CN116809062A - Yttrium oxide loaded atomic-level cluster palladium-based catalyst and its preparation method and use - Google Patents
Yttrium oxide loaded atomic-level cluster palladium-based catalyst and its preparation method and use Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 83
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 25
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000007341 Heck reaction Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 26
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 25
- 239000002071 nanotube Substances 0.000 claims description 22
- 239000012300 argon atmosphere Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000001555 benzenes Chemical class 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- SNHMUERNLJLMHN-IDEBNGHGSA-N iodobenzene Chemical group I[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 SNHMUERNLJLMHN-IDEBNGHGSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- CCRCUPLGCSFEDV-UHFFFAOYSA-N cinnamic acid methyl ester Natural products COC(=O)C=CC1=CC=CC=C1 CCRCUPLGCSFEDV-UHFFFAOYSA-N 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 8
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 1
- SCCCFNJTCDSLCY-UHFFFAOYSA-N 1-iodo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1 SCCCFNJTCDSLCY-UHFFFAOYSA-N 0.000 description 1
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical compound NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to an yttrium oxide loaded atomic-level cluster palladium-based catalyst and a preparation method and application thereof, wherein the yttrium oxide loaded atomic-level cluster palladium-based catalyst consists of a carrier and an active component loaded on the carrier, the active component is a metal palladium cluster, and the carrier is yttrium oxide with yttrium vacancies; palladium is dispersed on the surface of the yttrium oxide carrier in an atomic-scale cluster form; the palladium loading is 0.1-1wt% of the carrier mass. The cluster catalyst provided by the invention has higher catalytic activity and selectivity in Heck reaction, and the preparation method is simple, low in cost, environment-friendly and efficient, and can be recycled for multiple times.
Description
Technical Field
The invention relates to a palladium catalyst, in particular to an yttrium oxide supported atomic-level cluster palladium-based catalyst, a preparation method and application thereof.
Background
The Heck reaction refers to the coupling reaction of unsaturated halogenated benzene and olefin to generate substituted olefin, is one of the most important reactions for generating C-C bond in organic synthesis, and is widely applied to the industrial synthesis fields of natural products, luminescent materials, medicines and fine chemicals. Palladium catalysts are one of the most widely used catalysts in this reaction. The traditional homogeneous palladium catalyst has good activity on Heck reaction, but the homogeneous catalyst is not easy to separate and recycle, has serious palladium loss, is easy to generate palladium black pollution products, and is not suitable for large-scale application. Heterogeneous catalysts with palladium nanoparticles as the active metal are of great interest in Heck reactions, but the activity, selectivity and metal utilization of palladium nanoparticles are low. In recent years, an atomically dispersed exposed cluster catalyst has been receiving increasing attention because atomically dispersed metal atoms are supported on a carrier as an active component. Compared with metal nano particle catalysts, the catalyst not only has high atom utilization rate, but also can provide abundant metal active sites for catalytic reaction. Thus, an exposed cluster catalyst with multiple metal active sites and atomic scale dispersion provides the possibility for Heck reactions.
Disclosure of Invention
The invention aims to provide an yttrium oxide-supported atomic-scale cluster-state palladium-based catalyst, which is used for solving the problems that the traditional homogeneous palladium catalyst is not easy to separate and recycle, the palladium loss is serious, and palladium black pollution products are easy to generate; the second object of the invention is to provide a method for preparing the yttrium oxide-supported atomic-scale clustered palladium-based catalyst; a third object of the present invention is to provide the use of such yttria-supported atomic-scale clustered palladium-based catalysts.
The technical scheme adopted for solving the technical problems is as follows: the yttrium oxide loaded atomic-level cluster palladium-based catalyst consists of a carrier and an active component loaded on the carrier, wherein the active component is a metal palladium cluster, and the carrier is yttrium oxide with yttrium vacancies; palladium is dispersed on the surface of the yttrium oxide carrier in an atomic-scale cluster form; the palladium loading is 0.1-1wt% of the carrier mass.
The preparation method of the yttrium oxide supported atomic-level cluster palladium-based catalyst comprises the following steps:
step one, synthesizing yttrium oxide nanotubes: dissolving yttrium nitrate hexahydrate in deionized water, adding a sodium hydroxide solution into the solution, adjusting the pH value to 12, performing hydrothermal reaction on the obtained mixed solution at 100-500 ℃, washing and drying the mixed solution, roasting the mixed solution at 400-1000 ℃ for 1-5 hours, and obtaining the yttrium oxide nanotube at a roasting temperature rising rate of 2-10 ℃ per minute;
step two, synthesizing yttrium oxide nanotubes containing yttrium vacancies: placing the yttrium oxide nanotube in a plasma machine under argon atmosphere for 5-40 min to obtain yttrium oxide nanotube containing yttrium vacancy;
step three, synthesizing an yttrium oxide supported cluster palladium-based catalyst: dispersing yttrium oxide nanotubes containing yttrium vacancies in ethanol and carrying out ultrasonic treatment for 0.5-5 h, then adding a sodium tetrachloropalladate solution, continuing ultrasonic treatment for 0.5-5 h, calculating the dosage of sodium tetrachloropalladate according to the load of palladium in a catalyst to form a mixed solution, magnetically stirring the mixed solution at room temperature for 8-24 h, centrifugally separating to obtain gray powder, washing the powder with ethanol for three times, and drying at 50-80 ℃ for 12-24 h under vacuum condition; and finally, roasting the dried gray powder for 1-3 hours at 300-500 ℃ in an argon atmosphere, wherein the temperature rising rate of roasting is 2-10 ℃ per minute, and obtaining the yttrium oxide-loaded atomic-scale cluster palladium-based catalyst.
The yttrium oxide supported atomic-level cluster palladium-based catalyst is used in Heck reaction, reactants are halogenated benzene and olefin, a solvent is N, N-dimethylformamide, and an acid binding agent is triethylamine; the ratio of the yttrium oxide supported atomic-level cluster palladium-based catalyst to the halogenated benzene is (2-50) mg/200 mu mol, the ratio of the yttrium oxide supported atomic-level cluster palladium-based catalyst to the solvent is (2-50) mg/5 mL, the molar ratio of the halogenated benzene to the olefin is 1:1-1:4, the molar ratio of the halogenated benzene to the triethylamine is 1:1-1:6, the reaction temperature is 90-140 ℃ under the argon atmosphere of 1 atmosphere, and the reaction time is 1-8 h.
The yttrium oxide-supported atomic-cluster-state palladium-based catalyst is used in a Heck reaction, reactants are iodobenzene and methyl acrylate, the proportion of the yttrium oxide-supported atomic-cluster-state palladium-based catalyst to iodobenzene is (3-30) mg/200 mu mol, the proportion of the yttrium oxide-supported atomic-cluster-state palladium-based catalyst to a solvent is (3-30) mg/5 mL, the molar ratio of iodobenzene to methyl acrylate is 1:1-1:3, the molar ratio of iodobenzene to triethylamine is 1:2-1:5, the reaction temperature is 110-140 ℃ C, and the reaction time is 2-7 h.
Advantageous effects
1. The cluster catalyst provided by the invention has higher catalytic activity and selectivity in Heck reaction. From an electronic structural point of view, as the size of the metal particles decreases to atomically dispersed clusters, the stronger electron transfer between the metal-carrier makes it increasingly appear as a cationic charge state. Compared with metal nano particles, the metal cluster has lower work function, so that the transfer of electrons to the reverse bond orbit of the adsorbate molecules is easier to promote, and the activation of reactants is more facilitated. The atomically dispersed clusters not only have small size, but also have smaller contact angle with the carrier, so that the interaction between the metal atoms and the carrier can be enhanced, and the stability of the clusters is improved.
2. The yttrium oxide supported palladium cluster catalyst prepared by the invention realizes the atomic-level dispersion of low-load noble metal on a carrier, so that more noble metal active sites are exposed, the utilization rate of noble metal atoms is improved, and the catalyst has excellent atomic economy.
3. The invention takes the palladium cluster catalyst loaded by yttrium oxide as the catalyst for the coupling reaction of the iodobenzene and the methyl acrylate for the first time, and the catalyst has excellent catalytic performance in the reaction of catalyzing the iodobenzene and the methyl acrylate to generate the methyl cinnamate. Under the preferred catalytic conditions, the conversion rate of the iodobenzene is more than 99 percent, and the selectivity of the methyl cinnamate is more than 99 percent.
4. The catalyst used in the invention has low cost, simple preparation method, environment protection, high efficiency and recycling.
Drawings
FIG. 1 is an SEM image of a yttria-supported palladium cluster catalyst of example 1.
FIG. 2 is a HAADF-STEM diagram of the yttria-supported palladium cluster catalyst of example 1.
FIG. 3 is an XRD pattern for the yttria-supported palladium cluster catalyst of example 1, the yttria nanotubes prepared in example 1, and the yttria nanotubes containing yttrium vacancies prepared in example 1.
FIG. 4 is a graph of catalytic performance of various catalysts.
Detailed Description
The invention is further described below with reference to the accompanying drawings:
examples
The yttrium oxide loaded atomic-level cluster palladium-based catalyst consists of a carrier and an active component loaded on the carrier, wherein the active component is a metal palladium cluster, and the carrier is yttrium oxide with yttrium vacancies; palladium is dispersed on the surface of the yttrium oxide carrier in an atomic-scale cluster form; the palladium loading is 0.1-1wt% of the carrier mass.
The preparation method of the yttrium oxide supported atomic-scale cluster palladium-based catalyst comprises the following steps:
step one: synthesizing yttrium oxide nano-tube, dissolving 1.724 g hexahydrate yttrium nitrate in 12 mL deionized water, adding 1 mol/L sodium hydroxide solution, and regulating pH to 12. Carrying out hydrothermal reaction on the obtained mixed solution at 130 ℃, then washing and drying, roasting at 700 ℃ for 2h, wherein the temperature rising rate of roasting is 5 ℃/min, and the yttrium oxide nanotubes are white.
Step two: and (3) synthesizing yttrium oxide nanotubes containing yttrium vacancies, and placing the yttrium oxide nanotubes in a plasma machine for 15 min under argon atmosphere to obtain the catalyst carrier containing yttrium vacancies.
Step three: and (3) synthesizing a yttrium oxide loaded palladium cluster catalyst, dispersing yttrium oxide nanotubes containing yttrium vacancies in ethanol, performing ultrasonic treatment for 2 hours, calculating the dosage of sodium tetrachloropalladate according to the palladium loading amount of 0.67wt%, adding sodium tetrachloropalladate solution, continuing ultrasonic treatment for 2 hours to form a mixed solution, magnetically stirring the mixed solution at room temperature for 12 hours, performing centrifugal separation to obtain gray powder, washing the gray powder with ethanol for three times, and drying at 80 ℃ under vacuum for 12 hours. Finally, roasting the dried gray powder for 2 hours at 350 ℃ in an argon atmosphere to obtain the yttrium oxide supported palladium cluster catalyst, wherein the roasting heating rate is 5 ℃ per minute.
The yttrium oxide supported palladium cluster catalysts obtained in the above examples were subjected to a series of structural characterizations to verify the structure thereof.
An SEM spectrum of the yttria-supported palladium cluster catalyst of example 1 is shown in fig. 1, which demonstrates the tubular morphology of the yttria-supported palladium cluster catalyst obtained in example 1.
As shown in FIG. 2, the HAADF-STEM spectrum of the yttrium oxide supported palladium cluster catalyst of example 1 demonstrates that example 1 provides a catalyst in which palladium is supported on the surface of yttrium oxide nanotubes in a cluster form.
The XRD patterns of the yttria-supported palladium cluster catalyst of example 1 and the yttria prepared in example 1 are shown in FIG. 3, in which the upper part is the XRD pattern of the yttria-supported palladium cluster catalyst, the middle part is the yttrium oxide nanotube containing yttrium vacancies, and the lower part is the XRD pattern of the yttrium oxide nanotube.
Examples
The yttria-supported palladium cluster catalyst prepared in example 1 was applied to a Heck coupling reaction, and 3 mg catalyst was dispersed in 5mL of N, N-dimethylformamide, 200. Mu. Mol of iodobenzene and 400. Mu. Mol of methyl acrylate were added, while 600. Mu. Mol of triethylamine was added. In an argon atmosphere of 1atm, after reaction 3h at a reaction temperature of 110 ℃, the conversion rate of iodobenzene was 78% and the selectivity of methyl cinnamate was 99%.
Examples
The yttria-supported palladium cluster catalyst prepared in example 1 was applied to a Heck coupling reaction, and 5 mg catalyst was dispersed in 5mL of N, N-dimethylformamide, 200. Mu. Mol of iodobenzene and 400. Mu. Mol of methyl acrylate were added, while 600. Mu. Mol of triethylamine was added. In an argon atmosphere of 1atm, when the reaction temperature is 110 ℃, the conversion rate of the iodobenzene is 99% and the selectivity of the methyl cinnamate is 99% after the reaction is carried out at 3 h.
Examples
The yttria-supported palladium cluster catalyst prepared in example 1 was applied to a Heck coupling reaction, and 10 mg catalyst was dispersed in 5mL of N, N-dimethylformamide, 200. Mu. Mol of iodobenzene and 400. Mu. Mol of methyl acrylate were added, while 600. Mu. Mol of triethylamine was added. In an argon atmosphere of 1atm, when the reaction temperature is 110 ℃, the conversion rate of the iodobenzene is 99% and the selectivity of the methyl cinnamate is 99% after the reaction is carried out at 3 h.
Examples
The yttria-supported palladium cluster catalyst prepared in example 1 was applied to a Heck coupling reaction, and 5 mg catalyst was dispersed in 5mL of N, N-dimethylformamide, 200. Mu. Mol of iodobenzene and 400. Mu. Mol of methyl acrylate were added, while 600. Mu. Mol of triethylamine was added. After reaction 3h, no product was detected at 0 conversion at 100 ℃ under 1atm argon atmosphere.
Examples
The yttria-supported palladium cluster catalyst prepared in example 1 was applied to a Heck coupling reaction, and 5 mg catalyst was dispersed in 5mL of N, N-dimethylformamide, 200. Mu. Mol of iodobenzene and 400. Mu. Mol of methyl acrylate were added, while 600. Mu. Mol of triethylamine was added. In an argon atmosphere of 1atm, when the reaction temperature is 120 ℃, the conversion rate of the iodobenzene is 99% and the selectivity of the methyl cinnamate is 99% after the reaction is carried out at 3 and h.
Examples
The yttria-supported palladium cluster catalyst prepared in example 1 was applied to a Heck coupling reaction, 5 mg catalyst was weighed and dispersed in 5mL of n, n-dimethylformamide, and the substrates were p-amino iodobenzene, p-nitro iodobenzene, p-bromotoluene, bromobenzene and p-nitro bromobenzene, respectively, and reacted with methyl acrylate, wherein the amount of the substrate was 200. Mu. Mol, the amount of the methyl acrylate was 400. Mu. Mol, and 600. Mu. Mol of triethylamine was added simultaneously. In an argon atmosphere of 1atm, the reaction temperature is 120-140 ℃ and the reaction time is 2-7 h. Table 7 shows the results of evaluating the catalyst activity.
Comparative example 1:
the yttrium vacancy-containing yttria catalyst of 5 mg was dispersed in 5mL of N, N-dimethylformamide, 200. Mu. Mol of iodobenzene and 400. Mu. Mol of methyl acrylate were added, and 600. Mu. Mol of triethylamine was added. In an argon atmosphere of 1atm, no product was detected after reaction 3h at a reaction temperature of 110 ℃, with a conversion of 0.
Comparative example 2:
the yttrium oxide supported palladium nanoparticle catalyst is adopted in the example, and the preparation process of the catalyst in the example 1 is only different in that the dosage of sodium tetrachloropalladate is calculated according to the palladium loading amount of 6.65 percent, and after structural characterization of the palladium-based catalyst obtained in the comparative example, palladium in the prepared catalyst is supported on an yttrium oxide carrier in a particle state. The catalyst was dispersed in 5mL of N, N-dimethylformamide, 200. Mu. Mol of iodobenzene and 400. Mu. Mol of methyl acrylate were added, and 600. Mu. Mol of triethylamine was added. In an argon atmosphere of 1atm, after reaction 3h at a reaction temperature of 110 ℃, the conversion rate of iodobenzene was 50% and the selectivity of methyl cinnamate was 99%.
The results of the performance evaluation of the different catalysts on iodobenzene and methyl acrylate are shown in FIG. 4. Wherein 1 is a yttrium oxide supported palladium cluster catalyst; 2 is yttrium oxide loaded palladium nanoparticle catalyst; 3 is sodium tetrachloropalladate; 4 is palladium acetylacetonate; and 5 is yttrium oxide containing yttrium vacancy.
The above example shows that the yttrium oxide-supported cluster palladium-based catalyst provided by the invention has high catalytic activity in the reaction of iodobenzene and methyl acrylate, and can obtain 99% iodobenzene conversion rate and 99% methyl cinnamate selectivity after reacting for 3 hours at 110 ℃ under the atmosphere of 1 standard atmospheric pressure argon.
The above examples are only referred to, and the technical solutions of the present invention and the present invention or extending from the present patent idea are all within the protection scope of the present invention.
The invention provides an atomically dispersed palladium cluster catalyst: the yttrium oxide is used as a carrier, firstly, plentiful yttrium vacancies are prepared on the yttrium oxide carrier, and palladium clusters are anchored on the carrier containing yttrium vacancies, so that the yttrium oxide-loaded clustered palladium-based catalyst is obtained.
Claims (4)
1. An yttrium oxide supported atomic-cluster palladium-based catalyst, which is characterized in that: the yttrium oxide loaded atomic-level cluster palladium-based catalyst consists of a carrier and an active component loaded on the carrier, wherein the active component is a metal palladium cluster, and the carrier is yttrium oxide with yttrium vacancies; palladium is dispersed on the surface of the yttrium oxide carrier in an atomic-scale cluster form; the palladium loading is 0.1-1wt% of the carrier mass.
2. A method for preparing the yttrium oxide supported atomic-cluster palladium-based catalyst according to claim 1, comprising the steps of:
step one, synthesizing yttrium oxide nanotubes: dissolving yttrium nitrate hexahydrate in deionized water, adding a sodium hydroxide solution into the solution, adjusting the pH value to 12, performing hydrothermal reaction on the obtained mixed solution at 100-500 ℃, washing and drying the mixed solution, roasting the mixed solution at 400-1000 ℃ for 1-5 hours, and obtaining the yttrium oxide nanotube at a roasting temperature rising rate of 2-10 ℃ per minute;
step two, synthesizing yttrium oxide nanotubes containing yttrium vacancies: placing the yttrium oxide nanotube in a plasma machine under argon atmosphere for 5-40 min to obtain yttrium oxide nanotube containing yttrium vacancy;
step three, synthesizing an yttrium oxide supported cluster palladium-based catalyst: dispersing yttrium oxide nanotubes containing yttrium vacancies in ethanol and carrying out ultrasonic treatment for 0.5-5 h, then adding a sodium tetrachloropalladate solution, continuing ultrasonic treatment for 0.5-5 h, calculating the dosage of sodium tetrachloropalladate according to the load of palladium in a catalyst to form a mixed solution, magnetically stirring the mixed solution at room temperature for 8-24 h, centrifugally separating to obtain gray powder, washing the powder with ethanol for three times, and drying at 50-80 ℃ for 12-24 h under vacuum condition; and finally, roasting the dried gray powder for 1-3 hours at 300-500 ℃ in an argon atmosphere, wherein the temperature rising rate of roasting is 2-10 ℃ per minute, and obtaining the yttrium oxide-loaded atomic-scale cluster palladium-based catalyst.
3. An yttria-supported atomic-level cluster palladium-based catalyst according to claim 1 or 2 for use in Heck reactions, characterized in that: the reaction products of the Heck reaction are halogenated benzene and olefin, the solvent is N, N-dimethylformamide, and the acid binding agent is triethylamine; the ratio of the yttrium oxide supported atomic-level cluster palladium-based catalyst to the halogenated benzene is (2-50) mg/200 mu mol, the ratio of the yttrium oxide supported atomic-level cluster palladium-based catalyst to the solvent is (2-50) mg/5 mL, the molar ratio of the halogenated benzene to the olefin is 1:1-1:4, the molar ratio of the halogenated benzene to the triethylamine is 1:1-1:6, the reaction temperature is 90-140 ℃ under the argon atmosphere of 1 atmosphere, and the reaction time is 1-8 h.
4. The yttrium oxide supported atomic-cluster palladium-based catalyst according to claim 3 for Heck reaction, wherein: the halogen benzene is iodobenzene, the olefin is methyl acrylate, the ratio of yttrium oxide loaded atomic-level cluster palladium-based catalyst to iodobenzene is (3-30) mg, the ratio of yttrium oxide loaded atomic-level cluster palladium-based catalyst to solvent is (3-30) mg, the molar ratio of iodobenzene to methyl acrylate is 1:1-1:3, the molar ratio of iodobenzene to triethylamine is 1:2-1:5, the reaction temperature is 110-140 ℃, and the reaction time is 2-7 h.
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003021004A1 (en) * | 2001-08-30 | 2003-03-13 | The University Of Dundee | Process for making thin film porous ceramic-metal composites and composites obtained by this process |
JP2009184881A (en) * | 2008-02-06 | 2009-08-20 | Sumitomo Osaka Cement Co Ltd | Sintered compact and manufacturing process of the same |
CN102762519A (en) * | 2010-02-09 | 2012-10-31 | 住友大阪水泥股份有限公司 | Sintered objects and processes for producing same |
WO2014002667A1 (en) * | 2012-06-28 | 2014-01-03 | エヌ・イーケムキャット株式会社 | Catalyst composition for exhaust gas purification and exhaust gas purifying catalyst for automobiles |
CN104549256A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst |
CN105312052A (en) * | 2014-06-02 | 2016-02-10 | 丰田自动车株式会社 | Exhaust gas purification catalyst, method of producing the same, and exhaust gas purification method using the same |
WO2019004318A1 (en) * | 2017-06-27 | 2019-01-03 | トヨタ自動車株式会社 | Cluster-supporting porous carrier and method for producing same |
CN112191246A (en) * | 2020-10-15 | 2021-01-08 | 东北石油大学 | Supported palladium monatomic catalyst and application thereof in selective hydrogenation of cinnamaldehyde |
US10987657B1 (en) * | 2020-09-23 | 2021-04-27 | King Abdulaziz University | Gold supported yttrium oxide nanorods and methods of use thereof |
CN112892530A (en) * | 2021-01-26 | 2021-06-04 | 昆明贵研催化剂有限责任公司 | Atom-level dispersed noble metal three-way catalyst and preparation method thereof |
-
2023
- 2023-06-29 CN CN202310789118.6A patent/CN116809062A/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003021004A1 (en) * | 2001-08-30 | 2003-03-13 | The University Of Dundee | Process for making thin film porous ceramic-metal composites and composites obtained by this process |
JP2009184881A (en) * | 2008-02-06 | 2009-08-20 | Sumitomo Osaka Cement Co Ltd | Sintered compact and manufacturing process of the same |
CN102762519A (en) * | 2010-02-09 | 2012-10-31 | 住友大阪水泥股份有限公司 | Sintered objects and processes for producing same |
WO2014002667A1 (en) * | 2012-06-28 | 2014-01-03 | エヌ・イーケムキャット株式会社 | Catalyst composition for exhaust gas purification and exhaust gas purifying catalyst for automobiles |
CN104549256A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst |
CN105312052A (en) * | 2014-06-02 | 2016-02-10 | 丰田自动车株式会社 | Exhaust gas purification catalyst, method of producing the same, and exhaust gas purification method using the same |
WO2019004318A1 (en) * | 2017-06-27 | 2019-01-03 | トヨタ自動車株式会社 | Cluster-supporting porous carrier and method for producing same |
US10987657B1 (en) * | 2020-09-23 | 2021-04-27 | King Abdulaziz University | Gold supported yttrium oxide nanorods and methods of use thereof |
CN112191246A (en) * | 2020-10-15 | 2021-01-08 | 东北石油大学 | Supported palladium monatomic catalyst and application thereof in selective hydrogenation of cinnamaldehyde |
CN112892530A (en) * | 2021-01-26 | 2021-06-04 | 昆明贵研催化剂有限责任公司 | Atom-level dispersed noble metal three-way catalyst and preparation method thereof |
Non-Patent Citations (5)
Title |
---|
J. X. ZHENG ET AL.: "Native point defects in yttria and relevance to its use as a high-dielectric-constant gate oxide material: First-principles study", 《PHYSICAL REVIEW B》, vol. 73, 3 March 2006 (2006-03-03), pages 1 - 7 * |
JIAXIN LI ET AL.: "Highly efficient methanol electrooxidation catalyzed by co-action of PdeY2O3 in alkaline solution for fuel cells", 《I N T E RNA T I ONAL JOURNAL O F HYDROGEN ENERGY》, vol. 42, 21 March 2017 (2017-03-21), pages 12236 - 12245, XP085023529, DOI: 10.1016/j.ijhydene.2017.02.181 * |
S. MURUGESAN, R. THIRUMURUGESAN AND P. PARAMESWARAN: "Understanding Microstrain Anisotropy in Yttrium Oxide Synthesized by Sol-Gel Route", 《DAE SOLID STATE PHYSICS SYMPOSIUM》, 31 December 2017 (2017-12-31), pages 1 - 5 * |
XIAOWEN LU ET AL.: "Electronic and structural engineering of supported single atomic layer, low-nuclearity palladium catalysts for conversion of levulinic acid to 1, 4-pentanediol", 《CHEMICAL ENGINEERING JOURNAL》, vol. 464, 27 March 2023 (2023-03-27), pages 1 - 8 * |
熊晓玲等: "铕掺杂氧化钇的密度泛函第一性原理研究", 《四川大学学报(自然科学版)》, vol. 55, no. 1, 31 August 2018 (2018-08-31), pages 162 * |
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