CN108452821A - The application of Pd/ crystal type carbonitride heterojunction photocatalysts and preparation method and photocatalysis Liv Ullmann coupling reaction - Google Patents
The application of Pd/ crystal type carbonitride heterojunction photocatalysts and preparation method and photocatalysis Liv Ullmann coupling reaction Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 63
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000007146 photocatalysis Methods 0.000 title abstract description 7
- 230000001699 photocatalysis Effects 0.000 title abstract description 7
- 238000006887 Ullmann reaction Methods 0.000 title abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 104
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000005859 coupling reaction Methods 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 14
- -1 halogenated aryl hydrocarbon Chemical class 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 239000004305 biphenyl Substances 0.000 claims abstract description 7
- 239000001103 potassium chloride Substances 0.000 claims abstract description 6
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000008878 coupling Effects 0.000 claims description 10
- 238000010168 coupling process Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- 238000002474 experimental method Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
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- 230000000694 effects Effects 0.000 description 3
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- CDKCEZNPAYWORX-UHFFFAOYSA-N 1-tert-butyl-4-(4-tert-butylphenyl)benzene Chemical group C1=CC(C(C)(C)C)=CC=C1C1=CC=C(C(C)(C)C)C=C1 CDKCEZNPAYWORX-UHFFFAOYSA-N 0.000 description 2
- YRNWIFYIFSBPAU-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]-n,n-dimethylaniline Chemical class C1=CC(N(C)C)=CC=C1C1=CC=C(N(C)C)C=C1 YRNWIFYIFSBPAU-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
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- 125000004429 atom Chemical group 0.000 description 2
- 150000001555 benzenes Chemical group 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
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- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- QBELEDRHMPMKHP-UHFFFAOYSA-N 1-bromo-2-chlorobenzene Chemical compound ClC1=CC=CC=C1Br QBELEDRHMPMKHP-UHFFFAOYSA-N 0.000 description 1
- WJIFKOVZNJTSGO-UHFFFAOYSA-N 1-bromo-3-methylbenzene Chemical compound CC1=CC=CC(Br)=C1 WJIFKOVZNJTSGO-UHFFFAOYSA-N 0.000 description 1
- XHCAGOVGSDHHNP-UHFFFAOYSA-N 1-bromo-4-tert-butylbenzene Chemical class CC(C)(C)C1=CC=C(Br)C=C1 XHCAGOVGSDHHNP-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical class COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- HQSCPPCMBMFJJN-UHFFFAOYSA-N 4-bromobenzonitrile Chemical compound BrC1=CC=C(C#N)C=C1 HQSCPPCMBMFJJN-UHFFFAOYSA-N 0.000 description 1
- 229910019131 CoBr2 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/39—Photocatalytic properties
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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
- B01J35/396—Distribution of the active metal ingredient
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/80—Preparation of compounds containing amino groups bound to a carbon skeleton by photochemical reactions; by using free radicals
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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Abstract
The invention discloses the applications of a kind of Pd/ crystal types carbonitride heterojunction photocatalyst and preparation method and photocatalysis Liv Ullmann coupling reaction, the catalyst is using crystal type carbonitride as carrier, uniform load grain size is the Pd nano-particles of 3~7nm, it is in terms of 100% by the quality of catalyst, the load capacity of Pd is 1%~10%.The present invention prepares g C first with melamine thermal polycondensation3N4Nanometer sheet is then calcined to obtain crystal azotized carbon nano band with potassium chloride, anhydrous lithium chloride, then is reacted in enclosed system with palladium, methanol, and Pd/ crystal type carbonitride heterojunction photocatalysts are obtained.For being catalyzed halogenated aryl hydrocarbon Ullmann C C coupling reactions synthesis biphenyl compound occurs for Pd/ crystal types carbonitride heterojunction photocatalyst of the present invention, and catalytic activity and stability are high, reaction condition is mild, the time is short, product yield high.
Description
Technical field
The invention belongs to Liv Ullmann (Ullmann C-C) coupling reaction technical fields, and in particular to a kind of Pd/ crystal types nitrogen
The preparation method and the catalyst for changing carbon heterojunction photocatalyst and the catalyst are being catalyzed Ullmann C-C coupling reactions
In application.
Background technology
The formation and fracture of C-C and C-X (X N, O, S hetero atom) key are highly important organic synthesis processes.From 1901
Year Liv Ullmann (Ullmann) et al. finds that two molecule halogenated aryl hydrocarbons can pass through carbon-to-carbon coupling and generate biphenyl compound, and thus
Since this kind of reaction is named as Ullmann coupling reactions, the reactions such as associated C-C couplings, C-N couplings and C-O couplings
As classical one of organic synthesis approach, it is widely used for the changes such as fuel, drug and liquid crystal, semiconductor and organic conductor
Close the synthesis of object.Simultaneously from reaction condition, the research of Ullmann coupling reactions also makes great progress, by initial
Monometallic catalysis develops to bimetallic catalytic；Recyclable multiphase is developed to by not re-usable homogeneous catalysis system
Catalyst system and catalyzing；It is gradually dropped to close to room temperature by initial 200 DEG C or more of reaction temperature；From being initially required tens small the reaction times
Foreshortening to only needs a few houres can be completed.But it is overall to see, Ullmann couplings are there are still high cost, high energy consumption, environment are unfriendly,
Reaction is slow and multiple problems such as substrate applicability difference, green, environmental-friendly, the clean and atom advocated with modern organic chemistry
There are gaps for cost-effectiveness requirement.Therefore, Ullmann C-C coupling reactions are significantly improved space, low temperature, low cost and efficiently
The exploration of rate green approach is current catalytic science and one of the research topic that Synthetic Organic Chemistry faces.
Transition metal or its loaded catalyst is commonly used in Ullmann C-C coupling reactions.Dependent on catalysis
The state of agent, it is main using homogeneous and two kinds of reactive modes of multiphase.Homogeneous catalysis system mainly uses the metals such as Pd, Fe, Co and Ni
Organic compound, such as Pd (dppf) Cl2、Fe(acac)3、CoBr2PPh3Deng being used as catalyst, it is high (general that there are reaction temperatures
At 50~200 DEG C), unstable, toxic, the difficult separation of catalyst and the shortcomings of cannot reuse.Heterogeneous catalytic system is led at present
To use the metal nanoparticles such as Cu, Pd, Au and Rh as catalyst, exist need certain activation temperature, activity relatively low and
The problems such as use cost is high.It is well known that photochemistry and photocatalysis technology can utilize, sunlight, easy to operate, low energy consumption, reaction
Mild condition, it is considered to be a kind of very important green oxidation reduction technique is gradually extended in recent years
Organic synthesis field shows good development prospect.It, especially can using luminous energy if efficient photochemical catalyst can be selected
Light-exposed to realize Ullmann C-C couplings at room temperature, that will be to substitute conventional method to open up a new reaction path of green.
Graphite phase carbon nitride (g-C3N4) it is a kind of semi-conducting material with layer structure, g-C3N4Band gap be
2.7eV, can be by excited by visible light, and conduction band and valence band potential are respectively -1.3V and+1.4V, are used as semiconductor base materials, tool
There is the advantages of nontoxic, cheap and easy to get, visible light-responded and stable structure etc. meets environmentally protective and sustainable development.From three
The large volume nitrogen carbon polymer of the richness nitrogen precursor polymerization such as poly cyanamid, dicyandiamide and cyanamide and acquisition, since Van der Waals force is in C-N
The effect of intensive π-π stackings, makes it show relatively low surface area, limited active site and quick charge between layer
Recombination rate, these can limit application of the nitrogen carbon polymer in fields such as photocatalysis.In view of the above problems, reporting at present
A variety of method of modifying are used to widen the light abstraction width of carbonitride and improve light induced electron and hole having in material bodies phase
Effect separation and migration, including co-catalyst load, semiconductors coupling, element doping, Morphological control (structure defect and structural disorder
Change) etc..
Invention content
Technical problem to be solved by the present invention lies in a kind of Pd/ crystal types carbonitride heterojunction photocatalysts of offer, and
A kind of preparation method and purposes are provided for the catalyst.
It is using crystal type carbonitride as carrier to solve catalyst used by above-mentioned technical problem, and uniform load grain size is 3
The Pd nano-particles of~7nm are in terms of 100% by the quality of catalyst, and the load capacity of Pd is 1%~10%, the preferably load of Pd
Amount is 5%~6%.
The preparation method of above-mentioned Pd/ crystal types carbonitride heterojunction photocatalyst is made of following step：
1, g-C is prepared3N4Nanometer sheet
By melamine at 550 DEG C thermal polycondensation 4 hours, obtain g-C3N4Nanometer sheet.
2, crystal azotized carbon nano band is prepared
By g-C3N4The mixture of nanometer sheet, potassium chloride and anhydrous lithium chloride is calcined 4 hours for 450 DEG C in argon gas atmosphere, from
It is so cooled to room temperature, is cleaned with deionized water and ethyl alcohol, be dried in vacuo, obtain crystal azotized carbon nano band.
3, Pd/ crystal type carbonitride heterojunction photocatalysts are prepared
It is in terms of 100% by the quality of catalyst, is 1%~10% according to the load capacity of Pd, by crystal azotized carbon nano band
It is dispersed in methanol, and palladium methanol solution is added, in the enclosed system of inert gas shielding, 30~70 DEG C of stirrings
Reaction 12~24 hours, removes methanol, and vacuum drying obtains Pd/ crystal type carbonitride heterojunction photocatalysts.
In above-mentioned steps 2, the g-C3N4Nanometer sheet, potassium chloride, anhydrous lithium chloride mass ratio be 1:5.5:4.5.
Purposes of the Pd/ crystal types carbonitride heterojunction photocatalyst of the present invention in being catalyzed Ullmann C-C coupling reactions,
Application method is：By halogenated aryl hydrocarbon and alkali in molar ratio 1:2~3 are added in organic solvent, and it is different that Pd/ crystal type carbonitrides are added
Matter knot photochemical catalyst, normal-temperature reaction 2~10 hours, obtain biphenyl compound under light illumination.
In above-mentioned catalysis Ullmann C-C coupling reactions, Pd/ crystal type carbonitride heterojunction photocatalysts press every mM
Amount is that 20~30mg is added in halogenated aryl hydrocarbon.
Above-mentioned halogenated aryl hydrocarbon is halogeno-benzene, C1~C4Alkyl-substituted halogeno-benzene, C1~C4Alkoxy replaces halogenated
Benzene, cyano substitution halogeno-benzene, N, N- dimethyl substitution halogeno-benzene in any one.
Above-mentioned alkali is potassium carbonate or sodium carbonate.
Above-mentioned organic solvent is ethyl alcohol, methanol or isopropanol.
In above-mentioned catalysis Ullmann C-C coupling reactions, the light is the visible light of λ >=420nm.
Beneficial effects of the present invention are as follows：
1, the present invention is prepared for Pd/ crystal types carbonitride (Pd/CN-C) heterojunction photocatalysis in very mild conditions
Agent, surface carries negative electrical charge due to the presence of unsaturated nitrogen atom, and has larger specific surface area.When crystal type nitrogenizes
When carbon (CN-C) is mixed with palladium methanol solution, Pd2+Ion is more likely to be combined with undersaturated nitrogen-atoms, to Pd nanometers
Nucleation evenly dispersed under the reducing conditions and growth are finally deposited on the surfaces CN-C by particle, realize that small particles nano Pd particle is equal
It is even to be supported on the surfaces CN-C.
2, the present invention is using ethyl alcohol as reaction dissolvent, by halogenated aryl hydrocarbon and alkali in Pd/ crystal type carbonitride heterojunction photocatalysis
Under the catalytic action of agent, illumination reaction can be obtained biphenyl compound.The reaction system is green, environmental-friendly, reaction condition
Mildly, the reaction time is short, and Atom economy is high, and target product post-processing is simple and yield is high, and repeatability and stability are good.This is anti-
Products therefrom is answered to have a good application prospect in the preparation of the compounds such as fuel, drug, liquid crystal, semiconductor and organic conductor
Very big potentiality.
Description of the drawings
Fig. 1 is Pd/ crystal type carbonitride heterojunction photocatalysts prepared by embodiment 1 and Pd/g- prepared by comparative example 1
C3N4The XRD comparison diagrams of photochemical catalyst.
Fig. 2 is the SEM figures of Pd/ crystal type carbonitride heterojunction photocatalysts prepared by embodiment 1.
Fig. 3 is the TEM light field figures of Pd/ crystal type carbonitride heterojunction photocatalysts prepared by embodiment 1.
Fig. 4 is the TEM dark field plots of Pd/ crystal type carbonitride heterojunction photocatalysts prepared by embodiment 1.
Fig. 5 is the TEM potassium element analysis charts of Pd/ crystal type carbonitride heterojunction photocatalysts prepared by embodiment 1.
Fig. 6 is the TEM carbon analysis charts of Pd/ crystal type carbonitride heterojunction photocatalysts prepared by embodiment 1.
Fig. 7 is the TEM nitrogen analysis charts of Pd/ crystal type carbonitride heterojunction photocatalysts prepared by embodiment 1.
Fig. 8 is the TEM palladium elemental analysis figures of Pd/ crystal type carbonitride heterojunction photocatalysts prepared by embodiment 1.
Fig. 9 is the recycling figure of Pd/ crystal type carbonitride heterojunction photocatalysts prepared by embodiment 1.
Specific implementation mode
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1, g-C is prepared3N4Nanometer sheet
3g melamines are placed in a crucible with cover, are placed it in Muffle furnace, with the heating rate of 5 DEG C/min
550 DEG C are warming up to, and keeps the temperature 4 hours, obtains 600mg g-C3N4Nanometer sheet.
2, crystal azotized carbon nano band is prepared
By 600mg g-C3N4Nanometer sheet, 3.3g potassium chloride and 2.7g anhydrous lithium chloride ground and mixeds it is uniform after be put into porcelain boat
In, it is calcined 4 hours for 450 DEG C in argon gas atmosphere, cooled to room temperature is cleaned with deionized water and ethyl alcohol, and 60 DEG C of vacuum are dry
Dry 12 hours, obtain crystal azotized carbon nano band.
3, Pd/ crystal type carbonitride heterojunction photocatalysts are prepared
It is in terms of 100% by the quality of catalyst, the load capacity according to Pd is 6%, and 300mg crystal azotized carbon nano bands is equal
It is even to be scattered in 40mL methanol, and 40mL 0.0042mol/L palladium methanol solutions are added, in the enclosed system of argon gas protection
In, 30 DEG C are stirred to react 24 hours, and rotary evaporation removes methanol after having reacted, and 60 DEG C are dried in vacuo 12 hours, obtain Pd/ crystallizations
Type carbonitride heterojunction photocatalyst (is denoted as Pd6/CN-C)。
Comparative example 1
It is in terms of 100% by the quality of catalyst, is 6% according to the load capacity of Pd, by 300mg g-C3N4Nanometer sheet is scattered in
In 40mL methanol, and 40mL 0.0042mol/L palladium methanol solutions are added, in the enclosed system of argon gas protection, 30 DEG C are stirred
Reaction 24 hours is mixed, rotary evaporation removes methanol after having reacted, and 60 DEG C are dried in vacuo 12 hours, obtain Pd/g-C3N4Photochemical catalyst
(it is denoted as Pd6/g-C3N4)。
Inventor is using x-ray diffractometer, Flied emission transmission electron microscope and cold field emission scanning electron microscope respectively to embodiment 1
The photochemical catalyst prepared with comparative example 1 is characterized, the result is shown in Figure 1~8.As seen from Figure 1, the Pd that prepared by embodiment 16/CN-C
Photochemical catalyst does not have a Pd peak positions, and Pd prepared by comparative example 16/g-C3N4Photochemical catalyst has apparent Pd peak positions, illustrates Pd particles
It is larger；By Fig. 2~8 as it can be seen that the uniform load on crystal carbonitride for preparing in product of embodiment 1 has a Pd nano particles, Pd nanometers
Particle size is about 2~5nm.The characterization result of complex chart 1~8, it was demonstrated that Pd in the form of nano particle uniform load in CN-C
Surface.
Embodiment 2
In the present embodiment, it is in terms of 100% by the quality of catalyst, is 1% according to the load capacity of Pd, by 300mg crystal nitrogen
Change carbon nanobelts to be dispersed in 40mL methanol, and 40mL 0.0007mol/L palladium methanol solutions, other steps are added
It is same as Example 1, it obtains Pd/ crystal type carbonitride heterojunction photocatalysts and (is denoted as Pd1/CN-C)。
Embodiment 3
In the present embodiment, it is in terms of 100% by the quality of catalyst, is 3% according to the load capacity of Pd, by 300mg crystal nitrogen
Change carbon nanobelts to be dispersed in 40mL methanol, and 40mL 0.0021mol/L palladium methanol solutions, other steps are added
It is same as Example 1, it obtains Pd/ crystal type carbonitride heterojunction photocatalysts and (is denoted as Pd3/CN-C)。
Embodiment 4
In the present embodiment, it is in terms of 100% by the quality of catalyst, is 8% according to the load capacity of Pd, by 300mg crystal nitrogen
Change carbon nanobelts to be dispersed in 40mL methanol, and 40mL 0.0056mol/L palladium methanol solutions, other steps are added
It is same as Example 1, it obtains Pd/ crystal type carbonitride heterojunction photocatalysts and (is denoted as Pd8/CN-C)。
Embodiment 5
In the present embodiment, it is in terms of 100% by the quality of catalyst, is 10% according to the load capacity of Pd, by 300mg crystal nitrogen
Change carbon nanobelts to be dispersed in 40mL methanol, and 40mL 0.0060mol/L palladium methanol solutions, other steps are added
It is same as Example 1, it obtains Pd/ crystal type carbonitride heterojunction photocatalysts and (is denoted as Pd10/CN-C)。
Embodiment 6
Purposes of the Pd/ crystal type carbonitride heterojunction photocatalysts in being catalyzed Ullmann C-C coupling reactions
1,4,4'- dimethyl diphenyls are prepared
0.0691g (0.5mmol) potassium carbonate, 5mg photochemical catalysts, 34.4mg are added into 10mL Shrek pipes
(0.2mmol) parabromotoluene and 3mL ethyl alcohol are vigorously stirred and deaerate 15 minutes under argon gas to remove air.By the effective envelope
Membrana oralis seals, and keeps inertia closed atmosphere, and reaction 5 hours is carried out under the irradiation of 300W xenon lamps, and (PLS-SXE300UV moors luxuriant and rich with fragrance Lay, λ
>=420nm edge filters are used for the irradiation of visible light, light intensity 710mW/cm2), reaction temperature is maintained at 30 DEG C.It has reacted
After be separated by filtration solid catalyst, product 4,4'- dimethyl diphenyls are quantitative (Agilent 7890A) by gas-chromatography, as a result see
Table 1.
Table 1
| Catalyst | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Yield | 7% | 94% | 51% | 65% | 81% | 83% |
Cyclical stability experiment is carried out to the photochemical catalyst of embodiment 1 according to the method described above, as a result sees Fig. 9.As seen from the figure,
The repeatability and stability of catalyst of the present invention are good, recycle 9 times, the yield of 4,4'- dimethyl diphenyls does not occur obviously to become
Change.
The spectral data of product is as follows：
1H NMR(400MHz,CDCl3) δ 7.47 (d, J=7.8Hz, 4H), 7.23 (d, J=7.6Hz, 4H), 2.39 (d, J
=6.7Hz, 6H)
13C NMR(101MHz,CDCl3)δ138.31,136.72,129.46,126.84,21.11.
2, biphenyl is prepared
Using the catalyst of embodiment 1, the parabromotoluene in experiment 1 is replaced with the bromobenzene of equimolar amounts, other steps with
It tests 1 identical, obtains biphenyl, the spectral data of yield 92%, product is as follows：
1H NMR(400MHz,CDCl3) δ 7.63 (d, J=7.5Hz, 2H), 7.48 (t, J=7.4Hz, 2H), 7.38 (t, J
=7.1Hz, 1H)
13C NMR(151MHz,CDCl3)δ141.30,128.82,127.31,127.23.
3,4,4'- dicyanobiphenyls are prepared
Using the catalyst of embodiment 1, the parabromotoluene in experiment 1 is replaced with the bromo- 4- cyano benzene of the 1- of equimolar amounts,
Its step is identical as experiment 1, obtains 4,4'- dicyanobiphenyls, the spectral data of yield 95%, product is as follows：
1H NMR(400MHz,CDCl3) δ 7.78 (d, J=7.6Hz, 4H), 7.69 (d, J=7.8Hz, 4H)
13C NMR(101MHz,CDCl3)δ143.53,132.92,127.97,118.48,112.41.
4,4,4'- dichlorobenzenes are prepared
Using the catalyst of embodiment 1, the parabromotoluene in experiment 1, Qi Tabu are replaced with the para chlorobromobenzene of equimolar amounts
Suddenly identical as experiment 1,4,4'- dichlorobenzenes are obtained, the spectral data of yield 70%, product is as follows：
1H NMR(400MHz,CDCl3) δ 7.48 (d, J=8.4Hz, 4H), 7.41 (d, J=8.4Hz, 4H)
13C NMR(101MHz,CDCl3)δ138.36,133.71,129.00,128.16.
5,4,4'- diethyl biphenyls are prepared
Using the catalyst of embodiment 1, the parabromotoluene in experiment 1 is replaced with the bromo- 4- ethylo benzenes of the 1- of equimolar amounts,
Its step is identical as experiment 1, obtains 4,4'- diethyl biphenyls, the spectral data of yield 96%, product is as follows：
1H NMR(600MHz,CDCl3) δ 7.51 (s, 4H), 7.26 (d, J=4.7Hz, 4H), 2.69 (s, 4H), 1.27 (s,
6H).
13C NMR(101MHz,CDCl3)δ143.08,138.59,128.25,126.95,28.53,15.62.
6,4,4'- di-t-butyl biphenyl is prepared
Using the catalyst of embodiment 1, the parabromotoluene in experiment 1 is replaced with the bromo- 4- tert-butyl benzenes of the 1- of equimolar amounts,
Reaction time extends to 10 hours, other steps and experiment are 1 identical, obtains 4,4'- di-t-butyl biphenyl, yield 98%,
The spectral data of product is as follows：
1H NMR(400MHz,CDCl3) (d, J=7.2Hz, the 18H) of δ 7.57 (s, 4H), 7.49 (s, 4H), 1.40
13C NMR(101MHz,CDCl3)δ149.93,138.25,126.73,125.70,34.56,31.45.
7,4,4'- dimethoxy-biphenyls are prepared
Using the catalyst of embodiment 1, the parabromotoluene in experiment 1 is replaced with the bromo- 4- methoxybenzenes of the 1- of equimolar amounts,
Other steps are identical as experiment 1, obtain 4,4'- dimethoxy-biphenyls, the spectral data of yield 90%, product is as follows：
1H NMR(400MHz,CDCl3) δ 7.48 (d, J=7.8Hz, 4H), 6.96 (d, J=7.8Hz, 4H), 3.85 (s,
6H).
13C NMR(101MHz,CDCl3)δ158.67,133.47,127.76,114.15,55.37.
8, N, N, N', N'- tetramethyl benzidines are prepared
Using the catalyst of embodiment 1, with the N of equimolar amounts, N- dimethyl bromobenzenes replace the parabromotoluene in experiment 1,
Other steps are identical as experiment 1, obtain N, N, N', N'- tetramethyl benzidines, yield 70%, the spectral data of product is such as
Under：
1H NMR(400MHz,CDCl3) δ 7.46 (d, J=8.0Hz, 4H), 6.80 (d, J=8.0Hz, 4H), 2.97 (s,
12H).
13C NMR(101MHz,CDCl3)δ149.28,129.83,127.01,113.09,40.84.
9,3,3'- dimethyl diphenyls are prepared
Using the catalyst of embodiment 1, the parabromotoluene in experiment 1, Qi Tabu are replaced with the m-bromotoluene of equimolar amounts
Suddenly identical as experiment 1,3,3'- dimethyl diphenyls are obtained, the spectral data of yield 86%, product is as follows：
1H NMR(600MHz,CDCl3) δ 7.47-7.42 (m, 4H), 7.37 (t, J=7.6Hz, 2H), 7.21 (d, J=
7.5Hz,2H),2.47(s,6H).
13C NMR(151MHz,CDCl3)δ141.41,138.31,128.67,128.04,127.97,124.35,21.61.
10,4,4'- DfBPs are prepared
Using the catalyst of embodiment 1, the parabromotoluene in experiment 1, Qi Tabu are replaced with the fluorobromobenzene of equimolar amounts
Suddenly identical as experiment 1,4,4'- DfBPs are obtained, the spectral data of yield 60%, product is as follows：
1H NMR(400MHz,CDCl3) δ 7.49 (dd, J=8.2,5.5Hz, 4H), 7.13 (t, J=8.6Hz, 4H)
13C NMR(101MHz,CDCl3)δ163.67,161.22,136.42,136.39,128.63,128.54,
115.80,115.59。
Claims (10)
1. a kind of Pd/ crystal types carbonitride heterojunction photocatalyst, it is characterised in that：The catalyst is to be with crystal type carbonitride
Carrier, uniform load grain size are the Pd nano-particles of 3~7nm, are in terms of 100% by the quality of catalyst, the load capacity of Pd is 1%
~10%.
2. Pd/ crystal types carbonitride heterojunction photocatalyst according to claim 1, it is characterised in that：With catalyst
Quality is 100% meter, and the load capacity of Pd is 5%~6%.
3. the preparation method of Pd/ crystal types carbonitride heterojunction photocatalyst described in claim 1, it is characterised in that this method
It is made of following step：
(1) g-C is prepared3N4Nanometer sheet
By melamine at 550 DEG C thermal polycondensation 4 hours, obtain g-C3N4Nanometer sheet；
(2) crystal azotized carbon nano band is prepared
By g-C3N4The mixture of nanometer sheet, potassium chloride and anhydrous lithium chloride is calcined 4 hours for 450 DEG C in argon gas atmosphere, naturally cold
But it to room temperature, is cleaned with deionized water and ethyl alcohol, is dried in vacuo, obtains crystal azotized carbon nano band；
(3) Pd/ crystal type carbonitride heterojunction photocatalysts are prepared
It is in terms of 100% by the quality of catalyst, the load capacity according to Pd is 1%~10%, and crystal azotized carbon nano band is uniform
It is scattered in methanol, and palladium methanol solution is added, in the enclosed system of inert gas shielding, 30~70 DEG C are stirred to react
12~24 hours, methanol is removed, vacuum drying obtains Pd/ crystal type carbonitride heterojunction photocatalysts.
4. the preparation method of Pd/ crystal types carbonitride heterojunction photocatalyst according to claim 3, it is characterised in that：
The g-C3N4Nanometer sheet, potassium chloride, anhydrous lithium chloride mass ratio be 1:5.5:4.5.
5. Pd/ crystal types carbonitride heterojunction photocatalyst described in claim 1 is in being catalyzed Ullmann C-C coupling reactions
Purposes, application method is：By halogenated aryl hydrocarbon and alkali in molar ratio 1:2~3 are added in organic solvent, and Pd/ crystal types are added
Carbonitride heterojunction photocatalyst, normal-temperature reaction 2~10 hours, obtain biphenyl compound under light illumination.
6. Pd/ crystal types carbonitride heterojunction photocatalyst according to claim 5 is anti-in catalysis Ullmann C-C couplings
Purposes in answering, it is characterised in that：The Pd/ crystal types carbonitride heterojunction photocatalyst is halogenated aryl hydrocarbon by every mM of amount
20~30mg is added.
7. Pd/ crystal types carbonitride heterojunction photocatalyst according to claim 5 or 6 is even in catalysis Ullmann C-C
Purposes in connection reaction, it is characterised in that：The halogenated aryl hydrocarbon is halogeno-benzene, C1~C4Alkyl-substituted halogeno-benzene, C1~C4
Alkoxy substitution halogeno-benzene, cyano substitution halogeno-benzene, N, N- dimethyl substitution halogeno-benzene in any one.
8. Pd/ crystal types carbonitride heterojunction photocatalyst according to claim 5 is anti-in catalysis Ullmann C-C couplings
Purposes in answering, it is characterised in that：The alkali is potassium carbonate or sodium carbonate.
9. Pd/ crystal types carbonitride heterojunction photocatalyst according to claim 5 is anti-in catalysis Ullmann C-C couplings
Purposes in answering, it is characterised in that：The light is the visible light of λ >=420nm.
10. Pd/ crystal types carbonitride heterojunction photocatalyst according to claim 5 is in catalysis Ullmann C-C couplings
Purposes in reaction, it is characterised in that：The organic solvent is ethyl alcohol, methanol or isopropanol.
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