CN111841611B - Noble metal monatomic catalyst and preparation method assisted by using notch polyacid - Google Patents
Noble metal monatomic catalyst and preparation method assisted by using notch polyacid Download PDFInfo
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- CN111841611B CN111841611B CN202010774295.3A CN202010774295A CN111841611B CN 111841611 B CN111841611 B CN 111841611B CN 202010774295 A CN202010774295 A CN 202010774295A CN 111841611 B CN111841611 B CN 111841611B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 13
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229940040102 levulinic acid Drugs 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000005530 etching Methods 0.000 claims abstract description 8
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 7
- 238000005342 ion exchange Methods 0.000 claims abstract description 7
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000008188 pellet Substances 0.000 claims description 6
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 6
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- UTXIKCCNBUIWPT-UHFFFAOYSA-N 1,2,4,5-tetrakis(bromomethyl)benzene Chemical compound BrCC1=CC(CBr)=C(CBr)C=C1CBr UTXIKCCNBUIWPT-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- GVONPBONFIJAHJ-UHFFFAOYSA-N imidazolidin-4-one Chemical compound O=C1CNCN1 GVONPBONFIJAHJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Chemical group 0.000 claims description 4
- 239000011733 molybdenum Chemical group 0.000 claims description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000197 pyrolysis Methods 0.000 abstract description 4
- 229920006318 anionic polymer Polymers 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000002028 Biomass Substances 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000013460 polyoxometalate Substances 0.000 description 5
- 241000350481 Pterogyne nitens Species 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- -1 4-imidazolidylphenyl Chemical group 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a noble metal single-atom catalyst, a preparation method assisted by using nicked polyacid, and application of the prepared ruthenium single-atom catalyst in catalyzing levulinic acid to prepare gamma-valerolactone through hydrogenation cyclization. The method mainly comprises the steps of preparing a metal precursor by using notch polyacid, carrying out ion exchange and high-temperature pyrolysis, and then etching to remove a template, wherein the method comprises the following steps: firstly preparing a nicked polyoxometallate (M @ N-POM) with noble metal ions, then replacing the prepared M @ N-POM into an anionic polymer coated on silicon dioxide in an ion exchange mode, finally pyrolyzing the collected powder in an inert atmosphere, then etching by ammonium bifluoride or sodium hydroxide to remove a silicon dioxide template to obtain a target M1@ WO x a/CN monatomic catalyst. The ruthenium monatomic catalyst prepared by the method has excellent reaction effect when being used for preparing gamma-valerolactone by hydrogenation cyclization of levulinic acid, and is superior to the monatomic ruthenium catalyst prepared by the conventional method. The invention has important practical significance for realizing resource utilization of biomass such as levulinic acid and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of monatomic catalysts, and relates to a noble metal monatomic catalyst, a preparation method assisted by using a notched polyacid and application of the monatomic catalyst.
Background
Emerging monatomic catalysts have attracted tremendous interest to scientists due to maximum atom utilization and unsaturated coordination characteristics. Recently, several methods for synthesizing monatomic catalysts have been developed and used. Among them, the wet chemical method is widely used because of its easy processability and low cost. In addition, synthetic methods such as atomic layer deposition and top-down strategies have also been developed to prepare monatomic catalysts. Although various methods of synthesizing monatomic catalysts have been reported, there still remain limitations, particularly with respect to noble metal monatomic catalysts, such as Ru, ag, rh, and the like. Therefore, the development of a novel monatomic catalyst synthesis route is crucial to the practical application of monatomic catalysts.
Currently, materials functionalized by polyoxometallates have been widely used in fields such as medicine, magnetic materials, environmental protection, catalysis, energy conversion, and energy storage materials. In addition, polyoxometalates have other diverse uses, such as showing good application in the development of monatomic catalysts. The Yan topic group reports a platinum monatomic catalyst wherein platinum atoms are supported on the polyoxometalate surface and anchored by the polyoxometalate surface oxygen atoms (angelw. Chem. Int. Ed.2016,55, 8319-8323.). However, since platinum atoms are supported only on the surface of polyoxometallate, this may result in a slight lack of stability of the attached platinum atoms. A notched polyoxometalate is a defective polyoxometalate and can be obtained by adjusting the pH of an aqueous polyoxometalate solution. The controlled defects of the notched polyoxometalates and the versatility of polyoxometalates make them very promising for the preparation of monatomic catalysts.
Disclosure of Invention
Technical problem to be solved
Aiming at the prior technical situation that metals are easy to agglomerate due to high surface free energy of monodisperse metals in the high-temperature reduction or pyrolysis process of the conventional preparation process of the noble metal monatomic catalyst, the method for preparing the noble metal monatomic catalyst by the aid of the nick polyacid is provided, so that the prepared catalyst has high metal loading capacity, and meanwhile, the method can be used for preparing various metal types. Another object of the present invention is to provide the use of the above monatomic catalyst.
Technical scheme
The noble metal single-atom catalyst is characterized by comprising a noble metal supported on a metal oxide cluster M' O x M @ M' O of x (ii)/CN, wherein: the content of M is 0.001 to 10wt percent; the catalyst has the structural feature of a hollow sphere; the M' = tungsten or molybdenum.
The M comprises sulfate, nitrate or acetylacetone salt of Ru, rh or Ag.
The metal oxide cluster M' O x Including tungsten, molybdenum, phosphotungstic/molybdic acid or phosphotungstic/molybdate, or silicotungsten/molybdic acid or silicotungsten/molybdate.
The thickness of the hollow spherical microstructure is 2nm, and the metal loading is 0.001-10 wt%.
A method for preparing a noble metal monoatomic catalyst by using a notched polyacid assistant is characterized by comprising the following steps:
step 1, dissolving 20 g of phosphotungstic acid in hot water, and adding 1g of potassium chloride; adding aqueous sodium bicarbonate solution such that the solution pH =5; filtering after 5-15 minutes, concentrating the filtrate, and standing at room temperature to precipitate white crystals as M @ N-POM;
step 2, replacing the prepared M @ N-POM into the anionic polymer coated on the silicon dioxide in an ion exchange mode: reacting [ Ru (pcymene) Cl 2 ] 2 Addition to 50mL K 7 [PW 11 O 39 ]·14H 2 In aqueous O solution, ru (pcymene) Cl 2 ] 2 And K 7 [PW 11 O 39 ]·14H 2 The molar ratio of O is 1: 2; refluxing the obtained solution for 1-3 h, and filtering by using filter paper; adding excessive CsCl into the filtrate to separate out oily red orange precipitate; recrystallizing the obtained precipitate in boiling water to separate out Cs 5 [PW 11 O 39 {Ru(p-cymene)(H 2 O)}]·6H 2 Thin orange crystals of O, filtered to give a powder;
step 3, adding 0.5-1 g of SiO 2 Adding the pellets into 20mL of DMF solution of tri (4-imidazolidone) amine to obtain emulsion, wherein the amount of the tri (4-imidazolidone) amine is 0.4-0.8 mmol; adding 20mL of 1,2,4,5-tetrakis (bromomethyl) benzene solution in DMF after the obtained emulsion is subjected to ultrasonic treatment at room temperature, wherein the molar ratio of tri (4-imidozolylphenyl) amine to 1,2,4,5-tetrakis (bromomethyl) benzene is 4: 3; after stirring at 100-120 ℃ for 18-32 hours, the reactor is cooled to room temperature, 1mL of benzyl bromide is added to the solution, and the mixture is heated to 70 &Keeping the temperature for 5 to 8 hours at 90 ℃; when the reaction is finished, centrifugally collecting precipitates, washing the precipitates for 2 to 3 times by using DMF (dimethyl formamide), washing the precipitates for 2 to 3 times by using ethanol, and finally drying the precipitates overnight in vacuum at the temperature of between 60 and 80 ℃;
then collecting the powder and Cs 5 [PW 11 O 39 {Ru(p-cymene)(H 2 O)}]·6H 2 Dissolving O in the water solution according to the mass ratio of 3: 2, and carrying out ion exchange at 50-80 ℃ for 18-24 hours; centrifugally separating and drying the ion-exchanged material; then, putting the ion-exchanged substance into a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min in a flowing inert atmosphere, maintaining for 2-3 h, and then naturally cooling to room temperature; etching the obtained substance in water solution at 60-80 deg.C to remove SiO 2 The template is collected by centrifugation, washed by water and ethanol for 2 to 3 times, and finally dried overnight under vacuum at 30 to 50 ℃ to obtain the target noble metal monatomic catalyst.
The etching aqueous solution is etched by using ammonium bifluoride or sodium hydroxide.
The SiO 2 Diameter of the pellet:
the DMF was washed three times and twice with ethanol.
The inert gas is nitrogen or argon.
The application method for preparing the noble metal monatomic catalyst by utilizing the notch polyacid in an auxiliary way is characterized by comprising the following steps: the prepared ruthenium monatomic catalyst is applied to catalyzing levulinic acid hydrogenation cyclization to prepare gamma-valerolactone: 1mL levulinic acid and 10mg Ru1@ WO x the/CN was placed in a 10mL screw-top flask equipped with a stir bar and the mixture was stirred at 20bar H 2 Stirring for 2 hours at the temperature of 100 ℃ under the pressure; ru/substrate =0.08mmol%.
Advantageous effects
The invention provides a noble metal monoatomic catalyst, a preparation method assisted by using a notch polyacid, and application of the prepared ruthenium monoatomic catalyst in catalyzing levulinic acid to prepare gamma-valerolactone through hydrogenation cyclization.The method is mainly prepared by preparing a metal precursor by using a notched polyacid, and removing a template by etching after ion exchange and high-temperature pyrolysis, and comprises the following steps: firstly preparing a nicked polyoxometallate (M @ N-POM) with noble metal ions, then replacing the prepared M @ N-POM into an anionic polymer coated on silicon dioxide in an ion exchange mode, finally pyrolyzing the collected powder in an inert atmosphere, then etching by ammonium bifluoride or sodium hydroxide to remove a silicon dioxide template to obtain a target M1@ WO x a/CN monatomic catalyst. The ruthenium monatomic catalyst prepared by the method has excellent reaction effect when being used for preparing gamma-valerolactone by hydrogenation cyclization of levulinic acid, and is superior to the monatomic ruthenium catalyst prepared by the conventional method. The invention has important practical significance for realizing resource utilization of biomass such as levulinic acid and the like.
Compared with the prior art, the invention has the following advantages and prominent technical effects: (1) the preparation method of the noble metal monatomic catalyst provided by the invention comprises the following steps: the notch polyacid is used as an auxiliary fixing noble metal monoatomic atom to prevent aggregation in the pyrolysis process. Ru, rh and Ag in the material are loaded on the secondary carrier polyacid oxide cluster in a single-atom form and then loaded on the hollow carbon nitride. (2) The Ru, rh and Ag elements in the invention are stabilized by oxygen atoms on the carrier, and have good thermal stability and high metal atom loading concentration. (3) The ruthenium monatomic catalyst has extremely high catalytic activity and selectivity in the reaction of catalyzing levulinic acid to generate gamma-valerolactone through hydrogenation cyclization.
Drawings
FIG. 1 is an image of the Ru monatomic catalyst prepared in example 1 under a high angle annular dark field scanning transmission electron microscope;
FIG. 2 is an image and element distribution under a high-resolution electron microscope of the Ag monatomic catalyst prepared in example 2;
fig. 3 is an image and element distribution under a high-resolution electron microscope of the Rh monatomic catalyst prepared in example 2.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
preparation of Ru1@ WO x /CN:
1) 20 g of phosphotungstic acid was dissolved in 100 ml of hot water, and 1g of potassium chloride was then added to the solution. 1M aqueous potassium bicarbonate solution was added dropwise with vigorous stirring until the pH of the suspension became 5, and filtered after a few minutes. And (4) concentrating the filtrate, standing at room temperature to precipitate white crystals, and drying for later use.
2) Reacting [ Ru (pcymene) Cl 2 ] 2 (0.31g, 0.5mmol) was added to 50mL of K 7 [PW 11 O 39 ]·14H 2 O (3.22g, 1.0 mmol) in an aqueous solution, and the resulting solution was refluxed for 1 hour and then filtered through a filter paper. An excess of CsCl (4.00g, 23.8 mmol) was then added to the filtrate to precipitate an oily reddish orange precipitate. Recrystallizing the obtained precipitate in boiling water, and precipitating Cs after 1 day 5 [PW 11 O 39 {Ru(p-cymene)(H 2 O)}]·6H 2 Orange thin crystals of O. The crystals were filtered off and dried for use.
3) 1g of SiO 2 Pellet (diameter:
) To 20mL of a DMF solution of tri (4-imidazolidylphenyl) amine (TIPA, 0.80mmol,355 mg), the obtained emulsion was sonicated at room temperature for 30 minutes, and then 20mL of a 1,2,4,5-tetrakis (bromomethyl) bezene (TBMB, 0.60mmol, 270mg) DMF solution was added. After the mixture was stirred at 100 ℃ for 24 hours, the reactor was cooled to room temperature, benzyl bromide (1 mL) was added to the solution and the mixture was held at 80 ℃ for an additional 7 hours. When the reaction was complete, the precipitate was collected by centrifugation, then washed three times with DMF, twice with ethanol and finally dried under vacuum at 80 ℃ overnight. The collected powder (300 mg) was then mixed with 200mg Cs 5 [PW 11 O 39 {Ru(p-cymene)(H 2 O)}]·6H 2 O was dissolved and dispersed in 10mL of an aqueous solution, and ion-exchanged at 60 ℃ for 24 hours. The ion-exchanged sample was centrifuged, dried and used. Then, the ion-exchanged sample was placed in a tube furnace, heated to 600 ℃ in flowing Ar gas at a heating rate of 5 ℃/min for 3 hours, and then naturally cooledAnd cooling to room temperature. The obtained sample was etched in 5M aqueous ammonium bifluoride solution at 60 ℃ for 24 hours to remove SiO 2 The template was collected by centrifugation, then washed three times with water and ethanol, and finally dried under vacuum at 30 ℃ overnight.
Example 2
Preparation of Ag1@ WO x /CN:
1) 20 g of phosphotungstic acid was dissolved in 100 ml of hot water, and 1g of potassium chloride was then added to the solution. 1M aqueous potassium bicarbonate solution was added dropwise with vigorous stirring until the pH of the suspension became 5, and filtered after a few minutes. Concentrating the filtrate, standing at room temperature to precipitate white crystal, and drying for use.
2) Will K 7 [PW 11 O 39 ]·12H 2 O (5g, 1.6 mmol) sample was dissolved in 60mL H 2 O, and heating the solution to 50-60 ℃. The second solution, 20mL of AgNO, was added slowly dropwise 3 (0.28g, 1.65mmol) of an aqueous solution, the solution was slightly milky white. In the presence of AgNO 3 The pH is reduced from about 5.8 to 4.7-4.8. The mixture was kept at 50 ℃ for 15 minutes with continuous stirring and then treated with KNO dissolved in 40mL of water 3 (6.0 g,59.3 mmol) was treated to a final pH of 4.5. The solution was filtered and the filtrate was crystallized in the open air.
3) 1g of SiO 2 Pellet (diameter:
) To a 20mL solution of TIPA (0.80mmol, 355mg) in DMF, the emulsion obtained was sonicated at room temperature for 30 minutes, then 20mL of TBMB (0.60mmol, 270mg) in DMF was added. After the mixture was stirred at 100 ℃ for 24 hours, the reactor was cooled to room temperature, benzyl bromide (1 mL) was added to the solution and the mixture was held at 80 ℃ for an additional 7 hours. When the reaction was complete, the precipitate was collected by centrifugation, then washed three times with DMF, twice with ethanol and finally dried under vacuum at 80 ℃ overnight. The collected powder (300 mg) was then mixed with 200mg K 6 [AgPW 11 O 39 ]·12H 2 O was dissolved and dispersed in 10mL of an aqueous solution, and ion-exchanged at 60 ℃ for 24 hours. Ion exchangeThe replaced sample was used after being separated by centrifugation and dried. Then, the ion-exchanged sample was placed in a tube furnace, heated to 600 ℃ in flowing Ar gas at a heating rate of 5 ℃/min for 3 hours, and then naturally cooled to room temperature. The obtained sample was etched in 5M aqueous ammonium bifluoride solution at 60 ℃ for 24 hours to remove SiO 2 The template was collected by centrifugation, then washed three times with water and ethanol, and finally dried under vacuum at 30 ℃ until use.
Example 3
1) Preparation of Rh1@ WO x Adding a small amount of lithium carbonate to 4.3g of H 3 PW 12 O 40 ·xH 2 O (about 1.5 mmol) in 36mL of aqueous solution until the pH reached 4.8, then 2.0g LiCl was added to the solution. To this solution, 0.391g of RhCl, dissolved beforehand in 14mL of water, are added dropwise, with constant stirring 3 ·xH 2 O (1.48 mmol). Finally, the pH was adjusted to 3.6 by adding lithium carbonate. Finally, the mixture was transferred to a 125mL Teflon liner and the hydrothermal temperature was maintained at 150 ℃ for 20h. Then, 1g of (CH) was added to the resulting solution 3 ) 4 NCl, produced an orange precipitate, which was collected by filtration. Washing with deionized water for three times, and air-drying for later use.
2) 1g of SiO 2 Pellet (diameter:
) To a 20mL solution of TIPA (0.80mmol, 355mg) in DMF, the emulsion obtained was sonicated at room temperature for 30 minutes, then 20mL of TBMB (0.60mmol, 270mg) in DMF was added. After the mixture was stirred at 100 ℃ for 24 hours, the reactor was cooled to room temperature, benzyl bromide (1 mL) was added to the solution and the mixture was held at 80 ℃ for an additional 7 hours. When the reaction was complete, the precipitate was collected by centrifugation, followed by three washes with DMF, two washes with ethanol, and finally dried under vacuum at 80 ℃ overnight. The collected powder (300 mg) and 200mg [ (CH) 3 ) 4 N] 5 [PW 11 O 39 RhCl]·H 2 O was dissolved and dispersed in 10mL of an aqueous solution, and ion-exchanged at 60 ℃ for 24 hours. Centrifuging the ion-exchanged sample, dryingThe preparation is used. Then, the ion-exchanged sample was placed in a tube furnace, heated to 600 ℃ in flowing Ar gas at a heating rate of 5 ℃/min for 3 hours, and then naturally cooled to room temperature. The obtained sample was etched in 5M aqueous ammonium bifluoride solution at 60 ℃ for 24 hours to remove SiO 2 The template was collected by centrifugation, then washed three times with water and ethanol, and finally dried under vacuum at 30 ℃ overnight.
Example 4
Levulinic acid (1 mL) and Ru1@ WO x the/CN (10 mg, ru/substrate =0.08 mmol%) was placed in a 10mL screw-top flask equipped with a stir bar, and the mixture was stirred at 20bar H 2 The mixture was stirred at 100 ℃ under pressure for 2 hours. After the reaction was complete, the reaction mixture was analyzed by GC and GC-MS using dodecane as an internal standard, and both the gamma valerolactone yield and selectivity were above 99%.
Claims (9)
1. The noble metal monatomic catalyst is characterized by comprising noble metal supported on a metal oxide cluster M' O x M @ M' O of x a/CN, wherein: the content of M is 0.001 to 10wt percent; the catalyst has the structural morphology characteristic of hollow spheres; the M' = tungsten or molybdenum.
2. The noble metal monoatomic catalyst according to claim 1, wherein: the M comprises sulfate, nitrate or acetylacetone salt of Ru, rh or Ag.
3. The noble metal monoatomic catalyst according to claim 1, wherein: the metal oxide cluster M' O x Including tungsten, molybdenum, phosphotungstic/molybdic acid or phosphotungstic/molybdate, or silicotungsten/molybdic acid or silicotungsten/molybdate.
4. The noble metal monoatomic catalyst according to claim 1, wherein: the thickness of the hollow spherical microstructure is 2nm, and the metal loading is 0.001-10 wt%.
5. A method for preparing the noble metal monatomic catalyst of any one of claims 1 to 4 with the assistance of a notched polyacid, characterized by comprising the steps of:
step 1, dissolving 20 g of phosphotungstic acid in hot water, and adding 1g of potassium chloride; adding aqueous sodium bicarbonate solution such that the solution pH =5; filtering after 5-15 minutes, concentrating the filtrate, and standing at room temperature to precipitate white crystals as M @ N-POM;
step 2, mixing [ Ru (pcymene) Cl 2 ] 2 Addition to 50mL K 7 [PW 11 O 39 ]·14H 2 In aqueous O solution, ru (pcymene) Cl 2 ] 2 And K 7 [PW 11 O 39 ]·14H 2 The molar ratio of O is 1: 2; refluxing the obtained solution for 1-3 h, and filtering by using filter paper; adding excessive CsCl into the filtrate to separate out oily red orange precipitate; recrystallizing the obtained precipitate in boiling water to separate out Cs 5 [PW 11 O 39 {Ru(p-cymene)(H 2 O)}]·6H 2 Orange thin crystals of O, which are filtered off to give a powder;
step 3, adding 0.5-1 g of SiO 2 Adding the pellets into 20mL of DMF solution of tri (4-imidazolidone) amine to obtain emulsion, wherein the amount of the tri (4-imidazolidone) amine is 0.4-0.8 mmol; adding 20mL of 1,2,4,5-tetrakis (bromomethyl) benzene solution in DMF after the obtained emulsion is subjected to ultrasonic treatment at room temperature, wherein the molar ratio of tri (4-imidozolylphenyl) amine to 1,2,4,5-tetrakis (bromomethyl) benzene is 4: 3; stirring for 18-32 hours at 100-120 ℃, cooling the reactor to room temperature, adding 1mL of benzyl bromide into the solution, and keeping the mixture at 70-90 ℃ for 5-8 hours; when the reaction is finished, centrifugally collecting the precipitate, washing the precipitate for 2 to 3 times by using DMF (dimethyl formamide), washing the precipitate for 2 to 3 times by using ethanol, and finally drying the precipitate in vacuum at the temperature of between 60 and 80 ℃ overnight;
then collecting the powder and Cs 5 [PW 11 O 39 {Ru(p-cymene)(H 2 O)}]·6H 2 Dissolving O in the water solution according to the mass ratio of 3: 2, and carrying out ion exchange at 50-80 ℃ for 18-24 hours; centrifugally separating and drying the ion-exchanged material; the ion-exchanged material was then placed in a tube furnace and heated at a rate of 5 deg.C/min in a flowing inert atmosphereHeating to 600 ℃, maintaining for 2-3 h, and then naturally cooling to room temperature; etching the obtained substance in water solution at 60-80 deg.C to remove SiO 2 The template is collected by centrifugation, washed with water and ethanol 2-3 times, and finally dried overnight under vacuum at 30-50 ℃ to obtain the target noble metal monatomic catalyst.
6. The method of claim 5, further comprising: the etching aqueous solution is etched by using ammonium bifluoride or sodium hydroxide.
7. The method of claim 5, wherein: the SiO 2 Diameter:
8. the method of claim 5, further comprising: the DMF was washed three times and twice with ethanol.
9. The method for preparing noble metal monatomic catalyst using a notched polyacid as set forth in claim 5, wherein: the prepared ruthenium monatomic catalyst is applied to catalyzing levulinic acid hydrogenation cyclization to prepare gamma-valerolactone: 1mL levulinic acid and 10mg Ru1@ WO x the/CN was placed in a 10mL screw-top flask equipped with a stir bar and the mixture was stirred at 20bar H 2 Stirring for 2 hours at the pressure of 100 ℃; ru/substrate =0.08mmol%.
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| CN107626294A (en) * | 2017-10-23 | 2018-01-26 | 清华大学 | A kind of preparation method of the monatomic site catalyst of metal |
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