CN104998631A - Nitrogen-doped graphene, Pd-loaded nitrogen-doped graphene catalyst and preparation method and application thereof - Google Patents
Nitrogen-doped graphene, Pd-loaded nitrogen-doped graphene catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN104998631A CN104998631A CN201510390364.XA CN201510390364A CN104998631A CN 104998631 A CN104998631 A CN 104998631A CN 201510390364 A CN201510390364 A CN 201510390364A CN 104998631 A CN104998631 A CN 104998631A
- Authority
- CN
- China
- Prior art keywords
- preparation
- water
- azepine
- nitrogen
- nrgo
- 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.)
- Pending
Links
Abstract
The invention provides nitrogen-doped graphene, a Pd-loaded nitrogen-doped graphene catalyst and its preparation method and application. The preparation method of the Pd-loaded nitrogen-doped graphene catalyst comprises the following steps: mixing graphene oxide, urea and water, and conducting ultrasonic treatment for 3h; transferring the mixture into a reaction vessel and stirring at 180 DEG C to react for 10 h; conducting suction filtration, washing and drying to obtain NRGO-x; mixing NRGO-x, a palladium chloride solution and water, and conducting ultrasonic treatment for 1 h; pouring the mixture into a reaction vessel, heating to 40 DEG C, and stirring at 2MPaH2 to react for 8 h; and conducting suction filtration after the reaction, washing, and conducting vacuum drying at 60 DEG C for 12 h, so as to obtain Pd/NRGO-x. In comparison with a traditional carbon material-loaded Pd catalyst, the nitrogen-doped graphene-loaded Pd catalyst has higher catalytic activity and stability. High temperature and high pressure are avoided by a method for preparing the nitrogen-doped graphene, and content of nitrogen is easy to adjust.
Description
Technical field
The present invention relates to chemical technology field, particularly relate to the azepine graphen catalyst and its preparation method and application of a kind of azepine Graphene, load P d.
Background technology
Recently, the focus of everybody research of a kind of carbon nanosheet-Graphene that is emerging, that have monoatomic thickness-become.Find from current research: Graphene not only has specific activity charcoal and the larger theoretical specific surface area of CNT (up to 2630m
2/ g), and there is the performances such as more excellent conduction and heat conduction.Meanwhile, because two-layer being easy to up and down of graphene nanometer sheet is come out, thus there is very high specific area utilization ratio.In addition, there is a lot of oxy radicals and the defect such as carbon or oxygen in graphenic surface.Thus many chemical active sites can be brought, or as the anchored site of metallic particles.But for CNT, Graphene is that one is easy to synthesis, and cheap material with carbon element, is thus easier to large-scale production.Can predict, Graphene can be used for heterogeneous catalytic reaction as superior catalyst carrier.
Along with the progressively expansion of research, it is found that the physical and chemical performance that can change Graphene by introducing assorted element (N, B, and P) further.Such as, in Graphene skeleton, introduce the graphited again generation that atom N can not only suppress it in drying and use procedure, defect can also be served as and strengthen the nucleation of particle and subtract short grained size.Compared to simple Graphene, azepine Graphene is the catalyst carrier that a class has clear superiority, the azepine material with carbon element of development of new, probes into its application in heterogeneous catalytic reaction, has great importance and be worth.
In recent years, prepare various novel azepine Graphene and can adopt multiple method, such as organic matter pyrolysis method, high-voltage arc method, laser lift-off or chemical vapour deposition technique etc., but the price of the preparation condition of harshness and costliness constrains its large-scale practical application.Along with Green Chemistry concept deeply and people's improving constantly that energy-saving and emission-reduction are required, searching environmental friendliness and the preparation method synthesizing easy azepine carbon graphite alkene becomes certainty.
Summary of the invention
The object of the invention is to the defect solving the existence of above-mentioned prior art, a kind of preparation method, highly active Supported Pd-Catalyst and preparation method thereof of simple and easy to do azepine Graphene.The graphene-supported Pd catalyst of this azepine has higher catalytic activity and stability compared to the Pd catalyst of conventional carbon material load.This method preparing azepine Graphene is avoided using HTHP, and the content of nitrogen is easy to regulate.Use hydrogen as reducing agent in the process of supported palladium, avoid using protective agent and non-green reducing agent, mild condition, be convenient to the exposure of washing and avtive spot.Described catalyst for carrier, take palladium as activated centre with azepine Graphene.With its weight for benchmark, it consists of: the load capacity of palladium is 0-20wt%, and the content of nitrogen is 0-7.5wt%.
A preparation method for azepine Graphene, comprises the following steps;
(1), by GO join in certain water gaging, in ultrasonic generator, process 1-3h; The mass volume ratio of described GO and water is (10-90) mg:(10-80) mL;
(2) proceed to, subsequently in reactor, stirring reaction 5-24h at 150-200 DEG C;
(3), suction filtration, 30-60 DEG C of vacuum drying 12-24h after washing, obtain sample RGO.
Further, the preparation method of azepine Graphene as above, described step 1 comprises:
By in GO and a certain amount of urea, water, in ultrasonic generator, process 1-3h, finally obtain sample NRGO
-xthe mass volume ratio of described GO, urea, water is: A mg:B g:C mL, wherein, and 10≤A≤90,0<B≤27,10≤C≤80, described x represents the mass ratio of urea and graphene oxide, 0<X<300.
Further, the preparation method of azepine Graphene as above, comprises the following steps:
(1), a certain amount of NRGO is got
-xbe distributed in water, in ultrasonic generator, process 1h, wherein, NRGO
-xbe (5-100) mg:(10-200 with the mass volume ratio of water) mL;
(2) PdCl of 0-0.84mL, is got
2the aqueous solution, stirred at ambient temperature 10-120min;
(3) proceed to, subsequently in reactor, in 20-50 DEG C and 0.5-3MPa H
2lower stirring reaction 2-12h;
(4), suction filtration, after fully washing with distilled water, at 30-80 DEG C, vacuum drying 12-24h, obtains Pd/NRGO
-x.
Further, the preparation method of azepine Graphene as above, in step (2), in palladium chloride solution, palladium content is 1-24mg/mL.
The azepine graphen catalyst of the load P d utilizing preparation method as above to prepare.
The application of azepine graphen catalyst in carbon carbon coupling synthesis biphenyl of load P d as above.
The present invention is directed at present azepine Graphene preparation and there is the situation of larger difficulty in using, with the urea of cheapness and graphene oxide for raw material, by the ratio of both modulations, under hydrothermal treatment consists, obtain the azepine Graphene of different nitrogen contents.Recycling hydrogen has prepared the nanoparticle palladium (Pd/NRGO) of high degree of dispersion in azepine graphenic surface in-situ reducing.Apply it in Suzuki carbon carbon coupling reaction, show the catalytic activity of the Pd catalyst being obviously better than normal activated carbon and conventional oxide load.This method preparing azepine Graphene is avoided using HTHP, and the content of nitrogen is easy to regulate.Avoid in the process of supported palladium using protective agent and non-green reducing agent, mild condition, be convenient to the exposure of washing and avtive spot.The method of the graphene-supported palladium catalyst of this azepine, realizes industrialization provide possibility for attempting the possible developing direction in this field and Graphene catalysis.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearly, below technical scheme in the present invention be clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of preparation method of azepine Graphene, comprise the following steps;
(1), by GO join in certain water gaging, in ultrasonic generator, process 1-3h; The mass volume ratio of described GO and water is (10-90) mg:(10-80) mL;
(2) proceed to, subsequently in reactor, stirring reaction 5-24h at 150-200 DEG C;
(3), suction filtration, 30-60 DEG C of vacuum drying 12-24h after washing, obtain sample RGO.
Further, the preparation method of azepine Graphene as above, also needs in step 1 to add urea, is specially:
By in GO and a certain amount of urea, water, in ultrasonic generator, process 1-3h, finally obtain sample NRGO
-xthe mass volume ratio of described GO, urea, water is: A mg:B g:C mL, wherein, and 10≤A≤90,0<B≤27,10≤C≤80, described x represents the mass ratio of urea and graphene oxide, 0<X<300.
Further, the preparation method of azepine Graphene as above, comprises the following steps:
(1), a certain amount of NRGO is got
-xbe distributed in water, in ultrasonic generator, process 1h, wherein, NRGO
-xbe (5-100) mg:(10-200 with the mass volume ratio of water) mL;
(2) PdCl of 0-0.84mL, is got
2the aqueous solution, stirred at ambient temperature 10-120min; In palladium chloride solution, palladium content is 1-24mg/mL;
(3) proceed to, subsequently in reactor, in 20-50 DEG C and 0.5-3MPa H
2lower stirring reaction 2-12h;
(4), suction filtration, after fully washing with distilled water, at 30-80 DEG C, vacuum drying 12-24h, obtains Pd/NRGO
-x.
The described catalyst utilizing above-mentioned preparation method to prepare is with azepine Graphene for carrier, and take palladium as activated centre, with its weight for benchmark, it consists of: the load capacity of palladium is 0-20wt%, and the content of nitrogen is 0-7.5wt%.
Embodiment 1:
The preparation of graphene oxide (GO)
1) in the beaker of 500mL, add the concentrated sulfuric acid of appropriate 98%, control temperature is 0 DEG C.
2) add 10g graphite powder and 5g sodium nitrate, and stir 1h.
3) 30g potassium permanganate powder (add speeds control good, temperature had better not be made more than 20 DEG C) is added under vigorous stirring.
4) low temperature ice bath is removed, at the stirred in water bath 30min of 35 DEG C.
5) under agitation add 460mL deionized water, reacting liquid temperature is risen to about 98 DEG C, continue stirring reaction 1h.
6) reactant liquor is released rare with 1.4L deionization warm water, add the hydrogen peroxide solution of a certain amount of 3% subsequently.
7) filter while hot, with 5% aqueous hydrochloric acid solution (warm) prepared in advance fully washing leaching cake, until sulfate radical-free ion in filtrate.
8) the filter cake average mark naturally drained is contained in the vial of five sealings.
Embodiment 2:
The preparation technology of azepine Graphene
(1) GO (about containing 81mg C) and a certain amount of urea are joined in 70mL water, process 3h in ultrasonic generator (200W).
(2) proceed to subsequently in 100mL reactor, stirring reaction 10h at 180 DEG C.
(3) suction filtration, wash rear 30 DEG C of vacuum drying 12h.This identified as samples is designated as NRGO
-x(x represents weight ratio=10 of urea and GO, 75,150,300 etc.), regulates x value, can obtain the azepine Graphene of different nitrogen contents.
Embodiment 3:
Pt-supported catalyst (2.5%Pd/NRGO
-x) preparation technology
(1) 50mgNRGO is got
-x, be distributed in 43mL water, process 1h in ultrasonic generator (200W).
(2) PdCl of 0.21mL
2(12mg Pd/mL) aqueous solution, stirred at ambient temperature 30min.
(3) proceed to subsequently in reactor, in 40 DEG C and 2MPa H
2lower stirring reaction 8h.
(4) suction filtration, after fully washing with distilled water, vacuum drying 12h at 60 DEG C.This identified as samples is designated as 5%Pd/NRGO
-x.
Embodiment 4:
Suzuki carbon carbon coupling reaction technique under the effect of azepine Graphene:
Carbon carbon coupling reaction is carried out in the test tube of 10mL with rubber stopper.0.5mmol halogeno-benzene is joined the mixed solution of 6mL ethanol/water (V/V=1), add 0.55mmol phenyl boric acid, 1.0mmol K
2cO
3with a certain amount of catalyst, then at 80 DEG C, stir (2600 revs/min).After reaction terminates, take a morsel reactant liquor, is extracted with ethyl acetate 3 times (3 × 10mL), by gained organic phase anhydrous Na
2sO
4drying, then carries out gas chromatographic analysis (HP 5890, USA) by internal standard method.All product are determined by GC-MS (Agilent 6890-5973N).
Embodiment 5
Get 0.5mmol bromobenzene, 0.55mmol phenyl boric acid, 1.0mmol K
2cO
3with a certain amount of Pd/NRGO
-300catalyst (0.023mol%Pd) is placed in the test tube of 10mL with rubber stopper, adds the mixed solution of 6mL ethanol/water (V/V=1).Then at 80 DEG C, (2600 revs/min) 0.5h is stirred.After reaction terminates, take a morsel reactant liquor, is extracted with ethyl acetate 3 times (3 × 10mL), by gained organic phase anhydrous Na
2sO
4drying, promoting the circulation of qi analysis of hplc of going forward side by side.Result shows: biphenyl productive rate is 99.1%.
Embodiment 6
With reference to preparation method and the step of embodiment 5, become Pd/NRGO unlike by catalyst
-150.Result shows:
Embodiment 7
With reference to preparation method and the step of embodiment 5, become Pd/NRGO unlike by catalyst
-75.Result shows:
Embodiment 8
With reference to preparation method and the step of embodiment 5, become Pd/NRGO unlike by catalyst
-10.Result shows:
Embodiment 9
With reference to preparation method and the step of embodiment 5, become Pd/GO unlike by catalyst.Result shows:
Embodiment 10
With reference to preparation method and the step of embodiment 5, become Pd/RGO unlike by catalyst.Result shows:
Embodiment 11
With reference to preparation method and the step of embodiment 5, become commodity Pd/C unlike by catalyst.Result shows: biphenyl productive rate is 42.3%.
Embodiment 12
With reference to preparation method and the step of embodiment 5, become chlorobenzene unlike by substrate.Result shows:
Embodiment 13
With reference to the examination condition of embodiment 12, become commodity Pd/C unlike by catalyst.Result shows:
Embodiment 14
With reference to preparation method and the step of embodiment 5, catalyst is reused.Result shows:
Last it is noted that above embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (6)
1. a preparation method for azepine Graphene, is characterized in that, comprises the following steps;
(1), by GO join in certain water gaging, in ultrasonic generator, process 1-3h; The mass volume ratio of described GO and water is (10-90) mg:(10-80) mL;
(2) proceed to, subsequently in reactor, stirring reaction 5-24h at 150-200 DEG C;
(3), suction filtration, 30-60 DEG C of vacuum drying 12-24h after washing, obtain sample RGO.
2. the preparation method of azepine Graphene according to claim 1, is characterized in that, described step 1 comprises:
By in GO and a certain amount of urea, water, in ultrasonic generator, process 1-3h, finally obtain sample NRGO
-xthe mass volume ratio of described GO, urea, water is: A mg:B g:C mL, wherein, and 10≤A≤90,0<B≤27,10≤C≤80, described x represents the mass ratio of urea and graphene oxide, 0<X<300.
3. an azepine graphen catalyst preparation method of load P d, is characterized in that, comprise the following steps:
(1), a certain amount of NRGO is got
-xbe distributed in water, in ultrasonic generator, process 1h, wherein, NRGO
-xbe (5-100) mg:(10-200 with the mass volume ratio of water) mL;
(2) PdCl of 0-0.84mL, is got
2the aqueous solution, stirred at ambient temperature 10-120min;
(3) proceed to, subsequently in reactor, in 20-50 DEG C and 0.5-3MPa H
2lower stirring reaction 2-12h;
(4), suction filtration, after fully washing with distilled water, at 30-80 DEG C, vacuum drying 12-24h, obtains Pd/NRGO
-x.
4. the azepine graphen catalyst preparation method of load P d according to claim 3, is characterized in that, in step (2), in palladium chloride solution, palladium content is 1-24mg/mL.
5. the azepine graphen catalyst of the load P d utilizing the preparation method described in claim 3 to prepare.
6. the application of azepine graphen catalyst in carbon carbon coupling synthesis biphenyl of load P d according to claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510390364.XA CN104998631A (en) | 2015-07-06 | 2015-07-06 | Nitrogen-doped graphene, Pd-loaded nitrogen-doped graphene catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510390364.XA CN104998631A (en) | 2015-07-06 | 2015-07-06 | Nitrogen-doped graphene, Pd-loaded nitrogen-doped graphene catalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104998631A true CN104998631A (en) | 2015-10-28 |
Family
ID=54371647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510390364.XA Pending CN104998631A (en) | 2015-07-06 | 2015-07-06 | Nitrogen-doped graphene, Pd-loaded nitrogen-doped graphene catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104998631A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105562057A (en) * | 2016-01-30 | 2016-05-11 | 镇江市高等专科学校 | Palladium nano-composite catalyst loaded by N-doped three-dimensional graphene and preparing method and application thereof |
| CN105862094A (en) * | 2016-05-27 | 2016-08-17 | 哈尔滨工程大学 | Graphene-containing metal-matrix composite plating solution capable of improving brushing electroplating coating quality by using hydrogen absorption effect |
| CN107176601A (en) * | 2016-03-08 | 2017-09-19 | 财团法人工业技术研究院 | Metal-doped graphene and growth method thereof |
| CN107774293A (en) * | 2017-10-20 | 2018-03-09 | 四川理工学院 | A kind of N doped graphenes Pt-supported catalyst, its preparation method and application |
| CN109174085A (en) * | 2018-09-06 | 2019-01-11 | 中国科学院金属研究所 | Atom level disperses palladium base Nano diamond/graphene composite material catalyst and its preparation method and application |
| CN112403500A (en) * | 2020-07-22 | 2021-02-26 | 北京化工大学 | Method for preparing supported metal monatomic catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
| CN104028293A (en) * | 2014-06-24 | 2014-09-10 | 常州大学 | Method for preparing low-temperature nitrogen-doped graphene supported nano Pd hydrogenation catalyst |
| CN104043841A (en) * | 2014-06-06 | 2014-09-17 | 苏州创科微电子材料有限公司 | Method for preparing metal nano material by utilizing hydrogen |
| CN104525192A (en) * | 2014-12-22 | 2015-04-22 | 浙江大学 | Method for preparing catalyst used in preparation of cyclohexene by virtue of selective hydrogenation of benzene |
-
2015
- 2015-07-06 CN CN201510390364.XA patent/CN104998631A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
| CN104043841A (en) * | 2014-06-06 | 2014-09-17 | 苏州创科微电子材料有限公司 | Method for preparing metal nano material by utilizing hydrogen |
| CN104028293A (en) * | 2014-06-24 | 2014-09-10 | 常州大学 | Method for preparing low-temperature nitrogen-doped graphene supported nano Pd hydrogenation catalyst |
| CN104525192A (en) * | 2014-12-22 | 2015-04-22 | 浙江大学 | Method for preparing catalyst used in preparation of cyclohexene by virtue of selective hydrogenation of benzene |
Non-Patent Citations (1)
| Title |
|---|
| SIYAVASH KAZEMI MOVAHED ET AL: "Palladium nanoparticle decorated high nitrogen-doped grapheme with high catalytic activity for Suzuki–Miyaura and Ullmann-type coupling reactions in aqueous media", 《APPLIED CATALYSIS A: GENERAL》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105562057A (en) * | 2016-01-30 | 2016-05-11 | 镇江市高等专科学校 | Palladium nano-composite catalyst loaded by N-doped three-dimensional graphene and preparing method and application thereof |
| CN107176601A (en) * | 2016-03-08 | 2017-09-19 | 财团法人工业技术研究院 | Metal-doped graphene and growth method thereof |
| US10079392B2 (en) * | 2016-03-08 | 2018-09-18 | Industrial Technology Research Institute | Metal-doped graphene and growth method of the same |
| CN107176601B (en) * | 2016-03-08 | 2019-07-05 | 财团法人工业技术研究院 | Metal-doped graphene and growth method thereof |
| CN105862094A (en) * | 2016-05-27 | 2016-08-17 | 哈尔滨工程大学 | Graphene-containing metal-matrix composite plating solution capable of improving brushing electroplating coating quality by using hydrogen absorption effect |
| CN105862094B (en) * | 2016-05-27 | 2018-01-19 | 哈尔滨工程大学 | Utilize the graphene-containing metal-based compound plating solution for inhaling hydrogen effect raising Brush quality |
| CN107774293A (en) * | 2017-10-20 | 2018-03-09 | 四川理工学院 | A kind of N doped graphenes Pt-supported catalyst, its preparation method and application |
| CN107774293B (en) * | 2017-10-20 | 2020-06-09 | 四川理工学院 | N-doped graphene-loaded Pd catalyst, and preparation method and application thereof |
| CN109174085A (en) * | 2018-09-06 | 2019-01-11 | 中国科学院金属研究所 | Atom level disperses palladium base Nano diamond/graphene composite material catalyst and its preparation method and application |
| CN112403500A (en) * | 2020-07-22 | 2021-02-26 | 北京化工大学 | Method for preparing supported metal monatomic catalyst |
| CN112403500B (en) * | 2020-07-22 | 2023-05-26 | 北京化工大学 | Method for preparing supported metal monoatomic catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104998631A (en) | Nitrogen-doped graphene, Pd-loaded nitrogen-doped graphene catalyst and preparation method and application thereof | |
| CN104525237A (en) | Nitrogen-doped active carbon catalyzer and application thereof in chloroethylene synthesis | |
| CN106423204A (en) | Method using graphene loaded palladium-nickel nano alloy to catalytically reduce nitro-aromatic compounds | |
| CN108479855A (en) | A kind of nucleocapsid metal organic framework base composite photocatalyst and preparation method thereof | |
| CN109908903A (en) | A kind of high-specific surface area Lignin-Based Activated Carbon is nickel-base catalyst and its preparation and application of carrier | |
| CN102407147A (en) | Preparation method and application of ZnIn2S4-graphene composited photochemical catalyst | |
| CN105148990B (en) | A kind of preparation method and applications of sulfonic acid carbon nano tube/graphene oxide composite catalyst | |
| CN106824200A (en) | A kind of carbon load nickel metallic catalyst and preparation method thereof | |
| CN104941613A (en) | Preparation method of supported flower-shaped copper oxide and method for deeply removing hydrogen phosphide from yellow phosphorus tail gas | |
| CN104741119A (en) | Nanometer Au catalyst for ethyne hydrochlorination and preparation method and application of catalyst | |
| CN108404983A (en) | A kind of preparation and its application of ordered mesoporous phenolic resin Polymer-supported silver catalyst | |
| CN106395742A (en) | Hydrogen storage composite material MgH2-Ni-rGO and method for preparing same | |
| CN104307523B (en) | A kind of method being prepared year Fischer-Tropsch synthesis by rice husk thermal decomposition charcoal one step | |
| CN105713017A (en) | High selectivity metal organic skeleton material and preparation method thereof | |
| CN103170354B (en) | Structured non-mercuric catalyst, and preparation method and application thereof | |
| CN103143357A (en) | Catalyst for synthesizing dimethyl carbonate through continuous oxidative carbonylation of liquid phase methanol and preparation method and application of catalyst | |
| CN115555005B (en) | Production method of mercury-free catalyst carrier activated carbon with strong adsorption capacity | |
| CN109453762A (en) | A kind of preparation method and application of modified clay mine loaded palladium catalyst | |
| Wu et al. | Mechanism insights on single-atom catalysts for CO 2 conversion | |
| CN110404575A (en) | CO2Add carbon containing ferrum-based catalyst of hydrogen hydrocarbon and preparation method thereof | |
| CN104971758A (en) | High-activity aza active carbon loaded palladium catalyst, preparation method and application of | |
| CN108246277A (en) | One kind efficiently synthesizes trifluoroiodomethane method | |
| CN102357366A (en) | Non-mercury catalyst used for acetylene hydrochlorination | |
| CN103977835A (en) | Sulfonated-graphene-based novel Ru(bpy)3<2+> nano heterogeneous catalyst and preparation method thereof | |
| CN101822987B (en) | Method for modifying active carbon for catalytically decomposing hydrogen iodide by adding active metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151028 |
|
| RJ01 | Rejection of invention patent application after publication |