CN114904587A - Preparation method of cesium-modified phosphotungstic acid @ UiO-66/porous carbon-based composite material - Google Patents
Preparation method of cesium-modified phosphotungstic acid @ UiO-66/porous carbon-based composite material Download PDFInfo
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- CN114904587A CN114904587A CN202210579623.3A CN202210579623A CN114904587A CN 114904587 A CN114904587 A CN 114904587A CN 202210579623 A CN202210579623 A CN 202210579623A CN 114904587 A CN114904587 A CN 114904587A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002028 Biomass Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 15
- 239000001913 cellulose Substances 0.000 claims abstract description 14
- 229920002678 cellulose Polymers 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 239000011259 mixed solution 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
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 241000219000 Populus Species 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 3
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 3
- 239000011670 zinc gluconate Substances 0.000 claims description 3
- 229960000306 zinc gluconate Drugs 0.000 claims description 3
- 235000011478 zinc gluconate Nutrition 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 2
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 abstract description 11
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 abstract 4
- 239000000463 material Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/56—
-
- 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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Abstract
The invention discloses a preparation method of cesium modified phosphotungstic acid @ UiO-66/porous carbon-based composite material. Belongs to the field of biomass resource utilization, and the composite material is prepared from biomass frame carbon with a porous structure and Cs uniformly distributed in pore channels of a biochar-based material x H 3‑x PW 12 O 40 @ UiO-66. The prepared catalyst is placed in a high-pressure reaction kettle for preparing furfural through cellulose conversion, so that the high-efficiency reaction activity is realized, the reaction condition is mild, the selectivity of 5-hydroxymethylfurfural is excellent, and the reusability is good. In addition, the catalyst has simple synthesis process, simple and convenient recovery mode, low raw material cost, environmental protection and no pollution, and can be used for synthesizing 5-hydroxymethylThe large-scale industrial production of the furfural has profound significance.
Description
Technical Field
The invention belongs to the field of biomass resource utilization, relates to a preparation method of cesium-modified phosphotungstic acid @ UiO-66/porous carbon-based composite material, and particularly relates to a Cs x H 3-x PW 12 O 40 Preparation method of @ UiO-66/biomass porous carbon-based composite material and application thereof in cellulose dehydrationThe application is as follows.
Background
In the prior art, the development and progress of socioeconomic and scientific technologies are highly dependent on traditional fossil resources, and the reserves of the non-renewable resources are increasingly consumed along with the increase of the human demands. Therefore, replacing non-renewable energy sources by renewable energy sources is one of the key steps to achieve sustainable development. Cellulose is a renewable resource with abundant reserves, wide sources and low price in the nature, has the characteristics of cleanness, environmental protection and no pollution, is widely concerned, and is considered to be a biomass utilization mode with attractive force and development potential by converting the cellulose into a chemical product with high added value through catalysis. Among numerous biomass-based derivatives, 5-hydroxymethylfurfural (5-HMF) is an important platform compound, has high economic utilization value and is generally applied to the fields of medicines, petrochemical industry and the like.
The 5-HMF prepared by taking cellulose as a raw material is mainly prepared by a chemical catalysis method, and a catalyst needs to have an acid catalysis site and a base catalysis site at the same time, so that the catalyst has higher requirements on the design of catalysis. Patent CN103028424A discloses a preparation method of a solid acid catalyst for 5-hydroxymethylfurfural synthesis, wherein the solid acid catalyst is oxide-supported sulfate ions or chromium ions, and can be used for synthesizing 5-hydroxymethylfurfural with higher yield. The main active components of the catalyst are sulfate particles and chromium ions, which can burden the environment to a certain extent. Patent CN 109749738A discloses an application of sulfonated carbon quantum dots in preparation of 5-hydroxymethylfurfural, biomass is taken as a raw material, and H is utilized firstly 2 O 2 And preparing the carbon quantum dots with hydroxyl and carboxyl on the surfaces by an auxiliary hydrothermal method, and then sulfonating the carbon quantum dots to finally obtain the sulfonated carbon quantum dots. The sulfonated carbon quantum dots can be used as a catalyst for catalyzing fructose dehydration to generate 5-hydroxymethylfurfural, and have high fructose conversion activity, good 5-HMF yield and excellent stability, but the preparation process of the catalyst needs sulfonation, and certain pollution is caused to the environment.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of cesium modified phosphotungstic acid @ UiO-66/porous carbon-based composite material and an application thereof in cellulose dehydration; the catalyst provided by the invention has the advantages of high catalytic performance, simple synthesis process, simple and convenient recovery mode, excellent reusability, low raw material cost, environmental protection and no pollution, and has profound significance for large-scale industrial production.
The technical scheme of the invention is as follows: the invention discloses a preparation method of cesium modified phosphotungstic acid @ UiO-66/porous carbon-based composite material; the method takes a porous carbon-based material derived from biomass as a carrier, and cesium modified phosphotungstic acid @ UiO-66 (Cs) x H 3-x PW 12 O 40 @ UO-66) as active component, and uniformly dispersing the active component in porous carbon-based material pore channels to obtain cesium-modified phosphotungstic acid @ UO-66/porous carbon-based composite material (namely Cs) x H 3-x PW 12 O 40 @ UiO-66/biomass porous carbon-based composite); the specific operation steps are as follows:
step (1): fully mixing a biomass raw material with a pore-forming agent, wherein the mass ratio of the biomass to the pore-forming agent is (10-1): 1, adding 10-100 mL of ultrapure water, heating to a boiling state, performing reflux treatment for 2-6 h in the boiling state, washing, drying, and then performing N 2 Calcining for 1-4 h at 500-1000 ℃ in the atmosphere, and cooling to room temperature to obtain a porous carbon-based material;
step (2): dissolving metal salt and terephthalic acid by using a mixed solution containing N, N-dimethylformamide and formic acid, adding phosphotungstic acid, and uniformly stirring to obtain H 3 PW 12 O 40 @ UiO-66 precursor solution;
and (3): mixing porous carbon-based material with H 3 PW 12 O 40 Mixing and uniformly stirring the @ UiO-66 precursor solution, and then performing hydrothermal treatment at 100-220 ℃ for 12-40 h; after the reaction is finished, cooling, filtering, stirring and washing for 3 times by ethanol, filtering and drying to obtain H 3 PW 12 O 40 @ UiO-66/biomass porous carbon-based material;
and (4): h is to be 3 PW 12 O 40 Adding the @ UiO-66/biomass porous carbon-based material into the cesium salt solution, and stirring for 6-12Standing for 6-12 h, and rotating and evaporating at 60-100 ℃ to dryness to obtain cesium modified phosphotungstic acid @ UiO-66/porous carbon-based composite material (Cs) x H 3-x PW 12 O 40 @ UiO-66/porous carbon-based material).
Further, in the step (1), the biomass is any one of poplar, bamboo, soybean straw and fruit shell;
the pore-forming agent is any one of zinc acetylacetonate, zinc gluconate, zinc acetate and zinc oxalate;
the mass ratio of the biomass to the pore-forming agent is as follows: 10-1: 1;
the volume of the added ultrapure water is as follows: 10-100 mL;
the boiling state is as follows: 100-120 ℃;
the room temperature: 15 to 30 ℃.
Further, in the step (2), the metal salt is any one of zirconium chloride, hafnium chloride and cerium chloride;
the mass ratio of the phosphotungstic acid to the terephthalic acid to the metal salt is (100-1): 1: (10-1); the volume ratio of the N, N-dimethylformamide to the formic acid in the mixed solution is (20-1): 1.
further, in the step (3), the porous carbon-based material and H 3 PW 12 O 40 The mass ratio of the @ UiO-66 precursor is 1: (50-1).
Further, in the step (4), the cesium salt is any one of cesium carbonate, cesium nitrate and cesium acetate;
the cesium salt and H 3 PW 12 O 40 The mass ratio of the @ UiO-66 to the biomass porous carbon-based material is 1: (50-1).
Further, the Cs prepared by the preparation method x H 3-x PW 12 O 40 The application of the @ UiO-66/porous carbon-based composite material in the cellulose dehydration reaction; the specific conditions are as follows: an application method of catalyzing cellulose to dehydrate and convert in a high-pressure reaction kettle to prepare 5-hydroxymethylfurfural, which comprises the steps of mixing cellulose with a two-phase solvent H 2 O/THF in a mass ratio of 1: (40-80) preparing into a solutionLoading into a high-pressure reaction kettle, and keeping the mass ratio of the catalyst to the cellulose raw material to be 1: (2 to 20), H 2 The volume ratio of O to THF was 1: (6-3) introducing N 2 The protective gas is used, the initial pressure of the system is adjusted to be 0.5-1.5 MPa, the reaction temperature is 160-240 ℃, the heating rate is 5-15 ℃/min, the reaction time is 1-5 h, and the stirring speed is 500-1200 r/min.
The invention has the beneficial effects that: the invention is characterized in that: 1. the method researches the dehydration and conversion of the cellulose to obtain the 5-HMF, can effectively relieve the problem of environmental pollution caused by excessive consumption of fossil energy, reduces the dependence on non-renewable energy, and has a key effect on a sustainable development strategy; 2. the method adopts the porous carbon-based material prepared by using biomass as a precursor as a carrier, and the raw material is natural and renewable, has wide sources, low cost, environmental protection and no pollution; 3. the method optimizes the traditional production process, has simple synthesis process, realizes high-efficiency conversion of cellulose, has simple and high-efficiency recovery mode and excellent recycling performance, and is favorable for large-scale industrial production.
Drawings
FIG. 1 is a flow chart of the operation of the present invention;
FIG. 2 shows Cs obtained in example 4 of the present invention x H 3-x PW 12 O 40 SEM topography of @ UiO-66 (Hf)/porous poplar carbon-based composite material.
Detailed Description
In order to more clearly explain the technical scheme of the invention, the technical scheme of the invention is further explained in detail by combining the drawings as follows:
as shown in the figure, Cs of the present invention x H 3-x PW 12 O 40 @ UiO-66/porous carbon-based composite material, which takes biomass-derived porous carbon-based material as a carrier and cesium-modified phosphotungstic acid @ UiO-66 (Cs) x H 3-x PW 12 O 40 @ UiO-66) as an active component, wherein the active component is uniformly dispersed in pore channels of the porous carbon-based material; the specific operation steps are as follows:
step 1: fully mixing the biomass raw material with a pore-forming agent, wherein the biomass is mixed with the pore-forming agentThe mass ratio of the pore-forming agent is (10-1): 1, adding 10-00 mL of ultrapure water, carrying out reflux treatment for 2-6 h in a boiling state, washing, drying, and then carrying out N 2 Calcining for 1-4 h at 500-1000 ℃ in the atmosphere, and cooling to room temperature to obtain a porous carbon-based material;
step 2: dissolving metal salt and terephthalic acid by using a mixed solution of N, N-dimethylformamide and formic acid, adding phosphotungstic acid, and uniformly stirring to obtain H 3 PW 12 O 40 @ UiO-66 precursor solution;
and step 3: mixing a biomass porous carbon-based material with H 3 PW 12 O 40 Mixing and uniformly stirring the @ UiO-66 precursor solution, and then performing hydrothermal treatment at 100-220 ℃ for 12-40 h; after the reaction is finished, cooling, filtering, stirring and washing for 3 times by using ethanol, filtering and drying to obtain H 3 PW 12 O 40 @ UiO-66/biomass porous carbon-based material;
and 4, step 4: h is to be 3 PW 12 O 40 Adding the @ UiO-66/biomass porous carbon-based material into a cesium salt solution, stirring for 6-12 h, standing for 6-12 h, controlling the temperature to be 60-100 ℃ and rotating to evaporate to dryness to obtain cesium modified Cs x H 3-x PW 12 O 40 @ UiO-66/porous carbon-based composite;
the technical solution of the present invention is further illustrated by the following examples.
Example 1
Mixing 1.5g poplar wood with 1g zinc gluconate, adding 50mL ultrapure water, refluxing for 4 hr under boiling, washing, drying, and adding N 2 Calcining for 2h at 800 ℃ in the atmosphere, and cooling to room temperature to obtain the porous poplar carbon-based material.
Example 2
Dissolving 0.48g of hafnium chloride and 0.27g of terephthalic acid in 54mL of a mixed solution of N, N-dimethylformamide and 6mL of formic acid, and adding 0.3g of phosphotungstic acid to obtain H 3 PW 12 O 40 @ UiO-66 precursor solution.
Example 3
1.0g of biomass porous carbon-based material was mixed with H 3 PW 12 O 40 Mixing and uniformly stirring the @ UiO-66 precursor solution, and then performing hydrothermal treatment at 100-220 ℃ for 12-40 h; after the reaction is finished, cooling, filtering, stirring and washing for 3 times by ethanol, filtering and drying to obtain H 3 PW 12 O 40 @ UiO-66/biomass porous carbon-based material.
Example 4
1g of H 3 PW 12 O 40 Adding the @ UiO-66/biomass porous carbon-based material into 50mL of 5 wt% cesium nitrate solution, stirring for 12h, standing for 12h, controlling the temperature to 60 ℃ and rotating for evaporation to dryness to obtain Cs x H 3-x PW 12 O 40 @ UiO-66/biomass porous carbon-based material.
Example 5
1.0g of the prepared Cs was taken x H 3-x PW 12 O 40 @ UiO-66/biomass porous carbon-based material catalyst, 2.5g cellulose, 20mL distilled water, 30mL tetrahydrofuran were placed in a high pressure autoclave. Introducing nitrogen with the pressure of 1MPa, emptying, and repeating the steps for three times to remove the air in the reaction kettle. The heating temperature is adjusted to 180 ℃, the heating rate is 10 ℃/min, the reaction time is 4h, and the stirring speed is 800 r/min.
Example 6
Several Cs x H 3-x PW 12 O 40 The catalytic performance of @ UiO-66/biomass porous carbon-based material is shown in Table 1, and the reaction conditions are the same as in example 5.
TABLE 1 several Cs x H 3-x PW 12 O 40 Comparing the catalytic performance of the @ UiO-66/biomass porous carbon-based material catalyst;
finally, it should be understood that the embodiments described herein are merely illustrative of the principles of embodiments of the present invention; other variations are also possible within the scope of the invention; thus, by way of example, and not limitation, alternative configurations of embodiments of the invention may be considered consistent with the teachings of the present invention; accordingly, the embodiments of the invention are not limited to the embodiments explicitly described and depicted.
Claims (6)
1. The preparation method of the cesium modified phosphotungstic acid @ UiO-66/porous carbon-based composite material is characterized by comprising the following steps of: uniformly dispersing active components in pore channels of the porous carbon-based material by taking a porous carbon-based material derived from biomass as a carrier and the cesium modified phosphotungstic acid @ UiO-66 as the active components, thereby preparing the cesium modified phosphotungstic acid @ UiO-66/porous carbon-based composite material;
the specific operation steps are as follows:
mixing a biomass raw material with a pore-forming agent, adding ultrapure water, heating to a boiling state, performing reflux treatment for 2-6 h in the boiling state, washing, drying, and then performing N 2 Calcining for 1-4 h at 500-1000 ℃ in the atmosphere, and cooling to room temperature to obtain the porous carbon-based material; standby;
step (2), dissolving metal salt and terephthalic acid by using a mixed solution containing N, N-dimethylformamide and formic acid, adding phosphotungstic acid, and stirring to obtain H 3 PW 12 O 40 @ UiO-66 precursor solution; standby;
step (3) mixing the porous carbon-based material to be used with H 3 PW 12 O 40 Mixing and stirring the @ UiO-66 precursor solution, and then performing hydrothermal treatment at 100-220 ℃ for 12-40 h; after the reaction is finished, cooling, filtering, stirring and washing with ethanol for 3 times, filtering and drying; thereby producing H 3 PW 12 O 40 @ UiO-66/biomass porous carbon-based material;
step (4), the prepared H 3 PW 12 O 40 The @ UiO-66/biomass porous carbon-based material is added into a cesium salt solution, stirred for 6-12 h and then kept stand for 6-12 h, the temperature is controlled to be 60-100 ℃ and then the cesium modified phosphotungstic acid @ UiO-66/porous carbon-based composite material is obtained through rotary evaporation.
2. The method for preparing cesium modified phosphotungstic acid @ UiO-66/porous carbon-based composite material according to claim 1, characterized in that,
in the step (1), the biomass-derived porous carbon-based material is any one of poplar, bamboo, soybean straw and fruit shell;
the pore-forming agent is any one of zinc acetylacetonate, zinc gluconate, zinc acetate and zinc oxalate;
the mass ratio of the porous carbon-based material to the pore-forming agent is as follows: 10-1: 1;
the weight of the added ultrapure water is as follows: 10-100 mL;
the boiling state is: 100-120 ℃;
the room temperature is: 15 to 30 ℃.
3. The preparation method of cesium modified phosphotungstic acid @ UiO-66/porous carbon-based composite material according to claim 1, characterized in that,
in the step (2), the metal salt is any one of zirconium chloride, hafnium chloride and cerium chloride;
in the mixed solution, the volume ratio of the N, N-dimethylformamide to the formic acid is as follows: 20-1: 1;
the mass ratio of the phosphotungstic acid to the terephthalic acid to the metal salt is as follows: 100-1: 1: 10 to 1.
4. The preparation method of cesium modified phosphotungstic acid @ UiO-66/porous carbon-based composite material according to claim 1, characterized in that,
in step (3), the porous carbon-based material is mixed with H 3 PW 12 O 40 The mass ratio of the @ UiO-66 precursor solution is as follows: 1: 50 to 1.
5. The preparation method of cesium modified phosphotungstic acid @ UiO-66/porous carbon-based composite material according to claim 1, characterized in that,
in the step (4), the cesium salt solution is any one of cesium carbonate, cesium nitrate and cesium acetate;
the cesium salt solution with H 3 PW 12 O 40 The mass ratio of the @ UiO-66 to the biomass porous carbon-based material is 1: 50-1.
6. Use of cesium modified phosphotungstic acid @ UiO-66/porous carbon based composite prepared by the preparation method as described in claims 1-5 in cellulose dehydration reaction.
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