CN101372440A - Method for preparing biaryl compound in supercritical carbon dioxide by SBA-15 load palladium catalysis - Google Patents

Method for preparing biaryl compound in supercritical carbon dioxide by SBA-15 load palladium catalysis Download PDF

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CN101372440A
CN101372440A CNA2008100135060A CN200810013506A CN101372440A CN 101372440 A CN101372440 A CN 101372440A CN A2008100135060 A CNA2008100135060 A CN A2008100135060A CN 200810013506 A CN200810013506 A CN 200810013506A CN 101372440 A CN101372440 A CN 101372440A
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冯秀娟
包明
颜美
张涛
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Dalian University of Technology
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Abstract

The invention provides a method for preparing a biaryl compound in supercritical carbon dioxide by SBA-15-supported palladium catalyst, which belongs to the technical fields of fine chemical engineering and material chemistry. The method is characterized by replacing the conventional organic solvents with a pollution-free solvent supercritical carbon dioxide; low viscosity and high diffusivity of the supercritical carbon dioxide are adopted for driving a substrate to react in the pore passages of the SBA-15, after the reaction finishes, the substrate is brought out from the pore passages; meanwhile, supported catalyst is adopted, so the catalyst can be reused by simple filtration. The effects and benefits of the method are as follows: the pollution-free solvent is used, and the pollution problem of the conventional solvents is solved, the catalyst has high activity, and the activity is not obviously reduced and no palladium black is separated out after a plurality of recycles. And a product is separated out in a crystal form after the reaction finishes.

Description

The preparation method of aryl-linking compound in the supercritical co of SBA-15 load palladium catalysis
Technical field
The invention belongs to fine chemistry industry and material chemistry technical field, relate to synthetic aryl-linking compound, particularly be implemented in the greenization technology of synthetic aryl-linking compound in the supercritical co with the coordination catalysis method.
Background technology
The dibenzyl structure extensively is present in the compound of complicated natural product and biologically active, and the Suzuki linked reaction usually is the committed step of synthetic this compounds.Fundamental research through two more than ten years, the Suzuki linked reaction has obtained bigger development, the Application and Development of novel and high-efficiency catalyzer particularly, make the linked reaction of chlorinated aromatic hydrocarbons that some reactive behavioies are relatively poor and sterically hindered bigger halogenated aryl hydrocarbon under the condition of gentleness, just can carry out, particularly contain the synthetic of heteroatomic biaryl compounds, make the synthetic route of some baroque natural products become simple.
Suzuki reaction in the conventional solvent can both obtain good yield greatly, with an organic solvent, makes the sepn process of catalyzer, alkali and product need a large amount of time and input in still reacting.Not only bring very big financial loss, and very unfavorable to environment.(supercritical carbondioxide is abbreviated as scCO to supercritical co 2), not only because it is cheap, nontoxic, do not fire, environmentally friendly, but also because of having the not available specific physical character of organic solvent (low viscosity and high diffusibility), and become one of reaction medium of Green Chemistry and technology.
Supercritical co (scCO 2) in organic synthesis, caused people's great attention as the replace solvents of conventional solvent.Relevant in supercritical co, utilize palladium catalysis to form the reaction of C-C key: Heck reaction, Stille reaction, Suzuki reaction etc. have become the heat subject of domestic and international chemical research.The Suzuki reaction also is subjected to scientific research person's favor deeply as a kind of important reaction of synthetic C-C key.
People's reported first such as Holmes in 1998 in scCO 2In the linked reaction of carrying out, they have synthesized new fluorine-containing phosphine part and have been used for the Suzuki linked reaction, can access with conventional solvent in the reacting phase yield of working as, but the reaction times require oversize [Carroll M.A.; Holmes A.B.Chem.Commun.1998,1395-1396.].
1999 and calendar year 2001, people such as Fu have reported for the catalytic Heck reaction of palladium, P (t-Bu) 3Be the extraordinary part of effect [Littke A.F.; Fu G.C.J.Org.Chem.1999,64,10-11.], [Littke A.F.; Fu G.C.J.Am.Chem.Soc.2001,123,6989-7000.].People such as Holmes have reported the Suzuki reaction under the katalysis of tri-butyl phosphine palladium again under their work inspires, the author attempts catalyst cupport is carried out scCO to polymkeric substance 2In the Suzuki linked reaction.The Suzuki reaction of iodobenzene and bromobenzene and phenylo boric acid all can be carried out, but the reaction yield of bromobenzene is not fine [Early T.R.; Gordon R.S.; Carroll M.A.et al.Chem.Commun.2001,1966-1967.].
People such as Kerton are applied to scCO with silica supported nano Pd catalyst 2Middle Heck reaction and Suzuki linked reaction.For fine to the reactive behavior of methyl iodobenzene and phenylo boric acid, productive rate surpasses 90%, catalyst P d (PDMS-PPh 2) 2Cl 2Reuse and do not see active the reduction for 4 times yet, yet when using the 5th, its activity is reduced to half [Saffarzdeh-Matin S. of live catalyst approximately; Kerton F.M.; Lynam J.M.et al.Green Chem.2006,8,965-971.].
Summary of the invention
The technical problem to be solved in the present invention provides a kind of Green Chemical Technology of synthetic aryl-linking compound, adopt supercritical co to make solvent, substituted traditional organic solvent, thereby solved problem of environmental pollution, adopt loaded catalyst simultaneously, by the repeated use of simple filtering realization catalyzer, solved the losing issue of noble metal.
The technical solution used in the present invention:
The SBA-15 functional materials that at first synthesizes outside surface protection internal surface grafting phosphine part, and then load P d 2(dba) 3Make the SBA-15 loaded palladium catalyst.This catalyzer is applied to the Suzuki linked reaction of aromatic series halides and aromatic boric acid in the supercritical co, thereby synthesizes aryl-linking compound, simultaneously catalyzer is filtered, the washing back is reused.
Specific operation process:
1) preparation SBA-15 loaded palladium catalyst
The SBA-15 that 2.0g is not removed template is behind 80 ℃ of vacuum-drying 2h; join in the exsiccant 100mL there-necked flask; add the trimethoxy-benzene base silane of dewater oxy picolinate and 2mL of the deaerated toluene that dewaters, the 2mL of 50mL under nitrogen protection successively, 115 ℃ are stirred 2h down.Suction filtration behind the cool to room temperature, filter cake are used a spot of dehydrated alcohol, ether and washing with acetone successively, and vacuum-drying 6h makes the SBA-15 of outside surface modification.With ethanol is extraction agent, uses apparatus,Soxhlet's to extract the template of the SBA-15 inside of above-mentioned outside surface modification.Behind the reflux 48h, oven dry 6h obtains outside surface and modifies the inner SBA-15 that removes template.Outside surface is modified the inner SBA-151.5g that removes template to be had in joining in the there-necked flask of 250mL of stirrer, 80 ℃ down behind the dry 2h with nitrogen replacement three times, add the deaerated toluene that dewaters of 50mL, dewater oxy picolinate and the 1.5g (MeO) of 1.5mL 3SiCH 2CH 2CH 2SCH 2C 6H 4(p-PPh 2), stir 24h at 115 ℃.With the reaction mixture cool to room temperature, suction filtration, filter cake are used a spot of methyl alcohol successively, ether, and acetone after the normal hexane washing, is inserted it in the cable type extractor according, under nitrogen protection, with the impurity 12h in the dichloromethane extraction duct.Vacuum-drying 6h obtains white solid PE-SBA-15-PPh 3With 1.0g PE-SBA-15-PPh 3Have in joining in the there-necked flask of the 100mL that stirs magneton, use nitrogen replacement three times behind 80 ℃ of dry 2h, add the deoxygenation methylene dichloride that dewaters, the 0.1000g Pd of 50mL 2(dba) 3Stir 24h under the catalyzer, room temperature.Suction filtration, filter cake cleans with a spot of methylene dichloride, and filtrate concentrates the back and reclaims catalyzer.The grey black solid that obtains wrapped with filter paper be put in the Soxhlet extraction element, methylene dichloride is made solvent and clean impurity 12h in the duct, dry 6h under the vacuum, the SBA-15 loaded palladium catalyst PE-SBA-15-PPh that obtains under nitrogen protection 3-Pd.
2) aryl-linking compound synthetic in the supercritical co sees reaction formula (1).
In the stainless steel autoclave of 25mL, add catalyzer, aromatic series halides, aromatic boric acid and alkali under the nitrogen protection successively, pour carbonic acid gas then, heated and stirred reaction in 90 ℃ of oil baths, pressure is 18-20MPa.After reaction finishes, treat the autoclave cool to room temperature after, put it into freezing 0.5h in the frozen water, slowly put carbonic acid gas, open still after, can see that product separates out on the still wall with crystalline form.Because therefore this reaction, still adopts the method purified product of column chromatography for a spot of trial response.With ethyl acetate catalyzer and product are washed out in still, filter out catalyzer, filtrate concentrates back column chromatography for separation product, by 1H NMR spectrogram identifies that through water and absolute ethanol washing after, utilize again again by dried recovered for catalyzer.
3) adopt respectively Varian-400 type nuclear magnetic resonance analyser ( 1H 400MHz; 13C 100MHz) CDCl 3Be solvent; Identify the structure of product.
Described aromatic series halides, the ortho para that is halogeno-benzene is by the derivative of R base replacement, the straight chained alkyl of R=alkoxyl group, carbonyl, cyano group, nitro, other halogens, hydrogen, 1-12 carbon, cyclohexane radical derivative or phenyl derivatives;
Described aromatic boric acid, the ortho para that is phenylo boric acid is by the derivative of R base replacement; The straight chained alkyl of R=hydrogen, alkoxyl group, other halogens, 1-12 carbon, cyclohexane radical derivative, phenyl derivatives, carbonyl, cyano group or nitro;
Described aryl-linking compound is the product that is generated through cross-coupling reaction by aromatic series halides and aromatic boric acid.
Effect of the present invention and benefit are:
1, reaction selects for use supercritical co to make medium, meets the requirement of Green Chemistry.
2, catalyst activity height, after repeatedly recycling, active not obviously reduction.
3, reaction end after product is just separated out with crystalline form, and catalyzer just can be repeatedly used through simple filtering, and does not have palladium black to separate out.
Description of drawings
Fig. 1 is the 4-nitrobiphenyl 1H NMR spectrogram.
Fig. 2 is the 4-acetyl biphenyl 1The HNMR spectrogram.
Fig. 3 is the 4-xenol 1H NMR spectrogram.
Fig. 4 is a 4-aldehyde radical biphenyl 1H NMR spectrogram.
Fig. 5 is the 3-phenylpyridine 1H NMR spectrogram.
Fig. 6 be 4-methoxyl group-4 '-nitrobiphenyl 1The HNMR spectrogram.
Fig. 7 be 4-fluoro-4 '-nitrobiphenyl 1H NMR spectrogram.
Fig. 8 be 4-methyl-4 '-nitrobiphenyl 1H NMR spectrogram.
Fig. 9 is 3,4-two fluoro-4 '-nitrobiphenyl 1H NMR spectrogram.
Figure 10 is that catalyst recirculation is used the interior phenomenon of reaction back still for the third time.
Figure 11 is that catalyst recirculation is used the phenomenon in the still behind the 5th secondary response.
Figure 12 is that catalyst recirculation is used the phenomenon in the still behind the 8th secondary response.
Embodiment
Below in conjunction with technical scheme and the detailed specific embodiments of the invention of accompanying drawing.
Embodiment 1: synthetic 4-nitrobiphenyl
In the stainless steel autoclave of 25mL, add successively under the nitrogen protection p-Nitrobromobenzene (0.5mmol, 0.1010g), phenylo boric acid (0.75mmol, 0.0914g) and K 3PO 43H 2O (1.0mmol, 0.2663g), PE-SBA-15-PPh 3-Pd (1.0%, 0.0380g).Then, pour the 15g carbonic acid gas, stirring reaction 24h in 90 ℃ of oil baths.
After reaction finishes, treat the autoclave cool to room temperature after, put it in the frozen water, behind the cooling 0.5h, slowly put carbonic acid gas, open still after, can see that light yellow crystal separates out at the bottom of still.With ethyl acetate product is washed out at the bottom of still, be spin-dried for, the column chromatography for separation product.Developping agent is pure sherwood oil.
Embodiment 2: synthetic 4-acetyl biphenyl
In the stainless steel autoclave of 25mL, add successively under the nitrogen protection parabromoacetophenone (0.5mmol, 0.0995g), phenylo boric acid (0.75mmol, 0.0914g) and K 3PO 43H 2O (1.0mmol, 0.2663g), PE-SBA-15-PPh 3-Pd (1.0%, 0.0380g).Then, pour the 15g carbonic acid gas, stirring reaction 24h in 90 ℃ of oil baths.
After reaction finishes, treat the autoclave cool to room temperature after, put it in the frozen water, behind the cooling 0.5h, slowly put carbonic acid gas, open still after, can see that white crystal separates out at the bottom of still.With ethyl acetate product is washed out at the bottom of still, be spin-dried for, the column chromatography for separation product.Developping agent is sherwood oil: ethyl acetate=45:1.
Embodiment 3 synthetic 4-aldehyde radical biphenyl
In the stainless steel autoclave of 25mL, add successively under the nitrogen protection p-bromobenzaldehyde (0.5mmol, 0.0925g), phenylo boric acid (0.75mmol, 0.0914g) and K 3PO 43H 2O (1.0mmol, 0.2663g), PE-SBA-15-PPh 3-Pd (0.8%, 0.0304g).Then, pour the 15g carbonic acid gas, stirring reaction 24h in 90 ℃ of oil baths.
After reaction finishes, treat the autoclave cool to room temperature after, put it in the frozen water, behind the cooling 0.5h, slowly put carbonic acid gas, open still after, can see that white crystal separates out at the bottom of still.With ethyl acetate product is washed out at the bottom of still, be spin-dried for, the column chromatography for separation product.Developping agent is normal hexane: ethyl acetate=45:1.Embodiment 4: synthetic 4-methoxyl group-4 '-nitrobiphenyl
In the stainless steel autoclave of 25mL, add successively under the nitrogen protection p-Nitrobromobenzene (0.5mmol, 0.1010g), to methoxyphenylboronic acid (0.75mmol, 0.1140g) and K 3PO 43H 2O (1.0mmol, 0.2663g), PE-SBA-15-PPh 3-Pd (1.0%, 0.0380g).Then, pour the 15g carbonic acid gas, stirring reaction 24h in 90 ℃ of oil baths.
After reaction finishes, treat the autoclave cool to room temperature after, put it in the frozen water, behind the cooling 0.5h, slowly put carbonic acid gas, open still after, can see that yellow crystals separates out at the bottom of still.With ethyl acetate product is washed out at the bottom of still, be spin-dried for, the column chromatography for separation product.Developping agent is normal hexane: ethyl acetate=10:1.Embodiment 5: synthetic 4-methyl-4 '-nitrobiphenyl
In the stainless steel autoclave of 25mL, add successively under the nitrogen protection p-Nitrobromobenzene (0.5mmol, 0.1010g), to methylphenylboronic acid (0.75mmol, 0.1020g) and K 3PO 43H 2O (1.0mmol, 0.2663g), PE-SBA-15-PPh 3-Pd (0.8%, 0.0304g).Then, pour the 15g carbonic acid gas, stirring reaction 24h in 90 ℃ of oil baths.
After reaction finishes, treat the autoclave cool to room temperature after, put it in the frozen water, behind the cooling 0.5h, slowly put carbonic acid gas, open still after, can see that yellow crystals separates out at the bottom of still.With ethyl acetate product is washed out at the bottom of still, be spin-dried for, the column chromatography for separation product.Developping agent is pure sherwood oil.
Embodiment 6: synthetic 4-fluoro-4 '-nitrobiphenyl
In the stainless steel autoclave of 25mL, add successively under the nitrogen protection p-Nitrobromobenzene (0.5mmol, 0.1010g), to fluorobenzoic boric acid (0.75mmol, 0.1049g) and K 3PO 43H 2O (1.0mmol, 0.2663g), PE-SBA-15-PPh 3-Pd (0.8%, 0.0304g).Then, pour the 15g carbonic acid gas, stirring reaction 24h in 90 ℃ of oil baths.
After reaction finishes, treat the autoclave cool to room temperature after, put it in the frozen water, behind the cooling 0.5h, slowly put carbonic acid gas, open still after, can see that yellow crystals separates out at the bottom of still.With ethyl acetate product is washed out at the bottom of still, be spin-dried for, the column chromatography for separation product.Developping agent is pure sherwood oil.
Embodiment 7: synthesize 3, and 4-two fluoro-4 '-nitrobiphenyl
In the stainless steel autoclave of 25mL, add successively under the nitrogen protection p-Nitrobromobenzene (0.5mmol, 0.1010g), 3,4-two fluorobenzoic boric acids (0.75mmol, 0.1184g) and K 3PO 43H 2O (1.0mmol, 0.2663g), PE-SBA-15-PPh 3-Pd (0.8%, 0.0304g).Then, pour the 15g carbonic acid gas, stirring reaction 24h in 90 ℃ of oil baths.
After reaction finishes, treat the autoclave cool to room temperature after, put it in the frozen water, behind the cooling 0.5h, slowly put carbonic acid gas, open still after, can see that yellow crystals separates out at the bottom of still.With ethyl acetate product is washed out at the bottom of still, be spin-dried for, the column chromatography for separation product.Developping agent is pure sherwood oil.
Embodiment 8: catalyzer is reused
In the stainless steel autoclave of 25mL, add successively under the nitrogen protection parabromoacetophenone (3.0mmol, 0.5971g), phenylo boric acid (4.5mmol, 0.5487g) and K 3PO 43H 2O (6.0mmol, 1.6000g), PE-SBA-15-PPh 3-Pd (1.0%, 0.2300g).Then, pour the 15g carbonic acid gas, stirring reaction 24h in 90 ℃ of oil baths.
After reaction finishes, treat the autoclave cool to room temperature after, put it in the frozen water, behind the cooling 0.5h, slowly put carbonic acid gas, open still after, can see that yellow crystals separates out at the bottom of still.With ethyl acetate product is washed out at the bottom of still, be spin-dried for, the column chromatography for separation product.Developping agent is normal hexane: ethyl acetate=45:1.Catalyzer is through the flushing of water and dehydrated alcohol, and 80 ℃ of following vacuum-dryings are weighed behind the cool to room temperature, changes in the autoclave, adds the amount of required substrate and alkali in proportion according to the quality of the catalyzer that reclaims, and enters circulation experiment next time then.
Table 1 is PE-SBA-15-PPh 3The experimental result of the synthetic aryl-linking compound of Suzuki linked reaction in the-Pd catalysis supercritical co.
Figure A200810013506D00131
Table 2 is that catalyst recirculation is used 8 times experimental result.
Figure A200810013506D00132

Claims (2)

1. the preparation method of aryl-linking compound in the supercritical co of a SBA-15 load palladium catalysis, with the supercritical co is medium, Suzuki linked reaction with SBA-15 loaded palladium catalyst catalyze aromatic halides and aromatic boric acid, utilize the low viscosity and the high diffusibility of supercritical co to drive substrate in the duct of SBA-15 internal reaction, reaction is slowly emitted carbonic acid gas after finishing, obtain the aryl-linking compound of crystalline form, it is characterized in that following steps:
1) preparation SBA-15 loaded palladium catalyst: the SBA-15 that 2.0g is not removed template is behind 80 ℃ of vacuum-drying 2h, join in the exsiccant 100mL there-necked flask, add the trimethoxy-benzene base silane of dewater oxy picolinate and 2mL of the deaerated toluene that dewaters, the 2mL of 50mL under nitrogen protection successively, 115 ℃ are stirred 2h down; Suction filtration behind the cool to room temperature, filter cake are used a spot of dehydrated alcohol, ether and washing with acetone successively, and vacuum-drying 6h makes the SBA-15 of outside surface modification; With ethanol is extraction agent, uses apparatus,Soxhlet's to extract the template of the SBA-15 inside of above-mentioned outside surface modification; Behind the reflux 48h, oven dry 6h obtains outside surface and modifies the inner SBA-15 that removes template; Outside surface is modified the inner SBA-151.5g that removes template to be had in joining in the there-necked flask of 250mL of stirrer, 80 ℃ down behind the dry 2h with nitrogen replacement three times, add the deaerated toluene that dewaters of 50mL, dewater oxy picolinate and the 1.5g (MeO) of 1.5mL 3SiCH 2CH 2CH 2SCH 2C 6H 4(p-PPh 2), stir 24h at 115 ℃; With the reaction mixture cool to room temperature, suction filtration, filter cake with after a spot of methyl alcohol, ether, acetone, the normal hexane washing, are inserted it in the cable type extractor according successively, under nitrogen protection, with the impurity 12h in the dichloromethane extraction duct; Vacuum-drying 6h obtains white solid PE-SBA-15-PPh 3With 1.0g PE-SBA-15-PPh 3Have in joining in the there-necked flask of the 100mL that stirs magneton, use nitrogen replacement three times behind 80 ℃ of dry 2h, add the deoxygenation methylene dichloride that dewaters, the 0.1000g Pd of 50mL 2(dba) 3Stir 24h under the catalyzer, room temperature; Suction filtration, filter cake cleans with a spot of methylene dichloride, and filtrate concentrates the back and reclaims catalyzer; The grey black solid that obtains wrapped with filter paper be put in the Soxhlet extraction element, methylene dichloride is made solvent and clean dry 6h under the impurity 12h vacuum in the duct, the SBA-15 loaded palladium catalyst PE-SBA-15-PPh that obtains under nitrogen protection 3-Pd;
2) aryl-linking compound synthetic in the supercritical co sees reaction formula (1);
Figure A200810013506C00031
In the stainless steel autoclave of 25mL, add catalyzer, aromatic series halides, aromatic boric acid and alkali under the nitrogen protection successively, pour carbonic acid gas then, heated and stirred reaction in 90 ℃ of oil baths, pressure is 18-20MPa; After reaction finishes, treat the autoclave cool to room temperature after, put it into freezing 0.5h in the frozen water, slowly put carbonic acid gas; Adopt the method purified product of column chromatography; With ethyl acetate catalyzer and product are washed out in still, filter out catalyzer, filtrate concentrates back column chromatography for separation product, by 1H NMR spectrogram identifies, catalyzer again behind water and absolute ethanol washing, the dried recovered utilization;
Described aromatic series halides, the ortho para that is halogeno-benzene is by the derivative of R base replacement, the straight chained alkyl of R=alkoxyl group, carbonyl, cyano group, nitro, other halogens, hydrogen, 1-12 carbon, cyclohexane radical derivative or phenyl derivatives;
Described aromatic boric acid, the ortho para that is phenylo boric acid is by the derivative of R base replacement; The straight chained alkyl of R=hydrogen, alkoxyl group, other halogens, 1-12 carbon, cyclohexane radical derivative, phenyl derivatives, carbonyl, cyano group or nitro;
Described aryl-linking compound is the product that is generated through cross-coupling reaction by aromatic series halides and aromatic boric acid.
2. the preparation method of aryl-linking compound in the supercritical co of a kind of SBA-15 load palladium catalysis according to claim 1 is characterized in that: Primary Catalysts is the SBA-15 supported palladium type catalyzer that contains the phosphine part,
(1) the SBA-15 supported palladium type catalyzer that contains the phosphine part of indication is that the SBA-15 of outside surface modification internal surface phosphine ligand functionization (uses PE-SBA-15-PPh 3-Pd represents):
(2) the outside surface modification of indication is meant that outside surface silicon hydroxyl is by the SBA-15 of trimethoxyphenyl protected silane;
(3) the phosphine part among the SBA-15 of the internal surface phosphine ligand functionization of indication is:
Figure A200810013506C00041
(4) alkali of the linked reaction of indication is meant DIPEA, triethylamine, tetrabutylammonium acetate ammonium, K 2PO 33H 2O, Cs 2CO 3Etc. organic and mineral alkali.
CNA2008100135060A 2008-09-28 2008-09-28 Method for preparing biaryl compound in supercritical carbon dioxide by SBA-15 load palladium catalysis Pending CN101372440A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101791567A (en) * 2010-03-05 2010-08-04 黑龙江大学 Preparation method of V-SBA-16 mesoporous catalyst
CN101791567B (en) * 2010-03-05 2011-10-19 黑龙江大学 Preparation method of V-SBA-16 mesoporous catalyst
CN102229534A (en) * 2011-05-11 2011-11-02 武汉工程大学 Method for synthesizing alkyl carbonic ester
CN102229534B (en) * 2011-05-11 2013-10-30 武汉工程大学 Method for synthesizing alkyl carbonic ester
CN107497472A (en) * 2017-07-25 2017-12-22 上海纳米技术及应用国家工程研究中心有限公司 For VOCsThe load type palladium catalyst of low-temperature catalyzed elimination
CN109420526A (en) * 2017-08-21 2019-03-05 中国科学院大连化学物理研究所 A kind of braiding mesoporous polymer carries silver catalyst and the preparation method and application thereof
CN109420526B (en) * 2017-08-21 2021-06-15 中国科学院大连化学物理研究所 Woven mesoporous polymer silver-loaded catalyst and preparation method and application thereof
CN108201897A (en) * 2018-02-01 2018-06-26 黑龙江省科学院石油化学研究院 The method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts
CN116273169A (en) * 2021-12-20 2023-06-23 安庆莱霆光电科技有限公司 Supported catalyst and preparation method thereof

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