CN111302992B - 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 69
- 238000002360 preparation method Methods 0.000 title description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 229910002666 PdCl2 Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 238000006053 organic reaction Methods 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000003021 water soluble solvent Substances 0.000 abstract description 3
- 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 10
- 238000006243 chemical reaction Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 101150003085 Pdcl gene Proteins 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
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 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
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052758 niobium Inorganic materials 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
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910009819 Ti3C2 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000002910 aryl thiol group Chemical group 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
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry 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
- 239000011156 metal matrix composite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification 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
- 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
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 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
- 230000009466 transformation Effects 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
- 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
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- 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
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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
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- 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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Abstract
Description
技术领域technical field
本发明涉及二维材料技术领域，具体涉及一种巯基功能化的MXene材料及其制备方法和应用。The invention relates to the technical field of two-dimensional materials, in particular to a thiol-functionalized MXene material and a preparation method and application thereof.
背景技术Background technique
MXene材料是一类结构新颖、性质独特的层状纳米二维材料，自2011年被发现以来，因其高比表面积、高纵横比、具有独特的电子结构等性质而受到广泛的关注和研究，目前已被广泛应用于能源存储以及环境治理等领域。MXene materials are a class of layered nano-2D materials with novel structures and unique properties. Since their discovery in 2011, they have received extensive attention and research due to their high specific surface area, high aspect ratio, and unique electronic structure. At present, it has been widely used in the fields of energy storage and environmental governance.
MXene通常通过化学蚀刻法抽离其母相材料MAX相(Mn+1AXn，n＝1-3，M为过渡金属，可以为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、Ce中的一种或多种；A为IIIA或IVA族元素，X为C或N)中的A层原子层得到，其反应过程如下：MXene is usually extracted from its parent material MAX phase (Mn +1 AX n , n=1-3, M is a transition metal, which can be Sc, Ti, V, Cr, Mn, Fe, Co, Ni) by chemical etching. , one or more of Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Au, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, La, Ce; A is a group IIIA or IVA element, and X is obtained from the atomic layer of the A layer in C or N), and the reaction process is as follows:
2Ti3AlC2+6HF＝2AlF3+3H2↑+2Ti3C2；2Ti 3 AlC 2 +6HF=2AlF 3 +3H 2 ↑+2Ti 3 C 2 ;
Ti3C2+2H2O＝Ti3C2(OH)2+H2↑；Ti 3 C 2 +2H 2 O=Ti 3 C 2 (OH) 2 +H 2 ↑;
Ti3C2+2HF＝Ti3C2F2+H2↑。Ti 3 C 2 +2HF=Ti 3 C 2 F 2 +H 2 ↑.
目前能够成功合成的MXene类型多于20种，由于元素组成和层结构的不同它们的性质也各异。如，硕士学位论文(氧化铝及MXene(Ti3C2)负载钯催化剂的催化加氢性能研究，浙江工业大学，2018)公开了一种Pd/Ti3C2-NaOH和Pd/Ti3C2-HM催化剂及其在香草醛催化加氢反应中的应用。文献(ACS Applied Materials&Interfaces，2015，7：1795-1803)使用Ti3C2Tx MXene吸附还原Cr6+，从而达到去毒目的。公开号为CN108275683A的中国发明专利申请公开了一种金属基复合材料及其作为耐腐蚀材料中的应用，包括金属基底以及直接包覆在所述金属基底表面的具有Mn+1Xn(Tm)的结构式的MXene材料膜层，Tm为MXene材料表面的末端基团。There are currently more than 20 types of MXenes that can be successfully synthesized, and their properties vary due to their elemental composition and layer structure. For example, the master's thesis (Research on the catalytic hydrogenation performance of alumina and MXene (Ti 3 C 2 ) supported palladium catalyst, Zhejiang University of Technology, 2018) disclosed a kind of Pd/Ti 3 C 2 -NaOH and Pd/Ti 3 C 2 -HM catalyst and its application in the catalytic hydrogenation of vanillin. Literature (ACS Applied Materials & Interfaces, 2015, 7: 1795-1803) used Ti 3 C 2 Tx MXene to adsorb and reduce Cr 6+ to achieve detoxification. The Chinese invention patent application with publication number CN108275683A discloses a metal matrix composite material and its application as a corrosion-resistant material, including a metal base and a metal base directly coated on the surface of the metal base with Mn + 1Xn (T m ) of the MXene material film layer, where T m is the terminal group on the surface of the MXene material.
然而，二维MXene表面裸露的金属原子在富氧环境如空气和水中易被氧化，导致碳/氮化物MXene部分相变成氧化物，从而限制了这种新型二维材料的工业化应用。However, the exposed metal atoms on the surface of 2D MXenes are easily oxidized in oxygen-rich environments such as air and water, resulting in partial phase transformation of carbon/nitride MXenes into oxides, thus limiting the industrial application of this novel 2D material.
发明内容SUMMARY OF THE INVENTION
本发明提供了一种巯芳基-MXene材料，通过重氮化反应将巯芳基通过共价键键合到MXene材料上，提升了MXene材料的抗氧化性能和结构稳定性，增强了材料疏水性，使其易于从水溶性溶剂中分离去除。The invention provides a mercaptoaryl-MXene material, which can bond the mercaptoaryl group to the MXene material through a covalent bond through a diazotization reaction, so as to improve the oxidation resistance and structural stability of the MXene material, and enhance the hydrophobicity of the material. properties, making it easy to separate and remove from water-soluble solvents.
本发明解决上述技术问题所提供的技术方案为：The technical scheme provided by the present invention to solve the above-mentioned technical problems is:
一种巯基功能化的MXene材料，所述的巯基功能化的MXene材料为巯芳基-MXene材料，具有Mn+1Xn-(Ph-SH)结构；A sulfhydryl-functionalized MXene material, the sulfhydryl-functionalized MXene material is a mercaptoaryl-MXene material, and has a Mn + 1Xn-(Ph-SH) structure;
其中，in,
所述的M为第IIIB、IVB、VB、VIB、VIIB族中的任意一种或至少两种金属元素；Described M is any one or at least two metal elements in Group IIIB, IVB, VB, VIB, VIIB;
X为C、N元素中的任意一种或两种的组合；X is any one of C and N elements or a combination of both;
n为1、2或3；n is 1, 2 or 3;
所述的Ph-SH为
本发明所述的巯芳基-MXene材料因引入巯芳基，巯芳基电子云密度高，提升了MXene材料的抗氧化性能和结构稳定性，另一方面芳香基团具有脂溶性，增强了材料的疏水性，尤其是在酸性条件下，使其易于从水溶性溶剂中分离去除。The mercaptoaryl-MXene material of the present invention has high electron cloud density due to the introduction of a mercaptoaryl group, which improves the antioxidant performance and structural stability of the MXene material. The hydrophobicity of the material, especially under acidic conditions, makes it easy to separate and remove from water-soluble solvents.
所述的M为Ti、Zr、Nb、Ta、V、Mo、Hf中的任意一种或至少两种金属元素。The M is any one or at least two metal elements among Ti, Zr, Nb, Ta, V, Mo, and Hf.
所述的Mn+1Xn为Ti3C2。The Mn +1 X n is Ti 3 C 2 .
所述的MXene材料为Ti3C2 
本发明还提供了所述的巯芳基-MXene材料的制备方法，包括如下步骤：The present invention also provides a method for preparing the mercaptoaryl-MXene material, comprising the following steps:
(1)将MXene材料加入到碱的水溶液中，10～40℃搅拌6～10h，分离出沉淀，水洗至中性后分散于水中，得混悬液；去除MXene材料中的F、Cl基团；(1) Add the MXene material to the aqueous alkali solution, stir at 10-40°C for 6-10 hours, separate the precipitate, wash it with water until neutral, and then disperse in water to obtain a suspension; remove the F and Cl groups in the MXene material ;
(2)将氨基苯硫酚加到水中分散均匀，冷却至0～5℃后，依次加入盐酸，亚硝酸钠，再加入步骤(1)得到的混悬液，搅拌3.5-5h，分离得到固体，洗涤、干燥固体后得到巯芳基-MXene材料。(2) Add aminothiophenol to water to disperse evenly, after cooling to 0～5℃, add hydrochloric acid and sodium nitrite in turn, then add the suspension obtained in step (1), stir for 3.5-5h, and separate to obtain a solid , and the solid was washed and dried to obtain a mercaptoaryl-MXene material.
步骤(2)中所述的MXene材料与氨基苯硫酚的质量比为1∶0.6～1.5。The mass ratio of the MXene material described in step (2) to aminothiophenol is 1:0.6-1.5.
本发明所述的碱的水溶液为氢氧化钠水溶液或氢氧化钾的水溶液，所述的氢氧化钠水溶液或氢氧化钾的水溶液的浓度为4-8mol/L。The aqueous alkali solution of the present invention 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 4-8 mol/L.
本发明所述的MXene材料由MAX相材料刻蚀得到，具体步骤包括：将MAX相材料加入到LiF/HCl复合溶液中，30～50℃搅拌25-36h，刻蚀去除A原子层，得到Mn+1XnTm，所述的Tm为F、Cl或OH；所述的MAX相材料分子式为Mn+1AXn，所述的A为为IIIA或IVA族元素。The MXene material of the present invention is obtained by etching the MAX phase material, and the specific steps include: adding the MAX phase material to the LiF/HCl composite solution, stirring at 30-50° C. for 25-36 hours, and etching to remove the A atomic layer to obtain M n+1 X n T m , the T m is F, Cl or OH; the molecular formula of the MAX phase material is Mn +1 AX n , and the A is a group IIIA or IVA element.
所述的MAX相材料为Ti3AlC2。The MAX phase material is Ti 3 AlC 2 .
所述的LiF/HCl复合溶液中盐酸浓度为9-12mol/L。The concentration of hydrochloric acid in the LiF/HCl composite solution is 9-12 mol/L.
所述的MAX相材料与LiF的质量比为1∶1.2～1.5。The mass ratio of the MAX phase material to LiF is 1:1.2-1.5.
本发明还提供了所述的巯芳基-MXene材料在重金属离子去除中的应用。The invention also provides the application of the mercaptoaryl-MXene material in the removal of heavy metal ions.
Mxene材料因其本身容易氧化，可以将Cr6+还原成Cr3+，巯芳基具有还原性也可以作为还原剂；此外，巯芳基也是一个较强的配体，吸附金属离子的能力强，可以有效地吸附还原后的Cr3+，且巯芳基的引入也增加了载体的疏水性，因此，巯芳基-MXene材料去除废水中的重金属离子后，易于从废水中分离去除。Mxene material can reduce Cr 6+ to Cr 3+ because of its easy oxidation. The mercaptoaryl group has reducibility and can also be used as a reducing agent. In addition, the mercaptoaryl group is also a strong ligand and has a strong ability to adsorb metal ions. , can effectively adsorb the reduced Cr 3+ , and the introduction of the mercaptoaryl group also increases the hydrophobicity of the carrier. Therefore, the mercaptoaryl-MXene material can be easily separated and removed from the wastewater after removing the heavy metal ions in the wastewater.
所述的重金属为Cr元素。The heavy metal is Cr element.
本发明还提供了一种巯芳基-MXene材料负载型钯催化剂。The invention also provides a mercaptoaryl-MXene material-supported palladium catalyst.
所述的巯芳基-MXene材料负载型钯催化剂中钯负载量为0.5-3wt％。The palladium loading in the mercaptoaryl-MXene material-supported palladium catalyst is 0.5-3wt%.
本发明所述的巯芳基-MXene材料负载型钯催化剂的制备方法包括如下步骤：在20～40℃下，巯芳基-MXene材料与Pd(OAc)2或PdCl2混合后超声5-10h后，分离、干燥后，得到巯芳基-MXene材料负载型钯催化剂。The preparation method of the mercaptoaryl-MXene material-supported palladium catalyst according to the present invention comprises the following steps: at 20-40° C., the mercaptoaryl-MXene material is mixed with Pd(OAc) 2 or PdCl 2 and then ultrasonicated for 5-10 h. Then, after separation and drying, a mercaptoaryl-MXene material-supported palladium catalyst is obtained.
MXene在催化剂中主要是起到载体的作用，但是其容易氧化，在超声波作用下可以辅助将Pd2+还原成Pd0；巯基(-SH)一方面可以作为还原剂，另一方面巯基SH也是一个较强的配体，可以络合生成的Pd(0)催化剂，不仅可以提高Pd(0)负载量，还使Pd(0)均匀分散，在反应过程中不易流失。MXene mainly acts as a carrier in the catalyst, but it is easily oxidized, and can assist in the reduction of Pd 2+ to Pd 0 under the action of ultrasonic waves; mercapto (-SH) can be used as a reducing agent on the one hand, and mercapto SH is also a reducing agent. A stronger ligand can complex the generated Pd(0) catalyst, which can not only increase the Pd(0) loading, but also make the Pd(0) evenly dispersed, which is not easy to be lost during the reaction.
所述的巯芳基-MXene材料与Pd(OAc)2或PdCl2的质量比为1∶0.005～0.06。The mass ratio of the mercaptoaryl-MXene material to Pd(OAc) 2 or PdCl 2 is 1:0.005-0.06.
本发明还提供了巯芳基-MXene材料负载型钯催化剂在催化有机偶联反应中的应用。The invention also provides the application of the mercaptoaryl-MXene material-supported palladium catalyst in catalyzing organic coupling reactions.
所述的有机偶联反应为Suzuki偶联反应。The organic coupling reaction is Suzuki coupling reaction.
以巯芳基-MXene材料作为Pd的载体，根据相似相溶原理，在脂溶性环境下有机反应底物的吸附能力提高，有利于巯芳基-MXene材料与有机反应底物结合，提高催化剂活性中心Pd与有机反应底物的接触，从而催化剂活性提高。Using mercaptoaryl-MXene material as the carrier of Pd, according to the principle of similar compatibility, the adsorption capacity of organic reaction substrates in a fat-soluble environment is improved, which is conducive to the combination of mercaptoaryl-MXene materials with organic reaction substrates and improves catalyst activity. The contact between the central Pd and the organic reaction substrate increases the catalyst activity.
本发明的有益效果主要体现在：The beneficial effects of the present invention are mainly reflected in:
(1)本发明首次实现了在MXene材料中引入-PhSH作为表面基团，提高了MXene材料与还原产物Cr3+的结合能力；同时，降低了MXene材料在废水中溶解度，也利于MXene材料与溶剂的分离。(1) The present invention realizes the introduction of -PhSH as a surface group into the MXene material for the first time, which improves the binding ability of the MXene material and the reduction product Cr 3+ ; Separation of Solvents.
(2)以巯芳基-MXene材料作为Pd的载体，巯芳基-MXene拥有较高的比表面积、丰富的活性吸附位点，有利于催化活性的分散及保护；且芳巯基的引入进一步提高有机反应底物的吸附能力，有利于巯芳基-MXene材料与有机反应底物结合，有利于催化剂活性的提高。(2) Using mercaptoaryl-MXene material as the Pd carrier, mercaptoaryl-MXene has high specific surface area and abundant active adsorption sites, which is conducive to the dispersion and protection of catalytic activity; and the introduction of arylthiol group further improves The adsorption capacity of organic reaction substrates is beneficial to the combination of mercaptoaryl-MXene materials with organic reaction substrates, which is beneficial to the improvement of catalyst activity.
附图说明Description of drawings
附图1为实施例1制得产物的扫描电镜图。
附图2为实施例1制得产物的红外光谱图。Accompanying drawing 2 is the infrared spectrogram of the product obtained in Example 1.
附图3为实施例1制得产物的X射线衍射图。Figure 3 is the X-ray diffraction pattern of the product obtained in Example 1.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below with reference to specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that, for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
实施例1 Ti3C2 
(1)刻蚀Ti3AlC2：(1) Etching Ti 3 AlC 2 :
在室温下将LiF(1.4g)溶解于15ml 12mol/L盐酸溶液和4.5ml水中后，将此溶液加热至40℃继续搅拌10min；将Ti3AlC2(1g)少量分批加入至上述溶液中，40℃继续搅拌24h后，完全除去化合物中的Al元素，得到手风琴状的具有Ti3C2的结构式的多层MXene材料，将此混合物进行离心、洗涤、超声、真空干燥后得Ti3C2Tm(MXene材料)，Tm为表面基团F、Cl或OH。After dissolving LiF (1.4g) in 15ml of 12mol/L hydrochloric acid solution and 4.5ml of water at room temperature, the solution was heated to 40°C and stirred for 10min; a small amount of Ti 3 AlC 2 (1 g) was added to the above solution in batches , after stirring at 40 °C for 24 h, the Al element in the compound was completely removed to obtain an accordion-shaped multilayer MXene material with the structural formula of Ti 3 C 2 , and the mixture was centrifuged, washed, ultrasonicated, and vacuum-dried to obtain Ti 3 C 2 Tm (MXene material), Tm is the surface group F, Cl or OH.
(2)将步骤(1)得到的0.5g Ti3C2Tm加入到10ml 4mol/L的氢氧化钠碱溶液中，在室温下搅拌8h后，离心分离，并用水洗涤固体至洗出液呈中性，然后将固体分散在5ml水中，得混悬液。(2) 0.5g Ti 3 C 2 T m obtained in step (1) was added to 10ml of 4mol/L sodium hydroxide alkali solution, stirred at room temperature for 8h, centrifuged, and washed the solid with water to the eluate Neutral, then the solid was dispersed in 5ml of water to obtain a suspension.
(3)Ti3C2 
将对氨基苯硫酚(0.5g)加入到10ml水中超声30min，0℃下搅拌1h，得白色混合液；0℃下加入13.5ml 4.2mol/L盐酸，充分搅拌后加入10ml 0.52mol/L亚硝酸钠溶液，继续搅拌4h得棕红色溶液；向此溶液中加入步骤(2)制得的混悬液，搅拌5h。整个实验过程均在0～5℃条件下进行。P-aminothiophenol (0.5g) was added to 10ml of water and sonicated for 30min, stirred at 0°C for 1h to obtain a white mixture; 13.5ml of 4.2mol/L hydrochloric acid was added at 0°C, and 10ml of 0.52mol/L hydrochloric acid was added after thorough stirring. Sodium nitrate solution, continue stirring for 4h to obtain a brown-red solution; add the suspension obtained in step (2) to this solution, and stir for 5h. The whole experimental process was carried out at 0-5 °C.
反应结束后离心分离、取沉淀、水洗、醇洗后，并于真空烘箱中干燥6h，得到产物巯基功能化的Ti3C2：Ti3C2 
利用扫描电镜(SEM)观察产物的微观结构，结果如附图1所示，产物呈现层状结构。利用红外光谱仪检测产物表面的官能团，结果如附图2所示，在3100～3000cm-1，1600～1400cm-1出现苯环骨架的特征峰，这证实巯芳基通过共价键已成功键合到MXene材料上。用X射线衍射仪对产物进行物相分析，结果如附图3所示，Ti3AlC2特征峰消失，Ti3C2Tm特征峰出现。Scanning electron microscope (SEM) was used to observe the microstructure of the product, and the results were shown in FIG. 1 , and the product showed a layered structure. The functional groups on the surface of the product were detected by infrared spectrometer. The results are shown in Figure 2. The characteristic peaks of the benzene ring skeleton appear at 3100-3000 cm -1 and 1600-1400 cm -1 , which confirms that the mercaptoaryl group has been successfully bonded by covalent bonds. onto MXene materials. Phase analysis of the product was carried out with X-ray diffractometer. The results are shown in Figure 3. The characteristic peak of Ti 3 AlC 2 disappeared and the characteristic peak of Ti 3 C 2 T m appeared.
应用例1 Ti3C2 
在室温下，将20mg Ti3C2 
实施例2 Ti3C2 
将0.2g实施例1制得的Ti3C2 
应用例2 Ti3C2 
在反应管中加入溴苯(78mg，0.50mmol，1eq)和苯硼酸(120mg，1.0mmol，2eq)、15mgTi3C2 
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