CN104624216A - Palladium/carbon nanotube-foam silicon carbide integrated composite material and preparation method and application of composite material - Google Patents
Palladium/carbon nanotube-foam silicon carbide integrated composite material and preparation method and application of composite material Download PDFInfo
- Publication number
- CN104624216A CN104624216A CN201310564383.0A CN201310564383A CN104624216A CN 104624216 A CN104624216 A CN 104624216A CN 201310564383 A CN201310564383 A CN 201310564383A CN 104624216 A CN104624216 A CN 104624216A
- Authority
- CN
- China
- Prior art keywords
- palladium
- foam silicon
- cnt
- silicon carbon
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a palladium/carbon nanotube-foam silicon carbide integrated composite material and a preparation method and application of the composite material, belonging to the field of composite materials and preparation technologies and application of the composite materials. The integrated composite material contains foam silicon carbide, carbon nanotubes and palladium nanoparticles, and based on percentage by weight, the loading capacity of the carbon nanotubes is 0.5-9%, and the content of palladium is 0.006-4%. The preparation method of the integrated composite material comprises the following steps: firstly, growing carbon nanotubes on foam silicon carbide by using a chemical vapor deposition method so as to obtain a carbon nanotube-foam silicon carbide composite material; and then, loading palladium on the carbon nanotube-foam silicon carbide composite material by using impregnation and hydrogen reduction methods. The integrated composite material prepared according to the invention has a high mechanical strength, a strong binding force among palladium and carbon nanotubes, a penetrating three-dimensional network channel, and a characteristic of easiness in separation. In a liquid phase catalytic reaction, the integrated composite material shows more excellent stability, catalytic activity and circularity in comparison with powdered catalysts.
Description
Technical field
The invention belongs to composite and technology of preparing thereof and application, be specifically related to a kind of palladium/CNT-foam silicon carbon monoblock type composite and its preparation method and application.
Background technology
Palladium is a kind of noble metal catalyst, because the physicochemical properties of its uniqueness and application prospect cause the extensive concern of people.In heterogeneous catalytic system, palladium nano-particles shows excellent catalytic performance, catalysis C-C coupling reaction etc. in such as organic synthesis.But, directly use palladium nano-particles, usually can run into the problem of reunion, limit its in liquid phase reactor scale application.For solving this problem, Pd nano particle loads on various solid carrier by people, as silica, and molecular sieve, material with carbon element and polymer etc.In these carriers, active carbon, due to high-ratio surface sum resistance to acids and bases, is widely used.But, have a large amount of micropore to exist in active carbon, the diffusion of reactant molecule in course of reaction can be suppressed; Meanwhile, its mechanical strength foreign atom that is low and that contain can reduce its stability.
In material with carbon element, CNT has large specific area, strong Support-metal strong interaction, corrosion resistance, high purity and pore-free and exists, and receives much concern in recent years in catalytic field.Using CNT as carrier material, in liquid phase reactor, higher catalytic activity is shown after supported palladium, but directly the carbon nanotube powder of working load palladium is easy to reunite, and be difficult to be separated from reactant mixture and recovery can run into and is separated and the difficulty such as recovery.In order to overcome these problems, need aggregation CNT being prepared into macroscopic view.
Summary of the invention
The object of the invention is to the weak point overcoming prior art existence, a kind of palladium/CNT-foam silicon carbon monoblock type composite and its preparation method and application is provided.
Technical scheme of the present invention is:
A kind of palladium/CNT-foam silicon carbon monoblock type composite, in this composite, even carbon nanotube is immobilized at foam silicon carbon carrier surface, and palladium nano-particles uniform load is on the surface of CNT; Wherein: the load capacity of described CNT is 0.5 ~ 9wt.% of composite gross weight; Palladium load capacity is 0.006 ~ 4wt.% of composite gross weight; Described CNT average length is 0.5 ~ 300 μm, and average diameter is 15 ~ 40nm; Described palladium nano-particles granularity is 1 ~ 10nm.
The preparation method of above-mentioned palladium/CNT-foam silicon carbon monoblock type composite, comprises the steps:
(1) foam silicon carbon is put into the aqueous solution of metal inorganic salt and adjuvant after stirring and refluxing, carry out drying process, then tube furnace is put into, adopt the method for chemical vapour deposition (CVD) at foam silicon carbon superficial growth CNT, obtain the composite of CNT-foam silicon carbon; Detailed process is as follows:
The deionized water of 5-20g foam silicon carbon, 2-20g metal inorganic salt, 10-50g adjuvant and 100-500mL is mixed, cooling after 60-90 DEG C of backflow, after freeze-day with constant temperature, put it in tube furnace, after passing into protective gas, furnace temperature is risen to 550-1000 DEG C, then pass into reacting gas, reaction 0.1-6h, obtains CNT-foam silicon carbon composite crude product; Mixed with nitric acid by this CNT-foam silicon carbon composite crude product, reflux under 60-200 DEG C of condition, washing post-drying 4-15h, obtains the CNT-foam silicon carbon composite through purifying and functionalization.
(2) in step (1) gained CNT-foam silicon carbon composite, palladium mixed salt solution is added by the method for wet impregnation, the quartz ampoule of tube furnace is put into after drying, after passing into hydrogen reducing, obtain palladium/CNT-foam silicon carbon monoblock type composite.Detailed process is as follows:
Be 0.001 ~ 1mol L by concentration
-1metal Palladium saline solution and organic solvent are according to (1-5): the volume ratio of 1 mixes and is made into palladium mixed salt solution; Get CNT-foam silicon carbon composite, measure the palladium mixed salt solution of respective volume by required palladium load capacity, then the palladium mixed salt solution measured slowly dropwise is joined in CNT-foam silicon carbon composite, then dry; Composite after drying process is put into tube furnace, passes into hydrogen, at 80 ~ 300 DEG C of reduction 1-10h, obtain palladium/CNT-foam silicon carbon monoblock type composite.
In above-mentioned steps (1), described metal inorganic salt is one or more in iron chloride, ferric nitrate, ammonium molybdate, magnesium nitrate, magnesium chloride and aluminum nitrate; Described adjuvant is one or more in ethylenediamine, urea, monoethanolamine, ethanol and acetone.
In above-mentioned steps (1), in the process of foam silicon carbon superficial growth CNT, described protection gas is nitrogen, argon gas or helium; Described reaction gas is hydrogen and ethene, or reaction gas is hydrogen and acetylene.
In above-mentioned steps (2), described Metal Palladium salt is PdCl
2, Pd (NO
3)
2with Pd (CH
3cOO)
2in one or more; Described organic solvent is one or more in ethanol, acetone, acetic acid and formic acid.
Described tube furnace is horizontal tube furnace.
Using above-mentioned palladium/CNT-foam silicon carbon monoblock type composite as catalyst, as the coupling reaction (as: Suzuki reaction, Heck reaction, Sonogashira reaction etc.) of hydrogenation reaction (as: hydrogenation reaction etc. of the hydrogenation reaction of alkene and alkynes, the hydrogenation reaction of nitro, unsaturated aldehyde), C-C key, oxidation reaction (epoxidation reaction etc. of the selective oxidation reaction of alcohol, the oxidation reaction of CO, alkene), the isomerization reaction reaction etc. of saturated aldehyde (as: the isopropyl alcohol isomerization generate) and dehydrogenation reaction etc.
Compared with prior art, tool of the present invention has the following advantages:
1, foam silicon carbon has excellent heat conductivility, high Mechanics of Machinery intensity, corrosion resistance, three-dimensional net structure and open large hole path, is a kind of good carrier material.Such as, foam silicon carbon load molecular sieve shows good catalytic activity in methanol to olefins reaction.CNT and foam silicon carbon are assembled into a kind of novel structural composite material by the present invention, then after this composite being carried out nitric acid treatment, depositing Pd catalyst preparing becomes a kind of CNT-foam silicon carbon monoblock type composite of supported palladium, and this composite realizes commercial Application in catalytic field.
2, the monoblock type composite of supported palladium that prepared by the present invention has realized palladium and has assembled in the macroscopic view of functionalized carbon nano-tube, and has good mechanical strength, avoids the separation difficulty of powder carbon nanotube in liquid phase reactor of supported palladium.
3, the structure carrier in the present invention is foam silicon carbon, has three-dimensional net structure and open large hole path, is conducive to the mass transfer reacted.
4, in the present invention, the content of palladium on CNT-foam silicon carbon composite is controlled, mainly by regulating concentration and the content of the Metal Palladium mixed salt solution of dipping, and the quality of CNT-foam silicon carbon composite.
Accompanying drawing explanation
Fig. 1 (a) is the optical photograph of foam silicon carbon (SiC foam), CNT-foam silicon carbon composite (CNT-SiC monolith) and palladium/CNT-foam silicon carbon monoblock type composite (Pd/CNT-SiC monolith); Fig. 1 (b-d) is the scanning electron microscopic picture of Pd/CNT-SiC monolith under different multiples.
Fig. 2 is the transmission electron microscope picture of Pd/CNT-SiC monolith in the present invention; Wherein, (b) is the transmission electron microscope picture after amplifying further (a).
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, and what be necessary to herein means out is that following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the scope of the invention.
Embodiment 1
The first step: the deionized water mixing of getting 10g foam silicon carbon (Fig. 1 (a)), 5g ferric nitrate, 20g urea and 500mL, 90 DEG C of backflows, cooling, after freeze-day with constant temperature, put it in tube furnace, after passing into helium, furnace temperature is risen to 800 DEG C, then pass into hydrogen and ethene, reaction 4h, obtains CNT-foam silicon carbon composite crude product.Get this composite crude product to mix with red fuming nitric acid (RFNA), reflux at 80 DEG C, wash, dry 15h, obtain the CNT-foam silicon carbon composite (Fig. 1 (a)) through purifying and functionalization.
Second step: be 0.01mol L by concentration
-1metal Palladium saline solution mixes with organic solvent and is made into palladium mixed salt solution, and the volume ratio of Metal Palladium saline solution and organic solvent is 3:1.Get CNT-foam silicon carbon composite, the amount of required palladium mixed salt solution is calculated according to palladium content 0.05wt% in silicon monoblock type composite, then measure the amount of required palladium mixed salt solution and it slowly dropwise joined in CNT-foam silicon carbon composite, then dry.Dried composite is put into tube furnace, passes into hydrogen, at 200 DEG C of reduction 3h, obtain palladium/CNT-foam silicon carbon monoblock type composite.
The surface topography of the palladium/CNT-foam silicon carbon monoblock type composite of this enforcement preparation is as shown in Fig. 1 (a-d), Fig. 2 (a-b) is shown in by its transmission electron microscope picture, can find out, even carbon nanotube is immobilized at foam silicon carbon carrier surface, and palladium nano-particles uniform load is on the surface of CNT.
Palladium/the CNT of above-mentioned preparation-foam silicon carbon monoblock type composite is used as catalyst, verifies its catalytic activity in Suzuki coupling reaction.By 5mmol iodobenzene, 10mmol phenyl boric acid, 20mmol tripotassium phosphate, 5mL water and 20mL alcohol solution-forming, use 600mg catalyst, carry out return stirring at a certain temperature, its product is biphenyl.60 DEG C time, after reaction 5min, the conversion ratio of Pd/CNT-SiC monolith reaches 80%, and the conversion ratio of other catalyst is less than 10%, shows that integral catalyzer has good initial activity.After reaction 60min, conversion ratio is close to 100%, and the catalytic activity of Pd/CNTs and Pd/SiC foam is respectively 62% and 7%, and this illustrates that Pd/CNT-SiC monolith catalytic activity is higher than Pd/CNTs and Pd/SiC foam.
Embodiment 2
The first step: the deionized water mixing of getting 10g foam silicon carbon, 5g magnesium nitrate, 5g aluminum nitrate, 20g urea and ethylenediamine and 300mL, 70 DEG C of backflows, cooling, after freeze-day with constant temperature, put it in tube furnace, after passing into helium, furnace temperature is risen to 750 DEG C, then pass into hydrogen and ethene, reaction 4h, obtains CNT-foam silicon carbon composite.Get this composite to mix with red fuming nitric acid (RFNA), reflux at 120 DEG C, wash, dry 15h, obtain the CNT-foam silicon carbon composite through purifying and functionalization.
Second step: be 0.01mol L by concentration
-1metal Palladium saline solution mixes with organic solvent and is made into palladium mixed salt solution.The volume ratio of Metal Palladium saline solution and organic solvent is 4:1.Get CNT-foam silicon carbon composite, the amount of required palladium mixed salt solution is calculated according to palladium content 0.01wt% in silicon monoblock type composite, then measure the amount of required palladium mixed salt solution and it slowly dropwise joined in CNT-foam silicon carbon composite, then dry.Composite is put into tube furnace, passes into hydrogen, at 200 DEG C of reductase 12 h, obtain palladium/CNT-foam silicon carbon monoblock type composite.
Palladium/the CNT of above-mentioned preparation-foam silicon carbon monoblock type composite is used as catalyst, verifies its catalytic activity in Suzuki coupling reaction.By 5mmol iodobenzene, 10mmol phenyl boric acid, 20mmol tripotassium phosphate, 5mL water and 20mL alcohol solution-forming, use 600mg catalyst, carry out return stirring at a certain temperature, its product is biphenyl.85 DEG C time, after reaction 5min, the conversion ratio of iodobenzene is 71%, and after reaction 30min, the conversion ratio of iodobenzene is close to 100%.
Embodiment 3
The first step: the deionized water mixing of getting 10g foam silicon carbon, 5g magnesium nitrate, 5g aluminum nitrate, 20g urea and monoethanolamine and 300mL, 70 DEG C of backflows, cooling, after freeze-day with constant temperature, put it in tube furnace, after passing into helium, furnace temperature is risen to 850 DEG C, then pass into hydrogen and ethene, reaction 3h, obtains CNT-foam silicon carbon composite.Get this composite to mix with red fuming nitric acid (RFNA), reflux at 120 DEG C, wash, dry 15h, obtain the CNT-foam silicon carbon composite through purifying and functionalization.
Second step: be 0.01mol L by concentration
-1metal Palladium saline solution mixes with organic solvent and is made into palladium mixed salt solution.The volume ratio of Metal Palladium saline solution and organic solvent is 4:1.Get CNT-foam silicon carbon composite, the amount of required palladium mixed salt solution is calculated according to palladium content 0.06wt% in silicon monoblock type composite, then measure the amount of required palladium mixed salt solution and it slowly dropwise joined in CNT-foam silicon carbon composite, then dry.Composite is put into tube furnace, passes into hydrogen, at 200 DEG C of reductase 12 h, obtain palladium/CNT-foam silicon carbon monoblock type composite.
Palladium/the CNT of above-mentioned preparation-foam silicon carbon monoblock type composite is used as catalyst, verifies its catalytic activity in Suzuki coupling reaction.By 5mmol iodobenzene, 10mmol phenyl boric acid, 20mmol tripotassium phosphate, 5mL water and 20mL alcohol solution-forming, use 600mg catalyst, carry out return stirring at a certain temperature, its product is biphenyl.85 DEG C time, after reaction 5min, the conversion ratio of iodobenzene is 85%, and after reaction 30min, the conversion ratio of iodobenzene is 100%.
Embodiment 4
The first step: the deionized water mixing of getting 8g foam silicon carbon, 10g ferric nitrate, 5g magnesium nitrate, 20g urea and 300mL, 70 DEG C of backflows, cooling, after freeze-day with constant temperature, put it in tube furnace, after passing into helium, furnace temperature is risen to 850 DEG C, then pass into hydrogen and ethene, reaction 4h, obtains CNT-foam silicon carbon composite.Get this composite to mix with red fuming nitric acid (RFNA), reflux at 120 DEG C, wash, dry 15h, obtain the CNT-foam silicon carbon composite through purifying and functionalization.
Second step: be 0.01mol L by concentration
-1metal Palladium saline solution mixes with organic solvent and is made into palladium mixed salt solution.The volume ratio of Metal Palladium saline solution and organic solvent is 4:1.Get CNT-foam silicon carbon composite, the amount of required palladium mixed salt solution is calculated according to palladium content 0.08wt% in silicon monoblock type composite, then measure the amount of required palladium mixed salt solution and it slowly dropwise joined in CNT-foam silicon carbon composite, then dry.Composite is put into tube furnace, passes into hydrogen, at 200 DEG C of reduction 4h, obtain palladium/CNT-foam silicon carbon monoblock type composite.
Palladium/the CNT of above-mentioned preparation-foam silicon carbon monoblock type composite is used as catalyst, verifies its catalytic activity in Suzuki coupling reaction.By 5mmol iodobenzene, 10mmol phenyl boric acid, 20mmol tripotassium phosphate, 5mL water and 20mL alcohol solution-forming, use 600mg catalyst, carry out return stirring at a certain temperature, its product is biphenyl.85 DEG C time, after reaction 5min, the conversion ratio of iodobenzene is 90%, and after reaction 30min, the conversion ratio of iodobenzene is 100%.
Claims (14)
1. palladium/CNT-foam silicon carbon monoblock type composite, is characterized in that: in this composite, even carbon nanotube is immobilized at foam silicon carbon carrier surface, and palladium nano-particles uniform load is on the surface of CNT.
2. palladium/CNT according to claim 1-foam silicon carbon monoblock type composite, is characterized in that: the load capacity of described CNT is 0.5 ~ 9wt.% of composite gross weight; Palladium load capacity is 0.006 ~ 4wt.% of composite gross weight.
3. palladium/CNT according to claim 1-foam silicon carbon monoblock type composite, it is characterized in that: described CNT average length is 0.5 ~ 300 μm, average diameter is 15 ~ 40nm; Described palladium nano-particles granularity is 1 ~ 10nm.
4. the preparation method of palladium/CNT according to claim 1-foam silicon carbon monoblock type composite, is characterized in that: the method comprises the steps:
(1) foam silicon carbon is put into the aqueous solution of metal inorganic salt and adjuvant after stirring and refluxing, carry out drying process, then tube furnace is put into, adopt the method for chemical vapour deposition (CVD) at foam silicon carbon superficial growth CNT, obtain the composite of CNT-foam silicon carbon;
(2) in step (1) gained CNT-foam silicon carbon composite, palladium mixed salt solution is added by the method for wet impregnation, the quartz ampoule of tube furnace is put into after drying, after passing into hydrogen reducing, obtain palladium/CNT-foam silicon carbon monoblock type composite.
5. the preparation method of palladium/CNT according to claim 4-foam silicon carbon monoblock type composite, it is characterized in that: the detailed process of described step (1) is: the deionized water of 5-20g foam silicon carbon, 2-20g metal inorganic salt, 10-50g adjuvant and 100-500mL is mixed, cooling after 60-90 DEG C of backflow, after freeze-day with constant temperature, put it in tube furnace, after passing into protective gas, furnace temperature is risen to 550-1000 DEG C, then reacting gas is passed into, reaction 0.1-6h, obtains CNT-foam silicon carbon composite crude product; Mixed with nitric acid by this CNT-foam silicon carbon composite crude product, reflux under 60-200 DEG C of condition, washing post-drying 4-15h, obtains the CNT-foam silicon carbon composite through purifying and functionalization.
6. the preparation method of palladium/CNT according to claim 4-foam silicon carbon monoblock type composite, is characterized in that: the detailed process of described step (2) is: be 0.001 ~ 1mol L by concentration
-1metal Palladium saline solution and organic solvent are according to (1-5): the volume ratio of 1 mixes and is made into palladium mixed salt solution; Get CNT-foam silicon carbon composite, measure the palladium mixed salt solution of respective volume by required palladium load capacity, then the palladium mixed salt solution measured slowly dropwise is joined in CNT-foam silicon carbon composite, then dry; Composite after drying process is put into tube furnace, passes into hydrogen, at 80 ~ 300 DEG C of reduction 1-10h, obtain palladium/CNT-foam silicon carbon monoblock type composite.
7. the preparation method of the palladium/CNT according to claim 4 or 5-foam silicon carbon monoblock type composite, is characterized in that: described metal inorganic salt is one or more in iron chloride, ferric nitrate, ammonium molybdate, magnesium nitrate, magnesium chloride and aluminum nitrate.
8. the preparation method of the palladium/CNT according to claim 4 or 5-foam silicon carbon monoblock type composite, is characterized in that: described adjuvant is one or more in ethylenediamine, urea, monoethanolamine, ethanol and acetone.
9. the preparation method of palladium/CNT according to claim 5-foam silicon carbon monoblock type composite, is characterized in that: in the process of foam silicon carbon superficial growth CNT, and described protection gas is nitrogen, argon gas or helium; Described reaction gas is hydrogen and ethene, or reaction gas is hydrogen and acetylene.
10. the preparation method of palladium/CNT according to claim 6-foam silicon carbon monoblock type composite, is characterized in that: described Metal Palladium salt is PdCl
2, Pd (NO
3)
2with Pd (CH
3cOO)
2in one or more.
The preparation method of 11. palladium/CNT according to claim 6-foam silicon carbon monoblock type composites, is characterized in that: described organic solvent is one or more in ethanol, acetone, acetic acid and formic acid.
The preparation method of 12. palladium/CNT according to claim 4-foam silicon carbon monoblock type composites, is characterized in that: described tube furnace is horizontal tube furnace.
The application of 13. palladium/CNT according to claim 1-foam silicon carbon monoblock type composites, is characterized in that: using described palladium/CNT-foam silicon carbon monoblock type composite as catalyst.
The application of 14. palladium/CNT according to claim 13-foam silicon carbon monoblock type composites, is characterized in that: described palladium/CNT-foam silicon carbon monoblock type composite is used for the catalyst in hydrogenation reaction, the coupling reaction of C-C key, oxidation reaction, isomerization reaction or dehydrogenation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310564383.0A CN104624216A (en) | 2013-11-12 | 2013-11-12 | Palladium/carbon nanotube-foam silicon carbide integrated composite material and preparation method and application of composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310564383.0A CN104624216A (en) | 2013-11-12 | 2013-11-12 | Palladium/carbon nanotube-foam silicon carbide integrated composite material and preparation method and application of composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104624216A true CN104624216A (en) | 2015-05-20 |
Family
ID=53203738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310564383.0A Pending CN104624216A (en) | 2013-11-12 | 2013-11-12 | Palladium/carbon nanotube-foam silicon carbide integrated composite material and preparation method and application of composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104624216A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107661755A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | Catalyst with the effect of hydrocarbon catalysis dehydrogenation and its preparation method and application and hydrocarbon dehydrogenation reaction method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120258850A1 (en) * | 2011-04-07 | 2012-10-11 | National Cheng Kung University | Methods of preparing carbinized nanotube composite and metal-nanotube composite catalyst |
| CN102814188A (en) * | 2012-08-25 | 2012-12-12 | 中国科学院金属研究所 | Activated carbon coating/foam silicon carbide structural catalyst and preparation method thereof |
| CN102962087A (en) * | 2011-08-31 | 2013-03-13 | 中国科学院金属研究所 | Carbon nanotube/silicon carbide foam catalytic composite material and preparation method thereof |
-
2013
- 2013-11-12 CN CN201310564383.0A patent/CN104624216A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120258850A1 (en) * | 2011-04-07 | 2012-10-11 | National Cheng Kung University | Methods of preparing carbinized nanotube composite and metal-nanotube composite catalyst |
| CN102962087A (en) * | 2011-08-31 | 2013-03-13 | 中国科学院金属研究所 | Carbon nanotube/silicon carbide foam catalytic composite material and preparation method thereof |
| CN102814188A (en) * | 2012-08-25 | 2012-12-12 | 中国科学院金属研究所 | Activated carbon coating/foam silicon carbide structural catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘玉荣著: "《介孔碳材料的合成及应用》", 30 June 2012, 北京：国防工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107661755A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | Catalyst with the effect of hydrocarbon catalysis dehydrogenation and its preparation method and application and hydrocarbon dehydrogenation reaction method |
| CN107661755B (en) * | 2016-07-27 | 2020-09-22 | 中国石油化工股份有限公司 | Catalyst with hydrocarbon dehydrogenation catalysis, preparation method and application thereof, and hydrocarbon dehydrogenation reaction method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106694017B (en) | A kind of catalyst, its optimization method and application for low-carbon alkanes oxidative dehydrogenation alkene | |
| Fan et al. | Palladium clusters confined in triazinyl-functionalized COFs with enhanced catalytic activity | |
| Hao et al. | Synergistic effect of segregated Pd and Au nanoparticles on semiconducting SiC for efficient photocatalytic hydrogenation of nitroarenes | |
| Pham-Huu et al. | Carbon nanofiber supported palladium catalyst for liquid-phase reactions: An active and selective catalyst for hydrogenation of cinnamaldehyde into hydrocinnamaldehyde | |
| Zhao et al. | Nickel nanoparticles supported on MOF-5: Synthesis and catalytic hydrogenation properties | |
| Liu et al. | Ordered mesoporous carbon catalyst for dehydrogenation of propane to propylene | |
| Hu et al. | Fe/ZSM-5 catalysts for ammonia decomposition to COx-free hydrogen: Effect of SiO2/Al2O3 ratio | |
| Liu et al. | Synthesis of ordered mesoporous carbon materials and their catalytic performance in dehydrogenation of propane to propylene | |
| Yang et al. | N-Doped porous carbon nanotubes: synthesis and application in catalysis | |
| CN104447209A (en) | Method for preparing cyclohexanol by catalyzing by base metal catalyst | |
| Peng et al. | Ultra-small gold nanoparticles immobilized on mesoporous silica/graphene oxide as highly active and stable heterogeneous catalysts | |
| Li et al. | One-step synthesis of B-doped mesoporous carbon as supports of Pd nanoparticles for liquid phase catalytic hydrodechlorination | |
| Duong-Viet et al. | Nitrogen-doped carbon nanotubes on silicon carbide as a metal-free catalyst | |
| Fu et al. | Understanding the catalytic sites in porous hexagonal boron nitride for the epoxidation of styrene | |
| Fang et al. | Highly selective visible-light photocatalytic benzene hydroxylation to phenol using a new heterogeneous photocatalyst UiO-66-NH 2-SA-V | |
| Hu et al. | Mesoporous carbons as metal-free catalysts for propane dehydrogenation: Effect of the pore structure and surface property | |
| Jiang et al. | Synthesis of p-aminophenol from p-nitrophenol reduction over Pd@ ZIF-8 | |
| Zhang et al. | Polymer@ silica composites with tunable outer and inner surface properties: a platform for aqueous asymmetric transfer hydrogenation | |
| Ramesh et al. | Selectivity oxidation of benzyl alcohol using mesoporous g-C3N4 catalysts prepared by hard template method | |
| Li et al. | Effect of the morphology on the vapor phase benzene catalytic hydrogenation over Pd/CeO2 catalyst | |
| Li et al. | Mo2N nanobelts for dehydrogenation of aromatic alcohols | |
| Du et al. | The short-channel function of hollow carbon nanoparticles as support in the dehydrogenation of cyclohexane | |
| Pan et al. | Highly dispersed Co species in N-doped carbon enhanced the aldehydes ammoxidation reaction activity | |
| CN103447097A (en) | Preparation method of novel nano carbon composite material of SiC base | |
| Cao et al. | Boron and nitrogen co-doped porous carbon nanospheres for oxidative dehydrogenation of ethane to ethylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150520 |
|
| RJ01 | Rejection of invention patent application after publication |