CN106466602A - A kind of carbon-carried palladium catalyst and its preparation method and application - Google Patents
A kind of carbon-carried palladium catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of carbon-carried palladium catalyst and its preparation method and application, belong to load type palladium catalyst technical field.This carbon-carried palladium catalyst is to be formed on nano-carbon material carrier by palladium particulate load；Described nano-carbon material carrier is nucleocapsid structure, wherein：Nano diamond is core, and class Graphene is shell, and described class Graphene is to be formed by 13 layer graphene material stackings.Compared with other carbon material supported palladium catalysts, not only activity is high for carbon-carried palladium catalyst of the present invention, and has anti-caking power well.
Description
Technical field
The present invention relates to load type palladium catalyst technical field is and in particular to a kind of carbon-carried palladium catalyst and its preparation
Methods and applications.
Background technology
Precious metals palladium catalyst is that in industry, purposes is also at most one of most widely used catalyst.Last century,
In reacting in hydrogenation/dehydrogenation, use in most technical process is all homogeneous palladium catalysts.But all
Phase catalyst is not readily separated, and can produce pollution to product.In the nearest more than ten years, load type palladium catalyst obtains
Increasing application, such as hydrogenation reaction, C-C coupling reaction and oxidation reaction etc..Urge in support type
In agent, the selection of carrier is very important.Its surface nature, structure etc. often to the activity of catalyst,
Selectivity and stability have a huge impact.Industrial conventional carrier has aluminium oxide, silicon oxide, activity
Charcoal etc..For noble metal catalyst, because your gold activated carbon can be by being simply flared off so that
Genus can be readily available recovery, and therefore for noble metal catalyst, activated carbon is the more commonly used carrier.
Activated carbon generally has very high specific surface area, and this is conducive to the dispersion of metallic particles.But it is big in activated carbon
Part specific surface area is contributed by irregular micropore.In activated carbon supported catalyst, most metals
Grain can be distributed in micropore, so may result in reactant molecule, especially do not allow than larger reactant molecule
Easily and contact catalytic sites, thus the catalytic efficiency of catalyst can be affected.In addition, activated carbon mechanical stability
Difference, occurs some abrasions thus leading to the loss of active component and growing up of metallic particles under fierce stirring；
Oxidation resistance is relatively low, under the high temperature with the presence of oxygen (>500K) can not use.
Content of the invention
It is an object of the invention to provide a kind of carbon-carried palladium catalyst and its preparation method and application, this material with carbon element is born
The activity of carried palladium catalyst is high, high-temperature stability good (350-650 DEG C), and method for preparing catalyst is simple,
Apply catalytic effect in C-C coupling reaction and CO oxidation reaction more preferable.
For achieving the above object, the technical solution adopted in the present invention is：
A kind of carbon-carried palladium catalyst, this catalyst is to be formed on nano-carbon material carrier by palladium particulate load；Institute
Stating nano-carbon material carrier is nucleocapsid structure, wherein：Nano diamond is core, and class Graphene is shell.Described
On shell class Graphene, described class Graphene is to be formed by 1-3 layer graphene material stacking to palladium particulate load.
The specific surface area of described nano-carbon material carrier is in 300-400m2Between/g, total pore volume is 1.3-1.5cm3/g.
In described carbon-carried palladium catalyst, the content of palladium is 0.5-2.3wt.%, and palladium mean particle size is 1.5-2.0nm,
The dispersion of palladium is up to 40-50%.
The preparation of above-mentioned carbon-carried palladium catalyst comprises the steps：
(1) preparation of nano-carbon material carrier：
Nano-carbon material carrier is to be obtained by the fresh Nano diamond of roasting (i.e. original Nano diamond),
Detailed process is：Fresh Nano diamond powder is put in magnetic boat, magnetic boat is put into tube furnace, is passed through inertia
Atmosphere, rises to 500-1100 DEG C with the speed of 5K/min, is incubated 4-6h, that is, obtain and have receiving of nucleocapsid structure
Rice material with carbon element carrier；
(2) by nano-carbon material support dispersion in water, obtain carbon carrier suspension, use sodium carbonate liquor
(0.2-0.25mol/L) its pH value is adjusted to 9-10；
(3) Palladous nitrate. is dissolved in formation Palladous nitrate. in dilute nitric acid solution (dust technology concentration is 10-20%) molten
Palladium nitrate solution pH value is adjusted to 7-8 with sodium carbonate liquor (0.2-0.25mol/L) by liquid；
(4) by pH value, the palladium nitrate solution for 7-8 adds in the carbon carrier suspension that pH value is 9-10；?
Stir 0.5-1h, cooling at 80-100 DEG C, filter, be dried, reduced at 150-200 DEG C with hydrogen, that is, obtain
Described carbon-carried palladium catalyst.
The above-mentioned carbon-carried palladium catalyst of the present invention can be applied in Suzuki coupling reaction and CO oxidation reaction, its
In：In described Suzuki coupling reaction, solvent used is the mixed liquor of second alcohol and water, and reaction temperature is
50-85℃.In described CO oxidation reaction, process conditions are：Air speed 17040mL h-1·gcat -1, CO
Volumetric concentration 0.9%, CO and O2Volume ratio be 1:2～1:10.
Carbon-carried palladium catalyst of the present invention also has high-temperature stability, and by its roasting at high temperature, sintering temperature is
350-650 DEG C, atmosphere is inert atmosphere, and after roasting, the palladium particle mean size in catalyst increases inconspicuous (negative
The palladium mean particle size carrying increases to 2.0-2.6nm from 1.5-2.0nm).
The present invention has advantages below and beneficial effect：
Although traditional absorbent charcoal material specific surface area is big, contain a large amount of micropores, during as catalyst carrier
It is unfavorable for the diffusion of reactant molecule in catalytic reaction, thus hampering being fully contacted of reactant and active sites,
Reduce reaction efficiency, and the present invention is the nano-sized carbon being combined with a kind of new class Graphene and Nano diamond
Material is carrier, and this complex carbon material carrier does not almost have micropore to exist, and reactant molecule can easily expand
It is dissipated to catalyst surface to react.In addition, this carbon material surface contains a lot of defects, and it is a kind of sp2Miscellaneous
Change structure and sp3The composite of hybrid structure, enhances the interaction between metal and carrier so that receiving
Rice grain can firmly be carried on this carbon material surface very much, also can affect loaded metallic catalyst simultaneously
Catalytic performance.
Brief description
Fig. 1 is the transmission electron microscope picture of fresh Nano diamond.
Fig. 2 is the transmission electron microscope picture of the acquisition after 900 DEG C of roastings.
Fig. 3 is the transmission electron microscope picture of the acquisition after 1100 DEG C of roastings.
Fig. 4 is the transmission electron microscope picture of Bulbus Allii Cepae carbon.
Specific embodiment
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
In following examples, the concentration adjusting sodium carbonate liquor used by pH value is 0.2-0.25mol/L, for molten
The dust technology concentration of solution Palladous nitrate. is 10-20vol.%.
Embodiment 1
(1) weigh the commercially available original Nano diamond (Fig. 1) of 1-2g, put in crucible, crucible is put into pipe
In formula stove, it is passed through noble gases, (the present embodiment is respectively to rise to 500-1100 DEG C with the programming rate of 5K/min
It is warming up to 900 DEG C and 1100 DEG C), it is incubated 4-6 hour.It is cooled to room temperature under inert atmosphere, that is, obtain class graphite
The nano-carbon material carrier that alkene and Nano diamond are combined.
As Figure 2-3, resulting vehicle be with Nano diamond as core, the nucleocapsid structure as shell for the class Graphene,
Described class Graphene is to be formed by 1-3 layer graphene material stacking.The specific surface area of this nano-carbon material carrier exists
300-400m2Between/g, total pore volume is 1.3-1.5cm3/ g, does not almost have micropore to exist, and surface has in a large number admittedly
The position determining palladium granule exists.
(2) weigh this carrier 200g, be dispersed in 300mL water, adjusting its pH value with sodium carbonate liquor is
10 about, obtain the suspension of high-area carbon；Palladous nitrate. is dissolved in dilute nitric acid solution, obtains certain density nitre
Sour palladium solution, adding sodium carbonate liquor to adjust pH value is 7-8.This palladium solution is added dropwise to the outstanding of above-mentioned high-area carbon
In supernatant liquid, stir 40min, cooling under the conditions of 100 DEG C, filter, washing, it is vacuum dried 10h at 80 DEG C,
The charcoal load obtaining palladium particulate load on nano-carbon material carrier is reduced afterwards under the conditions of hydrogen atmosphere and 100 DEG C
Palladium catalyst.It is respectively the carbon carrier Pt-supported catalyst (1# catalyst) and 1100 that 900 DEG C of roastings obtain
DEG C carbon carrier Pt-supported catalyst that roasting obtains (2# catalyst).
Embodiment 2
The 1# catalyst that embodiment 1 is prepared is applied in Suzuki coupling reaction, and solvent used is second
The mixed liquor 40ml of alcohol and water, the consumption of palladium is 0.0021mmol, and the amount of bromobenzene is 4mmol, phenylboric acid
Measure as 4.8mmol, the amount of potassium carbonate is 8mmol.When reaction temperature is 30 DEG C, after reaction 10min,
The conversion ratio of bromobenzene is 28%, and when reaction temperature is 50 DEG C, after reaction 10min, the conversion ratio of bromobenzene is
99%.
The 1# catalyst that embodiment 1 is prepared is applied to be catalyzed CO oxidation reaction, and wherein air speed is 17040
ml·h-1·gcat -1, the volumetric concentration 0.9% of CO, CO and O2Volume ratio be 1:10, when CO conversion ratio
Reaching corresponding temperature when 50% is 70 DEG C.
Embodiment 3
The 1# catalyst roasting at high temperature that embodiment 1 is prepared.
Weigh a certain amount of catalyst and put in tube furnace, under inert atmosphere, the heating rate with 5k/min is raised to
350-800 DEG C, it is incubated 6h, under inert atmosphere, is cooled to room temperature.Urge with the carbon nanotube loaded palladium after oxidation
The palladium catalyst of agent and the load of class Bulbus Allii Cepae carbon is compared, after roasting 6h at 500 DEG C, 1# palladium catalyst granule
Average-size is changed into 2.6nm from 1.9nm.After sintering temperature is increased to 800 DEG C, palladium granule just there occurs bright
Aobvious grows up.
Comparative example 1
The carbon nanotube loaded palladium catalyst of business is used in Suzuki coupling reaction, reaction condition and embodiment
Identical in 1, when reaction temperature is 30 DEG C, after reaction 10min, the conversion ratio of bromobenzene is 9%, works as reaction
When temperature is 30 DEG C, after reaction 10min, the conversion ratio of bromobenzene is 64%；Commercially carbon nanotube loaded palladium
Catalyst, the palladium catalyst of Bulbus Allii Cepae carbon load and business palladium-carbon catalyst are used for being catalyzed CO oxidation reaction, instead
Answer condition with embodiment 1, when CO conversion ratio reaches 50% corresponding temperature be 93 DEG C successively, 95 DEG C and
105℃.
Comparative example 2
Palladium catalyst roasting at high temperature by palladium catalyst carbon nanotube loaded for business and the load of class Bulbus Allii Cepae carbon
(Fig. 4).Roasting condition is with embodiment 3.Find that in both catalyst, palladium particle average size becomes from 2.2nm
For 7-8nm.After sintering temperature is increased to 800 DEG C, in the catalyst obtaining in embodiment 1, palladium granule is just sent out
Give birth to and significantly grown up.
Obviously, compared with the catalyst that heretofore described catalyst is loaded with other nano-carbon materials, either
In the Suzuki coupling reaction of liquid phase, or in the CO oxidation reaction of gas phase, all there is more preferable catalysis
Effect, and there is good high-temperature stability.
Claims (10)
1. a kind of carbon-carried palladium catalyst it is characterised in that：This catalyst is in nano-carbon material by palladium particulate load
Formed on carrier；Described nano-carbon material carrier is nucleocapsid structure, wherein：Nano diamond is core, class graphite
Alkene is shell.
2. carbon-carried palladium catalyst according to claim 1 it is characterised in that：Described palladium particulate load is in shell
On layer class Graphene, described class Graphene is to be formed by 1-3 layer graphene material stacking.
3. carbon-carried palladium catalyst according to claim 2 it is characterised in that：Described nano-carbon material carrier
Specific surface area in 300-400m2Between/g, total pore volume is 1.3-1.5cm3/g.
4. carbon-carried palladium catalyst according to claim 1 it is characterised in that：In described carbon-carried palladium catalyst,
The content of palladium is 0.5-2.3wt.%, and palladium mean particle size is 1.5-2.0nm.
5. carbon-carried palladium catalyst according to claim 1 it is characterised in that：Described carbon-carried palladium catalyst exists
After roasting under the conditions of 350-650 DEG C, the palladium mean particle size of load increases to 2.0-2.6nm from 1.5-2.0nm.
6. the preparation method according to the arbitrary described carbon-carried palladium catalyst of claim 1-4 it is characterised in that：Should
Method comprises the steps：
(1) preparation of nano-carbon material carrier：
Nano-carbon material carrier is to be obtained by the fresh Nano diamond of roasting, and detailed process is：Will be fresh
Nano diamond powder put in magnetic boat, magnetic boat is put into tube furnace, is passed through inert atmosphere, with 5K/min
Speed rise to 500-1100 DEG C, be incubated 4-6h, that is, obtain and there is the nano-carbon material carrier of nucleocapsid structure；
(2) by nano-carbon material support dispersion in water, obtain carbon carrier suspension, with sodium carbonate liquor by its
PH value is adjusted to 9-10；
(3) Palladous nitrate. is dissolved in dilute nitric acid solution formation palladium nitrate solution, with sodium carbonate liquor by Palladous nitrate.
Solution ph is adjusted to 7-8；
(4) by pH value, the palladium nitrate solution for 7-8 adds in the carbon carrier suspension that pH value is 9-10；?
Stir 0.5-1h, cooling at 80-100 DEG C, filter, be dried, reduce 1-2h with hydrogen at 150-200 DEG C,
Obtain described carbon-carried palladium catalyst.
7. the application according to the arbitrary described carbon-carried palladium catalyst of claim 1-4 it is characterised in that：Described charcoal
Carried palladium catalyst is applied in Suzuki coupling reaction.
8. carbon-carried palladium catalyst according to claim 7 application it is characterised in that：Described Suzuki
In coupling reaction, solvent used is the mixed liquor of second alcohol and water, and reaction temperature is 50-85 DEG C.
9. the application according to the arbitrary described carbon-carried palladium catalyst of claim 1-4 it is characterised in that：Described charcoal
Carried palladium catalyst is applied in CO oxidation reaction.
10. carbon-carried palladium catalyst according to claim 9 application it is characterised in that：Described CO oxygen
Changing the process conditions reacted is：Air speed 17040mL h-1·gcat -1, the volumetric concentration 0.9% of CO, CO and
O2Volume ratio be 1:2～1:10.
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| CN109174085A (en) * | 2018-09-06 | 2019-01-11 | 中国科学院金属研究所 | Atom level disperses palladium base Nano diamond/graphene composite material catalyst and its preparation method and application |
| CN109806867A (en) * | 2019-02-27 | 2019-05-28 | 中国科学院金属研究所 | Nano-sized carbon loads atom level dispersion copper-based catalysts and its preparation method and application |
| CN110479253A (en) * | 2019-09-12 | 2019-11-22 | 大连理工大学 | A kind of Nano diamond-carried palladium catalyst and its preparation method and application for benzyl alcohol producing benzaldehyde |
| CN110790669A (en) * | 2019-11-15 | 2020-02-14 | 中国科学院金属研究所 | Application of nano-carbon-supported single-atom palladium-based catalyst in preparation of secondary amine by catalytic hydrogenation of nitrile compound |
| CN110813281A (en) * | 2019-11-15 | 2020-02-21 | 中国科学院金属研究所 | Application of nano-carbon supported cluster-state palladium-based catalyst in preparation of primary amine by catalytic hydrogenation of nitrile compound |
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| CN109174085A (en) * | 2018-09-06 | 2019-01-11 | 中国科学院金属研究所 | Atom level disperses palladium base Nano diamond/graphene composite material catalyst and its preparation method and application |
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| CN109806867A (en) * | 2019-02-27 | 2019-05-28 | 中国科学院金属研究所 | Nano-sized carbon loads atom level dispersion copper-based catalysts and its preparation method and application |
| CN110479253A (en) * | 2019-09-12 | 2019-11-22 | 大连理工大学 | A kind of Nano diamond-carried palladium catalyst and its preparation method and application for benzyl alcohol producing benzaldehyde |
| CN110790669A (en) * | 2019-11-15 | 2020-02-14 | 中国科学院金属研究所 | Application of nano-carbon-supported single-atom palladium-based catalyst in preparation of secondary amine by catalytic hydrogenation of nitrile compound |
| CN110813281A (en) * | 2019-11-15 | 2020-02-21 | 中国科学院金属研究所 | Application of nano-carbon supported cluster-state palladium-based catalyst in preparation of primary amine by catalytic hydrogenation of nitrile compound |
| CN110790669B (en) * | 2019-11-15 | 2021-10-15 | 中国科学院金属研究所 | Application of nano-carbon-supported single-atom palladium-based catalyst in preparation of secondary amine by catalytic hydrogenation of nitrile compound |
| CN110813281B (en) * | 2019-11-15 | 2022-08-16 | 中国科学院金属研究所 | Application of nano-carbon supported cluster-state palladium-based catalyst in preparation of primary amine by catalytic hydrogenation of nitrile compound |
| CN111804291A (en) * | 2020-07-20 | 2020-10-23 | 中国科学技术大学 | Small-size Pd3Pb intermetallic compound and preparation method and application thereof |
| CN114768798A (en) * | 2022-04-21 | 2022-07-22 | 黑龙江省科学院石油化学研究院 | Preparation method and application of partially graphitized charcoal-loaded nano palladium catalyst |
| CN114768798B (en) * | 2022-04-21 | 2023-08-22 | 黑龙江省科学院石油化学研究院 | Preparation method and application of partially graphitized biochar supported nano palladium catalyst |
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