CN109046328B - Photo-thermal catalytic hydrogenation catalyst, preparation thereof and application thereof in 3, 4-dichloronitrobenzene selective hydrogenation reaction - Google Patents
Photo-thermal catalytic hydrogenation catalyst, preparation thereof and application thereof in 3, 4-dichloronitrobenzene selective hydrogenation reaction Download PDFInfo
- Publication number
- CN109046328B CN109046328B CN201810664224.0A CN201810664224A CN109046328B CN 109046328 B CN109046328 B CN 109046328B CN 201810664224 A CN201810664224 A CN 201810664224A CN 109046328 B CN109046328 B CN 109046328B
- Authority
- CN
- China
- Prior art keywords
- reaction
- catalyst
- temperature
- quantum dots
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 74
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 55
- 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 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 229910052751 metal Chemical class 0.000 claims abstract description 63
- 239000002184 metal Chemical class 0.000 claims abstract description 63
- 239000004005 microsphere Substances 0.000 claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 57
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 53
- SDYWXFYBZPNOFX-UHFFFAOYSA-N 3,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C(Cl)=C1 SDYWXFYBZPNOFX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002096 quantum dot Substances 0.000 claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 150000002940 palladium Chemical class 0.000 claims abstract description 3
- 150000003057 platinum Chemical class 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 105
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 70
- 238000000034 method Methods 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 239000008367 deionised water Substances 0.000 claims description 56
- 229910021641 deionized water Inorganic materials 0.000 claims description 56
- 239000011268 mixed slurry Substances 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 238000001816 cooling Methods 0.000 claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims description 35
- 239000012298 atmosphere Substances 0.000 claims description 34
- 229910052799 carbon Inorganic materials 0.000 claims description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 32
- 238000011068 loading method Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 22
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 21
- 229940018563 3-aminophenol Drugs 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 230000005855 radiation Effects 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000000120 microwave digestion Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 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
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000007789 sealing Methods 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 claims description 2
- VVKBUFYSWPMDNG-UHFFFAOYSA-N nitroxyl anion platinum(2+) Chemical compound N(=O)[Pt]N=O VVKBUFYSWPMDNG-UHFFFAOYSA-N 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
- 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 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
- 239000002243 precursor Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- WSYKQUWHSAOKDO-UHFFFAOYSA-K azane;platinum(2+);trichloride Chemical compound N.[Cl-].[Cl-].[Cl-].[Pt+2] WSYKQUWHSAOKDO-UHFFFAOYSA-K 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 59
- 239000007787 solid Substances 0.000 description 47
- 230000035484 reaction time Effects 0.000 description 31
- 239000000843 powder Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 24
- 238000001914 filtration Methods 0.000 description 18
- 150000002431 hydrogen Chemical class 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 16
- 208000012839 conversion disease Diseases 0.000 description 16
- 239000012065 filter cake Substances 0.000 description 16
- 239000008098 formaldehyde solution Substances 0.000 description 15
- 230000007935 neutral effect Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 12
- 238000006298 dechlorination reaction Methods 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- VNWKTOKETHGBQD-YPZZEJLDSA-N carbane Chemical compound [10CH4] VNWKTOKETHGBQD-YPZZEJLDSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000000382 dechlorinating effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000004064 recycling Methods 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- CMVQZRLQEOAYSW-UHFFFAOYSA-N 1,2-dichloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1Cl CMVQZRLQEOAYSW-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- UXHQLGLGLZKHTC-CUNXSJBXSA-N 4-[(3s,3ar)-3-cyclopentyl-7-(4-hydroxypiperidine-1-carbonyl)-3,3a,4,5-tetrahydropyrazolo[3,4-f]quinolin-2-yl]-2-chlorobenzonitrile Chemical compound C1CC(O)CCN1C(=O)C1=CC=C(C=2[C@@H]([C@H](C3CCCC3)N(N=2)C=2C=C(Cl)C(C#N)=CC=2)CC2)C2=N1 UXHQLGLGLZKHTC-CUNXSJBXSA-N 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
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 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
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a photo-thermal catalytic hydrogenation catalyst, a preparation method thereof and application thereof in 3, 4-dichloronitrobenzene selective hydrogenation reaction. The photo-thermal catalytic hydrogenation catalyst consists of a mesoporous carbon microsphere carrier, and carbon quantum dots and metal quantum dots which are loaded on the surface of the carrier, wherein the size of the catalyst is 50-100 nm, the particle size range of the carbon quantum dots is 4.5-6.5 nm, the metal quantum dots are one or the combination of two of palladium quantum dots and platinum quantum dots, and the particle size range of the metal quantum dots is 10-15 nm; in the catalyst, the mass fractions of the carbon quantum dots and the metal quantum dots are respectively 10-30% and 1-2%. The invention provides application of the photo-thermal catalytic hydrogenation catalyst in the reaction of synthesizing 3, 4-dichloroaniline through selective catalytic hydrogenation of 3, 4-dichloronitrobenzene under the irradiation of 280-350 nm ultraviolet light, and the photo-thermal catalytic hydrogenation catalyst has the characteristics of high conversion rate, good selectivity, high hydrogenation reaction rate and good stability.
Description
(I) technical field
The invention relates to a photo-thermal catalytic hydrogenation catalyst, and preparation and application thereof, in particular to application of the catalyst in photo-thermal catalytic 3, 4-dichloronitrobenzene selective hydrogenation reaction.
(II) technical background
3, 4-dichloroaniline is an important medicine, pesticide, dye and daily chemical organic intermediate, and is widely applied to synthesis of herbicides and azo dyes. 3, 4-dichloroaniline is usually prepared by reducing 3, 4-dichloronitrobenzene by an iron powder reduction method, a sodium sulfide reduction method and a catalytic hydrogenation reduction method. Because the iron powder reduction method can generate a large amount of metal residues, and the sodium sulfide reduction method can generate organic waste water containing hydrochloric acid, which causes serious damage to the environment and is gradually eliminated. The catalytic hydrogenation reduction method has simple operation process and environmental protection, and is more concerned by researchers. However, the catalytic hydrogenation reduction method has a process of hydrogenolysis dechlorination, and how to effectively inhibit dechlorination is always concerned.
There are two main solutions at present: one is adding antichlor to inhibit the generation of dechlorination product in the catalytic hydrogenation reaction; the other is to develop a catalyst with high selectivity to inhibit the dechlorination reaction. For example, the Chinese invention patent CN1962608 discloses a method for preparing 3, 4-dichloroaniline by catalytic hydrogenation, which takes alcoholic solution as a solvent system, and introduces H under the conditions of 0.5-1.5MPa and 80-120 ℃ in the presence of Raney-Ni catalyst and dechlorination inhibitor ethanolamine2The selectivity of the prepared 3, 4-dichloroaniline is more than 99 percent and the dechlorination amount is less than 2 percent by carrying out catalytic hydrogenation reduction reaction. In the invention of the United states patent US3546297A1, Pt-Ni-Cr/C is used as a catalyst, ammonia water, morpholine or piperazine which is a dechlorination inhibitor is added at the same time, and 3, 4-dichloronitrobenzene is subjected to catalytic hydrogenation under the conditions of 30-150 ℃ and 1.4-4.1MPa, wherein the dechlorination rate is less than 0.03%. The selectivity of catalytic hydrogenation can be improved by adding the dechlorinating inhibitor, but the problems that the separation of the catalyst after reaction and the dechlorinating inhibitor is difficult, the recycling performance of the catalyst is reduced, the quality of the obtained product is reduced, the cost is increased and the like exist at the same time. Chinese patent CN200510050594.8 with Ru-Fe/Al2O3The selectivity of 3, 4-dichloroaniline is 99.3 percent when the catalyst is used for catalytic hydrogenation reaction. However, the binary active component used in the patent has a complex preparation process and high recovery cost of the noble metal Ru. The Chinese patent CN02148509.7 uses Pd/NCT and Pt/NCT as catalysts respectively, and the selectivity of 3, 4-dichloroaniline is99.2 percent and 99 percent, but the carbon nano tube is used as a carrier, so the price is high and the cost is high. The Chinese patent CN102241595A provides a method for preparing 3, 4-dichloroaniline by photocatalytic reduction, the method selects a photocatalytic reactor, the reactor is provided with an air inlet system, an air outlet system, a cooling water inlet system and a cooling water outlet system, the wall of the reactor is required to be capable of transmitting ultraviolet light with the wavelength less than 387.5nm, the photocatalytic reactor is filled with an organic solvent, and 3, 4-dichloronitrobenzene and a solid powder catalyst TiO are added2Adding the mixture into an organic solvent, simultaneously adding surfactant subwet159 as an additive, dissolving the 3, 4-dichloronitrobenzene and solid powdery catalyst TiO in the organic solvent in an inert gas nitrogen atmosphere2Dark adsorbing for 10min, and irradiating with ultraviolet light at power of 250W and radiation intensity of 4120 μ W/cm in inert gas nitrogen atmosphere2Irradiating under the irradiation with 3, 4-dichloronitrobenzene and solid powdery TiO2The yield of 3, 4-dichloroaniline in the light-transmitting reactor of the catalyst is 71.30%. The method has complex operation steps and low yield of the 3, 4-dichloroaniline obtained by single photocatalytic hydrogenation reaction.
This patent invents a light and heat catalytic hydrogenation catalyst, introduces the light source in traditional thermal reaction catalytic hydrogenation's reation kettle, utilizes not unidimensional carbon quantum dot and metal quantum dot to constitute two ingredient active ingredient, is 200 ~ 400nm condition at ultraviolet illumination wavelength for carbon quantum dot stores and electron transfer with higher speed, and hydrogen forms rich electron adsorption state H after the dissociation absorption on active metal particle surface-Attack of N in nitro groups+The center inhibits the dechlorination reaction, thereby greatly improving the selectivity of the reaction.
Disclosure of the invention
The invention aims to provide a photo-thermal catalytic hydrogenation catalyst, which comprises 4.5-6.5 nm carbon dots and 10-15 nm metal dots, and under the action of 280-350 nm ultraviolet light and thermal coupling, excited photoelectrons modulate the electronic characteristics of an active site, so that adsorbed hydrogen is modulated, and the photo-thermal catalytic hydrogenation catalyst is particularly suitable for the reaction of synthesizing 3, 4-dichloroaniline by selective hydrogenation of 3, 4-dichloronitrobenzene.
The invention also aims to provide a method for preparing the photo-thermal catalytic hydrogenation catalyst, which is simple to operate, can realize the generation and growth of the carbon quantum dots on the surface of the carbon sphere in situ in one step, and has a precise and controllable particle size distribution range.
The invention further aims to provide the application of the photo-thermal catalytic hydrogenation catalyst in the photo-thermal catalytic hydrogenation reaction of 3, 4-dichloronitrobenzene, and the photo-thermal catalytic hydrogenation catalyst has the characteristics of high conversion rate, good selectivity, high hydrogenation reaction rate and good stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a photo-thermal catalytic hydrogenation catalyst comprises a mesoporous carbon microsphere carrier, and carbon quantum dots and metal quantum dots which are loaded on the surface of the carrier, wherein the size of the catalyst is 50-100 nm, the particle size range of the carbon quantum dots is 4.5-6.5 nm, the metal quantum dots are one or the combination of two of palladium quantum dots and platinum quantum dots, and the particle size range of the metal quantum dots is 10-15 nm; in the catalyst, the mass fractions of the carbon quantum dots and the metal quantum dots are respectively 10-30% and 1-2%.
A preparation method of a photo-thermal catalytic hydrogenation catalyst comprises the following steps:
1) carrying out polycondensation reaction in an alcohol-water solution system by using 3-aminophenol and formaldehyde as carbon source precursors and ammonia water as a catalyst to obtain polymer microspheres;
2) preparing mixed slurry from the polymer microspheres obtained in the step 1) and deionized water, placing the prepared mixed slurry into a microwave digestion instrument, carrying out microwave reaction for 20-30 minutes at 180-210 ℃, cooling, taking out the mixed slurry, and carrying out vacuum drying to obtain the polymer microspheres modified by the carbon quantum dots, wherein the carbon quantum dots are distributed on the surfaces of the polymer microspheres and have particle sizes ranging from 4.5 nm to 6.5 nm;
3) loading metal salt to the carbon quantum dot modified polymer microspheres obtained in the step 2) through wet impregnation, and drying to obtain a catalyst precursor;
4) calcining and cooling the catalyst precursor obtained in the step 3) in an inert atmosphere to obtain the photo-thermal catalytic hydrogenation catalyst, wherein the calcining process is a temperature programming process: raising the temperature from room temperature to 200-300 ℃ at a heating rate of 0.5-3.5 ℃/min, and keeping the temperature for 1-4 hours; raising the temperature from 200-300 ℃ to 400-600 ℃ at a heating rate of 3.5-8.5 ℃/min, and keeping the temperature for 3-6 hours.
The step 1) of the invention, namely the polymerization of the phenolic resin microspheres, can refer to the existing documents, and the invention specifically recommends the step 1) to be carried out as follows: preparing a mixed solution consisting of 20-25% by mass of ammonia water, alcohol, deionized water, 3-aminophenol and 33-38% by mass of formaldehyde aqueous solution, wherein the volume ratio of the ammonia water to the formaldehyde aqueous solution to the alcohol to the deionized water is 1: 2-8: 20-60: 70-100, and the molar ratio of the 3-aminophenol to the formaldehyde is 1: 2-5; stirring the prepared mixed solution at room temperature for 2-10 h, transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 100-300 ℃ for 12-48 h, and drying to obtain the polymer microspheres. Further, the alcohol is preferably ethanol or propanol. The drying conditions are preferably as follows: drying the mixture for 12 to 48 hours at a temperature of between 20 and 80 ℃.
In the step 2), the size of the carbon quantum dots is controlled by controlling the microwave reaction conditions. The feeding ratio of the polymer microspheres to the deionized water is preferably 1g: 10-25 ml. The vacuum drying conditions are preferably: and drying the mixed slurry obtained by the microwave method for 12-48 hours at the temperature of 20-80 ℃ under the relative vacuum degree of-0.099-0.05 MPa.
The wet impregnation of step 3) of the present invention is a conventional step in the art. Wherein the metal salt can be one or more of the following in combination: palladium nitrate, chloropalladic acid, ethylenediamine palladium chloride, ammonium tetrachloropalladate, sodium chloropalladate, tetraamminepalladium nitrate, tetraamminepalladium dihydrogencarbonate, chloroplatinic acid, platinum nitrate, sodium chloroplatinate, tetraammineplatinum nitrate, dinitrosoplatinum, potassium trichloroammoplatinate, sodium hexachloroplatinate and the like. The step 3) is preferably performed as follows: preparing an aqueous solution of metal salt with the metal mass concentration of 0.001-0.05 g/mL, mixing the polymer microsphere modified by the carbon quantum dots, the aqueous solution of the metal salt and deionized water obtained in the step 2), wherein the feeding ratio of the polymer microsphere modified by the carbon quantum dots, the aqueous solution of the metal salt and the deionized water is 1g: 5-20 mL: 10-25 mL, and drying an impregnated sample after impregnating for 5-10 hours to obtain a catalyst precursor. Wherein the drying conditions are preferably: drying the dipped sample at 40-80 ℃ for 12-48 hours.
In the step 4) of the invention, the inert atmosphere is N2(ii) a And in the calcining process, the volume flow of the inert atmosphere is 10-80 ml/min.
The invention further provides application of the photo-thermal catalytic hydrogenation catalyst in a reaction of synthesizing 3, 4-dichloroaniline shown in a formula II by selective catalytic hydrogenation of 3, 4-dichloronitrobenzene shown in a formula I under the irradiation of 280-350 nm ultraviolet light.
Specifically, the application method of the catalyst comprises the following steps:
putting a photo-thermal catalytic hydrogenation catalyst and 3, 4-dichloronitrobenzene shown in formula I into a high-pressure hydrogenation reaction kettle with ultraviolet irradiation, sealing the reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen at the pressure of 0.5-1.5MPa, opening a heating bond of the reaction kettle, heating to 30-120 ℃, opening a 280-350 nm ultraviolet lamp for irradiation after the temperature is stable, starting stirring to start the reaction, continuing stirring at constant temperature and constant pressure for a period of time when the pressure in the kettle does not decrease, stopping stirring and cooling to room temperature, opening the kettle, taking out a hydrogenation liquid, and separating and treating the hydrogenation liquid to obtain 3, 4-dichloroaniline shown in formula II;
further, in the application, the feeding mass ratio of the compound shown in the formula I to the photo-thermal catalytic hydrogenation catalyst is 100: 0.5-4, preferably 100: 1.0 to 2.0.
Furthermore, the compound shown in the formula I can also be subjected to hydrogenation reaction under the conditions of solvent and no solvent. When the solvent-free hydrogenation reaction is carried out, firstly, the raw material is preheated and melted to be in a liquid state, and then the temperature is raised to the reaction temperature for hydrogenation reaction; in the solvent hydrogenation reaction, the solvent is preferably methanol or ethanol, wherein the feeding ratio of the catalyst to the solvent is 1g to 10-30 ml.
Furthermore, the irradiation wavelength range of the ultraviolet lamp is 280-350 nm, the power is 200-250W, and the radiation intensity is 3660-3980 muW/cm2。
Further, the method for separating and post-treating the hydrogenation liquid comprises the following steps: filtering the hydrogenation liquid to separate out the catalyst, and carrying out vacuum rectification on the filtrate to obtain a product; in the post-treatment process, the catalyst obtained by filtering the hydrogenation liquid can be returned to the reaction kettle for catalyst reuse.
Compared with the prior art, the invention has the beneficial effects that:
1) the mesoporous carbon microspheres are used as carriers of photo-thermal catalysts, groups are simple and controllable, the preparation repeatability is high, and the particle size of spheres is 50-100 nm, so that the influence of mass transfer can be eliminated; the pi-pi bonding bond formed between the carbon quantum dot and the mesoporous carbon microsphere can modulate the anchoring capability of the metal active component, so that the metal is better dispersed on the mesoporous carbon carrier and is not easy to agglomerate, and the metal utilization rate is improved; in addition, under the action of ultraviolet light of 280-350 nm and thermal coupling, excited photoelectrons of 4.5-6.5 nm carbon dots and 10-15 nm metal dots modulate the electronic characteristics of active sites, and a special size effect and quantum effect are presented.
2) The preparation of the carbon quantum dots can achieve more accurate and controllable particle size distribution range of the carbon quantum dots only by simply and conveniently regulating and controlling the microwave temperature and time. In addition, the organic matter based on the synthesized carbon quantum dots is orderly adsorbed on the surface of the polymer microsphere, and a microwave modulation polymerization process is applied to realize the generation and growth of the carbon quantum dots on the surface of the carbon sphere in one step in situ. Compared with the traditional hydrothermal and impregnation loading step-by-step operation, the method is simpler and more convenient.
3) The load type catalyst with 4.5-6.5 nm carbon points and 10-15 nm metal points modulates the electronic characteristic of an active site by excited photoelectrons under the action of 280-350 nm ultraviolet light and thermal coupling, and further modulates the adsorbed hydrogen, so that the load type catalyst is particularly suitable for the reaction of synthesizing 3, 4-dichloroaniline by selective hydrogenation of 3, 4-dichloronitrobenzene. The catalyst has the advantages of mild condition, good stability, low catalyst consumption, multiple times of application, long service life, high catalytic activity and selectivity, high hydrogenation reaction rate and 100 percent of selectivity of the 3, 4-dichloroaniline in the recycling process.
(IV) description of the drawings
FIG. 1 is a transmission electron micrograph of a catalyst prepared according to example 1, in which the spherical balls with the largest particle size are mesoporous carbon microspheres; the carbon quantum dots with the smallest particle size; darker colored are metal dots.
Fig. 2 is a graph showing dynamic light scattering of carbon quantum dots prepared in example 1.
(V) detailed description of the preferred embodiments
Example 1
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the mixture is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃ to obtain the polymer microspheres.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with palladium concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-75 nm, the particle size of the carbon dots is 5-6 nm, and the particle size of the metal is 11-12 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 2%.
Example 2
Measuring 1ml of ammonia water with the mass concentration of 20%, 20ml of ethanol and 70ml of deionized water, mixing and fully stirring, then adding 2g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 2ml of formaldehyde solution with the mass concentration of 33%, stirring for 2 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 12 hours at 100 ℃, cooling to room temperature, and then putting the mixture into an oven to dry for 12 hours at 20 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
The particle size of the catalyst carrier is 50-65 nm, the particle size of the carbon dots is 5.5-6 nm, and the particle size of the metal is 12-13 nm through TEM test; by TG, ICP and material balance, the loading of carbon points is 19 percent, and the loading of metal is 1.8 percent.
Example 3
Measuring 1ml of ammonia water with the mass concentration of 25%, 60ml of ethanol and 100ml of deionized water, mixing and fully stirring, then adding 5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 8ml of formaldehyde solution with the mass concentration of 38%, stirring for 10h at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 48h at 300 ℃, cooling to room temperature, and then putting the mixture into an oven to be dried for 48h at 80 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 85-100 nm, the particle size of the carbon dots is 5.5-6 nm, and the particle size of the metal is 12-13 nm; by TG, ICP and material balance, the loading of carbon points is 17%, and the loading of metal is 2%.
Example 4
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 10ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 180 ℃ and the microwave reaction time at 20 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 20 ℃ for 12 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
The particle size of the catalyst carrier is 70-80 nm, the particle size of the carbon dots is 4.5-5 nm and the particle size of the metal is 11-12 nm through TEM test; by TG, ICP and material balance, the loading of carbon points is 10%, and the loading of metal is 2%.
Example 5
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in an atmosphere with the volume flow of an inert atmosphere of 50ml/min, keeping the temperature for 2 hours at 300 ℃ and keeping the temperature for 4 hours at 600 ℃ (wherein the temperature rise procedure is 1 ℃/min from room temperature to 300 ℃,300 ℃ to 600 ℃ at 5 ℃/min) to obtain the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 65-75 nm, the particle size of the carbon dots is 5.5-6 nm, and the particle size of the metal is 12-13 nm; by TG, ICP and material balance, the loading of carbon points is 21 percent, and the loading of metal is 1.7 percent.
Example 6
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 25ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 210 ℃ and the microwave reaction time at 30 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 80 ℃ for 48 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in an atmosphere with the volume flow of 50ml of inert atmosphere, keeping the temperature at 300 ℃ for 2 hours and keeping the temperature at 600 ℃ for 4 hours (wherein the temperature rising procedure is that the temperature is 1 ℃/minute from room temperature to 300 ℃ and 5 ℃/minute from 300 ℃ to 600 ℃) so as to obtain the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-75 nm, the particle size of the carbon dots is 6-6.5 nm, and the particle size of the metal is 11-13 nm; by TG, ICP and material balance, the loading of carbon points is 30%, and the loading of metal is 2%.
Example 7
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
And (3) mixing 1g of the quantum dot-loaded carbon microsphere solid powder prepared by the method with 10mL of deionized water, uniformly stirring, dripping 20mL of chloropalladate solution with the concentration of 0.001g/mL into the mixed solution, stirring for 5 hours, washing to be neutral, and drying in an oven at 40 ℃ for 12 hours.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
The particle size of the catalyst carrier is 70-80 nm, the particle size of the carbon dots is 5.5-5 nm, and the particle size of the metal is 10-11 nm through TEM test; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 1%.
Example 8
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 8 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-80 nm, the particle size of the carbon dots is 5.5-6.5 nm, and the particle size of the metal is 11-12 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 2%.
Example 9
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
And (3) mixing 1g of the quantum dot-loaded carbon microsphere solid powder prepared by the method with 25mL of deionized water, uniformly stirring, dripping 4mL of chloropalladate solution with the concentration of 0.05g/mL into the mixed solution, stirring for 10 hours, washing to be neutral, and drying in an oven at 80 ℃ for 48 hours.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-75 nm, the particle size of the carbon dots is 4.5-5.5 nm, and the particle size of the metal is 13.5-15 nm; by TG, ICP and material balance, the loading of carbon points is 18 percent, and the loading of metal is 1.8 percent.
Example 10
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in atmosphere with volume flow of inert atmosphere of 10ml/min at 200 deg.C for 1 hr and at 400 deg.C for 3 hr (wherein the temperature rise procedure is 0.5 deg.C/min from room temperature to 200 deg.C and 3.5 deg.C from 200 deg.C to 400 deg.C)C/min) to obtain the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 65-75 nm, the particle size of the carbon dots is 5-5.5 nm, and the particle size of the metal is 11-13 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 1%.
Example 11
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept at 250 ℃ for 2 hours, and the temperature is kept at 500 ℃ for 5 hours, (wherein the temperature rise program is that the temperature is between room temperature and 250 ℃ for 1.5 ℃/minute, and between 250 ℃ and 500 ℃ for 5 ℃/minute), so as to obtain the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-80 nm, the particle size of the carbon dots is 5.5-6 nm, and the particle size of the metal is 11-12 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 1.8%.
Example 12
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 80ml/min, the temperature rise process is that the temperature is kept for 4 hours at 300 ℃ and is kept for 6 hours at 600 ℃ (the temperature rise program is that the temperature is 3.5 ℃/min from room temperature to 300 ℃, and is 8.5 ℃/min from 300 ℃ to 600 ℃) so as to obtain the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-85 nm, the particle size of the carbon dots is 4.5-5.5 nm, and the particle size of the metal is 12-13 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 2%.
Comparative example 1
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
And (3) mixing 1g of the carbon microsphere solid powder prepared by the method with 15mL of deionized water, uniformly stirring, dripping 10mL of chloropalladate solution with the concentration of 0.002g/mL into the mixed solution, stirring for 5 hours, washing to be neutral, and drying in an oven at 60 ℃ for 24 hours.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus the catalytic hydrogenation catalyst without quantum dot load is obtained.
The particle size of the catalyst carrier is 70-75 nm through TEM test, and the particle size of the metal is 11-12 nm; the metal loading was 2% by TG, ICP and mass balance.
Comparative example 2
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the mixture is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃ to obtain the polymer microspheres.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 165 ℃ and the microwave reaction time at 15 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with palladium concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at 60 ℃.
The solid obtained is then in N2Calcining in an atmosphere with an inert atmosphere volume flow of 50ml/min at 300 deg.C for 2 hr and 600 deg.C for 4 hr (wherein the temperature rise is from room temperature to 300 deg.C at 1 deg.C/min and from 300 deg.C to 600 deg.C at 5 deg.C/min)) Thereby obtaining the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-75 nm, the particle size of the carbon dots is 2-3 nm, and the particle size of the metal is 11-12 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 2%.
Comparative example 3
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the mixture is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃ to obtain the polymer microspheres.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 225 ℃ and the microwave reaction time at 35 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with palladium concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-75 nm, the particle size of the carbon dots is 7.5-8.5 nm, and the particle size of the metal is 11-12 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 2%.
Example 13
0.5g of the catalyst of example 1, 25 g of 3,4-Putting dichloronitrobenzene and 30mL methanol solvent into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, sealing the reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen, starting stirring, controlling the wavelength of ultraviolet light to be 350nm, the power to be 250W, and the radiation intensity to be 3980 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 120 ℃ and the hydrogen pressure is 1.5 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100%, the selectivity of 3, 4-dichloroaniline is 99.94%, and the reaction time is 35 minutes.
Example 14
0.5g of the catalyst of example 3, 50 g of 3, 4-dichloronitrobenzene and 10mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 280nm, the power is 200W, and the radiation intensity is 3660 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 30 ℃ and the hydrogen pressure is 0.5 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 99.8 percent, the selectivity of the 3, 4-dichloroaniline is 99.2 percent, and the reaction time is 45 minutes.
Example 15
0.5g of the catalyst of example 1, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 325nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100%, the selectivity of 3, 4-dichloroaniline is 100%, and the reaction time is 25 minutes.
Example 16
0.5g of the catalyst from example 5, 40 g of 3, 4-dichloronitrobenzene, and 15mL of methanol solvent were placed in a UV lampSealing the reaction kettle in a high-pressure hydrogenation reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen, starting stirring, controlling ultraviolet wavelength at 325nm, power at 225W, and radiation intensity at 3820 μ W/cm2,The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 99.8 percent, the selectivity of the 3, 4-dichloroaniline is 99.94 percent, and the reaction time is 35 minutes.
Example 17
0.5g of the catalyst of example 6, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 315nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100%, the selectivity of 3, 4-dichloroaniline is 99.96%, and the reaction time is 35 minutes.
Example 18
0.5g of the catalyst of example 10, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 315nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100%, the selectivity of 3, 4-dichloroaniline is 99.94%, and the reaction time is 45 minutes.
Example 19
0.5g of the catalyst of example 1 and 25 g of 3, 4-dichloronitrobenzene are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, and air is replaced by nitrogenReplacing nitrogen with hydrogen, stirring, controlling ultraviolet wavelength at 350nm, power at 250W, and radiation intensity at 3980 μ W/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 120 ℃ and the hydrogen pressure is 1.5 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 3, 4-dichloroaniline is 99.96 percent, and the reaction time is 120 minutes.
Example 20
0.5g of the catalyst of example 8 and 50 g of 3, 4-dichloronitrobenzene are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 280nm, the power is 200W, and the radiation intensity is 3660 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 0.5 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 99.8 percent, the selectivity of the 3, 4-dichloroaniline is 99.94 percent, and the reaction time is 120 minutes.
Example 21
0.5g of the catalyst of example 1 and 40 g of 3, 4-dichloronitrobenzene are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 315nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 90 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 3, 4-dichloroaniline is 99.96 percent, and the reaction time is 80 minutes.
Example 22
0.5g of the catalyst of example 7 and 40 g of 3, 4-dichloronitrobenzene are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 350nm, the power is 250W,the radiation intensity is 3980 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 120 ℃ and the hydrogen pressure is 1.5 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 99.7 percent, the selectivity of the 3, 4-dichloroaniline is 99.94 percent, and the reaction time is 120 minutes.
Example 23
0.5g of the catalyst of example 8 and 25 g of 3, 4-dichloronitrobenzene are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 315nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 3, 4-dichloroaniline is 99.95 percent, and the reaction time is 120 minutes.
Comparative example 4
0.5g of the catalyst of comparative example 1 and 25 g of 3, 4-dichloronitrobenzene are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 315nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 92%, the selectivity of 3, 4-dichloroaniline is 94%, and the reaction time is 250 minutes.
Comparative example 5
0.5g of the catalyst of comparative example 2, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 325nm, the power is 225W, and the radiation intensity is 3820 muW/cm2At a temperature of 80 ℃ and a hydrogen pressure of 1MPaHydrogenation reaction is carried out. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100%, the selectivity of 3, 4-dichloroaniline is 95.6%, and the reaction time is 225 minutes.
Comparative example 6
0.5g of the catalyst of comparative example 3, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is closed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 325nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 97,9 percent, the selectivity of 3, 4-dichloroaniline is 93.7 percent, and the reaction time is 215 minutes.
Comparative example 7
0.5g of the catalyst of example 1, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 364nm, the power is 275W, and the radiation intensity is 4070 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 98.7%, the selectivity of 3, 4-dichloroaniline is 94.9%, and the reaction time is 250 minutes.
Comparative example 8
0.5g of the catalyst of example 1, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 240nm, the power is 175W, and the radiation intensity is 3480 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle is not lowerAnd (3) reducing, continuing stirring at constant temperature and constant pressure for 20 minutes, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and obtaining an analysis result as follows: the reaction conversion rate is 96.3 percent, the selectivity of the 3, 4-dichloroaniline is 92.8 percent, and the reaction time is 244 minutes.
Comparative examples 9 to 19
Comparative examples 9 to 19 show the results of the catalytic hydrogenation of 3, 4-dichloronitrobenzene using the catalyst of example 1 in the absence of light under the other reaction conditions described in examples 13 to 23, respectively, as shown in the following table.
Examples | Conversion rate% | Selectivity% | 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 example12 | 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 |
Example 24
Example 24 is the results of using the catalyst of example 1 in the catalytic hydrogenation of 3, 4-dichloronitrobenzene in multiple applications under light conditions, reaction conditions referred to the reaction conditions of example 15, as shown in the following table.
Claims (9)
1. A preparation method of a photo-thermal catalytic hydrogenation catalyst comprises a mesoporous carbon microsphere carrier, and carbon quantum dots and metal quantum dots which are loaded on the surface of the carrier, wherein the size of the catalyst is 50-100 nm, the particle size range of the carbon quantum dots is 4.5-6.5 nm, the metal quantum dots are one or the combination of two of palladium quantum dots and platinum quantum dots, and the particle size range of the metal quantum dots is 10-15 nm; in the catalyst, the mass fractions of the carbon quantum dots and the metal quantum dots are respectively 10-30% and 1-2%;
the preparation method comprises the following steps:
1) carrying out polycondensation reaction in an alcohol-water solution system by using 3-aminophenol and formaldehyde as carbon source precursors and ammonia water as a catalyst to obtain polymer microspheres;
2) preparing mixed slurry from the polymer microspheres obtained in the step 1) and deionized water, placing the prepared mixed slurry into a microwave digestion instrument, carrying out microwave reaction for 20-30 minutes at 180-210 ℃, cooling, taking out the mixed slurry, and carrying out vacuum drying to obtain the polymer microspheres modified by the carbon quantum dots, wherein the carbon quantum dots are distributed on the surfaces of the polymer microspheres and have particle sizes ranging from 4.5 nm to 6.5 nm;
3) loading metal salt to the carbon quantum dot modified polymer microspheres obtained in the step 2) through wet impregnation, and drying to obtain a catalyst precursor;
4) calcining and cooling the catalyst precursor obtained in the step 3) in an inert atmosphere to obtain the photo-thermal catalytic hydrogenation catalyst, wherein the calcining process is a temperature programming process: raising the temperature from room temperature to 200-300 ℃ at a heating rate of 0.5-3.5 ℃/min, and keeping the temperature for 1-4 hours; raising the temperature from 200-300 ℃ to 400-600 ℃ at a heating rate of 3.5-8.5 ℃/min, and keeping the temperature for 3-6 hours.
2. The method of claim 1, wherein: step 1) was carried out as follows: preparing a mixed solution consisting of 20-25% by mass of ammonia water, alcohol, deionized water, 3-aminophenol and 33-38% by mass of formaldehyde aqueous solution, wherein the volume ratio of the ammonia water to the formaldehyde aqueous solution to the alcohol to the deionized water is 1: 2-8: 20-60: 70-100, and the molar ratio of the 3-aminophenol to the formaldehyde is 1: 2-5; stirring the prepared mixed solution at room temperature for 2-10 h, transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 100-300 ℃ for 12-48 h, and drying to obtain the polymer microspheres.
3. The method of claim 1, wherein: in the step 2), the feeding ratio of the polymer microspheres to the deionized water is 1g: 10-25 ml; the vacuum drying conditions were: and drying the mixed slurry obtained by the microwave method for 12-48 hours at the temperature of 20-80 ℃ under the relative vacuum degree of-0.099-0.05 MPa.
4. The method of claim 1, wherein: in the step 3), the metal salt is one or more of the following combinations: palladium nitrate, chloropalladic acid, ethylenediamine palladium chloride, ammonium tetrachloropalladate, sodium chloropalladate, tetraamminepalladium nitrate, tetraamminepalladium bicarbonate, chloroplatinic acid, platinum nitrate, sodium chloroplatinate, tetraammineplatinum nitrate, dinitrosoplatinum, potassium trichloroammine platinate and sodium hexachloroplatinate; the step 3) is carried out as follows: preparing an aqueous solution of metal salt with the metal mass concentration of 0.001-0.05 g/mL, mixing the polymer microsphere modified by the carbon quantum dots, the aqueous solution of the metal salt and deionized water obtained in the step 2), wherein the feeding ratio of the polymer microsphere modified by the carbon quantum dots, the aqueous solution of the metal salt and the deionized water is 1g: 5-20 mL: 10-25 mL, and drying an impregnated sample after impregnating for 5-10 hours to obtain a catalyst precursor.
5. The photo-thermal catalytic hydrogenation catalyst prepared by the preparation method of claim 1 is applied to the reaction of synthesizing 3, 4-dichloroaniline shown in formula II by selective catalytic hydrogenation of 3, 4-dichloronitrobenzene shown in formula I under the irradiation of ultraviolet light of 280-350 nm;
6. the use of claim 5, wherein: the application method of the catalyst comprises the following steps:
the method comprises the steps of putting a photo-thermal catalytic hydrogenation catalyst and 3, 4-dichloronitrobenzene shown in a formula I into a high-pressure hydrogenation reaction kettle with ultraviolet irradiation, sealing the reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen at the pressure of 0.5-1.5MPa, opening a heating bond of the reaction kettle, heating to 30-120 ℃, opening a 280-350 nm ultraviolet lamp for irradiation after the temperature is stable, starting stirring to start reaction, continuing stirring at constant temperature and constant pressure for a period of time when the pressure in the kettle does not decrease, stopping stirring, cooling to room temperature, opening the kettle, taking out hydrogenation liquid, and separating and treating the hydrogenation liquid to obtain the 3, 4-dichloroaniline shown in a formula II.
7. The use of claim 6, wherein: the feeding mass ratio of the compound shown in the formula I to the photo-thermal catalytic hydrogenation catalyst is 100: 0.5 to 4.
8. The use of claim 6, wherein: carrying out hydrogenation reaction on the compound shown in the formula I in the presence of a solvent or in the absence of the solvent; when the solvent-free hydrogenation reaction is carried out, firstly, the raw material is preheated and melted to be in a liquid state, and then the temperature is raised to the reaction temperature for hydrogenation reaction; when the hydrogenation reaction with the solvent is carried out, the solvent is methanol or ethanol.
9. The use of claim 6, wherein: the irradiation wavelength range of the ultraviolet lamp is 280-350 nm, the power is 200-250W, and the radiation intensity is 3660-3980 muW/cm2。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810664224.0A CN109046328B (en) | 2018-06-25 | 2018-06-25 | Photo-thermal catalytic hydrogenation catalyst, preparation thereof and application thereof in 3, 4-dichloronitrobenzene selective hydrogenation reaction |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810664224.0A CN109046328B (en) | 2018-06-25 | 2018-06-25 | Photo-thermal catalytic hydrogenation catalyst, preparation thereof and application thereof in 3, 4-dichloronitrobenzene selective hydrogenation reaction |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109046328A CN109046328A (en) | 2018-12-21 |
CN109046328B true CN109046328B (en) | 2021-07-27 |
Family
ID=64821514
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810664224.0A Active CN109046328B (en) | 2018-06-25 | 2018-06-25 | Photo-thermal catalytic hydrogenation catalyst, preparation thereof and application thereof in 3, 4-dichloronitrobenzene selective hydrogenation reaction |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109046328B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111266107B (en) * | 2020-03-18 | 2022-12-20 | 河北工业大学 | Preparation method and application of resin carbon sphere supported palladium catalyst |
CN114618467A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Carbon sphere and preparation method and application of bimetallic catalyst loaded by carbon sphere |
CN113200876A (en) * | 2021-05-20 | 2021-08-03 | 安徽东至广信农化有限公司 | Synthesis process of p-aminophenol |
CN114797934A (en) * | 2022-04-06 | 2022-07-29 | 福州大学 | Nitrogen-doped carbon nanotube supported palladium platinum catalyst and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103387219A (en) * | 2013-07-22 | 2013-11-13 | 苏州大学 | A preparation method for water-soluble multicolor carbon quantum points by microwave radiation |
CN104531148A (en) * | 2014-12-31 | 2015-04-22 | 天津大学 | Preparation method of assembly of carbon quantum dots (CQDS) |
CN105692581A (en) * | 2014-11-28 | 2016-06-22 | 天津大学 | Preparation method of high-crystallization graphene quantum dots capable of replacing fullerene |
CN107413335A (en) * | 2017-03-31 | 2017-12-01 | 浙江工业大学 | A kind of mesoporous carbon microspheres carry composite catalyst and preparation method and application |
CN107413330A (en) * | 2017-03-31 | 2017-12-01 | 浙江工业大学 | A kind of catalyst and preparation method and application |
-
2018
- 2018-06-25 CN CN201810664224.0A patent/CN109046328B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103387219A (en) * | 2013-07-22 | 2013-11-13 | 苏州大学 | A preparation method for water-soluble multicolor carbon quantum points by microwave radiation |
CN105692581A (en) * | 2014-11-28 | 2016-06-22 | 天津大学 | Preparation method of high-crystallization graphene quantum dots capable of replacing fullerene |
CN104531148A (en) * | 2014-12-31 | 2015-04-22 | 天津大学 | Preparation method of assembly of carbon quantum dots (CQDS) |
CN107413335A (en) * | 2017-03-31 | 2017-12-01 | 浙江工业大学 | A kind of mesoporous carbon microspheres carry composite catalyst and preparation method and application |
CN107413330A (en) * | 2017-03-31 | 2017-12-01 | 浙江工业大学 | A kind of catalyst and preparation method and application |
Also Published As
Publication number | Publication date |
---|---|
CN109046328A (en) | 2018-12-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109046328B (en) | Photo-thermal catalytic hydrogenation catalyst, preparation thereof and application thereof in 3, 4-dichloronitrobenzene selective hydrogenation reaction | |
CN107008290B (en) | Preparation method and catalytic application of monoatomic dispersion palladium-based catalyst | |
CN100428989C (en) | Method for preparing loading type nano Pd/C catalyst from colloidal solution | |
CN109046334B (en) | Photo-thermal catalytic hydrogenation catalyst, preparation thereof and application thereof in p-benzoquinone selective hydrogenation reaction | |
CN111530485B (en) | Carbon and nitrogen co-doped titanium dioxide nano material and preparation method and application thereof | |
CN109453766B (en) | Ag-loaded TiO with atomic-level dispersion2Preparation method of mesoporous nanobelt photocatalyst | |
CN109331860B (en) | Low-platinum alloy composite nano photocatalyst for air purification and preparation method and application thereof | |
CN109248680B (en) | Low-energy-consumption chemical field-driven organic pollutant degradation catalyst and application thereof | |
CN114011434B (en) | Two-dimensional ZnIn2S4Photocatalyst loaded with protruding noble metal monoatoms and application thereof | |
CN104399535B (en) | The preparation method and application that a kind of magnetic partner is catalyst based | |
CN113522279A (en) | Gold palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole and preparation method thereof | |
CN115805072B (en) | Supported AgPt alloy photocatalyst and preparation method and application thereof | |
CN107308967B (en) | Catalyst promoter for photocatalytic decomposition of formic acid to produce hydrogen, photocatalytic system and method for decomposing formic acid to produce hydrogen | |
CN113441157A (en) | Photoreduction synthesis method of supported high-dispersion metal monatomic catalyst | |
CN111359652A (en) | Carbon nitride-based nickel-gold bimetallic supported catalyst and preparation method thereof | |
CN112774718A (en) | Cuprous oxide/tubular graphite-like phase carbon nitride composite catalyst and preparation method and application thereof | |
CN109046332B (en) | Photo-thermal catalytic hydrogenation catalyst, and preparation method and application thereof | |
CN109174084B (en) | Catalytic hydrogenation catalyst, preparation thereof and application thereof in selective hydrogenation reaction of tetrahydrofarnesyl acetone | |
CN109331818B (en) | Catalytic hydrogenation catalyst, preparation thereof and application thereof in selective hydrogenation reaction of aromatic nitro compound | |
CN111939957A (en) | Preparation method of photocatalytic nitrogen fixation material porous carbon nitride nanofiber/graphene | |
CN109225272B (en) | Pt-ZnS/C catalyst and preparation method and application thereof | |
CN110694655A (en) | Preparation method of silver sulfide/silver phosphate/graphene oxide composite photocatalyst | |
Yu et al. | Cu and Ni dual-doped ZnO nanostructures templated by cellulose nanofibrils for the boosted visible-light photocatalytic degradation of wastewater pollutants | |
CN109395709A (en) | A kind of graphene quantum dot/two dimension titanium dioxide and preparation method thereof | |
Guan et al. | In-situ synthesis of highly efficient direct Z-scheme Cu3P/g-C3N4 heterojunction photocatalyst for N2 photofixation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |