CN112871154A - MOF-derived Pt1@CeO2Monoatomic catalyst, preparation method and application thereof - Google Patents
MOF-derived Pt1@CeO2Monoatomic catalyst, preparation method and application thereof Download PDFInfo
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- CN112871154A CN112871154A CN202110057362.4A CN202110057362A CN112871154A CN 112871154 A CN112871154 A CN 112871154A CN 202110057362 A CN202110057362 A CN 202110057362A CN 112871154 A CN112871154 A CN 112871154A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 74
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 68
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 34
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- -1 nitrate amine Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000011261 inert gas Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 19
- 238000001816 cooling Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000011943 nanocatalyst Substances 0.000 description 12
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000013207 UiO-66 Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012684 catalyst carrier precursor Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/391—
-
- B01J35/394—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
Abstract
The invention provides a platinum monatomic catalyst, a preparation method thereof and application thereof in the reaction of preparing styrene by selective hydrogenation of phenylacetylene, wherein the styrene selectivity can reach 99.5% under mild conditions. The catalyst consists of a carrier taking MOF as a precursor and an active component loaded on the carrier, wherein the active component is noble metal platinum, and the platinum is uniformly dispersed on the carrier in a single atom mode. The catalyst has high utilization rate of noble metals and strong atom economy, and can effectively reduce the cost of the catalyst. The reaction system is simple, the reaction condition is mild, and the catalyst and the solvent are easy to separate and recycle. The platinum monatomic catalyst provided by the invention has a novel structure, metal is uniformly dispersed on a carrier, and the platinum monatomic catalyst has good phenylacetylene hydrogenation activity and high styrene selectivity, and has a wide application prospect in the utilization field of styrene preparation through phenylacetylene selective hydrogenation.
Description
Technical Field
The invention relates to the technical field of catalytic hydrogenation, in particular to a platinum monatomic catalyst (SAC) and application thereof in a reaction for preparing styrene by selective hydrogenation of phenylacetylene.
Background
Styrene (ST) is an important organic chemical raw material in downstream petroleum products, and is mainly used for producing monomers such as Polystyrene (PS), resin, styrene-butadiene rubber (SBR) and the like. However, styrene monomers produced industrially often contain small amounts of phenylacetylene, which not only decreases the build-up of polymeric chains and polymerization rate during radical polymerization, but also increases the amount of catalyst consumed and leads to catalyst deactivation. In addition, the presence of these acetylenic impurities can also adversely affect the properties of polystyrene, causing discoloration, degradation, off-taste, etc. (Angewandte Chemie International Edition,2008,47(48): 9274-. Phenylacetylene and styrene have similar physicochemical properties, so it is difficult to separate them efficiently and fundamentally by extractive distillation alone. Currently, the most efficient route is to convert phenylacetylene to styrene by selective hydrogenation. Therefore, in order to reduce the loss caused by the excessive hydrogenation reaction of the styrene while converting the phenylacetylene, the research and development of the selective hydrogenation catalyst with high activity and high styrene selectivity have important industrial application significance.
At present, the most widely used reaction for selectively hydrogenating phenylacetylene into styrene is a heterogeneous metal catalyst, and noble metal nanoparticles such as Pd, Au, Pt, Ru, Rh and the like are mainly used as metal centers. Among them, Pt-based catalysts exhibit better selective hydrogenation performance, and Li et al report a carbon nanotube-supported Pt nano catalyst (Pt/CNT) for phenylacetylene hydrogenation reaction in which the conversion of phenylacetylene and the selectivity of styrene reach 98% and 86%, respectively (Catalysis Today,2012,186(1): 69-75). The zeolite-templated carbon-supported Pt nanocatalyst (Pt/ZTC) reported by Fukuoka et al exhibited 85% phenylacetylene conversion and 82% styrene selectivity (Chemistry Letters,2014,43(11): 1794-1796). The noble metal nano particles are expensive and have rare reserves, and the nano noble metal particles have high hydrogenation activity and are difficult to control selective hydrogenation. Therefore, the method effectively improves the atom utilization rate of the noble metal and regulates the hydrogenation selectivity of the metal, and is a key problem in the reaction of preparing styrene by hydrogenation of phenylacetylene.
Compared with the nanoparticle counterparts, the metal centers of the monatomic catalyst are isolated and dispersed, which can effectively increase the metal utilization rate, and exhibit excellent olefin selectivity in the reaction of selective hydrogenation of alkynes to olefins due to the absence of adjacent metal atoms (Accounts of Chemical Research,2013,46(8): 1740-1748). The accurate preparation of the monatomic catalyst can effectively solve the problems of low metal utilization rate in the reaction of selectively hydrogenating phenylacetylene into styrene, low selectivity caused by excessive hydrogenation of the styrene and the like. However, the metal monoatomic species used as the catalytic center is prone to aggregation, which presents challenges for the preparation of monoatomic catalysts. The preparation of the currently common monatomic catalyst requires that a catalyst carrier is synthesized first and then a metal active component is loaded through impregnation, and the preparation process is complex. In addition, to ensure that the metal center is distributed in a single atom, the metal content is required to be reduced to below 0.1 wt%, which is not favorable for the application and characterization of the catalyst.
Disclosure of Invention
Based on the above background art, the present invention aims to provide a platinum monatomic catalyst, which can realize the conversion of phenylacetylene into styrene with high activity and high selectivity under mild reaction conditions.
The catalyst is a carrier-supported platinum single-atom catalyst prepared by an MOF precursor, wherein a metal organic framework-based material UiO-66(Ce) is used as the catalyst carrier precursor, an active component metal precursor solution is added during the synthesis of the UiO-66(Ce) material, and the catalyst carrier is cerium dioxide (CeO) obtained by calcining2) Specifically, the following technique is adoptedThe scheme is as follows:
the invention provides a supported catalyst, which comprises a carrier prepared by taking MOF as a precursor and an active component loaded on the carrier; the carrier is cerium dioxide; the active component is noble metal platinum which is dispersed on the carrier in a single atom form.
Further, the mass loading of the active component in the catalyst is 0.01 to 5 wt%, preferably 0.05 to 3 wt%.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
(1) dispersing a carrier precursor metal salt into water, dispersing an organic ligand into N, N-dimethylformamide, ultrasonically mixing the two solutions to obtain a raw material solution, adding an active component metal salt, and reacting for 5-50min under stirring of an oil bath at 50-150 ℃ to obtain a mixture; the concentration of the active component metal salt is 0.001-0.5 mol/L;
(2) carrying out suction filtration, washing and drying on the mixture obtained in the step (1);
(3) and (3) roasting the sample obtained after drying in the step (2) at the temperature of 400-800 ℃ for 1-24h in an air atmosphere, and reducing the roasted solid at the temperature of 100-500 ℃ for 1-12h in a hydrogen/inert atmosphere to obtain the catalyst.
Furthermore, the mass ratio of the organic ligand to the active component metal salt is 2-1000:1, and the mass ratio of the carrier precursor metal salt to the active component metal salt is 8-4000: 1.
Further, the active component metal salt is chloroplatinic acid; the organic ligand is terephthalic acid; the metal salt of the carrier precursor is ceric nitrate.
Further, the washing process in the step (2) is sequentially subjected to N, N-dimethylformamide washing, water washing and ethanol washing; the drying condition is drying at 30-100 deg.C for 3-24 h.
Further, in the hydrogen/inert atmosphere in the step (3), the inert atmosphere is N2Or one or two of Ar, and the volume ratio of the hydrogen is 2-50%.
The invention also provides an application of the catalyst, and the catalyst is used for the reaction of preparing styrene by selectively hydrogenating phenylacetylene.
Further, the reaction is carried out in a closed high-pressure reaction kettle by stirring, and the raw materials for the reaction are pure phenylacetylene and methylbenzene solution; the reaction temperature is 25-120 ℃; the reaction time is 30min-24 h; the mass ratio of the phenylacetylene to the toluene pure solution is 1: 10-1: 50.
Further, the hydrogen pressure in the reaction is 0.1-6 MPa.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst directly combines the load of the platinum in the catalytic center and the synthesis of the MOF precursor into one step, and the monatomic catalyst can be obtained only by roasting, so that the preparation process is simple. In addition, the framework structure of the MOF material is regular, the chemical property is easy to modify, platinum atoms can be highly dispersed on the MOF, the preparation of a platinum monatomic catalyst is facilitated, and the metal loading can be increased to 5 wt%.
(2) The catalyst of the invention takes the platinum monoatomic as an active center, the platinum monoatomic is uniformly dispersed on the carrier, the utilization rate of noble metals in the catalyst is high, the atom economy is strong, the cost of the catalyst can be effectively reduced, and the catalyst has potential industrial application value.
(3) The catalyst of the invention shows excellent styrene selectivity when used for catalyzing the reaction of preparing styrene by selectively hydrogenating phenylacetylene, and the styrene selectivity can reach more than 99 percent.
(4) When the catalyst provided by the invention is used for catalyzing the reaction of preparing styrene by selectively hydrogenating phenylacetylene, the reaction system is simple, the reaction condition is mild, and the catalyst and the reaction liquid are easy to separate and recycle.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The present invention will be described in detail with reference to specific examples.
Example 1
0.12wt%Pt1@CeO2Preparation of monatomic catalyst
0.953g of ceric amine nitrate was weighed and dissolved in 2.3mL of water, and weighed againDissolving 0.282g of terephthalic acid in 9.6ml of N-dimethylformamide solution, dissolving the two solutions by ultrasonic waves, uniformly mixing the two solutions, and adding 1.3mLH2PtCl6And (3) heating the solution (7.4mgPt/ml) in an oil bath at 100 ℃, stirring for 20min, filtering the solution, washing the solution with N, N-dimethylformamide, water and ethanol for three times respectively, and then putting the sample into an oven at 60 ℃ for drying to obtain the Pt @ UiO-66(Ce) material. After grinding, transferring the Pt @ UiO-66(Ce) sample into a tubular furnace, heating to the pyrolysis temperature of 600 ℃ at the heating rate of 5 ℃/min, pyrolyzing the sample for 5 hours in the air atmosphere, and naturally cooling to obtain the Pt @ CeO2A precursor. The dried precursor was then transferred to a tube furnace at 10% H2Reducing at 300 ℃ in a/Ar atmosphere at the heating rate of 2 ℃/min for 3h to obtain 0.12 wt% of single atom Pt1@CeO2A catalyst.
Comparative example 1
0.02wt%Pt1@CeO2Preparation of monatomic catalyst
Weighing 0.953g ceric amine nitrate and dissolving in 2.3mL water, weighing 0.282g terephthalic acid and dissolving in 9.6mL LN, N-dimethyl formamide solution, ultrasonic dissolving, mixing the two solutions, adding 1.3mLH2PtCl6And (3) heating the solution (0.74mgPt/ml) in an oil bath at 100 ℃, stirring for 20min, filtering the solution, washing the solution with N, N-dimethylformamide, water and ethanol for three times respectively, and then putting the sample into an oven at 60 ℃ for drying to obtain the Pt @ UiO-66(Ce) material. After grinding, transferring the Pt @ UiO-66(Ce) sample into a tubular furnace, heating to the pyrolysis temperature of 600 ℃ at the heating rate of 5 ℃/min, pyrolyzing the sample for 5 hours in the air atmosphere, and naturally cooling to obtain the Pt @ CeO2A precursor. The dried precursor was then transferred to a tube furnace at 10% H2Reducing at 300 ℃ in a/Ar atmosphere at the heating rate of 2 ℃/min for 3h to obtain 0.02 wt% of single atom Pt1@CeO2A catalyst.
Comparative example 2
1.22wt%Pt@CeO2Preparation of nano-catalyst
0.953g of ceric amine nitrate was dissolved in 2.3mL of water, and 0.282g of terephthalic acid was dissolved in 9.6mL of N-dimethyl benzeneDissolving in formamide solution, mixing the two solutions, adding 1.3mLH2PtCl6And (3) heating the solution (74mgPt/ml) in an oil bath at 100 ℃, stirring for 20min, filtering the solution, washing the solution with N, N-dimethylformamide, water and ethanol for three times respectively, and then putting the sample into an oven at 60 ℃ for drying to obtain the Pt @ UiO-66(Ce) material. After grinding, transferring the Pt @ UiO-66(Ce) sample into a tubular furnace, heating to the pyrolysis temperature of 600 ℃ at the heating rate of 5 ℃/min, pyrolyzing the sample for 5 hours in the air atmosphere, and naturally cooling to obtain the Pt @ CeO2A precursor. The dried precursor was then transferred to a tube furnace at 10% H2Reducing at 300 ℃ in an Ar atmosphere at the heating rate of 2 ℃/min for 3h to obtain 1.22 wt% of Pt @ CeO2And (3) a nano catalyst.
Comparative example 3
0.12wt%Pt@CeO2Preparation of-300 nm catalyst
Weighing 0.953g ceric amine nitrate and dissolving in 2.3mL water, weighing 0.282g terephthalic acid and dissolving in 9.6mL LN, N-dimethyl formamide solution, ultrasonic dissolving, mixing the two solutions, adding 1.3mLH2PtCl6And (3) heating the solution (7.4mgPt/ml) in an oil bath at 100 ℃, stirring for 20min, filtering the solution, washing the solution with N, N-dimethylformamide, water and ethanol for three times respectively, and then putting the sample into an oven at 60 ℃ for drying to obtain the Pt @ UiO-66(Ce) material. After grinding, transferring the Pt @ UiO-66(Ce) sample into a tube furnace, heating to 300 ℃ at the temperature rise rate of 5 ℃/min, pyrolyzing the sample for 5 hours in the air atmosphere, and naturally cooling to obtain the Pt @ CeO2A precursor. The dried precursor was then transferred to a tube furnace at 10% H2Reducing at 300 ℃ in an Ar atmosphere at the heating rate of 2 ℃/min for 3h to obtain 0.12 wt% of Pt @ CeO2-300 nm catalyst.
Comparative example 4
0.12wt%Pt@CeO2Preparation of-900 nm catalyst
0.953g of ceric amine nitrate is weighed and dissolved in 2.3mL of water, 0.282g of terephthalic acid is weighed and dissolved in 9.6mL of N-dimethylformamide solution, after ultrasonic dissolution, the two solutions are mixed evenly,1.3mLH was added2PtCl6And (3) heating the solution (7.4mgPt/ml) in an oil bath at 100 ℃, stirring for 20min, filtering the solution, washing the solution with N, N-dimethylformamide, water and ethanol for three times respectively, and then putting the sample into an oven at 60 ℃ for drying to obtain the Pt @ UiO-66(Ce) material. After grinding, transferring the Pt @ UiO-66(Ce) sample into a tubular furnace, heating to the pyrolysis temperature of 900 ℃ at the heating rate of 5 ℃/min, pyrolyzing the sample for 5 hours in the air atmosphere, and naturally cooling to obtain the Pt @ CeO2A precursor. The dried precursor was then transferred to a tube furnace at 10% H2Reducing at 300 ℃ in an Ar atmosphere at the heating rate of 2 ℃/min for 3h to obtain 0.12 wt% of Pt @ CeO2-900 nm catalyst.
Comparative example 5
0.06wt%Pt1/CeO2Preparation of monatomic catalyst
0.06mL of H was taken at room temperature2PtCl6Solution (7.4mgPt/ml) according to 1gCeO2The water absorption amount of (A) is dissolved in 0.5mL of water and subjected to ultrasonic treatment for 10min, and then 1g of CeO is weighed2Soaking 0.13mL of H in an equal volume2PtCl6Solution (7.4mgPt/ml) and CeO2After mixing and stirring well, the mixture was allowed to stand overnight. Afterwards, the sample was placed in an oven set at 60 ℃ for 10 h. The dried precursor was then transferred to a tube furnace at 10% H2Reducing at 300 ℃ in a/Ar atmosphere at the heating rate of 2 ℃/min for 3h to obtain 0.06 wt% Pt1/CeO2A monatomic catalyst.
Comparative example 6
0.06wt%Pt1Preparation of/C monatomic catalyst
0.06mL of H was taken at room temperature2PtCl6Dissolving the solution (7.4mgPt/mL) in water 0.5mL according to water absorption of 1g activated carbon, performing ultrasonic treatment for 10min, weighing 1g activated carbon, and soaking the above 0.13mL H by equal volume2PtCl6The solution (7.4mgPt/ml) was mixed with activated carbon, stirred well and then allowed to stand overnight. Afterwards, the sample was placed in an oven set at 60 ℃ for 10 h. The dried precursor was then transferred to a tube furnace at 10% H2Reducing at 300 ℃ in a/Ar atmosphere at the heating rate of 2 ℃/min for 3h to obtain 0.06 wt% Pt1a/C monatomic catalyst.
Comparative example 7
Preparation of 0.12 wt% Pt @ UiO-66(Ce) nano-catalyst
Weighing 0.953g ceric amine nitrate and dissolving in 2.3mL water, weighing 0.282g terephthalic acid and dissolving in 9.6mL LN, N-dimethyl formamide solution, ultrasonic dissolving, mixing the two solutions, adding 5mLH2PtCl6And (3) heating the solution (7.4mgPt/ml) in an oil bath at 100 ℃, stirring for 20min, filtering the solution, washing the solution with N, N-dimethylformamide, water and ethanol for three times respectively, and then putting the sample into an oven at 60 ℃ for drying to obtain the Pt @ UiO-66(Ce) nano catalyst.
Comparative example 8
0.12wt%Pt/CeO2Preparation of nano-catalyst
0.13mL of H was taken at room temperature2PtCl6Solution (7.4mgPt/ml) according to 1gCeO2The water absorption amount of (A) is dissolved in 0.5mL of water and subjected to ultrasonic treatment for 10min, and then 1g of CeO is weighed2Soaking 0.13mL of H in an equal volume2PtCl6Solution (7.4mgPt/ml) and CeO2After mixing and stirring well, the mixture was allowed to stand overnight. Afterwards, the sample was placed in an oven set at 60 ℃ for 10 h. The dried precursor was then transferred to a tube furnace at 10% H2Reducing at 300 ℃ in a/Ar atmosphere at the heating rate of 2 ℃/min for 3h to obtain 0.12 wt% of Pt/CeO2And (3) a nano catalyst.
Comparative example 9
Preparation of 0.12 wt% Pt/C nano-catalyst
0.13mL of H was taken at room temperature2PtCl6Dissolving the solution (7.4mgPt/mL) in water 0.5mL according to water absorption of 1g activated carbon, performing ultrasonic treatment for 10min, weighing 1g activated carbon, and soaking the above 0.13mL H by equal volume2PtCl6The solution (7.4mgPt/ml) was mixed with activated carbon, stirred well and then allowed to stand overnight. Afterwards, the sample was placed in an oven set at 60 ℃ for 10 h. Then, the dried precursor is driedTransferring the mixture into a tube furnace at 10% H2Reducing at 300 ℃ in an Ar atmosphere at the heating rate of 2 ℃/min for 3h to obtain the 0.12 wt% Pt/C nano catalyst.
Example 2
0.12 wt% Pt prepared as described above for example 11@CeO2The monatomic catalyst is used for catalyzing the reaction of preparing the styrene by selectively hydrogenating the phenylacetylene, firstly, the catalyst and 2mL of methylbenzene are taken at room temperature to be put in a 10mL high-pressure reaction kettle, and N is introduced2Replacement 3 times and then introduction of H2Replacement 3 times, with H2Putting the reaction kettle into a water bath kettle under the pressure of 2Mpa, stirring, starting the reaction when the temperature of the water bath kettle rises to 60 ℃, cooling after the reaction for 6 hours, taking a proper amount of reaction liquid, performing centrifugal separation, and performing gas chromatography analysis.
Example 3
0.02 wt% Pt prepared in comparative example 1 above was added1@CeO2The monatomic catalyst is used for catalyzing the reaction of preparing the styrene by selectively hydrogenating the phenylacetylene, firstly, the catalyst and 2mL of methylbenzene are taken at room temperature to be put in a 10mL high-pressure reaction kettle, and N is introduced2Replacement 3 times and then introduction of H2Replacement 3 times, with H2Putting the reaction kettle into a water bath kettle under the pressure of 2Mpa, stirring, starting the reaction when the temperature of the water bath kettle rises to 60 ℃, cooling after the reaction for 6 hours, taking a proper amount of reaction liquid, performing centrifugal separation, and performing gas chromatography analysis.
Example 4
1.22 wt% Pt prepared in comparative example 2 above1@CeO2The monatomic catalyst is used for catalyzing the reaction of preparing the styrene by selectively hydrogenating the phenylacetylene, firstly, the catalyst and 2mL of methylbenzene are taken at room temperature to be put in a 10mL high-pressure reaction kettle, and N is introduced2Replacement 3 times and then introduction of H2Replacement 3 times, with H2Putting the reaction kettle into a water bath kettle under the pressure of 2Mpa, stirring, starting the reaction when the temperature of the water bath kettle rises to 60 ℃, cooling after the reaction for 6 hours, taking a proper amount of reaction liquid, performing centrifugal separation, and performing gas chromatography analysis.
Example 5
0.12 wt% Pt prepared in comparative example 3 above1@CeO2The-300 nanometer catalyst is used for catalyzing the reaction of preparing styrene by selectively hydrogenating phenylacetylene, firstly, the catalyst and 2mL of methylbenzene are taken at room temperature to be put in a 10mL high-pressure reaction kettle, and N is introduced2Replacement 3 times and then introduction of H2Replacement 3 times, with H2Putting the reaction kettle into a water bath kettle under the pressure of 2Mpa, stirring, starting the reaction when the temperature of the water bath kettle rises to 60 ℃, cooling after the reaction for 6 hours, taking a proper amount of reaction liquid, performing centrifugal separation, and performing gas chromatography analysis.
Example 6
0.12 wt% Pt @ CeO prepared in comparative example 4 above2The-900 nanometer catalyst is used for catalyzing the reaction of preparing styrene by selectively hydrogenating phenylacetylene, firstly taking the catalyst and 2mL of methylbenzene in a 10mL high-pressure reaction kettle at room temperature, and introducing N2Replacement 3 times and then introduction of H2Replacement 3 times, with H2Putting the reaction kettle into a water bath kettle under the pressure of 2Mpa, stirring, starting the reaction when the temperature of the water bath kettle rises to 60 ℃, cooling after the reaction for 6 hours, taking a proper amount of reaction liquid, performing centrifugal separation, and performing gas chromatography analysis.
Example 7
0.06 wt% Pt prepared in comparative example 5 above was added1/CeO2The monatomic catalyst is used for catalyzing the reaction of preparing the styrene by selectively hydrogenating the phenylacetylene, firstly, the catalyst and 2mL of methylbenzene are taken at room temperature to be put in a 10mL high-pressure reaction kettle, and N is introduced2Replacement 3 times and then introduction of H2Replacement 3 times, with H2Putting the reaction kettle into a water bath kettle under the pressure of 2Mpa, stirring, starting the reaction when the temperature of the water bath kettle rises to 60 ℃, cooling after the reaction for 6 hours, taking a proper amount of reaction liquid, performing centrifugal separation, and performing gas chromatography analysis.
Example 8
0.06 wt% Pt prepared in comparative example 6 above was added1The method is characterized in that a/C monatomic catalyst is used for catalyzing the reaction of preparing styrene by selectively hydrogenating phenylacetylene, firstly, the catalyst and 2mL of toluene are taken at room temperature to be put in a 10mL high-pressure reaction kettle, and N is introduced2Replacement 3 times and then introduction of H2Replacement 3 times, with H2Placing the reaction kettle into a water bath kettle under 2Mpa, stirring, heating to 60 deg.C, and boilingAfter the reaction was started for 6 hours, the reaction mixture was cooled, and an appropriate amount of the reaction mixture was centrifuged and analyzed by gas chromatography.
Example 9
The 0.12 wt% Pt @ UiO-66(Ce) nano-catalyst prepared in the comparative example 7 is used for catalyzing the reaction of preparing styrene by selectively hydrogenating phenylacetylene, firstly, the catalyst and 2mL of toluene are taken in a 10mL high-pressure reaction kettle at room temperature, and N is introduced2Replacement 3 times and then introduction of H2Replacement 3 times, with H2Putting the reaction kettle into a water bath kettle under the pressure of 2Mpa, stirring, starting the reaction when the temperature of the water bath kettle rises to 60 ℃, cooling after the reaction for 6 hours, taking a proper amount of reaction liquid, performing centrifugal separation, and performing gas chromatography analysis.
Example 10
0.12 wt% Pt/CeO prepared in comparative example 8 above2The nanometer catalyst is used for catalyzing the reaction of preparing styrene by selectively hydrogenating phenylacetylene, firstly taking the catalyst and 2mL of methylbenzene in a 10mL high-pressure reaction kettle at room temperature, and introducing N2Replacement 3 times and then introduction of H2Replacement 3 times, with H2Putting the reaction kettle into a water bath kettle under the pressure of 2Mpa, stirring, starting the reaction when the temperature of the water bath kettle rises to 60 ℃, cooling after the reaction for 6 hours, taking a proper amount of reaction liquid, performing centrifugal separation, and performing gas chromatography analysis.
Example 11
The 0.12 wt% Pt/C nano-catalyst prepared in the comparative example 9 is used for catalyzing the reaction of preparing styrene by selectively hydrogenating phenylacetylene, firstly, the catalyst and 2mL toluene are taken at room temperature to be put in a 10mL high-pressure reaction kettle, and N is introduced2Replacement 3 times and then introduction of H2Replacement 3 times, with H2Putting the reaction kettle into a water bath kettle under the pressure of 2Mpa, stirring, starting the reaction when the temperature of the water bath kettle rises to 60 ℃, cooling after the reaction for 6 hours, taking a proper amount of reaction liquid, performing centrifugal separation, and performing gas chromatography analysis.
Example 12
Comparison of catalytic reaction Performance of the catalyst
The catalysts prepared in the embodiments and the comparative examples of the invention are applied to the reaction of preparing styrene by catalyzing the selective hydrogenation of phenylacetylene, and the performance comparison is shown in table 1.
TABLE 1 comparison of catalytic reaction Performance of different catalysts
As can be seen from Table 1 ("-" indicates no detection), 0.12 wt% Pt was prepared according to the invention as in example 11@CeO2The monatomic catalyst has higher conversion rate and styrene selectivity.
Claims (10)
1. A supported catalyst, characterized in that the catalyst comprises an active component and a support; the carrier is cerium dioxide; the active component is noble metal platinum which is dispersed on the carrier in a single atom form.
2. The catalyst of claim 1, wherein: the loading amount of the active component is 0.01-5 wt%, and preferably 0.05-3 wt%.
3. A process for preparing a catalyst as claimed in any one of claims 1 to 2, characterized in that: the method comprises the following steps:
(1) dispersing a carrier precursor metal salt into water, dispersing an organic ligand into N, N-dimethylformamide, ultrasonically mixing the two solutions to obtain a raw material solution, adding an active component metal salt, and reacting for 5-50min under stirring of an oil bath at 50-150 ℃ to obtain a mixture; the concentration of the active component metal salt is 0.001-0.5 mol/L;
(2) carrying out suction filtration, washing and drying on the mixture obtained in the step (1);
(3) roasting the sample obtained after drying in the step (2) for 1-24h at 400-800 ℃ in an air atmosphere, and reducing the roasted solid for 1-12h at 100-500 ℃ in a hydrogen/inert atmosphere to obtain the catalyst.
4. The preparation method according to claim 3, wherein the mass ratio of the organic ligand to the active component metal salt is 2-1000: 1; the mass ratio of the carrier precursor metal salt to the active component metal salt is 8-4000: 1.
5. The production method according to claim 3, wherein the active component metal salt is chloroplatinic acid; the organic ligand is terephthalic acid; the carrier precursor metal salt is ceric nitrate amine.
6. The preparation method according to claim 3, wherein in the step (2), the washing process is sequentially performed by N, N-dimethylformamide washing, water washing and ethanol washing; the drying condition is drying for 3-24 hours at 30-100 ℃.
7. The method according to claim 3, wherein in the step (3), the hydrogen gas/inert gas atmosphere is N2Or one or two of Ar, wherein the volume ratio of the hydrogen is 2-50%.
8. Use of a catalyst according to any one of claims 1-2 in the selective hydrogenation of phenylacetylene to styrene.
9. The application of the method as claimed in claim 8, wherein the reaction is carried out in a closed high-pressure reaction kettle by stirring, the reaction raw materials are phenylacetylene and toluene, and the reaction temperature is 25-120 ℃; the reaction time is 30min-24 h; the mass ratio of the phenylacetylene to the toluene is 1: 10-1: 50.
10. Use according to claim 8, characterized in that: in the reaction, the hydrogen pressure is 0.1-6 MPa.
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113663716A (en) * | 2021-09-28 | 2021-11-19 | 南京工业大学 | Indium oxide loaded metal monatomic catalyst and application thereof |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108855069A (en) * | 2018-06-19 | 2018-11-23 | 华侨大学 | A kind of nano bar-shape Pt/CeO2The preparation method of loaded catalyst and the application in CO catalysis reaction |
CN109126778A (en) * | 2017-06-15 | 2019-01-04 | 中国科学院大连化学物理研究所 | A kind of preparation method of the monatomic catalyst of high carrying capacity |
WO2019164797A1 (en) * | 2018-02-20 | 2019-08-29 | The Johns Hopkins University | Method for preparation of nanoceria supported atomic noble metal catalysts and the application of platinum single atom catalysts for direct methane conversion |
CN110465291A (en) * | 2019-08-09 | 2019-11-19 | 太原理工大学 | A kind of monatomic noble metal type catalyst Ru/Cr2O3And its preparation method and application |
-
2021
- 2021-01-15 CN CN202110057362.4A patent/CN112871154B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109126778A (en) * | 2017-06-15 | 2019-01-04 | 中国科学院大连化学物理研究所 | A kind of preparation method of the monatomic catalyst of high carrying capacity |
WO2019164797A1 (en) * | 2018-02-20 | 2019-08-29 | The Johns Hopkins University | Method for preparation of nanoceria supported atomic noble metal catalysts and the application of platinum single atom catalysts for direct methane conversion |
CN108855069A (en) * | 2018-06-19 | 2018-11-23 | 华侨大学 | A kind of nano bar-shape Pt/CeO2The preparation method of loaded catalyst and the application in CO catalysis reaction |
CN110465291A (en) * | 2019-08-09 | 2019-11-19 | 太原理工大学 | A kind of monatomic noble metal type catalyst Ru/Cr2O3And its preparation method and application |
Non-Patent Citations (1)
Title |
---|
YANFU MA ET AL.: "Tailoring of the Proximity of Platinum Single Atoms on CeO2 Using Phosphorus Boosts the Hydrogenation Activity", 《ACS CATALYSIS》 * |
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