiently production formic acid Cu-Sn-Cu layered laminate foam electrodes and preparation method thereof |
| CN111129431A (en) * | 2019-08-29 | 2020-05-08 | 天津大学 | Preparation method and application of porous zinc electrode based on dynamic bubble template method |
| CN110629258A (en) * | 2019-10-16 | 2019-12-31 | 东莞领杰金属精密制造科技有限公司 | Preparation method of porous copper liquid absorption core |
| KR20240006894A (en) * | 2022-07-07 | 2024-01-16 | 국립부경대학교 산학협력단 | Manufacturing method of copper microplate, manufacturing method of hybrid microplate containing copper microplate, and hybrid microplate manufactured thereby |
| CN116519766B (en) * | 2023-05-04 | 2024-05-17 | 华北理工大学 | PAMAM/nano-pore gold modified screen printing carbon electrode aptamer biosensor and preparation method and application thereof |
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| WO2012093880A2 (en) * | 2011-01-06 | 2012-07-12 | 성균관대학교산학협력단 | Nano-porous electrode for super capacitor and manufacturing method thereof |
| CN102688756A (en) * | 2012-05-23 | 2012-09-26 | 山东大学 | Integrated porous palladium-gold alloy catalyst and preparation method thereof |
| CN102925923A (en) * | 2012-10-26 | 2013-02-13 | 复旦大学 | Preparation method of nano-palladium or palladium-nickel alloy catalyst having three-dimensional porous structure |
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Patent Citations (4)
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| WO2012093880A2 (en) * | 2011-01-06 | 2012-07-12 | 성균관대학교산학협력단 | Nano-porous electrode for super capacitor and manufacturing method thereof |
| CN102335613A (en) * | 2011-07-12 | 2012-02-01 | 山东大学 | Graded-hole gold-copper alloy monolithic catalyst and preparation method thereof |
| CN102688756A (en) * | 2012-05-23 | 2012-09-26 | 山东大学 | Integrated porous palladium-gold alloy catalyst and preparation method thereof |
| CN102925923A (en) * | 2012-10-26 | 2013-02-13 | 复旦大学 | Preparation method of nano-palladium or palladium-nickel alloy catalyst having three-dimensional porous structure |
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