CN106964346B - A kind of palladium/graphene catalyst and preparation method thereof for ten dihydro ethyl carbazole dehydrogenations - Google Patents
A kind of palladium/graphene catalyst and preparation method thereof for ten dihydro ethyl carbazole dehydrogenations Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 94
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 27
- HOQAPVYOGBLGOC-UHFFFAOYSA-N 1-ethyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CC HOQAPVYOGBLGOC-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 238000002604 ultrasonography Methods 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 239000004615 ingredient Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 206010013786 Dry skin Diseases 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000002826 coolant Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- ZJKABZNFELLAQQ-UHFFFAOYSA-N octane Chemical compound CCCCCCCC.CCCCCCCC ZJKABZNFELLAQQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 23
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 238000003860 storage Methods 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 241000446313 Lamella Species 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- -1 Hummer method Chemical compound 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention discloses a kind of preparation methods of palladium/graphene catalyst for the ten dihydro ethyl carbazole dehydrogenation of ethyl carbazole complete hydrogenation product, the ingredient of the catalyst is carbon, oxygen and palladium, and it is respectively 70%-88%, 10%-25% and 1%-10% that wherein carbon, oxygen and palladium, which account for the percentage of catalyst gross mass,；Carrier graphene sheet layer is 1-3 layers in catalyst；Preparation method includes two steps: the preparation of graphene oxide dispersion, the preparation of palladium/graphene catalyst；The method that the present invention assists prestripping and the removing of two-stage ultrasound by ball milling, solves the problems, such as the graphene film thickness of conventional oxidation reduction method preparation；The palladium/graphene catalyst prepared using the reduction system of water-ethylene glycol, partial size is small and is evenly distributed, and overcomes that traditional preparation methods active metal partial size in the case where not adding dispersing agent and surfactant is big and defect unevenly distributed；The catalytic performance of catalyst of the present invention is excellent, and while the reaction time greatly shortens, the selectivity of final dehydrogenation product ethyl carbazole is greatly improved to 97% or more, total amount of dehydrogenation 5.74wt% or more.
Description
Technical field
The invention belongs to ten dihydro ethyl carbazole De-hydrogen Technology fields, and in particular to one kind is de- for ten dihydro ethyl carbazoles
Palladium/graphene catalyst of hydrogen and preparation method thereof.
Background technique
A kind of ideal clean fuel of the Hydrogen Energy as possible substitute fossil fuels, answering especially in fuel cell car
With, be constantly subjected to widely pay close attention to and research.A series of result of study shows, its use in mobile traffic can be with
The significant discharge for reducing oxycarbide, nitrogen oxides, oxysulfide.However Hydrogen Energy develops simultaneously as the commercial of renewable energy
It is undesirable, mainly since there are technological difficulties for the storage link of hydrogen.Commercial fuel cell hydrogen storage mode is main at this stage
There are high-pressure gaseous hydrogen storage and low-temperature liquefaction hydrogen storage, both hydrogen storage modes have more apparent disadvantage: storage facilities cost is high
High, use environment and condition are harsh, and hydrogen loss is more in use process, and safety coefficient is low, and accidental risk is big, promotes base on a large scale
Infrastructure builds valuableness, and dispenses transport difficult.
Organic liquid hydride hydrogen storage starts to be suggested as a kind of preferred embodiment in this context, it has by unsaturation
The reversible reaction of machine liquid and hydrogen is realized plus hydrogen and dehydrogenation, it can continue to use existing base fossil fuel conveying and used completely
Basis is built, storage is convenient and using safe.
It is most expected in organic liquid hydride hydrogen storage system, and with ethyl carbazole.It is suggested earliest 200
DEG C or less achievable complete hydrogenation/dehydrogenation organic liquid hydrogen storage material, for theoretical hydrogen-storage density up to 5.79wt%, hydrogen is pure
Degree 99.9%, and generated without any polluted gas, while meeting the on-board hydrogen source system of International Energy Agency and U.S. Department of Energy proposition
System technical indicator.For vehicle-mounted fuel cell system, lower plus/desorption temperature, while having more thorough plus/dehydrogenation anti-
Performance is answered, the loss of energy during adding dehydrogenation cycle could be reduced to the greatest extent in this way, promotes energy utilization rate.
To ten dihydro ethyl carbazole dehydrogenations studies have shown that different platinum or palladium load catalyst at 180-260 DEG C
There is good dehydrogenation in temperature range.Some scholars have studied palladium/active carbon, palladium/silica, palladium/aluminium oxide,
Platinum/aluminium oxide catalytic performance, however have to mention, higher noble metal usage amount, cannot under mild conditions effectively
Ground carries out complete dehydrogenation, and amount of dehydrogenation just corresponds to 3.71wt%, and the theoretical hydrogen-storage density difference relative to 5.78wt% is more.
Graphene as a kind of new material with excellent properties developed in recent years, be used for biology, medicine,
The multiple fields such as photoelectricity, semiconductor.The existing common oxidation-reduction method for preparing graphene such as Hummer method, resulting lamella
It is thicker, metallic atom utilization rate can be reduced as catalyst carrier, increases metal consumption, increases cost.
The bottleneck of the technology is how exploitation high conversion, highly selective efficient dehydrogenation at present, to mention
The energy conversion efficiency problem of high vehicle-mounted hydrogen fuel cell system.
Summary of the invention
In order to solve above-mentioned problems of the prior art, the purpose of the present invention is to provide one kind to be used for ten dihydro second
The palladium/graphene catalyst and preparation method thereof of base carbazole dehydrogenation, catalyst energy catalytic performance of the present invention is excellent, is reacting
While time greatly shortens, the selectivity of final dehydrogenation product ethyl carbazole is greatly improved；Preparation method simplicity, condition temperature
With easily operated, cost is low, particularly suitable for large-scale production.
In order to achieve the above objectives, the present invention is adopted the following technical scheme that
A kind of palladium/graphene catalyst for ten dihydro ethyl carbazole dehydrogenations, the ingredient of the catalyst be carbon, oxygen and
Palladium, it is respectively 70%-88%, 10%-25% and 1%-10% that wherein carbon, oxygen and palladium, which account for the percentage of catalyst gross mass,；Institute
Stating carrier graphene sheet layer in catalyst is 1-3 layers.
The preparation method of the palladium/graphene catalyst for being used for ten dihydro ethyl carbazole dehydrogenations, includes the following steps:
Step 1, the preparation of graphene oxide dispersion, specifically includes the following steps:
1) graphite oxide, is prepared with used preparation method, product is filtered, is then washed with distilled water to pH=3-7,
60 DEG C of dryings are for 24 hours in vacuum drying oven for finally obtained graphite oxide gel；
2), desciccate is added in the ball grinder containing coolant liquid, carries out auxiliary prestripping 4h, ball milling using ball mill
300-1600 revs/min of machine revolving speed；
3) it, weighs the graphite oxide powder 0.5g that ball milling obtains to be placed in conical flask, it is mixed that 50ml distilled water stirring 2h is added
It is even, conical flask is placed in ultrasound 1h in the supersonic cleaning machine of 75-200w, then small-power prestripping oxidized graphite flake layer is used
400-1000w cell disruptor Ultrasonic Pulverization 1h, high-power removing oxidized graphite flake layer obtain graphene oxide dispersion；
Step 2, the preparation of palladium/graphene catalyst, specifically includes the following steps:
1) palladium chloride, is added into graphene oxide dispersion obtained in step 1, adds quality according in step 13
The weighed graphite oxide powder quality score 1%-10% addition of institute, stirs 12h for solution；
2), the solution after stirring is added in the three-necked flask of 500ml, be added ethylene glycol 150-350ml, in 100 DEG C-
130 DEG C of reaction 3-24h react whole logical argon gas protection；
3), solution after the reaction was completed after filtering, washs to no chloride ion to be detected and (uses silver nitrate using dehydrated alcohol
Solution detection), by filter cake in vacuum drying oven 60 DEG C of dry 12h.Grinding obtains palladium/graphite that palladium mass fraction is 1%-10%
Alkene catalyst, carrier graphene sheet layer are 1-3 layers.
The preparation method of the above-mentioned palladium/graphene catalyst for being used for ten dihydro ethyl carbazole dehydrogenations, the graphite oxide
Redox preparation method can also select other preparations in addition to Hummer method, Brodie method or Standenmaier method
The oxidation-reduction method of graphite oxide.
The preparation method of the above-mentioned palladium/graphene catalyst for being used for ten dihydro ethyl carbazole dehydrogenations, the ball milling auxiliary are pre-
The coolant liquid used when removing, can select n-hexane, the arbitrary volume ratio of one of normal heptane, octane etc. or 2-3 kind
Mixed liquor, it is preferred to use normal heptane.It can be easy to terminate in ball milling while guaranteeing cooling effect using above-mentioned coolant liquid cooling
It thoroughly removes afterwards.
The preparation method of the above-mentioned palladium/graphene catalyst for being used for ten dihydro ethyl carbazole dehydrogenations, the material of material used can
It is increased or decreased by equal proportion.
Ultrasonic stripping process in step 1, the two-stage for having used the removing of small-power ultrasound and large power supersonic removing to crush
Step had not only avoided the problem of only not fully stripping oxidized graphite flake layer with small-power ultrasound in this way, but also prevented for a long time
Large power supersonic destroy oxidized graphite flake layer form.
Compared to the prior art, the present invention has the advantage that
1, the present invention have preparation method simplicity, mild condition, easily operated, cost is low, particularly suitable for scale
Metaplasia produces.
2, the graphene of conventional oxidation reduction method preparation, piece thickness, poor catalytic activity when being used as carrier.The present invention passes through ball
The method of mill auxiliary prestripping and the removing of two-stage ultrasound solves asking for the graphene film thickness of conventional oxidation reduction method preparation
Topic, carrier graphene sheet layer are 1-3 layers.
3, when conventional graphite alkenyl catalyst reduction method is restored using sodium borohydride or hydrazine hydrate, dispersion need to be added
Agent or surfactant, and for metal it occur frequently that reuniting, the catalyst particle size being prepared is larger when reduction.The present invention uses
The palladium/graphene catalyst of the reduction system preparation of water-ethylene glycol, partial size is small and is evenly distributed, and overcomes traditional preparation methods
In the case where not adding dispersing agent and surfactant, active metal partial size is big and defect unevenly distributed.
4, the catalyst obtained by the present invention, has excellent performance, while greatly shortening in the reaction time, final dehydrogenation product
The selectivity of ethyl carbazole is greatly improved to 97% or more, and amount of dehydrogenation reaches 5.74wt% or more.
Detailed description of the invention
Fig. 1 is the X-ray diffraction photo of palladium/graphene catalyst obtained by the present invention.
Fig. 2 a is that the carbon swarming of the x-ray photoelectron spectroscopy photo of palladium/graphene catalyst obtained by the present invention is quasi-
It closes.
Fig. 2 b is that the palladium element swarming of the x-ray photoelectron spectroscopy photo of palladium/graphene catalyst obtained by the present invention is quasi-
It closes.
Fig. 3 is the Raman spectrum photo of palladium/graphene catalyst obtained by the present invention.
Fig. 4 a is the macroscopic view of the transmission electron microscope photo 100nm scale of palladium/graphene catalyst obtained by the present invention
Pattern.
Fig. 4 b is the microcosmic shape of the transmission electron microscope photo 20nm scale of palladium/graphene catalyst obtained by the present invention
Looks and partial size statistical chart.
Specific embodiment
With specific embodiment, invention is further described in detail below.
Embodiment one:
Graphite oxide is prepared with Hummer method, product is filtered, is then washed with distilled water to pH=6, in vacuum drying oven
60 DEG C of dryings are for 24 hours；Desciccate is added in the ball grinder containing n-heptane solution, carries out auxiliary prestripping using ball mill
4h, 500 revs/min of drum's speed of rotation；It weighs the graphite oxide powder 0.5g that ball milling obtains to be placed in conical flask, 50ml distillation is added
Water stirs 2h and mixes, and conical flask is placed in ultrasound 1h in the supersonic cleaning machine of 150w, then uses 600w cell disruptor ultrasound powder
Broken 1h, obtains graphene oxide dispersion.
Palladium chloride is added into obtained graphene oxide dispersion, is added according to palladium mass fraction 5wt%, solution is stirred
After mixing 12h, above-mentioned solution is added in the three-necked flask of 500ml, ethylene glycol 200ml is added, in 120 DEG C of reaction 12h, reaction
The logical argon gas protection of whole process.Solution after the reaction was completed after filtering, is washed to no chloride ion using dehydrated alcohol and is detected, and will be filtered
Cake 60 DEG C of dry 12h in vacuum drying oven.Grinding obtains the palladium/graphene catalyst that palladium mass fraction is 4.5wt%, carrier stone
Black alkene lamella is 1-3 layers.
Performance evaluation is carried out to the catalyst, the results are shown in Table 1.
The catalyst performance of 10 dihydro ethyl carbazole dehydrogenation of table formation ethyl carbazole process
The catalyst is characterized, X-ray diffraction photo as shown in Figure 1, it can be seen that graphite oxide
It is reduced to graphene completely, the well-crystallized of palladium, mainly single crystal form exist, with highest Pd (111) crystal face of activity
Based on.X-ray photoelectron spectroscopy photo is as shown in Figure 2 a and 2 b, can be seen that C, tri- kinds of elements of O, Pd after carrying out swarming fitting
Specific bonding form.Its Raman spectrum photo by empirical equation ω G=1581.6+11/ (1+n^1.6) as shown in figure 3, can be obtained
Carrier graphene sheet layer is 1 layer.Its transmission electron microscope photo is as shown in figures 4 a and 4b, it is seen that the partial size of palladium is smaller and divides
Cloth is uniform.
Performance evaluation is carried out to gained catalyst, after reaction carries out 9 hours, the selectivity of ethyl carbazole is 97.79%, is taken off
Hydrogen amount is 5.75wt%.
Embodiment two:
Graphite oxide is prepared with Brodie method, product is filtered, is then washed with distilled water to pH=5, in vacuum drying oven
60 DEG C of dryings are for 24 hours；Desciccate is added in the ball grinder containing hexane solution, carries out auxiliary prestripping using ball mill
4h, 800 revs/min of drum's speed of rotation；It weighs the graphite oxide powder 0.5g that ball milling obtains to be placed in conical flask, 50ml distillation is added
Water stirs 2h and mixes, and conical flask is placed in ultrasound 1h in the supersonic cleaning machine of 200w, then uses 800w cell disruptor ultrasound powder
Broken 1h, obtains graphene oxide dispersion.
Palladium chloride is added into obtained graphene oxide dispersion, is added according to palladium mass fraction 3wt%, solution is stirred
After mixing 12h, above-mentioned solution is added in the three-necked flask of 500ml, ethylene glycol 250ml is added, for 24 hours in 110 DEG C of reactions, reaction
The logical argon gas protection of whole process.Solution after the reaction was completed after filtering, is washed to no chloride ion using dehydrated alcohol and is detected, and will be filtered
Cake 60 DEG C of dry 12h in vacuum drying oven.Grinding obtains the palladium/graphene catalyst that palladium mass fraction is 2.5wt%, carrier stone
Black alkene lamella is 1 layer.Performance evaluation is carried out to the catalyst, after reaction carries out 9 hours, the selectivity of ethyl carbazole is
97.79%, amount of dehydrogenation 5.75wt%.
Embodiment three:
Graphite oxide is prepared with Standenmaier method, product is filtered, is then washed with distilled water to pH=3, vacuum
60 DEG C of dryings are for 24 hours in baking oven；Desciccate is added in the ball grinder containing n-heptane solution, assist using ball mill pre-
Remove 4h, 1000 revs/min of drum's speed of rotation；It weighs the graphite oxide powder 0.5g that ball milling obtains to be placed in conical flask, be added
50ml distilled water stirs 2h and mixes, and conical flask is placed in ultrasound 1h in the supersonic cleaning machine of 100w, then uses 450w cell pulverization
Machine Ultrasonic Pulverization 1h, obtains graphene oxide dispersion.
Palladium chloride is added into obtained graphene oxide dispersion, is added according to palladium mass fraction 7wt%, solution is stirred
After mixing 12h, above-mentioned solution is added in the three-necked flask of 500ml, ethylene glycol 200ml is added, in 110 DEG C of reaction 10h, reaction
The logical argon gas protection of whole process.Solution after the reaction was completed after filtering, is washed to no chloride ion using dehydrated alcohol and is detected, and will be filtered
Cake 60 DEG C of dry 12h in vacuum drying oven.Grinding obtains the palladium/graphene catalyst that palladium mass fraction is 6.5wt%, carrier stone
Black alkene lamella is layer 2-3.Performance evaluation is carried out to the catalyst, after reaction carries out 8 hours, the selectivity of ethyl carbazole is
97.58%, amount of dehydrogenation 5.74wt%.
Claims (2)
1. a kind of preparation method of the palladium/graphene catalyst for ten dihydro ethyl carbazole dehydrogenations, the ingredient of the catalyst
For carbon, oxygen and palladium, wherein carbon, oxygen and palladium account for the percentage of catalyst gross mass be respectively 70%-88%, 10%-25% and
1%-10%；Carrier graphene sheet layer is 1-3 layers in the catalyst；
It is characterized by: the preparation method includes the following steps:
Step 1, the preparation of graphene oxide dispersion, specifically includes the following steps:
1) graphite oxide, is prepared, product is filtered, is then washed with distilled water to pH=3-7, finally obtained graphite oxide is solidifying
60 DEG C of dryings are for 24 hours in vacuum drying oven for glue；
2), desciccate is added in the ball grinder containing coolant liquid, carries out auxiliary prestripping 4h using ball mill, ball mill turns
Fast 300-1600 revs/min；
3) it, weighs the graphite oxide powder 0.5g that ball milling obtains to be placed in conical flask, 50ml distilled water stirring 2h is added and mixes, it will
Conical flask is placed in ultrasound 1h in the supersonic cleaning machine of 75-200w, then small-power prestripping oxidized graphite flake layer uses 400-
1000w cell disruptor Ultrasonic Pulverization 1h, high-power removing oxidized graphite flake layer obtain graphene oxide dispersion；
Step 2, the preparation of palladium/graphene catalyst, specifically includes the following steps:
1), it is added palladium chloride into graphene oxide dispersion obtained in step 1, addition quality is according to alleged by step 13
The graphite oxide powder quality score 1%-10% addition taken, stirs 12h for solution；
2), the solution after stirring is added in the three-necked flask of 500ml, ethylene glycol 150-350ml is added, in 100 DEG C -130
DEG C reaction 3-24h, reacts whole logical argon gas protection；
3), solution after the reaction was completed after filtering, is washed to no chloride ion using dehydrated alcohol and is detected, by filter cake in vacuum
60 DEG C of dry 12h in baking oven；Grinding obtains palladium/graphene catalyst.
2. preparation method according to claim 1, it is characterised in that: in the step 1 2) in coolant liquid use just oneself
Alkane, one of normal heptane, octane or a variety of mixed liquors with arbitrary volume ratio.
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| CN108394892B (en) * | 2018-05-11 | 2020-03-13 | 西安交通大学 | Preparation method of graphene dispersion liquid for directly modifying graphene |
| CN110560046B (en) * | 2019-09-09 | 2020-06-26 | 西安交通大学 | Platinum/titanium dioxide catalyst for dehydrogenation of dodecahydroethylcarbazole and preparation method thereof |
| CN112054222B (en) * | 2020-09-04 | 2021-12-28 | 西安交通大学 | Carbon-supported palladium-nickel-tantalum nitride nano electro-catalyst for direct methanol fuel cell and preparation method thereof |
| CN113351201A (en) * | 2021-06-04 | 2021-09-07 | 武汉氢能与燃料电池产业技术研究院有限公司 | Thin film catalyst, precious metal/graphene composite thin film, and preparation method and application thereof |
| CN113522309A (en) * | 2021-07-16 | 2021-10-22 | 西安海望能源科技有限公司 | Palladium-gold-nickel/graphene catalyst for dehydrogenation of dodecahydroethylcarbazole and preparation method thereof |
| CN113522279A (en) * | 2021-07-16 | 2021-10-22 | 西安海望能源科技有限公司 | Gold palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole and preparation method thereof |
| 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 |
| CN115041229B (en) * | 2022-06-18 | 2023-11-10 | 哈尔滨理工大学 | Preparation of COF-316/THFB-COF-Zn material and photocatalysis CO 2 Reduction of |
| CN117225403A (en) * | 2023-11-14 | 2023-12-15 | 北京海望氢能科技有限公司 | Dehydrogenation catalyst and preparation method and application thereof |
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