CN101229511A - Noble metal carrier catalyst, preparing method and applications thereof - Google Patents
Noble metal carrier catalyst, preparing method and applications thereof Download PDFInfo
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- CN101229511A CN101229511A CNA2007100630468A CN200710063046A CN101229511A CN 101229511 A CN101229511 A CN 101229511A CN A2007100630468 A CNA2007100630468 A CN A2007100630468A CN 200710063046 A CN200710063046 A CN 200710063046A CN 101229511 A CN101229511 A CN 101229511A
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Abstract
The invention discloses a noble metal supported catalyst and a preparation method and application thereof. The preparation method of the noble metal supported catalyst of the invention comprises the following steps: (a) titanium dioxide precursor dispersed solution with rich hydroxyl group and stannous salt solution are mixed, stirred, washed and dispersed into the water; (b) when stirring, soluble noble metal salt solution is added into the titanium dioxide precursor dispersed solution after being processed by the stannous salt solution, which is stirred, washed and dried, thus obtaining the noble metal supported catalyst. The method of the invention has no high requirements for preparation conditions which can be carried out under room temperature and atmospheric pressure and does not need heat and pressure; meanwhile, the raw materials adopted in the reaction have wide source and lower toxicity with the advantages of simplicity, economy, low energy consumption, convenient operation and convenience on realizing scale production.
Description
Technical field
The present invention relates to a kind of noble metal carrier catalyst and preparation method thereof and application.
Background technology
Catalysis is an important research theme in the chemical scientific research, and catalyst comprises homogeneous catalyst and different-phase catalyst.For the ease of the separation of catalysis afterproduct and the repeated use of catalyst, the industrial different-phase catalysts that adopt more; Thereby many homogeneous catalysts are also supported on suitable carriers, become different-phase catalyst for use.
Noble metal (as gold, silver, platinum, palladium, rhodium etc.) is widely used in the various catalytic reactions, connects or the like as catalytic hydrogenation, catalytic oxidation, carbon carbon.In order to improve catalytic activity, noble metal generally is to be dispersed on the solid carrier with form of nanoparticles, uses as loaded catalyst.For noble metal carrier catalyst, carrier can also produce synergy with noble metal nano particles sometimes, thereby show novel catalytic performance except playing a part fixing and disperseing the noble metal nano particles.A good example is exactly to go up resulting loaded catalyst with gold-nanoparticle-supported at reproducibility oxide (as titanium oxide, iron oxide and cerium oxide etc.), this class gold nano grain loaded catalyst has beat all catalytic performance, in room temperature even be lower than under the temperature of room temperature and just catalyzing carbon monoxide can be oxidized to carbon dioxide.
A kind of good catalyst must have advantages such as catalytic activity height, selectivity is good, the life-span is long, recovery is easy simultaneously.The catalytic performance of catalyst and preparation method have very big relation, adopt the performance of the different resultant catalyst of preparation method to differ greatly.
At present, the preparation method of common noble metal carrier catalyst mainly contains three kinds: (1) infusion process, carrier is immersed in the solution that contains noble metal precursor, and evaporating solvent restores noble metal at last under atmosphere of hydrogen, thereby forms supported catalyst.(2) coprecipitation adds alkali in the solution that contains noble metal precursor and precursor carrier, both coprecipitations, thus form supported catalyst.(3) deposition-precipitation method add solid carrier in the solution that contains noble metal precursor, make noble metal under the carrier surface deposition by regulating the pH value, thereby form supported catalyst.In addition, can also prepare noble metal nano particles in advance, its dispersion liquid is mixed with corresponding carrier, noble metal nano particles just can load on the carrier.When adopting this method, in order to improve the adsorption capacity of carrier to noble metal nano particles, carrier generally will pass through preliminary treatment, makes that sulfydryl or amino etc. have the group of pretending usefulness to noble metal nano particles in its finishing.When adopting the immersion process for preparing noble metal carrier catalyst, though can control the load capacity of noble metal well, resulting noble metal size is bigger, and its dispersiveness on carrier is also not satisfactory.Adopt coprecipitation and deposition-precipitation method to prepare the influence of various factors such as type, pH value of solution value and concentration that loaded catalyst then is subjected to carrier, simultaneously, resulting noble metal granule Size Distribution broad.And be difficult to guarantee that all noble metal nano particles all are adsorbed onto on the carrier surface when adopting the colloidal solution contain noble metal nano particles to prepare loaded catalyst.Obviously, all there is certain weak point in above-mentioned described preparation method, and therefore, the preparation method of the noble metal carrier catalyst that development is novel is imperative.
Summary of the invention
The purpose of this invention is to provide a kind of noble metal carrier catalyst and preparation method thereof.
The preparation method of noble metal carrier catalyst provided by the present invention comprises the steps:
(a) the titanium dioxide precursor dispersion liquid that will be rich in hydroxyl mixes, stirs with tin salt solution, it is distributed in the water after the washing again;
(b) under agitation,, stir to the above-mentioned solubility precious metal salt solution that in the titanium dioxide precursor dispersion liquid of tin salt solution-treated, adds, washing, drying obtains noble metal carrier catalyst.
Wherein, titanium dioxide precursor is titanium hydroxide or alkyd titanium, is preferably the alkyd titanium.These titanium dioxide precursor both can obtain according to literature method is synthetic, also can be prepared according to following process:
The titanium hydroxide that is rich in hydroxyl prepares according to the following procedure:
Under stirring condition, in the ethanolic solution of alkyl titanate, add entry, gained precipitation is washed with water, drying obtains being rich in the titanium hydroxide of hydroxyl.
The alkyd titanium that is rich in hydroxyl prepares according to the following procedure:
Under stirring condition, the ethylene glycol solution of alkyl titanate is joined in the mixed solution of acetone and water, with the ethanol washing precipitation, drying obtains being rich in the alkyd titanium of hydroxyl.
In the present invention, tin salt is selected from one or more in stannous chloride, the inferior tin of nitric acid, the stannous sulfate; Be preferably stannous chloride.The mass ratio of tin salt and titanium dioxide precursor can be in 1: 10 to 1: 0.5 scope.The solubility precious metal salt is selected from one or more in the soluble-salt of silver, gold, palladium, platinum, rhodium, and the mass ratio of solubility precious metal salt and titanium dioxide precursor can be in 1: 50 to 1: 0.5 scope.In order to guarantee that precious metal salt all is reduced, also be added with reducing agent in the step (b), described reducing agent is selected from one or more in aldehyde, formic acid, formates, ascorbic acid, ascorbate and the sodium borohydride; Be preferably sodium formate.The molar ratio of reducing agent and precious metal salt can be in 1: 0.01 to 1: 1 scope.
The noble metal carrier catalyst that the inventive method is prepared also belongs to protection scope of the present invention.This catalyst is the carrier of catalyst with the titanium dioxide precursor, and noble metal nano particles is fine in the carrier surface dispersiveness, does not have and reunites and obscission.By changing the amount of the precious metal salt that is added, can easily change the load capacity of noble metal, the size that can also regulate noble metal nano particles on the carrier surface easily simultaneously.Under the very high situation of load capacity, noble metal nano particles still can keep less size, and this just can guarantee that noble metal nano particles has very high specific area, thereby has very high catalytic activity.
Another object of the present invention provides the purposes of noble metal supported catalyst of the present invention.
The inventor confirms that by test noble metal supported catalyst provided by the present invention has good catalytic activity, can be widely used in catalytic hydrogenation reaction, oxidation reaction and the coupled reaction of carbon carbon.
The present invention is earlier at carrier surface absorption stannous ion, utilization is adsorbed on the in-situ reducing effect of the stannous ion on the carrier surface noble metal precursor in-situ reducing is come out, resulting noble metal granule can be adsorbed on carrier surface well, and can be used as the nucleation seed and further grow up.
Compare with other existing technology of preparing, the present invention has following characteristics:
1. the titanium dioxide precursor that hydroxyl is rich in utilization of the present invention is as carrier, and these class carrier wide material sources, preparation are simply.
2. the titanium dioxide precursor surface energy strong adsorption stannous ion that is rich in hydroxyl that the present invention utilized, and stannous ion has stronger reduction, utilizes the in-situ reducing effect that is adsorbed on the stannous ion on the carrier surface, and the precious metal salt in-situ reducing is come out.The noble metal that is restored loads on the carrier securely with very little form of nanoparticles.Simultaneously, these noble metal nano particles can be used as the nucleation seed and further grow up, thereby improve the load capacity of noble metal.
3. the inventive method has very big universality, and many noble metals (as gold, silver, platinum, palladium, rhodium etc.) can successfully adopt this technology to load on the carrier.In addition, can pass through to add two or more precious metal salt, thereby prepare the precious metal alloys loaded catalyst; And can change the load capacity of noble metal to a great extent by the addition that changes precious metal salt.
4. in the prepared noble metal carrier catalyst of the present invention, noble metal all loads on the carrier securely, and no obscission takes place.Noble metal nano particles is dispersed fine on carrier surface simultaneously, and no agglomeration takes place.
5. in the prepared noble metal carrier catalyst of the present invention, even under the situation of very high noble metal load capacity, noble metal nano particles still has very little size, thereby guarantees that this class catalyst still keeps advantages of high catalytic activity under higher load capacity situation.
6. in the prepared noble metal carrier catalyst of the present invention, the surface of noble metal nano particles is " exposing ", the coating protection of no organic protective agent.Like this, the lip-deep catalytic active center of noble metal nano particles just can directly contact with reactant, thereby has very high catalytic activity.
7. the present invention's less demanding to preparation condition carries out under the room temperature normal pressure, need not the heating pressurization, the reaction raw materials wide material sources that adopted simultaneously, and toxicity is also lower, has simple economy, energy consumption is low, easy to operate and the advantage being convenient to accomplish scale production.
8. the prepared noble metal carrier catalyst of the present invention shows good catalytic performance in multiple catalyst system and catalyzing, have the catalytic activity height, reclaim advantages such as easy and reusable, also all have application potential widely in fields such as solar cell, fuel cell and sensings.
Description of drawings
Fig. 1 is a kind of stereoscan photograph that is rich in the titanium dioxide precursor of hydroxyl.
Fig. 2 is for being the catalyst (TiO of 15wt% in preparation palladium mass loading amount
2The transmission electron microscope photo of sample during different phase in the process of precursor-Pd).
Fig. 3 is respectively the transmission electron microscope photo of the palladium loaded catalyst of 3wt% and 30wt% for the mass loading amount.
Fig. 4 is the transmission electron microscope photo of the loaded catalyst of silver and gold.
Fig. 5 is the transmission electron microscope photo of the loaded catalyst of electrum.
Fig. 6 is the conversion ratio and the time chart of iodobenzene when adopting (～25 ℃) the catalysis Suzuki carbon carbon coupled reaction at room temperature of the resulting palladium loaded catalyst of the present invention.
The specific embodiment
The preparation method of noble metal carrier catalyst involved in the present invention comprises following several steps:
(a) prepare the titanium dioxide precursor that hydroxyl is rich on the surface;
(b) the titanium dioxide precursor dispersion liquid is mixed with tin salt solution, stir about is the centrifuge washing several after ten minutes, precursor is distributed in the water again;
(c) under condition of stirring, toward the above-mentioned noble metal soluble-salt solution that in the titanium dioxide precursor dispersion liquid of tin salt solution-treated, adds; In order to guarantee that precious metal salt can all be reduced, improve the load capacity of catalyst, after adding precious metal salt solution, can also in solution system, add reducing agent;
(d) continue stirred for several hour, centrifuge washing can obtain required noble metal carrier catalyst with drying precipitate for several times.
Wherein, titanium dioxide precursor comprises as titanium hydroxide and alkyd titanium etc., preferred alkyd titanium; The titanium dioxide precursor that hydroxyl is rich on this surface can be prepared (Adv.Mater.2003,15,1205) according to literature method, also can be prepared according to following method:
Titanium hydroxide prepares according to the following procedure: 0.5～5mL butyl titanate is dissolved in the 30mL ethanol, under stirring condition, add 0.5～10mL water, continue to stir behind the 1h and resulting precipitation to be washed with water repeatedly and dry about 60 ℃, can obtain being rich in the titanium hydroxide of hydroxyl.
The alkyd titanium prepares according to the following procedure: with 0.2～10mL water mix with 170mL acetone solution A.0.1～5mL butyl titanate is joined in the 50mL ethylene glycol, pour in the above-mentioned solution A after at room temperature stirring 8h, continue to stir behind the 1h with the ethanol washing repeatedly and dry about 60 ℃, can obtain being rich in the titanium dioxide precursor alkyd titanium of hydroxyl resulting precipitation.
In the present invention, tin salt comprises stannous chloride, the inferior tin of nitric acid and stannous sulfate etc. or its combination, preferred stannous chloride; The mass ratio of tin salt and titanium dioxide precursor can be in 1: 10 to 1: 0.5 scope.Precious metal salt solution comprises the soluble-salt of silver, gold, palladium, platinum, rhodium etc. or its combination, and commonly used have silver nitrate, gold chloride, palladium bichloride, chloroplatinic acid, radium chloride or the like.When using a kind of slaine of element, the gained catalyst is single metal supported catalyst; When using the slaine of two or more element, the gained catalyst is the alloying metal supported catalyst; The mass ratio of solubility precious metal salt and titanium dioxide precursor can be in 1: 50 to 1: 0.5 scope.In step (c), the reducing agent that is added comprises aldehyde, formic acid, formates, ascorbic acid and ascorbate etc. or its combination, preferable formic acid sodium; The molar ratio of the consumption of reducing agent and precious metal salt can be in 1: 0.01 to 1: 1 scope.In preparation process, the load capacity of noble metal can be regulated and control by the amount that changes the precious metal salt that is added easily.Adopt the inventive method, the mass loading amount of noble metal can effectively be controlled in 0% to 50% scope.
In step (b), stannous ion is adsorbed onto on the titanium dioxide precursor surface by various chemistry and/or physical action; In step (c), the reduction of the stannous ion by being adsorbed on the titanium dioxide precursor surface is reduced precious metal salt, and the resulting noble metal that reduces is adsorbed on carrier surface, thereby forms the noble metal supported catalyst.In step (c), by adding reducing agent, the precious metal salt in the solution is further reduced, the noble metal granule on the carrier surface is further grown up.
Fig. 1 represents a kind of stereoscan photograph that is rich in the titanium dioxide precursor of hydroxyl.This precursor is made up of the glycolic titanium, and the surface has abundant hydroxyl.As can be seen from Figure 1, this titanium dioxide precursor is the nanosphere of diameter about 200nm.
It is the catalyst (TiO of 15wt% that Fig. 2 is illustrated in preparation palladium mass loading amount
2The transmission electron microscope photo of sample during different phase in the process of precursor-Pd), among the figure (a) (c) (e) be macrograph (g), (b) (d) (f) (h) be the high power photo.Wherein, (a) with the transmission electron microscope photo of (b) scheming the expression titanium dioxide precursor that preparation process adopted, as can be seen, the surface of this titanium dioxide precursor is very smooth; (c) and (d) scheme expression through SnCl
2The transmission electron microscope photo of the pretreated titanium dioxide precursor of solution, as can be seen, through SnCl
2After the solution preliminary treatment, it is smooth that the surface of titanium dioxide precursor also keeps, in insert in (c) figure for through SnCl
2The energy spectrogram of the pretreated titanium dioxide precursor of solution can be seen the characteristic peak that belongs to the Sn element from this energy spectrogram, shows that stannous ion successfully is adsorbed onto on the surface of titanium dioxide precursor; (e) and (f) transmission electron microscope photo of the titanium dioxide precursor after going up palladium nano-particles is modified in expression through the stannous ion in-situ reducing, as can be seen, these palladium nano-particles sizes are 3.8 ± 0.4nm, be evenly distributed on very much on the surface of titanium dioxide precursor, in insert among (e) figure for this sample can spectrogram, can see the characteristic peak that belongs to the Pd element from this energy spectrogram, show that palladium is come out by in-situ reducing, and be attached on the carrier surface; The transmission electron microscope photo of the supported catalyst after (g) and (h) the expression palladium nano-particles is further grown up, as can be seen, palladium nano-particles has become greatly 6.4 ± 1.2nm, these palladium nano-particles still are dispersed on the surface of titanium dioxide precursor well simultaneously, do not reunite, do not come off, in insert among (g) figure for this sample can spectrogram.
Fig. 3 represents that the mass loading amount is respectively the transmission electron microscope photo of the palladium loaded catalyst of 3wt% and 30wt%.Wherein, (a) for load capacity be the transmission electron microscope photo of the sample of 3wt%, from this photo, be difficult to pick out palladium nano-particles, illustrate that under the situation of this low load capacity, palladium nano-particles is very little.(b) for load capacity be the transmission electron microscope photo of the sample of 30wt%, from this photo as can be seen, the size of palladium nano-particles is 8.8 ± 1.0nm.Simultaneously can also see that under the situation of this high capacity amount, palladium nano-particles still keeps fine dispersiveness at carrier surface, does not reunite, and does not come off.
Fig. 4 represents the transmission electron microscope photo of the loaded catalyst of silver (a) and gold (b).As can be seen from the figure, by technology of preparing involved in the present invention, can successfully successfully load to the nano particle of silver and gold on the titanium dioxide precursor, these silver and gold nano grain keep the dispersiveness of height on carrier surface.
Fig. 5 represents the transmission electron microscope photo of the loaded catalyst of electrum.As can be seen from the figure, the nano particle of electrum is dispersed on the carrier surface well, and this shows that preparation method involved in the present invention is suitable for preparing the precious metal alloys loaded catalyst equally.
Further describe the present invention below in conjunction with embodiment.
Embodiment 1: preparation 15wt% palladium supported catalyst
Be rich in the preparation of the titanium dioxide precursor (glycolic titanium) of hydroxyl: with 2.7mL water mix with 170mL acetone solution A.The 2mL butyl titanate is joined in the 50mL ethylene glycol, pour in the above-mentioned solution A after at room temperature stirring 8h, continue to stir behind the 1h with the ethanol washing repeatedly and dry about 60 ℃, can obtain being rich in the titanium dioxide precursor (glycolic titanium) of hydroxyl resulting precipitation.
Load capacity is the preparation of the palladium loaded catalyst of 15wt%: the 0.1g titanium dioxide precursor is distributed in the 20mL deionized water, joining 20mL behind the stir about 10min contains in the solution of 0.1g stannous chloride, after continuing to stir 10min, centrifugation, and spending deionised water 5 times, the precipitation after will washing again is distributed in the 40mL deionized water.Under condition of stirring, adding 2.5mL concentration toward above-mentioned dispersion liquid is the palladium chloride solution of 0.056M, adds the sodium formate solution that 10mL concentration is 0.15M behind the 5min again.After continuing to stir 5h, with resulting precipitation centrifuge washing and dry, can obtain the mass loading amount is the palladium loaded catalyst of 15wt% again.
Embodiment 2: preparation 3wt% palladium supported catalyst
Be rich in the preparation of the titanium dioxide precursor (glycolic titanium) of hydroxyl: prepare titanium dioxide precursor by program identical among the embodiment 1, but butyl titanate is replaced by tetraethyl titanate.
Load capacity is the preparation of the palladium loaded catalyst of 3wt%: press program identical among the embodiment 1, the addition of palladium chloride solution is 0.5mL (0.056M).
Same, when the addition of palladium chloride solution was 5mL (0.056M), obtaining load capacity was the palladium loaded catalyst of 30wt%
Embodiment 3: the preparation of silver-colored loaded catalyst
Be rich in the preparation of the titanium dioxide precursor (glycolic titanium) of hydroxyl:
With 2.7mL water mix with 170mL acetone solution A.The 2mL butyl titanate is joined in the 50mL ethylene glycol, pour in the above-mentioned solution A after at room temperature stirring 8h, continue to stir behind the 1h with the ethanol washing repeatedly and dry about 60 ℃, can obtain being rich in the titanium dioxide precursor of hydroxyl resulting precipitation.
Load capacity is the preparation of the silver-colored loaded catalyst of 15wt%:
The 0.1g titanium dioxide precursor is distributed in the 20mL deionized water, join 20mL behind the stir about 10min and contain in the solution of 0.1g stannous chloride, after continuing to stir 10min, centrifugation, and spending deionised water 5 times, the precipitation after will washing again is distributed in the 40mL deionized water.Under condition of stirring, adding 2.5mL concentration toward above-mentioned dispersion liquid is the liquor argenti nitratis ophthalmicus of 0.055M, adds the sodium formate solution that 10mL concentration is 0.15M behind the 5min again.After continuing to stir 5h, with resulting precipitation centrifuge washing and dry, can obtain the mass loading amount is the palladium loaded catalyst of 15wt% again.
What deserves to be mentioned is,, also can obtain noble metal carrier catalyst if in preparation process, further do not add the reducing agent of sodium formate and so on.But the lip-deep stannous ion of titanium dioxide precursor is limited owing to being adsorbed on, and the amount of the precious metal salt that can reduce is also limited, and therefore, if further do not add the reducing agent of sodium formate and so on, the load capacity of noble metal will be lower.With silver-colored loaded catalyst is example, does not add the reducing agent of sodium formate and so on, and the load capacity of silver is generally less than 5%.
Being one does not below add sodium formate and prepares the embodiment that load capacity is the silver-colored loaded catalyst of 1wt%: the 0.1g titanium dioxide precursor is distributed in the 20mL deionized water, joining 20mL behind the stir about 10min contains in the solution of 0.1g stannous chloride, after continuing to stir 10min, centrifugation, and spending deionised water 5 times, the precipitation after will washing again is distributed in the 40mL deionized water.Under condition of stirring, adding 0.17mL concentration toward above-mentioned dispersion liquid is the liquor argenti nitratis ophthalmicus of 0.055M, and after continuing to stir 5h, with resulting precipitation centrifuge washing and dry, can obtain the mass loading amount is the silver-colored loaded catalyst of 1wt%.
Embodiment 4: the preparation of golden loaded catalyst
Press program identical among the embodiment 2, but replace palladium chloride solution with chlorauric acid solution.
The preparation of other noble metal carrier catalyst can be carried out according to program identical among the embodiment 2, only need to use corresponding precious metal salt solution to replace palladium chloride solution to get final product, as use platinum acid chloride solution can obtain the platinum supported catalyst, use rhodium chloride solution can obtain the rhodium supported catalyst.
Embodiment 5: the preparation of Polarium loaded catalyst
Press program identical among the embodiment 2, use the mixed solution of palladium bichloride and gold chloride to replace palladium chloride solution can obtain the Polarium loaded catalyst, wherein, the palladium bichloride consumption is 1.25mL (0.056M), and the gold chloride consumption is 1.25ml (0.058M).
Embodiment 6: the preparation of electrum loaded catalyst
Press program identical among the embodiment 2, use the mixed solution of silver nitrate and gold chloride to replace palladium chloride solution can obtain the Polarium loaded catalyst, wherein, the silver nitrate consumption is 1.25ml (0.055M), and the gold chloride consumption is 1.25ml (0.058M).
The preparation of other alloy loaded catalyst can be carried out according to program identical among the embodiment 2, only needs to use the mixed solution of corresponding precious metal salt to replace palladium chloride solution to get final product.
Embodiment 7: be rich in hydroxyl titanium dioxide precursor (titanium hydroxide) preparation and be the preparation of the noble metal carrier catalyst of carrier with resulting titanium hydroxide
The 2mL butyl titanate is dissolved in the 30mL ethanol, under stirring condition, adds 4mL water, continue to stir behind the 1h and resulting precipitation to be washed with water repeatedly and dry about 60 ℃, can obtain being rich in the titanium hydroxide of hydroxyl.
With above-mentioned resulting titanium hydroxide is carrier, replaces the glycolic titanium, according to program identical among the embodiment 1～6, can prepare noble metal carrier catalyst.
Embodiment 8: the palladium loaded catalyst is applied to the coupled reaction of catalysis Suzuki carbon carbon
With the 1mmol iodobenzene, the 2mmol phenyl boric acid, 4mmol potassium phosphate and 1mmol pentamethylbenzene (internal standard compound that detects as chromatogram uses) join in the 15mL ethanol, under condition of stirring, add 10mg and adopt embodiment 1 (the palladium loaded catalyst of 15wt%) and the resulting catalyst of embodiment 2 (the palladium loaded catalyst of 3wt%), add after hot reflux half an hour solution centrifugal, get supernatant liquor and carry out gas chromatographic analysis, extrapolate the stupid conversion ratio of iodine.Experimental result shows that when adopting these two kinds of catalyst, the conversion ratio of iodobenzene all is 100%.
Embodiment 9: the palladium loaded catalyst is applied to the coupled reaction of room temperature catalysis Suzuki carbon carbon
At room temperature (～25 ℃) investigate the catalytic activity when adopting the resulting palladium loaded catalyst of the present invention to be applied to the coupled reaction of catalysis Suzuki carbon carbon: press program identical among the embodiment 8, but catalyst system and catalyzing need not heat, but at room temperature carry out the back at set intervals circumstances in which people get things ready for a trip analysis of spectrum of going forward side by side of taking a sample.
The conversion ratio and the time chart of iodobenzene when Fig. 6 represents to adopt the catalysis Suzuki carbon carbon coupled reaction at room temperature of the resulting palladium loaded catalyst of the present invention.As can be seen, at room temperature, adopt the resulting palladium loaded catalyst of the present invention to have quite high catalytic activity, and the catalyst of low load capacity have higher catalytic activity.
Embodiment 10: the reuse of catalyst
But the reuse when the resulting palladium loaded catalyst of investigation the present invention is applied to the coupled reaction of catalysis Suzuki carbon carbon: press program identical among the embodiment 8, after every backflow half an hour and the sampling, in reaction system, add the 1mmol iodobenzene, 2mmol phenyl boric acid, 4mmol potassium phosphate again; Employed catalyst is the palladium loaded catalyst of 15wt%.
Palladium loaded catalyst iodobenzene conversion ratio and recycle the number of times relation table during coupled reaction of catalysis Suzuki carbon carbon under reflux temperature is adopted in table 1 expression.
The relation of table 1 catalyst circulation access times and conversion ratio
As can be seen, adopt the resulting palladium loaded catalyst of the present invention activity very high, and can reuse repeatedly and not reduction of catalytic performance.
Embodiment 11: golden loaded catalyst is applied to the coupled reaction of catalysis Suzuki carbon carbon
With the 1mmol iodobenzene, the 2mmol phenyl boric acid, 4mmol potassium phosphate and 1mmol pentamethylbenzene (internal standard compound that detects as chromatogram uses) join in the 15mL ethanol, under condition of stirring, add 10mg and adopt the resulting catalyst of embodiment 4 (the golden loaded catalyst of 15wt%), add after hot reflux half an hour solution centrifugal, get supernatant liquor and carry out gas chromatographic analysis, extrapolate the stupid conversion ratio of iodine.Experimental result shows that the conversion ratio of iodobenzene is 54%.
Embodiment 12: the porpezite loaded catalyst is applied to the coupled reaction of catalysis Suzuki carbon carbon
With the 1mmol iodobenzene, the 2mmol phenyl boric acid, 4mmol potassium phosphate and 1mmol pentamethylbenzene (internal standard compound that detects as chromatogram uses) join in the 15mL ethanol, (load capacity of palladium is 7.5% to add 10mg employing embodiment 5 under condition of stirring, the mol ratio of palladium and gold is 1: 1) resulting catalyst, add after hot reflux half an hour solution centrifugal, get supernatant liquor and carry out gas chromatographic analysis, extrapolate the stupid conversion ratio of iodine.Experimental result shows that the conversion ratio of iodobenzene is 100%.
Embodiment 13: the platinum loaded catalyst is applied to the cyclohexene catalytic hydrogenation reaction
Under condition of stirring, in the 10mL cyclohexene, add the 20mg employing resulting platinum loaded catalyst of the present invention (the platinum load capacity is 15%), feed 1 standard atmospheric pressure hydrogen again.Behind the room temperature reaction two hours, get oil phase and carry out chromatography.Experimental result shows that used platinum loaded catalyst is about 600h to the conversion efficiency (TOF) of cyclohexene catalytic hydrogenation
-1(here, conversion efficiency (TOF) is defined as the per hour molal quantity of every mole of platinum conversion cyclohexene molecule)
Need to prove, the foregoing description just is used for illustrating the present invention, it or not the application range that is used for limiting patent of the present invention, such as, the present invention described precious metal salt be not limited to precious metal salt involved among the embodiment 1～7, can use other precious metal salt fully, the addition of these precious metal salts also can change as required simultaneously.In addition, the foregoing description is mentioned the palladium loaded catalyst and is applied to the coupled reaction of catalysis Suzuki carbon carbon, but it is pointed out that the resulting palladium loaded catalyst of the present invention also can be applied to other catalytic reaction, as catalytic hydrogenation and catalytic oxidation or the like; Simultaneously, resulting other noble metal carrier catalyst of the present invention (as silver-colored loaded catalyst and golden loaded catalyst or the like) and precious metal alloys loaded catalyst (as the Polarium loaded catalyst) also can be applied in the various catalytic reactions.These all belong to patent application category of the present invention.
Claims (12)
1. the preparation method of a noble metal carrier catalyst comprises the steps:
(a) the titanium dioxide precursor dispersion liquid that will be rich in hydroxyl mixes, stirs with tin salt solution, it is distributed in the water after the washing again;
(b) under agitation,, stir to the above-mentioned solubility precious metal salt solution that in the titanium dioxide precursor dispersion liquid of tin salt solution-treated, adds, washing, drying obtains noble metal carrier catalyst.
2. preparation method according to claim 1 is characterized in that: described titanium dioxide precursor is titanium hydroxide or alkyd titanium; Be preferably the alkyd titanium.
3. preparation method according to claim 2 is characterized in that: the described titanium hydroxide that is rich in hydroxyl prepares according to the following procedure:
Under stirring condition, in the ethanolic solution of alkyl titanate, add entry, gained precipitation is washed with water, drying obtains being rich in the titanium hydroxide of hydroxyl.
4. preparation method according to claim 2 is characterized in that: the described alkyd titanium that is rich in hydroxyl prepares according to the following procedure:
Under stirring condition, the ethylene glycol solution of alkyl titanate is joined in the mixed solution of acetone and water, with the ethanol washing precipitation, drying obtains being rich in the alkyd titanium of hydroxyl.
5. preparation method according to claim 1 is characterized in that: the mass ratio of tin salt and titanium dioxide precursor is 1: 10 to 1: 0.5.
6. preparation method according to claim 5 is characterized in that: described tin salt is selected from one or more in stannous chloride, the inferior tin of nitric acid, the stannous sulfate; Be preferably stannous chloride.
7. preparation method according to claim 1 is characterized in that: the mass ratio of solubility precious metal salt and titanium dioxide precursor is 1: 50 to 1: 0.5.
8. preparation method according to claim 7 is characterized in that: the solubility precious metal salt is selected from one or more in the soluble-salt of silver, gold, palladium, platinum, rhodium.
9. preparation method according to claim 1 is characterized in that: also be added with reducing agent in the step b), described reducing agent is selected from one or more in aldehyde, formic acid, formates, ascorbic acid, ascorbate and the sodium borohydride; Be preferably sodium formate.
10. preparation method according to claim 9 is characterized in that: the molar ratio of reducing agent and precious metal salt is 1: 0.01 to 1: 1.
11. the prepared noble metal carrier catalyst of the arbitrary described preparation method of claim 1-10.
12. the application of the described noble metal carrier catalyst of claim 11 in catalytic hydrogenation reaction, oxidation reaction or the coupled reaction of carbon carbon.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111185156A (en) * | 2019-12-25 | 2020-05-22 | 中国航空工业集团公司金城南京机电液压工程研究中心 | Titanium-tin composite oxide loaded noble metal catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| IL104349A (en) * | 1993-01-08 | 1997-01-10 | Mul T Lock Ltd | Locking apparatus |
| CN1257570C (en) * | 2004-02-23 | 2006-05-24 | 北京科技大学 | Method of preparing direct methanol fuel sell anode catalyst by sub-stannic acid method |
| US20070238605A1 (en) * | 2004-04-26 | 2007-10-11 | Wolfgang Strehlau | Catalysts for the Simultaneous Removal of Carbon Monoxide and Hydrocarbons from Oxygen-Rich Exhaust Gases and Processes for the Manufacture Thereof |
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| CN101774635A (en) * | 2010-03-15 | 2010-07-14 | 彩虹集团公司 | Method for preparing titanium dioxide microballoon sphere modified with noble metals |
| CN102267684A (en) * | 2010-06-03 | 2011-12-07 | 中国科学院化学研究所 | Metallic nano particle/ carbon composite material and preparation method and application thereof |
| CN102267684B (en) * | 2010-06-03 | 2013-09-11 | 中国科学院化学研究所 | Metallic nano particle/ carbon composite material and preparation method and application thereof |
| CN101979480A (en) * | 2010-10-27 | 2011-02-23 | 合肥学院 | Molybdenum disulfide nanosphere/titanium dioxide composite material and preparation method thereof |
| CN101979480B (en) * | 2010-10-27 | 2013-10-30 | 合肥学院 | Molybdenum disulfide nanosphere/titanium dioxide composite material and preparation method thereof |
| CN102897883A (en) * | 2012-10-10 | 2013-01-30 | 盐城工学院 | Preparation method for humic acid degradable material Ag-TiO2 |
| CN106861684B (en) * | 2015-12-10 | 2019-07-12 | 中国科学院大连化学物理研究所 | A kind of titania oxide supported sub-nanometer rhodium catalyst and its preparation and application |
| CN106861684A (en) * | 2015-12-10 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of titania oxide supported sub- nanometer rhodium catalyst and its preparation and application |
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| CN111185156A (en) * | 2019-12-25 | 2020-05-22 | 中国航空工业集团公司金城南京机电液压工程研究中心 | Titanium-tin composite oxide loaded noble metal catalyst and preparation method thereof |
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| CN111632604B (en) * | 2020-05-26 | 2023-06-16 | 盐城师范学院 | Modified clay mineral/iron-palladium bimetallic composite material, preparation method and application thereof |
| CN112691641A (en) * | 2020-12-08 | 2021-04-23 | 辽宁大学 | Hydroxyl-modified tremella-shaped three-dimensional carbon nanosheet, preparation method thereof and application thereof in gallium recovery |
| CN112691641B (en) * | 2020-12-08 | 2023-09-15 | 辽宁大学 | Hydroxyl-modified tremella three-dimensional carbon nano sheet, preparation method thereof and application thereof in gallium recovery |
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| CN113782277B (en) * | 2021-09-13 | 2023-09-19 | 江西云泰铜业有限公司 | Manufacturing process of alloy copper wire |
| CN117210694A (en) * | 2023-11-09 | 2023-12-12 | 云南贵金属实验室有限公司 | Method for enriching and recovering noble metal from rhodium-precipitated DETA solution |
| CN117210694B (en) * | 2023-11-09 | 2024-01-19 | 云南贵金属实验室有限公司 | Method for enriching and recovering noble metal from rhodium-precipitated DETA solution |
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