CN111229314B - Carboxyl aryl functionalized MXene material and preparation method and application thereof - Google Patents
Carboxyl aryl functionalized MXene material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- -1 aryl boric acid Chemical compound 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 239000004327 boric acid Substances 0.000 claims abstract description 13
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 8
- 230000033444 hydroxylation Effects 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 125000005026 carboxyaryl group Chemical group 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 150000001543 aryl boronic acids Chemical class 0.000 claims description 8
- 150000002989 phenols Chemical class 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 101150003085 Pdcl gene Proteins 0.000 claims description 4
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000536 complexating effect Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000006193 diazotization reaction Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- WGLQHUKCXBXUDV-UHFFFAOYSA-N 3-aminophthalic acid Chemical compound NC1=CC=CC(C(O)=O)=C1C(O)=O WGLQHUKCXBXUDV-UHFFFAOYSA-N 0.000 abstract 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 description 1
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 description 1
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- ZIQCCIAIROIHHR-UHFFFAOYSA-N benzene;boric acid Chemical compound OB(O)O.C1=CC=CC=C1 ZIQCCIAIROIHHR-UHFFFAOYSA-N 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000011208 chromatographic data Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical group O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0218—Sulfides
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4266—Sonogashira-type, i.e. RY + HC-CR' triple bonds, in which R=aryl, alkenyl, alkyl and R'=H, alkyl or aryl
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- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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Abstract
The invention discloses a carboxyl aryl functionalized MXene material with M n+1 X n ‑Ph(COOH) 2 Structure; wherein M is any one or at least two metal elements in IIIB, IVB, VB, VIB and VIIB groups; x is any one or a combination of two of C, N elements; n is 1, 2 or 3. The carboxyl aryl functionalized MXene material has strong complexing ability with heavy metals, can catalyze the reaction of synthesizing phenol from aryl boric acid, avoids the use of hydrogen peroxide, and improves the safety of the synthesis method. The invention also discloses a preparation method of the MXene material with the carboxyl aryl functionalization, and the MXene material is subjected to alkaline hydrolysis and then is subjected to diazotization reaction with aminobenzene dicarboxylic acid to obtain a new material of the MXene with the carboxyl aryl functionalization. The preparation process is simple and easy to implement, and the conditions are mild. The invention also discloses application of the MXene material with the carboxyl aryl functionalization in wastewater purification and synthesis of phenol by catalyzing aryl boric acid in-situ hydroxylation. The invention also discloses a carboxyl aryl functionalized MXene material supported palladium catalyst, and a preparation method and application thereof.
Description
Technical Field
The invention relates to the technical field of two-dimensional materials, in particular to a carboxyl functionalized MXene material and a preparation method and application thereof.
Background
MXene material is a kind of layered two-dimensional carbonNitride, which is typically extracted from its parent phase material MAX phase (M) by chemical etching n+1 AX n N-1-3, M is a transition metal, a is a group IIIA or IVA element, and X is C or N). Due to high specific surface area, hydrophilicity, adsorbability and high surface reactivity, MXene attracts extensive attention of researchers in many fields and can be used for adsorbing heavy metals, supercapacitors, lithium ion batteries, catalysis and other fields.
Etching of MXene prepared from MAX phase using fluoride-containing acidic solution tends to have groups-OH, -Cl, and-F, abbreviated as M n+1 X n T m Wherein T is m Represents a surface terminal group. Although MXene with specific end groups can be synthesized by post-treatment, there have been few reports to date (MXene based on titanium and molybdenum is used in catalysis, thesis, 2019).
Phenolic compounds play an important role in the prevention and treatment of a wide variety of diseases and have attracted a great deal of interest to chemists. The industrial synthesis of phenolic compounds mainly includes oxidation or hydrolysis of aromatic halide, and has harsh reaction conditions and high production cost. In order to solve the problem, chemists use aryl boric acid to directly carry out in-situ hydroxylation to synthesize phenol, on one hand, the aryl boric acid is low in toxicity; on the other hand, the arylboronic acid has high stability in air, is directly sold in the market and is low in price. Therefore, the reaction for synthesizing phenol using arylboronic acid has received much attention in organic synthesis. The oxidizing agents generally adopted for synthesizing the phenolic compounds by in-situ hydroxylation of the arylboronic acid are oxygen and hydrogen peroxide. The document ACS Sustainable Chemistry & Engineering,2019,7: 9028-. However, the raw material hydrogen peroxide is regulated due to safety problems. Therefore, it is important to develop a new method for synthesizing phenolic compounds by hydroxylation of arylboronic acids.
Disclosure of Invention
The invention provides a carboxyl aryl functionalized MXene material, wherein a p-phthalic acid phenyl group is bonded to the MXene material through a covalent bond through a diazotization reaction, so that the bonding capability of the MXene material and an organic substance and the complexing capability of the MXene material and heavy metals are improved while the structure and the characteristics of the MXene material are maintained. In addition, the MXene material with the carboxyl aryl functionalization can catalyze the benzene boric acid to hydroxylate and synthesize the phenol, so that the use of hydrogen peroxide is avoided, and the safety of the synthesis method is improved.
The technical scheme provided by the invention for solving the technical problems is as follows:
a carboxyaryl functionalized MXene material having M n+1 X n -Ph(COOH) 2 Structure;
wherein the content of the first and second substances,
m is any one or at least two metal elements in IIIB, IVB, VB, VIB and VIIB families; x is any one or the combination of two of C, N elements;
n is 1, 2 or 3;
the-Ph (COOH) 2 Is composed of
Because the benzene dicarboxylate is introduced into the MXene material with the carboxyl aryl functionalization, the MXene material contains rich coordination groups to participate in heavy metal coordination, and the complexing capability of the MXene material and heavy metals is enhanced; and due to the introduction of the aromatic group, the liposolubility of the MXene material under an acidic condition is improved, the hydrophobicity of the MXene material is improved, the MXene material is easier to separate from a water-soluble solvent, and the recovery rate is improved.
And M is any one or at least two metal elements of Ti, Zr, Nb, Ta, V, Mo and Hf.
Said M n+1 X n Is Ti 3 C 2 。
The carboxyl aryl functionalized MXene material is Ti 3 C 2 
The invention also provides a preparation method of the carboxyl aryl functionalized MXene material, which comprises the following steps:
(1) adding MXene material into an alkali water solution, stirring for 6-10 h at 10-40 ℃, separating out precipitate, washing the precipitate with water until the precipitate is neutral, and dispersing in water to obtain a suspension;
(2) ph (COOH) 2 NH 2 And (2) adding the mixture into water, uniformly dispersing, cooling to 0-5 ℃, sequentially adding hydrochloric acid and sodium nitrite, then adding the suspension obtained in the step (1), stirring for 3.5-5 h, separating to obtain a solid, and washing and drying the solid to obtain the carboxyaryl functionalized MXene material.
MXene materials and Ph (COOH) in the step (2) 2 NH 2 The mass ratio of (A) to (B) is 1: 1-2.
The aqueous solution of the alkali is an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide, and the concentration of the aqueous solution of sodium hydroxide or the aqueous solution of potassium hydroxide is 3-8 mol/L.
The MXene material is obtained by etching a MAX phase material, and the specific steps comprise: adding MAX phase materials into LiF/HCl composite solution, stirring for 25-36h at 30-50 ℃, and etching to remove A atomic layer to obtain M n+1 X n T m Said T m F, Cl or OH; the molecular formula of the MAX phase material is M n+1 AX n Wherein A is an element of group IIIA or IVA;
the MAX phase material is Ti 3 AlC 2 。
The hydrochloric acid concentration in the LiF/HCl composite solution is 9-12 mol/L.
The mass ratio of the MAX phase material to the LiF is 1: 1.2-1.5.
The invention also provides application of the carboxyl aryl functionalized MXene material in removing heavy metal ions in wastewater.
The heavy metal is chromium, cadmium, lead and mercury.
The MXene material has stronger adsorption capacity due to modification of carboxyl, is a stronger adsorbent, the introduction of benzene rings in the carboxyl aryl increases the hydrophobicity of the carrier, and the MXene material with the carboxyl aryl function is easy to separate from the wastewater after removing heavy metal ions in the wastewater.
The invention also provides application of the carboxyl aryl functionalized MXene material in catalyzing aryl boric acid to synthesize phenol through in-situ hydroxylation.
The aryl boric acid is phenylboronic acid, p-bromophenylboronic acid or p-methylphenylboronic acid.
The invention also provides a method for synthesizing phenol by catalyzing aryl boric acid by using the MXene material with the carboxyl aryl functionalization, which comprises the following steps:
and adding the MXene material with the carboxyl aryl functionalization, aryl boric acid and alkali into a solvent, and reacting for 4-12 hours at 50-120 ℃ to obtain the corresponding phenolic compound.
The amount of the MXene material with the carboxyl aryl functionalization is 5-25% of the mass of the arylboronic acid.
The quantity ratio of the aryl boric acid to the alkali substance is 1:1 to 3.
The alkali is potassium carbonate, sodium hydroxide or potassium hydroxide.
The solvent is water, benzene or N, N-dimethylformamide.
The MXene material with the functionalized carboxyl aryl can catalyze the aryl boric acid to synthesize the phenolic compound through in-situ hydroxylation, the carboxyl aryl improves the binding capacity of the MXene material and the aryl boric acid, the catalytic performance of the MXene material and the aryl boric acid is improved, and the use of hydrogen peroxide is avoided.
The invention also provides a carboxyl aryl functionalized MXene material supported palladium catalyst. Preferably, the MXene material supported palladium catalyst with the carboxyl aryl functionalization is Ti 3 C 2 
A supported palladium catalyst.
The palladium loading of the MXene material supported palladium catalyst with the carboxyl aryl functionalization is 1-6 wt%.
The preparation method of the MXene material supported palladium catalyst with the carboxyl aryl functionalization comprises the following steps: at the temperature of 20-40 ℃, the MXene material functionalized by the carboxyl aryl group and NaPdCl 4 、PdCl 2 Or K 2 PdCl 6 Adding the mixed solution into a mixed solvent, stirring for 0.5-8h, aging at the temperature of 150 ℃ for 10-26h at the temperature of 100-.
MXene mainly plays a role of a carrier in the catalyst, but is easy to oxidize and can assist Pd in the aging process 2+ Reduction to Pd 0 (ii) a On the other hand, -COOH is also a stronger ligand, can complex to generate a Pd (0) catalyst, which not only can improve the Pd loading capacity, but also can ensure that Pd is uniformly dispersed and is not easy to run off in the reaction process.
The mixed solvent is a mixed solvent of water and alcohols.
The volume ratio of water to alcohol is 1:1 to 5.
The alcohol is methanol.
The carboxyl aryl functionalized MXene material supported palladium catalyst and NaPdCl 4 The mass ratio of (A) to (B) is 1: 0.028-0.17.
The invention also provides application of the MXene material supported palladium catalyst with the carboxyl aryl functionalization in catalytic coupling reaction.
The coupling reaction is Sonogashira cross-coupling reaction.
The invention has the following beneficial effects:
(1) the carboxyl aryl functionalized MXene material provided by the invention has strong complexing ability with heavy metal and can efficiently remove heavy metal ions.
(2) The carboxyl aryl functionalized MXene material provided by the invention can effectively catalyze the hydroxylation reaction of arylboronic acid, the reaction condition is mild, the pollution is small, the catalyst can be repeatedly used, and the activity is not obviously reduced.
(3) The carboxyl aryl functionalized MXene material provided by the invention can be effectively combined with a Pd catalyst, so that on one hand, the Pd catalytic activity center can be uniformly dispersed, and the loss in the reaction process can be avoided; on the other hand, the obtained catalyst can be repeatedly used for multiple times without obvious reduction of activity.
Drawings
FIG. 1 is a scanning electron micrograph of the product obtained in example 1.
FIG. 2 is an infrared spectrum of the product obtained in example 1.
FIG. 3 is a graph showing the activity of the catalyst of application example 3 repeatedly used in an aqueous Sonogashira reaction.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1 Ti 3 C 2 
Preparation of (2)
(1) Etching of Ti 3 AlC 2 ：
After LiF (2.6g) was dissolved in 30ml of a 12mol/L hydrochloric acid solution and 9ml of water at room temperature, the solution was heated to 40 ℃ and stirred for 10 min; mixing Ti 3 AlC 2 (2g) Adding small amount of the above solution, stirring at 40 deg.C for 27 hr, and completely removing Al element to obtain accordion-shaped Ti 3 C 2 The multi-layer MXene material with the structural formula is prepared by centrifuging, washing, ultrasonically treating and vacuum drying the mixture to obtain Ti 3 C 2 T m (MXene materials), T m Is a surface group F, Cl or OH.
(2) Subjecting 1.0g of Ti obtained in step 1 to 3 C 2 T m Adding into 20ml of 4mol/L KOH solution, stirring at room temperature for 7h, centrifuging to obtain solid precipitate, washing the solid with water until the eluate is neutral, and removing the solid precipitateThe solid was then dispersed in 10ml of water to give a suspension.
(3)Ti 3 C 2 
The synthesis of (2):
adding 2-amino terephthalic acid (0.5g) into water, performing ultrasonic treatment for 25min to disperse uniformly, and stirring at 0 ℃ for 30min to obtain yellow suspension; adding 13.5ml of 4.2mol/L hydrochloric acid at 0 ℃, fully stirring, adding 10ml of 0.52mol/L sodium nitrite solution, and continuously stirring for 3 hours to obtain a white solution; the suspension obtained in step (2) is added to this solution and stirred for 4 h. The whole experiment process is carried out at the temperature of 0-5 ℃.
After the reaction is finished, centrifugally separating, taking precipitate, washing with water, washing with alcohol, and drying in an oven for 6 hours to obtain a product Ti 3 C 2 
The microstructure of the product was observed by a Scanning Electron Microscope (SEM), and as a result, the product showed a layered structure as shown in fig. 1. Detecting functional groups on the surface of the product by using an infrared spectrometer, wherein the result is shown in figure 2 and is 3500-3000 cm -1 Corresponding to the absorption peak of O-H, 1620cm in FIG. 2 -1 The absorption peak at (a) is characteristic of C ═ O in the carboxyl group, indicating that the carboxyaryl group has been bonded to MXene.
Application example 1 Ti 3 C 2 
Adsorption removal of Cd as adsorbent 2+
10mg of Ti were added in order to the flask 3 C 2 
And 20ml of an acidic metal ion solution (Cd) 2+ Is 20mg/L), then placing the mixture into an oscillator to react for 2 hours at the temperature of 25 ℃, centrifugally separating, taking supernatant, analyzing the content of metal ions by ICP (inductively coupled plasma), and calculating the adsorption rateUp to 99%.
Application example 2 Ti 3 C 2 
Catalytic phenylboronic acid hydrolysis reaction
10mg of Ti were sequentially added to a 25ml open reaction tube 3 C 2 
0.5mmol of phenylboronic acid, 1.0mmol of potassium carbonate and 3ml of water, and heating them to 80 ℃ with stirring, allowing them to react well for 6 h. After the reaction was complete, the organics were extracted with ethyl acetate and analyzed by GC-MS. From the chromatographic data, the conversion of the reactant was 89%, wherein the yield of the target product phenol was 89%.
Example 2 Ti 3 C 2 
Preparation of supported palladium catalyst
200mg of Ti thus obtained 3 C 2 
Adding 5ml of water and 15ml of methanol, stirring at 30 ℃ for 30min, and adding NaPdCl into the mixed solution 4 (0.01g), stirring for 1h, aging in a hydrothermal kettle at 120 deg.C for 16h, centrifuging, washing with water and alcohol for several times, and vacuum drying for 10h to obtain Ti catalyst 3 C 2 
A supported palladium catalyst.
The Pd loading was 1.80 wt%. Through nitrogen adsorption-desorption isotherm tests, the specific surface area of the catalyst is reduced, the successful loading of the Pd catalyst is proved, and the actual loading amount of the catalyst in an ICP-MS test is 1.75 wt%.
Application example 3 Ti 3 C 2 
Load type palladium catalyst for catalyzing Sonogashira cross-coupling reaction
10mgTi was sequentially added to a 25ml reaction tube 3 C 2 
A supported palladium catalyst, 0.5mmol bromobenzene, 0.75mmol phenylacetylene, 1.0mmol triethylamine and 3ml water were heated to 80 ℃ with stirring and allowed to react sufficiently for 5 hours. And after the reaction is finished, centrifugally filtering the reaction solution, taking the lower-layer solid as the catalyst, washing the catalyst with ethyl acetate to obtain an eluate, extracting the supernatant with ethyl acetate, combining the supernatant with the extract, and analyzing the extract by GC-MS. Calculated from gas chromatography data, the conversion of the reactants was 98%, both of which were the target product diphenylacetylene. The content of Pd in the recovered catalyst by ICP-MS test was 1.72 wt%. As shown in fig. 3, the activity was not significantly reduced by repeated use.
Claims (8)
1. A carboxyaryl functionalized MXene material, wherein the carboxyaryl functionalized MXene material has M n+1 X n -Ph(COOH) 2 Structure;
wherein, M is n+1 X n -Ph(COOH) 2 Is Ti 3 C 2 
2. A method of preparing the carboxyaryl functionalized MXene material of claim 1, comprising the steps of:
(1) adding MXene material into an alkali water solution, stirring for 6-10 h at 10-40 ℃, separating out precipitate, washing the precipitate with water until the precipitate is neutral, and dispersing in water to obtain a suspension;
(2) ph (COOH) 2 NH 2 And (2) adding the mixture into water, uniformly dispersing, cooling to 0-5 ℃, sequentially adding hydrochloric acid and sodium nitrite, then adding the suspension obtained in the step (1), stirring for 3.5-5 hours, separating to obtain a solid, washing and drying the solid to obtain the MXene material with the carboxyl aryl functionalization.
3. Use of the carboxyaryl functionalized MXene material of claim 1 for the removal of heavy metal ions from wastewater.
4. Use of the carboxyaryl functionalized MXene material of claim 1 in the catalytic in situ hydroxylation of arylboronic acids to produce phenols.
5. The method for synthesizing phenol by catalyzing arylboronic acid by the carboxyaryl functionalized MXene material according to claim 1, specifically comprising the following steps: and adding the MXene material with the carboxyl aryl functionalization, aryl boric acid and alkali into a solvent, and reacting for 4-12 hours at 50-120 ℃ to obtain the corresponding phenolic compound.
6. A Pd catalyst, characterized in that the Pd catalyst is a carboxyaryl functionalized MXene material supported Pd catalyst, supported by the carboxyaryl functionalized MXene material of claim 1; the palladium loading of the MXene material supported palladium catalyst with the carboxyl aryl functionalization is 1-6 wt%.
7. A method for preparing the Pd catalyst according to claim 6, comprising the steps of: under the temperature of 20-40 ℃, the MXene material functionalized by the carboxyl aryl group and NaPdCl 4 、PdCl 2 Or K 2 PdCl 6 Adding into the mixed solvent to be stirred for 0.5-8h, aging for 10-26h at the temperature of 100 ℃ and 150 ℃, separating and drying to obtain the carboxyl aryl functionalizedMXene material supported palladium catalyst.
8. Use of the Pd catalyst of claim 6 in catalyzing an aqueous Sonogashira coupling reaction.
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