CN108201897A - The method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts - Google Patents
The method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts Download PDFInfo
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- CN108201897A CN108201897A CN201810103008.9A CN201810103008A CN108201897A CN 108201897 A CN108201897 A CN 108201897A CN 201810103008 A CN201810103008 A CN 201810103008A CN 108201897 A CN108201897 A CN 108201897A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 37
- 230000009467 reduction Effects 0.000 title claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 238000006722 reduction reaction Methods 0.000 claims description 40
- 238000007598 dipping method Methods 0.000 claims description 16
- 239000000523 sample Substances 0.000 claims description 14
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 11
- 229910003244 Na2PdCl4 Inorganic materials 0.000 abstract description 7
- 238000007385 chemical modification Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000003381 stabilizer Substances 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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Abstract
The method that ultrasonic wave added local reduction way prepares 15 loaded nanometer palladium catalysts of SBA, the invention belongs to the green preparation fields of support type efficient nano noble metal catalyst, and in particular to a kind of method that ultrasonic wave added local reduction way prepares 15 loaded nanometer palladium catalysts of SBA.The technical issues of present invention is to solve the palladium nano-particles of surface chemical modification and load to be needed easily to reunite, be easy to run off before SBA 15 is loaded.Method：SBA 15 after calcination process is added to Na2PdCl4It in aqueous solution, after impregnating, drying, is added in ethylene glycol, nitrogen reaches reduction temperature, carry out ultrasonic reaction, after solution blackening, after centrifuging, drying, obtain 15 loaded nanometer palladium catalysts of SBA as protective gas.The present invention replaces surface chemical modification using simple calcination process SBA 15, in the case where being added without any stabilizer, using ultrasonic wave added method, palladium nano-particles being prepared in situ in carrier duct is realized, catalyst has high metal dispersity, shows good stability.
Description
Technical field
The invention belongs to the green preparation fields of support type efficient nano noble metal catalyst, and in particular to a kind of ultrasound is auxiliary
The method that local reduction way is helped to prepare SBA-15 loaded nanometer palladium catalysts.
Background technology
In recent years, loaded nano palladium catalyst is non-due to having big specific surface area, high surface energy, the optics of height
Linearly, the characteristics such as specific catalytic and photocatalytic, in hydrogenation reduction, oxidation reaction, electrochmical power source, photocatalytic degradation etc.
It is extensively studied and is applied in specific reaction.And the support type of high dispersive high activity is prepared by simple and practicable means
Nano Pd catalyst is one of emphasis of research.
For loaded catalyst, carrier is not only that the load of noble metal provides big specific surface area, improves gold
Belong to the dispersion degree of nano-particle, and its different pore passage structure also generates larger shadow to the structure of nano-particle and pattern
It rings, influence of the different carriers to prepared nano Pd catalyst structure, pattern and catalytic performance.
Using activated carbon as carrier, during preparing loaded nano palladium catalyst, the collection of Pd nano particle in order to prevent
It is poly-, generally require addition stabilizer, such as functionalized polymer, surfactant, quaternary ammonium salt etc. to stablize palladium nanoparticles, then
Stable palladium nanoparticles are adsorbed onto on activated carbon surface again, since the stabilizer of these macromoleculars can strong adsorption nanoparticle
The active position of son is so as to reduce catalytic activity, it is therefore necessary to by way of washing or roasting, remove these stabilizers, not only increase
Add manufacturing cost, and produce pollutant.
Molecular sieve SBA-15 has narrow the mesopore orbit structure of two-dimentional six side's through-holes, pore-size distribution, large specific surface area and heat
Stability is high, has very big application value in separation, catalysis and nanometer assembling etc., but lives due to there is chemical reaction
Property it is not high inherent the shortcomings that, greatly limit its practical ranges.Usually using SBA-15 as carrier before, be required for into
Row chemical modification, i.e., by having the silanol key of certain chemical reactivity on meso pore silicon oxide material surface, and containing not
Silane coupling agent with functional group is reacted, and the modification to material skeleton and the functionalization to channel surfaces could meet
Different requirements in practical application.SBA-15 surface chemical modifications process not only increases manufacture cost, but also can generate chemistry
Pollution.For this purpose, by simple method, SBA-15 is pre-processed, and can be equably by Pd2+Adsorb SBA-15 ducts
It is interior, be not added with it is any it is protectant under the conditions of, select green solvent, in-situ reducing prepares efficient SBA-15 loaded nanos palladium and urge
Agent is necessary.
Invention content
The palladium nanometer of surface chemical modification and load is needed before being loaded the purpose of the present invention is to solve SBA-15
It the technical issues of grain easily reunites, is easy to run off provides a kind of ultrasonic wave added local reduction way preparation SBA-15 load Technique of Nano Pd and urges
The method of agent.
The method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts follows the steps below：
First, after 0.5g molecular sieve SBA-15s are dried, it is added directly into 5 milliliters of a concentration of 0.01~0.1mol/L's
Na2PdCl4In aqueous solution, dipping 12~24 hours are stood, drying obtains Pd2+SBA-15 after dipping；
2nd, by Pd2+SBA-15 after dipping is added in the reaction bulb equipped with 20~50 milliliters of ethylene glycol, and ultrasound is visited
Head addition reaction bulb, is passed through nitrogen displaced air, nitrogen is as protective gas in reaction process, and reaction temperature is by external water-bath temperature
It spends to control, reaches 20~60 DEG C of reduction reaction temperature, open ultrasound, under conditions of 300~600W of ultrasonic power, ultrasound is also
After solution blackening, upper liquid is removed through centrifugation for original reaction 10~60 minutes, dry, obtains SBA-15 loaded nanometer palladium catalysts.
Drying temperature described in step 1 is 150~300 DEG C, and drying time is 2~10h.
The present invention is exactly based on the mode simply roasted, and SBA-15 is pre-processed, and impregnates Na2PdCl4Afterwards, it and selects
Ethylene glycol is solvent, reducing agent and sonification medium, and ultrasonic wave added in-situ reducing is prepared for Pd/SBA-15 catalyst.With chemistry
Reduction method is compared, and the catalyst catalytic performance which prepares is more excellent, and has good repeat performance.
The present invention replaces surface chemical modification using simple calcination process SBA-15, is being added without any stabilizer
In the case of, using ultrasonic wave added method, palladium nano-particles being prepared in situ in carrier duct is realized, had both avoided environment dirt
Dye, and reduce production cost.Compared with chemical method, load type palladium nanocatalyst made from the method has higher gold
Belong to dispersion degree and stability, better catalytic activity and recycling are shown in Suzuki coupling reactions are catalyzed.
Description of the drawings
Fig. 1 is obtained Pd (5)/SBA-15 and Pd (5) in experiment one and contrast experiment/SBA-15-C catalytic performances comparison
Scheme, in figure ▲ representing Pd (5)/SBA-15-C catalytic performance curves, ▼ represents Pd (5)/SBA-15 catalytic performance curves；
Fig. 2 is that obtained Pd (5)/SBA-15 and Pd (5)/SBA-15-C recycles catalysis in experiment one and contrast experiment
Performance comparison figure, in figure ▲ representing that Pd (5)/SBA-15 recycles catalytic performance curve, ▼ represents that Pd (5)/SBA-15-C is followed
Ring uses catalytic performance curve；
Fig. 3 is the TEM photos for testing Pd (5)/SBA-15 catalyst obtained in one；
Fig. 4 is the TEM photos for testing Pd (1)/SBA-15 catalyst obtained in two；
Fig. 5 is the TEM photos for testing Pd (3)/SBA-15 catalyst obtained in three；
Fig. 6 is the TEM photos of Pd (5)/SBA-15-C catalyst obtained in contrast experiment.
Specific embodiment
Technical solution of the present invention is not limited to act specific embodiment set forth below, further includes between each specific embodiment
Arbitrary combination.
Specific embodiment one：Present embodiment ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts
Method follow the steps below：
First, after 0.5g molecular sieve SBA-15s are dried, it is added directly into 5 milliliters of a concentration of 0.01~0.1mol/L's
Na2PdCl4In aqueous solution, dipping 12~24 hours are stood, drying obtains Pd2+SBA-15 after dipping；
2nd, by Pd2+SBA-15 after dipping is added in the reaction bulb equipped with 20~50 milliliters of ethylene glycol, and ultrasound is visited
Head addition reaction bulb, is passed through nitrogen displaced air, nitrogen is as protective gas in reaction process, and reaction temperature is by external water-bath temperature
It spends to control, reaches 20~60 DEG C of reduction reaction temperature, open ultrasound, under conditions of 300~600W of ultrasonic power, ultrasound is also
After solution blackening, upper liquid is removed through centrifugation for original reaction 10~60 minutes, dry, obtains SBA-15 loaded nanometer palladium catalysts.
Specific embodiment two：The present embodiment is different from the first embodiment in that drying temperature described in step 1
It it is 150~300 DEG C, drying time is 2~10h.It is other same as the specific embodiment one.
Specific embodiment three：Unlike one of present embodiment and specific embodiment one or two described in step 1
Na2PdCl4A concentration of 0.02~0.09mol/L of aqueous solution.It is other identical with one of specific embodiment one or two.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three described in step 1
Na2PdCl4A concentration of 0.03~0.07mol/L of aqueous solution.It is other identical with one of specific embodiment one to three.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four described in step 1
Na2PdCl4A concentration of 0.05mol/L of aqueous solution.It is other identical with one of specific embodiment one to four.
Specific embodiment six：It is stood in step 1 unlike one of present embodiment and specific embodiment one to five
Dipping 20 hours.It is other identical with one of specific embodiment one to five.
Specific embodiment seven：It is restored in step 2 unlike one of present embodiment and specific embodiment one to six
Reaction temperature is 30 DEG C.It is other identical with one of specific embodiment one to six.
Specific embodiment eight：Super in step 2 unlike one of present embodiment and specific embodiment one to seven
Under conditions of 350~550W of acoustical power, ultrasonic reduction reaction 15~55 minutes.Other phases one of with specific embodiment one to seven
Together.
Specific embodiment nine：Super in step 2 unlike one of present embodiment and specific embodiment one to eight
Under conditions of 400~500W of acoustical power, ultrasonic reduction reaction 20~50 minutes.Other phases one of with specific embodiment one to eight
Together.
Specific embodiment ten：Super in step 2 unlike one of present embodiment and specific embodiment one to nine
Under conditions of acoustical power 450W, ultrasonic reduction reaction 30 minutes.It is other identical with one of specific embodiment one to nine.
Using following experimental verifications effect of the present invention：
Experiment one：
By 0.5g molecular sieve SBA-15s at a temperature of 200 DEG C after dry 4h, it is added directly into 5 milliliters a concentration of
The Na of 0.05mol/L2PdCl4In aqueous solution, dipping 20h is stood, dries sample；
The above-mentioned sample for preparing is added in equipped with 30 milliliters of ethylene glycol glass reaction bottle, and ultrasonic probe is added in and is reacted
Bottle, is passed through nitrogen displaced air, nitrogen is as protective gas in reaction process.Reaction temperature is controlled by external bath temperature,
Reduction reaction temperature control is 30 DEG C, opens ultrasound, controls the ultrasonic power of 400W, carries out ultrasonic reduction reaction 30min, solution
After blackening, upper liquid is removed through centrifugation, it is dry, Pd (5)/SBA-15 catalyst of 5wt% load capacity is made.
Experiment two：
By 0.5g molecular sieve SBA-15s at a temperature of 220 DEG C after dry 6h, it is added directly into 5 milliliters a concentration of
The Na of 0.01mol/L2PdCl4In aqueous solution, dipping 16h is stood, dries sample；
The above-mentioned sample for preparing is added in equipped with 40 milliliters of ethylene glycol glass reaction bottle, and ultrasonic probe is added in and is reacted
Bottle, is passed through nitrogen displaced air, nitrogen is as protective gas in reaction process.Reaction temperature is controlled by external bath temperature,
Reduction reaction temperature control is 40 DEG C, opens ultrasound, controls the ultrasonic power of 450W, carries out ultrasonic reduction reaction 40min, solution
After blackening, upper liquid is removed through centrifugation, it is dry, Pd (1)/SBA-15 catalyst of 1wt% load capacity is made.
Experiment three：
By 0.5g molecular sieve SBA-15s at a temperature of 250 DEG C after dry 7h, it is added directly into 5 milliliters a concentration of
The Na of 0.03mol/L2PdCl4In aqueous solution, dipping 18h is stood, dries sample；
The above-mentioned sample for preparing is added in equipped with 20 milliliters of ethylene glycol glass reaction bottle, and ultrasonic probe is added in and is reacted
Bottle, is passed through nitrogen displaced air, nitrogen is as protective gas in reaction process.Reaction temperature is controlled by external bath temperature,
Reduction reaction temperature control is 45 DEG C, opens ultrasound, controls the ultrasonic power of 500W, carries out ultrasonic reduction reaction 30min, solution
After blackening, upper liquid is removed through centrifugation, it is dry, Pd (3)/SBA-15 catalyst of 3wt% load capacity is made.
Contrast experiment:
By 0.5g molecular sieve SBA-15s at a temperature of 200 DEG C after dry 4h, it is added directly into 5 milliliters a concentration of
The Na of 0.05mol/L2PdCl4In aqueous solution, dipping 20h is stood, dries sample；
The above-mentioned sample for preparing is added in equipped with 30 milliliters of ethylene glycol glass reaction bottle, is passed through nitrogen displaced air, instead
Nitrogen is as protective gas during answering.At 80 DEG C, reduction reaction 4h is carried out, after solution blackening, upper liquid is removed through centrifugation,
It is dry, Pd (5)/SBA-15-C catalyst of 5wt% load capacity is made.
Catalytic performance investigates experiment：
It is the Suzuki coupling reactions of substrate as probe reaction, volume ratio 1 using parabromotoluene and phenyl boric acid:1 EtOH/
H2O is solvent, K2CO3For alkali, 60 DEG C of reaction temperature, catalyst amount is the 0.1mol% of substrate, respectively using palladium load capacity as
Pd (the 5)/SBA-15 and Pd (5)/SBA-15 of 5wt% is catalyst, carries out Suzuki coupling reactions, and catalytic performance is compared
The results are shown in Figure 1.Catalyst circulation prepared by two kinds of preparation methods is as shown in Figure 2 using catalytic performance.SBA-15、Pd(1,
3,5) structural parameters of/SBA-15 and Pd (5)/SBA-15-C are as shown in table 1.
Table 1
| Sample | SBET(m2/g) | V(cm3/g) | D(nm) |
| SBA-15 | 530.737 | 1.0220 | 6.246 |
| Pd(5)/SBA-15-C | 500.469 | 0.9808 | 6.234 |
| Pd(1)/SBA-15 | 431.048 | 0.8195 | 5.554 |
| Pd(3)/SBA-15 | 362.375 | 0.7056 | 5.543 |
| Pd(5)/SBA-15 | 332.806 | 0.5932 | 5.555 |
As shown in Table 1, compared with the structural parameters of carrier S BA-15, Pd (5)/SBA-15-C of chemical reduction method preparation,
Specific surface area (SBET), Kong Rong (V) and average pore size (D) reduce very little, illustrate that the Technique of Nano Pd to be formed is not substantially into SBA-15
Hole in, but load on the outer surface；And ultrasonic wave added restores rule with the increase specific surface area (S of load capacityBET) and hole
Hold (V) to continuously decrease, the amplitude of reduction is larger, illustrates that the Technique of Nano Pd to be formed enters in the hole of SBA-15, is supported on the interior table in hole
On face, average pore size (D) is declined, but is remained unchanged with the increase of palladium load capacity, illustrates that ultrasonic wave added reduction method can be with
Promote diffusion of the ethylene glycol into hole, make Pd of the absorption on the inside of hole wall in dipping process2+In-situ reducing is palladium nano-particles, and
It is distributed evenly on the inside of hole wall, forms class palladium nano tubular structure, keep duct unobstructed, both increased Technique of Nano Pd in duct
The high degree of dispersion and adhesion on surface, and be conducive to mass transport process makes the abundant of substrate molecule and the palladium nanoparticles of high dispersive
Contact, improves the catalytic activity of Pd (x)/SBA-15, and this point is consistent with TEM characterizations.
In conclusion the present invention is by only having carried out simple calcination process to SBA-15, and eliminate cumbersome change
Surface is learned to be modified, be added without it is any it is protectant under the conditions of, can prepare the negative of high dispersive using ultrasonic wave added reduction method
Load property nano Pd catalyst, prepared catalyst catalytic performance and excellent in stability.
Claims (10)
1. the method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts, it is characterised in that ultrasonic wave added is former
The method that position reduction method prepares SBA-15 loaded nanometer palladium catalysts follows the steps below：
First, after 0.5g molecular sieve SBA-15s are dried, it is added directly into the Na of 5 milliliters of a concentration of 0.01~0.1mol/L2PdCl4
In aqueous solution, dipping 12~24 hours are stood, drying obtains Pd2+SBA-15 after dipping；
2nd, by Pd2+SBA-15 after dipping is added in the reaction bulb equipped with 20~50 milliliters of ethylene glycol, and ultrasonic probe is added
Enter reaction bulb, be passed through nitrogen displaced air, in reaction process nitrogen as protective gas, reaction temperature by external bath temperature Lai
Control reaches 20~60 DEG C of reduction reaction temperature, opens ultrasound, and under conditions of 300~600W of ultrasonic power, ultrasound reduction is anti-
It answers 10~60 minutes, after solution blackening, upper liquid is removed through centrifugation, it is dry, obtain SBA-15 loaded nanometer palladium catalysts.
2. the method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts according to claim 1,
It is 150~300 DEG C to be characterized in that drying temperature described in step 1, and drying time is 2~10h.
3. the method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts according to claim 1,
It is characterized in that Na described in step 12PdCl4A concentration of 0.02~0.09mol/L of aqueous solution.
4. the method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts according to claim 1,
It is characterized in that Na described in step 12PdCl4A concentration of 0.03~0.07mol/L of aqueous solution.
5. the method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts according to claim 1,
It is characterized in that Na described in step 12PdCl4A concentration of 0.05mol/L of aqueous solution.
6. the method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts according to claim 1,
It is characterized in that standing dipping 20 hours in step 1.
7. the method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts according to claim 1,
It is characterized in that in step 2 that reduction reaction temperature is 30 DEG C.
8. the method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts according to claim 1,
It is characterized in that in step 2 under conditions of 350~550W of ultrasonic power, ultrasonic reduction reaction 15~55 minutes.
9. the method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts according to claim 1,
It is characterized in that in step 2 under conditions of 400~500W of ultrasonic power, ultrasonic reduction reaction 20~50 minutes.
10. the method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts according to claim 1,
It is characterized in that in step 2 under conditions of ultrasonic power 450W, ultrasonic reduction reaction 30 minutes.
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