CN113198541B - MOFs@M 1 Monoatomic site catalyst of polyacid, preparation and application - Google Patents

MOFs@M 1 Monoatomic site catalyst of polyacid, preparation and application Download PDF

Info

Publication number
CN113198541B
CN113198541B CN202110543493.3A CN202110543493A CN113198541B CN 113198541 B CN113198541 B CN 113198541B CN 202110543493 A CN202110543493 A CN 202110543493A CN 113198541 B CN113198541 B CN 113198541B
Authority
CN
China
Prior art keywords
metal
polyacid
catalyst
mofs
organic framework
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
CN202110543493.3A
Other languages
Chinese (zh)
Other versions
CN113198541A (en
Inventor
连超
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.)
Hefei Danyuan Catalytic Technology Co ltd
Original Assignee
Beijing Single Atom Catalysis Technology Co ltd
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 Single Atom Catalysis Technology Co ltd filed Critical Beijing Single Atom Catalysis Technology Co ltd
Priority to CN202110543493.3A priority Critical patent/CN113198541B/en
Publication of CN113198541A publication Critical patent/CN113198541A/en
Application granted granted Critical
Publication of CN113198541B publication Critical patent/CN113198541B/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
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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
    • B01J31/18—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
    • 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
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • 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
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • 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
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • 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
    • 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
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • 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
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a MOFs@M 1 Monoatomic site catalysts for polyacids, preparation and use. According to the single-atom catalyst, polyacid and a metal precursor are simultaneously introduced into a metal organic framework limiting space, and the anchoring of metal single atoms on the surface of the polyacid is realized by utilizing a space limiting effect. Compared with the traditional polyacid-based metal nano catalyst, the single-atom site catalyst provided by the invention has the characteristics of high atom utilization rate, simple synthesis method and easiness in catalyst recovery, and is beneficial to large-scale industrial application. Pt monoatomic catalysts show superior performance over traditional nanocatalysts in phenylacetylene diboride reactions.

Description

MOFs@M 1 Monoatomic site catalyst of polyacid, preparation and application
Technical Field
The invention belongs to the technical field of preparation of catalytic materials, and particularly relates to a preparation method of a polyacid stable monoatomic site catalyst.
Background
The metal nano catalyst has high catalytic activity and good selectivity, and is widely applied. The catalytic active center is usually a metal atom in coordination unsaturated state at the top, side, corner or step position of the nano particle, and the metal atom activates substrate molecules to realize catalysis through coordination, adsorption and the like. Reducing the particle size can increase the atomic proportion of the metal in the coordination unsaturated state, and is an effective method for obtaining a high-activity catalyst, and the most ideal state of the method is to realize the monodispersion of metal atoms so that each metal atom is in the coordination unsaturated state. However, since isolated monatomic surface energy is high and is easily agglomerated into nanoclusters or nanoparticles, developing a stable monatomic site catalyst synthesis process is extremely challenging.
At present, the carrier for stabilizing the single-atom site catalyst mainly comprises oxides, metals, carbon materials and the like, and the ideal single-atom catalyst carrier has certain intrinsic catalytic activity to realize synergistic catalysis besides stabilizing the single-atom site. The polyoxometallate, commonly called polyacid, is a nano-scale inorganic metal-oxygen cluster compound formed by connecting a polyhedron formed by front transition metal (mainly high valence ions of Mo, W, V, nb, ta and the like) and oxygen through common edges, common corners or faces. The catalyst has a definite crystalline structure, a large number of coordinated oxygen atoms, rich element compositions and excellent acid catalytic and oxidation catalytic activities, and is expected to become an excellent single-atom-site catalyst carrier.
In the existing polyacid-based nano catalytic material, various structural types of polyacids are used as stabilizers to prepare Pt, pd, ru, rh, ir, au, ag and other nano particles, the particle size of the obtained nano particles can be controlled to be between a few nanometers and tens of nanometers, but the utilization rate of noble metal atoms in the catalyst is low due to the large nano particle size, and the cost of the catalyst is high. In the conventional liquid-phase open synthesis system, it is difficult to prepare metal monoatomic sites using polyacids as stabilizers. Because a large amount of metal precursor is adsorbed to the surface of the polyacid, in the reduction process, when the limited metal anchoring sites on the surface of the polyacid are fully occupied, the superfluous metal atoms are agglomerated on the surface of the polyacid to form nano particles. Although the size of the nanoparticles can be reduced to some extent by reducing the amount of metal precursor input, the formation of nanoparticles is unavoidable due to the non-uniformity of the spatial distribution of the precursor due to its high mobility in the open system.
Aiming at the defects of the existing polyacid-based nano catalyst, a novel synthetic method of the polyacid-based single-atom-site catalyst is needed to improve the atom utilization rate of noble metal and reduce the cost of the catalyst.
Disclosure of Invention
The invention discloses a MOFs@M 1 The material of the polyacid comprises MOFs porous metal-organic framework material, the polyacid and active metal M, wherein the active metal M is loaded or combined on a polyacid compound in a single-atom site state, and the polyacid compound is filled in a nano pore canal of the metal-organic framework.
The MOFs are three-dimensional porous metal organic framework materials and can be selected from any metal organic framework materials with the pore size of 0.5nm-5nm, preferably 0.5-2nm, and MIL-101, HKUST-1 and ZIF-67 materials are implemented.
The polyacid is Keggin type polyacid, and the chemical formula is H n XM 12 O 40 X is selected from P, si, ge, as or B, M is selected from Mo, W, V, nb or Ta, n is an integer of 1-10, and the valence states of X and M are different, so that the trimming rule is required to be satisfied; preferably dodecamolybdic phosphoric acid, of formula H 4 PMo 12 O 40 。
The active goldM is a transition metal, preferably a noble metal, such as Pt, pd, ru, rh, ir, ag, au, or the like, capable of being anchored by a polyacid, said M 1 Indicating that the metal is present in a single atomic site state.
The loading of polyacid in the material is 5-50wt% and the loading of metal monoatoms is 0.1-2wt%.
Due to the size limitation of the metal organic frame pore canal, the polyacid and the metal precursor can be orderly and monodisperse arranged in the limited space of the metal organic frame.
The MOFs@M 1 The polyacid material is MIL-101@Pt 1 -PMo、HKUST-1@Pt 1 -PMo or ZIF-67@Pt 1 -PMo, wherein PMo represents H 4 PMo 12 O 40 ，M 1 Indicating that the metal is present in a single atomic site state.
The invention also discloses a MOFs@M 1 A catalyst for polyacids comprising porous metal organic framework Materials (MOFs), a polyacid and an active metal, wherein the active metal M 1 The polyacid compound is loaded or combined on the polyacid compound in a single atom site state, and the polyacid compound is filled in the nano pore canal of the metal organic framework.
The present invention provides MOFs@M 1 The preparation process of polyacid material or catalyst includes in-situ synthesis to synthesize MOFs material, simultaneous limiting of polyacid and active metal precursor in the pore canal of metal-organic frame, and reduction of active metal as required.
The method specifically comprises the following steps: dissolving metal ions and organic ligands forming a metal organic framework, polyacid and an active metal precursor in a solvent, reacting under stirring, separating and recovering a sample after the reaction, and reducing to obtain MOFs@M according to the requirement 1 -polyacid materials or catalysts.
The solvent is selected according to the solubility of different raw materials, and is preferably water, methanol, ethanol or N, N' -dimethylformamide.
The polyacid is Keggin type dodecamolybdic phosphoric acid, and the chemical formula is H n XM 12 O 40 X is selected from P, si, ge, as or B, M is selected from Mo, W, V, nb or Ta, n is 1-1An integer of 0, which is different depending on the valence states of X and M, as long as the trim rule is satisfied; preferably dodecamolybdic phosphoric acid, of formula H 4 PMo 12 O 40 。
The three-dimensional porous metal organic framework can be selected from any metal organic framework material, and the pore size of the three-dimensional porous metal organic framework material is 0.5-5nm, preferably 0.5-2 nm. MIL-101, HKUST-1 and ZIF-67 are preferred.
The active metal is a transition metal which can be stabilized by a polyacid, preferably a noble metal such as Pt, pd, ru, rh, ir, ag, au and the like. The active metal precursor is a soluble salt or complex of the active metal, including inorganic salts, organic salts or complexes, preferably chlorides, nitrates, acetylacetonates, acetates, chlorine-containing complexes, ammonia-containing complexes of the soluble metal, more preferably platinum acetylacetonate, chloroplatinic acid and platinum chloride.
Wherein the loading of the polyacid is 5-50wt%, and the loading of the metal monoatoms is 0.1-2wt%
The in situ synthesis method includes in situ hydrothermal, solvothermal or other conventional synthesis methods. The in-situ synthesis method, namely MOFs synthesis method, adds polyacid before or simultaneously with the MOFs synthesis process to enter MOFs porous channels. The precursor of the active metal M may be added prior to the MOFs synthesis process, simultaneously with the synthesis, or after the formation of the mofs@polyacids.
The reduction is performed in a hydrogen atmosphere and the reduction is performed in a reduction apparatus, which is a calciner or kiln capable of providing the desired atmosphere and verification temperature, including but not limited to a tube furnace, a protective atmosphere furnace. The reduction is carried out under hydrogen atmosphere at 80-250deg.C, preferably 120-180deg.C, for 30-480min, preferably 60-120min.
Before reduction, the polyacid and metal precursor material carried by the obtained metal organic frame are dried in an oven at 60-100 ℃ for 24-48 hours according to the need.
The invention further discloses MOFs@M 1 Use of a polyacid catalyst for catalyzing the diboronation of phenylacetylene. MIL-101@Pt is preferred 1 Use of a PMo catalyst for catalyzing the diboronation of phenylacetyleneAnd (3) the way.
The invention also protects a method for diboronating phenylacetylene by using MOFs@M 1 The polyacid material acts as a catalyst, the reaction equation is as follows,
Figure BDA0003072612390000031
the MOFs@M 1 Polyacid materials see the definition above.
Noun interpretation:
polyacids, also known as polyoxometallate Polyacids (POMs), are nanoscale metal-oxygen cluster compounds formed from pre-transition metal ions (e.g., V, mo, W, etc.) and oxygen.
Metal organic framework Materials (MOFs) are a class of porous solid-state molecular materials with periodic network structures formed by coordination between metal ions and organic ligands, wherein metal or metal clusters are used as nodes, organic bridging ligands are used as connectors. Wherein MIL-101 is a metal organic framework material taking Cr as a metal node and terephthalic acid as a ligand; HKUST-1 is a metal organic frame material taking Cu as a metal node and trimesic acid as a ligand; ZIF-67 is a metal organic framework material with Co as a metal node and dimethyl imidazole as a ligand.
MOFs@M 1 -polyacids @ denotes M 1 The polyacid exists in the pores of MOFs, is wrapped by MOFs and M 1 Indicating that the active metal is in a single atomic site state and anchored on the polyacid carrier. PMo is an abbreviated form of dodecamolybdic acid having the formula H 4 PMo 12 O 40 . MOFs@M in the present application 1 The polyacids are sometimes written as M 1 Polyacids @ MOFs, both of which have the same meaning, but are written differently, e.g. Pt 1 -PMo@MIL-101 and MIL-101@Pt 1 PMo is only written differently in this application.
The method can effectively avoid agglomeration of metal atoms in the reduction process, realize preparation of the polyacid-stabilized metal single-atom site catalyst, improve the utilization rate of noble metal atoms, and overcome the problems of low activity, high cost and the like of the conventional multi-acid-based nano catalyst.
Drawings
FIG. 1 is a spherical aberration electron microscope spectrum of a Pt monoatomic site catalyst according to example 1 of the present invention, wherein white bright spots circled in the graph are Pt monoatoms;
FIG. 2 is an EXAFS spectrum of a Pt single-site catalyst according to example 1 of the present invention, wherein
Figure BDA0003072612390000041
The left and right are peaks of Pt-O bond, < >>
Figure BDA0003072612390000042
The left and right peaks for Pt-Pt bonds;
FIG. 3 is a graph of a spherical aberration electron microscope of the Pt single-atom-site catalyst according to example 2, wherein the white bright spots circled in the graph are Pt single atoms;
FIG. 4 is an EXAFS spectrum of a Pt single-site catalyst according to example 2 of the present invention, wherein
Figure BDA0003072612390000043
The left and right are peaks of Pt-O bond, < >>
Figure BDA0003072612390000044
The left and right peaks for Pt-Pt bonds;
FIG. 5 is a graph of a spherical aberration electron microscope of the Pt single-atom-site catalyst according to example 3, wherein the white bright spots circled in the graph are Pt single atoms;
FIG. 6 is an EXAFS spectrum of a Pt single-site catalyst according to example 3 of the present invention, wherein
Figure BDA0003072612390000045
The left and right are peaks of Pt-O bond, < >>
Figure BDA0003072612390000046
The left and right peaks for Pt-Pt bonds;
FIG. 7 is a transmission electron microscope spectrum of the Pt nanoparticle catalyst according to comparative example 1 of the present invention, wherein the white bright spots are Pt nanoparticles;
FIG. 8 is a transmission electron microscope spectrum of the Pt nanoparticle catalyst according to comparative example 2, in which the white bright spots are Pt nanoparticles;
FIG. 9 shows the results of the double borylation reaction of phenylacetylene catalyzed by the Pt single-site catalyst of the present invention, wherein the dark bars represent the conversion of the double borylation reaction catalyzed by the different catalysts, and the light bars represent the selectivity of the target double borylation product.
Detailed Description
The preparation method of the polyacid-stabilized single-site catalyst provided by the invention is described in detail below with reference to specific examples.
Abbreviations used in this example are explained as follows:
EXAFS: fine X-ray absorbing structure
NPs: nanoparticles
The reaction tube used in the application example is a commercial reaction tube, and is selected from a Xin-Weir reaction tube, the model is F891410, and other reaction tubes can be used.
Example 1
1.0g of chromium nitrate nonahydrate, 0.42g of terephthalic acid and 1.0g of dodecamolybdic phosphoric acid were weighed out and stirred in 10mL of distilled water for 4 hours. The pH of the solution was adjusted to 3. Transferring the mixed solution into a reaction kettle to react for 20 hours at 180 ℃ to obtain a solid product. After washing with N, N' -dimethylformamide and distilled water, the mixture was dried at 80℃for 24 hours. Subsequently, 20mg of platinum acetylacetonate was dissolved in 10mL of methanol, and 1.0g of the above solid product was added. After stirring continuously for 12 hours, the solid product was centrifuged and washed several times with methanol and dried at 80℃for 24 hours. Transferring the product into a tube furnace, and reducing at 150 ℃ for 1 hour under the hydrogen atmosphere to obtain MIL-101 supported H 3 PMo 12 O 40 Stable Pt monoatomic catalyst (noted Pt 1 -PMo@MIL-101). The obtained product is characterized by a spherical aberration correction scanning transmission electron microscope and an X-ray absorption fine structure (EXAFS). As shown in fig. 1, only an image of Pt monoatoms was observed without Pt nanoparticles; as shown in fig. 2, only Pt-O bonds were included without Pt-Pt bonds, indicating that a Pt single-atom site catalyst was obtained.
Example 2
25mg of platinum acetylacetonate, 0.25g of copper nitrate trihydrate, 0.3g of dodecamolybdic phosphoric acid and 0.23g of trimesic acid are weighed out and dissolved in 50mL of ethanol. The solution was stirred continuously for 12 hours. The resulting precipitate was collected by centrifugation and washed several times with ethanol and distilled water. Oven dried at 80℃for 24 hours. The product was then transferred to a tube furnace and reduced at 150℃for 1 hour under a hydrogen atmosphere to give HKUST-1 supported H 3 PMo 12 O 40 Stable Pt monoatomic catalyst (noted Pt 1 PMo@HKUST-1). The obtained product is characterized by a spherical aberration correction scanning transmission electron microscope and an X-ray absorption fine structure (EXAFS). As shown in fig. 3, only an image of Pt monoatoms was observed without Pt nanoparticles; as shown in fig. 4, only Pt-O bonds were included without Pt-Pt bonds, indicating that a Pt single-atom site catalyst was obtained.
Example 3
0.75g of cobalt nitrate hexahydrate was weighed into 25mL of methanol, and after weighing 0.05g of dodecamolybdic phosphoric acid into 10mL of distilled water, the two solutions were mixed and stirred for 30 minutes. Subsequently, 25mL of a methanol solution containing 1.7g of 2-methylimidazole and 30mg of platinum acetylacetonate was poured into the above mixed solution and stirring was continued for 4 hours. The resulting precipitate was collected by centrifugation and washed several times with methanol and distilled water. Oven dried at 80℃for 24 hours. Transferring the product into a tube furnace, and reducing at 150 ℃ for 1 hour under the hydrogen atmosphere to obtain the H supported by ZIF-67 3 PMo 12 O 40 Stable Pt monoatomic catalyst (noted Pt 1 PMo@ZIF-67). The obtained product is characterized by a spherical aberration correction scanning transmission electron microscope and an X-ray absorption fine structure (EXAFS). As shown in fig. 5, only an image of Pt monoatoms was observed without Pt nanoparticles; as shown in fig. 6, only pt—o bonds were included without pt—pt bonds, indicating that a Pt single-atom site catalyst was obtained.
Comparative example 1
20mg of platinum acetylacetonate was weighed, dissolved in 10mL of methanol, 1.0g of MIL-101 was added thereto and continuously stirred for 12 hours, and after the solid product was centrifuged and washed several times with methanol, it was dried at 80℃for 24 hours. The product was then transferred to a tube furnace and reduced at 150 ℃ for 1 hour under a hydrogen atmosphere. The resulting product was characterized by transmission electron microscopy and, as shown in FIG. 7, it was found that Pt nanoparticles (noted Pt NPs@MIL-101) were produced. Indicating that single-site catalysts cannot be obtained without the presence of polyacids.
Comparative example 2
20mg of platinum acetylacetonate and 1g of dodecamolybdic phosphoric acid were weighed out in 50mL of ethanol and stirred for 4 hours, after which the solvent was evaporated to dryness. The product was then transferred to a tube furnace and reduced at 150 ℃ for 1 hour under a hydrogen atmosphere. The resulting product was characterized by transmission electron microscopy and, as shown in fig. 8, it was found that Pt nanoparticles (noted Pt nps@pmo) were produced. Indicating that single-site catalysts are likewise not obtainable without the presence of a metal-organic framework.
Application examples
Catalytic phenylacetylene diboron reaction
0.5mmol phenylacetylene, 0.5mmol bis (pinacolato) diboron (designated B) 2 pin 2 ) And 20mg of catalyst are mixed and placed into a reaction tube, 2.0mL of toluene is injected, and then the mixed solution is heated to 100 ℃ for reaction, and the reaction is carried out for 0 to 48 hours at normal pressure. The product was analyzed by gas chromatography and mass spectrometry.
In the application test, the catalyst of example 1, pt NPs@MIL-101, MIL-101, PMo@MIL-101, pt NPs@Y zeolite, pt were used, respectively 1 The results of the catalytic properties at Y zeolite are shown in FIG. 9.
Example 1 a Pt single-atom catalyst prepared with MILs-101 supported dodecamolybdenum phosphoric acid was used to catalyze the phenylacetylene diboronation reaction, the performance of the single-atom catalyst being 7 times that of the corresponding Pt nanoparticle catalyst.
Experimental and application test conclusion:
1. examples 1-3, which both have polyacids and metal organic framework structures, were able to successfully prepare single-site catalysts compared to the catalysts of comparative examples 1-2, without stabilization of the polyacids or without confinement of the metal organic framework, resulting in nanoparticle formation.
2. In the phenylacetylene diboronation reaction, the performance of the Pt single-atom catalyst is obviously improved compared with that of the Pt nano-particle catalyst, which shows that the single-atom catalyst has a unique catalytic effect.
The foregoing examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention, and other variations or modifications of various forms may be made by those skilled in the art based on the foregoing description, and it is not intended to be exhaustive of all embodiments, and all obvious variations or modifications that come within the scope of the invention are defined by the following claims.

Claims (5)

1. MOFs@M 1 The use of a polyacid catalyst for catalyzing a phenylacetylene diboronation reaction characterized in that the phenylacetylene diboronation reaction equation is as follows,
Figure QLYQS_1
，
wherein,,
the metal M is Pt, said M 1 The metal M is shown to exist in a single atomic site state, and the loading amount of Pt is 0.1-2 wt%;
the polyacid is dodecamolybdic phosphoric acid, and the loading amount of the polyacid is 5-50 wt%;
the MOFs are three-dimensional porous metal organic framework materials and are selected from MIL-101;
the polyacid compound is filled in the nano pore canal of the metal organic framework, and the active metal M is loaded or combined on the polyacid compound in a single atom site state.
2. The use according to claim 1, wherein the catalyst is prepared according to a process comprising: dissolving metal ions and organic ligands forming a metal organic framework, polyacid and active metal precursors in a solvent, stirring for reaction, separating and recovering a sample after the reaction, and reducing to obtain MOFs@M 1 -a polyacid catalyst; the solvent is selected from water, methanol, ethanol, N-dimethylformamide;
the polyacid is dodecamolybdic phosphoric acid, and the chemical formula is H 3 PMo 12 O 40 ；
The metal-organic framework is MIL-101, wherein Cr is metal, and terephthalic acid is an organic ligand;
the active metal is Pt; the active metal precursor is platinum acetylacetonate.
3. Use according to claim 2, wherein the reduction is carried out under a hydrogen atmosphere, the reduction being carried out in a reduction device at a reduction temperature of 80-250 ℃ for a time of 30-480 min.
4. The use according to claim 3, wherein the reduction device is a tube furnace; the reduction temperature is 120-180 ℃ and the time is 60-120min.
5. The use according to claim 3, wherein the reduction device is a protective atmosphere furnace; the reduction temperature is 120-180 ℃ and the time is 60-120min.
CN202110543493.3A 2021-05-19 2021-05-19 MOFs@M 1 Monoatomic site catalyst of polyacid, preparation and application Active CN113198541B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110543493.3A CN113198541B (en) 2021-05-19 2021-05-19 MOFs@M 1 Monoatomic site catalyst of polyacid, preparation and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110543493.3A CN113198541B (en) 2021-05-19 2021-05-19 MOFs@M 1 Monoatomic site catalyst of polyacid, preparation and application

Publications (2)

Publication Number Publication Date
CN113198541A CN113198541A (en) 2021-08-03
CN113198541B true CN113198541B (en) 2023-05-26

Family

ID=77031709

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110543493.3A Active CN113198541B (en) 2021-05-19 2021-05-19 MOFs@M 1 Monoatomic site catalyst of polyacid, preparation and application

Country Status (1)

Country Link
CN (1) CN113198541B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113842936B (en) * 2021-10-22 2023-06-23 四川大学华西医院 Platinum-based monoatomic electrocatalytic material and preparation method and application thereof
CN114400339B (en) * 2021-12-06 2023-09-12 江苏大学 heteropolyacid@MOFs/polymer electrostatic spinning nanofiber
CN114622242B (en) * 2022-02-15 2023-01-06 苏州大学 Ni/NiO nano heterojunction porous graphite carbon composite material and preparation method and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3398679A1 (en) * 2015-12-28 2018-11-07 Toyota Jidosha Kabushiki Kaisha Cluster supported catalyst and production method therefor
CN110571442A (en) * 2019-09-19 2019-12-13 中国科学技术大学 Molybdenum monatomic catalyst and preparation method and application thereof
CN111841611B (en) * 2020-08-04 2023-03-14 西北工业大学 Noble metal monatomic catalyst and preparation method assisted by using notch polyacid

Also Published As

Publication number Publication date
CN113198541A (en) 2021-08-03

Similar Documents

Publication Publication Date Title
CN113198541B (en) MOFs@M 1 Monoatomic site catalyst of polyacid, preparation and application
Ye et al. Self-regeneration of Au/CeO2 based catalysts with enhanced activity and ultra-stability for acetylene hydrochlorination
Zhang et al. The effect of coordination environment on the activity and selectivity of single-atom catalysts
Yang et al. Unexpected “spontaneous” evolution of catalytic, MOF-supported single Cu (II) cations to catalytic, MOF-supported Cu (0) nanoparticles
Zahmakiran Iridium nanoparticles stabilized by metal organic frameworks (IrNPs@ ZIF-8): synthesis, structural properties and catalytic performance
Kobayashi et al. Metal nanoparticles covered with a metal–organic framework: from one-pot synthetic methods to synergistic energy storage and conversion functions
Guo et al. A minireview on the synthesis of single atom catalysts
Zhao et al. Constructing and controlling of highly dispersed metallic sites for catalysis
Kratzl et al. Generation and stabilization of small platinum clusters Pt12±x inside a metal–organic framework
Ertas et al. Rhodium nanoparticles stabilized by sulfonic acid functionalized metal-organic framework for the selective hydrogenation of phenol to cyclohexanone
US7381682B1 (en) Method for producing heterogeneous catalysts containing metal nanoparticles
WO2014045570A1 (en) Catalyst using pd-ru solid-solution-type alloy particles
US8080493B2 (en) Heteropolyanions with late transition metal addenda atoms and process for their preparation
Long et al. Synthesis and characterization of Pt–Pd nanoparticles with core-shell morphology: Nucleation and overgrowth of the Pd shells on the as-prepared and defined Pt seeds
Yang et al. Subnano-FeO x Clusters Anchored in an Ultrathin Amorphous Al2O3 Nanosheet for Styrene Epoxidation
Tang et al. Atomic, molecular and hybrid oxygen structures on silver
KR20140089349A (en) Ruthenium microparticles having essentially face-centered cubic structure and method for produicing same
Kim et al. In situ-generated metal oxide catalyst during CO oxidation reaction transformed from redox-active metal-organic framework-supported palladium nanoparticles
JP2007527788A (en) Preparation of metal / metal oxide supported catalysts by precursor chemical nanometallurgy in a predetermined reaction space of a porous carrier using a metal organic and / or inorganic precursor and a metal-containing reducing agent
Maligal‐Ganesh et al. Sub‐5 nm Intermetallic Nanoparticles Confined in Mesoporous Silica Wells for Selective Hydrogenation of Acetylene to Ethylene
Xue et al. Synthesis of Pt@ MAF-6 as a steric effect catalyst for selective hydrogenation of cinnamaldehyde
Bhat et al. Improving the thermal stability and n-butanol oxidation activity of Ag-TiO2 catalysts by controlling the catalyst architecture and reaction conditions
Wang et al. Isolated palladium atoms dispersed on silicoaluminophosphate-31 (SAPO-31) for the semihydrogenation of alkynes
An et al. Metal-organic-framework-based materials as green catalysts for alcohol oxidation
Sabounchei et al. [60] Fullerene-Based Pd (0) Complexes of Phosphorus Ylides as Efficient Nanocatalyst for Homo-and Heterogeneous Mizoroki–Heck Coupling Reactions

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
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20231218

Address after: North 4th Floor, Building 4 (3 # B), Phase II of Hefei Innovation and Entrepreneurship Park, No. 268 Furong Road, Shushan District, Hefei City, Anhui Province, 230051

Patentee after: Hefei Danyuan Catalytic Technology Co.,Ltd.

Address before: 100094 room 310, 3rd floor, incubation building, No.7 Fengxian Middle Road, Haidian District, Beijing

Patentee before: Beijing Single Atom Catalysis Technology Co.,Ltd.