CN109939718A - A kind of monatomic catalyst and the preparation method and application thereof with high catalytic activity - Google Patents
A kind of monatomic catalyst and the preparation method and application thereof with high catalytic activity Download PDFInfo
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Abstract
The invention discloses a kind of monatomic catalyst and the preparation method and application thereof with high catalytic activity.The preparation method of the catalyst includes the following steps: that (1) prepares the bimetallic containing Zn or more metallized metal organic framework compounds (MOF) by solvent-thermal method；(2) by above-mentioned MOF coated polymer；(3) material after above-mentioned cladding is carried out to high-temperature process in an inert atmosphere to get to the monatomic catalyst of metal on the hollow carbon shell for being scattered in N doping.The monatomic catalyst of the cobalt obtained by above-mentioned preparation method shows excellent activity and selectivity in the hydrogenation reaction of nitrobenzene.
Description
Technical field
The invention belongs to catalyst fields, are related to a kind of monatomic catalyst and preparation method thereof with high catalytic activity
With application.
Background technique
Monatomic catalyst is a research hotspot of heterogeneous catalysis field, refers to that single atom is carried on urging on carrier
Agent, these carriers are usually to have the metal oxide of more defect sites or contain heteroatomic carbon carrier, and carrier lacks
It is very high monatomic for anchoring surface free energy to fall into site.Monatomic catalyst has maximum atom utilization and uniqueness
Electronics, geometry, therefore there is excellent catalytic activity and selectivity, and for the mechanism study meaning of catalytic process
It is great.Pt is reported for the first time from 2011 Nian Zhangtao and its partner1/FeOxSince monatomic catalyst is applied to CO oxidation, Dan Yuan
Muonic catalysis agent has obtained extensive research, and the monatomic method for preparing catalyst developed at present has: wet chemistry method, high temperature atomic
Prize law, atomic layer deposition method, light Jie reduction method and metal organic complexes pyrolysismethod.The monatomic catalyst of various metals
Also it is seen in report, including the monatomic catalyst of noble metal is (such as: Pt/FeOx,Pd/CeO2,Pd/TiO2, Rh/ZnO etc.), He Feigui
The monatomic catalyst of metal (such as: Fe, Co, Ni, Cu etc.), these monatomic catalyst are applied to various heterogeneous catalytic reaction bodies
In system.
Aromatic amine is a kind of very important chemicals in fine chemistry industry, can be by aromatic nitro compound hydrogenation reaction system
?.But it is common expensive when in aromatic nitro compound containing another functional group (such as: halogen, carbonyl) being easily reduced
Metallic catalyst just can not selective reduction nitro, 2014, Zhang Tao reported Pt1/FeOxThe monatomic catalyst property of can choose
Be catalyzed the hydrogenation reaction of aromatic nitro compound, but when reacted between continue to increase, unsaturated group in addition still can be by
Reduction.For this problem, Beller seminar in 2013 has developed cobalt or the catalyst of iron can be catalyzed virtue with high selectivity
The hydrogenation reaction of aromatic nitro compounds, has well solved the above problem, but the activity of the catalyst of these base metal bases compared with
It is low.Based on above-mentioned research work, find a kind of high activity, the monatomic catalyst of highly selective base metal have it is important
Meaning.
Summary of the invention
The object of the present invention is to provide a kind of monatomic catalyst and the preparation method and application thereof with high catalytic activity.
The method that preparation provided by the invention has the monatomic catalyst of hollow shell structure, comprising:
1) metal salt, zinc nitrate and ligand are subjected to solvent thermal reaction, products therefrom is denoted as MxZny- MOF (namely metal has
Machine framework compound)；The MxZnyIn-MOF, the ratio of x and y are 0.2-1；M in Fe, Co, Ni, Cu, Ru, Pt and Pd extremely
Few one kind；
2) by the MxZny- MOF, which is dissolved in solvent, obtains MxZnyThe dispersion liquid of-MOF, then coated polymer, products therefrom
It is denoted as MxZny-MOF@PDA；
3) by the MxZny- MOF@PDA carries out high-temperature process in an inert atmosphere, obtains the list with hollow shell structure
Catalyst atom is denoted as MSAs/NCHS.
In the step 1) of the above method metal salt, the metal in Fe, Co, Ni, Cu, Ru, Pt and Pd at least
It is a kind of；The salt is at least one of nitrate, acetylacetonate, hydrochloride, acetate and sulfate；
The ligand is 2-methylimidazole；
The molar ratio of the metal salt and zinc nitrate is 1:4~1:1；
The molar ratio of the metal salt and ligand is 0.2-10；
The solvent is selected from least one of water, ethyl alcohol and methanol；
In the solvent thermal reaction step, the time be 2~for 24 hours；Temperature is 25~120 DEG C；
The MxZnyThe longest edge of the particle of-MOF is having a size of 50~300nm.
In the step 2), solvent is selected from least one of water, ethyl alcohol and methanol；
In the coated polymer step, the polymer is poly-dopamine；
The step of coated polymer includes: to stir the solution of trishydroxymethylaminomethane and dopamine hydrochloride
Under sequentially add to MxZnyIn the dispersion liquid of-MOF；
Specifically, in the whipping step, stirring rate 500-800r/min；By trishydroxymethylaminomethane and DOPA
Mixing time after amide hydrochloride is added is 4-10h.Dopamine can be in MxZnyThe auto polymerization of the surface-MOF is after a certain period of time
Obtain MxZny-MOF@PDA；
The adding manner is to be added dropwise or be poured slowly into；In the dropwise addition, drop rate is specially 0.5-10 drops/sec or 3
Drop/sec；
The mass ratio of the trishydroxymethylaminomethane and the dopamine hydrochloride is 13:9-13:3；Specially 13:5；
The dopamine hydrochloride and MxZnyThe mass ratio of-MOF is 1:3~3:1；
The concentration of the trihydroxy methyl aminopropane solution is 15-50g/L；
The concentration of the dopamine hydrochloride solution is 30-100g/L；
The MxZnyThe concentration of-MOF dispersion liquid is 0.5-3g/L.
In the step 3) high temperature processing step, atmosphere used is inert atmosphere；Specially nitrogen or argon atmosphere；
Temperature is 300~1100 DEG C；Concretely 500~1000 DEG C；Time is 1-4 hours；Concretely 2 hours；
Heating rate by the temperature of room temperature to high-temperature process is 1-5 DEG C/min；Concretely 2 DEG C/min；
In addition, the monatomic catalyst with hollow shell structure being prepared according to the method described above and this there is hollow shell structure
Monatomic catalyst as catalyst catalysis aromatic nitro compound hydrogenation reaction in application and in heterogeneous catalysis it is anti-
Application in answering, also belongs to protection scope of the present invention.
Specifically, the monatomic uniform anchoring in the monatomic catalyst with hollow shell structure, with nitrogen-atoms coordination
On the hollow carbon shell of N doping；
The load capacity of the monatomic catalyst with hollow shell structure is 0.5~3wt%；Specially 0.5~
1.9wt%.
The aromatic nitro compound is selected from least one of nitrobenzene, 3- iodonitrobenzene and 3- nitrobenzaldehyde；
Solvent for use is selected from least one of ethyl alcohol, tetrahydrofuran, water and methanol；
The amount ratio of the aromatic nitro compound, solvent and catalyst is 0.5mL:30mL:0.05~0.2g；
In the hydrogenation reaction, temperature is 40-110 DEG C；Hydrogen pressure is 3~6MPa；
Time is 10-360 minutes.
The invention has the following advantages that
The gold on the carbon carrier for being scattered in N doping has been made using the method for polymer overmold and high temperature pyrolysis by the present invention
Belong to monatomic catalyst, catalyst made from this method has hollow structure, big specific surface area and meso-hole structure and single original
The active site of son dispersion, these characteristics make it show excellent activity in catalysis reaction；And this method is suitable for more
Kind metal is expected to be applied in more catalysis reactions.
Detailed description of the invention
Fig. 1 is monatomic catalyst preparation schematic diagram.
Fig. 2 is the angle of elevation annular dark of the spherical aberration correction of the monatomic catalyst of Co.
Fig. 3 is that distribution map is swept in the face of the monatomic catalyst of Co.
Fig. 4 is the XANES spectrogram of the monatomic catalyst of Co.
Fig. 5 is the EXAFS spectrogram of the monatomic catalyst of Co.
Fig. 6 is kinetic curve of the monatomic catalyst of Co in nitrobenzene hydrogenation.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The raw material can obtain unless otherwise instructed from public commercial source.
The preparation of the monatomic catalyst of embodiment 1, Co
According to preparation method as shown in Figure 1, the specific steps are as follows:
5.63mmol cabaltous nitrate hexahydrate and 5.63mmol zinc nitrate hexahydrate are weighed in 150mL beaker, 90mL is added
Methanol, stirring is to being completely dissolved.22.5mmol2- methylimidazole is weighed in 250mL conical flask, stirring is to being completely dissolved.Acutely
The methanol solution of metal salt is poured into 2-methylimidazole solution under stirring, stirs 1min, ultrasonic 10min, it is suspended by what is obtained
Liquid is fitted into the water heating kettle of 3 100mL, 120 DEG C of holding 4h of hydro-thermal.After cooled to room temperature, obtained solid is centrifugated
And with ethanol washing 3 times, the dry 12h of room temperature in vacuo obtains the CoZn-MOF that size is about 100nm.
300mg CoZn-MOF ultrasonic disperse is weighed in 265mL methanol, obtains CoZn-MOF dispersion liquid.It weighs
0.3996g trishydroxymethylaminomethane (Tris) is dissolved in 55mL methanol, weighs 0.15g dopamine hydrochloride (DA)) dissolution
In 50mL methanol, the methanol solution of Tris and DA is successively added dropwise in CoZn-MOF dispersion liquid under stirring, it will after stirring 6h
Obtained solid centrifuge separation, room temperature is dried in vacuo 12h after methanol washs 4 times, obtains the CoZn-MOF that size is about 100nm
PDA。
CoZn-MOF@PDA is placed in porcelain boat, is pyrolyzed in tube furnace.In argon atmosphere, with 2 DEG C/min's
Heating rate is warming up to 1000 DEG C of holding 2h, later cooled to room temperature, obtains the monatomic cobalt that load capacity is 1.82wt%
Catalyst CoSAs/NCHS.
The angle of elevation annular dark of the spherical aberration correction of the catalyst is as shown in Fig. 2, the bright spot one by one in figure represents one
Each and every one Co atom, sweeping distribution map 3 from the face of the catalyst can prove that Co, N, C element are equally distributed in the catalyst.
As shown in Figure 4, Figure 5, from X-ray fine structure characterization it can be seen that only existing Co-N key in material of the present invention, there is no Co-Co
Key further demonstrates monoatomic presence.
Monatomic Co catalysts CoSAs/NCHS made from the above method is applied to the hydrogenation reaction of nitrobenzene, it is specific real
Apply step are as follows: it weighs the monatomic Co catalysts CoSAs/NCHS of 5mg and is placed in the polytetrafluoro reaction kettle of 15mL, 6mL ethyl alcohol is added,
The nitrobenzene substrate of 0.5mmol is added after ultrasonic disperse 5min, magneton is added, reaction kettle is closed, it is filled with into reaction kettle
It is discharged after 2MPa hydrogen, after being repeated 4 times, reaction kettle is heated to 110 DEG C, be then charged with 5MPa hydrogen, setting stirring rate is
800r/min, reaction time are 1 hour, and reaction kettle is placed in cold water to 1 hour cooling, taking-up reaction solution progress after reaction
Gas chromatographic analysis, result are that substrate nitro benzene is fully converted to aniline after 1 hour.Fig. 6 is corresponding kinetic curve.It calculates
Above-mentioned monatomic Co catalysts CoSAs/NCHS is 388.3h for the TOF value of nitrobenzene hydrogenation-1, it is higher than existing literature
10 times of the TOF value of report, shows excellent activity and selectivity.
The explanation of above example is only intended to illustrating the present processes and core technology, the invention is not limited to
This.For a person skilled in the art, all any modifications within the application principle, replacement and improvement etc., at this
Within the protection scope of application.
Claims (8)
1. a kind of method for preparing the monatomic catalyst with hollow shell structure, comprising:
1) metal salt, zinc nitrate and ligand are subjected to solvent thermal reaction, products therefrom is denoted as MxZny-MOF；The MxZny-MOF
In, the ratio of x and y are 0.2-1；M is selected from least one of Fe, Co, Ni, Cu, Ru, Pt and Pd；
2) by the MxZny- MOF, which is dissolved in solvent, obtains MxZnyThe dispersion liquid of-MOF, then coated polymer, products therefrom are denoted as
MxZny-MOF@PDA；
3) by the MxZny- MOF@PDA carries out high-temperature process in an inert atmosphere, obtains described monatomic with hollow shell structure
Catalyst is denoted as MSAs/NCHS.
2. according to the method described in claim 1, it is characterized by: the metal is selected from the step 1) metal salt
At least one of Fe, Co, Ni, Cu, Ru, Pt and Pd；The salt is nitrate, acetylacetonate, hydrochloride, acetate and sulfuric acid
At least one of salt；
The ligand is 2-methylimidazole；
The molar ratio of the metal salt and zinc nitrate is 1:4~1:1；
The molar ratio of the metal salt and ligand is 0.2-10；
The solvent is selected from least one of water, ethyl alcohol and methanol；
In the solvent thermal reaction step, the time be 2~for 24 hours；Temperature is 25~120 DEG C；
The MxZnyThe longest edge of the particle of-MOF is having a size of 50~300nm.
3. method according to claim 1 or 2, it is characterised in that: in the step 2), solvent is selected from water, ethyl alcohol and first
At least one of alcohol；
In the coated polymer step, the polymer is poly-dopamine；
The step of coated polymer include: by the solution of trishydroxymethylaminomethane and dopamine hydrochloride under stiring according to
It is secondary to be added to MxZnyIn the dispersion liquid of-MOF；
Specifically, in the whipping step, stirring rate 500-800r/min；By trishydroxymethylaminomethane and DOPA amine salt
Mixing time after acid salt solution is added is 4-10h.
The adding manner is to be added dropwise or be poured slowly into；In the dropwise addition, drop rate be specially 0.5-10 drops/sec or 3 drop/
Second；
The mass ratio of the trishydroxymethylaminomethane and the dopamine hydrochloride is 13:9-13:3；Specially 13:5；
The dopamine hydrochloride and MxZnyThe mass ratio of-MOF is 1:3~3:1；
The concentration of the trihydroxy methyl aminopropane solution is 15-50g/L；
The concentration of the dopamine hydrochloride solution is 30-100g/L；
The MxZnyThe concentration of-MOF dispersion liquid is 0.5-3g/L.
4. method according to claim 1 to 3, it is characterised in that: in the step 3) high temperature processing step, institute
It is inert atmosphere with atmosphere；Specially nitrogen or argon atmosphere；
Temperature is 300~1100 DEG C；Time is 1-4 hours；
Heating rate by the temperature of room temperature to high-temperature process is 1-5 DEG C/min.
5. the monatomic catalyst with hollow shell structure that any the method for claim 1-4 is prepared.
6. the monatomic catalyst according to claim 5 with hollow shell structure, it is characterised in that: described that there is ghost knot
Monatomic being uniformly anchored on the hollow carbon shell of N doping in the monatomic catalyst of structure, with nitrogen-atoms coordination；
The load capacity of the monatomic catalyst with hollow shell structure is 0.5~3wt%；Specially 0.5~1.9wt%.
7. claim 5 or the 6 monatomic catalyst with hollow shell structure are as catalyst in catalysis aromatic nitro compound
The hydrogenation reaction of object or the application in heterogeneous catalytic reaction.
8. application according to claim 7, it is characterised in that: the aromatic nitro compound is selected from nitrobenzene, 3- iodine nitre
At least one of base benzene and 3- nitrobenzaldehyde；
Solvent for use is selected from least one of ethyl alcohol, tetrahydrofuran, water and methanol；
The amount ratio of the aromatic nitro compound, solvent and catalyst is 0.5mL:30mL:0.05~0.2g；
In the hydrogenation reaction, temperature is 40-100 DEG C；Hydrogen pressure is 3~5MPa；
Time is 10-360 minutes.
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| CN113522339A (en) * | 2021-07-20 | 2021-10-22 | 厦门大学 | Preparation method and application of hydrogenation M @ C-N catalyst |
| CN113828319A (en) * | 2021-10-13 | 2021-12-24 | 江苏扬农化工集团有限公司 | Cu-Zn-M composite oxide catalyst and preparation method and application thereof |
| CN113828319B (en) * | 2021-10-13 | 2024-03-26 | 江苏扬农化工集团有限公司 | Cu-Zn-M composite oxide catalyst and preparation method and application thereof |
| CN115044927A (en) * | 2022-06-18 | 2022-09-13 | 福州大学 | Preparation method and application of carbide-supported metal catalyst |
| CN115044927B (en) * | 2022-06-18 | 2024-04-05 | 福州大学 | Preparation method and application of carbide supported metal catalyst |
| CN115990495A (en) * | 2022-11-22 | 2023-04-21 | 深圳大学 | Monoatomic catalyst dispersed in metal oxide cluster, synthesis method and application |
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