CN109046328A - A kind of photo-thermal catalytic hydrogenation catalyst and its preparation and the application in 3,4- dichloronitrobenzene selective hydrogenation - Google Patents
A kind of photo-thermal catalytic hydrogenation catalyst and its preparation and the application in 3,4- dichloronitrobenzene selective hydrogenation Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 61
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 48
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 60
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 28
- 239000002096 quantum dot Substances 0.000 claims abstract description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 239000004005 microsphere Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 74
- 238000003756 stirring Methods 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000008367 deionised water Substances 0.000 claims description 55
- 229910021641 deionized water Inorganic materials 0.000 claims description 55
- 239000001257 hydrogen Substances 0.000 claims description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims description 55
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000012298 atmosphere Substances 0.000 claims description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims description 36
- 210000002966 serum Anatomy 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 34
- SDYWXFYBZPNOFX-UHFFFAOYSA-N 3,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C(Cl)=C1 SDYWXFYBZPNOFX-UHFFFAOYSA-N 0.000 claims description 32
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 22
- 239000000908 ammonium hydroxide Substances 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 21
- 150000002431 hydrogen Chemical class 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 230000005855 radiation Effects 0.000 claims description 19
- 238000006073 displacement reaction Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical class NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 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 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 claims 1
- 239000007787 solid Substances 0.000 description 47
- 230000035484 reaction time Effects 0.000 description 31
- 238000001035 drying Methods 0.000 description 30
- 239000000843 powder Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 24
- 238000001914 filtration Methods 0.000 description 17
- 208000012839 conversion disease Diseases 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 238000005303 weighing Methods 0.000 description 15
- 239000012453 solvate Substances 0.000 description 10
- 238000006298 dechlorination reaction Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- VNWKTOKETHGBQD-YPZZEJLDSA-N carbane Chemical compound [10CH4] VNWKTOKETHGBQD-YPZZEJLDSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease 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
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain 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
- 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
- B01J23/42—Platinum
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a kind of photo-thermal catalytic hydrogenation catalyst and its preparations and the application in 3,4- dichloronitrobenzene selective hydrogenation.The photo-thermal catalytic hydrogenation catalyst, it is microsphere supported by mesoporous carbon and be supported on the carbon quantum dot of carrier surface and metal quantum point forms, catalyst size is between 50~100nm, the particle size range of the carbon quantum dot is between 4.5~6.5nm, the metal quantum point is the combination of one or both of palladium quantum dot and platinum quantum dot, and the particle size range of metal quantum point is between 10~15nm；In the catalyst, the mass fraction of carbon quantum dot and metal quantum point is respectively 10~30% and 1~2%.The present invention provides the photo-thermal catalytic hydrogenation catalysts 3, the selective catalytic hydrogenation synthesis 3 under 280~350nm ultraviolet light of 4- dichloronitrobenzene, application in the reaction of 4- dichloro- aniline has the characteristics that high conversion rate, selectivity is good, hydrogenation reaction rate is fast, stability is good.
Description
(1) technical field
The present invention relates to a kind of photo-thermal catalytic hydrogenation catalyst and its preparations and application, and in particular to catalyst is urged in photo-thermal
Change the application in 3,4- dichloronitrobenzene selective hydrogenation.
(2) technical background
3,4-DCA is a kind of important medicine, pesticide, dyestuff and daily-use chemical industry organic intermediate, is widely used in
The synthesis of herbicide and azo dyes.3,4- bis- is usually passed through by iron powder reducing method, sodium sulfide reducing method, catalytic hydrogenating reduction method
Chloronitrobenzene reduction preparation 3,4- dichloroaniline.Since iron powder reducing method can generate a large amount of metallic residue, sodium sulfide reducing method
Hydrochloric organic wastewater can be generated, serious destruction is caused to environment, so being gradually eliminated.The operation of catalytic hydrogenating reduction method
Process is simple, environmental-friendly, more by the concern of researcher.But catalytic hydrogenating reduction method is there are the process of hydrogenolysis dechlorination how
Effectively dechlorination is inhibited to have been a concern.
There are two types of current main solutions: one is additions to inhibit antichlor, inhibits dechlorination in catalytic hydrogenation reaction
The generation of product；Another kind is the high catalyst of exploitation selectivity, to inhibit the progress of dechlorination reaction.Such as Chinese invention patent
CN1962608 discloses a kind of method that catalytic hydrogenation prepares 3,4 dichloroanilines, this method using alcoholic solution as dicyandiamide solution,
In the presence of Raney-Ni catalyst and dechlorination inhibitor ethanol amine, under the conditions of 0.5-1.5MPa, 80-120 DEG C, it is passed through H2, into
The selectivity of the reaction of row catalytic hydrogenating reduction, the 3,4-DCA produced is greater than 99%, and dechlorination amount is less than 2%.American invention
Dechlorination inhibitor ammonium hydroxide, morpholine or piperazine is added using Pt-Ni-Cr/C as catalyst in patent US3546297A1, in 30-
150 DEG C, under the conditions of 1.4-4.1MPa, catalytic hydrogenation is carried out to 3,4- dichloronitrobenzene, dechlorination rate is less than 0.03%.Pass through addition
Inhibit antichlor that can improve the selectivity of catalytic hydrogenation, but exists simultaneously the catalyst after reaction and inhibit the separation of antichlor
The problems such as difficulty, catalyst circulation are applied performance and are declined, the quality decline of products obtained therefrom, cost improves.Chinese invention patent
CN200510050594.8 is with Ru-Fe/Al2O3Catalytic hydrogenation reaction is carried out for catalyst, the selectivity of 3,4-DCA is
99.3%.But two-element active component preparation process used in patent is complicated, while the cost recovery of noble metal Ru is high.Middle promulgated by the State Council
Bright patent CN02148509.7 uses Pd/NCT and Pt/NCT as catalyst respectively, and the selectivity of 3,4-DCA is respectively
99.2% and 99%, but carbon nanotube is as carrier, it is expensive, it is at high cost.Chinese invention patent CN102241595A is provided
A kind of method that photo catalytic reduction prepares 3,4-DCA, this method select photo catalysis reactor, reactor need to be equipped with into
Gas, outlet and disengaging cooling water system, and reactor wall needs the UV light permeability that wavelength can be made to be less than 387.5nm, in light
In catalytic reactor, it is packed into organic solvent, and by 3,4- dichloronitrobenzene and solid powder th-1 catalyst TiO2Organic solvent is added
In, while surfactant subwet159 is added as additive and is dissolved in organic solvent in inert nitrogen gas atmosphere
In 3,4- dichloronitrobenzene and solid powdery catalyst TiO2Dark absorption 10min is carried out, in inert nitrogen gas atmosphere,
With ultraviolet light power is 250W, radiation intensity is 4120 μ W/cm2Lower irradiation is equipped with 3,4- dichloronitrobenzene and solid powdery
TiO2The light transmission reactor of catalyst, 3,4-DCA yield rate are 71.30%.This method operating procedure is complicated, and single
The low yield of the one obtained 3,4-DCA of photocatalysis hydrogenation reaction.
A kind of photo-thermal catalytic hydrogenation catalyst of invention, draws in the reaction kettle of traditional thermal response catalytic hydrogenation
Enter light source, constitute two-component active constituent using different size carbon quantum dots and metal quantum point, is 200 in ultraviolet lighting wavelength
Under the conditions of~400nm, so that carbon quantum dot storage and acceleration electronics transfer, hydrogen is after the absorption of active metal particles surface dissociation
Form electron rich ADSORPTION STATE H-, N in attack nitryl group+Center, inhibits the progress of dechlorination reaction, to greatly improve reaction
Selectivity.
(3) summary of the invention
The object of the present invention is to provide a kind of photo-thermal catalytic hydrogenation catalyst, including 4.5~6.5nm carbon dots with 10~
15nm metal dots, under 280~350nm ultraviolet light and thermal coupling effect, the photoelectron modulation of excitation active sites characteristic electrons,
And then modulation ADSORPTION STATE hydrogen, so that it is particularly suitable for 3,4- dichloronitrobenzene selective hydrogenation synthesis 3,4- dichloro- aniline anti-
It answers.
It is a further object to provide a kind of method for preparing the photo-thermal catalytic hydrogenation catalyst, this method behaviour
Make it is simple, it can be achieved that the generation in situ on carbon ball surface of one step of carbon quantum dot with grow up, and the particle size distribution range of carbon quantum dot
Controllable precise.
It is also another object of the present invention to provide the photo-thermal catalytic hydrogenation catalysts to urge in 3,4- dichloronitrobenzene photo-thermal
Change the application in hydrogenation reaction, has the characteristics that high conversion rate, selectivity is good, hydrogenation reaction rate is fast, stability is good.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of photo-thermal catalytic hydrogenation catalyst, it is microsphere supported by mesoporous carbon and be supported on the carbon quantum dot and gold of carrier surface
Belong to quantum dot composition, catalyst size between 50~100nm, the particle size range of the carbon quantum dot 4.5~6.5nm it
Between, the metal quantum point is the combination of one or both of palladium quantum dot and platinum quantum dot, the partial size model of metal quantum point
It is trapped among between 10~15nm；In the catalyst, the mass fraction of carbon quantum dot and metal quantum point is respectively 10~30% and 1
~2%.
A kind of preparation method of photo-thermal catalytic hydrogenation catalyst, comprising:
1) using 3- amino phenols and formaldehyde as carbon source presoma, ammonium hydroxide is catalyst, in alcohol-water solution system, through polycondensation
Reaction obtains polymer microballoon；
2) polymer microballoon that step 1) obtains and deionized water are configured to mixed serum, and the mixed serum of preparation is put into
It is carried out microwave reaction 20~30 minutes at 180~210 DEG C in microwave dissolver, mixed serum is taken out after cooling, it is dry through vacuum
The dry polymer microballoon for obtaining carbon quantum dot modification, wherein carbon quantum dot is distributed in the surface of polymer microballoon and particle size range exists
Between 4.5~6.5nm；
3) metal salt is loaded to the polymer microballoon for the carbon quantum dot modification that step 2) obtains by wet impregnation, it is dry
Obtain catalyst precursor；
4) catalyst precursor that step 3) obtains is calcined under an inert atmosphere, cools down to obtain the catalysis of photo-thermal catalytic hydrogenation
Agent, wherein calcination process is Temperature Programmed Processes: first rising to 200~300 from room temperature with 0.5~3.5 DEG C/min of heating rate
DEG C, constant temperature 1~4 hour；From 200~300 DEG C to rise to 400~600 DEG C for 3.5~8.5 DEG C/min of heating rate, constant temperature 3
~6 hours.
Step 1) the i.e. of the present invention polymerization of phenolic resin microspheres, reaction condition can refer to existing literature, and the present invention is specific
Recommendation step 1) according to being implemented as follows: prepare by mass concentration be 20~25% ammonium hydroxide, alcohol, deionized water, 3- amino phenols and
The mixed liquor that the formalin that mass concentration is 33~38% forms, wherein ammonium hydroxide and formalin, pure and mild deionized water
Volume ratio be respectively 1:2~8:20~60:70~100, the molar ratio of 3- amino phenols and formaldehyde is 1:2~5；It is prepared mixed
Close liquid stir at room temperature be transferred in reaction kettle after 2~10h 100~300 DEG C hydro-thermal reaction 12~48 hours, be dried to obtain polymerization
Object microballoon.Further, the alcohol preferred alcohol or propyl alcohol.The condition of the drying is preferred are as follows: at 20~80 DEG C dry 12
~48 hours.
Step 2) of the present invention is by the condition of control microwave reaction to control carbon quantum dot size.Wherein, polymer microballoon
Feed ratio with deionized water is preferably 1g:10~25ml.Vacuum drying condition is preferred are as follows: the mixed serum for obtaining microwave method
At relative degree of vacuum -0.099~-0.05MPa, temperature is 20~80 DEG C 12~48 hours dry.
The wet impregnation of step 3) of the present invention is the conventional steps of this field.Wherein, metal salt can be following middle a kind of or
A variety of combination: palladium nitrate, chlorine palladium acid, ethylenediamine palladium chloride, tetrachloro-palladium acid ammonium, chlorine palladium acid sodium, four ammino palladium of nitric acid, tetramino
Two bicarbonate palladiums, chloroplatinic acid, platinum nitrate, platinic sodium chloride, four ammino platinum nitrates, dinitroso diammonia platinum, trichlorine ammino potassium platinate,
Hexachloro sodium platinate etc..The step 3) preferably proceeds as follows: preparing metal mass concentration is 0.001~0.05g/mL
Metal salt aqueous solution, take step 2) to obtain carbon quantum dot modification polymer microballoon, metal salt aqueous solution and go from
Sub- water mixing, wherein the feed ratio of the polymer microballoon of carbon quantum dot modification, the aqueous solution of metal salt and deionized water is 1g:5
Dipping sample was dried to obtain catalyst precursor after 5~10 hours by~20ml:10~25ml, dipping.Wherein drying condition is preferred
Are as follows: dipping sample is 12~48 hours dry at 40~80 DEG C.
In step 4) of the present invention, inert atmosphere N2；In calcination process, the volume flow of the inert atmosphere is 10~
80ml/min。
Invention further provides photo-thermal catalytic hydrogenation catalyst 3,4- dichloronitrobenzenes shown in Formulas I
Under 280~350nm ultraviolet light in the reaction of 3,4- dichloro- aniline shown in selective catalytic hydrogenation synthesis Formula II
Using.
Specifically, the application method of the catalyst are as follows:
The investment of 3,4- dichloronitrobenzene shown in photo-thermal catalytic hydrogenation catalyst, Formulas I is equipped with to the height of ultraviolet light
Press in hydrogenation reaction kettle, closed reactor, with nitrogen displaced air, then with hydrogen displacement nitrogen, Hydrogen Vapor Pressure for 0.5~
Then 1.5MPa opens reaction kettle heating key and is warming up to 30~120 DEG C, temperature is opened 280~350nm ultraviolet lamp after stablizing and shone
It penetrates, opens stirring and start reaction, when pressure no longer declines in kettle, continuation constant temperature and pressure stirring a period of time, stopping stirring cooling down
To room temperature, opens kettle and take out hydrogenation liquid, hydrogenation liquid is handled after separation obtains 3,4- dichloro- aniline shown in Formula II；
Further, in the application, the quality that feeds intake of compound shown in the Formulas I and the photo-thermal catalytic hydrogenation catalyst
Than for 100:0.5~4, preferably 100:1.0~2.0.
Further, compound shown in the Formulas I can also carry out hydrogenation reaction in the case where having solvent and condition of no solvent.Carry out nothing
When solvent hydrogenation reaction, raw material preheating must be melted to liquid first, then rise to reaction temperature and carry out hydrogenation reaction；There is solvent to add
The preferred methanol of solvent or ethyl alcohol in hydrogen reaction, wherein the feed ratio of catalyst and solvent is 1g:10~30ml.
Further, illumination wavelength 280~350nm of range of ultraviolet lamp, power are 200~250W, radiation intensity 3660
~3980 μ W/cm2。
Further, the method for the hydrogenation liquid separation post-processing are as follows: hydrogenation liquid filters to isolate catalyst, and filtrate is through depressurizing
Up to product after rectifying；In last handling process, the catalyst that hydrogenation liquid is obtained by filtration may return to reaction kettle and carry out catalyst set
With.
Compared with prior art, the beneficial effects of the present invention are embodied in:
1) carrier of the mesoporous carbosphere as photo-thermal catalyst, group is fairly simple controllable, prepares repeatability height, and sphere
Between 50~100nm of partial size, be conducive to eliminate mass transfer influence；π-π the associative key formed between carbon quantum dot and mesoporous carbosphere
It is capable of the anchoring ability of modulation metal active constituent, is dispersed in metal preferably on mesoporous carbon carrier, it is not easy to reunite, improve gold
Belong to utilization rate；In addition, 4.5~6.5nm carbon dots and 10~15nm metal dots are under 280~350nm ultraviolet light and thermal coupling effect,
The photoelectron modulation of the excitation characteristic electron of active sites, shows special dimensional effect and quantum effect.
2) preparation of carbon quantum dot of the present invention, it is only necessary to can reach by easy regulation microwave temperature and time
It is more accurate to the particle size distribution range of carbon quantum dot controllable.In addition, the organic matter based on synthesis carbon quantum dot is micro- in polymer
The orderly absorption of ball surface, imposes microwave modulation polymerization process, realize the generation in situ on carbon ball surface of one step of carbon quantum dot with
It grows up.The method is easier compared to traditional hydro-thermal+dip loading separate operations.
3) loaded catalyst of 4.5~6.5nm carbon dots of the invention and 10~15nm metal dots, in 280~350nm purple
Under outer light and heat coupling, the photoelectron modulation of excitation active sites characteristic electrons, and then modulation ADSORPTION STATE hydrogen, make its spy
It Shi He not 3,4- dichloronitrobenzene selective hydrogenation synthesis 3,4- dichloroaniline reaction.Catalyst circulation use process condition temperature
With stability is good, and catalyst amount is low, applies often, and the service life is long, and catalyst activity and selectivity are high, add hydrogen anti-
Answer rate fast, the selectivity of 3,4-DCA is up to 100%.
(4) Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of a kind of catalyst prepared of embodiment, and the maximum ball of partial size is that mesoporous carbon is micro- in figure
Ball；The smallest partial size is carbon quantum dot；Color is deeper for metal dots.
Fig. 2 is the dynamic light scattering diagram of the carbon quantum dot prepared in embodiment 1.
(5) specific embodiment
Embodiment 1
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 32ml ethyl alcohol and 80ml the deionized water mixing that mass concentration is 23%, then
3.5g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 5ml mass concentration is 35%, stirs at room temperature
After 4h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction at 200 DEG C and for 24 hours, after being cooled to room temperature, is put into baking oven 60 DEG C
Drying 24 hours, obtains polymer microballoon.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 15ml
Xie Yizhong, setting temperature are 195 DEG C, and the microwave reaction time is 25 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 60 DEG C 24 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 15ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the palladium concentration of 10mL is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put to neutrality after stirring 5 hours
Enter 60 DEG C drying 24 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 50ml/min, is heated up
Journey be 300 DEG C keep 2 hours, 600 DEG C keep 4 hours, (temperature program therein are as follows: room temperature to 300 DEG C be 1 DEG C/min, 300
DEG C to 600 DEG C be 5 DEG C/min) to obtaining photo-thermal catalytic hydrogenation catalyst.
Through TEM test catalyst carrier partial size be 70~75nm, carbon dots partial size be 5~6nm, metal partial size be 11~
12nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 20%, and the load capacity of metal is 2%.
Embodiment 2
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 20ml ethyl alcohol and 70ml the deionized water mixing that mass concentration is 20%, then
2g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 2ml mass concentration is 33%, stirs 2h at room temperature
Afterwards, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction 12h at 100 DEG C, after being cooled to room temperature, is put into 20 DEG C of bakings in baking oven
It is 12 hours dry.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 15ml
Xie Yizhong, setting temperature are 195 DEG C, and the microwave reaction time is 25 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 60 DEG C 24 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 15ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the concentration of 10mL is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put into neutrality after stirring 5 hours
60 DEG C drying 24 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 50ml/min, is heated up
Journey be 300 DEG C keep 2 hours, 600 DEG C keep 4 hours, (temperature program therein are as follows: room temperature to 300 DEG C be 1 DEG C/min, 300
DEG C to 600 DEG C be 5 DEG C/min) to obtaining photo-thermal catalytic hydrogenation catalyst.
Through TEM test catalyst carrier partial size be 50~65nm, carbon dots partial size be 5.5~6nm, metal partial size be 12~
13nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 19%, and the load capacity of metal is 1.8%.
Embodiment 3
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 60ml ethyl alcohol and 100ml the deionized water mixing that mass concentration is 25%, with
5g3- amino phenols is added afterwards, stirring is to being completely dissolved, then instills the formalin that 8ml mass concentration is 38%, stirs at room temperature
After 10h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction 48h at 300 DEG C, after being cooled to room temperature, is put into 80 in baking oven
DEG C drying 48 hours.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 15ml
Xie Yizhong, setting temperature are 195 DEG C, and the microwave reaction time is 25 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 60 DEG C 24 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 15ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the concentration of 10mL is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put into neutrality after stirring 5 hours
60 DEG C drying 24 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 50ml/min, is heated up
Journey be 300 DEG C keep 2 hours, 600 DEG C keep 4 hours, (temperature program therein are as follows: room temperature to 300 DEG C be 1 DEG C/min, 300
DEG C to 600 DEG C be 5 DEG C/min) to obtaining photo-thermal catalytic hydrogenation catalyst.
Through TEM test catalyst carrier partial size be 85~100nm, carbon dots partial size be 5.5~6nm, metal partial size be 12~
13nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 17%, and the load capacity of metal is 2%.
Embodiment 4
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 32ml ethyl alcohol and 80ml the deionized water mixing that mass concentration is 23%, then
3.5g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 5ml mass concentration is 35%, stirs at room temperature
After 4h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction at 200 DEG C and for 24 hours, after being cooled to room temperature, is put into baking oven 60 DEG C
Drying 24 hours.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 10ml
Xie Yizhong, setting temperature are 180 DEG C, and the microwave reaction time is 20 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 20 DEG C 12 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 15ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the concentration of 10mL is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put into neutrality after stirring 5 hours
60 DEG C drying 24 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 50ml/min, is heated up
Journey be 300 DEG C keep 2 hours, 600 DEG C keep 4 hours, (temperature program therein are as follows: room temperature to 300 DEG C be 1 DEG C/min, 300
DEG C to 600 DEG C be 5 DEG C/min) to obtaining photo-thermal catalytic hydrogenation catalyst.
Through TEM test catalyst carrier partial size be 70~80nm, carbon dots partial size be 4.5~5nm, metal partial size be 11~
12nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 10%, and the load capacity of metal is 2%.
Embodiment 5
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 32ml ethyl alcohol and 80ml the deionized water mixing that mass concentration is 23%, then
3.5g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 5ml mass concentration is 35%, stirs at room temperature
After 4h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction at 200 DEG C and for 24 hours, after being cooled to room temperature, is put into baking oven 60 DEG C
Drying 24 hours.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 15ml
Xie Yizhong, setting temperature are 195 DEG C, and the microwave reaction time is 25 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 60 DEG C 24 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 15ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the concentration of 10mL is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put into neutrality after stirring 5 hours
60 DEG C drying 24 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 50ml/min, is heated up
Journey be 300 DEG C keep 2 hours, 600 DEG C keep 4 hours, (temperature program therein are as follows: room temperature to 300 DEG C be 1 DEG C/min, 300
DEG C to 600 DEG C be 5 DEG C/min) to obtaining photo-thermal catalytic hydrogenation catalyst.
Through TEM test catalyst carrier partial size be 65~75nm, carbon dots partial size be 5.5~6nm, metal partial size be 12~
13nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 21%, and the load capacity of metal is 1.7%.
Embodiment 6
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 32ml ethyl alcohol and 80ml the deionized water mixing that mass concentration is 23%, then
3.5g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 5ml mass concentration is 35%, stirs at room temperature
After 4h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction at 200 DEG C and for 24 hours, after being cooled to room temperature, is put into baking oven 60 DEG C
Drying 24 hours.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 25ml
Xie Yizhong, setting temperature are 210 DEG C, and the microwave reaction time is 30 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 80 DEG C 48 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 15ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the concentration of 10mL is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put into neutrality after stirring 5 hours
60 DEG C drying 24 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 50ml, and temperature-rise period is
300 DEG C keep 2 hours, 600 DEG C keep 4 hours, (temperature program therein are as follows: room temperature to 300 DEG C be 1 DEG C/min, 300 DEG C are extremely
600 DEG C are 5 DEG C/min) to obtain photo-thermal catalytic hydrogenation catalyst.
Through TEM test catalyst carrier partial size be 70~75nm, carbon dots partial size be 6~6.5nm, metal partial size be 11~
13nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 30%, and the load capacity of metal is 2%.
Embodiment 7
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 32ml ethyl alcohol and 80ml the deionized water mixing that mass concentration is 23%, then
3.5g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 5ml mass concentration is 35%, stirs at room temperature
After 4h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction at 200 DEG C and for 24 hours, after being cooled to room temperature, is put into baking oven 60 DEG C
Drying 24 hours.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 15ml
Xie Yizhong, setting temperature are 195 DEG C, and the microwave reaction time is 25 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 60 DEG C 24 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 10ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the concentration of 20mL is that 0.001g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put into neutrality after stirring 5 hours
40 DEG C drying 12 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 50ml/min, is heated up
Journey be 300 DEG C keep 2 hours, 600 DEG C keep 4 hours, (temperature program therein are as follows: room temperature to 300 DEG C be 1 DEG C/min, 300
DEG C to 600 DEG C be 5 DEG C/min) to obtaining photo-thermal catalytic hydrogenation catalyst.
Through TEM test catalyst carrier partial size be 70~80nm, carbon dots partial size be 5.5~5nm, metal partial size be 10~
11nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 20%, and the load capacity of metal is 1%.
Embodiment 8
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 32ml ethyl alcohol and 80ml the deionized water mixing that mass concentration is 23%, then
3.5g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 5ml mass concentration is 35%, stirs at room temperature
After 4h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction at 200 DEG C and for 24 hours, after being cooled to room temperature, is put into baking oven 60 DEG C
Drying 24 hours.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 15ml
Xie Yizhong, setting temperature are 195 DEG C, and the microwave reaction time is 25 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 60 DEG C 24 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 15ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the concentration of 10mL is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put into neutrality after stirring 8 hours
60 DEG C drying 24 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 50ml/min, is heated up
Journey be 300 DEG C keep 2 hours, 600 DEG C keep 4 hours, (temperature program therein are as follows: room temperature to 300 DEG C be 1 DEG C/min, 300
DEG C to 600 DEG C be 5 DEG C/min) to obtaining photo-thermal catalytic hydrogenation catalyst.
Through TEM test catalyst carrier partial size be 70~80nm, carbon dots partial size be 5.5~6.5nm, metal partial size be 11~
12nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 20%, and the load capacity of metal is 2%.
Embodiment 9
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 32ml ethyl alcohol and 80ml the deionized water mixing that mass concentration is 23%, then
3.5g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 5ml mass concentration is 35%, stirs at room temperature
After 4h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction at 200 DEG C and for 24 hours, after being cooled to room temperature, is put into baking oven 60 DEG C
Drying 24 hours.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 15ml
Xie Yizhong, setting temperature are 195 DEG C, and the microwave reaction time is 25 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 60 DEG C 24 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 25ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the concentration of 4mL is that 0.05g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put into neutrality after stirring 10 hours
80 DEG C drying 48 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 50ml/min, is heated up
Journey be 300 DEG C keep 2 hours, 600 DEG C keep 4 hours, (temperature program therein are as follows: room temperature to 300 DEG C be 1 DEG C/min, 300
DEG C to 600 DEG C be 5 DEG C/min) to obtaining photo-thermal catalytic hydrogenation catalyst.
It is 70~75nm through TEM test catalyst carrier partial size, carbon dots partial size is 4.5~5.5nm, and metal partial size is 13.5
~15nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 18%, and the load capacity of metal is 1.8%.
Embodiment 10
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 32ml ethyl alcohol and 80ml the deionized water mixing that mass concentration is 23%, then
3.5g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 5ml mass concentration is 35%, stirs at room temperature
After 4h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction at 200 DEG C and for 24 hours, after being cooled to room temperature, is put into baking oven 60 DEG C
Drying 24 hours.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 15ml
Xie Yizhong, setting temperature are 195 DEG C, and the microwave reaction time is 25 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 60 DEG C 24 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 15ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the concentration of 10mL is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put into neutrality after stirring 5 hours
60 DEG C drying 24 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 10ml/min, is heated up
Journey be 200 DEG C keep 1 hour, 400 DEG C keep 3 hours, (temperature program therein are as follows: room temperature to 200 DEG C be 0.5 DEG C/min,
200 DEG C to 400 DEG C are 3.5 DEG C/min) to obtain photo-thermal catalytic hydrogenation catalyst.
Through TEM test catalyst carrier partial size be 65~75nm, carbon dots partial size be 5~5.5nm, metal partial size be 11~
13nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 20%, and the load capacity of metal is 1%.
Embodiment 11
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 32ml ethyl alcohol and 80ml the deionized water mixing that mass concentration is 23%, then
3.5g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 5ml mass concentration is 35%, stirs at room temperature
After 4h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction at 200 DEG C and for 24 hours, after being cooled to room temperature, is put into baking oven 60 DEG C
Drying 24 hours.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 15ml
Xie Yizhong, setting temperature are 195 DEG C, and the microwave reaction time is 25 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 60 DEG C 24 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 15ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the concentration of 10mL is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put into neutrality after stirring 5 hours
60 DEG C drying 24 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 50ml/min, is heated up
Journey be 250 DEG C keep 2 hours, 500 DEG C keep 5 hours, (temperature program therein are as follows: room temperature to 250 DEG C be 1.5 DEG C/min,
250 DEG C to 500 DEG C are 5 DEG C/min) to obtain photo-thermal catalytic hydrogenation catalyst.
Through TEM test catalyst carrier partial size be 70~80nm, carbon dots partial size be 5.5~6nm, metal partial size be 11~
12nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 20%, and the load capacity of metal is 1.8%.
Embodiment 12
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 32ml ethyl alcohol and 80ml the deionized water mixing that mass concentration is 23%, then
3.5g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 5ml mass concentration is 35%, stirs at room temperature
After 4h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction at 200 DEG C and for 24 hours, after being cooled to room temperature, is put into baking oven 60 DEG C
Drying 24 hours.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 15ml
Xie Yizhong, setting temperature are 195 DEG C, and the microwave reaction time is 25 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 60 DEG C 24 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 15ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the concentration of 10mL is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put into neutrality after stirring 5 hours
60 DEG C drying 24 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 80ml/min, is heated up
Journey be 300 DEG C keep 4 hours, 600 DEG C keep 6 hours, (temperature program therein are as follows: room temperature to 300 DEG C be 3.5 DEG C/min,
300 DEG C to 600 DEG C are 8.5 DEG C/min) to obtain photo-thermal catalytic hydrogenation catalyst.
Through TEM test catalyst carrier partial size be 70~85nm, carbon dots partial size be 4.5~5.5nm, metal partial size be 12~
13nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 20%, and the load capacity of metal is 2%.
Comparative example 1
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 32ml ethyl alcohol and 80ml the deionized water mixing that mass concentration is 23%, then
3.5g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 5ml mass concentration is 35%, stirs at room temperature
After 4h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction at 200 DEG C and for 24 hours, after being cooled to room temperature, is put into baking oven 60 DEG C
Drying 24 hours.
After taking carbosphere solid powder 1g made from the above method and 15ml deionized water to be mixed evenly, take 10mL's
Concentration is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put into baking oven and does for 60 DEG C to neutrality after stirring 5 hours
Dry 24 hours.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 50ml/min, is heated up
Journey be 300 DEG C keep 2 hours, 600 DEG C keep 4 hours, (temperature program therein are as follows: room temperature to 300 DEG C be 1 DEG C/min, 300
DEG C to 600 DEG C be 5 DEG C/min) to obtain the catalytic hydrogenation catalyst of no quantum dot load.
It is 70~75nm through TEM test catalyst carrier partial size, metal partial size is 11~12nm；Through TG, ICP and material weighing apparatus
It calculates, the load capacity of metal is 2%.
Comparative example 2
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 32ml ethyl alcohol and 80ml the deionized water mixing that mass concentration is 23%, then
3.5g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 5ml mass concentration is 35%, stirs at room temperature
After 4h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction at 200 DEG C and for 24 hours, after being cooled to room temperature, is put into baking oven 60 DEG C
Drying 24 hours, obtains polymer microballoon.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 15ml
Xie Yizhong, setting temperature are 165 DEG C, and the microwave reaction time is 15 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 60 DEG C 24 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 15ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the palladium concentration of 10mL is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put to neutrality after stirring 5 hours
Enter 60 DEG C drying 24 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 50ml/min, is heated up
Journey be 300 DEG C keep 2 hours, 600 DEG C keep 4 hours, (temperature program therein are as follows: room temperature to 300 DEG C be 1 DEG C/min, 300
DEG C to 600 DEG C be 5 DEG C/min) to obtaining photo-thermal catalytic hydrogenation catalyst.
Through TEM test catalyst carrier partial size be 70~75nm, carbon dots partial size be 2~3nm, metal partial size be 11~
12nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 20%, and the load capacity of metal is 2%.
Comparative example 3
It is sufficiently stirred after measuring 1ml ammonium hydroxide, 32ml ethyl alcohol and 80ml the deionized water mixing that mass concentration is 23%, then
3.5g3- amino phenols is added, stirring is to being completely dissolved, then instills the formalin that 5ml mass concentration is 35%, stirs at room temperature
After 4h, it is transferred into hydrothermal reaction kettle the hydro-thermal reaction at 200 DEG C and for 24 hours, after being cooled to room temperature, is put into baking oven 60 DEG C
Drying 24 hours, obtains polymer microballoon.
The mixed serum of preparation after mixing evenly, is put into microwave and disappeared by the deionized water for weighing 1g polymer microballoon and 15ml
Xie Yizhong, setting temperature are 225 DEG C, and the microwave reaction time is 35 minutes, carry out microwave reaction, take out mixed serum after cooling,
It is put into vacuum drying oven, at relative degree of vacuum -0.099~-0.05MPa, temperature is 60 DEG C 24 hours dry, obtains solid powder
End.
Carbosphere solid powder 1g and the 15ml deionized water for taking quantum dot made from the above method to load is mixed equal
After even, taking the palladium concentration of 10mL is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, and washing is put to neutrality after stirring 5 hours
Enter 60 DEG C drying 24 hours in baking oven.
Then above-mentioned obtained solid is in N2It is calcined in atmosphere, inert atmosphere volume flow is 50ml/min, is heated up
Journey be 300 DEG C keep 2 hours, 600 DEG C keep 4 hours, (temperature program therein are as follows: room temperature to 300 DEG C be 1 DEG C/min, 300
DEG C to 600 DEG C be 5 DEG C/min) to obtaining photo-thermal catalytic hydrogenation catalyst.
Through TEM test catalyst carrier partial size be 70~75nm, carbon dots partial size be 7.5~8.5nm, metal partial size be 11~
12nm；Through TG, ICP and mass balance, the load capacity of carbon dots are 20%, and the load capacity of metal is 2%.
Embodiment 13
1 catalyst of 0.5g embodiment, 25 grams of 3,4- dichloronitrobenzenes, 30mL methanol solvate investment ultraviolet lighting high pressure are added
In hydrogen reaction kettle, closed reactor stirs with nitrogen displaced air, then with opening after hydrogen displacement nitrogen, controls ultraviolet light wave
A length of 350nm, power 250W, 3980 μ W/cm of radiation intensity2, under conditions of temperature is 120 DEG C, Hydrogen Vapor Pressure is 1.5MPa
Carry out hydrogenation reaction.When pressure no longer declines in kettle, continuation constant temperature and pressure is stirred 20 minutes, stops reaction, is separated by filtration and is added hydrogen
Liquid and catalyst cake analyze result are as follows: reaction conversion ratio 100%, 3,4-DCA selectivity 99.94%, reaction time
It is 35 minutes.
Embodiment 14
3 catalyst of 0.5g embodiment, 50 grams of 3,4- dichloronitrobenzenes, 10mL methanol solvate investment ultraviolet lighting high pressure are added
In hydrogen reaction kettle, closed reactor stirs with nitrogen displaced air, then with opening after hydrogen displacement nitrogen, controls ultraviolet light wave
A length of 280nm, power 200W, radiation intensity are 3660 μ W/cm2, under conditions of temperature is 30 DEG C, Hydrogen Vapor Pressure is 0.5MPa
Carry out hydrogenation reaction.When pressure no longer declines in kettle, continuation constant temperature and pressure is stirred 20 minutes, stops reaction, is separated by filtration and is added hydrogen
Liquid and catalyst cake analyze result are as follows: reaction conversion ratio 99.8%, 3,4-DCA selectivity 99.2%, reaction time
It is 45 minutes.
Embodiment 15
1 catalyst of 0.5g embodiment, 40 grams of 3,4- dichloronitrobenzenes, 15mL methanol solvate investment ultraviolet lighting high pressure are added
In hydrogen reaction kettle, closed reactor stirs with nitrogen displaced air, then with opening after hydrogen displacement nitrogen, controls ultraviolet light wave
A length of 325nm, power 225W, radiation intensity are 3820 μ W/cm2, under conditions of temperature is 80 DEG C, Hydrogen Vapor Pressure is 1MPa into
Row hydrogenation reaction.When pressure no longer declines in kettle, continuation constant temperature and pressure is stirred 20 minutes, is stopped reaction, is separated by filtration hydrogenation liquid
And catalyst cake, analyze result are as follows: reaction conversion ratio 100%, 3,4-DCA selectivity 100%, reaction time 25
Minute.
Embodiment 16
5 catalyst of 0.5g embodiment, 40 grams of 3,4- dichloronitrobenzenes, 15mL methanol solvate investment ultraviolet lighting high pressure are added
In hydrogen reaction kettle, closed reactor stirs with nitrogen displaced air, then with opening after hydrogen displacement nitrogen, controls ultraviolet light wave
A length of 325nm, power 225W, radiation intensity are 3820 μ W/cm2,Under conditions of temperature is 80 DEG C, Hydrogen Vapor Pressure is 1MPa into
Row hydrogenation reaction.When pressure no longer declines in kettle, continuation constant temperature and pressure is stirred 20 minutes, is stopped reaction, is separated by filtration hydrogenation liquid
And catalyst cake, analyze result are as follows: reaction conversion ratio 99.8%, 3,4-DCA selectivity 99.94%, the reaction time is
35 minutes.
Embodiment 17
6 catalyst of 0.5g embodiment, 40 grams of 3,4- dichloronitrobenzenes, 15mL methanol solvate investment ultraviolet lighting high pressure are added
In hydrogen reaction kettle, closed reactor stirs with nitrogen displaced air, then with opening after hydrogen displacement nitrogen, controls ultraviolet light wave
A length of 315nm, power 225W, radiation intensity are 3820 μ W/cm2, under conditions of temperature is 80 DEG C, Hydrogen Vapor Pressure is 1MPa into
Row hydrogenation reaction.When pressure no longer declines in kettle, continuation constant temperature and pressure is stirred 20 minutes, is stopped reaction, is separated by filtration hydrogenation liquid
And catalyst cake, analyze result are as follows: reaction conversion ratio 100%, 3,4-DCA selectivity 99.96%, the reaction time is
35 minutes.
Embodiment 18
10 catalyst of 0.5g embodiment, 40 grams of 3,4- dichloronitrobenzenes, 15mL methanol solvate are put into ultraviolet lighting high pressure
In hydrogenation reaction kettle, closed reactor stirs with nitrogen displaced air, then with opening after hydrogen displacement nitrogen, controls ultraviolet light
Wavelength is 315nm, and power 225W, radiation intensity is 3820 μ W/cm2, under conditions of temperature is 80 DEG C, Hydrogen Vapor Pressure is 1MPa
Carry out hydrogenation reaction.When pressure no longer declines in kettle, continuation constant temperature and pressure is stirred 20 minutes, stops reaction, is separated by filtration and is added hydrogen
Liquid and catalyst cake analyze result are as follows: reaction conversion ratio 100%, 3,4-DCA selectivity 99.94%, reaction time
It is 45 minutes.
Embodiment 19
1 catalyst of 0.5g embodiment, 25 grams of 3,4- dichloronitrobenzenes are put into ultraviolet lighting high-pressure hydrogenation reaction kettles, it is close
Reaction kettle is closed, is stirred with nitrogen displaced air, then with being opened after hydrogen displacement nitrogen, controls a length of 350nm of ultraviolet light wave, power
For 250W, radiation intensity is 3980 μ W/cm2, hydrogenation reaction is carried out under conditions of temperature is 120 DEG C, Hydrogen Vapor Pressure is 1.5MPa.
When pressure no longer declines in kettle, continuation constant temperature and pressure is stirred 20 minutes, stops reaction, is separated by filtration hydrogenation liquid and catalyst filter
Cake analyzes result are as follows: reaction conversion ratio 100%, 3,4-DCA selectivity 99.96%, reaction time are 120 minutes.
Embodiment 20
8 catalyst of 0.5g embodiment, 50 grams of 3,4- dichloronitrobenzenes are put into ultraviolet lighting high-pressure hydrogenation reaction kettles, it is close
Reaction kettle is closed, is stirred with nitrogen displaced air, then with being opened after hydrogen displacement nitrogen, controls a length of 280nm of ultraviolet light wave, power
For 200W, radiation intensity is 3660 μ W/cm2, hydrogenation reaction is carried out under conditions of temperature is 80 DEG C, Hydrogen Vapor Pressure is 0.5MPa.
When pressure no longer declines in kettle, continuation constant temperature and pressure is stirred 20 minutes, stops reaction, is separated by filtration hydrogenation liquid and catalyst filter
Cake analyzes result are as follows: reaction conversion ratio 99.8%, 3,4-DCA selectivity 99.94%, reaction time are 120 minutes.
Embodiment 21
1 catalyst of 0.5g embodiment, 40 grams of 3,4- dichloronitrobenzenes are put into ultraviolet lighting high-pressure hydrogenation reaction kettles, it is close
Reaction kettle is closed, is stirred with nitrogen displaced air, then with being opened after hydrogen displacement nitrogen, controls a length of 315nm of ultraviolet light wave, power
For 225W, radiation intensity is 3820 μ W/cm2, hydrogenation reaction is carried out under conditions of temperature is 90 DEG C, Hydrogen Vapor Pressure is 1MPa.When
Pressure no longer declines in kettle, continues constant temperature and pressure and stirs 20 minutes, stops reaction, be separated by filtration hydrogenation liquid and catalyst cake,
Analyze result are as follows: reaction conversion ratio 100%, 3,4-DCA selectivity 99.96%, reaction time are 80 minutes.
Embodiment 22
7 catalyst of 0.5g embodiment, 40 grams of 3,4- dichloronitrobenzenes are put into ultraviolet lighting high-pressure hydrogenation reaction kettles, it is close
Reaction kettle is closed, is stirred with nitrogen displaced air, then with being opened after hydrogen displacement nitrogen, controls a length of 350nm of ultraviolet light wave, power
For 250W, radiation intensity is 3980 μ W/cm2, hydrogenation reaction is carried out under conditions of temperature is 120 DEG C, Hydrogen Vapor Pressure is 1.5MPa.
When pressure no longer declines in kettle, continuation constant temperature and pressure is stirred 20 minutes, stops reaction, is separated by filtration hydrogenation liquid and catalyst filter
Cake analyzes result are as follows: reaction conversion ratio 99.7%, 3,4-DCA selectivity 99.94%, reaction time are 120 minutes.
Embodiment 23
8 catalyst of 0.5g embodiment, 25 grams of 3,4- dichloronitrobenzenes are put into ultraviolet lighting high-pressure hydrogenation reaction kettles, it is close
Reaction kettle is closed, is stirred with nitrogen displaced air, then with being opened after hydrogen displacement nitrogen, controls a length of 315nm of ultraviolet light wave, power
For 225W, radiation intensity is 3820 μ W/cm2, hydrogenation reaction is carried out under conditions of temperature is 80 DEG C, Hydrogen Vapor Pressure is 1MPa.When
Pressure no longer declines in kettle, continues constant temperature and pressure and stirs 20 minutes, stops reaction, be separated by filtration hydrogenation liquid and catalyst cake,
Analyze result are as follows: reaction conversion ratio 100%, 3,4-DCA selectivity 99.95%, reaction time are 120 minutes.
Comparative example 4
1 catalyst of 0.5g comparative example, 25 grams of 3,4- dichloronitrobenzenes are put into ultraviolet lighting high-pressure hydrogenation reaction kettles, it is close
Reaction kettle is closed, is stirred with nitrogen displaced air, then with being opened after hydrogen displacement nitrogen, controls a length of 315nm of ultraviolet light wave, power
For 225W, radiation intensity is 3820 μ W/cm2, hydrogenation reaction is carried out under conditions of temperature is 80 DEG C, Hydrogen Vapor Pressure is 1MPa.When
Pressure no longer declines in kettle, continues constant temperature and pressure and stirs 20 minutes, stops reaction, be separated by filtration hydrogenation liquid and catalyst cake,
Analyze result are as follows: reaction conversion ratio 92%, 3,4-DCA selectivity 94%, reaction time are 250 minutes.
Comparative example 5
2 catalyst of 0.5g comparative example, 40 grams of 3,4- dichloronitrobenzenes, 15mL methanol solvate investment ultraviolet lighting high pressure are added
In hydrogen reaction kettle, closed reactor stirs with nitrogen displaced air, then with opening after hydrogen displacement nitrogen, controls ultraviolet light wave
A length of 325nm, power 225W, radiation intensity are 3820 μ W/cm2, under conditions of temperature is 80 DEG C, Hydrogen Vapor Pressure is 1MPa into
Row hydrogenation reaction.When pressure no longer declines in kettle, continuation constant temperature and pressure is stirred 20 minutes, is stopped reaction, is separated by filtration hydrogenation liquid
And catalyst cake, analyze result are as follows: reaction conversion ratio 100%, 3,4-DCA selectivity 95.6%, the reaction time is
225 minutes.
Comparative example 6
3 catalyst of 0.5g comparative example, 40 grams of 3,4- dichloronitrobenzenes, 15mL methanol solvate investment ultraviolet lighting high pressure are added
In hydrogen reaction kettle, closed reactor stirs with nitrogen displaced air, then with opening after hydrogen displacement nitrogen, controls ultraviolet light wave
A length of 325nm, power 225W, radiation intensity are 3820 μ W/cm2, under conditions of temperature is 80 DEG C, Hydrogen Vapor Pressure is 1MPa into
Row hydrogenation reaction.When pressure no longer declines in kettle, continuation constant temperature and pressure is stirred 20 minutes, is stopped reaction, is separated by filtration hydrogenation liquid
And catalyst cake, analyze result are as follows: reaction conversion ratio 97,9%, 3,4-DCA selectivity 93.7%, the reaction time is
215 minutes.
Comparative example 7
1 catalyst of 0.5g embodiment, 40 grams of 3,4- dichloronitrobenzenes, 15mL methanol solvate investment ultraviolet lighting high pressure are added
In hydrogen reaction kettle, closed reactor stirs with nitrogen displaced air, then with opening after hydrogen displacement nitrogen, controls ultraviolet light wave
A length of 364nm, power 275W, radiation intensity are 4070 μ W/cm2, under conditions of temperature is 80 DEG C, Hydrogen Vapor Pressure is 1MPa into
Row hydrogenation reaction.When pressure no longer declines in kettle, continuation constant temperature and pressure is stirred 20 minutes, is stopped reaction, is separated by filtration hydrogenation liquid
And catalyst cake, analyze result are as follows: reaction conversion ratio 98.7%, 3,4-DCA selectivity 94.9%, the reaction time is
250 minutes.
Comparative example 8
1 catalyst of 0.5g embodiment, 40 grams of 3,4- dichloronitrobenzenes, 15mL methanol solvate investment ultraviolet lighting high pressure are added
In hydrogen reaction kettle, closed reactor stirs with nitrogen displaced air, then with opening after hydrogen displacement nitrogen, controls ultraviolet light wave
A length of 240nm, power 175W, radiation intensity are 3480 μ W/cm2, under conditions of temperature is 80 DEG C, Hydrogen Vapor Pressure is 1MPa into
Row hydrogenation reaction.When pressure no longer declines in kettle, continuation constant temperature and pressure is stirred 20 minutes, is stopped reaction, is separated by filtration hydrogenation liquid
And catalyst cake, analyze result are as follows: reaction conversion ratio 96.3%, 3,4-DCA selectivity 92.8%, the reaction time is
244 minutes.
Comparative example 9~19
Comparative example 9~19 is using 1 catalyst of embodiment under non-illuminated conditions, other reaction conditions respectively refer to implement
Under the reaction condition of example 13~23, the application of 3, the 4- dichloronitrobenzene catalytic hydrogenation reaction of progress is as a result, as shown in the table.
| Embodiment | Conversion ratio % | Selective % | Reaction time min |
| Comparative example 9 | 97.68 | 97.29 | 190 |
| Comparative example 10 | 94.42 | 96.36 | 250 |
| Comparative example 11 | 98.66 | 99.98 | 80 |
| Comparative example 12 | 97.25 | 97.25 | 210 |
| Comparative example 13 | 97.45 | 97.34 | 210 |
| Comparative example 14 | 96.12 | 96.58 | 200 |
| Comparative example 15 | 97.23 | 95.85 | 400 |
| Comparative example 16 | 90.21 | 92.47 | 400 |
| Comparative example 17 | 94.82 | 95.15 | 200 |
| Comparative example 18 | 96.52 | 94.47 | 350 |
| Comparative example 19 | 93.44 | 95.13 | 350 |
Embodiment 24
Embodiment 24 is 1 catalyst of embodiment under illumination condition, under reaction condition of the reaction condition referring to embodiment 15,
3, the 4- dichloronitrobenzene carried out repeatedly applies the application of catalytic hydrogenation reaction as a result, as shown in the table.
Claims (10)
- It is microsphere supported by mesoporous carbon and be supported on the carbon quantum dot and metal of carrier surface 1. a kind of photo-thermal catalytic hydrogenation catalyst Quantum dot composition, catalyst size between 50~100nm, the particle size range of the carbon quantum dot 4.5~6.5nm it Between, the metal quantum point is the combination of one or both of palladium quantum dot and platinum quantum dot, the partial size model of metal quantum point It is trapped among between 10~15nm；In the catalyst, the mass fraction of carbon quantum dot and metal quantum point is respectively 10~30% and 1 ~2%.
- 2. a kind of preparation method of photo-thermal catalytic hydrogenation catalyst as described in claim 1, comprising:1) using 3- amino phenols and formaldehyde as carbon source presoma, ammonium hydroxide is catalyst, in alcohol-water solution system, through polycondensation reaction Obtain polymer microballoon；2) polymer microballoon that step 1) obtains and deionized water are configured to mixed serum, and the mixed serum of preparation is put into microwave It is carried out microwave reaction 20~30 minutes at 180~210 DEG C in resolution instrument, mixed serum is taken out after cooling, it is vacuum dried to obtain The polymer microballoon modified to carbon quantum dot, surface that wherein carbon quantum dot is distributed in polymer microballoon and particle size range is 4.5 Between~6.5nm；3) polymer microballoon that metal salt is loaded to the carbon quantum dot modification that step 2) obtains by wet impregnation, is dried to obtain Catalyst precursor；4) catalyst precursor that step 3) obtains is calcined under an inert atmosphere, cools down to obtain photo-thermal catalytic hydrogenation catalyst, Wherein calcination process is Temperature Programmed Processes: 200~300 DEG C first are risen to from room temperature with 0.5~3.5 DEG C/min of heating rate, Constant temperature 1~4 hour；From 200~300 DEG C to rise to 400~600 DEG C for 3.5~8.5 DEG C/min of heating rate, constant temperature 3~6 Hour.
- 3. preparation method as claimed in claim 2, it is characterised in that: step 1) is according to being implemented as follows: preparing by mass concentration For 20~25% ammonium hydroxide, alcohol, deionized water, 3- amino phenols and mass concentration be 33~38% formalin composition it is mixed Liquid is closed, wherein the volume ratio of ammonium hydroxide and formalin, pure and mild deionized water is respectively 1:2~8:20~60:70~100,3- The molar ratio of amino phenols and formaldehyde is 1:2~5；Prepared mixed liquor is transferred in reaction kettle after stirring 2~10h at room temperature 100~300 DEG C hydro-thermal reaction 12~48 hours, be dried to obtain polymer microballoon.
- 4. preparation method as claimed in claim 2, it is characterised in that: in step 2), the throwing of polymer microballoon and deionized water Material is than being 1g:10~25ml；Vacuum drying condition are as follows: the mixed serum for obtaining microwave method relative degree of vacuum -0.099~- Under 0.05MPa, temperature is 20~80 DEG C 12~48 hours dry.
- 5. preparation method as claimed in claim 2, it is characterised in that: in step 3), metal salt is one or more in following Combination: palladium nitrate, chlorine palladium acid, ethylenediamine palladium chloride, tetrachloro-palladium acid ammonium, chlorine palladium acid sodium, four ammino palladium of nitric acid, two carbon of tetramino Sour hydrogen palladium, chloroplatinic acid, platinum nitrate, platinic sodium chloride, four ammino platinum nitrates, dinitroso diammonia platinum, trichlorine ammino potassium platinate, chlordene For sodium platinate；The step 3) proceeds as follows: preparing metal mass concentration is the metal salt of 0.001~0.05g/mL Aqueous solution, the polymer microballoon for the carbon quantum dot modification for taking step 2) to obtain, the aqueous solution of metal salt and deionized water mixing, The feed ratio of the polymer microballoon of middle carbon quantum dot modification, the aqueous solution of metal salt and deionized water be 1g:5~20ml:10~ Dipping sample was dried to obtain catalyst precursor after 5~10 hours by 25ml, dipping.
- 6. photo-thermal catalytic hydrogenation catalyst as described in claim 1 3,4- dichloronitrobenzene shown in Formulas I 280~ Application under 350nm ultraviolet light in the reaction of 3,4- dichloro- aniline shown in selective catalytic hydrogenation synthesis Formula II；
- 7. application as claimed in claim 6, it is characterised in that: the application method of the catalyst are as follows:The investment of 3,4- dichloronitrobenzene shown in photo-thermal catalytic hydrogenation catalyst, Formulas I is added equipped with the high pressure of ultraviolet light In hydrogen reaction kettle, closed reactor, with nitrogen displaced air, then with hydrogen displacement nitrogen, Hydrogen Vapor Pressure is 0.5~1.5MPa, Then it opens reaction kettle heating key and is warming up to 30~120 DEG C, temperature opens the ultraviolet light irradiation of 280~350nm after stablizing, and unlatching is stirred Starting reaction is mixed, when pressure no longer declines in kettle, the stirring of continuation constant temperature and pressure for a period of time, stops stirring and is cooled to room temperature, open Kettle takes out hydrogenation liquid, and hydrogenation liquid is handled after separation obtains 3,4- dichloro- aniline shown in Formula II.
- 8. the use as claimed in claim 7, it is characterised in that: compound shown in the Formulas I is urged with the photo-thermal catalytic hydrogenation The mass ratio that feeds intake of agent is 100:0.5~4.
- 9. the use as claimed in claim 7, it is characterised in that: compound shown in the Formulas I is having solvent or condition of no solvent Lower carry out hydrogenation reaction；When carrying out solvent-free hydrogenation reaction, raw material preheating must be melted to liquid first, then rise to reaction temperature Carry out hydrogenation reaction；When having carried out solvent hydrogenation reaction, solvent is methanol or ethyl alcohol.
- 10. the use as claimed in claim 7, it is characterised in that: illumination wavelength 280~350nm of range of ultraviolet lamp, power are 200~250W, radiation intensity are 3660~3980 μ W/cm2。
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