CN107597109A - Load type gold catalyst of nano-metal-oxide doping and preparation method and application - Google Patents
Load type gold catalyst of nano-metal-oxide doping and preparation method and application Download PDFInfo
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Abstract
The invention discloses load type gold catalyst of a kind of nano-metal-oxide doping and its preparation method and application, its catalyst is represented using chemical general formula xAu yMO zMSN, x:y:z=(0.5~10):(1~100):100, x:y:Z is the mass ratio of gold, metal oxide and silica；Its initial feed is：The nitrate and nano SiO 2 particle of gold chloride, metal；It is prepared：A kind of dendroid mesoporous silica nano-particle is doped with metal nitrate and prepares carrier, after by obtaining nano catalyst in the method for the carrier surface in-situ reducing gold chloride for being grafted amino；Effect assessment is carried out to prepared catalyst using selective oxidation phenmethylol producing benzaldehyde reaction on fixed bed reactors.The present invention prepares catalyst by the way that nanogold is supported on the mesoporous silicon oxide of doped metallic oxide, and metal oxide is in the same SiO of nanogold2Between play iris action, while and can forms strong interaction with nanogold particle, the nano catalyst of preparation is kept excellent catalytic activity and stability.
Description
Technical field
The present invention relates to a kind of Au catalyst, specifically a kind of load type gold catalysis of nano-metal-oxide doping
Agent and preparation method and application, more particularly to the catalyst of phenmethylol high efficiency selected oxidation benzaldehyde reaction and its preparation side
Method.
Background technology
Benzaldehyde as a kind of important fine-chemical intermediate and raw material, be widely used in medicine, dyestuff, spices,
In the fields such as agricultural chemicals.At present, industrially the method for production benzaldehyde mainly has benzyl chloride Hydrolyze method and chlorination toluene Hydrolyze method again,
The benzaldehyde that both approaches are produced containing chloride because seriously constrain these products in medicine and food service industry
Application.Therefore the synthesis technique without chlorobenzaldehyde such as toluene direct oxidation method, toluene electrochemical oxidation process, benzyl alcohol oxidation
Method, methyl benzoate catalytic hydrogenation method etc. cause the great interest of researcher.And toluene oxidation method generally existing product yield
Low, the problems such as accessory substance is more, hydrogenating reduction method is because higher production cost limits its application, and phenmethylol direct oxidation method is because of tool
There is the characteristics of technique is simple, environment-friendly and show good application prospect.
Find that the nano catalyst that metal oxide supports has higher urge from scientific research personnel such as Haruta in 1987
After changing activity（Sensors and Actuators, 13(1988):339-249）, nano catalyst becomes to be studied for one
Focus.The CuO of the preparations such as Fan Weibin supports nano-Au catalyst in O2In the phenmethylol liquid phase oxidation reaction of participation, 99% is obtained
Benzaldehyde selectivity and 85.7% phenmethylol conversion ratio（Journal of Catalysis, 299(2013):10-19）.
The nano gold grain catalytic agent that the MgO that Choudhary etc. is prepared using deposition-precipitation is supported, with TBHP
Under conditions of oxidant, 100% phenmethylol conversion ratio is can obtain in the reaction of phenmethylol selective oxidation benzaldehyde（Catalysis
Communication, 10(2009):1738-1742）, but be difficult in above-mentioned catalyst to gold grain size and particle diameter
Distribution is effectively regulated and controled, and large scale metal oxide carrier specific surface area is smaller, is unfavorable for the dispersed of gold grain
Contacted with the effective of reactant, especially in phenmethylol selective oxidation benzaldehyde course of reaction, nanogold particle is easily rolled into a ball
Poly-, there is poor stability in performance, and the service life of catalyst is short, therefore can not realize commercial Application.Model is outstanding to be waited mesoporous
Prefabricated nanogold particle is impregnated on silica FDU-12 the nano catalyst that mesoporous silicon oxide supports is made, in benzene first
In 450 hours that the reaction of alcohol selective oxidation benzaldehyde is carried out, 90% benzaldehyde yield is obtained（Journal of the
American Chemical Society, 132(2010):9596-9597）Although the catalyst benzaldehyde yield is higher, with
And preferable catalyst service life is shown, but the catalyst not only grow by the synthetic method complexity of carrier, synthesis cycle（About 3
My god）, and prefabricated nanogold particle prepare it is costly, it is more difficult to realize industrial applications.Therefore, a kind of preparation method is found
Simply, cost is cheap, controllable particle size, the nano gold catalysis of well dispersed high efficiency selected Oxybenzene methyl alcohol producing benzaldehyde
Agent has very important meaning.
The content of the invention
For above-mentioned deficiency, it is an object of the invention to provide a kind of preparation method is simple, cost is cheap, gold grain size
Controllable and well dispersed nano catalyst of high efficiency selected Oxybenzene methyl alcohol producing benzaldehyde and preparation method thereof.
Present invention uses a kind of dendroid nanometer silicon dioxide particle with level meso-hole structure（Chinese patent
CN102616795A）As carrier, the metal oxide particle less than 3nm is consolidated using the nanometer confinement effect of its meso-hole structure
It is scheduled in duct, while the method for gold grain is formed using in-situ reducing after grafted amino group, has efficiently controlled the chi of gold grain
Very little and decentralization.And previously-introduced metal oxide plays a part of barrier so that nanogold particle can not be directly same
SiO2Species contact, so as to avoid because of nanogold particle and SiO2Species interaction is weaker and reunites grow up at high temperature.With this
Carrier S iO simultaneously2The metal oxide of confinement is not susceptible to migration aggregation, can effectively ensure nanogold particle at high temperature
The stabilization of size, so as to significantly improve the reactivity of catalyst and life-span.
Catalyst of the present invention is by metal nitrate and mesoporous silica nano-particle（Chinese patent
CN102616795A）Mixing, after ground, roasting, obtain the mesoporous silica nano-particle conduct of doped metallic oxide
Carrier, then by carrier, 3- aminopropyl trimethoxysilanes（APTMS）Mix, agitated, suction filtration, washing, dry with ethanol
Afterwards, then with gold chloride ethanol solution mix, stir, be eventually adding sodium borohydride, agitated, suction filtration, washing, after drying, obtain
The load type gold catalyst of doped metallic oxide, the catalyst represent that wherein MO is using chemical general formula xAu-yMO-zMSN
Co3O4、MgO、ZnO、NiO、MnO2、Fe2O3, CuO or CeO2, x:y:z=(0.5~10):(1~100):100, x:y:Z is gold, gold
Belong to the mass ratio of oxide and silica；The initial feed for forming the chemical general formula is：Gold chloride, metal nitrate and
Nano SiO 2 particle.
The specific preparation process of above-mentioned catalyst is as follows：
The first step, it is first that metal nitrate and mesoporous silica nano-particle mixed grinding is uniform, afterwards under air atmosphere
250-350 DEG C is calcined 5 hours, obtains the mesoporous silica nano-particle carrier of doped metallic oxide；Wherein, the metal
Metal oxide of the addition of nitrate as obtained by metal nitrate heat resolve:The quality of mesoporous silica nano-particle
Than being calculated as 1~100:100；
Second step, by resulting vehicle, 3- aminopropyl trimethoxysilanes in the first step（APTMS）Three-necked flask is added with ethanol,
80 DEG C of constant temperature are stirred at reflux 6 hours, are filtered, washed and are dried after being cooled to room temperature；Wherein, the doped metallic oxide
Mesoporous silica nano-particle, 3- aminopropyl trimethoxysilanes be that the ratio of components of APTMS and ethanol is metal oxide
The mesoporous silica nano-particle of doping:APTMS:Ethanol=1g:1.74g:40mL；
3rd step, gold chloride ethanol solution is mixed with gained solid in second step, is stirred at room temperature 6 hours, adds afterwards excessive
Sodium borohydride stirs 30 minutes, suction filtration, washing, obtains the load type gold catalysis of the nano-metal-oxide doping after drying
Agent, wherein, gold chloride ethanol solution concentration is 5.08 ~ 101.60 mmol/L；The addition of solid is 1g/5mL.
The metal nitrate is Co (NO3)2、Mg(NO3)2、Zn(NO3)2、Ni(NO3)2、Mn(NO3)2、Fe(NO3)3、Cu
(NO3)2、Ce(NO3)3In one or more.
Described mesoporous silica nano-particle has dendritic structure, and possesses the open ball-type of size uniformity
Hole, its specific surface area reach 534 m2/ g, pore volume are 1.57 ml/g, and aperture is 2 ~ 50 nm.
Golden weight/mass percentage composition is 0.5~10 wt% in the load type gold catalyst of the doped metallic oxide.
Gold grain diameter is in 1~5nm, favorable dispersibility in prepared Au catalyst.
Application of the Au catalyst in the reaction of phenmethylol selective oxidation producing benzaldehyde.
Application of the Au catalyst in the reaction of phenmethylol selective oxidation producing benzaldehyde, it is specially：Using air as oxidation
Agent, phenmethylol is contacted with upper or downward stream mode in fixed bed gas-solid catalysis device with catalyst.Reaction condition is：
200~350 DEG C, volume space velocity 1000~4000 h-1, wherein O2Mol ratio with phenmethylol is 2:3.
The method for preparing catalyst of the present invention be first by metal oxide confinement to mesoporous silica nano-particle, it
When preparing nano catalyst again afterwards, metal oxide is in nanogold particle and SiO2Between play iris action, while and can
Strong interaction is formed with nanogold particle, so that the nano catalyst prepared keeps excellent catalytic activity and stably
Property.
Compared with published load type nano gold catalyst, the present invention has advantages below：
1）Nanogold particle size uniformity of the present invention, decentralization is good, and especially thermostabilization is good, in gating catalytic oxidation phenmethylol system
Excellent catalytic performance is shown in benzaldehyde reaction.
2）Preparation method of the present invention is simple, and synthesis cycle is short, compared with pure metal oxides load type nano gold catalyst,
, as carrier, to reduce the dosage of metal oxide with the mesoporous nano SiO 2 particle of ball-type, greatly reduce life
Cost is produced, can scale commodity production.
Brief description of the drawings
Fig. 1 is the transmission electron microscope of the prepared catalyst of the embodiment of the present invention 1（TEM）Figure；
Fig. 2 is reactivity figure of the prepared catalyst of the embodiment of the present invention 1 with feed time；
Fig. 3 is reactivity figure of the prepared catalyst of the embodiment of the present invention 2 with feed time；
Fig. 4 is reactivity figure of the prepared catalyst of the embodiment of the present invention 3 with feed time；
Fig. 5 is reactivity figure of the prepared catalyst of the embodiment of the present invention 4 with feed time；
Fig. 6 is reactivity figure of the prepared catalyst of the embodiment of the present invention 5 with feed time.
Embodiment
The present invention will be further described for example below, and protection scope of the present invention is not limited by these embodiments
System.
Embodiment 1
Take cabaltous nitrate hexahydrate 0.22g in mortar with 1g mesoporous silica nano-particles（MSN, by patent
CN102616795A is synthesized）Ground and mixed is uniform, afterwards under air atmosphere 270 DEG C be calcined 5 hours, obtain 6 wt% Co3O4Mix
Miscellaneous MSN is as carrier；Afterwards by carrier, 3- aminopropyl trimethoxysilanes（APTMS）Carrier is pressed with ethanol:APTMS:Ethanol
=1g:1.74g:40mL adds three-necked flask, and 80 DEG C of constant temperature are stirred at reflux 6 hours, is cooled to after room temperature and is filtered, washed simultaneously
Dry；By solid obtained by 1g and 5 mL gold chloride ethanol solutions（5.08 mmol/L）Mixing, is stirred at room temperature 6 hours, adds afterwards
Stirred 30 minutes after 30mg sodium borohydrides, suction filtration, washing, obtain the 6 wt% Co that Au loadings are 0.5 wt% after drying3O4Mix
Miscellaneous catalyst, labeled as 0.5%Au-6%Co3O4-MSN。
(20 × 500mm of Ф) does not dilute catalyst obtained by filling 0.7mL in fixed bed reactors, and oxidation is used as using air
Agent carries out benzyl alcohol oxidation reaction, and reaction condition is：250 DEG C, the h of volume space velocity 3800-1, O in raw material2With mole of phenmethylol
Than for 2:3.
Reaction evaluating result such as Fig. 2, phenmethylol conversion ratio maintain about 95% always, and benzaldehyde selectively maintains always
About 98%, catalyst life was up to more than 500 hours, the either conversion ratio of phenmethylol, or catalyst life is much better than document
The result of report.
Embodiment 2
Cabaltous nitrate hexahydrate 0.22g in embodiment 1 is changed to 1.10g, remaining preparation condition is identical, obtains Au loadings as 0.5
Wt% 30 wt% Co3O4Doped catalyst, labeled as 0.5%Au-30%Co3O4-MSN.Reaction evaluating condition and embodiment 1 are complete
It is exactly the same.
Reaction evaluating result such as Fig. 3：The conversion ratio of phenmethylol and the selectivity of benzaldehyde respectively may be about 85% and 98%, catalysis
The agent life-span was up to more than 350 hours.
Embodiment 3
Gold chloride ethanol solution concentration in embodiment 1 is changed to 101.60 mmol/L by 5.08 mmol/L, remaining preparation condition
It is identical, obtain the 6 wt% Co that Au loadings are 10 wt%3O4Doped catalyst, labeled as 10%Au-6%Co3O4-MSN.Reaction
Appreciation condition is identical with embodiment 1.
Reaction evaluating result such as Fig. 4：The conversion ratio of phenmethylol and the selectivity of benzaldehyde are held in 93% or so, catalysis
The agent life-span is also up to 300 hours.
Embodiment 4
Take magnesium nitrate hexahydrate 0.32g to add in mortar and be heated to 150 DEG C, add 1g mesoporous silica nano-particles
（MSN, synthesized by patent CN102616795A）Be ground, afterwards under air atmosphere 330 DEG C be calcined 5 hours, obtain 3 wt%
The MSN of MgO doping is as carrier；Afterwards by carrier, 3- aminopropyl trimethoxysilanes（APTMS）Carrier is pressed with ethanol:
APTMS:Ethanol=1g:1.74g:40mL adds three-necked flask, and 80 DEG C of constant temperature are stirred at reflux 6 hours, taken out after being cooled to room temperature
Filter, wash and dry；By solid obtained by 1g and 5mL gold chloride ethanol solutions（20.32 mmol/L）Mixing, it is small to be stirred at room temperature 6
When, stirred 30 minutes after adding 30mg sodium borohydrides afterwards, suction filtration, washing, obtain 5 that Au loadings are 2 wt% after drying
Wt% MgO doped catalysts, labeled as 2%Au-5%MgO-MSN.Reaction evaluating condition is identical with embodiment 1.
Reaction evaluating result such as Fig. 5：It is left that the conversion ratio of phenmethylol and the selectivity of benzaldehyde are kept at 96% and 92%
The right side, catalyst life was up to 240 hours.
Embodiment 5
Catalyst preparation conditions are the same as embodiment 1.Reaction temperature in fixed bed reaction is promoted to 350 DEG C by 250 DEG C, remaining reaction
Condition is the same as embodiment 1.
Reaction evaluating result such as Fig. 6：The conversion ratio of phenmethylol and the selectivity of benzaldehyde respectively may be about 64% and 90%, catalysis
The agent life-span is more than 100 hours.
Embodiment 6
Reaction evaluating result is shown, cabaltous nitrate hexahydrate 0.22g in embodiment 1 is changed into 0.04g, and remaining preparation condition is identical,
Obtain the 1 wt% Co that Au loadings are 0.5 wt%3O4Doped catalyst, labeled as 0.5%Au-1%Co3O4-MSN.Reaction evaluating
Condition is identical with embodiment 1.
The conversion ratio of phenmethylol and the selectivity of benzaldehyde respectively may be about 86% and 94%, catalyst life up to 180 hours with
On.
Embodiment 7
Cabaltous nitrate hexahydrate 0.22g in embodiment 1 is changed to 0.06g, gold chloride ethanol solution concentration is changed to by 5.08 mmol/L
50.80 mmol/L, remaining preparation condition is identical, obtains the 1.5 wt% Co that Au loadings are 5 wt%3O4Doped catalyst, mark
It is designated as 5%Au-1.5%Co3O4-MSN.Reaction evaluating condition is identical with embodiment 1.
Reaction evaluating result shows that the conversion ratio of phenmethylol and the selectivity of benzaldehyde respectively may be about 88% and 96%, catalysis
The agent life-span was up to 200 hours.
Embodiment 8
Cabaltous nitrate hexahydrate 0.22g in embodiment 1 is changed to Gerhardite 0.18g, sintering temperature is 180 DEG C, remaining system
Standby condition is identical, the 6 wt% CuO doped catalysts that Au loadings are 0.5 wt% is obtained, labeled as 0.5%Au-6%CuO-MSN.
Reaction evaluating condition is identical with embodiment 1.
Reaction evaluating result shows that the conversion ratio of phenmethylol and the selectivity of benzaldehyde respectively may be about 91% and 97%, catalysis
The agent life-span was up to more than 400 hours.
Comparative example 1
By mesoporous silica nano-particle（MSN）, 3- aminopropyl trimethoxysilanes（APTMS）MSN is pressed with ethanol:APTMS:
Ethanol=1g:1.74g:40mL adds three-necked flask, and 80 DEG C of constant temperature are stirred at reflux 6 hours, is cooled to after room temperature and is filtered, washed
Wash and dry；By solid obtained by 1g and 5mL gold chloride ethanol solutions（5.08 mmol/L）Mixing, is stirred at room temperature 6 hours, afterwards
Stir 30 minutes after adding 30mg sodium borohydrides, filter, washing, dry after to obtain Au loadings be 0.5 wt% catalyst, mark
For 0.5%Au-MSN.Reaction evaluating condition is identical with embodiment 1.
Reaction evaluating result shows that the conversion ratio of phenmethylol is only about 70%, and catalyst life is short, after reacting 100 hours
The activity of catalyst is rapid to be declined.This shows, gold directly load to MSN on made from catalyst, because lack in the present invention it is golden-
Strong interaction between metal oxide-MSN, and show poor catalytic activity and stability.
Comparative example 2
According to document（Journal of Catalysis, 299(2013):10-19）14.52g six is hydrated by described method
Cobalt nitrate, 0.04g gold chloride solids are dissolved in 30mL deionized waters, form uniform solution；2.5 mol/L NaOH is utilized afterwards
PH value of solution is transferred to 10, centrifugal treating after stirring 10 minutes, washs the chlorion for removing residual repeatedly using deionized water；It will wash
Solid after washing is dried 12 hours at 100 DEG C, obtains the Co that Au loadings are 0.5 wt%3O4Catalyst, labeled as 0.5%Au-
Co3O4.Reaction evaluating condition is identical with embodiment 1.
Reaction evaluating result shows that the conversion ratio of phenmethylol is only about 73%, the conversion ratio of phenmethylol after reacting 80 hours
Less than 40% is dropped rapidly to, shows very poor catalyst stability.
Claims (7)
1. a kind of load type gold catalyst of nano-metal-oxide doping, it is characterised in that the catalyst uses chemical general formula
XAu-yMO-zMSN represents that wherein MO is Co3O4、MgO、ZnO、NiO、MnO2、Fe2O3, CuO or CeO2, x:y:z=(0.5~10):
(1~100):100, x:y:Z is the mass ratio of gold, metal oxide and silica；Form the initial feed of the chemical general formula
For：Gold chloride, metal nitrate and nano SiO 2 particle.
2. load type gold catalyst according to claim 1, it is characterised in that the metal nitrate is Co (NO3)2、Mg
(NO3)2、Zn(NO3)2、Ni(NO3)2、Mn(NO3)2、Fe(NO3)3、Cu(NO3)2、Ce(NO3)3In one or several kinds.
3. load type gold catalyst according to claim 1, it is characterised in that the mesoporous silica nano-particle aperture
For 2 ~ 50 nm, and possesses the open ball-type hole of size uniformity.
4. load type gold catalyst according to claim 1, it is characterised in that golden weight/mass percentage composition is 0.5~10
wt%；Gold grain diameter is in 1~5nm, favorable dispersibility.
5. the preparation method of load type gold catalyst described in a kind of claim 1, it is characterised in that this method is included in detail below
Step：
The first step, it is first that metal nitrate and mesoporous silica nano-particle mixed grinding is uniform, afterwards under air atmosphere
250-350 DEG C is calcined 5 hours, obtains the mesoporous silica nano-particle carrier of doped metallic oxide；Wherein, the metal
Metal oxide of the addition of nitrate as obtained by metal nitrate heat resolve:The quality of mesoporous silica nano-particle
Than being calculated as 1~100:100；
Second step, resulting vehicle, 3- aminopropyl trimethoxysilanes and ethanol in the first step are added into three-necked flask, 80 DEG C of constant temperature
It is stirred at reflux 6 hours, is filtered, washed and dried after being cooled to room temperature；Wherein, mesoporous the two of the doped metallic oxide
Silica nano particle, 3- aminopropyl trimethoxysilanes are that the ratio of components of APTMS and ethanol is Jie of doped metallic oxide
Hole nano SiO 2 particle:APTMS:Ethanol=1g:1.74g:40mL；
3rd step, gold chloride ethanol solution is mixed with gained solid in second step, is stirred at room temperature 6 hours, adds afterwards excessive
Sodium borohydride stirs 30 minutes, suction filtration, washing, obtains the load type gold catalysis of the nano-metal-oxide doping after drying
Agent, wherein, gold chloride ethanol solution concentration is 5.08 ~ 101.60 mmol/L；The addition of solid is 1g/5mL.
A kind of 6. application of the load type gold catalyst described in claim 1 in the reaction of phenmethylol selective oxidation producing benzaldehyde.
7. application according to claim 6, it is characterised in that using air as oxidant, by phenmethylol with upper or dirty
Mode contacts in fixed bed gas-solid catalysis device with catalyst, wherein, reaction condition is：210~350 DEG C of temperature,
The h of volume space velocity 1000~4000-1, O2Mol ratio with phenmethylol is 2:3.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616795A (en) * | 2012-04-23 | 2012-08-01 | 华东师范大学 | Method for preparing pure silicon-based mesoporous silica nanoparticles |
| CN103990489A (en) * | 2014-05-27 | 2014-08-20 | 天津大学 | Preparation method of cerium dioxide modified SBA-15 supported gold catalyst |
| CN105126838A (en) * | 2015-08-04 | 2015-12-09 | 上海应用技术学院 | Zinc oxide doped titanium dioxide-nano gold catalyst, preparation method and applications thereof |
| CN105268465A (en) * | 2014-07-22 | 2016-01-27 | 华东师范大学 | Silicon oxide-loaded ruthenium catalyst modified or unmodified with organic functional group and containing nickel or no nickel, and preparation method and application thereof |
| CN106334555A (en) * | 2016-11-15 | 2017-01-18 | 烟台大学 | High-activity and high-stability supported nanometer gold catalyst, preparation and application method |
-
2017
- 2017-08-09 CN CN201710673510.9A patent/CN107597109A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616795A (en) * | 2012-04-23 | 2012-08-01 | 华东师范大学 | Method for preparing pure silicon-based mesoporous silica nanoparticles |
| CN103990489A (en) * | 2014-05-27 | 2014-08-20 | 天津大学 | Preparation method of cerium dioxide modified SBA-15 supported gold catalyst |
| CN105268465A (en) * | 2014-07-22 | 2016-01-27 | 华东师范大学 | Silicon oxide-loaded ruthenium catalyst modified or unmodified with organic functional group and containing nickel or no nickel, and preparation method and application thereof |
| CN105126838A (en) * | 2015-08-04 | 2015-12-09 | 上海应用技术学院 | Zinc oxide doped titanium dioxide-nano gold catalyst, preparation method and applications thereof |
| CN106334555A (en) * | 2016-11-15 | 2017-01-18 | 烟台大学 | High-activity and high-stability supported nanometer gold catalyst, preparation and application method |
Non-Patent Citations (3)
| Title |
|---|
| GUICEN MA ET AL.: "Stabilizing gold clusters by heterostructured transition-metal oxide–mesoporous silica supports for enhanced catalytic activities for CO oxidation", 《CHEM. COMMUN.》 * |
| YE JUN YU ET AL.: "Facile Synthesis of Size Controllable Dendritic Mesoporous Silica Nanoparticles", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| 马桂岑: "有序超大孔介孔二氧化硅的合成及其作为金催化载体的应用", 《浙江大学博士论文》 * |
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| CN110124717B (en) * | 2019-05-13 | 2022-02-15 | 浙江师范大学 | Catalyst for converting benzyl alcohol into benzaldehyde and preparation method thereof |
| CN111939887A (en) * | 2019-05-17 | 2020-11-17 | 中国石油化工股份有限公司 | Catalyst, preparation method and application thereof in flue gas desulfurization and denitrification |
| CN111939887B (en) * | 2019-05-17 | 2022-10-21 | 中国石油化工股份有限公司 | Catalyst, preparation method and application thereof in flue gas desulfurization and denitrification |
| CN110721677A (en) * | 2019-11-19 | 2020-01-24 | 河北科技大学 | Nano manganese-based catalyst, preparation method and application thereof, and corresponding application method |
| CN111905726A (en) * | 2020-08-03 | 2020-11-10 | 大连理工大学 | Preparation method of Au-C high-selectivity oxidation catalyst with controllable size |
| CN111905726B (en) * | 2020-08-03 | 2022-12-20 | 大连理工大学 | Preparation method of Au-C high-selectivity oxidation catalyst with controllable size |
| CN113620334A (en) * | 2021-08-20 | 2021-11-09 | 武汉大学 | Dendritic ordered mesoporous copper oxide nano material and preparation method and application thereof |
| CN114950413A (en) * | 2022-06-08 | 2022-08-30 | 中国科学院化学研究所 | Preparation method of graphdiyne modified hydrophilic catalyst and application of graphdiyne modified hydrophilic catalyst in aqueous phase hydrogenation |
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