CN112371170A - Heterojunction nano composite catalyst and preparation method and application thereof - Google Patents
Heterojunction nano composite catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN112371170A CN112371170A CN202011234322.4A CN202011234322A CN112371170A CN 112371170 A CN112371170 A CN 112371170A CN 202011234322 A CN202011234322 A CN 202011234322A CN 112371170 A CN112371170 A CN 112371170A
- Authority
- CN
- China
- Prior art keywords
- sio
- dpa
- catalyst
- solution
- preparation
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 120
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 65
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 65
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 65
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 28
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003607 modifier Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003463 adsorbent Substances 0.000 claims abstract description 11
- 150000004718 beta keto acids Chemical class 0.000 claims abstract description 11
- 230000002860 competitive effect Effects 0.000 claims abstract description 11
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 9
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 42
- 229910052802 copper Inorganic materials 0.000 claims description 32
- 229910052707 ruthenium Inorganic materials 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- YCANAXVBJKNANM-UHFFFAOYSA-N 1-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2[N+](=O)[O-] YCANAXVBJKNANM-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000000741 silica gel Substances 0.000 claims description 18
- 229910002027 silica gel Inorganic materials 0.000 claims description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000006722 reduction reaction Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 238000011065 in-situ storage Methods 0.000 claims description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 8
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 7
- 238000006557 surface reaction Methods 0.000 claims description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims description 5
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000011160 research Methods 0.000 abstract description 7
- 239000011943 nanocatalyst Substances 0.000 abstract description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 50
- 239000002105 nanoparticle Substances 0.000 description 7
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000001000 anthraquinone dye Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0254—Nitrogen containing compounds on mineral substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a heterojunction Cu-Ru/Fe3O4@SiO2A DPA nano composite catalyst, a preparation method and application thereof, belonging to the field of nano catalyst research. The invention takes tetraethoxysilane as a silicon source and DMP-30 as an organic modifier in NH3·H2In the presence of O, Fe is prepared3O4@SiO2(ii) a With Fe3O4@SiO2Is used as a carrier, after the surface of DPA is functionalized, copper chloride and ruthenium chloride are used as raw materials, beta-ketoacid is used as a competitive adsorbent, and a deposition precipitation method is adopted to prepare Cu-Ru/Fe in the presence of an organic modifier3O4@SiO2-a DPA nanocomposite catalyst; and the catalyst is used for catalyzing and preparing the 1-aminoanthraquinone. The nano composite catalyst of the invention has high activityHigh selectivity, excellent catalytic activity and stability, mild reaction conditions, avoidance of generation of a large amount of by-products, and improvement of selectivity of target products.
Description
Technical Field
The invention relates to a heterojunction Cu-Ru/Fe3O4@SiO2a-DPA nano composite catalyst, a preparation method and application thereof, belonging to nano catalysisAgent research field.
Technical Field
1-aminoanthraquinone is an important intermediate of dye, and 1-aminoanthraquinone and derivatives thereof are used as raw materials to synthesize a plurality of varieties of vat dyes, disperse dyes, reactive dyes, acid dyes and the like. The 1-aminoanthraquinone can also be used for producing printing ink, coating and pigment, and is also used for liquid crystal dye, photosensitizer of photodegradable polyester and electrocatalytic reduction H in recent years2O2The catalyst, the photosensitive dye and the electrode material of the dye-sensitized solar cell.
Currently, the largest 1-aminoanthraquinone manufacturer in the world is Bayer, Germany, and the largest Japanese manufacturer is Kawasaki chemical company. Along with the development of dye industry in China, the demand of 1-amino anthraquinone is large, in recent years, the demand of anthraquinone dye in China exceeds 8000 tons/year, the anthraquinone dye is increased year by year at a growth rate of 15-20%, and the domestic market is very wide. In recent years, due to the problem of environmental pollution in the production process of preparing 1-aminoanthraquinone by reducing 1-nitroanthraquinone by traditional sulfur alkali, the production reduction or the production stop of anthraquinone dye intermediates, anthraquinone reduced and dispersed dyes is carried out in the countries of North America, Western Europe and the like, and the countries turn to developing countries to buy high-quality products. The demand of high-quality 1-aminoanthraquinone in domestic and foreign markets is very large and will continue to increase, so that improvement or development of new processes, improvement of product quality, reduction of production cost and reduction of environmental pollution are imminent for domestic l-aminoanthraquinone manufacturers.
Disclosure of Invention
The invention prepares heterojunction Cu-Ru/Fe3O4@SiO2-DPA nanocomposite catalyst and for the catalytic synthesis of 1-aminoanthraquinones. The process route is simple, no three wastes are generated, and the process is green and environment-friendly. Meanwhile, the catalyst has the advantages of small dosage, high catalytic activity, high selectivity and stable performance.
The technical scheme of the invention is as follows:
the invention firstly provides a heterojunction Cu-Ru/Fe3O4@SiO2A DPA nano composite catalyst, a preparation method thereof and research on the catalytic performance thereof.
The preparation method of the catalyst comprises the steps of firstly, taking tetraethoxysilane as a silicon source, taking 2,4, 6-tri (dimethylamino methyl) phenol (DMP-30) as an organic modifier and adding NH3·H2In the presence of O, preparing a magnetic silica gel carrier Fe3O4@SiO2(ii) a Then using the prepared magnetic silica gel Fe3O4@SiO2Is used as a carrier, is functionalized by the surface of di-n-propylamine (DPA), takes copper chloride and ruthenium chloride as raw materials and beta-keto acid as a competitive adsorbent, and prepares the binary Cu-Ru/Fe with the heterojunction structure by a deposition precipitation method in the presence of an organic modifier, namely poly dimethyl diallyl ammonium chloride3O4@SiO2-DPA nanocomposite catalyst.
Specifically, the preparation method of the catalyst comprises the following steps:
step 1: magnetic silica gel carrier Fe with core-shell structure3O4@SiO2Preparation of
At room temperature, adding Fe3O4After ultrasonic treatment with an organic modifier A, uniformly dispersing the organic modifier A and the organic modifier A in a mixed solvent of acetone and deionized water, adding an ammonia water solution, and uniformly mixing and stirring; then, ethyl orthosilicate (TEOS) is added dropwise, after hydrolysis reaction, the obtained precipitate is washed by absolute ethyl alcohol until the solution is neutral, and then is dried to obtain black-brown nano composite powder.
Wherein the organic modifier A is 2,4, 6-tri (dimethylaminomethyl) phenol (DMP-30) and the mass of the organic modifier A is Fe3O43-15 wt% of TEOS.
TEOS and Fe3O4And NH3·H2The molar ratio of O is: 1: 0.3-1.2: 0.5-4.
The ultrasonic treatment time is 0.5 h.
The volume ratio of the acetone to the deionized water is 4:1.
The mixing and stirring time is 0.5 h.
The hydrolysis reaction time is 2-5 h.
The drying condition is drying for 24 hours at 120 ℃.
Step 2: Cu-Ru/Fe3O4@SiO2Preparation of-DPA nanocomposite catalysts
Preparation of heterojunction structure binary Cu-Ru/Fe by deposition-precipitation method3O4@SiO2-DPA nanocomposite catalyst.
Firstly, the magnetic silica gel carrier Fe prepared in the step 13O4@SiO2After being treated by ultrasonic dispersion for 0.5h, the mixture is evenly dispersed in 100mL of absolute ethyl alcohol solution and transferred to a round-bottom flask. Adding a certain mass of organic modifier B, mixing and stirring, and carrying out surface functionalization reaction for 1-4 h at the water bath temperature of 30-50 ℃ to obtain Fe3O4@SiO2-DPA。
Wherein, the organic modifier B is di-n-propylamine (DPA), and the adding amount of the DPA is 5 to 25 weight percent of the mass of the TEOS in the step 1.
Next, a certain amount of the competitive adsorbent was weighed and dissolved in 20mL of anhydrous ethanol solution and recorded as solution (I). Dissolving Cu and Ru metal precursors and an organic modifier C in absolute ethyl alcohol respectively according to a certain ratio, mixing and stirring to obtain 140mL of mixed solution, and marking as a solution (II). The solution (I) and the solution (II) are respectively injected into the Fe-bearing magnetic silica gel carrier slowly by a syringe3O4@SiO2And (4) mixing and stirring in a round-bottom flask of-DPA, adsorbing and dispersing for 2-6 h.
Wherein the competitive adsorbent is beta-ketonic acid, and the dosage of the beta-ketonic acid is magnetic silica gel Fe3O4@SiO2-3 to 18 wt% of DPA mass.
The metal precursors of Cu and Ru are respectively CuCl2·2H2O and RuCl3·3H2O; the molar ratio of the Cu to the Ru metal ions is as follows: 1: 0.05-0.25.
The organic modifier C is poly dimethyl diallyl ammonium chloride, and the mass of the poly dimethyl diallyl ammonium chloride is CuCl2·2H2O and RuCl2·3H25-10 wt% of the total mass of O.
Then, NaOH ethanol solution with the concentration of 1.5moL/L is dripped into the flask at the dropping speed of 3mL/min at a constant speed to regulate the reactionThe pH value of the solution is 11. Raising the temperature to 60-80 ℃, dropwise adding 1.5moL/L tetrabutylammonium borohydride ethanol solution, carrying out in-situ reduction reaction for 5-8 h, and finally obtaining the heterojunction binary Cu-Ru/Fe3O4@SiO2-DPA nanocomposite catalyst.
Wherein, the molar ratio of the total amount of Cu and Ru metal ions to the reducing agent tetrabutylammonium borohydride is as follows: 1: 4-12.
The total load of the nano metal Cu and Ru in the nano catalyst finally obtained in the step 2 is as follows: 5-30 wt%, that is, the Cu-Ru/Fe to be finally obtained3O4@SiO2The mass fraction of Cu and Ru in the-DPA nano composite catalyst is 5-30 wt%.
The invention also provides the application of the catalyst in the reaction of preparing 1-aminoanthraquinone by catalytic reduction of 1-nitroanthraquinone through hydrogenation:
to prepare heterojunction binary Cu-Ru/Fe3O4@SiO2The high-quality 1-aminoanthraquinone is prepared by catalyzing 1-nitroanthraquinone to be hydrogenated and reduced under certain reaction temperature and pressure by using a-DPA nano compound as a catalyst and using methyl chloroform as a solvent. The specific method comprises the following steps:
placing the nano composite catalyst and 1-nitroanthraquinone in a high-pressure reaction kettle according to a certain proportion, adding 500mL of methyl chloroform, and introducing N2After purging for 15 minutes, high-purity hydrogen is introduced to replace N2And boosting the pressure to a certain reaction pressure, reacting for a certain time at a certain temperature and stirring speed, and analyzing the components and the content of the reaction product by adopting high performance liquid chromatography after the reaction is finished.
Wherein the mass ratio of the 1-nitroanthraquinone to the nano catalyst is as follows: 1: 0.01-0.05.
The reaction pressure of the catalyst in the reaction for selectively catalyzing and synthesizing the 1-aminoanthraquinone is 1.5-2.0 MPa, the reaction temperature is 70-130 ℃, and the reaction time is 3-9 h.
The invention has the advantages that:
the invention prepares Cu-Ru/Fe with a heterojunction structure3O4@SiO2-DPA nanocomposite catalyst. Aiming at the defects of poor dispersity of the traditional binary structure metal catalyst,The invention has the defects of easy agglomeration and the like, and the invention designs the structure of the Cu-Ru binary nano metal catalyst and regulates and controls the catalytic performance of the Cu-Ru binary nano metal catalyst. In the preparation process of the composite nano catalyst, the magnetic silica gel carrier Fe with the shell-core structure is synthesized under the action of the organic modifier DMP-30 containing polyfunctional groups3O4@SiO2. The surface of the Cu-Ru/Fe nano-particle is functionally modified by DPA, and the DPA is cooperated with an organic modifier to interact with a competitive adsorbent beta-keto acid to control the growth speed and direction of the nano-metal crystal particles, so that the Cu-Ru nano-particle with high dispersion and uniform size distribution is promoted to be obtained, the performance has important influence on the catalytic performance of the Cu-Ru/Fe nano-particle, and finally the binary Cu-Ru/Fe with high activity and high selectivity heterojunction structure is obtained3O4@SiO2-DPA nanocomposite catalyst.
Compared with a single nano Cu and Ru metal catalyst, the synergistic effect between the bimetallic Cu and the Ru not only improves the sintering resistance of particles, but also changes the electronic property and the geometric structure of active components of the catalyst, so that the heterojunction structure binary Cu-Ru/Fe3O4@SiO2The DPA nano composite catalyst shows higher activity and selectivity.
By changing the molar ratio, the particle size and the structure of the active components Cu and Ru, the binary Cu-Ru/Fe of the heterojunction structure can be regulated and controlled3O4@SiO2The nano composite catalyst has catalytic activity of selectively catalyzing 1-nitroanthraquinone to selectively hydrogenate to prepare 1-aminoanthraquinone.
Therefore, the Cu-Ru/Fe prepared by the invention3O4@SiO2The nano composite catalyst shows excellent catalytic activity and stability in the selective catalytic hydrogenation reaction process, has mild reaction conditions, avoids the generation of a large amount of byproducts, improves the selectivity of a target product, obtains a high-quality 1-aminoanthraquinone product, and can be directly used in high-end downstream product consumption markets. Meanwhile, the catalyst can be recycled. Compared with the traditional process, the method not only can greatly reduce the environmental pollution, but also optimizes the process flow, and finally obtains the high-quality 1-aminoanthraquinone product.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1 Cu1-Ru0.15/Fe3O4@SiO2Preparation of DPA nanocomposite catalyst:
ethyl orthosilicate is used as a silicon source, 2,4, 6-tri (dimethylaminomethyl) phenol (DMP-30) is used as an organic modifier, and NH is added3·H2Hydrolyzing Tetraethoxysilane (TEOS) in the presence of O to prepare magnetic silica gel carrier Fe3O4@SiO2；(2)Fe3O4@SiO2Is used as a carrier, is functionalized by the surface of di-n-propylamine (DPA), takes copper chloride and ruthenium chloride as raw materials and beta-keto acid as a competitive adsorbent, and prepares the binary Cu-Ru/Fe with the heterojunction structure by a deposition precipitation method in the presence of poly-dimethyl diallyl ammonium chloride3O4@SiO2-a DPA nanocomposite catalyst; wherein, TEOS, Fe3O4、NH3·H2The mass ratio of O is as follows: 1:0.75: 1; the molar ratio of Cu to Ru in the catalyst is 1:0.15, and the total loading of Cu and Ru is 15wt% of the total weight of the composition. The specific operation is as follows:
magnetic silica gel carrier Fe with core-shell structure3O4@SiO2The preparation of (1):
at room temperature, 10g of Fe3O4After being treated with 2.10g of DMP-30 by ultrasonic for 0.5h, the mixture is uniformly dispersed in a mixed solvent of 200mL of acetone and 50mL of deionized water, 9.8mL of ammonia water solution is added dropwise, and the mixture is mixed and stirred for 0.5 h. Then, 13.33g of TEOS is dropwise added, after hydrolysis reaction for 3.5h, the obtained substance is washed by absolute ethyl alcohol until the solution is neutral, and after drying for 24h at 120 ℃, black-brown nano composite powder is finally prepared.
Cu-Ru/Fe3O4@SiO2Preparation of DPA nanocomposite catalyst:
weigh 7.20g of Fe3O4@SiO2After being treated by ultrasonic wave for 0.5h, the mixture is evenly dispersed in 100mL of absolute ethanol solution and transferred to a 1000mL round-bottom flask. 2.00g of DPA was added to the flask, mixed and stirred, and surface functionalized at a bath temperature of 40 deg.CReacting for 2.5h to obtain Fe3O4@SiO2-DPA。
0.65g of the beta-keto acid was weighed out and dissolved in 20mL of absolute ethanol solution and identified as solution (I). 2.69g of CuCl2·2H2O, 0.62g RuCl2·3H2O and 0.17g of polydimethyldiallylammonium chloride were dissolved in 80mL, 40mL and 20mL of absolute ethanol, respectively, and the resulting solutions were mixed and stirred to obtain a mixed solution (solution II).
The solution (I) and the solution (II) were slowly injected with 7.2g of Fe containing the magnetic silica gel carrier by a syringe, respectively3O4@SiO2DPA in a round-bottom flask, stirring and mixing at 40 ℃ water bath temperature, adsorbing and dispersing for 3 h. Dropwise adding NaOH ethanol solution with the concentration of 1.5moL/L into the flask at a constant speed of 3mL/min, and adjusting the pH value of the reaction solution to 11. The temperature is increased to 70 ℃, 96.58mL of 1.5moL/L tetrabutylammonium borohydride ethanol solution is added dropwise to carry out in-situ reduction reaction for 6h, and the loading capacity is 15wt% of heterojunction structure binary Cu1-Ru0.15/Fe3O4@SiO2-DPA nanocomposite catalyst.
Example 2: TEOS, Fe3O4And NH3·H2Effect of the molar ratio of O on catalyst preparation
In the same way as in example 1, TEOS quality was unchanged and Fe was changed3O4And NH3·H2The mass of O is such that the molar ratio to TEOS is: 1:0.3:1, 1:1.2:1, 1:0.75:0.5, 1:0.75: 4. As a result, it was found that TEOS and Fe3O4Can change the molar ratio of SiO2The shell thickness of (2); TEOS and NH3·H2The molar ratio of O will affect the rate of hydrolysis of TEOS. When TEOS, Fe3O4And NH3·H2The molar ratio of O is: 1:0.75:4, in Fe3O4The surface generates compact and uniform SiO2And (3) granules.
Example 3: effect of different amounts of the substances on the preparation of the catalyst
Just as in example 1, the amounts of DMP-30 were varied to 0.70g and 3.50g, respectively; DPA, beta-keto acids andthe amounts of polydimethyldiallylammonium chloride used were 0.67g and 3.33g, 0.22g and 1.30g, 0.26g and 0.33g, respectively, as shown in Table 1, whereby these conditions were examined for the Cu produced1-Ru0.15/Fe3O4@SiO2-effect of DPA nanocomposite catalyst.
TABLE 1 Cu-Ru/Fe3O4@SiO2The amounts of the respective substances in the preparation of the DPA nanocomposite catalysts
| DMP-30/g | DPA/g | Beta-keto acid/g | Polydimethyldiallylammonium chloride/g |
| 0.70 | 2.00 | 0.65 | 0.17 |
| 2.10 | 2.00 | 0.65 | 0.17 |
| 3.50 | 2.00 | 0.65 | 0.17 |
| 2.10 | 0.67 | 0.65 | 0.17 |
| 2.10 | 3.33 | 0.65 | 0.17 |
| 2.10 | 2.00 | 0.22 | 0.17 |
| 2.10 | 2.00 | 1.30 | 0.17 |
| 2.10 | 2.00 | 0.65 | 0.26 |
| 2.10 | 2.00 | 0.65 | 0.33 |
Research and analysis show that proper amount of DMP-30 is beneficial to Fe3O4And SiO2Combination of (1); and proper amount of DPA can successfully convert Fe3O4@SiO2Fully functionalising the surface of (a); with the increase of the dosage of the competitive adsorbent beta-keto acid, the active components Cu and Ru are in Fe3O4@SiO2Increased dispersibility on DPA supports. When the dosage of the competitive adsorbent is magnetic silica gel Fe3O4@SiO29 of DPA qualitywt% of the total amount is not favorableCombining the active component with a carrier; the organic modifier poly dimethyl diallyl ammonium chloride with different dosages can regulate and control the size and the structure of the active components Cu and Ru nano particles.
To obtain heterojunction binary Cu-Ru/Fe3O4@SiO2The nano composite catalyst catalyzes 1-nitroanthraquinone, and the catalytic activity of the reaction for preparing the 1-aminoanthraquinone is inspected, and the result shows that when the mass of DMP-30 is Fe3O49 of total mass with TEOSwt% DPA mass is 15% of TEOS masswtPercent, the mass of the beta-ketoacid is magnetic silica gel Fe3O4@SiO29 of DPA qualitywtMass of poly dimethyl diallyl ammonium chloride is CuCl2·2H2O and RuCl2·3H25 of the total mass of Owt% of the total weight of the heterojunction binary Cu-Ru/Fe3O4@SiO2The DPA nanocomposite catalyst showed the highest catalytic performance (table 3).
Example 4: influence of different times during the respective reactions on the preparation of the catalyst
The hydrolysis reaction time of TEOS is changed to 2h, 3.5h and 5h respectively as in example 1; fe3O4@SiO2The surface functionalization reaction time is 1h, 2.5h and 4 h; fe3O4@SiO2-DPA to Cu2+、Ru2+The adsorption time of (3) is 2 and 6 hours; in-situ reduction of Cu with tetrabutylammonium borohydride2+、Ru2+The reaction time of (2) was 5, 8h, as shown in Table 2, whereby the conditions were examined for Cu produced1-Ru0.15/Fe3O4@SiO2-effect of DPA nanocomposite catalyst.
TABLE 2 heterojunction binary Cu-Ru/Fe3O4@SiO2Respective reaction time in the preparation of the-DPA nanocomposite catalyst
| TEOS hydrolysis reaction/h | Surface functionalization reaction/h | Adsorption/h | In situ reduction reaction/h |
| 2 | 1 | 3 | 6 |
| 3.5 | 1 | 3 | 6 |
| 5 | 1 | 3 | 6 |
| 3.5 | 2.5 | 3 | 6 |
| 3.5 | 4 | 3 | 6 |
| 3.5 | 2.5 | 2 | 6 |
| 3.5 | 2.5 | 6 | 6 |
| 3.5 | 2.5 | 3 | 5 |
| 3.5 | 2.5 | 3 | 8 |
Research and analysis show that TEOS is completely hydrolyzed when the hydrolysis reaction time reaches 3.5 h; DPA to Fe3O4@SiO2The surface functionalization reaction time of the catalyst reaches 2.5h, and Fe can be successfully prepared3O4@SiO2Fully functionalising the surface of (a); fe3O4@SiO2-DPA to Cu2+、Ru2+The adsorption time of the copper-based copper alloy can reach adsorption balance when being 3 hours, so that the Cu is2+、Ru2+The Cu is uniformly dispersed on the carrier, and the longer adsorption and stirring time leads to the Cu2+、Ru2+Easy to fall off the carrier; under the preferable experimental conditions of the invention, Cu can be reduced for 6h in situ2+、Ru2+And (3) completely reducing to generate Cu and Ru nano particles with small particle size and uniform particle size distribution. The sizes of the Cu and Ru nano particles are gradually increased along with the prolonging of the in-situ reduction reaction time.
Example 5: influence of different molar ratios of nano metal Cu, Ru and tetrabutylammonium borohydride on catalyst preparation
The same as example 1, but the amount of the tetrabutylammonium borohydride ethanol solution was changed to 48.3mL and 144.9 mL. Research and analysis show that when the molar ratio of the total amount of the nano metal Cu and Ru to the reducing agent tetrabutylammonium borohydride is 1:8, Cu-Ru/Fe with small particle size and uniform dispersion is obtained3O4@SiO2-DPA nanocomposite catalyst. Along with the increase of the reducing agent, heterojunction binary Cu-Ru/Fe3O4@SiO2The sizes of Cu and Ru nano-particles in the DPA nano-composite catalyst are gradually increased.
Example 6: cu1-Ru0.15/Fe3O4@SiO2Preparation of 1-aminoanthraquinone by catalytic hydrogenation of-DPA nano composite catalyst
The loading amount prepared in example 1 was 15wt% heterojunction binary Cu1-Ru0.15/Fe3O4@SiO2The application of the-DPA nano composite catalyst in the reaction of preparing 1-aminoanthraquinone by catalytic hydrogenation of 1-nitroanthraquinone comprises the following steps:
0.21g of the nanocomposite catalyst and 7.00g of 1-nitroanthraquinone were placed in a high-pressure reactor, 500mL of methyl chloroform was added, and N was introduced2After purging for 15 minutes, high-purity hydrogen is introduced to replace N2And increasing the pressure to 1.5MPa, reacting for 3h at the reaction temperature of 90 ℃ and the stirring speed of 600rpm, and after the reaction is finished, analyzing the components and the content of a reaction product by adopting high performance liquid chromatography, wherein the selectivity and the conversion rate of the raw materials of the obtained product are shown in Table 3.
Example 7: preparation of 1-aminoanthraquinone by catalytic hydrogenation of nano composite catalyst obtained under different conditions
Like example 1, the molar ratio of copper to ruthenium was varied only as: 1:0.05, 1:0.25, adding RuCl3·3H2The quality of O is changed as follows: 0.21g and 1.03g, wherein the mass of the poly dimethyl diallyl ammonium chloride is changed to be as follows: the dosage of 0.15g, 0.19g and 1.5moL/L reducer of tetrabutylammonium borohydride ethanol solution is changed as follows: 88.2mL and 105.0mL, respectively, with a prepared loading of 15wtThe mol ratio of copper to ruthenium is as follows: 1:0.05, 1:0.25 Cu-Ru/Fe3O4@SiO2-DPA nanocomposite catalyst. In the same way as in example 6, the prepared binary Cu-Ru/Fe with different ruthenium and copper ratios3O4@SiO2The DPA nano composite catalyst is applied to the hydrogenation reaction of 1-nitroanthraquinone, and the selectivity and the conversion rate of the raw material of the obtained product are shown in a table 3;
as in example 1, only Fe was changed3O4@SiO2The mass of DPA is: 21.59g and 3.60g, and the prepared loading capacity is 5wt% and 30wt% of Cu1-Ru0.15/Fe3O4@SiO2-DPA nanocomposite catalyst. In the same way as example 6, the prepared binary Cu-Ru/Fe with different Cu and Ru loading amounts3O4@SiO2The DPA nano composite catalyst is applied to the hydrogenation reaction of 1-nitroanthraquinone, and the selectivity and the conversion rate of the raw material of the obtained product are shown in a table 3;
as in example 6, only the amounts of catalyst used were changed, respectively: 0.07g and 0.35 g; the reaction temperature is as follows: at 70 ℃ and 130 ℃; the reaction time is as follows: and 6h and 9h, carrying out 1-nitroanthraquinone selective hydrogenation reaction. The product selectivity and feedstock conversion are shown in table 3.
TABLE 3 heterojunction binary Cu-Ru/Fe3O4@SiO2Selective catalysis of 1-nitroanthraquinone hydrogenation reaction by using-DPA nano composite catalyst
Research and analysis show that the binary Cu-Ru/Fe exists in the heterojunction3O4@SiO2In the reaction of selectively catalyzing 1-nitroanthraquinone hydrogenation by the DPA nano composite catalyst, the catalytic activity of the nano composite catalyst for selectively catalyzing 1-nitroanthraquinone hydrogenation to prepare 1-aminoanthraquinone can be regulated and controlled by changing the molar ratio of Cu to Ru, the loading amounts of nano metals Cu and Ru, the reaction temperature, the reaction time and the dosage of the catalyst. When the mass of use is 3wtThe load capacity of the nano metal Cu and Ru is 15 percentwt% of heterojunction structure binary Cu1-Ru0.15/Fe3O4@SiO2the-DPA nano composite catalyst selectively catalyzes the hydrogenation reaction of 1-nitroanthraquinone for 3 hours at the temperature of 90 ℃, the conversion rate of the 1-nitroanthraquinone reaches 99.2 percent, and the selectivity of the 1-aminoanthraquinone reaches 99.1 percent.
Example 7 (comparative experiment):
according to the conventional method, single nano-copper and nano-ruthenium catalysts are respectively prepared. In the course of catalytic reaction, single nano copperThe dosage of the nano ruthenium is 15 in the example 6wt% of Cu1-Ru0.15/Fe3O4@SiO2The molar amounts of copper and ruthenium in the-DPA catalyst are the same. The single metal Cu and Ru nano catalyst is subjected to 1-nitroanthraquinone selective hydrogenation reaction, and the selectivity and the conversion rate of the obtained product are shown in a table 3.
The comparison shows that the single metal nano Cu catalyst has no catalytic hydrogenation activity at the reaction temperature of 90 ℃. The activity of the single metal nano Ru catalyst is slightly higher, but the selectivity is low. And the heterojunction structure is binary Cu1-Ru0.15/Fe3O4@SiO2The DPA nano composite catalyst simultaneously shows good catalytic activity and selectivity. This is because of Cu1-Ru0.15/Fe3O4@SiO2-magnetic silica gel support Fe in DPA catalyst3O4@SiO2The synergistic effect between the DPA and the bimetallic Cu and Ru not only improves the dispersibility of the nanometer metal Cu and Ru, but also changes the electronic property and the geometric structure of the active component of the catalyst, so that the catalyst shows better hydrogenation performance.
Example 8 (comparative experiment):
same as example 1, Fe3O4Does not participate in the preparation process, and prepares single SiO2And (3) a carrier. In the same manner as in example 6, Cu thus prepared was used1-Ru0.15/SiO2The application of the-DPA nano composite catalyst to the hydrogenation reaction of 1-nitroanthraquinone, and the selectivity of the obtained product and the conversion rate of the raw material are shown in table 3. Compared with binary Cu in a heterojunction structure, the catalytic activity and selectivity of the catalyst are far lower than those of the binary Cu in the heterojunction structure1-Ru0.15/Fe3O4@SiO2-DPA nanocomposite catalyst.
1-aminoanthraquinones are important fine chemicals. At present, the domestic production process of 1-aminoanthraquinone mainly adopts a sodium sulfide reduction method, and the process is aged and has poor environmental effect. The liquid phase catalytic hydrogenation method has the characteristics of good product quality, high yield, mild reaction conditions, short process and few three wastes, and is a better choice for replacing the old process. Heterojunction structure binary Cu-Ru prepared by the method0.15/Fe3O4@SiO2The 1-aminoanthraquinone prepared by hydrogenation of 1-nitroanthraquinone under the catalysis of a DPA nano composite material as a catalyst shows excellent catalytic activity, and the selected Cu and Ru loading capacity is 30wt％Cu-Ru0.15/Fe3O4@SiO2the-DP is a catalyst, and when the reaction temperature is 90 ℃ and the reaction lasts for 3 hours, the conversion rate of the 1-nitroanthraquinone reaches 99.9 percent, and the selectivity of the 1-aminoanthraquinone reaches 99.9 percent.
Claims (10)
1.Cu-Ru/Fe3O4@SiO2-DPA nanocomposite catalyst, said nanocomposite catalyst being a heterojunction structure, the total loading of the nanometals Cu, Ru in said nanocomposite catalyst being: 5 to 30 wt%.
2. Cu-Ru/Fe3O4@SiO2-a process for the preparation of a DPA nanocomposite catalyst, characterized in that it comprises:
magnetic silica gel carrier Fe with core-shell structure3O4@SiO2The preparation of (1):
at room temperature, adding Fe3O4After ultrasonic treatment with an organic modifier A, uniformly dispersing the organic modifier A and the organic modifier A in a mixed solvent of acetone and deionized water, adding an ammonia water solution, and uniformly mixing and stirring; dropwise adding Tetraethoxysilane (TEOS), washing the obtained precipitate with absolute ethyl alcohol after hydrolysis reaction until the solution is neutral, and drying to obtain black-brown nano composite powder, namely the magnetic silica gel carrier Fe3O4@SiO2；
Cu-Ru/Fe3O4@SiO2Preparation of DPA nanocomposite catalyst:
the prepared magnetic silica gel carrier Fe3O4@SiO2Uniformly dispersing the mixture into absolute ethyl alcohol solution after ultrasonic dispersion treatment, adding an organic modifier B, mixing and stirring, and carrying out surface functionalization reaction under a water bath condition to obtain Fe3O4@SiO2-DPA；
Weighing competitive adsorbent, dissolving the competitive adsorbent in absolute ethyl alcohol solution, and marking as solution (I);
respectively dissolving Cu and Ru metal precursors and an organic modifier C in absolute ethyl alcohol, and then mixing and stirring to obtain a mixed solution, which is marked as a solution (II);
slowly injecting the solution (I) and the solution (II) into a magnetic silica gel carrier Fe3O4@SiO2-DPA in a vessel, mixing, stirring, dispersing;
dropwise adding NaOH ethanol solution into a container at a constant speed, adjusting the pH value of the reaction solution, raising the temperature to 60-80 ℃, dropwise adding tetrabutylammonium borohydride ethanol solution, carrying out in-situ reduction reaction, and finally obtaining the binary Cu-Ru/Fe of the heterojunction structure3O4@SiO2-DPA nanocomposite catalyst.
3. Cu-Ru/Fe according to claim 23O4@SiO2-a process for the preparation of a DPA nanocomposite catalyst,
the organic modifier A is 2,4, 6-tri (dimethylaminomethyl) phenol (DMP-30), and the added mass of the organic modifier A is Fe3O43-15 wt% of the total mass of TEOS;
the volume ratio of the acetone to the deionized water is 4: 1;
TEOS and Fe3O4And NH3·H2The molar ratio of O is: 1: 0.3-1.2: 0.5-4, preferably: 1:0.75:4.
4. Cu-Ru/Fe according to claim 23O4@SiO2The preparation method of the-DPA nano composite catalyst is characterized in that the hydrolysis reaction time is 2-5 h.
5. Cu-Ru/Fe according to claim 23O4@SiO2The preparation method of the DPA nano composite catalyst is characterized in that the organic modifier B is di-n-propylamine (DPA), and the adding amount of the DPA is 5-25 wt% of the mass of TEOS; the surface functionalization reaction under the water bath condition is specifically a surface functionalization reaction for 1-4 hours at a water bath temperature of 30-50 ℃.
6. Cu-Ru/Fe according to claim 23O4@SiO2The preparation method of the-DPA nano composite catalyst is characterized in that the competitive adsorbent is beta-keto acid, and the dosage of the beta-keto acid is magnetic silica gel Fe3O4@SiO2-3 to 18 wt% of DPA mass.
7. Cu-Ru/Fe according to claim 23O4@SiO2The preparation method of the-DPA nano composite catalyst is characterized in that the Cu and Ru metal precursors are respectively CuCl2·2H2O and RuCl2·3H2O; the molar ratio of the Cu to the Ru metal ions is as follows: 1: 0.05-0.25;
the organic modifier C is poly dimethyl diallyl ammonium chloride, and the mass of the poly dimethyl diallyl ammonium chloride is CuCl2·2H2O and RuCl2·3H25-10 wt% of the total mass of O.
8. Cu-Ru/Fe according to claim 23O4@SiO2The preparation method of the-DPA nano composite catalyst is characterized in that the solution (I) and the solution (II) are mixed, stirred and dispersed for 2-6 h.
9. Cu-Ru/Fe according to claim 23O4@SiO2The preparation method of the-DPA nano composite catalyst is characterized in that NaOH ethanol solution is dropwise added at a constant speed to adjust the pH value of a reaction solution to 11, preferably, the concentration of the NaOH ethanol solution is 1.5moL/L, and the dropwise adding speed is 3 mL/min;
the concentration of the dropwise added tetrabutylammonium borohydride ethanol solution is 1.5 moL/L; the molar ratio of the total amount of the Cu and Ru metal ions to the reducing agent tetrabutylammonium borohydride is as follows: 1: 4-12;
the in-situ reduction reaction time is 5-8 h.
10. A Cu-Ru/Fe as claimed in claim 13O4@SiO2Application of the DPA nano composite catalyst in the reaction of preparing 1-aminoanthraquinone by catalytic reduction of 1-nitroanthraquinone through hydrogenation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011234322.4A CN112371170B (en) | 2020-11-07 | 2020-11-07 | Heterojunction nano composite catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011234322.4A CN112371170B (en) | 2020-11-07 | 2020-11-07 | Heterojunction nano composite catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112371170A true CN112371170A (en) | 2021-02-19 |
| CN112371170B CN112371170B (en) | 2022-10-28 |
Family
ID=74579378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011234322.4A Active CN112371170B (en) | 2020-11-07 | 2020-11-07 | Heterojunction nano composite catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112371170B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286478A (en) * | 2022-07-17 | 2022-11-04 | 曲阜师范大学 | Method for preparing lignin-derived phenolic monomer by catalyzing Ni-Cu alloy through selective hydrogenation and aromatic ring protection mechanism |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497448A (en) * | 2017-08-30 | 2017-12-22 | 江苏大学 | A kind of rhodium/copper alloy nanocatalyst and its preparation method and application |
| CN108295850A (en) * | 2018-01-22 | 2018-07-20 | 江苏欣诺科催化剂有限公司 | A kind of catalyst and its catalysis process preparing amino anthraquinones |
| CN110252383A (en) * | 2019-05-17 | 2019-09-20 | 江苏大学 | A kind of Cu@Ru/MCM-41 nanocatalyst and its preparation method and application |
-
2020
- 2020-11-07 CN CN202011234322.4A patent/CN112371170B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497448A (en) * | 2017-08-30 | 2017-12-22 | 江苏大学 | A kind of rhodium/copper alloy nanocatalyst and its preparation method and application |
| CN108295850A (en) * | 2018-01-22 | 2018-07-20 | 江苏欣诺科催化剂有限公司 | A kind of catalyst and its catalysis process preparing amino anthraquinones |
| CN110252383A (en) * | 2019-05-17 | 2019-09-20 | 江苏大学 | A kind of Cu@Ru/MCM-41 nanocatalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| R. B. NASIR BAIG, ET AL: "Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds", 《ACS SUSTAINABLE CHEM. ENG.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286478A (en) * | 2022-07-17 | 2022-11-04 | 曲阜师范大学 | Method for preparing lignin-derived phenolic monomer by catalyzing Ni-Cu alloy through selective hydrogenation and aromatic ring protection mechanism |
| CN115286478B (en) * | 2022-07-17 | 2023-11-24 | 曲阜师范大学 | Ni-Cu alloy is catalyzed and prepared into lignin-derived phenolic monomer through selective hydrogenation and aromatic ring protection mechanism |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112371170B (en) | 2022-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109453773B (en) | Supported bimetallic core-shell structure catalyst and preparation method thereof | |
| CN114192140B (en) | Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof | |
| CN107497448B (en) | Rhodium/copper alloy nano catalyst and preparation method and application thereof | |
| CN112371170B (en) | Heterojunction nano composite catalyst and preparation method and application thereof | |
| CN114588940B (en) | Nickel-based catalyst for hydrogenation of phenolic compounds, and preparation method and application thereof | |
| CN106582709B (en) | Catalyst for synthesizing aromatic primary amine by hydrogenation of aromatic nitrile and preparation method thereof | |
| Garcia et al. | γ-valerolactone from levulinic acid and its esters: Substrate and reaction media determine the optimal catalyst | |
| CN113304760A (en) | High-dispersion platinum-based catalyst and preparation method and application thereof | |
| CN111167515B (en) | Monomolecular heteropoly acid inlaid honeycomb-shaped carbon material loaded nano metal catalyst and preparation method and application thereof | |
| CN114870853B (en) | Core-shell catalyst for preparing cyclohexanol by catalyzing guaiacol to be subjected to selective hydrodeoxygenation | |
| CN116178244A (en) | Fullerene pyrrolidine derivative, and preparation method and application thereof | |
| CN110624571B (en) | Catalyst for synthesizing 3, 5-dichloroaniline and preparation method and application thereof | |
| CN113649049B (en) | Maleic anhydride selective hydrogenation catalyst and preparation method and application method thereof | |
| CN113560594B (en) | Synthesis method for synthesizing intermetallic palladium copper nanocrystalline in one step and application thereof | |
| CN107442134A (en) | A kind of rhodium/nickel alloy nanocatalyst and its preparation method and application | |
| CN110252383A (en) | A kind of Cu@Ru/MCM-41 nanocatalyst and its preparation method and application | |
| CN107952443B (en) | Novel ethynylation catalyst for synthesizing 1, 4-butynediol and preparation method thereof | |
| CN115715982B (en) | Catalyst suitable for preparing VA and MMP, catalyst preparation method and catalysis method | |
| CN116571263B (en) | Preparation method of silicon dioxide supported nickel-based catalyst and application of catalyst in hydrogenation of 5-hydroxymethylfurfural | |
| CN115850003B (en) | Production method of o-xylene | |
| CN114471580B (en) | Synthesis and application method of supported nickel-gallium catalyst | |
| CN115532290B (en) | Specific crystal face selective hydrogenation catalyst and preparation method and application thereof | |
| CN107497426A (en) | A kind of preparation method and applications of palladium/silver alloy nanocatalyst | |
| CN115254188B (en) | Method for preparing amphiphilic composite catalyst Pd@IL/CNT-COOH by one-pot method | |
| CN118217981A (en) | Supported copper-based nano metal catalyst and preparation method and application thereof |
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 |