CN113198541A - MOFs @ M1Single atom site catalyst of polyacid, preparation and application - Google Patents
MOFs @ M1Single atom site catalyst of polyacid, preparation and application Download PDFInfo
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- CN113198541A CN113198541A CN202110543493.3A CN202110543493A CN113198541A CN 113198541 A CN113198541 A CN 113198541A CN 202110543493 A CN202110543493 A CN 202110543493A CN 113198541 A CN113198541 A CN 113198541A
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- polyacid
- metal
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 51
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000001308 synthesis method Methods 0.000 claims abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 14
- PDDXOPNEMCREGN-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum;hydrate Chemical compound O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O PDDXOPNEMCREGN-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 239000013177 MIL-101 Substances 0.000 claims description 9
- 229910020881 PMo12O40 Inorganic materials 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000013110 organic ligand Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 2
- MBUJACWWYFPMDK-UHFFFAOYSA-N pentane-2,4-dione;platinum Chemical compound [Pt].CC(=O)CC(C)=O MBUJACWWYFPMDK-UHFFFAOYSA-N 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000012795 verification Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011943 nanocatalyst Substances 0.000 abstract description 4
- 238000004873 anchoring Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 21
- 125000004429 atom Chemical group 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 11
- 230000004075 alteration Effects 0.000 description 6
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- -1 comprise oxides Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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- 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
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- 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
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- 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
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- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- B01J2531/62—Chromium
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- 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
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- 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
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Abstract
The invention provides MOFs @ M1-single atom site catalyst of polyacid, preparation and application. The single atom catalyst is characterized in that polyacid and a metal precursor are simultaneously introduced into a metal organic framework confinement space, and the anchoring of metal single atoms on the surface of the polyacid is realized by utilizing the space confinement effect. Compared with the traditional polyacid-based metal nano-catalyst, the monoatomic 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. Double boronation of phenylacetylene with Pt monatomic catalystThe excellent performance of the reaction is better than that of the traditional nanometer catalyst.
Description
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 single-atom-site catalyst.
Background
The metal nano-catalyst is widely applied due to high catalytic activity and good selectivity. The catalytic active center is usually a metal atom which is located at the vertex, edge, corner or step of the nanoparticle and is in a coordination unsaturated state, and the atom activates a substrate molecule through coordination, adsorption and the like to realize catalytic action. Reducing the particle size increases the proportion of atoms of the metal in coordinatively unsaturated state, and is an effective method for obtaining a highly active catalyst, and the most desirable method is to achieve monodispersion of the metal atoms so that each metal atom is in coordinatively unsaturated state. However, the development of stable monatomic site catalyst synthesis methods is extremely challenging due to the high surface energy of isolated monatomic atoms, which tend to agglomerate into nanoclusters or nanoparticles.
At present, carriers for stabilizing single-atom-site catalysts mainly comprise oxides, metals, carbon materials and the like, and ideal single-atom-site catalyst carriers can stabilize single-atom sites and also have certain intrinsic catalytic activity to realize a synergistic catalytic action. Polyoxometallate, commonly known as polyacid, is a kind of inorganic metal-oxygen cluster compound with nanometer scale formed by connecting polyhedrons formed by early transition metals (mainly high valence ions of Mo, W, V, Nb, Ta and the like) and oxygen through common edges, common angles or common planes. The catalyst has a clear crystalline structure, a large number of coordinatable oxygen atoms, rich element compositions and excellent acid catalysis and oxidation catalytic activities, and is expected to be an excellent single-atom-site catalyst carrier.
In the existing polyacid-based nano catalytic material, polyacid with various structural types is used as a stabilizer to prepare nano particles such as Pt, Pd, Ru, Rh, Ir, Au, Ag and the like, the particle size of the obtained nano particles can be controlled to be between a few nanometers and tens of nanometers, but the larger size of the nano particles causes the lower utilization rate of noble metal atoms in the catalyst, and the cost of the catalyst is high. In a traditional liquid-phase open synthesis system, a polyacid is used as a stabilizer, so that a metal monoatomic site is difficult to prepare. Because a large amount of metal precursor is adsorbed to the surface of the polyacid, when the limited metal anchoring sites on the surface of the polyacid are completely occupied in the reduction process, redundant metal atoms can be agglomerated on the surface of the polyacid to form nanoparticles. Although the size of nanoparticles can be reduced to some extent by reducing the input amount of the metal precursor, the formation of nanoparticles cannot be avoided due to the non-uniformity of spatial distribution caused by the high mobility of the precursor in an open system.
Aiming at the defects of the existing polyacid-based nano catalyst, a new synthesis method of the polyacid-based single atomic 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 @ M1-a polyacid material comprising a MOFs porous metal organic framework material, a polyacid and an active metal M, wherein the active metal M is supported or bound on a polyacid compound in a monoatomic site state, and the polyacid compound is filled in the nanopores of the metal organic framework.
The MOFs are three-dimensional porous metal organic framework materials, can be selected from metal organic framework materials with arbitrary pore sizes of 0.5nm-5nm, preferably 0.5-2nm, and implement MIL-101, HKUST-1 and ZIF-67 materials.
The polyacid is Keggin type polyacid with chemical formula of HnXM12O40X 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 balancing rule is required to be met; preferably dodecamolybdophosphoric acid having the formula H4PMo12O40。
The active metal M is a transition metal capable of being anchored by a polyacid, preferably a noble metal, such as one or more combinations of Pt, Pd, Ru, Rh, Ir, Ag, Au, etc., the M1Indicating that the metal is present in a single atomic site state.
The supporting capacity of polyacid in the material is 5-50 wt%, and the supporting capacity of metal monoatomic is 0.1-2 wt%.
Due to the size limitation of the metal organic framework pore channel, the polyacid and the metal precursor can be orderly and monodispersely arranged in the limited space of the metal organic framework.
Said MOFs @ M1-polyacid material is, MIL-101@ Pt1-PMo、HKUST-1@Pt1-PMo or ZIF-67@ Pt1-PMo, wherein PMo represents H4PMo12O40，M1Indicating that the metal is present in a monoatomic site state.
The invention also discloses a MOFs @ M1A polyacid catalyst comprising porous metal organic framework Materials (MOFs), a polyacid and an active metal, wherein the active metal M1Loaded or bound in a monoatomic site stateAnd on the polyacid compound, the polyacid compound is filled in the nanometer pore canal of the metal organic framework.
The present invention provides MOFs @ M1The preparation method of the polyacid material or the catalyst comprises the steps of synthesizing the MOFs material by using an in-situ synthesis method, simultaneously confining polyacid and an active metal precursor in a pore channel of a metal organic framework, and reducing the active metal according to needs.
The method specifically comprises the following steps: dissolving metal ions and organic ligands which form a metal organic framework, polyacid and active metal precursor in a solvent, reacting under stirring, separating and recovering a sample after reaction, and reducing to obtain MOFs @ M according to needs1-a polyacid material or catalyst.
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 dodecamolybdophosphoric acid with chemical formula of HnXM12O40X 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 long As the balancing rule is satisfied; preferably dodecamolybdophosphoric acid having the formula H4PMo12O40。
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, etc. The active metal precursor is soluble salt or complex of the active metal, including inorganic salt, organic salt or complex, preferably soluble metal chloride, nitrate, acetylacetone salt, acetate, chlorine-containing complex, and ammonia-containing complex, more preferably acetylacetone platinum, chloroplatinic acid, and platinum chloride.
Wherein the supporting amount of polyacid is 5-50 wt%, and the supporting amount of metal monoatomic is 0.1-2 wt%
The in situ synthesis methods include in situ hydrothermal, solvothermal or other conventional synthesis methods. The in-situ synthesis method, namely the MOFs synthesis method, adds polyacid before or simultaneously in the MOFs synthesis process so as to enter the MOFs porous channel. The precursor of the active metal M can be added before the synthesis process of the MOFs, at the same time of the synthesis, or after the MOFs @ polyacid is formed.
The reduction is carried out under a hydrogen atmosphere and is carried out in a reduction apparatus, which is a roasting furnace or kiln capable of providing the required atmosphere and verification temperature, including but not limited to a tube furnace, a protective atmosphere furnace. The reduction is carried out in a hydrogen atmosphere at a temperature of 80-250 ℃, preferably at 120-180 ℃ for a period of 30-480min, preferably 60-120 min.
Before reduction, the polyacid and the metal precursor material carried by the obtained metal organic framework are dried in an oven for 24 to 48 hours at the temperature of between 60 and 100 ℃ according to requirements.
The invention further discloses MOFs @ M1-use of a polyacid catalyst for catalyzing a phenylacetylene diboronation reaction. Preferably MIL-101@ Pt1-use of a PMo catalyst for catalyzing a phenylacetylene diboronation reaction.
The invention also discloses a method for double boronization of phenylacetylene, which uses MOFs @ M1-a polyacid material as a catalyst, the reaction equation is as follows,
said MOFs @ M1Polyacid materials see the previous definition.
The noun explains:
polyacids, also known as Polyoxometalates (POMs), are nanoscale metal-oxygen cluster compounds formed by pre-transition metal ions (such as V, Mo, W, etc.) and oxygen.
The metal organic framework Materials (MOFs) are porous solid molecular materials with periodic network structures, which are formed by taking metal or metal clusters as nodes and organic bridging ligands as connectors through coordination between metal ions and the organic ligands. Wherein MIL-101 is a metal organic framework material which takes Cr as a metal node and terephthalic acid as a ligand; HKUST-1 is a metal organic framework material which takes Cu as a metal node and trimesic acid as a ligand; ZIF-67 is a metal organic framework material which takes Co as a metal node and dimethyl imidazole as a ligand.
MOFs@M1-polyacid, @ denotes M1The polyacid being present in the pores of the MOFs, being encapsulated by the MOFs, M1Indicating that the active metal is in a single atom site state and anchored on the polyacid carrier. PMo is an abbreviated form of dodecamolybdophosphoric acid having the formula H4PMo12O40. MOFs @ M in the present application1Polyacid sometimes written as M1-polyacid @ MOFs, both meaning the same, only written differently, e.g. Pt1-PMo @ MIL-101 and MIL-101@ Pt1PMo is only written differently in this application.
The method can effectively avoid the agglomeration of metal atoms in the reduction process, realize the preparation of the metal single-atom site catalyst with stable polyacid, improve the utilization rate of noble metal atoms and overcome the problems of low activity, high cost and the like of the existing polyacid-based nano catalyst.
Drawings
FIG. 1 is a spherical aberration electron microscope atlas of the Pt monatomic site catalyst of example 1 of the present invention, and the white bright spots circled in the figure are Pt monatomics;
FIG. 2 is an EXAFS plot of a Pt monatomic site catalyst according to example 1 of the present invention, wherein
The left and right are peaks of Pt-O bonds,
the left and right are peaks of Pt-Pt bonds;
FIG. 3 is a spherical aberration electron microscope atlas of the Pt monatomic site catalyst of example 2 of the present invention, and the white bright spots circled in the figure are Pt monatomics;
FIG. 4 is an EXAFS plot of a Pt monatomic site catalyst according to example 2 of the present invention, wherein
The left and right are peaks of Pt-O bonds,
the left and right are peaks of Pt-Pt bonds;
FIG. 5 is a spherical aberration electron microscope atlas of the Pt monatomic site catalyst according to example 3 of the present invention, and the white bright spots circled in the figure are Pt monatomics;
FIG. 6 is an EXAFS plot of a Pt monatomic site catalyst according to example 3 of the present invention, wherein
The left and right are peaks of Pt-O bonds,
the left and right are peaks of Pt-Pt bonds;
FIG. 7 is a transmission electron microscope image of the Pt nanoparticle catalyst of comparative example 1 according to the present invention, in which the white bright spots are Pt nanoparticles;
FIG. 8 is a transmission electron microscope image of the Pt nanoparticle catalyst of comparative example 2 according to the present invention, in which the white bright spots are Pt nanoparticles;
FIG. 9 shows the results of the Pt single-atom-site catalyst of the present invention catalyzing the reaction of phenylacetylene with diboronation, wherein the dark bars represent the conversion rates of different catalysts catalyzing the reaction of diboronation, and the light bars represent the selectivity of the target diboronation product.
Detailed Description
The method for preparing the polyacid-stabilized single-atom-site catalyst provided by the invention is described in detail with reference to specific examples.
The abbreviations used in this example are explained below:
EXAFS: x-ray absorbing fine structure
NPs (neutral phosphorus complexes): nanoparticles
The reaction tube used in the application example was a commercially available reaction tube selected from the group consisting of the Xinville reaction tube, model F891410, and other reaction tubes were used.
Example 1
1.0g of chromium nitrate nonahydrate, 0.42g of terephthalic acid and 1.0g of dodecamolybdophosphoric acid were weighed out and dissolved in 10mL of distilled water and stirred 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. Fully washing the mixture by using N, N' -dimethylformamide and distilled water, and drying the mixture for 24 hours at 80 ℃. 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 then dried at 80 ℃ for 24 hours. Then transferring the product to a tube furnace, and reducing the product for 1 hour at 150 ℃ under a hydrogen atmosphere to obtain MIL-101 supported H3PMo12O40Stable Pt monatomic catalyst (noted as 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 images of Pt single atoms were observed without Pt nanoparticles; as shown in fig. 2, only including Pt-O bonds and no Pt-Pt bonds, illustrates that a Pt single-atom-site catalyst is obtained.
Example 2
25mg of platinum acetylacetonate, 0.25g of copper nitrate trihydrate, 0.3g of dodecamolybdophosphoric acid and 0.23g of trimesic acid were weighed out and dissolved in 50mL of ethanol. The solution was continuously stirred for 12 hours. The resulting precipitate was collected by centrifugation and washed several times with ethanol and distilled water. Drying for 24 hours at 80 ℃. Then transferring the product to a tubular furnace, and reducing the product for 1 hour at 150 ℃ under a hydrogen atmosphere to obtain HKUST-1 supported H3PMo12O40Stable Pt monatomic catalyst (noted as 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 images of Pt single atoms were observed without Pt nanoparticles; as shown in fig. 4, only including Pt-O bonds and no Pt-Pt bonds, illustrates that a Pt single-atom-site catalyst is obtained.
Example 3
0.75g of cobalt nitrate hexahydrate was weighed out and dissolved in 25mL of methanol, and 0.05g of dodecamolybdophosphoric acid was weighed out and dissolved in 10mL of distilled water, and then the two solutions were mixed and stirred for 30 minutes. Then 25mL of a methanol solution containing 1.7g of 2-methylimidazole and 30mg of platinum acetylacetonate were 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. Drying for 24 hours at 80 ℃. Then transferring the product to a tube furnace, and reducing the product at 150 ℃ for 1 hour in a hydrogen atmosphere to obtain H supported by ZIF-673PMo12O40Stable Pt monatomic catalyst (noted as 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 images of Pt single atoms were observed without Pt nanoparticles; as shown in fig. 6, only including Pt-O bonds and no Pt-Pt bonds, illustrates that a Pt single-atom-site catalyst is obtained.
Comparative example 1
20mg of platinum acetylacetonate was dissolved in 10mL of methanol, 1.0g of MIL-101 was added thereto and the mixture was continuously stirred for 12 hours, and after the solid product was centrifuged and washed with methanol several times, 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 obtained product was characterized by transmission electron microscopy, and as shown in FIG. 7, Pt nanoparticles (denoted as Pt NPs @ MIL-101) were found to be generated. Indicating that no monatomic site catalyst could be obtained in the absence of the polyacid.
Comparative example 2
20mg of platinum acetylacetonate and 1g of dodecamolybdophosphoric acid are weighed out and dissolved in 50mL of ethanol and the solution is stirred for 4 hours before the solvent is 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 as Pt NPs @ PMo) were produced. Indicating that a monatomic site catalyst is likewise not available without the presence of a metal-organic framework.
Application examples
Catalytic phenylacetylene diboronation reaction
0.5mmol of phenylacetylene and 0.5mmol of bis (pinacolato) diboron (denoted B)2pin2) Mixing with 20mg of catalyst, placing the mixture into a reaction tube, injecting 2.0mL of toluene, heating the mixed solution to 100 ℃ for reaction, and reacting for 0-48 hours under 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,Pt1@ Y zeolite, catalytic performance results are shown in FIG. 9.
Example 1 a Pt monatomic catalyst prepared with MIL-101 supporting dodecamolybdophosphoric acid was used to catalyze the phenylacetylene diboronation reaction, the monatomic catalyst performance being 7 times that of the corresponding Pt nanoparticle catalyst.
Experimental and application test conclusions:
1. in comparison with the catalysts of comparative examples 1-2, examples 1-3, in which both polyacid and metal-organic framework structures are present, can successfully prepare monatomic site catalysts, without either the stabilization of the polyacid or the confinement of the metal-organic framework, leading to the formation of nanoparticles.
2. In the phenylacetylene diboronation reaction, the Pt monatomic catalyst has obviously improved performance compared with a Pt nanoparticle catalyst, and the monatomic catalyst has a unique catalytic effect.
The above examples are given for the purpose of illustrating the invention clearly and not for the purpose of limiting the same, and it will be apparent to those skilled in the art that, in light of the foregoing description, numerous modifications and variations can be made in the form and details of the embodiments of the invention described herein, and it is not intended to be exhaustive or to limit the invention to the precise forms disclosed.
Claims (10)
1. MOFs @ M1-a polyacid material comprising MOFs porous metal organic framework material, a polyacid and an active metal M, wherein,
the active metal M is a transition metal, preferably a noble metal, which can be anchored by a polyacid, the M1Indicating that the metal exists in a single atomic site state;
the polyacid is Keggin type polyacid with chemical formula of HnXM12O40X 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 balancing rule is required to be met;
the MOFs are three-dimensional porous metal organic framework materials, and can be selected from metal organic framework materials with arbitrary pore sizes of 0.5nm-5nm, preferably 0.5-2 nm;
the polyacid compound is filled in the nanometer 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 material of claim 1, wherein in the material, the active metal M is selected from a combination of one or more of Pt, Pd, Ru, Rh, Ir, Ag, Au; the polyacid is dodecamolybdophosphoric acid with chemical formula H4PMo12O40(ii) a The supporting amount of the polyacid is 5-50 wt%, and the supporting amount of the metal monoatomic is 0.1-2 wt%.
3. The material of claim 1 or 2, wherein the metal organic framework material is selected from one or more combinations of MIL-101, HKUST-1, and ZIF-67 materials.
4. Material according to any of claims 1 to 3, said MOFs @ M1-polyacid material is MIL-101@ Pt1-PMo、HKUST-1@Pt1-PMo or ZIF-67@ Pt1-PMo。
5. MOFs @ M1-a polyacid catalyst comprising the material of any one of claims 1 to 4 as the active part of a catalyst useful for catalyzing the use of phenylacetylene diboronation.
6. MOFs @ M1-a method of preparing a polyacid material or catalyst, the method comprising: synthesizing MOFs material by using an in-situ synthesis method, and simultaneously confining polyacid and an active metal precursor in a pore channel of a metal organic framework; and reducing the active metal as required.
7. The preparation method according to claim 6, wherein the in situ synthesis method is selected from in situ hydrothermal, solvothermal or other conventional synthesis methods for synthesizing MOFs material; adding polyacid before or simultaneously during the synthesis process of MOFs to enter into the MOFs porous channel; the precursor of the active metal M can be added before the synthesis process of the MOFs, at the same time of the synthesis, or after the MOFs @ polyacid is formed.
8. The production method according to claim 6 or 7, comprising: dissolving metal ions and organic ligands which form a metal organic framework, polyacid and active metal precursor in a solvent, reacting under stirring, separating and recovering a sample after reaction, and reducing to obtain MOFs @ M according to needs1-a polyacid material or catalyst; the solvent is selected according to the solubility of raw materials, and preferably water, methanol, ethanol and N, N' -dimethylformamide;
the polyacid is Keggin type dodecamolybdophosphoric acid with chemical formula of HnXM12O40X 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 balancing rule is required to be met; preferably dodecamolybdophosphoric acid having the formula H4PMo12O40；
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 0.5-2nm, preferably MIL-101, HKUST-1 and ZIF-67;
the active metal is transition metal which can be stabilized by polyacid, preferably noble metal, and is selected from one or more combinations of Pt, Pd, Ru, Rh, Ir, Ag, Au and the like;
the active metal precursor is soluble salt or complex of the active metal, including inorganic salt, organic salt or complex, preferably acetylacetone platinum, chloroplatinic acid and platinum chloride.
9. The process according to any one of claims 6 to 8, wherein the supporting amount of the polyacid is 5 to 50% by weight and the supporting amount of the metal monoatomic atom is 0.1 to 2% by weight; the reduction is carried out under a hydrogen atmosphere, and the reduction is carried out in a reduction device which is a roasting furnace or a roasting kiln capable of providing a required atmosphere and a verification temperature, and comprises but is not limited to a tube furnace and a protective atmosphere furnace; the reduction temperature is 80-250 ℃, preferably 120-180 ℃, and the time is 30-480min, preferably 60-120 min.
10. Method for double boronization of phenylacetylene by using MOFs @ M1-a polyacid material as a catalyst, the reaction equation is as follows,
said MOFs @ M1-the polyacid material is selected from any one of claims 1 to 4.
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