CN104399523A - Method for preparing load type nanogold catalyst - Google Patents
Method for preparing load type nanogold catalyst Download PDFInfo
- Publication number
- CN104399523A CN104399523A CN201410519661.5A CN201410519661A CN104399523A CN 104399523 A CN104399523 A CN 104399523A CN 201410519661 A CN201410519661 A CN 201410519661A CN 104399523 A CN104399523 A CN 104399523A
- Authority
- CN
- China
- Prior art keywords
- solution
- load type
- deionized water
- catalyst
- concentration
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing a load type nanogold catalyst, which comprises the following steps: weighing a polyoxypropylene/polyoxyethylene copolymer solution and dissolving in deionized water to form a haze-free solution A; mixing a formaldehyde aqueous solution with concentration of 37wt.% and deionized water to obtain a haze-free solution B, then adding melamine and thiourea for stirring to obtain a solution C; dumping the solution A in the solution C for stirring to obtain a solution D, dissolving soluble glass in deionized water to obtain a solution E, rapidly dumping the solution D in acetate acid gracial, dumping the solution E in the solution D, performing microwave heating and soxhlet extraction by ethanol to obtain a mesoporous organic-inorganic interpenetrating network material, and dispersing in deionized water, then adding a HAuCl4 aqueous solution with concentration of 0.24M drop by drop, using NaOH with concentration of 1M to adjust pH value to 7-8, stirring, and filtering to obtain the load type nanogold catalyst. The load type nanogold catalyst has advantages of good catalytic activity and stability, the chemical materials with cheap price can be used for preparing the load type nanogold catalyst, and the load type nanogold catalyst enables multitime usage.
Description
Technical field
The present invention relates to a kind of preparation method of load type nano gold catalyst.
Background technology
Load type nano gold catalyst shows excellent catalytic performance in many important selective oxidation reactions, but the minimum gold particle of size has larger surface free energy and lower fusing point, self assemble fast can occur when not having space obstacle makes gold particle size sharply increase, thus loses catalytic activity.Therefore, the physicochemical properties of carrier in load type nano gold catalyst, as structure composition, play critical effect to the affinity of golden species and the interaction between gold particle and carrier etc. to the catalytic activity of final load type nano gold catalyst and stability.With traditional load type nano gold catalyst carrier, as metal oxide or activated carbon are compared, mesoporous material has more regular pore passage structure, and texture character height is controlled, what is more important, mesoporous material has can the surface of cutting and structure, can synthesize the material of task ad hoc type according to demand, and this provides possibility for appropriate design synthesis load type nano gold catalyst carrier.
Inventor synthesizes a kind of bridge joint organosilicon precursor containing ionic liquid fragment and thioether before this and is compound in mesoporous material, because sulphur organic component is uniformly distributed in the material, golden nanometer particle can high degree of dispersion wherein, and gained nano catalyst shows high catalytic activity and stability in the epoxidation reaction of olefines taking hydrogen peroxide as oxidant; But synthesize very complicated and golden anchor point single property containing the bridge joint organosilicon precursor of ionic liquid fragment and thioether in above-mentioned catalyst, catalytic activity and the catalyst stability of catalyst restrict mutually.
Recently, the advantage that inventor is separated at concentration of precious metal with mesoporous material in conjunction with chelating resin, has synthesized carbamide-thiourea resin/SBA-15 composite that series of new is novel, 30
ounder C, the saturated extent of adsorption of this composite to Au (III) reaches 3.04 mmolg, and this implies that this type of material is likely the carrier of good nano catalyst.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art and a kind of catalytic activity and good stability be provided, the preparation method of the load type nano gold catalyst of cheap chemical preparation can be used.
In order to achieve the above object, the present invention is achieved in that it is a kind of preparation method of load type nano gold catalyst, it is characterized in that comprising the steps:
Step one
At 50-70
ounder C condition, the polyoxyethylene polyoxypropylene copolymer solution taking 15-23% is dissolved in deionized water and forms muddy solution A;
Step 2
The formaldehyde of 13-17% being prepared into concentration is after the formalin of 37 wt.%, muddy solution B is mixed to get again with deionized water, adjust the pH value of solution B to 8.5-9.0 with sodium hydrate aqueous solution again, then add the melamine of 8-14% and the thiocarbamide of 5-9%, at 50-70
ostir under C and obtain solution C in 1-3 hour;
Step 3
Solution A is poured in solution C and stirs 2-3 hour, obtain solution D, during solution D stirs, the waterglass of 35-45% is dissolved in deionized water, and at room temperature stir about 25-35 minute, obtains solution E, the glacial acetic acid of 7-9% is poured fast in solution D, under vigorous stirring, in solution D, pour solution E into, by gained mixed liquor in 50-70 at once
oafter stirring 0.5-1.5 hour under C, then at 50-70
oc heating using microwave 5-7 hour, filters, dry, and namely ethanol soxhlet type 46-50 hour obtains nitrogenous and mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer that is sulphur;
Step 4
Get the mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer obtained in the step 3 of 90-98% to be dispersed in 3-5% ml deionized water and to obtain material F, then by the HAuCl of 0.5-1.5%
4be diluted to the aqueous solution that concentration is 0.24M, 25-35
oin material F, dropwise HAuCl has been added under C
4the aqueous solution, with concentration be the NaOH adjust ph of 1 M to 7-8, stir 22-26 hour, filter, vacuum drying, obtain containing gold load type nano gold catalyst sample.
The present invention's advantage is compared with prior art: catalytic activity and good stability, can with cheap chemical preparation load type nano gold catalyst, and load type nano gold catalyst can be reused repeatedly.
accompanying drawing explanation
Fig. 1 is the N of catalyst (a) of the present invention and carrier (b)
2adsorption-desorption isothermal (left side) and pore size distribution curve (right side);
Fig. 2 is the FT-IR collection of illustrative plates of melamine of the present invention and carrier;
Fig. 3 is the N of carrier after roasting of the present invention
2adsorption-desorption isothermal (left side) and pore size distribution curve (right side);
Fig. 4 is the TEM figure of load type nano gold catalyst of the present invention;
Fig. 5 load type nano gold catalyst of the present invention epoxidation of styrene reaction in reuse result.
Detailed description of the invention
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further.It should be noted that at this, the explanation for these embodiments understands the present invention for helping, but does not form limitation of the invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can be combined with each other.
embodiment one
The preparation method of load type nano gold catalyst, comprises the steps:
Step one
60
ounder C condition, the polyoxyethylene polyoxypropylene copolymer solution taking 19% is dissolved in the solution A that deionized water forms muddiness;
Step 2
The formaldehyde of 15% being prepared into concentration is after the formalin of 37 wt.%, then is mixed to get muddy solution B with deionized water, then adjusts the pH value to 8.7 of solution B with sodium hydrate aqueous solution, then adds the melamine of 11% and the thiocarbamide of 7%, 60
ostir under C and obtain solution C in 2 hours;
Step 3
Solution A is poured in solution C and stir 2.5 hours, obtain solution D, during solution D stirs, the waterglass of 40% is dissolved in deionized water, and at room temperature stir about 30 minutes, obtains solution E, the glacial acetic acid of 8% is poured fast in solution D, under vigorous stirring, in solution D, pour solution E into, by gained mixed liquor in 60 at once
ostir after 1 hour under C, then 60
oc heating using microwave 6 hours, filters, dry, and namely ethanol soxhlet type 48 hours obtains nitrogenous and mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer that is sulphur;
Step 4
Get the mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer obtained in the step 3 of 93% to be dispersed in 5% ml deionized water and to obtain material F, then by the HAuCl of 2%
4be diluted to the aqueous solution that concentration is 0.24M, 30
oin material F, dropwise HAuCl has been added under C
4the aqueous solution, with concentration be the NaOH adjust ph of 1 M to 7-8, stir 24 hours, filter, vacuum drying, obtain containing gold load type nano gold catalyst sample.
embodiment two
The preparation method of load type nano gold catalyst, is characterized in that comprising the steps:
Step one
70
ounder C condition, the polyoxyethylene polyoxypropylene copolymer solution taking 23% is dissolved in the solution A that deionized water forms muddiness;
Step 2
The formaldehyde of 17% being prepared into concentration is after the formalin of 37 wt.%, then is mixed to get muddy solution B with deionized water, then adjusts the pH value of solution B to 8.5-9.0 with sodium hydrate aqueous solution, then adds the melamine of 9% and the thiocarbamide of 6%, 50
ostir under C and obtain solution C in 3 hours;
Step 3
Solution A is poured in solution C and stir 3 hours, obtain solution D, during solution D stirs, the waterglass of 38% is dissolved in deionized water, and at room temperature stir about 35 minutes, obtains solution E, the glacial acetic acid of 7% is poured fast in solution D, under vigorous stirring, in solution D, pour solution E into, by gained mixed liquor in 70 at once
ostir after 0.5 hour under C, then 70
oc heating using microwave 5 hours, filters, dry, and namely ethanol soxhlet type 50 hours obtains nitrogenous and mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer that is sulphur;
Step 4
Get the mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer obtained in the step 3 of 91% to be dispersed in 6% ml deionized water and to obtain material F, then by the HAuCl of 3%
4be diluted to the aqueous solution that concentration is 0.24M, 35
oin material F, dropwise HAuCl has been added under C
4the aqueous solution, with concentration be the NaOH adjust ph of 1 M to 7-8, stir 26 hours, filter, vacuum drying, obtain containing gold load type nano gold catalyst sample.
embodiment three
The preparation method of load type nano gold catalyst, is characterized in that comprising the steps:
Step one
50
ounder C condition, the polyoxyethylene polyoxypropylene copolymer solution taking 15% is dissolved in the solution A that deionized water forms muddiness;
Step 2
The formaldehyde of 13% being prepared into concentration is after the formalin of 37 wt.%, muddy solution B is mixed to get again with deionized water, adjust the pH value of solution B to 8.5-9.0 with sodium hydrate aqueous solution again, then add the melamine of 13% and the thiocarbamide of 8%, 70
ostir under C and obtain solution C in 1 hour;
Step 3
Solution A is poured in solution C and stir 2 hours, obtain solution D, during solution D stirs, the waterglass of 42% is dissolved in deionized water, and at room temperature stir about 25 minutes, obtains solution E, the glacial acetic acid of 9% is poured fast in solution D, under vigorous stirring, in solution D, pour solution E into, by gained mixed liquor in 50 at once
ostir after 1.5 hours under C, then 70
oc heating using microwave 5 hours, filters, dry, and namely ethanol soxhlet type 46 hours obtains nitrogenous and mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer that is sulphur;
Step 4
Get the mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer obtained in the step 3 of 95% to be dispersed in 4% ml deionized water and to obtain material F, then by the HAuCl of 1%
4be diluted to the aqueous solution that concentration is 0.24M, 25
oin material F, dropwise HAuCl has been added under C
4the aqueous solution, with concentration be the NaOH adjust ph of 1 M to 7-8, stir 22 hours, filter, vacuum drying, obtain containing gold load type nano gold catalyst sample.
the sign of load type nano gold catalyst sample
By the infrared spectrogram of Avatar 370 FT-IR type determination of infrared spectroscopy sample, select wave-number range at 4000-400 cm
-1in, resolution ratio is 4 cm
-1. with the specific area of Micromeritics Tristar 3000 type physical adsorption appearance test sample and pore-size distribution, adsorption temp is liquid nitrogen temperature-196
oc, by BET method calculation sample specific area, adsorbed by thermoisopleth and prop up by BJH model calculation sample pore-size distribution, the catalyst synthesized by the present invention is observed on JEM-2010 type transmission electron microscope, to analyze particle size and the decentralization of catalytic active center golden nanometer particle; The content of the metallic element gold in the catalyst synthesized by measuring with Thermo ICAP 6300 type inductive coupling plasma emission spectrograph, with the content of N, S element in Vario EL CUBE type elemental analyser working sample, as shown in Figure 1.
Fig. 1 is the N of load type nano gold catalyst and carrier thereof
2adsorption-desorption isothermal and pore size distribution curve, as seen from the figure, nano catalyst and carrier all have the IV type adsorption-desorption isothermal of typical mesoporous material feature, at N
2relative pressure p/p
0there is an obvious capillary condensation hop at=0.7-0.85 place, and possesses the H of SBA-15 type mesoporous material
1type hysteresis loop, these results show that catalyst and carrier have orderly meso-hole structure, the texture parameter (see table 1) of comparative catalyst and carrier, specific area and the pore volume opposite carrier of catalyst have obvious reduction, and aperture has been reduced to 10.6 nm from 11.0 nm, these result explanations, golden nanometer particle successfully introduce carrier mesoporous in, according to the result of ICP, in catalyst gold content be 2.1 wt%.
The physico-chemical property of table 1 load type nano gold catalyst and carrier thereof
| Sample | Pore size(nm) | Surface area (m 2/g) | Pore volume (cm 3/g) |
| Catalyst | 10.6 | 277 | 0.58 |
| Support | 11.0 | 376 | 0.65 |
Fig. 2 is the infrared spectrum of melamine and carrier.By relatively finding out that two spectrograms are all at 1531 cm
-1, 1456 cm
-1there is the stretching vibration peak belonging to C=N, 3380 cm in melamine
-1-NH
2absworption peak disappears in the carrier, illustrates in the building-up process of carrier, and melamine and formaldehyde there occurs polycondensation reaction, define organic network; In addition, carrier is at 3475 cm
-1there is the absworption peak of-OH, at 1146 cm
-1there is the absworption peak of Si-O-Si.
Together with organic network and the inorganic network of further probing into the present invention's synthesis be entrained in by which kind of mode, carrier is carried out following process: take 0.5 g carrier in 550
oc calcines 1 hour in air atmosphere, thus removes the organic component of the present invention's synthesis completely, then remaining inorganic component is carried out N
2adsorption-desorption is tested, gained N
2adsorption-desorption isothermal and pore size distribution curve are shown in Fig. 3, and the inorganic component after carrier calcination has the IV type adsorption-desorption isothermal of typical mesoporous material feature, at N
2relative pressure p/p
0there is an obvious capillary condensation hop at=0.7-0.9 place, and possesses the H of SBA-15 type mesoporous material
1type hysteresis loop, these results show, carrier still has orderly meso-hole structure after removal organic network; In addition, N
2adsorption-desorption result shows, and after roasting, the specific area of carrier is 718 m
2/ g, pore volume is 1.25 cm
3/ g, has had before comparing roasting and has increased significantly; It is worthy of note, after roasting, the pore size of carrier is 11.0 nm, not change; Tem analysis shows that load type nano gold catalyst has flourishing mesoporous space, and does not observe organic aggregation dephasign (left hand view see Fig. 4); In conjunction with N
2in adsorption-desorption analysis, before and after carrier calcination, carrier aperture is constant, the result that specific area and pore volume increase, and can infer that in catalyst, organic network and inorganic network define interpenetrating networks.
It can also be seen that (left hand view of Fig. 4 is 110 crystal faces to load type nano gold catalyst tool well-regulated hexagonal hole road structure from Fig. 4, the right part of flg of Fig. 4 is 001 crystal face), golden nanometer particle is evenly distributed on the mesopore orbit interior (see Fig. 4 circle place in vain) of carrier, and the diameter of golden nanometer particle is about 3 nm; This shows the carrier of the golden nanometer particle that our mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer has been, golden nanometer particle can high degree of dispersion thereon.
The catalyst of the present invention's synthesis obtains regenerated catalyst with absolute ethanol washing three to four ambient temperature in vacuum dryings after centrifugal, then carries out the examination of catalyst reusability.Can see from Fig. 5 result, the first five time is along with the cinnamic conversion ratio of increase of reusable number of times and the selective substantially constant of Styryl oxide, catalyst uses after five times, the selective decline of cinnamic conversion ratio and Styryl oxide. after ICP result display catalyst uses six times, its gold content have decreased to 1.4 wt% by 2.1 wt%, and thus the loss of golden nanometer particle result in the decline of catalyst catalytic activity after use five times.In the preparation of mesoporous organic-inorganic interpenetrating networks carrier, melamine is 1:1 with the ratio of the amount of substance of thiocarbamide, and the N that organic element analyzer measures, S constituent content shows that the melamine in final carrier is 5:1 with the ratio of the amount of substance of thiocarbamide.This shows that the amount that thiocarbamide enters carrier is less in mesoporous organic-inorganic interpenetrating networks carrier building-up process.Because element S is for element N, have stronger affinity to golden species, thus in final carrier, lower S content may be the catalyst reason that golden nanometer particle runs off after reusing 5 times.
Below by reference to the accompanying drawings detailed description is made to embodiments of the present invention, but the present invention is not limited to described embodiment.For the ordinary skill in the art, carry out multiple change, amendment and replace still falling within protection scope of the present invention to these embodiments when not departing from principle of the present invention and aim.
Claims (1)
1. a preparation method for load type nano gold catalyst, is characterized in that comprising the steps:
Step one
At 50-70
ounder C condition, the polyoxyethylene polyoxypropylene copolymer solution taking 15-23% is dissolved in deionized water and forms muddy solution A;
Step 2
The formaldehyde of 13-17% being prepared into concentration is after the formalin of 37 wt.%, muddy solution B is mixed to get again with deionized water, adjust the pH value of solution B to 8.5-9.0 with sodium hydrate aqueous solution again, then add the melamine of 8-14% and the thiocarbamide of 5-9%, at 50-70
ostir under C and obtain solution C in 1-3 hour;
Step 3
Solution A is poured in solution C and stirs 2-3 hour, obtain solution D, during solution D stirs, the waterglass of 35-45% is dissolved in deionized water, and at room temperature stir about 25-35 minute, obtains solution E, the glacial acetic acid of 7-9% is poured fast in solution D, under vigorous stirring, in solution D, pour solution E into, by gained mixed liquor in 50-70 at once
oafter stirring 0.5-1.5 hour under C, then at 50-70
oc heating using microwave 5-7 hour, filters, dry, and namely ethanol soxhlet type 46-50 hour obtains nitrogenous and mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer that is sulphur;
Step 4
Get the mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer obtained in the step 3 of 90-95% to be dispersed in 3-6% ml deionized water and to obtain material F, then by the HAuCl of 1-3%
4be diluted to the aqueous solution that concentration is 0.24M, 25-35
oin material F, dropwise HAuCl has been added under C
4the aqueous solution, with concentration be the NaOH adjust ph of 1 M to 7-8, stir 22-26 hour, filter, vacuum drying, obtain containing gold load type nano gold catalyst sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410519661.5A CN104399523B (en) | 2014-10-01 | 2014-10-01 | The preparation method of load type nano gold catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410519661.5A CN104399523B (en) | 2014-10-01 | 2014-10-01 | The preparation method of load type nano gold catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104399523A true CN104399523A (en) | 2015-03-11 |
| CN104399523B CN104399523B (en) | 2016-07-06 |
Family
ID=52637227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410519661.5A Expired - Fee Related CN104399523B (en) | 2014-10-01 | 2014-10-01 | The preparation method of load type nano gold catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104399523B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106378188A (en) * | 2016-08-25 | 2017-02-08 | 中国科学院广州能源研究所 | Polymer/mesoporous silicon composite material loaded Cu-Fe-Co based catalyst, preparation method and application thereof |
| CN107349960A (en) * | 2016-05-09 | 2017-11-17 | 中国科学院大连化学物理研究所 | A kind of nitrogenous cross-linked polymer supported nanometer gold catalyst and its preparation and the application in aqueous medium in alcohol selective oxidation reaction |
| CN107589163A (en) * | 2017-09-06 | 2018-01-16 | 重庆医科大学 | A kind of electrochemical sensor preparation method for the detection of MECP2 mutators |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304942A (en) * | 2000-05-12 | 2001-07-25 | 中国石油天然气股份有限公司兰州石化分公司 | Water-proof lower-aldehyde urea-formaldehyde resin and its preparing process |
| CN1865343A (en) * | 2005-05-20 | 2006-11-22 | 中国石油天然气股份有限公司 | Process for preparing urea-formaldehyde resin additive, preparation method and uses |
| CN102352006A (en) * | 2011-07-20 | 2012-02-15 | 合肥工业大学 | Ultrasonic preparation method of micron spherical melamine-formaldehyde-thiourea chelating resin |
| US20120316271A1 (en) * | 2010-03-18 | 2012-12-13 | Dynea Oy | Resin composition for the manufacture high gloss laminated panels |
-
2014
- 2014-10-01 CN CN201410519661.5A patent/CN104399523B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304942A (en) * | 2000-05-12 | 2001-07-25 | 中国石油天然气股份有限公司兰州石化分公司 | Water-proof lower-aldehyde urea-formaldehyde resin and its preparing process |
| CN1865343A (en) * | 2005-05-20 | 2006-11-22 | 中国石油天然气股份有限公司 | Process for preparing urea-formaldehyde resin additive, preparation method and uses |
| US20120316271A1 (en) * | 2010-03-18 | 2012-12-13 | Dynea Oy | Resin composition for the manufacture high gloss laminated panels |
| CN102352006A (en) * | 2011-07-20 | 2012-02-15 | 合肥工业大学 | Ultrasonic preparation method of micron spherical melamine-formaldehyde-thiourea chelating resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107349960A (en) * | 2016-05-09 | 2017-11-17 | 中国科学院大连化学物理研究所 | A kind of nitrogenous cross-linked polymer supported nanometer gold catalyst and its preparation and the application in aqueous medium in alcohol selective oxidation reaction |
| CN107349960B (en) * | 2016-05-09 | 2020-02-07 | 中国科学院大连化学物理研究所 | Nitrogen-containing cross-linked polymer supported nano-gold catalyst, preparation thereof and application thereof in alcohol selective oxidation reaction in aqueous medium |
| CN106378188A (en) * | 2016-08-25 | 2017-02-08 | 中国科学院广州能源研究所 | Polymer/mesoporous silicon composite material loaded Cu-Fe-Co based catalyst, preparation method and application thereof |
| CN106378188B (en) * | 2016-08-25 | 2018-12-07 | 中国科学院广州能源研究所 | A kind of polymer/mesoporous silicon composite loaded Cu-Fe-Co base catalyst, preparation method and its application |
| CN107589163A (en) * | 2017-09-06 | 2018-01-16 | 重庆医科大学 | A kind of electrochemical sensor preparation method for the detection of MECP2 mutators |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104399523B (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104923215B (en) | Support ordered mesoporous aluminium oxide material and its synthetic method and the application of noble metal | |
| CN103880020B (en) | Chirality mesoporous organic silica nanotube or core-shell type nanometer rod and preparation method thereof | |
| CN105618038B (en) | Load type gold catalyst and preparation method thereof and the method for preparing para-aminophenol | |
| CN103638944B (en) | A kind of magnetic coupling catalyst A g/HNTs/Fe 3o 4preparation method | |
| CN103738969B (en) | Mesoporous silica and preparation method thereof | |
| CN105149011B (en) | The preparation method of chlorite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals | |
| US20180178197A1 (en) | Hollow mesoporous carbon nanosphere composite material loaded with gold nanoparticles, and preparation method thereof and application in continuous processing of co | |
| Zou et al. | Amphiphilic hollow porous shell encapsulated Au@ Pd bimetal nanoparticles for aerobic oxidation of alcohols in water | |
| Lin et al. | Synthesis and catalytic activity of Ti-MCM-41 nanoparticles with highly active titanium sites | |
| CN104248986B (en) | The preparation method of the composite mesoporous carrier of spherical attapulgite and loaded catalyst and its preparation method and application and ethyl acetate | |
| Yuan et al. | Effects of SBA-15 physicochemical properties on performance of Pd/SBA-15 catalysts in 2-ethyl-anthraquinone hydrogenation | |
| CN105458295B (en) | A kind of multi-pore micron copper ball and preparation method thereof | |
| CN106044743A (en) | Preparation method and application of water-soluble carbon quantum dots based on eggshell membranes | |
| CN104399523A (en) | Method for preparing load type nanogold catalyst | |
| Liu et al. | One-pot synthesis and catalyst support application of mesoporous N-doped carbonaceous materials | |
| US6992039B2 (en) | Method for making monodispersed noble metal nanoparticles supported on oxide substrates | |
| CN105126828B (en) | A kind of porous carbon supported precious metal catalyst and preparation method thereof | |
| Odrozek et al. | Amine-stabilized small gold nanoparticles supported on AlSBA-15 as effective catalysts for aerobic glucose oxidation | |
| CN110203938A (en) | A kind of method and its application preparing multi-stage porous silicon dioxide ultrafine powder body for template based on glucan | |
| Jeong et al. | Au nanoparticle-embedded SiO 2–Au@ SiO 2 catalysts with improved catalytic activity, enhanced stability to metal sintering and excellent recyclability | |
| Liu et al. | Stabilization of ultrafine metal nanocatalysts on thin carbon sheets | |
| CN106345458A (en) | Mesoporous carbon-silicon dioxide complex loaded nano-palladium catalyst and synthesis method thereof | |
| CN105903484A (en) | Nano-catalyst for preparing methyl formate by oxidizing methyl alcohol at one step and preparation method thereof | |
| CN104445181B (en) | A kind of active carbon and preparation method thereof | |
| Taghavimoghaddam et al. | SBA-15 supported cobalt oxide species: Synthesis, morphology and catalytic oxidation of cyclohexanol using TBHP |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160706 Termination date: 20201001 |