CN107570149A - A kind of monatomic method for preparing catalyst using mesoporous TiO 2 as carrier - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010792 warming Methods 0.000 claims abstract description 5
- 229920000428 triblock copolymer Polymers 0.000 claims abstract 2
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 2
- 239000010936 titanium Substances 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 claims 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000000935 solvent evaporation Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000011167 hydrochloric acid Nutrition 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910015189 FeOx Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention provides a kind of monatomic method for preparing catalyst using mesoporous TiO 2 as carrier.PEO PPOX PEO triblock copolymer (P123) is dissolved in ethanol solution, a certain amount of concentrated sulfuric acid and concentrated hydrochloric acid are separately added into after to be dissolved, isopropyl titanate is added after certain time is stirred at room temperature, chlorine palladium acid is added after stirring certain time, Pd@TiO are prepared by solvent evaporation induced self-assembly technology2Presoma.Muffle furnace will be put into after presoma is dried to be warming up to certain temperature in a manner of temperature programming and kept for a period of time at such a temperature；After calcining, H is used at a certain temperature2/N2Gaseous mixture is reduced, and obtains the monatomic catalyst of evengranular palladium.Monatomic catalyst prepared by the present invention, technique is simple, and metallic atom is uniformly dispersed on carrier, reproducible, and applicable acid range is wide, and product is hexagon or spherical nanoparticle, therefore pore size distribution is uniform, and catalytic performance is splendid, can be mass-produced.
Description
Technical field
The invention belongs to monatomic catalyst preparation technical field, and in particular to a kind of using mesoporous TiO 2 as carrier
Monatomic method for preparing catalyst.
Background technology
In chemical process, it is one of main research contents to develop efficient catalyst.Load type metal is catalyzed
Agent due to excellent catalytic performance, as high activity, high selectivity or the two take into account, therefore be widely used in many important
In Industrial Catalysis reaction.Generally, the activated centre of loaded catalyst is only limitted to the part of atoms of its surface exposure, and substantial amounts of
Body phase atom is unable to haptoreaction molecule, therefore size of the active component on carrier and catalytic performance are closely related.
In some catalyst preparation process, in order to avoid the waste of catalyst activity component, by selecting the carrier of high-specific surface area to make
Metal cluster active component is uniformly distributed in carrier surface as far as possible, exists in the form of the nanocluster of high degree of dispersion, fully profit
With catalytic active component, and then improve the metallic atom utilization rate of catalyst.It is in order that each on load type metal catalyst
The catalytic effect of metallic atom reaches optimal, and researcher constantly reduces the particle size of active metal.Newest experiment and theory
Research finds that sub- nanocluster has more preferable catalytic activity or selectivity than nanometer particle.Theoretically, load type gold
The scattered limit of metal catalyst is that metal is evenly distributed on carrier in the form of monoatomic, and this is not only load type metal catalysis
The perfect condition of agent, and catalytic science is brought into a smaller Research scale --- atom level is catalyzed.But
In actual catalyst preparation process, when metallic is reduced to it is monatomic horizontal when, specific surface area increased dramatically, and cause metal
Surface free energy sharply increases, and easily occurs to reunite with coupling in preparation and reaction to form big cluster, so as to cause catalyst
Inactivation, this is to prepare the huge challenge that monatomic catalyst is faced.Zhang Tao seminars of the Dalian Chemistry and Physics Institute urge to high degree of dispersion
On the basis of agent is studied for a long period of time, monatomic catalyst Pt 1/FeOx and Ir1/ is prepared using coprecipitation first
FeOx.Then the Liu Zhigang seminar of Hunan University is calcined, obtained by the way that metalloporphyrin is distributed on silicon dioxide microsphere
The Co catalysts (such as Chinese patent 201310006133.5) of monatomic distribution are arrived.Due at present on monatomic catalyst
Preparation method is extremely limited, and can not still be mass produced, and technique is more harsh and complicated.
The successful preparation of monatomic catalyst is deep into smaller range scale by what catalytic field was studied, not only can be from
The complicated heterogeneous catalytic reaction of atom level understanding, and due to its superior catalytic performance have in Industrial Catalysis it is huge
Application potential.Once monatomic catalyst can be realized finally, huge economic benefit will be produced in Industrial Catalysis field.
The content of the invention
For in the above method the problem of process conditions harshness and the problem of monatomic method for preparing catalyst deficiency, this hair
Bright to provide a kind of monatomic method for preparing catalyst using mesoporous TiO 2 as carrier, this method utilizes solvent volatilization induction
Self-assembling technique is dispersed with carrier by metal precursor, and above-mentioned purpose of the invention is by following technology path and arranged
Apply to realize：
A kind of monatomic method for preparing catalyst using mesoporous TiO 2 as carrier, it is characterised in that methods described bag
Include following steps：
(1) a certain amount of P123 soft templates are dissolved in ethanol, stir 15~60 minutes is completely dissolved it at room temperature,
To ensure that template is uniformly distributed in ethanol；
(2) after P123 is completely dissolved, a certain amount of concentrated sulfuric acid and concentrated hydrochloric acid are added dropwise into solution, and is sufficiently stirred and makes it
It is well mixed；
(3) a certain amount of isopropyl titanate is added dropwise into its above-mentioned solution, and is stirred at room temperature 4~8 hours；
(4) a certain amount of chlorine palladium acid solution is added into above-mentioned solution, first ultrasonic disperse 30 minutes, is then stirred at room temperature
Mix 8 hours；
(5) above-mentioned solution is gone in culture dish, places standing in ventilating kitchen and finished until solvent volatilizees, then put
Enter in drying box and dried 12~24 hours at 100 DEG C；
(6) solid obtained by the 4th step is gone in dry pot, and with 10 DEG C/min liter in the Muffle furnace of temperature programming
Warm speed rises to 350 DEG C from room temperature and kept at such a temperature 1~2 hour, is then heated up again with 10 DEG C/min heating rate
To 450 DEG C and kept for 4~8 hours at such a temperature；
(4) after being cooled to room temperature, put it into tube furnace with 10 DEG C/min heating rate from room temperature rise to 350 DEG C it is logical
H2/N2 gaseous mixtures are reduced, and finally just can obtain the monoatomic catalyst of palladium.
A kind of monatomic method for preparing catalyst using mesoporous TiO 2 as carrier proposed by the present invention, its feature exist
In：Preparation process is relatively easy, and reaction condition is gentle, selective hydrogenation tool of the monoatomic catalyst of prepared palladium to alkene
There is preferable effect.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of the monatomic catalyst of palladium prepared using the method for the invention.
Fig. 2 is the average pore size spectrogram of the measure of the monatomic catalyst of palladium prepared using the method for the invention.
Fig. 3 is transmission electron microscope (TEM) photo of the monatomic catalyst of palladium prepared using the method for the invention.
Fig. 4 is the transmission electron microscope mapping spectrograms of the monatomic catalyst of palladium prepared using the method for the invention.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and detailed description, but present disclosure is not
Only it is limited to the embodiment.
Embodiment 1
Monatomic method for preparing catalyst described in the present embodiment using mesoporous TiO 2 as carrier specifically includes following step
Suddenly：
(1) 1.0g P123 is dissolved in 30g alcohol solvent, stir 30 minutes is completely dissolved it at room temperature；
(2) after P123 is completely dissolved, the 0.55g concentrated sulfuric acids (96%) and 1.5g concentrated hydrochloric acids (32%) are added dropwise into solution,
And being sufficiently stirred makes it well mixed；
(3) 3.6g isopropyl titanates are added dropwise into its above-mentioned solution, and are stirred at room temperature 6 hours；
(4) 2ml chlorine palladium acid solutions (0.01mol/L), first ultrasonic disperse 30 minutes, then in room are added into above-mentioned solution
The lower stirring of temperature 8 hours
(5) above-mentioned solution is gone in culture dish, is placed in ventilating kitchen and stands straight 48 hours until solvent is evaporated completely, so
After put it into drying box and to be dried 12 hours at 100 DEG C；
(6) solid obtained by the 4th step is gone in dry pot, and with 10 DEG C/min liter in the Muffle furnace of temperature programming
Warm speed rises to 350 DEG C from room temperature and kept for 1 hour at such a temperature, is then warming up to again with 10 DEG C/min heating rate
450 DEG C and at such a temperature keep 6 hours；
(7) after being cooled to room temperature, put it into tube furnace and be passed through 5% H2/N2Gaseous mixture, with 10 DEG C/min liter
Warm speed rises to 350 DEG C from room temperature and keeps being reduced for 1 hour at such a temperature, finally just can obtain the monoatomic catalysis of palladium
Agent 0.2wt%Pd@TiO2。
Embodiment 2
Monatomic method for preparing catalyst described in the present embodiment using mesoporous TiO 2 as carrier specifically includes following step
Suddenly：
(1) 1.0g P123 is dissolved in 30g alcohol solvent, stir 30 minutes is completely dissolved it at room temperature；
(2) after P123 is completely dissolved, the 0.55g concentrated sulfuric acids (96%) and 1.5g concentrated hydrochloric acids (32%) are added dropwise into solution,
And being sufficiently stirred makes it well mixed；
(3) isopropyl titanate is added dropwise into its above-mentioned solution, and is stirred at room temperature 3 hours；
(4) 4ml chlorine palladium acid solutions (0.01mol/L), first ultrasonic disperse 30 minutes, then in room are added into above-mentioned solution
The lower stirring of temperature 8 hours；
(5) above-mentioned solution is gone in culture dish, places standing in ventilating kitchen and finished until solvent volatilizees, then put
Enter in drying box and dried 24 hours at 100 DEG C；
(6) solid obtained by the 4th step is gone in dry pot, and with 5 DEG C/min heating in the Muffle furnace of temperature programming
Speed rises to 350 DEG C from room temperature and kept for 1~2 hour at such a temperature, is then warming up to again with 5 DEG C/min heating rate
450 DEG C and at such a temperature keep 6 hours；
(7) after being cooled to room temperature, put it into tube furnace and rise to 350 DEG C simultaneously from room temperature with 5 DEG C/min heating rate
1~2 hour logical H is kept at such a temperature2/N2Gaseous mixture is reduced, and finally just can obtain the monoatomic catalyst of palladium
0.5wt%Pd@TiO2。
Embodiment 3
Monatomic method for preparing catalyst described in the present embodiment using mesoporous TiO 2 as carrier specifically includes following step
Suddenly：
(1) 2.0g P123 is dissolved in 50g alcohol solvent, stir 30 minutes is completely dissolved it at room temperature；
(2) after P123 is completely dissolved, the 1.0g concentrated sulfuric acids (96%) and 2.0g concentrated nitric acids (67%) are added dropwise into solution, and
Being sufficiently stirred makes it well mixed；
(3) 3.6g isopropyl titanates are added dropwise into its above-mentioned solution, and are stirred at room temperature 6 hours；
(4) 15ml chlorine palladium acid solutions (0.01mol/L), first ultrasonic disperse 30 minutes, Ran Hou are added into above-mentioned solution
Stir 8 hours at room temperature；
(5) above-mentioned solution is gone in culture dish, is placed in ventilating kitchen and stands straight 72 hours until solvent is evaporated completely, so
After put it into drying box and to be dried 12 hours at 100 DEG C；
(6) solid obtained by the 4th step is gone in dry pot, and with 2 DEG C/min heating in the Muffle furnace of temperature programming
Speed rises to 350 DEG C from room temperature and kept for 1 hour at such a temperature, is then warming up to 450 DEG C again with 2 DEG C/min heating rate
And kept for 6 hours at such a temperature；
(7) after being cooled to room temperature, put it into tube furnace and be passed through 5% H2/N2Gaseous mixture, with 2 DEG C/min heating
Speed rises to 350 DEG C from room temperature and keeps being reduced for 1 hour at such a temperature, finally just can obtain the monoatomic catalyst of palladium
1.5wt%Pd@TiO2。
Claims (10)
1. a kind of monatomic method for preparing catalyst using mesoporous TiO 2 as carrier, it is characterised in that methods described includes
Following steps：
(1) a certain amount of P123 soft templates are dissolved in ethanol, stir 15~60 minutes is completely dissolved it at room temperature, to protect
Card template is uniformly distributed in ethanol；
(2) after P123 is completely dissolved, a certain amount of concentrated sulfuric acid and concentrated hydrochloric acid are added dropwise into solution, and is sufficiently stirred and makes its mixing
Uniformly；
(3) a certain amount of isopropyl titanate is added dropwise into its above-mentioned solution, and is stirred at room temperature 4~8 hours；
(4) a certain amount of chlorine palladium acid solution is added into above-mentioned solution, first ultrasonic disperse 30 minutes, is then stirred at room temperature 8
Hour；
(5) above-mentioned solution is gone in culture dish, places standing in ventilating kitchen and finished until solvent volatilizees, then put it into dry
Dried 12~24 hours at 100 DEG C in dry case；
(6) solid obtained by the 4th step is gone in dry pot, and with 10 DEG C/min heating speed in the Muffle furnace of temperature programming
Rate rises to 350 DEG C from room temperature and kept for 1~2 hour at such a temperature, is then warming up to 450 again with 10 DEG C/min heating rate
DEG C and at such a temperature keep 4~8 hours；
(7) after being cooled to room temperature, put it into tube furnace and 350 DEG C of logical H2/ are risen to from room temperature with 10 DEG C/min heating rate
N2 gaseous mixtures are reduced, and finally just can obtain the monoatomic catalyst of palladium.
2. the preparation method of monatomic catalyst according to claim 1, it is characterised in that：It is soft in the step (1)
Template is PEO-PPOX-PEO triblock copolymer, and its molecular formula is：PEOx-PPO y-
One or more in PEOz, P123, F127, F108, the dosage of template is 0.5~4.0g.
3. the preparation method of monatomic catalyst according to claim 1, it is characterised in that：It is molten in the step (1)
Agent is the one or more in water, alcohols, acetone, acetonitrile, and the dosage of solvent is 10~50 times of template dosage.
4. the preparation method of monatomic catalyst according to claim 1, it is characterised in that：Acid in the step (2)
For the one or more in the concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, concentrated phosphoric acid, sour dosage is 1~5 times of template dosage.
5. the preparation method of monatomic catalyst according to claim 1, it is characterised in that：Titanium in the step (3)
Presoma is the n-propyl of metatitanic acid four, isopropyl titanate, the one or more in butyl titanate, the dosages of titanium precursors for 2~
6g。
6. the preparation method of monatomic catalyst according to claim 1, it is characterised in that：It is expensive in the step (4)
Metal precursor is chlorine palladium acid, chloroplatinic acid, gold chloride, ruthenic chloride, the one or more in chloro-iridic acid, its concentration for 0.001~
0.5mol/L, the time of ultrasonic disperse is 1~60 minute, and the time being stirred at room temperature is 4~12 hours.
7. the preparation method of monatomic catalyst according to claim 1, it is characterised in that：Solvent in the step (5)
Rate of volatilization control volatilized and finish in 1~3 day, temperature control is at 20~50 DEG C.
8. the preparation method of monatomic catalyst according to claim 1, it is characterised in that：Muffle in the step (6)
Air or oxygen is passed through in stove, programmed rate is controlled in the range of 1~20 DEG C/min, and the temperature of first stage is room temperature,
The temperature of second stage is 250~350 DEG C, and second stage retention time is 0.5~2 hour, the temperature of phase III for 400~
800 DEG C, the time of phase III is kept for 4~10 hours.
9. the preparation method of monatomic catalyst according to claim 1, it is characterised in that：Tubular type in the step (6)
Programmed rate in stove is controlled in the range of 1~20 DEG C/min, and at 250~400 DEG C, the time keeps for final temperature control
0.5~2 hour, the concentration of H2/N2 gaseous mixtures was 2~60%, and the recovery time is 0.5~3 hour.
10. monatomic catalyst made from the preparation method according to claim any one of 1-9.Described monatomic catalysis
Agent, it is characterised in that：The catalyst particles grain slice, graininess or six prisms, the mesoporous average diameter formed 5~
15nm。
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| CN109289842A (en) * | 2018-11-09 | 2019-02-01 | 安徽工程大学 | A kind of Pd1+NPs/TiO2Monatomic collaboration hydrogenation catalyst of nanoparticle and its preparation method and application |
| CN111195532B (en) * | 2018-11-20 | 2021-05-25 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse iridium-based catalyst, preparation method thereof and application of atomic-level monodisperse iridium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation |
| CN111195532A (en) * | 2018-11-20 | 2020-05-26 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse iridium-based catalyst, preparation method thereof and application of atomic-level monodisperse iridium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation |
| CN109433192A (en) * | 2018-12-07 | 2019-03-08 | 东北大学 | A kind of noble metal single atomic dispersion type cleaning catalyst and preparation method thereof |
| CN109433192B (en) * | 2018-12-07 | 2021-06-01 | 东北大学 | Noble metal monoatomic dispersion type purification catalyst and preparation method thereof |
| CN109908899A (en) * | 2019-03-14 | 2019-06-21 | 浙江师范大学 | A kind of TiO2Load the preparation method and applications of monatomic Co catalyst |
| CN115212875A (en) * | 2022-07-10 | 2022-10-21 | 华东理工大学 | Preparation method of efficient photocatalytic methane dry reforming monoatomic ruthenium-doped porous titanium-silicon material |
| CN115212875B (en) * | 2022-07-10 | 2023-09-01 | 华东理工大学 | Preparation method of high-efficiency photocatalytic methane dry reforming monoatomic ruthenium doped-porous titanium silicon material |
| CN115652260A (en) * | 2022-11-11 | 2023-01-31 | 湖南大学 | Preparation method of monatomic germanium and few-atom cluster |
| CN115652260B (en) * | 2022-11-11 | 2023-05-16 | 湖南大学 | Preparation method of single-atom germanium and few-atom clusters |
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