CN104128199B - A kind of nano catalyst and its preparation method - Google Patents
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Abstract
The present invention relates to a kind of nano catalyst and its preparation method, this catalyzer first will be reduced to a nanometer Au containing auric acid, add silicon source with polymeric binder after being mixed by this nanometer of Au, aluminium source react to obtain catalyst precursor, template is added catalyst precursor and carries out the nano catalyst that hydro-thermal reaction obtains nucleocapsid structure, kernel is a nanometer Au, shell is the sial mesopore molecular sieve of one or several mixture of A type, X type, Y type or ZSM-5 type, and this catalyzer has higher thermostability and catalytic activity.
Description
Technical field
The present invention relates to a kind of nano catalyst and its preparation method, belong to the catalyst preparation technology of Industrial Catalysis technical field.
Background technology
The reserves of gold are limited has again unique anti-oxidant and corrosion resistance, always by as the material of decoration material and currency value preserving. In recent years, with the increase of vehicle maintenance service, new energy development demand, people more and more pay close attention to the research of nano-noble metal catalyst. Wherein, nano catalyst becomes a kind of research nano-noble metal catalyst the most widely gradually due to its catalytic perfomance such as more excellent catalyzed oxidation and shortening. Compared to traditional loaded catalyst, the metallic particles of nano-Au catalyst is less, thus has higher catalytic reaction activity.
CN102632232A patent discloses the method improving thermostability, suppressing sintering, this disclosure of the invention mechanical alloying preparation method of a kind of aluminium-based amorphous alloy composite powder, and adopt the aluminium base bulk amorphous alloys that obtains of powder consolidation moulding method with this amorphous powder, owing to being doped with the carbon material of high thermal stability material, and by reasonable component proportioning, the thermostability of non-crystaline amorphous metal is significantly improved. CN102181746A patent discloses a kind of high temperature resistant titanium alloy, it comprises take metal titanium as major ingredient, adding a small amount of metallic aluminium again, form hot strength, high-temperature oxidation resistance, the thermostability to improving alloy that is uniformly distributed keeping tiny has vital role. In catalyst pretreatment and reaction process, owing to the surface energy of Au nano particle is big, thus very easily occur to reunite and sintering, finally cause the reduction of catalytic activity. In addition, simplification, the simplification of catalyst structure make its Application Areas receive restriction to a certain degree, and these all seriously reduce the application prospect of Au catalyzer.Therefore, the structure design of innovation catalyzer, the preparation method of exploration catalyzer are problems with important research meaning to obtain the multi-functional new catalytic material with high thermal stability.
Currently, suppressing Au nano particle to occur the method for sintering to have a lot, the most common is exactly be oxidized shell its outer layer covers one layer, is formed taking nanometer Au as core, and oxide compound is the catalytic material with nucleocapsid structure of shell. This kind of structure is possible to prevent nanometer sintering that Au particle occurs in the treating processess such as roasting, and the contact being also possible to prevent between Au nano particle, increase specific surface area. Due to silicon-dioxide stable in properties, cheap, so the most frequently used oxidation shell is made up of silicon-dioxide. In order to enable reaction molecular enter into active sites smoothly, need oxidation shell is carried out the process such as follow-up etching, roasting, make its surface form loose pore passage structure, thus be conducive to the contact between reaction molecular and catalyst activity position, it is to increase the reactivity worth of catalyzer. But, silicon-dioxide is indifferent oxide, and itself does not possess catalytic activity, and its effect played is only protective layer, which greatly limits the catalytic efficiency of catalyzer. Molecular sieve has unique pore passage structure and higher catalytic performance, is widely used in the reactions such as aromizing, catalytic cracking, isomerization. Molecular sieve has bigger specific surface area in addition, good " appearance charcoal " ability, contributes to realizing the abundant dispersion of active ingredient at catalyst surface, it is to increase catalytic reaction activity and stability. So, the present invention replaces traditional silica shell to be expected to realize the multifunction of nano-Au catalyst with molecular sieve, thus expands the Application Areas of catalyzer.
Summary of the invention
Technical problem: it is an object of the invention to provide a kind of nano catalyst and its preparation method, this catalyzer first will be reduced to a nanometer Au containing auric acid, silicon source is added after being mixed with polymeric binder by this nanometer of Au, catalyst precursor is reacted to obtain in aluminium source, template is added catalyst precursor and carries out the nano catalyst that hydro-thermal reaction obtains nucleocapsid structure, kernel is a nanometer Au, shell is sial mesopore molecular sieve, this catalyzer has higher thermostability and catalytic activity, and there is good application prospect, the reaction at high temperature carried out had good catalytic performance.
Technical scheme: the present invention is to provide a kind of nano catalyst and its preparation method, this catalyzer first will be reduced to a nanometer Au containing auric acid, add silicon source with polymeric binder after being mixed by this nanometer of Au, aluminium source react to obtain catalyst precursor, template is added catalyst precursor and carries out the nano catalyst that hydro-thermal reaction obtains nucleocapsid structure, kernel is a nanometer Au, and shell is sial mesopore molecular sieve. The shell sial mesopore molecular sieve of this catalyzer is one or several mixture of A type, X type, Y type or ZSM-5 type.
The preparation method of nano catalyst is:
Step is a) under room temperature, the auric acid aqueous solution that contains that mass percent is 2wt��10wt% is added in reactor, by reductive agent with containing auric acid mass ratio be 5:1��20:1, add the reductive agent aqueous solution that concentration is 1��5mol/L, reaction 2��4h, then by polymeric binder with containing auric acid mass ratio be 0.2:1��1.5:1, add the polymeric binder aqueous solution that concentration is 0.01��0.1g/mL, continuing reaction 10��20h, centrifugation, obtains gold sol;
Step b) by the mass ratio 8:1��12:1 of ethanol and deionized water, obtained ethanol water mixture, by the mass ratio 50:1��200:1 of ethanol water mixture and gold sol, ethanol water mixture is added to step a) in obtained gold sol, ultrasonic disperse 0.5��2h, obtain gold sol ethanol water mixture, the mineral alkali being 0.05g/mL��0.5g/mL by concentration regulates this mixture pH to 8��12, silicon source is added by the mass ratio 1:1��5:1 of silicon source and gold sol under room temperature, 0.5��2h is stirred at 40��60 DEG C, aluminium source is added by the mass ratio 0.4:1��1:1 in aluminium source and silicon source, 12��24h is reacted at 60��100 DEG C, filter, with the deionized water of 50��100 times of silicon source qualities, the ethanol of 10��30 times of silicon source qualities is washing leaching cake respectively, vacuum-drying 8��10h at 60��100 DEG C, obtain catalyst precursor,
Step c) by deionized water and step b) mass ratio of obtained catalyst precursor is 10:1��50:1, deionized water and this presoma are added in water heating kettle, it is that 0.2:1��1:1 adds template by the mass ratio of template and catalyst precursor, hydro-thermal reaction 72��120h at 120��180 DEG C, filter after being down to room temperature, with the quality deionized water of 20��60 times of catalyst precursors, the ethanol of the quality of 10��20 times of catalyst precursors is washing leaching cake respectively, 60��100 DEG C of vacuum-drying 8��10h, 450��600 DEG C of roasting 4��8h, obtain nano catalyst.
Preparation method's step of above-mentioned nano catalyst a) described in be the combination of a kind of in tetra chlorauric acid, acetic acid gold or two kinds containing auric acid, described reductive agent is a kind of in sodium borohydride, trisodium citrate or both combinations, and described polymeric binder is one or several combination of polyvinylpyrrolidone, carboxymethyl cellulose or methylcellulose gum; Preparation method step b) described in silicon source be a kind of in tetraethyl orthosilicate, hexamethyldisiloxane or both combinations, described aluminium source is one or several the combination in sodium metaaluminate, Tai-Ace S 150 or aluminum nitrate, and described mineral alkali is sodium hydroxide or potassium hydroxide; Preparation method step c) described in template be one or several the combination in cetyl trimethylammonium bromide, quadrol or 4-propyl bromide.
Preparation method's step of above-mentioned nano catalyst a) in, when reductive agent is sodium borohydride, this solution needs to carry out at low temperatures existing preparation. The adition process of sodium borohydride should disposable rapidly add, with ensure reduction fully prevent secondary reduction. Polymeric binder add the formation that next step Si-Al molecular sieve can be promoted in gold surface, its consumption can determine the size of bonding degree. Step b) in, affect silicon source, the hydrolysis rate in aluminium source and deposit thickness respectively size and hydrolysis time with pH value have close relationship, it is necessary to strict control ph and hydrolysis time. Step c) in, the main effect of template forms pore passage structure on Si-Al molecular sieve surface. Steps d) in, the object of roasting mainly removes template on the one hand, can activate this kind of catalytic material on the other hand, carry out crystallization process. So roasting time needs to control well. Owing to the formation of molecular sieve is also had a certain impact by temperature, particularly at high temperature this kind of structure is easy to be destroyed, so should retain this kind of molecular sieve structure while ensureing to remove template, highly crystallized, prevents caving in of duct.
Catalyst performance evaluation: be the catalyzer dispersion liquid of 0.5g/L by concentration obtained in nano catalyst ultrasonic disperse to water, be the sodium borohydride aqueous solution of 0.25mol/L, 2mL concentration by 6.5mL concentration under room temperature it is that the 0.02mol/L p-NP aqueous solution adds in reaction tubes, add 10mL nano gold catalysis agent dispersing liquid after mixed even to react, it is p-aminophenol by p-NP catalytic reduction, by the continuous analytical reaction process of UV spectrum, stopped reaction after 6 minutes, investigates the transformation efficiency of nitrophenols and the reaction rate constant of catalyzer.
Useful effect: it is an object of the invention to provide a kind of nano catalyst and its preparation method, this catalyzer is to contain auric acid as Jin Yuan, in the presence of a reducing agent Jin Yuan is reduced into a nanometer Au particle, silicon source and aluminium source is added with polymeric binder after being mixed by this nanometer of Au, after adding template, hydro-thermal reaction obtains the nano catalyst of nucleocapsid structure, kernel is a nanometer Au, and shell is sial mesopore molecular sieve. This catalyzer has higher thermostability, good catalytic activity, and has good application prospect.
The feature of the present invention is:
(1) using gold as the active centre of catalyzer, and gold is always considered as having very much the precious metal of catalysis potentiality. The catalytic activity of gold is very high, and Application Areas is very wide. In this patent, gold is chosen as catalytic active center, is because the catalytic field of gold is wide on the one hand, the multi-field application realizing catalyzer is had good promoter action; On the other hand, metallographic, for other precious metals, has price advantage and superiority of reserves such as Pt, Pd etc., and a large amount of preparations of catalyzer are provided guarantee by this.
(2) at the surface parcel one layer of polymeric binding agent of gold; the load that this kind of polymeric binder is next step Si-Al molecular sieve provides guarantee; it can play bonding Si-Al molecular sieve and the effect of protection Au, and constructing of this catalyzer is served very important effect by this.
(3) at outer layer covers one layer of Si-Al molecular sieve of gold, first can protect nanometer gold, prevent gold from increasing in catalyst preparation process and sintering, ensure that catalyzer has higher activity; Secondly, the performance that Si-Al molecular sieve is stable, it is possible to for the structure of catalyzer plays a stabilization, in the reaction and preparation process can both stable existence, be not destroyed easily, it is to increase the physical strength of catalyzer, finally also ensure that the activity of catalyzer; The more important thing is that the performance to catalyzer that builds of Si-Al molecular sieve serves very big effect, this is mainly reflected in: this kind of molecular sieve structure inherently a kind of catalyzer on the one hand, this is to single golden catalytic active center, serves one and well supplements; On the other hand, other active centre of load in the above is further provided a carrier by being formed of molecular sieve, and the expansion in catalyst application field is had inestimable effect by this.
Embodiment
The nano catalyst of the present invention is: first will be reduced to a nanometer Au containing auric acid, add silicon source with polymeric binder after being mixed by this nanometer of Au, aluminium source react to obtain catalyst precursor, template is added catalyst precursor and carries out the nano catalyst that hydro-thermal reaction obtains nucleocapsid structure, kernel is a nanometer Au, and shell is sial mesopore molecular sieve. The shell sial mesopore molecular sieve of this catalyzer is one or several mixture of A type, X type, Y type or ZSM-5 type.
Embodiment 1:
At 25 DEG C, the tetra chlorauric acid aqueous solution that 1.5g mass percent is 4wt% is added in reactor, add the trisodium citrate aqueous solution that 66mL concentration is 3mol/L, after reaction 2h, add the polyvinylpyrrolidone aqueous solution that 1.5g concentration is 0.1g/mL, continuing reaction 18h, centrifugation, obtains gold sol;
150mL ethanol, 10mL deionized water are added in above-mentioned obtained gold sol, ultrasonic disperse 1h, obtains gold sol ethanol water mixture, regulates this mixture pH to 8.5 with the sodium hydroxide solution of 0.1g/mL, add 3g tetraethyl orthosilicate, at 40 DEG C, stir 0.5h, add 1.3g sodium metaaluminate, at 90 DEG C, react 16h, filter, with 150mL deionized water, 50mL ethanol washing leaching cake respectively, at 60 DEG C, vacuum-drying 8h, obtains catalyst precursor; 58mL deionized water and this catalyst precursor are added in water heating kettle, add 1.2g cetyl trimethylammonium bromide, hydro-thermal reaction 96h at 150 DEG C, filter after being down to room temperature, with 150mL deionized water, 50mL ethanol washing leaching cake respectively, 60 DEG C of vacuum-drying 8h, 550 DEG C of roasting 4h, obtain nano catalyst.
The catalytic performance of nano catalyst: the transformation efficiency of p-NP is 94.1%, the reaction rate constant of catalyzer is 0.0156s-1��
Embodiment 2:
Under room temperature, the tetra chlorauric acid aqueous solution that 1.5g mass percent is 4wt% is added in reactor, add the sodium borohydride aqueous solution that 66mL concentration is 3mol/L, after reaction 2h, add the polyvinylpyrrolidone aqueous solution that 1.5g concentration is 0.1g/mL, continuing reaction 18h, centrifugation, obtains gold sol;
150mL ethanol, 10mL deionized water are added in above-mentioned obtained gold sol, ultrasonic disperse 1h, obtains gold sol ethanol water mixture, regulates this mixture pH to 8.5 with the potassium hydroxide solution of 0.1g/mL, add 3g tetraethyl orthosilicate, at 40 DEG C, stir 0.5h, add 1.3g aluminum nitrate, at 90 DEG C, react 16h, filter, with 150mL deionized water, 50mL ethanol washing leaching cake respectively, at 60 DEG C, vacuum-drying 8h, obtains catalyst precursor; 58mL deionized water and this catalyst precursor are added in water heating kettle, add 1.2g 4-propyl bromide, hydro-thermal reaction 120h at 150 DEG C, filter after being down to room temperature, with 150mL deionized water, 50mL ethanol washing leaching cake respectively, 60 DEG C of vacuum-drying 8h, 550 DEG C of roasting 5h, obtain nano catalyst.
The catalytic performance of nano catalyst: the transformation efficiency of p-NP is 99.8%, rate constant is 0.0241s-1��
Embodiment 3:
At 20 DEG C, the tetra chlorauric acid aqueous solution that 1.5g mass percent is 4wt% is added in reactor, add 22mL concentration be the trisodium citrate of 3mol/L and 44mL concentration be 3mol/L sodium borohydride mixed solution in react 2h after, add the polyvinylpyrrolidone aqueous solution that 1.5g concentration is 0.1g/mL, continue reaction 18h, centrifugation, obtains gold sol;
150mL ethanol, 10mL deionized water are added in above-mentioned obtained gold sol, ultrasonic disperse 1h, obtains gold sol ethanol water mixture, regulates this mixture pH to 8.5 with the sodium hydroxide solution of 0.1g/mL, add 3g hexamethyldisiloxane, at 40 DEG C, stir 0.5h, add 1.3g sodium metaaluminate, at 90 DEG C, react 16h, filter, with 150mL deionized water, 50mL ethanol washing leaching cake respectively, at 60 DEG C, vacuum-drying 8h, obtains catalyst precursor; 58mL deionized water and this catalyst precursor are added in water heating kettle, adds 1.2g quadrol, hydro-thermal reaction 96h at 150 DEG C, filter after being down to room temperature, with 150mL deionized water, 50mL ethanol washing leaching cake respectively, 60 DEG C of vacuum-drying 8h, 580 DEG C of roasting 4h, obtain nano catalyst.
The catalytic performance of nano catalyst: the transformation efficiency of p-NP is 96.4%, rate constant is 0.0217s-1��
Embodiment 4:
At 25 DEG C, the tetra chlorauric acid aqueous solution that 1.5g mass percent is 4wt% is added in reactor, add 44mL concentration be the trisodium citrate of 3mol/L and 22mL concentration be 3mol/L sodium borohydride mixed solution in react 2h after, add the polyvinylpyrrolidone aqueous solution that 1.5g concentration is 0.1g/mL, continue reaction 18h, centrifugation, obtains gold sol;
150mL ethanol, 10mL deionized water are added in above-mentioned obtained gold sol, ultrasonic disperse 1h, obtains gold sol ethanol water mixture, regulates this mixture pH to 8.5 with the sodium hydroxide solution of 0.1g/mL, add 1.2g tetraethyl orthosilicate and 1.8g hexamethyldisiloxane, at 40 DEG C, stir 0.5h, add 1.3g sodium metaaluminate, at 90 DEG C, react 16h, filter, with 150mL deionized water, 50mL ethanol washing leaching cake respectively, at 60 DEG C, vacuum-drying 8h, obtains catalyst precursor; 58mL deionized water and this catalyst precursor are added in water heating kettle, add 0.6g cetyl trimethylammonium bromide and 0.6g 4-propyl bromide, hydro-thermal reaction 72h at 150 DEG C, filter after being down to room temperature, with 150mL deionized water, 50mL ethanol washing leaching cake respectively, 60 DEG C of vacuum-drying 8h, 580 DEG C of roasting 5h, obtain nano catalyst.
The catalytic performance of nano catalyst: the transformation efficiency of p-NP is 95.2%, rate constant is 0.0183s-1��
Embodiment 5:
At 25 DEG C, the tetra chlorauric acid aqueous solution that 1.5g mass percent is 4wt% is added in reactor, add the sodium borohydride aqueous solution that 66mL concentration is 3mol/L, after reaction 2h, add the polyvinylpyrrolidone aqueous solution that 0.5g concentration is 0.1g/mL and 1g concentration is the mixture of carboxymethyl cellulose aqueous solution of 0.1g/mL, continuing reaction 18h, centrifugation, obtains gold sol;
150mL ethanol, 10mL deionized water are added in above-mentioned obtained gold sol, ultrasonic disperse 1h, obtains gold sol ethanol water mixture, regulates this mixture pH to 8.5 with the potassium hydroxide solution of 0.1g/mL, add 3g tetraethyl orthosilicate, at 40 DEG C, stir 0.5h, add 0.8g sodium metaaluminate and 0.5 gram of Tai-Ace S 150, at 90 DEG C, react 16h, filter, with 150mL deionized water, 50mL ethanol washing leaching cake respectively, at 60 DEG C, vacuum-drying 8h, obtains catalyst precursor; 58mL deionized water and this catalyst precursor are added in water heating kettle, add 0.6g quadrol and 0.6g 4-propyl bromide, hydro-thermal reaction 96h at 150 DEG C, filter after being down to room temperature, with 150mL deionized water, 50mL ethanol washing leaching cake respectively, 60 DEG C of vacuum-drying 8h, 580 DEG C of roasting 6h, obtain nano catalyst.
The catalytic performance of nano catalyst: the transformation efficiency of p-NP is 98.3%, rate constant is 0.0205s-1��
Embodiment 6:
At 25 DEG C, the tetra chlorauric acid aqueous solution that 1.5g mass percent is 4wt% is added in reactor, add the sodium borohydride aqueous solution that 66mL concentration is 3mol/L, after reaction 2h, add the polyvinylpyrrolidone aqueous solution that 1g concentration is 0.1g/mL and 0.5g concentration is the mixture of carboxymethyl cellulose aqueous solution of 0.1g/mL, continuing reaction 18h, centrifugation, obtains gold sol;
150mL ethanol, 10mL deionized water are added in above-mentioned obtained gold sol, ultrasonic disperse 1h, obtains gold sol ethanol water mixture, regulates this mixture pH to 8.5 with the sodium hydroxide solution of 0.1g/mL, add 3g tetraethyl orthosilicate, at 40 DEG C, stir 0.5h, add 1.3g sodium metaaluminate, at 90 DEG C, react 16h, filter, with 150mL deionized water, 50mL ethanol washing leaching cake respectively, at 60 DEG C, vacuum-drying 8h, obtains catalyst precursor;58mL deionized water and this catalyst precursor are added in water heating kettle, add 0.6g quadrol and 0.6g cetyl trimethylammonium bromide, hydro-thermal reaction 120h at 150 DEG C, filter after being down to room temperature, with 150mL deionized water, 50mL ethanol washing leaching cake respectively, 60 DEG C of vacuum-drying 8h, 550 DEG C of roasting 4h, obtain nano catalyst.
The catalytic performance of nano catalyst: the transformation efficiency of p-NP is 99.1%, rate constant is 0.0237s-1��
Claims (4)
1. the preparation method of a nano catalyst, it is characterized in that this catalyzer will be reduced to a nanometer Au containing auric acid, add silicon source with polymeric binder after being mixed by this nanometer of Au, aluminium source react to obtain catalyst precursor, template is added catalyst precursor and carries out the nano catalyst that hydro-thermal reaction obtains nucleocapsid structure, kernel is a nanometer Au, and shell is sial mesopore molecular sieve; The preparation method of this catalyzer is:
Step is a) under room temperature, the auric acid aqueous solution that contains that mass percent is 2wt��10wt% is added in reactor, by reductive agent with containing auric acid mass ratio be 5:1��20:1, add the reductive agent aqueous solution that concentration is 1��5mol/L, reaction 2��4h, then by polymeric binder with containing auric acid mass ratio be 0.2:1��1.5:1, add the polymeric binder aqueous solution that concentration is 0.01��0.1g/mL, continuing reaction 10��20h, centrifugation, obtains gold sol;
Step b) by the mass ratio 8:1��12:1 of ethanol and deionized water, obtained ethanol water mixture, by the mass ratio 50:1��200:1 of ethanol water mixture and gold sol, ethanol water mixture is added to step a) in obtained gold sol, ultrasonic disperse 0.5��2h, obtain gold sol ethanol water mixture, the inorganic base aqueous solution being 0.05g/mL��0.5g/mL by concentration regulates this mixture pH to 8��12, silicon source is added by the mass ratio 1:1��5:1 of silicon source and gold sol under room temperature, 0.5��2h is stirred at 40��60 DEG C, aluminium source is added by the mass ratio 0.4:1��1:1 in aluminium source and silicon source, 12��24h is reacted at 60��100 DEG C, filter, with the deionized water of 50��100 times of silicon source qualities, the ethanol of 10��30 times of silicon source qualities is washing leaching cake respectively, vacuum-drying 8��10h at 60��100 DEG C, obtain catalyst precursor,
Step c) by deionized water and step b) mass ratio of obtained catalyst precursor is 10:1��50:1, deionized water and this presoma are added in water heating kettle, it is that 0.2:1��1:1 adds template by the mass ratio of template and catalyst precursor, hydro-thermal reaction 72��120h at 120��180 DEG C, filter after being down to room temperature, with the deionized water of 20��60 times of catalyst precursor quality, the ethanol of 10��20 times of catalyst precursor quality is washing leaching cake respectively, 60��100 DEG C of vacuum-drying 8��10h, 450��600 DEG C of roasting 4��8h, obtain nano catalyst.
2. the preparation method of a kind of nano catalyst according to claim 1, it is characterised in that the shell sial mesopore molecular sieve of this catalyzer is one or several mixture of A type, X type, Y type or ZSM-5 type.
3. the preparation method of a kind of nano catalyst according to claim 1, it is characterized in that being the combination of a kind of in tetra chlorauric acid, acetic acid gold or two kinds containing auric acid described in this preparation method's step is a), described reductive agent is the combination of a kind of in sodium borohydride, trisodium citrate or two kinds, and described polymeric binder is one or several combination of polyvinylpyrrolidone, carboxymethyl cellulose or methylcellulose gum.
4. the preparation method of a kind of nano catalyst according to claim 1, it is characterized in that this preparation method step b) described in mineral alkali be sodium hydroxide or potassium hydroxide, described silicon source is a kind of in tetraethyl orthosilicate, hexamethyldisiloxane or both combinations, described aluminium source is one or several the combination in sodium metaaluminate, Tai-Ace S 150 or aluminum nitrate, and described template is one or several the combination in cetyl trimethylammonium bromide, quadrol or 4-propyl bromide.
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| CN110076334B (en) * | 2019-06-05 | 2020-04-07 | 燕山大学 | Gold terbium alloy nanosphere and preparation method and application thereof |
| CN110687063A (en) * | 2019-10-18 | 2020-01-14 | 泉州师范学院 | Preparation method of nano material for detecting and removing 4-nitrophenol |
| CN112892586A (en) * | 2021-01-20 | 2021-06-04 | 济宁学院 | Preparation method of core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and method for preparing N, N-diethylhydroxylamine by using core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst |
| CN114160130B (en) * | 2021-12-21 | 2024-03-19 | 黑龙江省能源环境研究院 | Ordered porous monolithic catalyst of limited-domain nano-gold and preparation method thereof |
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