CN110227551A - A kind of nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified2The method for preparing cinnamyl alcohol for cinnamic acid transfer hydrogenation - Google Patents
A kind of nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified2The method for preparing cinnamyl alcohol for cinnamic acid transfer hydrogenation Download PDFInfo
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- CN110227551A CN110227551A CN201910585234.XA CN201910585234A CN110227551A CN 110227551 A CN110227551 A CN 110227551A CN 201910585234 A CN201910585234 A CN 201910585234A CN 110227551 A CN110227551 A CN 110227551A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/845—Cobalt
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Abstract
The invention discloses a kind of nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified2The method for preparing cinnamyl alcohol for cinnamic acid transfer hydrogenation.Under the conditions of this method is existing for the isopropanol, by the nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified2It is added to hydrogenation on cinnamic aldehyde to prepare in the reaction of cinnamyl alcohol, control reaction temperature is 160 ~ 190 DEG C, and the reaction time is 12 ~ 18 hours, and reaction pressure is 1 ~ 4MPa.Gained catalyst low in raw material price of the invention, using base metal, short preparation period, production cost is low, the nucleocapsid catalyst ZIF-67 SiO of gained hydrophobically modified2For hydrogenation on cinnamic aldehyde, not only increase the stability of ZIFs material, solves the problems, such as ZIFs structural instability, improve the performance of catalyst reuse, and its hydrophobic performance is also obviously improved, so as to largely improve the conversion ratio of cinnamic acid and the selectivity of target product cinnamyl alcohol.
Description
Technical field
The present invention relates to the preparation of catalyst, in particular to the nucleocapsid catalyst ZIF-67@SiO of a kind of hydrophobically modified2With
In the method that cinnamic acid transfer hydrogenation prepares cinnamyl alcohol.
Background technique
α, beta-unsaturated aldehyde are important chemical raw material and intermediate.Cinnamic acid is α, the Typical Representative of beta-unsaturated aldehyde,
The hydrogenation of its conjugated double bond C=C and C=O receives significant attention.The selective hydration of C=O obtains cinnamyl alcohol, cinnamyl alcohol be drug and
The important source material and intermediate of fragrance etc., the selective hydration of C=C obtain phenylpropyl aldehyde, it prepares HIV and other drugs
Important intermediate.As α, the Typical Representative of beta-unsaturated aldehyde, hydrogenation on cinnamic aldehyde has important theory significance and industrial application
Prospect.
Currently, the research about hydrogenation on cinnamic aldehyde is concentrated mainly on load type metal catalyst, it is broadly divided into two classes, one
Class is noble metal catalyst, such as Pt, Au etc.;Another kind is base metal, such as Cu, Co, Ni etc..Typical carrier includes acidity
Al2O3, SiO2, TiO2With alkaline MgO and CNT, active carbon, the research of MOFs material was more and more in recent years, but major part is ground
Emphasis is studied carefully still using MOFs material as carrier.
Someone uses Pt/UiO-66, is used for hydrogenation on cinnamic aldehyde, has obtained higher conversion ratio and target product cinnamyl alcohol
Selectivity, but production cost is improved using noble metal.
It has tried to be prepared for Pt/MIL-101, at 80 DEG C, 4Mpa H24h is reacted, obtaining cinnamyl alcohol is selectively
86.2%.Also the selectivity for being prepared for non-precious metal catalyst Ni-Co/MCNT bimetallic catalyst for cinnamic acid is had tried to
Hydrogenation reaction, obtaining cinnamic acid conversion ratio is 30%, and cinnamyl alcohol is selectively 68.5%.Although it can be seen that being dropped using non-metallic catalyst
Low cost, but conversion ratio and selectivity can not improve simultaneously.Therefore the new non-precious metal catalyst of one kind is developed to compel in eyebrow
Eyelash.
In recent years, the research and development of ZIFs class zeolite imidazole skeleton material is rapid, and open metallic site causes in ZIFs
It has acid and basic site, relative to conventional carrier there is bigger specific surface and porosity and structure and function can
Tonality, ZIFs are widely used in gas storage, gas separation and the fields such as functional material, and start to have in catalytic field it is involved,
Show huge potential value.
Summary of the invention
For ZIFs material, for structure there are the technical problems such as unstable, the present invention provides a kind of hydrophobically modified in the reaction
Nucleocapsid catalyst ZIF-67@SiO2The method for preparing cinnamyl alcohol for cinnamic acid transfer hydrogenation.
The technical solution of the present invention is as follows:
A kind of nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified2For the method that cinnamic acid transfer hydrogenation prepares cinnamyl alcohol,
It is characterized in that, under the conditions of existing for the isopropanol, by the nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified2Cinnamic acid is added to add
Hydrogen is prepared in the reaction of cinnamyl alcohol, control reaction temperature be 160 ~ 190 DEG C, the reaction time be 12 ~ 18 hours, reaction pressure be 1 ~
4MPa。
Further, the nucleocapsid catalyst ZIF-67@SiO of the hydrophobically modified2, preparation method is quickly stirring
Method includes the following steps:
(1) by Co (NO3)2·6H2O and 2-methylimidazole are added separately in solvent, and ultrasonic disperse is uniformly dispersed respectively
Liquid;
(2) 2-methylimidazole dispersant liquid drop obtained by step (1) is then added into Co (NO3)2·6H2In O dispersion liquid, Co is controlled
(NO3)2·6H2The molar ratio of O and 2-methylimidazole is 1:6 ~ 9, then stirs 18 ~ 30h at room temperature;
(3) centrifuge washing and drying, obtain ZIF-67;
(4) ZIF-67 is dispersed, obtains dispersion liquid, adjusted the pH value of dispersion liquid to 8 ~ 9, ten are then added into dispersion liquid
For six alkyl trimethyl ammonium bromides, that is, CTAB as pore-foaming agent, stirring 20 ~ 60min mixes it with homogeneous dispersion, controls CTAB
Mass ratio with ZIF-67 is 1:4 ~ 12;
(5) ethyl orthosilicate in the mixed liquor obtained by step (4), and 3- chloropropyl triethoxysilane is added, ethyl orthosilicate,
The amount ratio of 3- chloropropyl triethoxysilane and ZIF-67 are 8 ~ 15ml:4 ~ 8ml:0.08 ~ 0.12g(TEOS)/ethyl alcohol
(CH3CH2OH) mixed solution is added dropwise under agitation in mixed liquor obtained by step (6);Ethyl orthosilicate/ethyl alcohol mixing is molten
The amount ratio of liquid and ZIF-67 are 50 ~ 80 μ L:15 ~ 25mg, reaction are then stirred at room temperature 12 ~ 24 hours;
(6) be centrifugated, obtain violet precipitate, place it in ethanol solution be heated to reflux it is remaining in duct to remove
CTAB;
(7) dry after filtration washing, obtain the nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified2。
Further, in step (1), solvent is one or more of methanol, ethyl alcohol or water.
Further, in step (4), dispersion is using one or more of methanol, ethyl alcohol or water.
Further, it in step (4), adjusts pH and uses aqueous slkali, preferably NaOH solution, concentration is 0.06 ~ 0.2
mol/L。
The beneficial effects of the present invention are:
(1) the nucleocapsid catalyst ZIF-67@SiO of present invention gained hydrophobically modified2It is raw materials used cheap, using your non-gold
Belong to, short preparation period, production cost is low.
(2) the nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified of the present invention2For hydrogenation on cinnamic aldehyde, ZIFs is not only increased
The stability of material solves the problems, such as ZIFs structural instability, improves the performance of catalyst reuse, and its is hydrophobic
Performance is also obviously improved, so as to largely improve cinnamic acid conversion ratio and target product cinnamyl alcohol selection
Property.
Detailed description of the invention
Fig. 1 is the contact angle comparison diagram of the catalyst before and after hydrophobically modified.
Specific embodiment
The present invention is described in further details combined with specific embodiments below, but the present invention is not limited thereto.
1 ZIF-67-@SiO of embodiment2For spirit catalytic of cinnamaldehyde transfer hydrogenation
(1) ZIF-67-@SiO2Synthetic method
1.1 rapid agitations prepare ZIF-67@SiO2
By 3.4mmol Co (NO3)2·6H2O is dissolved in proper amount of methanol solution, ultrasonic disperse 10min.By 23.8mmol 2- methyl
Imidazoles is dissolved in proper amount of methanol, ultrasonic disperse 10min.The 2-methylimidazole solution of preparation is slowly dropped into preparation under stiring
Co(NO3)2·6H2It in O solution, stirs at room temperature for 24 hours, centrifuge washing, with appropriate DMF and each washing of methanol difference 3 times;It will be more
Gained is deposited at 80 DEG C after secondary washing centrifugation and is dried in vacuo to get catalyst Z IF-67.Take 0.1g ZIF-67 in ultrasonic wave
Under be dissolved in 133.3mL methanol.Then the pH of ZIF-67 solution is adjusted to 8 ~ 9 with 0.1mol/L NaOH, 500mg is added
Cetyl trimethylammonium bromide (CTAB) is used as pore-foaming agent, and stirring 30min mixes it with homogeneous dispersion, later in solution
Middle addition 12.4ml ethyl orthosilicate.Then 5ml 3- chloropropyl triethoxysilane is added in the solution.By mixture 30
It is quickly stirred at DEG C 18 hours.Finally, will isolate solid by (5 minutes, 10000rpm) collection violet precipitates of centrifugation and set
In a certain amount of ethanol solution, it is heated to reflux to remove remaining CTAB in duct, is thoroughly washed with ethyl alcohol again after reflux
It washs three times, then violet precipitate is dried in vacuo to 12 hours at 80 DEG C to obtain the modified ZIF-67@SiO of surface hydrophobicity2
Nucleocapsid catalyst.
(2) cinnamic acid transfer hydrogenation
In the mechanical stirring high-pressure machinery reaction kettle with 100ml liner, 5g cinnamic acid is added, 30g isopropanol adds
0.1 ~ 0.2g before modified or modified catalyst, after kettle is sealed, is replaced in kettle air 3-4 time, and opening inlet valve is passed through
The nitrogen of certain pressure begins to warm up and is warming up to 160 ~ 190 DEG C of reaction temperature;When temperature in the kettle reaches specified reaction temperature,
Nitrogen cylinder main valve and intake valve are opened, pressure is added into 1 ~ 4MPa of reaction pressure, and writes down the reaction time started;
Reaction terminates after 3 ~ 25 hours, closes nitrogen cylinder main valve and reaction kettle intake valve, and reaction kettle is placed in cold bath and is dropped
To room temperature;Cooling reaction solution is taken out, catalyst is centrifuged off, the amount of reaction product is determined using gas-chromatography.
It is reacted 18 hours under 180 DEG C, 1Mpa condition of nitrogen gas, cinnamic acid conversion ratio > 99%, the selectivity of product cinnamyl alcohol
93.25%.Other temperature, time, pressure are as shown in the table:
Catalyst | Temperature/DEG C | Time/h | Pressure/MPa | Cortex cinnamomi alcohol conversion | Cinnamyl alcohol selectivity |
ZIF-67 | 180 | 12 | 1 | 59.1 | 96.58 |
ZIF-67-SiO2 | 180 | 12 | 1 | 84.59 | 95.01 |
ZIF-67-SiO2 | 180 | 18 | 1 | >99 | 93.25 |
Material is coated on glass slide, water droplet is added dropwise on surface, by testing the contact angle of catalyst, after investigating before modified
The hydrophobic performance situation of change of catalyst.The contact angle comparison diagram of 1 gained catalyst of embodiment is as shown in Figure 1, can from Fig. 1
Out, the contact angle of (a) catalyst only has 64.8 ° before modified, and hydrophobic performance is poor.And pass through the modified catalyst of hydrophobic grouping
104.3 ° of contact angle (b), hydrophobic performance is good, illustrates modified ZIF-67@SiO2Catalyst has hydrophobic surface, hydrophobic
Performance comparison before modified for, hence it is evident that improve.
Embodiment 2
ZIF-67@SiO2It tests and tests for spirit catalytic of cinnamaldehyde reaction cycle
Catalyst after embodiment 1 is reacted is dried in vacuo 12 hours, by what is be recovered to through the multiple centrifuge washing of ethyl alcohol at 80 DEG C
Catalyst reacts 18 hours under 180 DEG C, 1Mpa condition of nitrogen gas, and cycle-index data are as follows:
Cycle-index | Temperature/DEG C | Time/h | Pressure/MPa | Cortex cinnamomi alcohol conversion | Cinnamyl alcohol selectivity |
1 | 180 | 18 | 1 | 98.63 | 93.65 |
2 | 180 | 18 | 1 | 98.79 | 93.26 |
3 | 180 | 18 | 1 | 97.65 | 94.01 |
4 | 180 | 18 | 1 | 97.32 | 94.28 |
It is highly stable from upper table, it can be seen that present invention gained catalyst is applied in the reaction of hydrogenation on cinnamic aldehyde cinnamyl alcohol,
With extraordinary cycle performance, after being recycled 4 times, catalytic performance does not decline, and it is subsequent the experimental results showed that, continue to follow
Ring uses, and catalytic effect can still be maintained.
Claims (6)
1. a kind of nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified2For the method that cinnamic acid transfer hydrogenation prepares cinnamyl alcohol,
It is characterized in that, under the conditions of existing for the isopropanol, by the nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified2Cinnamic acid is added to add
Hydrogen is prepared in the reaction of cinnamyl alcohol, control reaction temperature be 160 ~ 190 DEG C, the reaction time be 12 ~ 18 hours, reaction pressure be 1 ~
4MPa。
2. the nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified according to claim 12It is prepared for cinnamic acid transfer hydrogenation
The method of cinnamyl alcohol, which is characterized in that the nucleocapsid catalyst ZIF-67@SiO of the hydrophobically modified2, preparation method is fast
Fast paddling process, includes the following steps:
(1) by Co (NO3)2·6H2O and 2-methylimidazole are added separately in solvent, and ultrasonic disperse is uniformly dispersed respectively
Liquid;
(2) 2-methylimidazole dispersant liquid drop obtained by step (1) is then added into Co (NO3)2·6H2In O dispersion liquid, Co is controlled
(NO3)2·6H2The molar ratio of O and 2-methylimidazole is 1:6 ~ 9, then stirs 18 ~ 30h at room temperature;
(3) centrifuge washing and drying, obtain ZIF-67;
(4) ZIF-67 is dispersed, obtains dispersion liquid, adjusted the pH value of dispersion liquid to 8 ~ 9, ten are then added into dispersion liquid
For six alkyl trimethyl ammonium bromides, that is, CTAB as pore-foaming agent, stirring 20 ~ 60min mixes it with homogeneous dispersion, controls CTAB
Mass ratio with ZIF-67 is 1:4 ~ 12;
(5) ethyl orthosilicate in the mixed liquor obtained by step (4), and 3- chloropropyl triethoxysilane is added, ethyl orthosilicate,
The amount ratio of 3- chloropropyl triethoxysilane and ZIF-67 are 8 ~ 15ml:4 ~ 8ml:0.08 ~ 0.12g(TEOS)/ethyl alcohol
(CH3CH2OH) mixed solution is added dropwise under agitation in mixed liquor obtained by step (6);Ethyl orthosilicate/ethyl alcohol mixing is molten
The amount ratio of liquid and ZIF-67 are 50 ~ 80 μ L:15 ~ 25mg, reaction are then stirred at room temperature 12 ~ 24 hours;
(6) be centrifugated, obtain violet precipitate, place it in ethanol solution be heated to reflux it is remaining in duct to remove
CTAB;
(7) dry after filtration washing, obtain the nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified2。
3. the nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified according to claim 22It is prepared for cinnamic acid transfer hydrogenation
The method of cinnamyl alcohol, which is characterized in that in step (1), solvent is one or more of methanol, ethyl alcohol or water.
4. the nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified according to claim 22It is prepared for cinnamic acid transfer hydrogenation
The method of cinnamyl alcohol, which is characterized in that in step (4), dispersion is using one or more of methanol, ethyl alcohol or water.
5. the nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified according to claim 22It is prepared for cinnamic acid transfer hydrogenation
The method of cinnamyl alcohol, which is characterized in that in step (4), adjust pH and use aqueous slkali, concentration is 0.06 ~ 0.2 mol/L.
6. the nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified according to claim 22It is prepared for cinnamic acid transfer hydrogenation
The method of cinnamyl alcohol, which is characterized in that in step (4), adjust pH and use NaOH solution, concentration is 0.06 ~ 0.2 mol/L.
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Cited By (4)
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CN113351255A (en) * | 2021-06-16 | 2021-09-07 | 青岛理工大学 | Co complex catalyst for preparing isobutyric acid by oxidizing isobutyraldehyde and application thereof |
CN114849711A (en) * | 2022-04-27 | 2022-08-05 | 苏州大学 | Metal nano catalyst, preparation method and application thereof |
CN115353461A (en) * | 2022-07-19 | 2022-11-18 | 曲阜师范大学 | Core-shell structure polymerization ionic liquid catalytic hydrogenation reaction |
CN116571263A (en) * | 2023-05-15 | 2023-08-11 | 厦门大学 | Preparation method of silicon dioxide supported nickel-based catalyst and application of catalyst in hydrogenation of5-hydroxymethylfurfural |
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CN109678656A (en) * | 2018-12-29 | 2019-04-26 | 湘潭大学 | Class zeolite imidazole metal organic framework ZIFs is used for the method that alpha, beta-unsaturated aldehyde adds hydrogen to prepare alpha, beta unsaturated alcohol |
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Cited By (7)
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CN113351255A (en) * | 2021-06-16 | 2021-09-07 | 青岛理工大学 | Co complex catalyst for preparing isobutyric acid by oxidizing isobutyraldehyde and application thereof |
CN113351255B (en) * | 2021-06-16 | 2022-10-25 | 青岛理工大学 | Co complex catalyst for preparing isobutyric acid by oxidizing isobutyraldehyde and application thereof |
CN114849711A (en) * | 2022-04-27 | 2022-08-05 | 苏州大学 | Metal nano catalyst, preparation method and application thereof |
CN114849711B (en) * | 2022-04-27 | 2023-08-11 | 苏州大学 | Metal nano catalyst, preparation method and application thereof |
CN115353461A (en) * | 2022-07-19 | 2022-11-18 | 曲阜师范大学 | Core-shell structure polymerization ionic liquid catalytic hydrogenation reaction |
CN116571263A (en) * | 2023-05-15 | 2023-08-11 | 厦门大学 | Preparation method of silicon dioxide supported nickel-based catalyst and application of catalyst in hydrogenation of5-hydroxymethylfurfural |
CN116571263B (en) * | 2023-05-15 | 2024-05-03 | 厦门大学 | Preparation method of silicon dioxide supported nickel-based catalyst and application of catalyst in hydrogenation of 5-hydroxymethylfurfural |
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