CN113522279A - Gold palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole and preparation method thereof - Google Patents
Gold palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 54
- 239000001257 hydrogen Substances 0.000 title claims abstract description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000003795 desorption Methods 0.000 title claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 35
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 30
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052737 gold Inorganic materials 0.000 claims abstract description 24
- 239000010931 gold Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 22
- 239000003638 chemical reducing agent Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 239000011668 ascorbic acid Substances 0.000 claims description 11
- 229960005070 ascorbic acid Drugs 0.000 claims description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000012696 Pd precursors Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 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 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000003827 glycol group Chemical group 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- HOQAPVYOGBLGOC-UHFFFAOYSA-N 1-ethyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CC HOQAPVYOGBLGOC-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052763 palladium Inorganic materials 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 239000011258 core-shell material Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000035040 seed growth Effects 0.000 description 1
Images
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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
- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J37/0207—Pretreatment of the support
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- 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
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- 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
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Abstract
The invention discloses a gold palladium catalyst for hydrogen desorption of dodecahydro ethyl carbazole and a preparation method thereof, belonging to the technical field of catalyst preparation. The method comprises the following steps: firstly, pretreating a carrier, then adding a mixed solution into the pretreated carrier, stirring and then carrying out ultrasonic dispersion to obtain a carrier dispersion liquid; finally preparing the gold palladium catalyst. The invention can improve the supply quantity of active sites and the pore size distribution by pretreating the carrier, is favorable for improving the loading quantity of gold and palladium and the uniformity of gold and palladium loading, and is favorable for the occurrence of hydrogen discharge reaction of dodecahydroethylcarbazole. The gold palladium catalyst prepared by the method has excellent hydrogen release performance, and the selectivity of the obtained hydrogen release product ethyl carbazole is greatly improved while the reaction time is greatly shortened compared with that of the existing catalyst. The invention has the advantages of simple preparation method, mild condition, easy operation and low cost, and is particularly suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a gold palladium catalyst for hydrogen evolution of dodecahydroethylcarbazole and a preparation method thereof.
Background
The development of the hydrogen energy industry has been receiving more and more attention in recent years. Due to the physicochemical characteristics of hydrogen, storage and transportation become important bottlenecks restricting large-scale application, and the storage and transportation become one of the key points and difficulties in the industrial development of hydrogen energy. Compared with other hydrogen storage modes, the liquid organic hydrogen storage carrier has great engineering advantages, high hydrogen storage density, low hydrogen storage medium recycling cost, and safe and convenient storage and transportation. In particular, a dodecahydroethylcarbazole/ethylcarbazole system is an organic liquid hydrogen storage medium which is screened at the earliest time in thermodynamics and can realize reversible hydrogen storage and release at a medium-low temperature (lower than 200 ℃), but the dehydrogenation efficiency is not high, and the stored hydrogen cannot be completely released under a mild condition, so that the popularization and application of the technology are hindered.
Noble metal nanoparticles exhibit excellent activity and selectivity in a variety of catalytic reactions, particularly gold and palladium, and have also found wide application in industrial catalysis. Conventionally prepared catalysts are quite diverse in morphology, and typically, the core/shell structure exhibits superior catalytic properties relative to their respective elements or alloys due to its highly functional structure. However, the preparation of the bimetallic core/shell component is a complex process and therefore various strategies are available for the production of different kinds of catalysts. Step-wise preparation and seed-growth methods are commonly used to form regular core/shell structures. In the relatively simple one-pot preparation, the use of surfactants, dispersants, ionic liquids, and the like has been reported to virtually increase the complexity of subsequent processing with the aid of such aids.
The bottleneck of the prior art is how to prepare the catalyst with a stable core-shell structure by a simple process, so that the hydrogen release catalytic efficiency of the dodecahydro ethyl carbazole is improved, and the dehydrogenation selectivity is improved.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a gold palladium catalyst for hydrogen desorption of dodecahydro ethyl carbazole, the preparation method has simple process steps and easy operation, the gold palladium catalyst prepared by the method has excellent hydrogen desorption performance, the reaction time is greatly shortened compared with the existing catalyst, and the selectivity of the obtained hydrogen desorption product ethyl carbazole is greatly improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a gold palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole sequentially comprises the following steps:
a. pretreating the carrier
Adding the carrier treatment solution into an untreated carrier, and uniformly stirring;
condensing and refluxing the uniformly stirred solution at 60-100 ℃ for 1-12 h, filtering, washing the obtained filter cake with water until the pH value is 4-9, and drying for a period of time to obtain a treated carrier;
b. preparation of Carrier Dispersion
B, adding the mixed solution into the carrier pretreated in the step a, stirring and then performing ultrasonic dispersion to obtain carrier dispersion liquid;
c. preparation of gold Palladium catalyst
Adding a first reducing agent into the carrier dispersion liquid, stirring, and heating to 80-100 ℃ to obtain a first solution;
adding a gold precursor into the first solution, and reacting at the temperature of 80-100 ℃ for a period of time to obtain a second solution;
adding a palladium precursor into the second solution, adding a second reducing agent, and reacting at the temperature of 50-100 ℃ for a period of time to obtain a third solution;
and carrying out post-treatment on the solution III, collecting a filter cake, drying the filter cake, and carrying out ball milling to obtain the gold-palladium catalyst.
The beneficial technical effects directly brought by the technical scheme are as follows:
in the preparation of the gold-palladium catalyst, the carrier is pretreated, so that the supply quantity of active sites can be increased, the pore size distribution is improved, the uniformity of gold-palladium loading is facilitated, and the hydrogen desorption reaction of dodecahydroethylcarbazole is facilitated; the preparation process of the gold palladium catalyst is simple and easy to operate.
In a preferable embodiment of the invention, in the step a, the carrier treatment solution is 0.2-6 mol/L nitric acid aqueous solution, 0.2-6 mol/L sulfuric acid aqueous solution, 0.02-3 mol/L perchloric acid aqueous solution, 0.05-10 mol/L sodium hydroxide aqueous solution or 0.05-10 mol/L potassium hydroxide aqueous solution; in the step a, vacuum drying is carried out for 24 hours at the temperature of 50-70 ℃ to obtain a treated carrier; the carrier is graphite oxide or active carbon.
In another preferable embodiment of the invention, in the step b, the mixed solution is prepared by mixing distilled water and a solvent according to a volume ratio of 0.1-1: 1, the solvent is glycol, propylene glycol or glycerol; the mass-volume ratio of the pretreated carrier to the mixed solution is 1: 50-300 g/mL, stirring is carried out for 0.5-1.5 h, and ultrasonic dispersion is carried out for 20-40 min.
Preferably, in the step c, a gold precursor is added and then reacted for 3-60 min at the temperature of 80-100 ℃, wherein the gold precursor is selected from one or more of chloroauric acid, sodium chloroaurate and potassium chloroaurate, and the mass ratio of the addition amount of the gold element to the carrier in the carrier dispersion liquid is 0.01-0.2: 1.
Preferably, in the step c, the reducing agent I is one or more of sodium citrate, ascorbic acid, citric acid and glucose, and the mass ratio of the adding amount of the reducing agent I to the carrier in the carrier dispersion liquid is 1: 0.05-20; the second reducing agent is one or more of ascorbic acid, sodium citrate, citric acid, glucose, sodium borohydride, hydrazine hydrate and formaldehyde, and the mass ratio of the adding amount of the second reducing agent to the carrier in the carrier dispersion liquid is 1: 0.05-20.
Preferably, the first reducing agent is sodium citrate, and the mass ratio of the addition amount of the first reducing agent to the addition amount of the carrier in the carrier dispersion liquid is 1: 0.5-10; the second reducing agent is ascorbic acid, and the mass ratio of the addition amount of the second reducing agent to the addition amount of the carrier in the carrier dispersion liquid is 1: 0.2-10.
Preferably, the gold precursor is chloroauric acid, and the mass ratio of the addition amount of gold element to the addition amount of the carrier in the carrier dispersion liquid is 0.02-0.1: 1.
Preferably, in the step c, the palladium precursor is one or more selected from chloropalladic acid, sodium chloropalladate, palladium chloride, palladium acetate and palladium acetylacetonate, and the mass ratio of the addition amount of the palladium element to the carrier in the carrier dispersion liquid is 0.01-0.2: 1.
Preferably, the palladium precursor is palladium chloride acid, and the mass ratio of the adding amount of palladium element to the adding amount of the carrier in the carrier dispersion liquid is 0.04-0.12: 1.
The invention also aims to provide the gold-palladium catalyst prepared by the preparation method of the gold-palladium catalyst for hydrogen evolution of dodecahydroethylcarbazole.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) the invention has the advantages of simple preparation method, mild condition, easy operation and low cost, and is particularly suitable for large-scale production.
(2) The invention can improve the supply quantity of active sites, increase the loading capacity of the carrier to metal, improve the pore size distribution, facilitate the uniformity of gold and palladium loading and the hydrogen discharge reaction of dodecahydroethylcarbazole by carrying out targeted pretreatment on the carrier; and when preparing the carrier dispersion liquid, different from a dispersion system using water or oil in a conventional method, distilled water and one of ethylene glycol, propylene glycol or glycerol are mixed according to a certain proportion to prepare a solution, and the particle size distribution of the catalyst is improved by adjusting the polarity of the dispersion liquid.
(3) In the traditional preparation of the catalyst with the core-shell structure, the preparation steps are often complex, the pH value needs to be regulated and controlled in the reduction process of the precursor, a dispersing agent, a surfactant or other functional additives need to be added for assistance, and the particle size of the prepared catalyst is large due to poor metal dispersibility in the reduction process. The gold-palladium catalyst is prepared by a method of adding the precursor and the corresponding reducing agent step by a one-pot method, and the metal precursor is fixed and dispersed by fully utilizing various modified functional groups on the carrier, so that the use of other auxiliary additives is avoided; in the step-by-step reduction, the difference of reduction potentials of gold and palladium is utilized, so that the precursor of palladium can be directionally reduced to form a nuclear shell layer structure on the surface of gold. Therefore, the obtained catalyst has a regular core-shell structure, the particle size of the catalyst is smaller than that of a common core-shell structure catalyst, and the catalyst is uniformly distributed, so that the defects that the traditional preparation method has more steps, and the gold-palladium core-shell structure is difficult to form or irregular to form, large in particle size and non-uniform in distribution under the condition that a dispersing agent, a surfactant and other functional additives are not added are overcome.
(4) The catalyst provided by the invention is used for catalyzing and releasing hydrogen from dodecahydroethylcarbazole, the performance is very excellent, the reaction time is greatly shortened compared with that of the existing catalyst, and the selectivity of the final hydrogen release product ethylcarbazole is greatly improved to more than 99%.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a scanning electron microscope image of a gold palladium catalyst prepared in example 1 of the present invention;
FIG. 2 is a photograph of a transmission electron mirror scan of the gold palladium catalyst prepared in example 2 of the present invention;
FIG. 3 is a transmission electron micrograph of the gold palladium catalyst prepared in example 3 of the present invention.
Detailed Description
The invention provides a gold palladium catalyst for hydrogen evolution of dodecahydroethylcarbazole and a preparation method thereof, and the invention is described in detail with reference to specific examples in order to make the advantages and technical scheme of the invention clearer and clearer.
The raw materials required by the invention can be purchased from commercial sources.
Example 1:
a preparation method of a gold palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole specifically comprises the following steps:
adding 3mol/L nitric acid water solution into untreated carrier activated carbon, and stirring for 1h to mix uniformly. Then condensing and refluxing the solution at 80 ℃ for 1h, filtering, washing a filter cake to pH 6, and drying in vacuum at 60 ℃ for 24h to obtain a treated carrier;
mixing distilled water and ethylene glycol in a volume ratio of 0.3:1 to prepare a solution, adding 1g of treated activated carbon into a beaker, adding 100ml of the mixed solution, stirring for 1 hour, and performing ultrasonic dispersion for 30 minutes to obtain a carrier dispersion liquid;
adding the obtained carrier dispersion liquid into a flask, adding 0.4g of sodium citrate, stirring for 5min, and heating to 80 ℃; then adding 0.02mol/L chloroauric acid solution to ensure that the mass ratio of gold to the activated carbon is 3 wt%, and keeping the temperature to react for 20 min; continuously adding 0.01mol/L chloropalladite solution into the mixed solution to ensure that the mass ratio of palladium to the activated carbon is 3 wt%, and then adding 2mL aqueous solution containing 200mg of ascorbic acid for reaction at 90 ℃ for 100 min; and filtering and collecting the solution after the reaction is finished, washing the solution by using distilled water until no chloride ions are detected, drying the filter cake in vacuum at 80 ℃ for 24 hours, and then ball-milling the dried product to obtain the gold-palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole.
The obtained catalyst is characterized, and a high-resolution transmission electron microscope line scanning photo of the catalyst is shown in figure 1, so that the core-shell structure of the gold-palladium nano particles is excellent in forming, the shell layer only contains one element of palladium, the core layer only contains one element of gold, and the average particle size is about 9 nm.
The hydrogen release performance of dodecahydroethylcarbazole of the obtained catalyst is tested and shown in table 1, after 4 hours of reaction, the selectivity of ethylcarbazole reaches 100%, and the hydrogen release amount reaches 5.79 wt%.
TABLE 1 dodecahydroethylcarbazole dehydrogenation performance test
| Reaction time/hour | Hydrogen evolution volume/wt% | Ethyl carbazole selectivity |
| 0.25 | 3.32 | 10.56％ |
| 0.5 | 4.12 | 23.54％ |
| 0.75 | 4.83 | 51.99％ |
| 1 | 5.06 | 61.99％ |
| 1.5 | 5.37 | 78.26％ |
| 2 | 5.50 | 85.00％ |
| 3 | 5.64 | 92.46％ |
| 4 | 5.79 | 100.00％ |
Example 2:
a preparation method of a gold palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole specifically comprises the following steps:
adding 5mol/L sodium hydroxide aqueous solution into untreated carrier graphite oxide, and stirring for 1h for uniform mixing. Then condensing and refluxing the solution at 60 ℃ for 8h, filtering, washing a filter cake to pH 8.5, and drying in vacuum at 60 ℃ for 24h to obtain a treated carrier;
mixing distilled water and ethylene glycol in a volume ratio of 1:1 to prepare a solution, adding 1g of treated graphite oxide into a beaker, adding 200ml of the mixed solution, stirring for 1 hour, and performing ultrasonic dispersion for 30 minutes to obtain a carrier dispersion liquid;
adding the obtained carrier dispersion liquid into a flask, adding 0.5g of citric acid, stirring for 5min, and heating to 80 ℃; then adding 0.03mol/L sodium chloroaurate solution to enable the mass ratio of gold to graphite oxide to be 5 wt%, and keeping the temperature to react for 40 min; continuously adding 0.05mol/L sodium chloropalladate solution into the mixed solution to ensure that the mass ratio of palladium to graphite oxide is 3 wt%, and then adding 2mL aqueous solution containing 200mg of ascorbic acid to react at 100 ℃ for 180 min; and filtering and collecting the solution after the reaction is finished, washing the solution by using distilled water until no chloride ions are detected, drying the filter cake in vacuum at 80 ℃ for 24 hours, and then ball-milling the dried product to obtain the gold-palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole.
The obtained catalyst is characterized, and a high-resolution transmission electron microscope photo surface scanning photo is shown in figure 2, so that the gold-palladium nanoparticle has a good core-shell structure, an obvious boundary, uniform dispersion and an average particle size of about 10 nm.
The hydrogen release performance of the obtained catalyst is tested, after the reaction is carried out for 3.5 hours, the selectivity of ethyl carbazole reaches 99%, and the hydrogen release amount reaches 5.75 wt%.
Example 3:
adding 1mol/L perchloric acid aqueous solution into untreated carrier activated carbon, and stirring for 1 hour for uniformly mixing. Then condensing and refluxing the solution at 90 ℃ for 2h, filtering, washing a filter cake to pH 5, and drying in vacuum at 60 ℃ for 24h to obtain a treated carrier;
mixing distilled water and glycerol in a volume ratio of 0.5:1 to prepare a solution, adding 1g of treated activated carbon into a beaker, adding 100ml of the mixed solution, stirring for 1 hour, and performing ultrasonic dispersion for 30 minutes to obtain a carrier dispersion liquid;
adding the obtained carrier dispersion liquid into a flask, adding 0.1g of ascorbic acid, stirring for 5min, and heating to 80 ℃; then adding 0.02mol/L potassium chloroaurate solution to enable the mass ratio of gold to the activated carbon to be 4 wt%, and keeping the temperature to react for 10 min; continuously adding 0.015mol/L sodium chloropalladate solution into the mixed solution to ensure that the mass ratio of palladium to the activated carbon is 3 wt%, and then adding 2mL of formaldehyde aqueous solution to react at 100 ℃ for 240 min; and filtering and collecting the solution after the reaction is finished, washing the solution by using distilled water until no chloride ions are detected, drying the filter cake in vacuum at 80 ℃ for 24 hours, and then ball-milling the dried product to obtain the gold-palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole.
The obtained catalyst is characterized, and a high-resolution transmission electron microscope photo of the catalyst is shown in fig. 3, so that the core-shell structure of the gold-palladium nano particles is well formed, the average particle size is about 7nm, and the gold-palladium nano particles are uniformly dispersed.
The hydrogen release performance of the obtained catalyst is tested, after 4 hours of reaction, the selectivity of ethyl carbazole reaches 100%, and the hydrogen release amount reaches 5.79 wt%.
Comparative example 1:
mixing distilled water and glycerol in a volume ratio of 0.5:1 to prepare a solution, adding 1g of untreated carrier activated carbon into a beaker, adding 100mL of the mixed solution, stirring for 1h, and performing ultrasonic dispersion for 30 minutes to obtain a carrier dispersion liquid;
adding the obtained carrier dispersion liquid into a flask, adding 0.1g of ascorbic acid, stirring for 5min, and heating to 80 ℃; then adding 0.02mol/L potassium chloroaurate solution to enable the mass ratio of gold to the activated carbon to be 4 wt%, and keeping the temperature to react for 10 min; continuously adding 0.015mol/L sodium chloropalladate solution into the mixed solution to ensure that the mass ratio of palladium to the activated carbon is 3 wt%, and then adding 2mL of formaldehyde aqueous solution to react at 100 ℃ for 240 min; and filtering and collecting the solution after the reaction is finished, washing the solution by using distilled water until no chloride ions are detected, drying the filter cake in vacuum at 80 ℃ for 24 hours, and then ball-milling the dried product to obtain the gold-palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole.
The hydrogen release performance of the obtained catalyst is tested by the dodecahydroethylcarbazole, the catalyst performance is found to be poor, the selectivity of the ethylcarbazole only reaches 80% after the reaction is carried out for 6 hours, and the performance has a large difference from that of the catalyst in the embodiment 3.
Comparative example 2:
adding 3mol/L nitric acid water solution into untreated carrier activated carbon, and stirring for 1h to mix uniformly. Then condensing and refluxing the solution at 80 ℃ for 1h, filtering, washing a filter cake to pH 6, and drying in vacuum at 60 ℃ for 24h to obtain a treated carrier;
adding 1g of treated activated carbon into a beaker, adding 100ml of distilled water, stirring for 1 hour, and performing ultrasonic dispersion for 30 minutes to obtain a carrier dispersion liquid;
adding the obtained carrier dispersion liquid into a flask, adding 0.4g of sodium citrate, stirring for 5min, and heating to 80 ℃; then adding 0.02mol/L chloroauric acid solution to ensure that the mass ratio of gold to the activated carbon is 3 wt%, and keeping the temperature to react for 20 min; continuously adding 0.01mol/L chloropalladite solution into the mixed solution to ensure that the mass ratio of palladium to the activated carbon is 3 wt%, and then adding 2mL aqueous solution containing 200mg of ascorbic acid for reaction at 90 ℃ for 100 min; and filtering and collecting the solution after the reaction is finished, washing the solution by using distilled water until no chloride ions are detected, drying the filter cake in vacuum at 80 ℃ for 24 hours, and then ball-milling the dried product to obtain the gold-palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole.
The obtained catalyst is characterized, and the high-resolution transmission electron microscope line scanning photo shows that the core-shell structure of the palladium nanoparticle is not well formed, the boundary of the core-shell is not clear, and the average particle size is about 10 nm.
The hydrogen release performance of dodecahydroethylcarbazole of the obtained catalyst is tested, and after the reaction is carried out for 7 hours, the selectivity of ethylcarbazole reaches 100%, and the performance has a certain difference from that of the catalyst in the embodiment 1.
The parts which are not described in the invention can be realized by taking the prior art as reference.
It should be noted that: any equivalents or obvious modifications thereof which may occur to persons skilled in the art and which are given the benefit of this description are deemed to be within the scope of the invention.
Claims (10)
1. A preparation method of a gold palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole is characterized by sequentially comprising the following steps:
a. pretreating the carrier
Adding the carrier treatment solution into an untreated carrier, and uniformly stirring;
condensing and refluxing the uniformly stirred solution at 60-100 ℃ for 1-12 h, filtering, washing the obtained filter cake with water until the pH value is 4-9, and drying for a period of time to obtain a treated carrier;
b. preparation of Carrier Dispersion
B, adding the mixed solution into the carrier pretreated in the step a, stirring and then performing ultrasonic dispersion to obtain carrier dispersion liquid;
c. preparation of gold Palladium catalyst
Adding a first reducing agent into the carrier dispersion liquid, stirring, and heating to 80-100 ℃ to obtain a first solution;
adding a gold precursor into the first solution, and reacting at the temperature of 80-100 ℃ for a period of time to obtain a second solution;
adding a palladium precursor into the second solution, adding a second reducing agent, and reacting at the temperature of 50-100 ℃ for a period of time to obtain a third solution;
and carrying out post-treatment on the solution III, collecting a filter cake, drying the filter cake, and carrying out ball milling to obtain the gold-palladium catalyst.
2. The method for preparing a gold palladium catalyst for hydrogen evolution from dodecahydroethylcarbazole according to claim 1, wherein the gold palladium catalyst comprises: in the step a, the carrier treatment solution is 0.2-6 mol/L nitric acid aqueous solution, 0.2-6 mol/L sulfuric acid aqueous solution, 0.02-3 mol/L perchloric acid aqueous solution, 0.05-10 mol/L sodium hydroxide aqueous solution or 0.05-10 mol/L potassium hydroxide aqueous solution; in the step a, vacuum drying is carried out for 24 hours at the temperature of 50-70 ℃ to obtain a treated carrier; the carrier is graphite oxide or active carbon.
3. The method for preparing a gold palladium catalyst for hydrogen evolution from dodecahydroethylcarbazole according to claim 1, wherein the gold palladium catalyst comprises: in the step b, the mixed solution is prepared by mixing distilled water and a solvent according to a volume ratio of 0.1-1: 1, the solvent is glycol, propylene glycol or glycerol; the mass-volume ratio of the pretreated carrier to the mixed solution is 1: 50-300 g/mL, stirring is carried out for 0.5-1.5 h, and ultrasonic dispersion is carried out for 20-40 min.
4. The method for preparing a gold palladium catalyst for hydrogen evolution from dodecahydroethylcarbazole according to claim 1, wherein the gold palladium catalyst comprises: and c, adding a gold precursor, and reacting at the temperature of 80-100 ℃ for 3-60 min, wherein the gold precursor is selected from one or more of chloroauric acid, sodium chloroaurate and potassium chloroaurate, and the mass ratio of the addition amount of the gold element to the carrier in the carrier dispersion liquid is 0.01-0.2: 1.
5. The method for preparing a gold palladium catalyst for hydrogen evolution from dodecahydroethylcarbazole according to claim 1, wherein the gold palladium catalyst comprises: in the step c, the first reducing agent is one or more of sodium citrate, ascorbic acid, citric acid and glucose, and the mass ratio of the addition amount of the first reducing agent to the carrier in the carrier dispersion liquid is 1: 0.05-20; the second reducing agent is one or more of ascorbic acid, sodium citrate, citric acid, glucose, sodium borohydride, hydrazine hydrate and formaldehyde, and the mass ratio of the adding amount of the second reducing agent to the carrier in the carrier dispersion liquid is 1: 0.05-20.
6. The method for preparing a gold palladium catalyst for hydrogen evolution from dodecahydroethylcarbazole according to claim 5, wherein the gold palladium catalyst comprises: the first reducing agent is sodium citrate, and the mass ratio of the addition amount of the first reducing agent to the addition amount of the carrier in the carrier dispersion liquid is 1: 0.5-10; the second reducing agent is ascorbic acid, and the mass ratio of the addition amount of the second reducing agent to the addition amount of the carrier in the carrier dispersion liquid is 1: 0.2-10.
7. The method for preparing the gold palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole according to claim 4, wherein the gold palladium catalyst comprises: the gold precursor is chloroauric acid, and the mass ratio of the addition amount of gold element to the addition amount of carrier in the carrier dispersion liquid is 0.02-0.1: 1.
8. The method for preparing a gold palladium catalyst for hydrogen evolution from dodecahydroethylcarbazole according to claim 1, wherein the gold palladium catalyst comprises: in the step c, the palladium precursor is one or more of chloropalladic acid, sodium chloropalladate, palladium chloride, palladium acetate and palladium acetylacetonate, and the mass ratio of the addition amount of the palladium element to the carrier in the carrier dispersion liquid is 0.01-0.2: 1.
9. The method for preparing a gold palladium catalyst for hydrogen evolution from dodecahydroethylcarbazole according to claim 8, wherein the gold palladium catalyst comprises: the palladium precursor is selected from palladium chloride acid, and the mass ratio of the addition amount of palladium element to the addition amount of the carrier in the carrier dispersion liquid is 0.04-0.12: 1.
10. The gold-palladium catalyst prepared by the preparation method of the gold-palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole according to any one of claims 1 to 9.
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