CN110420669B - Method for preparing copper atom cluster and catalyzing CO2Reaction application - Google Patents

Method for preparing copper atom cluster and catalyzing CO2Reaction application Download PDF

Info

Publication number
CN110420669B
CN110420669B CN201910526396.6A CN201910526396A CN110420669B CN 110420669 B CN110420669 B CN 110420669B CN 201910526396 A CN201910526396 A CN 201910526396A CN 110420669 B CN110420669 B CN 110420669B
Authority
CN
China
Prior art keywords
copper
catalyst
cluster
supported
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910526396.6A
Other languages
Chinese (zh)
Other versions
CN110420669A (en
Inventor
祝艳
蔡潇
陈名扬
丁维平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Computational Science Research Center
Nanjing University
Original Assignee
Beijing Computational Science Research Center
Nanjing University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Computational Science Research Center, Nanjing University filed Critical Beijing Computational Science Research Center
Priority to CN201910526396.6A priority Critical patent/CN110420669B/en
Publication of CN110420669A publication Critical patent/CN110420669A/en
Application granted granted Critical
Publication of CN110420669B publication Critical patent/CN110420669B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C29/15—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 oxides of carbon exclusively
    • C07C29/151—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
    • B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0222—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

For catalytic conversion of CO2The supported copper cluster catalyst for preparing the basic chemicals has the following components in percentage by mass, wherein the number of gold atoms in the copper cluster is 24: x wt% -XX wt%, and the carrier is transition metal oxide. The invention has the beneficial effects that: the supported copper cluster catalyst material is prepared by using common copper salt and organic amine as reactants and a metal oxide carrier through chemical coordination and reduction and an ultrasonic supporting method, the copper content is adjustable in a certain range, and different supported carriers can have different catalytic properties, for example, the supported copper cluster catalyst material can be used for catalyzing and converting CO2The catalyst shows excellent catalytic performance in the aspect of preparing basic chemicals. The material has many advantages and can be produced in large scale. The method has the advantages of low copper content in the catalyst, high efficiency, low cost and little environmental pollution. The invention discloses a preparation method of the compound.

Description

Method for preparing copper atom cluster and catalyzing CO2Reaction application
The technical field is as follows:
the invention relates to a supported copper cluster catalyst material, a preparation method thereof and application thereof in reaction of preparing basic chemicals by catalytic conversion of CO 2.
Background art:
the carbon dioxide concentration in the atmosphere has been rising year by year due to the massive use of fossil fuels, and related studies have shown that, since the industrial revolution, CO in the atmosphere has been present2The concentration had risen from 280ppm to 355 ppm. CO22CO, one of the main gases responsible for the greenhouse effect2Excessive emissions into the atmosphere have a serious impact on the global environment. H obtained by renewable energy sources2With CO2The reaction generates basic chemicals, so that CO2 is recycled, the greenhouse effect can be relieved, and the dependence on petroleum resources in the chemical industrial production can be reduced. Due to CO2The molecular is relatively inert, the reaction conditions of the Cu/ZnO/Al2O3 catalyst used in the industry at present are high temperature and high pressure, the reaction temperature is 200-300 ℃, the reaction pressure is 50-100 bar, the economic benefit is reduced due to excessive investment in energy consumption, the catalyst is not environment-friendly, and the popularization of the CO2 hydrogenation reaction is limited.
At present, a metal atom cluster with determined atomic number and an accurate structure presents molecular-like behaviors and special electronic properties, and is a novel catalyst with an accurate structure between a homogeneous phase and a heterogeneous phase when serving as a catalyst together with a peripheral ligand, so that the influence of the catalyst structure on the performance of the catalyst can be truly reflected on an atomic level, more essential clear information is provided for catalytic research, and the method has important significance on accurate correlation of the structure and the catalytic performance. In addition, compared with the traditional catalyst, the metal atom cluster has smaller size, more exposed active sites and higher atom economy, and is an ideal green catalytic material.
Therefore, the supported gold cluster catalyst material attracts a wide range of attention as a novel catalytic material. A number of literature reports and patent applications relating to the synthesis of supported gold cluster catalyst materials are continuously published and published. For example, in 2018, an article published by the Guangdong university of Industrial science Yu Lin, Inc. on Colloids and Surfaces A, reported the use of iron oxide-supported Cu clusters for catalyzing the reduction of 4-nitrophenol; in 2017, the Wang Baojun title group, university of Tai principals, reported the use of Cu clusters for catalyzing selective hydrogenation of acetylene in an article published by Applied Catalysis A: General;
summarizing the literature results of the preparation of the supported copper cluster catalyst material for many years, no method for preparing the supported copper cluster catalyst material with controllable copper atom number and controllable content and the application of the supported copper cluster catalyst material in the reaction of preparing basic chemicals by catalytic conversion of CO2 can be found.
The invention content is as follows:
the technical scheme of the invention is as follows:
for catalytic conversion of CO2The supported copper cluster catalyst for preparing the basic chemicals is characterized in that the catalyst is a copper cluster with the atomic number of 6, and the mass content of the copper cluster catalyst is as follows: 0.1 wt% -10 wt%.
For catalytic conversion of CO2The preparation method of the supported copper cluster catalyst for preparing the basic chemicals comprises the following steps:
step 1, preparing a copper salt solution with the mass fraction of 0.1-0.5%;
step 2, preparing a solution of sodium borohydride (NaBH4) with the mass fraction of 0.1-0.3%;
step 3, adding 2-mercaptobenzoxazole (C7H5NOS) with the mass being 0.6 times that of the copper salt into the solution in the step 1;
and 4, adding the solution obtained in the step 3 into the solution of sodium borohydride (NaBH4) in the step 2, and stirring and standing for 3 hours at 25 ℃.
Step 5, removing the acetonitrile solvent from the mixture obtained in the step 4 by rotary evaporation, washing the remaining solid with diethyl ether, and then extracting the product with dichloromethane to obtain [ Cu ] with a precise structure6(C7H4NOS)6]2-. (the cluster is abbreviated as Cu6)。
Step 6, the Cu obtained in the step 5nAdding a certain amount of oxide (MO) carrier, placing in an ultrasonic instrument for 15 minutes, stirring overnight to age, drying the solvent, and then using a copper atom cluster with 6 atoms as a supported catalyst (Cu) with an active center6/MO)。
The copper salt in the step 1 is copper acetylacetonate or copper nitrate.
The sodium borohydride solution in the step 2 is one of water, methanol, ethanol, isopropanol or butanol.
The organic solvent in the step 5 is one of dichloromethane, toluene, acetone, acetonitrile, diethyl ether, dimethylformamide or tetrahydrofuran.
The oxide carrier in the step 6 is one of silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, molybdenum oxide, zinc oxide or cobalt oxide.
The use method of the catalyst for catalyzing the carbon dioxide hydrogenation reaction is characterized in that the temperature of the catalytic reaction is 100-150 ℃, and the pressure is 1-4 MPa; the reaction gases of CO2, H2 and N2 are H2, CO2 is 1-3, and N is2As an internal standard.
Description of the drawings:
FIG. 1 is a UV-Vis spectrum of Cu metal atom cluster prepared in example 1 of the present invention.
FIG. 2 is Cu prepared in example 2 of the present invention6/ZrO2IR spectrum of (a).
FIG. 3 is a graph showing the results of the catalytic carbon dioxide hydrogenation reaction of the catalysts prepared in examples 2 and 3 of the present invention.
FIG. 4 is an XPS spectrum of the catalyst prepared in example 4 of the present invention.
FIG. 5 is a TEM transmission electron micrograph of the prepared catalyst prepared in example 5 of the present invention. .
Fig. 6 is a XANES spectrum of the prepared catalyst prepared in example 6 of the present invention.
The specific implementation mode is as follows:
the present invention is further illustrated by the following examples.
Example 1:
at constant temperatureUnder constant stirring, 11.9mg of copper acetylacetonate (Cu (C)5H7O2)2) 7.2mL of acetonitrile was added and mixed in the flask for 10 min. Then 7.12mg of 2-mercaptobenzoxazole (C)7H5NOS) was added to the above solution, and the reaction was stirred for 15 minutes. At the same time, 10.8mg of NaBH is added in 1 hour4Dissolved in acetonitrile. Subsequently, the above two solutions were mixed in a flask and left to stand for 3 hours at 25 ℃ with stirring. The acetonitrile solvent was removed by rotary evaporation and the resulting solid was washed with diethyl ether to remove unreacted thiol and possible disulfide byproducts. The product was then extracted with dichloromethane to give [ Cu ] with a precise structure6(C7H4NOS)6]2-(abbreviated as Cu)6). The obtained copper atom cluster is Cu by ultraviolet-visible spectrum (UV-Vis) test6See fig. 1. Taking 15 mg of Cu 6500 mg of ZrO was added2Placing in an ultrasonic instrument for 15 minutes, stirring overnight for aging, drying the solvent, and then taking a copper atom cluster with the atom number of 6 as a supported catalyst (Cu) with an active center6/ZrO2). Wherein the Cu content is 0.8%.
The catalytic reaction conditions are as follows: preferably, the temperature of the catalytic reaction is 130 ℃, and the pressure is 2 MPa; the reaction gas is CO2:H2:N2In which H is2:CO2＝3,N2As an internal standard. Under the condition, 100 mg of catalyst is put into a high-pressure reaction kettle with a polytetrafluoroethylene lining, carbon dioxide is reduced to organic matters by hydrogen under the catalytic action of the catalyst, and after the reaction is carried out for 10 hours, the conversion rate of the carbon dioxide is 3.6 percent, wherein the selectivity of methanol is 36 percent, and the methyl formate is 64 percent. The catalytic performance is shown in FIG. 3.
Example 2:
under constant stirring, 8.52mg of copper nitrate (Cu (NO)3)2) 7.2mL of acetonitrile was added and mixed in the flask for 10 min. Then 7.12mg of 2-mercaptobenzoxazole (C)7H5NOS) was added to the above solution, and the reaction was stirred for 15 minutes. At the same time, 10.8mg of NaBH is added in 1 hour4Dissolved in acetonitrile. Subsequently, the two solutions were combined in a flask and brought to 25 deg.CThe mixture was left to stand for 3 hours with stirring. The acetonitrile solvent was removed by rotary evaporation and the resulting solid was washed with diethyl ether to remove unreacted thiol and possible disulfide byproducts. The product was then extracted with dichloromethane to give [ Cu ] with a precise structure6(C7H4NOS)6]2-(abbreviated as Cu)6). The obtained copper atom cluster is Cu by ultraviolet-visible spectrum (UV-Vis) test6See fig. 1. Taking 15 mg of Cu 6500 mg of ZrO was added2Placing in an ultrasonic instrument for 15 minutes, stirring overnight for aging, drying the solvent, and then taking a copper atom cluster with the atom number of 6 as a supported catalyst (Cu) with an active center6/ZrO2) Wherein the Cu content is 0.8%; the infrared pattern is shown in FIG. 2. The catalytic reaction conditions are as follows: the temperature of the catalytic reaction is 100-150 ℃, and the pressure is 1-4 MPa; the reaction gas is CO2:H2:N2Wherein H2: CO2 is 1-3, N2As an internal standard, the catalytic performance is shown in figure 3.
The catalytic reaction conditions are as follows: preferably, the temperature of the catalytic reaction is 130 ℃, and the pressure is 2 MPa; the reaction gas is CO2:H2:N2In which H is2:CO2＝3,N2As an internal standard. Under the condition, 100 mg of catalyst is put into a high-pressure reaction kettle with a polytetrafluoroethylene lining, carbon dioxide is reduced to organic matters by hydrogen under the catalytic action of the catalyst, and after the reaction is carried out for 10 hours, the conversion rate of the carbon dioxide is 3.6 percent, wherein the selectivity of methanol is 36 percent, and the methyl formate is 64 percent;
example 3:
under constant stirring, 11.9mg of copper acetylacetonate (Cu (C)5H7O2)2) 7.2mL of acetonitrile was added and mixed in the flask for 10 min. Then 7.12mg of 2-mercaptobenzoxazole (C)7H5NOS) was added to the above solution, and the reaction was stirred for 15 minutes. At the same time, 10.8mg of NaBH is added in 1 hour4Dissolved in acetonitrile. Subsequently, the above two solutions were mixed in a flask and left to stand for 3 hours at 25 ℃ with stirring. The acetonitrile solvent was removed by rotary evaporation and the solid obtained was washed with diethyl ether to remove unreacted thiol and possible disulfideA byproduct of the reaction. The product was then extracted with dichloromethane to give [ Cu ] with a precise structure6(C7H4NOS)6]2-(abbreviated as Cu)6). The obtained copper atom cluster is Cu by ultraviolet-visible spectrum (UV-Vis) test6See fig. 1. Taking 15 mg of Cu6Adding 500 mg MgO, placing in ultrasonic instrument for 15 min, stirring overnight to age, oven drying solvent, and loading catalyst (Cu) with copper atom cluster of 6 atom number as active center6MgO). Wherein the Cu content is 0.8%. The catalytic reaction conditions are as follows: the temperature of the catalytic reaction is 100-150 ℃, and the pressure is 1-4 MPa; the reaction gas is CO2:H2:N2Wherein H2: CO2 is 1-3, N2As an internal standard, the catalytic performance is shown in figure 3.
The catalytic reaction conditions are as follows: preferably, the temperature of the catalytic reaction is 130 ℃, and the pressure is 2 MPa; the reaction gas is CO2:H2:N2In which H is2:CO2＝3,N2As an internal standard. Under the condition, 100 mg of catalyst is put into a high-pressure reaction kettle with a polytetrafluoroethylene lining, carbon dioxide is reduced to organic matters by hydrogen under the catalytic action of the catalyst, and after the reaction is carried out for 10 hours, the conversion rate of the carbon dioxide is 2.7 percent, wherein the selectivity of methanol is 45 percent, and the methyl formate is 55 percent;
example 4:
under constant stirring, 8.52mg of copper nitrate (Cu (NO)3)2) 7.2mL of acetonitrile was added and mixed in the flask for 10 min. Then 7.12mg of 2-mercaptobenzoxazole (C)7H5NOS) was added to the above solution, and the reaction was stirred for 15 minutes. At the same time, 10.8mg of NaBH is added in 1 hour4Dissolved in acetonitrile. Subsequently, the above two solutions were mixed in a flask and left to stand for 3 hours at 25 ℃ with stirring. The acetonitrile solvent was removed by rotary evaporation and the resulting solid was washed with diethyl ether to remove unreacted thiol and possible disulfide byproducts. The product was then extracted with dichloromethane to give [ Cu ] with a precise structure6(C7H4NOS)6]2-(abbreviated as Cu)6). Measurement by ultraviolet-visible Spectroscopy (UV-Vis)The obtained copper cluster is Cu6See fig. 1. Taking 75 mg of Cu6Adding 500 mg MgO, placing in ultrasonic instrument for 15 min, stirring overnight to age, oven drying solvent, and loading catalyst (Cu) with copper atom cluster of 6 atom number as active center6MgO), wherein the Cu content is 4%. The XPS spectrum is shown in FIG. 4. The catalytic reaction conditions are as follows: the temperature of the catalytic reaction is 110 ℃, and the pressure is 1.5 MPa; the reaction gas is CO2:H2:N2In which H is2:CO2＝1, N2As an internal standard.
Example 5:
under constant stirring, 11.9mg of copper acetylacetonate (Cu (C)5H7O2)2) 7.2mL of acetonitrile was added and mixed in the flask for 10 min. Then 7.12mg of 2-mercaptobenzoxazole (C)7H5NOS) was added to the above solution, and the reaction was stirred for 15 minutes. At the same time, 10.8mg of NaBH is added in 1 hour4Dissolved in acetonitrile. Subsequently, the above two solutions were mixed in a flask and left to stand for 3 hours at 25 ℃ with stirring. The acetonitrile solvent was removed by rotary evaporation and the resulting solid was washed with diethyl ether to remove unreacted thiol and possible disulfide byproducts. The product was then extracted with dichloromethane to give [ Cu ] with a precise structure6(C7H4NOS)6]2-(abbreviated as Cu)6). The obtained copper atom cluster is Cu by ultraviolet-visible spectrum (UV-Vis) test6See fig. 1. Taking 150 mg of Cu6Adding 500 mg MgO, placing in ultrasonic instrument for 15 min, stirring overnight to age, oven drying solvent, and loading catalyst (Cu) with copper atom cluster of 6 atom number as active center6MgO), wherein the Cu content is 8%. The high-resolution electron microscope is shown in FIG. 5. The catalytic reaction conditions are as follows: the temperature of the catalytic reaction is 140 ℃, and the pressure is 3.5 MPa; the reaction gas is CO2:H2:N2In which H is2:CO2＝2, N2As an internal standard.
Example 6:
under constant stirring, 11.9mg of copper acetylacetonate (Cu (C)5H7O2)2) 7.2mL of acetonitrile was added and mixed in the flask for 10 min. Then 7.12mg of 2-mercaptobenzoxazole (C)7H5NOS) was added to the above solution, and the reaction was stirred for 15 minutes. At the same time, 10.8mg of NaBH is added in 1 hour4Dissolved in acetonitrile. Subsequently, the above two solutions were mixed in a flask and left to stand for 3 hours at 25 ℃ with stirring. The acetonitrile solvent was removed by rotary evaporation and the resulting solid was washed with diethyl ether to remove unreacted thiol and possible disulfide byproducts. The product was then extracted with dichloromethane to give [ Cu ] with a precise structure6(C7H4NOS)6]2-(abbreviated as Cu)6). The obtained copper atom cluster is Cu by ultraviolet-visible spectrum (UV-Vis) test6See fig. 1. Taking 38 mg of Cu 6500 mg of SiO are added2Placing in an ultrasonic instrument for 15 minutes, stirring overnight for aging, drying the solvent, and then taking a copper atom cluster with the atom number of 6 as a supported catalyst (Cu) with an active center6/SiO2) Wherein the Cu content is 2%. The XANES spectrum is shown in FIG. 6. The catalytic reaction conditions are as follows: the temperature of the catalytic reaction is 120 ℃, and the pressure is 4 MPa; the reaction gas is CO2:H2:N2In which H is2:CO2＝2, N2As an internal standard.

Claims (3)

1. A use method of a catalyst for catalyzing carbon dioxide hydrogenation reaction by using a supported copper cluster is characterized in that the temperature of the catalytic reaction is 100-150 ℃, and the pressure is 1-4 MPa; the reaction gas is CO2、H2、N2；
The number of atoms of the atomic cluster in the supported copper atomic cluster is 6, and the copper mass content is as follows: 0.1 wt% -10 wt%; the carrier is one of silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, molybdenum oxide, zinc oxide or cobalt oxide; the preparation method of the supported copper atom cluster comprises the following steps:
step 1, preparing an acetonitrile solution of copper salt with the mass fraction of 0.1-0.5%;
step 2, preparing acetonitrile solution of sodium borohydride with the mass fraction of 0.1-0.3%;
step 3, adding 2-mercaptobenzoxazole with the mass being 0.6 time of that of the copper salt into the solution in the step 1;
step 4, adding the solution obtained in the step 3 into the acetonitrile solution of sodium borohydride in the step 2, and stirring and standing for 3 hours at 25 ℃;
step 5, removing the acetonitrile solvent from the mixture obtained in the step 4 by rotary evaporation, washing the remaining solid with diethyl ether, and then extracting the product with dichloromethane to obtain [ Cu ] with a precise structure6(C7H4NOS) 6]2-; the atomic cluster is abbreviated as Cu6；
Step 6, the Cu obtained in the step 56Adding a certain amount of carrier, placing the carrier in an ultrasonic instrument for 15 minutes, stirring overnight for aging, and drying to obtain the supported catalyst taking the copper atom cluster with the atomic number of 6 as an active center.
2. The use method of the catalyst for catalyzing carbon dioxide hydrogenation reaction by using the supported copper atom cluster as the claim 1 is characterized in that the temperature of the catalytic reaction is 130 ℃; said H2:CO2＝1～3,N2As an internal standard.
3. The use method of the catalyst for catalyzing carbon dioxide hydrogenation reaction of the supported copper atom cluster according to claim 1, wherein the copper salt in the step 1 is copper acetylacetonate or copper nitrate.
CN201910526396.6A 2019-06-18 2019-06-18 Method for preparing copper atom cluster and catalyzing CO2Reaction application Active CN110420669B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910526396.6A CN110420669B (en) 2019-06-18 2019-06-18 Method for preparing copper atom cluster and catalyzing CO2Reaction application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910526396.6A CN110420669B (en) 2019-06-18 2019-06-18 Method for preparing copper atom cluster and catalyzing CO2Reaction application

Publications (2)

Publication Number Publication Date
CN110420669A CN110420669A (en) 2019-11-08
CN110420669B true CN110420669B (en) 2021-12-17

Family

ID=68408679

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910526396.6A Active CN110420669B (en) 2019-06-18 2019-06-18 Method for preparing copper atom cluster and catalyzing CO2Reaction application

Country Status (1)

Country Link
CN (1) CN110420669B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113769761B (en) * 2021-09-22 2022-07-29 电子科技大学 Preparation method and application of cadmium sulfide surface anchoring copper cluster
CN114588896A (en) * 2022-03-09 2022-06-07 南京大学 Precise metal cluster-based composite catalyst and preparation method and application thereof
CN114588929B (en) * 2022-03-16 2023-10-03 安徽大学 Supported copper nanocluster catalyst and application thereof in AHA coupling reaction
CN116393135B (en) * 2023-02-08 2024-09-27 天津大学 Preparation method of copper-based catalyst loaded with Cu atom clusters or Cu single atoms by mixed carrier
CN116371411A (en) * 2023-02-08 2023-07-04 天津大学 Copper-based catalyst loaded with Cu atom clusters or Cu single atoms by mixed carrier and application thereof
CN116371412B (en) * 2023-02-20 2024-09-06 天津大学 Method for regulating and controlling Cu atom cluster size in copper-based catalyst

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105985208A (en) * 2015-02-13 2016-10-05 中国科学院大连化学物理研究所 Application of supported gold cluster catalyst

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105985208A (en) * 2015-02-13 2016-10-05 中国科学院大连化学物理研究所 Application of supported gold cluster catalyst

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Carbon Dioxide Conversion to Methanol over Size-Selected Cu4 Clusters at Low Pressures";Cong Liu等;《Journal of the American Chemical Society》;20150626;第137卷;摘要 *
"Single Crystal Sub-Nanometer Sized Cu6(SR)6 Clusters: Structure, Photophysical Properties, and Electrochemical Sensing";Xiaohui Gao等;《Advanced Science》;20161231;第3卷;第6页左栏第4节 *
Xiaohui Gao等."Single Crystal Sub-Nanometer Sized Cu6(SR)6 Clusters: Structure, Photophysical Properties, and Electrochemical Sensing".《Advanced Science》.2016,第3卷 *

Also Published As

Publication number Publication date
CN110420669A (en) 2019-11-08

Similar Documents

Publication Publication Date Title
CN110420669B (en) Method for preparing copper atom cluster and catalyzing CO2Reaction application
Shao et al. Selective production of γ-valerolactone or 1, 4-pentanediol from levulinic acid/esters over Co-based catalyst: Importance of the synergy of hydrogenation sites and acidic sites
CN107128875B (en) Hydrogen production catalytic system, hydrogen production system comprising catalytic system and application of catalytic system
CN108298499B (en) Method for decomposing and releasing hydrogen by catalyzing formic acid with water-soluble metal complex
CN110339841B (en) Bimetal supported catalyst, preparation method thereof and method for preparing 2, 5-dihydroxymethyl furan
CN105399705B (en) A kind of method that furfuryl alcohol is prepared using hydrogen transfer reaction
CN113061122B (en) Preparation method of 2, 5-dihydroxymethyl tetrahydrofuran
CN106866364A (en) A kind of method that 1,3- ring pentanediols are prepared by furfuryl alcohol
CN113145113A (en) Carbon dioxide hydrogenation catalyst, preparation method and application thereof
CN106582666B (en) Gamma-valerolactone hydrogenation catalyst, preparation method and the method for being used to prepare 1,4- pentanediol and 2- methyltetrahydrofuran
CN113731441B (en) Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof
Li et al. Synthesis of 5-hydroxymethyl-2-furfurylamine via reductive amination of 5-hydroxymethyl-2-furaldehyde with supported Ni-Co bimetallic catalysts
CN110420665B (en) Method for preparing gold atomic clusterAnd catalyzing CO2Reaction application
CN103145545A (en) Method of preparing propanoldiacid through catalytic oxidation of glycerol
CN112547125B (en) CdS/NiPc photocatalyst for water photolysis and preparation method thereof
CN114570423B (en) Catalyst for preparing ethanol and propanol from synthesis gas, and preparation method and application thereof
CN1318140C (en) Catalyst for synthesizing low carbon mixed alcohol by synthetic gas and its preparation method
CN111389395B (en) Ruthenium iridium catalyst, preparation method thereof and application of ruthenium iridium catalyst in hydrogenolysis reaction of 5-hydroxymethylfurfural
CN111715252B (en) Method for catalytically synthesizing organic compound, catalyst and application thereof
CN114950478A (en) Catalyst for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid, and preparation method and application thereof
CN114573528A (en) Method for preparing organic alcohol by reducing organic aldehyde compound through catalytic ethanol
CN109999801B (en) M-B@Pd-B@Al2O3Catalyst and preparation method and application thereof
CN111732977A (en) Method for preparing furan alcohol biodiesel by in-situ hydrogenation of furylacrolein
CN115025781B (en) Catalyst for catalyzing non-hydrogenation and preparation method and application thereof
CN114671738B (en) Method for converting 5-methylfurfural into 2, 5-hexanediol

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant