CN109012732A - A method of preparing the monatomic catalyst of class - Google Patents
A method of preparing the monatomic catalyst of class Download PDFInfo
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- CN109012732A CN109012732A CN201810972677.XA CN201810972677A CN109012732A CN 109012732 A CN109012732 A CN 109012732A CN 201810972677 A CN201810972677 A CN 201810972677A CN 109012732 A CN109012732 A CN 109012732A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
Abstract
The invention discloses a kind of methods for preparing the monatomic catalyst of class, include the following steps: the first step, the preparation of transition metal precursor: weighing organic amine and substituted benzaldehyde is separately added into acetonitrile solution, obtain intermediate product;Finally organic ligand molecule product is obtained through reduction, extraction, drying steps again;Organic ligand molecule and transition metal salt are dissolved in acetonitrile solution respectively, continues to mix stirring until completely dissolved, obtain transition metal precursor product after filtration, washing and drying;Mechanical ball mill: second step is dispersed in transition metal precursor in the carbon black of high-specific surface area using the method for high-energy mechanical ball milling, obtains monatomic catalyst precursor;Third step, high-temperature roasting can obtain monatomic catalyst accordingly.The present invention realizes the preparation of the monatomic catalyst material of transition metal-type, has good expansion and reproducibility, solves in the prior art the problems such as tenor is low, type is few, preparation method is complicated.
Description
Technical field
The present invention relates to belonging to Materials Science and Engineering technical field, specifically, being related to a kind of preparing that class is monatomic to urge
Change the method for material.
Background technique
Monatomic catalyst refers to that metal active constituent is evenly dispersed in carrier surface in the form of monoatomic and is formed
The catalyst with excellent properties.Because to possess catalytic activity high and be easily isolated for it, selectivity is good, with uniform isolated gold
The advantages that category active site, metal active constituent utilization rate is high.It is put forward for the first time from the Dalian Chemistry and Physics Institute great waves academician in 2011 " single former
Since the concept of muonic catalysis agent ", greatly developed, becomes the research hotspot of field of heterogeneous catalysis.Common is single former
Muonic catalysis agent preparation method has coprecipitation, infusion process, atomic layer deposition method etc..Since in recent years, with former to support type list
Deepening continuously for muonic catalysis agent research, rises the correlative study of " class monoatomic metal catalyst " gradually.With monatomic catalysis
Agent is different, and this " class is monatomic " catalyst can provide and instead since there is a synergy between for its adjacent metal atom
The more matched active site distribution of object molecular dimension is answered, thus the energy barrier of certain reactions can be effectively reduced, forms new reaction road
Diameter has the advantages that monatomic catalyst cannot compare.
Tsinghua University Li Yadong academician is by by Ru3(CO)12Molecule is as presoma and is dispersed in ZIF zeolite molecules
Sieve cage in, after through pyrolysis form the uniform Ru stable by N ligand3Cluster, produce has unique knot at lower cost
The Ru of structure and excellent catalytic performance3/ CN catalyst.The results showed that Ru3/CN (4320 h-1) TOF ratio Ru1/
The monatomic catalyst of the CN (h of TOF=416-1) about 10 times high.But the growth of ZIF is amplified easily to condition responsive, and with system
Cause presoma dispersion uneven since mass transfer is limited.
The Lu Junling of China Science & Technology University carries out bottom layer treatment to graphene using atomic layer deposition method and generates suitably
Nucleation site, and deposit with this that first Pt is monatomic, and the Pt atom come on second batch can be deposited selectively
In these Pt1 On site, Pt that is uniform and isolating each other is formed2Diatomic structure.Due to there is electricity between two Pt atoms
Son synergistic effect, so that being in the Pt atom pair ammonia borine and H on top2Absorption ratio Pt1It is monatomic weaker, specific table
It is now Pt2Catalyst B atom when being catalyzed ammonia borane hydrolysis dehydrogenation reaction is remaining less on Pt atom, to catalyst
Poisoning effect it is small, therefore by Pt2The reaction rate of diatomic catalyst is Pt1Under monatomic catalyst
17 times.But the preparation method condition is harsh, more demanding to instrument and equipment and expensive, and synthesis cost is high.
Summary of the invention
Too small based on single metal atomic volume in monatomic catalyst, isolated monatomic site lacks electronics or space
The deficiencies of acting synergistically, limiting the promotion of rate instead in certain reactions, prepares the purpose of the present invention is to provide a kind of
The method of the monatomic catalyst of class is mismatched with solving monatomic catalyst and reaction substrate size, cannot form good connect
The problems such as touching.
To achieve the goals above, the present invention adopts the following technical scheme:
A method of the monatomic catalyst of class is prepared, is included the following steps:
The first step, the preparation of transition metal precursor:
The preparation of organic cryptand molecule (molecule cage): it weighs organic amine and substituted benzaldehyde is separately added into and fills acetonitrile solution
Round-bottomed flask in, stirring mixed to after being completely dissolved, continue to stir, filtration washing obtains intermediate product;Finally restored again,
Extraction, drying and other steps obtain organic cryptand molecular product;
The preparation of transition metal precursor: weighing a certain amount of organic cryptand molecule and transition metal salt is dissolved in acetonitrile respectively
Solution, continuess to mix stirring until completely dissolved, obtains transition metal precursor product after filtration, washing and drying;
Second step, mechanical ball mill:
Transition metal precursor is dispersed in the carbon black of high-specific surface area using the method for high-energy mechanical ball milling, is obtained monatomic
Catalyst precursor, levels of transition metals is in a ten thousandth to 5/1000ths;
Third step, high-temperature roasting:
Monatomic catalyst precursor obtained by second step is subjected to high-temperature roasting under an inert gas, can be obtained after being cooled to room temperature
The monatomic catalyst of corresponding class.The monatomic catalyst of the class that the present invention obtains is that the transition metal-type of N doping C load is monatomic
Material M2/N-C。
Preferably, in above-mentioned preparation method, the transition metal is Co, Ni, Cu, Fe, Pd, Pt, Ru,
One or more of Ir, Os, Rh mixing.
Preferably, the mechanical ball mill uses planetary ball mill, rotational speed of ball-mill in above-mentioned preparation method
For 100-586 r/min, Ball-milling Time 1-48h, milled sample amount is 0.5g-10g.
Preferably, the high-temperature roasting Conditions Temperature is 600-1000 DEG C, described lazy in above-mentioned preparation method
Property gas be one of nitrogen, argon gas or helium, the calcining time is 1-4 hours.
Preferably, the mechanical ball mill of second step: weighing transition metal precursor and charcoal in above-mentioned preparation method
It is black, it is added into 50 mL ball grinders, addition size ball milling pearl is several together, using planetary ball mill QM3SP2L, ball milling
Time 1-48h, revolving speed are 100-586 r/min, need repeatedly to scrape the carbon black for being stained with wall with plastic spoon in mechanical milling process.Ball milling
After bottle, 80 DEG C of vacuum be dried overnight it is spare.
Preferably, ball grinder used by the planetary ball mill is agate pot in above-mentioned preparation method,
Ball milling tank volume is 50-250 mL, and ball milling pearl is agate bead, and globule radius includes tri- kinds of mm of 3mm, 6 mm, 10;When ball milling
Between be 1-48h, ball milling frequency be 0.1-45.0HZ, ball milling condition be one of single-phase operation or way traffic, two-way fortune
Row alt time is 90min, and way traffic waiting time of machine halt is set as 0.
Preferably, the organic amine is three (2- aminoethyl) amine or 1,3,5- equal benzene in above-mentioned preparation method
One of trimethylamine.
Preferably, the substituted benzaldehyde is terephthalaldehyde or m-terephthal aldehyde in above-mentioned preparation method
One of.
Preparation method of the invention is made using the confinement of the cavity structure and transition metal ions of organic cryptand molecule
With enabling single or multiple transition metal ions on controllable space, be effectively anchored on organic cryptand molecule
In cavity structure, the controllable precise of transition metal atoms spacing is realized.Using in mechanical milling process, transition metal precursor and charcoal
It is black to be uniformly dispersed and be coordinated, realize that the monoatomic formation of transition metal-type and stabilization create good condition;This preparation side
Method makes full use of cheap and easily-available raw material, first synthesizes transition metal precursor, by simple ball milling: goal of regulation and control transition metal with
The ratio for diluting carbon black carries out ball milling, then high-temperature roasting, realizes the adjusting of content, type, stability.This transition metal-type
The controllable method for preparing of monatomic catalyst, reduces reaction cost and requirement of experiment, can open up to a variety of transition metal
Exhibition meets experiment diversification and requires, enriches the research of related fields.
Compared with prior art, the invention has the following beneficial effects: the present invention to utilize the sky of organic cryptand molecule
Transition metal precursor is prepared in the confinement effect of cavity configuration and transition metal ions.Made later using the method for mechanical ball mill
Transition metal precursor is dispersed in dilution carbon black, is adjusted by regulation transition metal precursor and the weight ratio of dilution carbon black
Control tenor;Regulate and control the monatomic type of metal class by regulating and controlling the type of different transition metal;By regulating and controlling roasting condition
It realizes from transition metal precursor and black stock to the transformation of the N doping C monatomic catalyst of class loaded.With following excellent
Point:
1. the cavity knot that the present invention on controllable space, can effectively be anchored on organic ligand molecule during the preparation process
In structure, the controllable precise of transition metal atoms spacing is realized.
2. the present invention is at low cost during the preparation process, preparation method is simple, is not necessarily to the precise instrument, is applicable to work
Industry metaplasia produces.
3. the ratio of accurate transition metal precursor of the present invention and dilution carbon black realizes the controllable of levels of transition metals
Standby (0.5 wt% of 0.01-);
Disperse metallic atom 4. the present invention makes full use of ball milling and transition metal precursor to dilute, it is widely applicable.
Detailed description of the invention:
Fig. 1 is organic cryptand molecule (molecule cage) schematic diagram;
Fig. 2 is transition metal precursor schematic diagram;
Fig. 3 is the Cu of preparation2The monatomic catalyst spherical aberration correction transmission electron microscope AC-HAADF-STEM figure of/N-C class;Annulus marks
Class monoatomic metal.
Specific embodiment
The present invention will be further explained with reference to the examples below, but protection scope of the present invention is not limited to implement
The range that example indicates.
Embodiment 1
The preparation of organic cryptand molecule: weighing appropriate three (2- aminoethyl) amine and m-terephthal aldehyde is separately added into and fills acetonitrile
In the round-bottomed flask of solution, stirring is mixed to after being completely dissolved, and continues to stir certain time, filtration washing obtains intermediate product.
Finally organic cryptand molecular product (such as Fig. 1) is obtained through reduction, extraction, drying and other steps again.
The preparation of transition metal precursor (such as Fig. 2): appropriate organic cryptand molecule and Cupric diperchlorate hexahydrate are weighed
It is dissolved in acetonitrile solution respectively, certain time is mixed until completely dissolved, obtains copper presoma after filtration, washing and drying
Product.
The mixture for weighing 0.02g copper presoma and 1 g carbon black is added in 50mL agate jar, and agate is placed in tank
Ball is several, and agate jar is put into planetary ball mill QM3SP2L, for 24 hours with the revolving speed ball milling of 400 r/min, uses halfway
The drug that wall is glued in ball grinder is scraped manual mixing by key, after be placed again into ball mill ball milling, ball milling condition is every 90min
Positive and negative rotation, full suspension waiting time are 0, and the good drug of ball milling is collected bottling, after take in right amount in tube furnace, in nitrogen item
With 600 DEG C of roasting 2h under part, the monatomic catalysis material of class is obtained.Spherical aberration correction transmission electron microscope is as shown in Figure 3.
Embodiment 2
The preparation of organic cryptand molecule: weighing appropriate three (2- aminoethyl) amine and m-terephthal aldehyde is separately added into and fills acetonitrile
In the round-bottomed flask of solution, stirring is mixed to after being completely dissolved, and continues to stir certain time, filtration washing obtains intermediate product.
Finally organic ligand molecule product is obtained through reduction, extraction, drying and other steps again.
The preparation of transition metal precursor: weighing appropriate organic ligand molecule and Cupric diperchlorate hexahydrate is dissolved in acetonitrile respectively
Solution, is mixed certain time until completely dissolved, obtains copper precursor product after filtration, washing and drying.
The mixture for weighing 0.06g copper presoma and 3 g carbon blacks is added in 100mL agate jar, and Ma is placed in tank
Nao ball is several, and agate jar is put into planetary ball mill QM3SP2L, for 24 hours with the revolving speed ball milling of 400 r/min, midway
The drug that wall is glued in ball grinder is scraped into manual mixing with key, after be placed again into ball mill ball milling, ball milling condition be every
90min positive and negative rotation, full suspension waiting time are 0, and the good drug of ball milling is collected bottling, after take in right amount in tube furnace,
With 600 DEG C of roasting 2h under condition of nitrogen gas, the monatomic catalysis material of class is obtained.
Embodiment 3
The preparation of organic cryptand molecule: weighing appropriate three (2- aminoethyl) amine and m-terephthal aldehyde is separately added into and fills acetonitrile
In the round-bottomed flask of solution, stirring is mixed to after being completely dissolved, and continues to stir certain time, filtration washing obtains intermediate product.
Finally organic ligand molecule product is obtained through reduction, extraction, drying and other steps again.
The preparation of transition metal precursor: weighing appropriate organic ligand molecule and Cupric diperchlorate hexahydrate is dissolved in acetonitrile respectively
Solution, is mixed certain time until completely dissolved, obtains copper precursor product after filtration, washing and drying.
The mixture for weighing 0.2g copper presoma and 10 g carbon blacks is added in 250mL agate jar, and Ma is placed in tank
Nao ball is several, and agate jar is put into planetary ball mill QM3SP2L, for 24 hours with the revolving speed ball milling of 400 r/min, midway
The drug that wall is glued in ball grinder is scraped into manual mixing with key, after be placed again into ball mill ball milling, ball milling condition be every
90min positive and negative rotation, full suspension waiting time are 0, and the good drug of ball milling is collected bottling, after take in right amount in tube furnace,
With 600 DEG C of roasting 2h under condition of nitrogen gas, the monatomic catalysis material of class is obtained.
Embodiment 4
The preparation of organic cryptand molecule: weighing appropriate three (2- aminoethyl) amine and m-terephthal aldehyde is separately added into and fills acetonitrile
In the round-bottomed flask of solution, stirring is mixed to after being completely dissolved, and continues to stir certain time, filtration washing obtains intermediate product.
Finally organic ligand molecule product is obtained through reduction, extraction, drying and other steps again.
The preparation of transition metal precursor: weighing appropriate organic ligand molecule and six perchloric acid hydrate cobalts are dissolved in acetonitrile respectively
Solution, is mixed certain time until completely dissolved, obtains cobalt precursor product after filtration, washing and drying.
The mixture for weighing 0.02g cobalt precursor and 1 g carbon black is added in 50mL agate jar, and agate is placed in tank
Ball is several, and agate jar is put into planetary ball mill QM3SP2L, for 24 hours with the revolving speed ball milling of 400 r/min, uses halfway
The drug that wall is glued in ball grinder is scraped manual mixing by key, after be placed again into ball mill ball milling, ball milling condition is every 90min
Positive and negative rotation, full suspension waiting time are 0, and the good drug of ball milling is collected bottling, after take in right amount in tube furnace, in nitrogen item
With 600 DEG C of roasting 2h under part, the monatomic catalysis material of class is obtained.
Embodiment 5
The preparation of organic cryptand molecule: weighing appropriate three (2- aminoethyl) amine and m-terephthal aldehyde is separately added into and fills acetonitrile
In the round-bottomed flask of solution, stirring is mixed to after being completely dissolved, and continues to stir certain time, filtration washing obtains intermediate product.
Finally organic ligand molecule product is obtained through reduction, extraction, drying and other steps again.
The preparation of transition metal precursor: weighing appropriate organic ligand molecule and six perchloric acid hydrate cobalts are dissolved in acetonitrile respectively
Solution, is mixed certain time until completely dissolved, obtains cobalt precursor product after filtration, washing and drying.
The mixture for weighing 0.06g cobalt precursor and 3 g carbon blacks is added in 100mL agate jar, and Ma is placed in tank
Nao ball is several, and agate jar is put into planetary ball mill QM3SP2L, for 24 hours with the revolving speed ball milling of 400 r/min, midway
The drug that wall is glued in ball grinder is scraped into manual mixing with key, after be placed again into ball mill ball milling, ball milling condition be every
90min positive and negative rotation, full suspension waiting time are 0, and the good drug of ball milling is collected bottling, after take in right amount in tube furnace,
With 600 DEG C of roasting 2h under condition of nitrogen gas, the monatomic catalysis material of class is obtained.
Embodiment 6
The preparation of organic cryptand molecule: weighing appropriate three (2- aminoethyl) amine and m-terephthal aldehyde is separately added into and fills acetonitrile
In the round-bottomed flask of solution, stirring is mixed to after being completely dissolved, and continues to stir certain time, filtration washing obtains intermediate product.
Finally organic ligand molecule product is obtained through reduction, extraction, drying and other steps again.
The preparation of transition metal precursor: weighing appropriate organic ligand molecule and six perchloric acid hydrate cobalts are dissolved in acetonitrile respectively
Solution, is mixed certain time until completely dissolved, obtains cobalt precursor product after filtration, washing and drying.
The mixture for weighing 0.2g cobalt precursor and 10 g carbon blacks is added in 250mL agate jar, and Ma is placed in tank
Nao ball is several, and agate jar is put into planetary ball mill QM3SP2L, for 24 hours with the revolving speed ball milling of 400 r/min, midway
The drug that wall is glued in ball grinder is scraped into manual mixing with key, after be placed again into ball mill ball milling, ball milling condition be every
90min positive and negative rotation, full suspension waiting time are 0, and the good drug of ball milling is collected bottling, after take in right amount in tube furnace,
With 600 DEG C of roasting 2h under condition of nitrogen gas, the monatomic catalysis material of class is obtained.
Embodiment 7
The preparation of organic cryptand molecule: weighing appropriate three (2- aminoethyl) amine and m-terephthal aldehyde is separately added into and fills acetonitrile
In the round-bottomed flask of solution, stirring is mixed to after being completely dissolved, and continues to stir certain time, filtration washing obtains intermediate product.
Finally organic ligand molecule product is obtained through reduction, extraction, drying and other steps again.
The preparation of transition metal precursor: weighing appropriate organic ligand molecule and six perchloric acid hydrate nickel are dissolved in acetonitrile respectively
Solution, is mixed certain time until completely dissolved, obtains nickel precursor product after filtration, washing and drying.
The mixture for weighing 0.02g nickel presoma and 1 g carbon black is added in 50mL agate jar, and agate is placed in tank
Ball is several, and agate jar is put into planetary ball mill QM3SP2L, for 24 hours with the revolving speed ball milling of 400 r/min, uses halfway
The drug that wall is glued in ball grinder is scraped manual mixing by key, after be placed again into ball mill ball milling, ball milling condition is every 90min
Positive and negative rotation, full suspension waiting time are 0, and the good drug of ball milling is collected bottling, after take in right amount in tube furnace, in nitrogen item
With 600 DEG C of roasting 2h under part, the monatomic catalysis material of class is obtained.
Embodiment 8
The preparation of organic cryptand molecule: weighing appropriate three (2- aminoethyl) amine and m-terephthal aldehyde is separately added into and fills acetonitrile
In the round-bottomed flask of solution, stirring is mixed to after being completely dissolved, and continues to stir certain time, filtration washing obtains intermediate product.
Finally organic ligand molecule product is obtained through reduction, extraction, drying and other steps again.
The preparation of transition metal precursor: weighing appropriate organic ligand molecule and six perchloric acid hydrate nickel are dissolved in acetonitrile respectively
Solution, is mixed certain time until completely dissolved, obtains nickel precursor product after filtration, washing and drying.
The mixture for weighing 0.06g nickel presoma and 3 g carbon blacks is added in 100mL agate jar, and Ma is placed in tank
Nao ball is several, and agate jar is put into planetary ball mill QM3SP2L, for 24 hours with the revolving speed ball milling of 400 r/min, midway
The drug that wall is glued in ball grinder is scraped into manual mixing with key, after be placed again into ball mill ball milling, ball milling condition be every
90min positive and negative rotation, full suspension waiting time are 0, and the good drug of ball milling is collected bottling, after take in right amount in tube furnace,
With 600 DEG C of roasting 2h under condition of nitrogen gas, the monatomic catalysis material of class is obtained.
Embodiment 8
The preparation of organic cryptand molecule: weighing appropriate three (2- aminoethyl) amine and m-terephthal aldehyde is separately added into and fills acetonitrile
In the round-bottomed flask of solution, stirring is mixed to after being completely dissolved, and continues to stir certain time, filtration washing obtains intermediate product.
Finally organic ligand molecule product is obtained through reduction, extraction, drying and other steps again.
The preparation of transition metal precursor: weighing appropriate organic ligand molecule and six perchloric acid hydrate nickel are dissolved in acetonitrile respectively
Solution, is mixed certain time until completely dissolved, obtains nickel precursor product after filtration, washing and drying.
The mixture for weighing 0.2g nickel presoma and 10g carbon black is added in 250mL agate jar, and agate is placed in tank
Ball is several, and agate jar is put into planetary ball mill QM3SP2L, for 24 hours with the revolving speed ball milling of 400 r/min, uses halfway
The drug that wall is glued in ball grinder is scraped manual mixing by key, after be placed again into ball mill ball milling, ball milling condition is every 90min
Positive and negative rotation, full suspension waiting time are 0, and the good drug of ball milling is collected bottling, after take in right amount in tube furnace, in nitrogen item
With 600 DEG C of roasting 2h under part, the monatomic catalysis material of class is obtained.
Claims (8)
1. a kind of method for preparing the monatomic catalyst of class, it is characterised in that include the following steps:
The first step, the preparation of transition metal precursor:
The preparation of organic cryptand molecule: weighing organic amine and substituted benzaldehyde is separately added into the round bottom burning for filling acetonitrile solution
In bottle, stirring is mixed to after being completely dissolved, and continues to stir, filtration washing obtains intermediate product;Finally again through reduction, extraction, do
Dry step obtains organic cryptand molecular product;
The preparation of transition metal precursor: weighing organic cryptand molecule and transition metal salt is dissolved in acetonitrile solution respectively, to
Continue to be mixed after being completely dissolved, obtains transition metal precursor product after filtration, washing and drying;
Second step, mechanical ball mill:
Transition metal precursor is dispersed in the carbon black of high-specific surface area using the method for high-energy mechanical ball milling, is obtained monatomic
Catalyst precursor, levels of transition metals is in a ten thousandth to 5/1000ths;
Third step, high-temperature roasting:
Monatomic catalyst precursor obtained by second step is subjected to high-temperature roasting under an inert gas, can be obtained after being cooled to room temperature
Corresponding monatomic catalyst.
2. preparation method according to claim 1, it is characterised in that the transition metal be Co, Ni, Cu, Fe, Pd,
One or more of Pt, Ru, Ir, Os, Rh mixing.
3. preparation method according to claim 1, it is characterised in that the mechanical ball mill uses planetary ball mill, ball
Mill revolving speed is 100-586 r/min, and Ball-milling Time 1-48h, milled sample amount is 0.5g-10g.
4. preparation method according to claim 1, it is characterised in that the high-temperature roasting condition is temperature 600-1000
DEG C, the inert gas is one of nitrogen, argon gas or helium, and the calcining time is 1-4 hours.
5. preparation method according to claim 1, which is characterized in that the mechanical ball mill of second step: before weighing transition metal
Body and carbon black are driven, is added into 50 mL ball grinders, addition size ball milling pearl is several together, using planetary ball mill
QM3SP2L, Ball-milling Time 1-48h, revolving speed are 100-586 r/min, need repeatedly to mould the carbon black for being stained with wall in mechanical milling process
Scoop scrapes;Bottle after ball milling, 80 DEG C of vacuum be dried overnight it is spare.
6. preparation method according to claim 1, which is characterized in that the organic amine be three (2- aminoethyl) amine or 1,3,
One of equal benzene trimethylamine of 5-.
7. preparation method according to claim 1, which is characterized in that the substituted benzaldehyde is terephthalaldehyde or isophthalic
One of dicarbaldehyde.
8. preparation method according to claim 3, it is characterised in that ball grinder used by the planetary ball mill is
Agate pot, ball milling tank volume are 50-250 mL, and ball milling pearl is agate bead, and globule radius includes tri- kinds of mm of 3mm, 6 mm, 10;
Ball-milling Time is 1-48h, and ball milling frequency is 0.1-45.0HZ, and ball milling condition is one of single-phase operation or way traffic,
Way traffic alt time is 90min, and way traffic waiting time of machine halt is set as 0.
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CN110586102A (en) * | 2019-08-21 | 2019-12-20 | 中山大学 | Preparation method of heteroatom-like catalyst |
CN110773156A (en) * | 2019-11-20 | 2020-02-11 | 苏州阿德旺斯新材料有限公司 | Transition metal monatomic catalyst, preparation method and application thereof |
CN112675849A (en) * | 2020-12-22 | 2021-04-20 | 安徽稞馨环境科技有限公司 | Preparation method and application of monatomic catalyst for removing carbon monoxide at room temperature by catalytic oxidation method |
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CN109603831B (en) * | 2018-12-26 | 2021-11-23 | 大连大学 | Cobalt and graphene composite nano material catalyst and preparation method thereof |
CN110586102A (en) * | 2019-08-21 | 2019-12-20 | 中山大学 | Preparation method of heteroatom-like catalyst |
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CN110773156A (en) * | 2019-11-20 | 2020-02-11 | 苏州阿德旺斯新材料有限公司 | Transition metal monatomic catalyst, preparation method and application thereof |
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CN110773156B (en) * | 2019-11-20 | 2021-07-06 | 苏州阿德旺斯新材料有限公司 | Transition metal monatomic catalyst, preparation method and application thereof |
CN112675849A (en) * | 2020-12-22 | 2021-04-20 | 安徽稞馨环境科技有限公司 | Preparation method and application of monatomic catalyst for removing carbon monoxide at room temperature by catalytic oxidation method |
CN113413903A (en) * | 2021-07-14 | 2021-09-21 | 中国科学院长春应用化学研究所 | Preparation method and application of carbon-based transition metal monoatomic material |
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