CN104549292A - Technological method for preparing nickel/silicon dioxide supported catalyst by laser liquid phase - Google Patents
Technological method for preparing nickel/silicon dioxide supported catalyst by laser liquid phase Download PDFInfo
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- CN104549292A CN104549292A CN201410768421.9A CN201410768421A CN104549292A CN 104549292 A CN104549292 A CN 104549292A CN 201410768421 A CN201410768421 A CN 201410768421A CN 104549292 A CN104549292 A CN 104549292A
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Abstract
The invention discloses a technological method for preparing a nickel/silicon dioxide supported catalyst by laser liquid phase. The technological method comprises the following steps of firstly, carrying out polishing and ultrasonic cleaning on a massive metallic nickel target used as a raw material, and blow-drying residual water on the surface of the nickel target; then dispersing silicon dioxide solid powder into deionized water; then putting the treated nickel target into the solution, and adjusting the liquid level height to be greater than 5mm and less than 25mm; ablasting the target by adopting nanosecond focused pulsed laser under the auxiliary action of magnetic stirring and electric translation for 1 hour so as to obtain nickel/silicon dioxide suspension; then carrying out suction filtration on the suspension, and drying so as to obtain the nickel/silicon dioxide powdery supported catalyst. According to the invention, the technological method is simple in synthesis method, is convenient to operate, and is easy to control; byproducts and impurities are not generated; a supported catalyst with small size which is synthesized in a liquid phase by one step at normal temperature and normal pressure is provided; the technological process is an environment-friendly synthesis process.
Description
Technical field
The invention relates to loaded catalyst, particularly a kind of laser method liquid phase prepares the process of nickel/silica supported catalyst.
Background technology
Transition metal Raney nickel has inexpensive and active advantages of higher, is widely used in catalytic oxidation, hydrogenation and dehydrogenation reaction, CH4/CO2 reforms, CNT is prepared and cracked oil reforming reaction.Nickel nanometer is doped in various catalyst carrier, the catalytic activity of catalyst can be significantly improved.Such as: Ni effectively can be decomposed methanol by catalytic methane on silica, see: Lei Li, Yao Yao etal.Highly Active and Stable Lanthanum-doped Core – Shellstructured NiSiO2 Catalysts for the Partial Oxidation of Methane to Syngas.ChemCatChem2013,5,3781 – 3787. are simultaneously relative to noble metal catalyst, the low price of nickel, be more easy to get large-scale promotion application.So improve the catalytic activity of nickel, replacing noble metal catalyst is also numerous worker's striving directions.At present mainly through reducing size, expose more active face to improve the catalytic activity of nickel, but nano particle to trend towards under Action of Surfactant reuniting not adding, add surfactant and then can suppress its superficial catalytic activation, surfactant is difficult to remove simultaneously, see: Kazuki Okaya, Hiroshi Yano Hiroyuki Uchida et al, Nanoscale, ACS, APPLIED MATERIALS & INTERFACES. what is more important, conventional method cannot obtain the nano nickel particles that size is less than 10nm at all.Ni is on specific support in addition, can effectively keep catalyst pattern, improves catalyst efficiency and stability.Current common carrier mainly contains Al
2o
3, SiO
2, C, TiO
2.SiO
2molecular sieve has that specific surface is large, porosity is high and the characteristic such as density is low, effectively can play and bear dispersed actives effect.
Tradition is prepared Supported Nickel Catalyst method and is mainly contained method of chemical immersion and chemical vapour deposition technique, but these two kinds of methods easily cause problems such as grain fraction is reunited, the little and catalytic activity of specific area is low.Such as: by nickel impregnation in active carbon suspension, form load by high-temperature roasting.See: Shubhangi P.Patil, Jayshri V.Pande, RajeshB.Biniwale, Non-noble Ni-Cu/ACC bimetallic catalyst for dehydrogenation of liquidorganic hydrides for hydrogen storage.International Journal of Hydrogen Energy 38 (2013) 15233-1524. is so be badly in need of a kind of novel process means, synthesize this small size, firm binding force Ni SiO 2 catalyst.Laser method, as a kind of novel physics synthesis technique, is subject to people's attention in recent years gradually.When the method is for the synthesis of metal nanoparticle, overcome the defect of chemical method, there is the many advantages such as synthesis particle size is little, how nontoxic blemish is many, technique is simple simultaneously, reaction time is short, is the green safety synthesizing mean under normal temperature, see Semaltianos N G.Nanoparticles by laser ablation [J] .Critical Reviews in SolidState and Materials Sciences, 2010,35 (2): 105-124.
Summary of the invention
Object of the present invention, little compared with difficult synthesis size for existing preparation technology, firm binding force, the problem of catalytic performance high capacity type catalyst, utilize short pulse nanosecond laser can regulate and control size and extremely the feature of uneven condition, splash-proofing sputtering metal nano-liquid droplet be combined with surrounding solid dielectric, provide one to utilize nanometer laser ablation controlledly synthesis excellent performance loaded catalyst in the liquid phase.
The present invention is achieved by following technical solution.
Laser liquid phase prepares a process for nickel/silica supported catalyst, has following steps:
(1) with reguline metal nickel target for raw material, target material surface is clean with sand papering, then nickel target is placed in distilled water ultrasonic cleaning 2min, dry up nickel target remained on surface moisture with hair-dryer cold wind afterwards;
(2) take 0.1 ~ 0.3g silica solid powder, be scattered in 200 ~ 400ml deionized water;
(3) the nickel target that step (1) is handled well is placed in step (2) solution, regulating liquid surface height, 5mm< liquid level <25mm; Adopt ns focused pulse laser ablation target under magnetic agitation condition and under motorized precision translation stage booster action, the ablation time is 1h, obtained nickel/silica suspension;
Described liquid height and the height between target upper surface and liquid level;
After nickel target is swept one time, again polish target material surface to remove surface oxide layer with sand paper, prevent surface from forming nickel oxide;
(4) by obtained for step (3) nickel/silica suspension suction filtration, and in 150 DEG C of dry 30min, obtained nickel/silicon dioxide powder powder loaded catalyst.
The metallic target of described step (1) can be nickel, cobalt, iron, platinum and other metal targets, and target purity is 99.999%, and its thickness is 3-5mm.
The nano-focusing pulse laser ablation target energy of described step (3) is 130mJ, and laser repetition rate is 10Hz.
The magnetic agitation of described step (3), adopts rotating speed to be the magnetic stirring apparatus of 540r/min.
The present invention has following effect:
(1) instant invention overcomes the deficiency of the more difficult preparation firm binding force of existing preparation technology, supported catalyst agent method that catalytic performance is good, provide the undersized loaded catalyst of one-step synthesis in a kind of liquid phase at normal temperatures and pressures.In addition, synthetic method of the present invention is simple, easy to operate, be easy to control, no coupling product and impurity, belongs to normal temperature and pressure and eco-friendly green synthesis process.
(2) the present invention is a kind of universality method, can be used for synthesizing most of loaded catalyst.
(3) by obtaining the regulation and control of different loads amount to different liquid level, for other load architectural studies follow-up provide a kind of important research thinking.
Accompanying drawing explanation
Fig. 1 is the process flow diagram that the present invention prepares nickel/silica supported catalyst;
Fig. 2 is that nickel of the present invention/silica supported catalyst XRD schemes;
Fig. 3 is nickel of the present invention/silica high power transmission electron microscope photo;
Fig. 4 is nickel of the present invention/silica overall low power transmission electron microscope photo and local high power transmission electron microscope photo;
Fig. 5 is nickel of the present invention/silica low power transmission electron microscope photo;
Fig. 6 is liquid level is the nickel/silica low power transmission electron microscope photo prepared under 5mm condition;
Fig. 7 is liquid level is the nickel/silica low power transmission electron microscope photo prepared under 15mm condition;
Fig. 8 is liquid level is the nickel/silica low power transmission electron microscope photo prepared under 25mm condition.
Detailed description of the invention
Below in conjunction with accompanying drawing, the invention will be further described.
First with reguline metal nickel target for raw material, target material surface is clean with sand papering, then nickel target is placed in distilled water ultrasonic cleaning 2min, dry up nickel target remained on surface moisture with hair-dryer cold wind afterwards, described nickel target purity be 99.99%, thickness is 5mm; Take 0.1g silica solid powder again, be scattered in 400ml deionized water.
As shown in Figure 1, be 99.99% by purity, the nickel target of thickness 5mm to be placed on support and to be positioned over silicon dioxde solution, regulation and control liquid level (namely target upper surface is apart from the height of upper liquid level) are implemented with 5mm, 15mm, 25mm respectively.Adopt nanosecond pulse Nd:YAG laser (fundamental frequency 1064nm) focusing radiation target surface, focused light energy is 130mJ, frequency is 10HZ, ns focused pulse laser ablation target is adopted under magnetic agitation condition and under motorized precision translation stage booster action, the rotating speed of described magnetic stirring apparatus is 540r/min, the ablation time is 1h, obtained nickel/silica suspension.Wherein controlled by regulation voltage by focused light energy, and monitored by energy meter, next utilizes the even inswept target material surface of motorized precision translation stage, can enlarge markedly load capacity.After target is swept one time, need the oxide layer again polishing to remove surface with sand paper.Because nickel target surface can form nickel oxide in irradiation process.Nickel oxide band gap is 3.5ev, does not absorb 1064nm energy.If do not removed, laser acts on same area again, can not form nano nickel particles again.
Finally will obtain nickel/silica suspension suction filtration, and in 150 DEG C of dry 30min, obtained nickel/silicon dioxide powder powder loaded catalyst.
Can find out from Fig. 2, Fig. 3, present invention achieves nickel and silicon dioxide carried, and nickel particle is long on silica supports as seen from Figure 3; Compared with conventional method, laser Liquid preparation methods catalyst firm binding force out, significantly improves the problem that catalyst comes off.As can be seen from Figure 4, the load nickel size that gets on levels off to about 10nm, and conventional method is even difficult to prepare the nickel-base catalyst that size is less than 30nm, and the present invention significantly reduces catalyst size.As can be seen from Figure 5, nano nickel particles uniform load on silica.Complex chart 2, Fig. 3, Fig. 4, Fig. 5 are known, and laser liquid phase ablation technology effectively can realize nano nickel particles and silicon dioxide carried and firm binding force, and Load Balanced, size is little.And firm binding force, uniform load and small size are three important indicators of the catalyst that evaluation one is good; Secondly, because nickel-base catalyst catalytic activity is relatively lower, so need corresponding increase load capacity;
As can be seen from Fig. 6, Fig. 7, Fig. 8, along with liquid level reduces, under identical action condition, transmission picture intuitively shows load capacity in remarkable lifting.Can find out when liquid level is 5mm, surface is a large amount of nickel particle of attachment obviously, when liquid level is 15mm, can find out that particle obviously reduces, and when liquid level increases to 25mm, then obviously can find out that silica surface does not have particulate load substantially, test display by Atomic absorption simultaneously, when liquid level is 5mm, load capacity is 4%, and when liquid level is 15mm, load capacity is 2.02%, and when liquid level is 25mm, load capacity is 0.207%.Further liquid level of having proved reduces to significantly improve load capacity.Wherein load capacity is 4% Ni SiO 2 catalyst is 3% at catalysis hexahydrotoluene conversion rate of dehydrogenation, and conventional method synthesizes catalyst under same load capacity, is without any conversion ratio under same test condition.Proved further, laser liquid phase ablation can prepare excellent performance catalyst.
Claims (4)
1. laser liquid phase prepares a process for nickel/silica supported catalyst, has following steps:
(1) with reguline metal nickel target for raw material, target material surface is clean with sand papering, then nickel target is placed in distilled water ultrasonic cleaning 2min, dry up nickel target remained on surface moisture with hair-dryer cold wind afterwards;
(2) take 0.1 ~ 0.3g silica solid powder, be scattered in 200 ~ 400ml deionized water;
(3) the nickel target that step (1) is handled well is placed in step (2) solution, regulating liquid surface height, 5mm< liquid level <25mm; Adopt ns focused pulse laser ablation target under magnetic agitation condition and under motorized precision translation stage booster action, the ablation time is 1h, obtained nickel/silica suspension;
Described liquid height and the height between target upper surface and liquid level;
After nickel target is swept one time, again polish target material surface to remove surface oxide layer with sand paper, prevent surface from forming nickel oxide;
(4) by obtained for step (3) nickel/silica suspension suction filtration, and in 150 DEG C of dry 30min, obtained nickel/silicon dioxide powder powder loaded catalyst.
2. the laser liquid phase according to claims 1 prepares the process of nickel/silica supported catalyst, it is characterized in that, the metallic target of described step (1) can be nickel, cobalt, iron, platinum and other metal targets, target purity is 99.999%, and its thickness is 3-5mm.
3. the laser liquid phase according to claims 1 prepares the process of nickel/silica supported catalyst, it is characterized in that, the nano-focusing pulse laser ablation target energy of described step (3) is 130mJ, and laser repetition rate is 10Hz.
4. the laser liquid phase according to claims 1 prepares the process of nickel/silica supported catalyst, it is characterized in that, the magnetic agitation of described step (3), adopts rotating speed to be the magnetic stirring apparatus of 540r/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106645805A (en) * | 2016-12-28 | 2017-05-10 | 西安交通大学青岛研究院 | Method of carrying out laser liquid phase ablation test by using laser liquid phase ablation system |
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| US7297626B1 (en) * | 2001-08-27 | 2007-11-20 | United States Of America As Represented By The Secretary Of The Army | Process for nickel silicide Ohmic contacts to n-SiC |
| CN101239391A (en) * | 2008-02-27 | 2008-08-13 | 天津大学 | Method for coating metal nano granule by laser synthesizing carbon |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106645805A (en) * | 2016-12-28 | 2017-05-10 | 西安交通大学青岛研究院 | Method of carrying out laser liquid phase ablation test by using laser liquid phase ablation system |
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