CN105521782A - Preparation method of Cu nanoparticles-embedded ordered mesoporous carbon catalyst - Google Patents
Preparation method of Cu nanoparticles-embedded ordered mesoporous carbon catalyst Download PDFInfo
- Publication number
- CN105521782A CN105521782A CN201510942968.0A CN201510942968A CN105521782A CN 105521782 A CN105521782 A CN 105521782A CN 201510942968 A CN201510942968 A CN 201510942968A CN 105521782 A CN105521782 A CN 105521782A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- particle
- preparation
- order mesoporous
- embedding cloth
- 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
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/01—Preparation of esters of carbonic or haloformic acids from carbon monoxide and oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a Cu nanoparticles-embedded ordered mesoporous carbon catalyst and belongs to the field of chemical heterogeneous catalysis. The preparation method comprises the following steps: Step 1, template mesoporous silica material SBA-15 filling-rolling over; Step 2, carbonization; and Step 3, silica removal. The process of template mesoporous silica material SBA-15 filling-rolling over comprises impregnation, dispersion, drying, pre-carbonization and single repetitive operation. The problem that catalytic activity of a catalyst will decrease with the reaction process is solved. The prepared chloride-free copper-based catalyst of the invention is a nanoscale catalyst with 5-25nm copper particles embedded in pores of and on the surface of the ordered mesoporous carbon. Dispersity is good, and migration and agglomeration are not easy to occur in the reaction process. The catalyst has high reaction activity and good stability when used in an atmospheric continuous fixed bed for methanol gaseous oxidative carbonylation for synthesis of dimethyl carbonate.
Description
Technical field
The invention belongs to the heterogeneous catalysis field of chemical, more particularly, relate to a kind of ordered mesopore carbon Catalysts and its preparation method and application of embedding cloth nano Cu particle.
Background technology
Dimethyl carbonate (DMC) is a kind of broad-spectrum green chemical, is described as " the new foundation stone " of organic synthesis.In the method for numerous synthesis DMC, with CO, O
2be that the oxidative carbonylation route of raw material is thermodynamically very favourable with methyl alcohol, and atom utilization being up to 80%, is one of synthetic route with prospects for commercial application most.For the activated carbon loaded copper chloride catalyst (CuCl of this reaction
2/ AC) and Wacker type catalyst (CuCl
2-PdCl
2/ AC) there is chlorion and to run off in course of reaction the catalysqt deactivation and equipment corrosion problem that cause, can improve catalytic activity although add auxiliary agent or improve preparation method and improve stability, the deactivation prob of catalyst fails basic solution.
Active carbon AC stable chemical nature, specific area are large and electronic conductivity is good, are the excellent catalyst carriers of methanol oxidation carbonylation.In recent years, non-chlorine mantoquita is adopted to be the Main way that the problems such as the copper source catalysqt deactivation of avoiding the introducing of Cl ion to cause from source become research.The people such as Li Zhong are by Cu (CH
3cOO)
2be immersed on AC, direct pyrolysis obtains Cu
2o/AC catalyst, catalytic activity is good.Chemical modification is carried out on AC surface group and can affect Cu (CH
3cOO)
2dispersion and pyrolytic process, cause catalyst surface to disperse copper species (Cu/Cu
+/ Cu
2+) grain size and the change of valence state, and then affect catalytic activity.Adopt hydrazine hydrate chemical preparation AC supported copper catalyst based, hydrazine hydrate addition can affect Cu species valence state, and when the mol ratio of hydrazine hydrate/copper nitrate material is 0.75, AC surface is with Cu
2o is main, and catalytic activity is higher.Adopting AC load basic copper nitrate, CuO/AC can be obtained respectively, Cu by strictly regulating and controlling heat-treat condition
2o/AC and Cu
0/ AC catalyst, the order of catalytic activity size is CuO<Cu
2o<Cu
0.With copper nitrate and soluble starch for raw material, Cu can be prepared through sol gel, high temperature cabonization and KOH activation
0/ AC catalyst, when carbonization, activation temperature are respectively 500 DEG C and 850 DEG C, during KOH:C=1, the specific area of catalyst reaches 1690m
2/ g, Micropore volume rate is 72.4%, and catalytic activity is the highest.
Although AC load to show good oxidation carbonylation without chlorine copper-based catalysts active, still there is the problem that catalytic activity declines along with the carrying out of reaction in such catalyst.The stability test of catalyst is shown, Cu
0/ AC catalyst is in reaction 95h, and the inactivation rate of DMC space-time yield is 0.64%/h, and fresh catalyst surface C u granular size is uneven, between 300 ~ 900nm, and reacted Cu
2o particle has obvious agglomeration, and particle diameter is increased to more than 1000nm.Cu is thought in the research of Zheng Huayan etc.
0o in simple substance Cu adsorption reaction atmosphere in/AC catalyst
2be converted into Cu
2o, along with the carrying out of reaction, Cu
2o grain growth, there occurs obvious agglomeration, causes catalytic activity to reduce.Therefore, need one badly migration not easily occurs in course of reaction and reunites, reactivity for normal pressure continuous Fixed Bed Gas Phase methanol oxidation carbonylation Synthesis of dimethyl carbonate is high, the catalyst of good stability, i.e. a kind of preparation method of order mesoporous C catalyst of embedding cloth nano Cu particle.
Summary of the invention
The problem that one, will solve
For the above-mentioned problems in the prior art, the invention provides a kind of ordered mesopore carbon Catalysts and its preparation method and application of embedding cloth nano Cu particle, efficiently solve the problem that catalyst activity declines along with the carrying out of reaction, prepared by the present invention is nanoscale without chlorine copper-based catalysts, the copper particle of 5 ~ 25nm inlays cloth in the duct and surface of ordered mesopore carbon, good dispersion, in course of reaction, not easily there is migration and reunite, reactivity for normal pressure continuous Fixed Bed Gas Phase methanol oxidation carbonylation Synthesis of dimethyl carbonate is high, good stability.
Two, technical scheme
In order to solve the problem, the technical solution adopted in the present invention is as follows:
A preparation method for the order mesoporous C catalyst of embedding cloth nano Cu particle, the preparation method of the order mesoporous C catalyst of described embedding cloth nano Cu particle comprises step one: template meso pore silicon oxide material SBA-15 filling sugar-turn over mould; Step 2: carbonization and step 3: silica removal.
Preferably, the step that in described step one, template meso pore silicon oxide material SBA-15 fills with sugar-turn over mold process is:
A1, dipping: template SBA-15 is joined in the mixed aqueous solution of mantoquita, sucrose and the concentrated sulfuric acid;
A2, dispersion: by described steps A 1 gained mixed solution ultrasonic disperse 0.1 ~ 1h;
A3 is dry: the mixture in described steps A 2 after ultrasonic disperse is placed in electric drying oven with forced convection, in 80 ~ 110
odry 2 ~ 10h under C;
A4, pre-carbonization: by dry for described steps A 3 gained thing in 120 ~ 200
opre-carbonization 2 ~ 10h under C condition;
A5, single repeats: the sample single that described steps A 4 obtains is repeated above-mentioned dipping, dispersion, drying and pre-carbonisation.
Preferably, in described steps A 1, template SBA-15, sucrose, the concentrated sulfuric acid, mantoquita and water 1:0.5 ~ 1.5:0.08 in mass ratio ~ 0.15:0 ~ 0.2:3 ~ 7 ratio mixes.
Preferably, described mantoquita is copper sulphate, copper nitrate, Schweinfurt green, cupric tartrate, one or more in the organic/inorganic copper compounds such as copper citrate.
Preferably, in described step 2, carbonisation is: after template SBA-15 being filled with sugar-turn over mould, gained sample is placed in the tube furnace of inert gas shielding, in 600 ~ 1200
ocalcine 4 ~ 12h under C condition, after calcining terminates, be cooled to room temperature.
Preferably, in described step 3, silica removal process is: by gained sample after carbonization through HF or NaOH solution etching removing template SBA-15, obtained nanoscale is without the order mesoporous C catalyst of chlorine copper base.
Preferably, the order mesoporous C catalyst of described embedding cloth nano Cu particle is obtained by above-mentioned preparation method.
Preferably, described embedding cloth nano Cu particle order mesoporous C catalyst be applied to gas-phase oxidation/carbonylation Synthesis of dimethyl carbonate.
Preferably, the concrete steps of described catalyst activity test are: be placed in the middle part of fixed-bed micro-reactor by 0.2 ~ 2g catalyst, methyl alcohol is introduced, with O by micro-sampling pump
2, CO tow channel gas is mixed into vaporizer, in 120 ~ 160 in vaporizer
oenter together in reactor after vaporization under C condition, after flowing through beds, obtain liquid-phase product through condensation.
Preferably, described CO and O
2be mixed into vaporizer for 5:1 ~ 15:1 in molar ratio, Feed space velocities is 2000h
-1~ 5000
-1.
Three, beneficial effect
Compared to prior art, beneficial effect of the present invention is:
The Cu that the present invention is more traditional
0o in simple substance Cu adsorption reaction atmosphere in/AC catalyst
2be converted into Cu
2o, along with the carrying out of reaction, Cu
2o grain growth, there occurs obvious agglomeration, causes catalytic activity to reduce.And prepared by the present invention is nanoscale without chlorine copper-based catalysts, the copper particle of 5 ~ 25nm inlays cloth in the duct and surface of ordered mesopore carbon, good dispersion, in course of reaction, not easily there is migration and reunite, reactivity for normal pressure continuous Fixed Bed Gas Phase methanol oxidation carbonylation Synthesis of dimethyl carbonate is high, good stability.The space-time yield of DMC reaches 130mg/ (gh), and active in declining in reaction 100h, activity is much higher than Cu prepared by Solid-state Ion-exchange
+/ Y catalyst, stability is far above CuCl
2/ AC, CuCl
2-PdCl
2/ AC catalyst, has good prospects for commercial application.It is large that catalyst prepared by the present invention also has specific area, duct uniform and ordered, the features such as pore-size distribution is narrow, efficiently solves the problem that catalyst activity declines along with the carrying out of reaction.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope view of the embodiment of the present invention 1 gained catalyst;
Fig. 2 is the transmission electron microscope view of the embodiment of the present invention 2 gained catalyst;
Fig. 3 is the transmission electron microscope view of the embodiment of the present invention 3 gained catalyst.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
1g mesoporous silicon material SBA-15 is added to containing 1.25g sucrose, in the mixed solution of the 0.14g concentrated sulfuric acid and 5ml deionized water, by mixture ultrasonic disperse 20min in ultrasonator; To be placed in electric drying oven with forced convection dry 6h at 80 DEG C, after drying terminates, temperature is adjusted to 160 DEG C, make sucrose pre-carbonization in the duct of SBA-15, the time is 6h.Take 0.8g sucrose, 0.09g sulfuric acid, 0.1g nitrate trihydrate copper and 5ml deionized water wiring solution-forming, this solution is joined in the composite sample of SBA-15 prepared by previous step and sucrose half polymers, ultrasonic disperse 20min, afterwards dry 6h at 80 DEG C, pre-carbonization 6h at 160 DEG C.Gained sample is placed in the tube furnace of nitrogen protection, with 2 DEG C/min ramp to 400 DEG C, is then warming up to 900 DEG C with 1 DEG C/min, constant temperature 4h.Finally, compound 1mol/LNaOH solution soaks 4h to remove SBA-15 template, and filtration, washing, drying obtain catalyst.As shown in Figure 1, as can be seen from test result, Cu-OMC catalyst has six side's phase meso-hole structures of high-sequential to described catalyst transmission electron microscope test result, and the Cu nano particle that particle diameter is about 10 ~ 30nm is evenly dispersed in the duct of OMC.
Fixed-bed micro-reactor is adopted to carry out active testing to catalyst.0.45g (about 2ml) catalyst is placed in the middle part of reactor.Methyl alcohol is introduced, with O by micro-sampling pump
2, CO tow channel gas is mixed into vaporizer, in vaporizer (140
oc) (temperature of reactor is 140 to enter reactor together after vaporization
oc), liquid-phase product is obtained through condensation after flowing through beds.Detect through gas chromatograph, dimethyl carbonate space-time yield 101.4mg/ (gh), methanol conversion 8.58%, dimethyl carbonate selective 95.6%.
Embodiment 2
1g mesoporous silicon material SBA-15 is added to containing 1.25g sucrose, the 0.14g concentrated sulfuric acid, in the mixed solution of 0.1g nitrate trihydrate copper and 5ml deionized water, by mixture ultrasonic disperse 20min in ultrasonator; Afterwards sample is placed in dry 6h at electric drying oven with forced convection 100 DEG C, after drying terminates, temperature is adjusted to 160 DEG C, makes sucrose prepolymerization 6h in the duct of SBA-15.Take 0.8g sucrose, 0.09g sulfuric acid and 5ml deionized water wiring solution-forming, this solution is joined in the composite sample of SBA-15 prepared by previous step and sucrose half polymers, ultrasonic disperse 20min, afterwards dry 6h at 100 DEG C, pre-carbonization 6h at 160 DEG C.Gained sample is placed in the tube furnace of nitrogen protection, with 2 DEG C/min ramp to 400 DEG C, is then warming up to 900 DEG C with 1 DEG C/min; constant temperature 4h; finally, composite sample 1mol/LNaOH solution soaks 4h to remove SBA-15 template, obtains catalyst after filtration, washing, drying.As shown in Figure 2, as can be seen from Electronic Speculum test result, Cu-OMC catalyst has six orderly side's phase meso-hole structures to described catalyst transmission electron microscope test result, and the Cu nano particle that particle diameter is about 3 ~ 7nm is evenly dispersed in the duct of OMC.
Fixed-bed micro-reactor is adopted to carry out active testing to catalyst.0.45g (about 2ml) catalyst is placed in the middle part of reactor.Methyl alcohol is introduced, with O by micro-sampling pump
2, CO tow channel gas is mixed into vaporizer, in vaporizer (140
oc) (temperature of reactor is 140 to enter reactor together after vaporization
oc), liquid-phase product is obtained through condensation after flowing through beds.Through chromatographic, dimethyl carbonate space-time yield 126.1mg/ (gh), methanol conversion 8.78%, dimethyl carbonate selective 95.4%.
Embodiment 3
1g mesoporous silicon material SBA-15 is added to containing 1.25g sucrose, the 0.14g concentrated sulfuric acid, in the mixed solution of 0.05g mono-water acetic acid copper and 5ml deionized water, by mixture ultrasonic disperse 20min in ultrasonator; Afterwards sample is placed in dry 6h at electric drying oven with forced convection 100 DEG C, after drying terminates, temperature is adjusted to 160 DEG C and makes sucrose pre-carbonization in the duct of SBA-15, the time is 6h.Take 0.8g sucrose, 0.09g sulfuric acid, 0.03g mono-water acetic acid copper and 5ml deionized water wiring solution-forming, this solution is joined in the composite sample of SBA-15 prepared by previous step and sucrose half polymers, ultrasonic disperse 20min, afterwards dry 6h at 100 DEG C, pre-carbonization 6h at 160 DEG C.Gained sample is placed in the tube furnace of nitrogen protection, with 2 DEG C/min ramp to 400 DEG C, is then warming up to 850 DEG C with 1 DEG C/min; constant temperature 4h; finally, the hydrogen fluoride solution of composite sample 5wt% soaks 4h to remove SBA-15 template, obtains catalyst after filtration washing through 100 DEG C of oven dry.Described catalyst transmission electron microscope test result as shown in Figure 3, as can be seen from test result, Cu-OMC catalyst has six side's phase meso-hole structures of high-sequential, and aperture is 8 ~ 11nm, and the Cu nano particle that particle diameter is about 10 ~ 20nm is evenly dispersed in the duct of OMC.
Fixed-bed micro-reactor is adopted to carry out active testing to catalyst.0.45g (about 2ml) catalyst is placed in the middle part of reactor.Methyl alcohol is introduced, with O by micro-sampling pump
2, CO tow channel gas is mixed into vaporizer, in vaporizer (140
oc) (temperature of reactor is 140 to enter reactor together after vaporization
oc), liquid-phase product is obtained through condensation after flowing through beds.Detect through gas chromatograph, dimethyl carbonate space-time yield 131.4mg/ (gh), methanol conversion 9.58%, dimethyl carbonate selective 94.6%.
Schematically above be described the present invention and embodiment thereof, this description does not have restricted, and also just one of the embodiments of the present invention shown in accompanying drawing, actual structure is not limited thereto.So, if those of ordinary skill in the art enlightens by it, when not departing from the invention aim, designing the frame mode similar to this technical scheme and embodiment without creationary, all should protection scope of the present invention be belonged to.
Claims (10)
1. a preparation method for the order mesoporous C catalyst of embedding cloth nano Cu particle, is characterized in that, the preparation method of the order mesoporous C catalyst of described embedding cloth nano Cu particle comprises step one: template meso pore silicon oxide material SBA-15 filling sugar-turn over mould; Step 2: carbonization and step 3: silica removal.
2. according to the preparation method of the order mesoporous C catalyst of a kind of embedding cloth nano Cu particle according to claim 1, it is characterized in that, in described step one, template meso pore silicon oxide material SBA-15 fills with the step of sugar-turn over mold process and is:
A1, dipping: template SBA-15 is joined in the mixed aqueous solution of mantoquita, sucrose and the concentrated sulfuric acid;
A2, dispersion: by described steps A 1 gained mixed solution ultrasonic disperse 0.1 ~ 1h;
A3 is dry: the mixture in described steps A 2 after ultrasonic disperse is placed in electric drying oven with forced convection, in 80 ~ 110
odry 2 ~ 10h under C;
A4, pre-carbonization: by dry for described steps A 3 gained thing in 120 ~ 200
opre-carbonization 2 ~ 10h under C condition;
A5, single repeats: the sample single that described steps A 4 obtains is repeated above-mentioned dipping, dispersion, drying and pre-carbonisation.
3. according to the preparation method of the order mesoporous C catalyst of a kind of embedding cloth nano Cu particle according to claim 2, it is characterized in that, in described steps A 1, template SBA-15, sucrose, the concentrated sulfuric acid, mantoquita and water 1:0.5 ~ 1.5:0.08 in mass ratio ~ 0.15:0 ~ 0.2:3 ~ 7 ratio mixes.
4. according to the preparation method of the order mesoporous C catalyst of a kind of embedding cloth nano Cu particle described in Claims 2 or 3, it is characterized in that, described mantoquita is copper sulphate, copper nitrate, Schweinfurt green, cupric tartrate, one or more in the organic/inorganic copper compounds such as copper citrate.
5. according to the preparation method of the order mesoporous C catalyst of a kind of embedding cloth nano Cu particle described in claim 1 or 2; it is characterized in that; in described step 2, carbonisation is: after template SBA-15 being filled with sugar-turn over mould, gained sample is placed in the tube furnace of inert gas shielding, in 600 ~ 1200
ocalcine 4 ~ 12h under C condition, after calcining terminates, be cooled to room temperature.
6. according to the preparation method of the order mesoporous C catalyst of a kind of embedding cloth nano Cu particle described in claim 1 or 5, it is characterized in that, in described step 3, silica removal process is: by gained sample after carbonization through HF or NaOH solution etching removing template SBA-15, obtained nanoscale is without the order mesoporous C catalyst of chlorine copper base.
7. an order mesoporous C catalyst for embedding cloth nano Cu particle, is characterized in that, the order mesoporous C catalyst of described embedding cloth nano Cu particle is obtained by above-mentioned preparation method.
8. an application for the order mesoporous C catalyst of embedding cloth nano Cu particle, is characterized in that, the order mesoporous C catalyst of described embedding cloth nano Cu particle be applied to gas-phase oxidation/carbonylation Synthesis of dimethyl carbonate.
9. the application of the order mesoporous C catalyst of a kind of embedding cloth nano Cu particle according to claim 8, it is characterized in that, the concrete steps of described catalyst activity test are: be placed in the middle part of fixed-bed micro-reactor by 0.2 ~ 2g catalyst, methyl alcohol is introduced, with O by micro-sampling pump
2, CO tow channel gas is mixed into vaporizer, in 120 ~ 160 in vaporizer
oenter together in reactor after vaporization under C condition, after flowing through beds, obtain liquid-phase product through condensation.
10. the application of the order mesoporous C catalyst of a kind of embedding cloth nano Cu particle according to claim 9, is characterized in that, described CO and O
2be mixed into vaporizer for 5:1 ~ 15:1 in molar ratio, Feed space velocities is 2000h
-1~ 5000
-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510942968.0A CN105521782A (en) | 2015-12-16 | 2015-12-16 | Preparation method of Cu nanoparticles-embedded ordered mesoporous carbon catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510942968.0A CN105521782A (en) | 2015-12-16 | 2015-12-16 | Preparation method of Cu nanoparticles-embedded ordered mesoporous carbon catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105521782A true CN105521782A (en) | 2016-04-27 |
Family
ID=55764505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510942968.0A Pending CN105521782A (en) | 2015-12-16 | 2015-12-16 | Preparation method of Cu nanoparticles-embedded ordered mesoporous carbon catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105521782A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582644A (en) * | 2016-12-15 | 2017-04-26 | 青海师范大学 | Copper-loaded mesoporous carbon catalyst for benzene hydroxylation and preparation method thereof |
| CN107311139A (en) * | 2017-05-04 | 2017-11-03 | 东莞理工学院 | The meso-porous carbon material prepared by carbon source of glucose and its application |
| CN107715877A (en) * | 2017-10-16 | 2018-02-23 | 太原理工大学 | A kind of hollow mesoporous carbosphere shell confinement copper catalyst and preparation method and application |
| CN107930674A (en) * | 2017-10-17 | 2018-04-20 | 太原理工大学 | A kind of catalyst and preparation method and application for preparing dimethyl carbonate |
| CN108144603A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | The catalyst of CO vapor phase method Synthesis of dimethyl carbonate and its preparation and application |
| CN110280300A (en) * | 2019-06-13 | 2019-09-27 | 中国科学技术大学 | A kind of preparation method and application loading Mn oxide ordered mesoporous carbon composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101482236B1 (en) * | 2013-11-22 | 2015-01-14 | 한국화학연구원 | Supported Copper Catalysts for Synthesis of Dimethyl Carbonate, and Method of Producing Them |
| CN104888779A (en) * | 2015-05-05 | 2015-09-09 | 中国矿业大学 | Preparation method of Cu nanoparticle-loaded ordered mesoporous carbon catalyst |
| CN104941661A (en) * | 2015-06-09 | 2015-09-30 | 同济大学 | Ordered mesoporous carbon adopting pore wall structure uniformly embedded with metal nanoparticles and controllable preparation method of ordered mesoporous carbon |
-
2015
- 2015-12-16 CN CN201510942968.0A patent/CN105521782A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101482236B1 (en) * | 2013-11-22 | 2015-01-14 | 한국화학연구원 | Supported Copper Catalysts for Synthesis of Dimethyl Carbonate, and Method of Producing Them |
| CN104888779A (en) * | 2015-05-05 | 2015-09-09 | 中国矿业大学 | Preparation method of Cu nanoparticle-loaded ordered mesoporous carbon catalyst |
| CN104941661A (en) * | 2015-06-09 | 2015-09-30 | 同济大学 | Ordered mesoporous carbon adopting pore wall structure uniformly embedded with metal nanoparticles and controllable preparation method of ordered mesoporous carbon |
Non-Patent Citations (1)
| Title |
|---|
| XINHUA XU ET AL.: "Development of amperometric laccase biosensor through immobilizing enzyme in copper-containing ordered mesoporous carbon (Cu-OMC)/chitosan matrix", 《MATERIALS SCIENCE AND ENGINEERING C》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108144603A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | The catalyst of CO vapor phase method Synthesis of dimethyl carbonate and its preparation and application |
| CN106582644A (en) * | 2016-12-15 | 2017-04-26 | 青海师范大学 | Copper-loaded mesoporous carbon catalyst for benzene hydroxylation and preparation method thereof |
| CN106582644B (en) * | 2016-12-15 | 2019-06-11 | 青海师范大学 | A kind of copper-loaded gold/mesoporous carbon catalyst and preparation method thereof for benzene hydroxylation |
| CN107311139A (en) * | 2017-05-04 | 2017-11-03 | 东莞理工学院 | The meso-porous carbon material prepared by carbon source of glucose and its application |
| CN107715877A (en) * | 2017-10-16 | 2018-02-23 | 太原理工大学 | A kind of hollow mesoporous carbosphere shell confinement copper catalyst and preparation method and application |
| CN107715877B (en) * | 2017-10-16 | 2021-02-19 | 山西潞安矿业(集团)有限责任公司 | Hollow mesoporous carbon microsphere shell confinement copper catalyst and preparation method and application thereof |
| CN107930674A (en) * | 2017-10-17 | 2018-04-20 | 太原理工大学 | A kind of catalyst and preparation method and application for preparing dimethyl carbonate |
| CN107930674B (en) * | 2017-10-17 | 2020-09-22 | 山西潞安矿业(集团)有限责任公司 | Catalyst for preparing dimethyl carbonate, preparation method and application |
| CN110280300A (en) * | 2019-06-13 | 2019-09-27 | 中国科学技术大学 | A kind of preparation method and application loading Mn oxide ordered mesoporous carbon composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105521782A (en) | Preparation method of Cu nanoparticles-embedded ordered mesoporous carbon catalyst | |
| CN109012722B (en) | Cerium dioxide/titanium nitride nanotube taking Ce-MOF as precursor and preparation method and application thereof | |
| KR101408045B1 (en) | Mesoporous carbon, manufacturing method thereof, and fuel cell using the same | |
| CN106902842A (en) | A kind of preparation and application for deriving load type palladium catalyst of the carbon-based material as carrier with MOFs | |
| KR20150108868A (en) | Carbon material for use as catalyst carrier | |
| CN110105580B (en) | Hierarchical pore zeolite imidazole ester framework material and preparation method thereof | |
| CN106466602B (en) | A kind of carbon-carried palladium catalyst and its preparation method and application | |
| CN104888779A (en) | Preparation method of Cu nanoparticle-loaded ordered mesoporous carbon catalyst | |
| CN104549515B (en) | Vinyl acetate catalyst and preparation method | |
| CN108126755B (en) | Preparation method of fluorine/chlorine exchange catalyst based on modified MOF | |
| CN106362719B (en) | A kind of modified activated carbon and preparation method and applications | |
| CN107597162B (en) | Nitrogen-doped carbon material with bifunctional oxygen catalysis performance and rich in CNTs and Co particles, and preparation method and application thereof | |
| Mao et al. | Highly active and stable heterogeneous catalysts based on the entrapment of noble metal nanoparticles in 3D ordered porous carbon | |
| Van Vaerenbergh et al. | Towards high-performance heterogeneous palladium nanoparticle catalysts for sustainable liquid-phase reactions | |
| Gao et al. | Metal and metal oxide supported on ordered mesoporous carbon as heterogeneous catalysts | |
| CN107413366B (en) | Preparation method of phenol hydrogenation catalyst | |
| CN112803031A (en) | Porous carbon-based catalyst based on hollow ZSM-5 and preparation method thereof | |
| CN106345461A (en) | Large-pore-size mesoporous carbon/silicon dioxide loaded gold nano-catalyst and synthesis method thereof | |
| CN103170354B (en) | Structured non-mercuric catalyst, and preparation method and application thereof | |
| CN107537476A (en) | Dehydrogenation, preparation method and its usage | |
| CN106944147B (en) | Heteropoly acid ammonium type catalyst and preparation method thereof | |
| CN105597755B (en) | A kind of cubic phase CuO catalyst and preparation method thereof | |
| CN104437474A (en) | Ordered mesoporous carbon material loaded platinum catalyst and application thereof to catalytic hydrogenation of aromatic nitro compound | |
| CN101947444A (en) | Attapulgite load nano Pd catalyst and method for preparing chloroaniline by catalyzing and deoxidating attapulgite load nano Pd catalyst | |
| CN106582644B (en) | A kind of copper-loaded gold/mesoporous carbon catalyst and preparation method thereof for benzene hydroxylation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160427 |
|
| WD01 | Invention patent application deemed withdrawn after publication |