CN111302992A - Mercapto aryl functionalized MXene material and preparation method and application thereof - Google Patents
Mercapto 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 80
- 238000002360 preparation method Methods 0.000 title description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 9
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 9
- 238000006053 organic reaction Methods 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000003021 water soluble solvent Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000007306 functionalization reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910009818 Ti3AlC2 Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Substances SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/26—Thiols
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0217—Mercaptans or thiols
-
- 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
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
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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
- 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
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses an MXene material with M mercapto aryl functionalization, which is called mercapto aryl-MXene material for shortn+1Xn- (Ph-SH) structure; wherein M is any one of IIIB, IVB, VB, VIB and VIIBOr at least two metal elements; x is any one or the combination of two of C, N elements; n is 1, 2 or 3. The mercapto aryl is used as a surface group to enhance the oxidation resistance and structural stability of the MXene material; improves MXene material and reduction product Cr3+The binding ability of (c); meanwhile, the solubility of the MXene material in the wastewater is reduced, and the separation of the MXene material and the water-soluble solvent is facilitated. The invention also discloses a mercapto aryl-MXene material supported palladium catalyst. The mercapto aryl improves the adsorption capacity of the mercapto aryl-MXene material supported palladium catalyst on an organic reaction substrate, and is beneficial to the combination of the mercapto aryl-MXene material and the organic reaction substrate, so that the activity of the catalyst is improved.
Description
Technical Field
The invention relates to the technical field of two-dimensional materials, in particular to a sulfydryl functionalized MXene material and a preparation method and application thereof.
Background
MXene materials are layered nanometer two-dimensional materials with novel structures and unique properties, have attracted extensive attention and research due to the properties of high specific surface area, high aspect ratio, unique electronic structures and the like since being discovered in 2011, and are widely applied to the fields of energy storage, environmental improvement and the like at present.
MXene is typically extracted from its parent phase material MAX phase (M) by chemical etchingn+1AXnN is 1-3, M is a transition metal and can be one or more of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Au, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, La and Ce; a is IIIA or IVA group element, X is C or N), the reaction process is as follows:
2Ti3AlC2+6HF＝2AlF3+3H2↑+2Ti3C2；
Ti3C2+2H2O＝Ti3C2(OH)2+H2↑；
Ti3C2+2HF＝Ti3C2F2+H2↑。
there are more than 20 types of MXene that can be successfully synthesized at present, and their properties vary due to differences in elemental composition and layer structure. For example, Master academic thesis (alumina and MX)ene(Ti3C2) Catalytic hydrogenation performance research of supported palladium catalyst, Zhejiang industrial university, 2018) discloses a Pd/Ti catalyst3C2NaOH and Pd/Ti3C2-HM catalyst and its use in the catalytic hydrogenation of vanillin. Literature (ACS Applied Materials)&Interfaces, 2015, 7: 1795-3C2Tx MXene adsorption reduction Cr6+Thereby achieving the aim of detoxification. The Chinese patent application with the publication number of CN108275683A discloses a metal-based composite material and application thereof as a corrosion-resistant material, comprising a metal substrate and a material M directly coated on the surface of the metal substraten+1Xn(Tm) MXene film layer of the formula TmIs the terminal group on the surface of MXene material.
However, the exposed metal atoms on the surface of the two-dimensional MXene are easily oxidized in oxygen-rich environment such as air and water, so that the partial phase of the carbon/nitride MXene is converted into oxide, thereby limiting the industrial application of the novel two-dimensional material.
Disclosure of Invention
The invention provides a sulfydryl-MXene material, which is bonded to the MXene material through a covalent bond through diazotization reaction, so that the oxidation resistance and the structural stability of the MXene material are improved, the hydrophobicity of the material is enhanced, and the material is easy to separate and remove from a water-soluble solvent.
The technical scheme provided by the invention for solving the technical problems is as follows:
the mercapto-functionalized MXene material is mercapto aryl-MXene material and has Mn+1Xn- (Ph-SH) 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 groups;
x is any one or the combination of two of C, N elements;
n is 1, 2 or 3;
the Ph-SH is
The mercapto aryl-MXene material has high mercapto aryl electron cloud density due to introduction of the mercapto aryl, improves the oxidation resistance and structural stability of the MXene material, has fat-soluble aromatic groups, enhances the hydrophobicity of the material, and is easy to separate and remove from a water-soluble solvent especially under an acidic condition.
And M is any one or at least two metal elements of Ti, Zr, Nb, Ta, V, Mo and Hf.
Said Mn+1XnIs Ti3C2。
The MXene material is Ti3C2 
The invention also provides a preparation method of the mercapto aryl-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 with water to neutrality, and dispersing in water to obtain a suspension; removing F, Cl groups in MXene materials;
(2) adding amino thiophenol into water, uniformly dispersing, cooling to 0-5 ℃, sequentially adding hydrochloric acid and sodium nitrite, adding the suspension obtained in the step (1), stirring for 3.5-5h, separating to obtain a solid, washing and drying the solid to obtain the mercaptoaryl-MXene material.
The mass ratio of the MXene material to the amino thiophenol in the step (2) is 1: 0.6-1.5.
The aqueous solution of the alkali is aqueous solution of sodium hydroxide or aqueous solution of potassium hydroxide, and the concentration of the aqueous solution of the sodium hydroxide or the aqueous solution of the potassium hydroxide is 4-8 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 Mn+1XnTmSaid TmF, Cl or OH; the molecular formula of the MAX phase material is Mn+1AXnAnd A is IIIA or IVA group element.
The MAX phase material is Ti3AlC2。
The concentration of hydrochloric acid 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 mercapto aryl-MXene material in heavy metal ion removal.
The Mxene material can oxidize Cr easily6+Reduction to Cr3+The mercapto aryl group with reducibility can also be used as a reducing agent; in addition, the mercaptoaryl is also a stronger ligand, has strong capability of adsorbing metal ions, and can effectively adsorb reduced Cr3+And the introduction of the sulfydryl also increases the hydrophobicity of the carrier, so that the sulfydryl-MXene material is easy to separate from the wastewater after removing heavy metal ions in the wastewater.
The heavy metal is Cr element.
The invention also provides a mercapto aryl-MXene material supported palladium catalyst.
The palladium loading amount in the mercapto aryl-MXene material supported palladium catalyst is 0.5-3 wt%.
The preparation method of the mercapto aryl-MXene material supported palladium catalyst comprises the following steps: mercaptoaryl-MXene materials with Pd (OAc) at 20-40 ℃2Or PdCl2After mixing, carrying out ultrasonic treatment for 5-10h, separating and drying to obtain the sulfydryl-MXene material supported palladium catalyst.
MXene mainly plays a role of a carrier in the catalyst, but is easy to oxidize and can assist Pd under the action of ultrasonic waves2+Reduction to Pd0(ii) a The sulfydryl (-SH) can be used as a reducing agent on one hand, and the sulfydryl SH is also a stronger ligand on the other hand, and can be used as a Pd (0) catalyst generated by complexation, so that the load capacity of Pd (0) can be improved, and the Pd (0) can be uniformly dispersed and is not easy to lose in the reaction process.
The mercaptoaryl-MXene materials with Pd (OAc)2Or PdCl2The mass ratio of (A) to (B) is 1: 0.005-0.06.
The invention also provides application of the mercapto aryl-MXene material supported palladium catalyst in catalyzing organic coupling reaction.
The organic coupling reaction is Suzuki coupling reaction.
The hydrosulfuryl aryl-MXene material is used as a carrier of Pd, and according to the principle of similarity and intermiscibility, the adsorption capacity of an organic reaction substrate in a fat-soluble environment is improved, so that the combination of the hydrosulfuryl aryl-MXene material and the organic reaction substrate is facilitated, the contact between the Pd as an active center of the catalyst and the organic reaction substrate is improved, and the activity of the catalyst is improved.
The invention has the following beneficial effects:
(1) the invention realizes the introduction of-PhSH as a surface group in the MXene material for the first time, and improves the MXene material and the reduction product Cr3+The binding ability of (c); meanwhile, the solubility of the MXene material in the wastewater is reduced, and the separation of the MXene material and the solvent is facilitated.
(2) The sulfydryl-MXene material is used as a Pd carrier, and the sulfydryl-MXene material has a high specific surface area and rich active adsorption sites, so that the dispersion and protection of catalytic activity are facilitated; and the introduction of the aromatic sulfydryl further improves the adsorption capacity of the organic reaction substrate, is beneficial to the combination of the sulfydryl-MXene material and the organic reaction substrate, and is beneficial to the improvement of the catalyst 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 an X-ray diffraction pattern of the product obtained in example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. 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 Ti3C2 
Preparation of
(1) Etching of Ti3AlC2：
After LiF (1.4g) was dissolved in 15ml of a 12mol/L hydrochloric acid solution and 4.5ml of water at room temperature, the solution was heated to 40 ℃ and stirred for 10 min; mixing Ti3AlC2(1g) Adding small amount of the above solution, stirring at 40 deg.C for 24 hr, and completely removing Al element to obtain accordion-shaped Ti3C2The multi-layer MXene material with the structural formula is prepared by centrifuging, washing, ultrasonically treating and vacuum drying the mixture to obtain Ti3C2Tm(MXene materials), TmIs a surface group F, Cl or OH.
(2) 0.5g of Ti obtained in the step (1)3C2TmAdding into 10ml of 4mol/L sodium hydroxide alkali solution, stirring at room temperature for 8h, centrifuging, washing the solid with water until the eluate is neutral, and dispersing the solid in 5ml of water to obtain a suspension.
(3)Ti3C2 
The synthesis of (2):
adding p-aminophenol (0.5g) into 10ml of water, performing ultrasonic treatment for 30min, and stirring for 1h at the temperature of 0 ℃ to obtain a white mixed solution; 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 4 hours to obtain a brownish red solution; the suspension obtained in step (2) is added to this solution and stirred for 5 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 a vacuum oven for 6 hours to obtain the product, namely the Ti with the mercapto-functionalized3C2：Ti3C2 
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 ranges from 3100 cm to 3000cm-1，1600～1400cm-1Characteristic peaks of the benzene ring backbone appear, confirming that the mercaptoaryl group has been successfully bonded to the MXene material through a covalent bond. The product was subjected to phase analysis by X-ray diffractometer, and the result is shown in FIG. 3, wherein Ti is3AlC2Disappearance of characteristic peaks, Ti3C2TmCharacteristic peaks appear.
Application example 1 Ti3C2 
Adsorption removal of Cr as adsorbent6+
At room temperature, 20mg of Ti3C2 
Adding the solution into 20ml of 200mg/L acid potassium dichromate solution, stirring for 12h, centrifugally separating to remove the adsorbent, measuring the content of Cr ions in the solution by an ultraviolet-visible spectrophotometer method and ICP-MS, and calculating to obtain the adsorption rate of 98%.
Example 2 Ti3C2 
Preparation of supported palladium catalyst
0.2g of Ti obtained in example 1 was added3C2 
Adding 10ml water, stirring at 25 deg.C for 30min, adding Pd (OAc)2(3ml 0.6mg/m1), ultrasonic processing for 6h, centrifuging, washing with water and ethanol for multiple times, and vacuum drying for 8h to obtain catalystTi3C2 
The supported palladium catalyst had a Pd loading of 0.42 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 ICP-MS tests is 0.39 wt%.
Application example 2 Ti3C2 
Supported palladium catalyst for catalyzing Suzuki reaction
Bromobenzene (78mg, 0.50mmol, 1eq) and phenylboronic acid (120mg, 1.0mmol, 2eq), 15mg Ti were added to the reaction tube3C2 
Reacting the mixture in a supported palladium catalyst, 2ml of water, 1ml of ethanol and potassium carbonate (104mg, 0.75mmol) at 60 ℃ for 6 hours, extracting a reaction solution by using ethyl acetate after the reaction is finished, analyzing an obtained organic layer by GC-MS, and calculating the yield of a reaction product to be 96% according to the result of the GC-MS.
Claims (10)
1. The mercapto-functionalized MXene material is characterized in that the mercapto-functionalized MXene material is a mercapto aryl-MXene material and has Mn+1Xn- (Ph-SH) 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-SH is
2. The mercapto-functionalized MXene material of claim 1, wherein M is any one or at least two metal elements selected from Ti, Zr, Nb, Ta, V, Mo, and Hf.
3. The mercapto-functionalized MXene material of claim 1, wherein M is selected from the group consisting ofn+1XnIs Ti3C2。
4. The mercapto-functionalized MXene material of claim 1, wherein M is selected from the group consisting ofn+1Xn- (Ph-SH) is Ti3C2 
5. A method for preparing the mercapto-functionalized MXene material according to any one of claims 1-4, 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 with water to neutrality, and dispersing in water to obtain a suspension;
(2) adding amino thiophenol into water, uniformly dispersing, cooling to 0-5 ℃, sequentially adding hydrochloric acid and sodium nitrite, adding the suspension obtained in the step (1), stirring for 3.5-5h, separating to obtain a solid, washing and drying the solid to obtain the mercaptoaryl-MXene material.
6. Use of the mercapto-functionalized MXene material according to any one of claims 1 to 4 for heavy metal ion removal.
7. The Pd catalyst for the mercapto-functionalized MXene material according to any one of claims 1-4, wherein the Pd catalyst is a palladium catalyst supported on mercapto aryl-MXene material.
8. The Pd catalyst as claimed in claim 7, wherein the palladium loading in the mercaptoaryl-MXene material supported palladium catalyst is in the range of 0.5-3 wt%.
9. A method for preparing the Pd catalyst according to claim 7, comprising the steps of: mercaptoaryl-MXene materials with Pd (OAc) at 20-40 ℃2Or PdCl2And after mixing and ultrasonic treatment for 5-10h, separating and drying to obtain the sulfydryl-MXene material supported palladium catalyst.
10. Use of the Pd catalyst of claim 7 in catalyzing a Suzuki coupling reaction.
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| CN111939953A (en) * | 2020-08-17 | 2020-11-17 | 杭州电子科技大学 | Preparation method of MXene-based catalyst for preparing furfural with high selectivity |
| CN115814828A (en) * | 2022-11-17 | 2023-03-21 | 天津大学 | Method for changing pollutant degradation path of peroxymonosulfate by using copper distribution mode and preparation method and application of composite catalyst |
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| CN110540236A (en) * | 2019-09-09 | 2019-12-06 | 中国科学院宁波材料技术与工程研究所 | MXene material and preparation method and application thereof |
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| CN115814828A (en) * | 2022-11-17 | 2023-03-21 | 天津大学 | Method for changing pollutant degradation path of peroxymonosulfate by using copper distribution mode and preparation method and application of composite catalyst |
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