Novel reversible additive-fragment transfer (RAFT) reagent based on black phosphorus and preparation method and application thereof

A new technology of black phosphorus, which is applied in the covalent grafting of RAFT reagents and black phosphorus nanosheets, and in the field of modification of black phosphorus nanosheets with diazonium salts, can solve the problems of poor Fermi level matching, weak charge transfer ability, Limiting practical applications and other issues, achieving good solubility, convenient BP modification methods, and diversified BP modification methods

Active Publication Date: 2019-11-05
EAST CHINA UNIV OF SCI & TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Most transition metal dichalcogenides are semiconductors with large band gaps (>1.5eV), such as molybdenum disulfide and tungsten disulfide, which have weak charge transfer ability and poor Fermi level matching at the semiconductor-metal interface. limit their practical application

Method used

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  • Novel reversible additive-fragment transfer (RAFT) reagent based on black phosphorus and preparation method and application thereof
  • Novel reversible additive-fragment transfer (RAFT) reagent based on black phosphorus and preparation method and application thereof
  • Novel reversible additive-fragment transfer (RAFT) reagent based on black phosphorus and preparation method and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0055] Embodiment 1: a kind of specific synthetic method of novel RAFT reagent based on black phosphorus:

[0056] 1) Synthesis of s-1-dodecyl-s'-(a, a'-dimethyl-a"-acetoxy) trithiocarbonate (DDAT): under the condition of nitrogen protection, twelve Alkyl mercaptan (16.16g), methyl trioctyl ammonium chloride (1.3g) join in 50ml acetone, dropwise add 8g50% sodium hydroxide solution under ice-water bath, after stirring for 15 minutes, add 10ml chloroform, and Slowly add 40g of 50% sodium hydroxide solution dropwise, stir overnight at room temperature, add 100ml of deionized water after the reaction, adjust the pH value to less than 2 with concentrated hydrochloric acid, stir vigorously and blow nitrogen to remove acetone, cool to 10°C and filter to obtain a solid And washed with deionized water several times, dried, dissolved in isopropanol and filtered to remove insoluble matter, spin-dried and recrystallized twice in n-hexane for purification. 1 H–NMR (CDCl 3 ,500MHz): d / ppm...

Embodiment 2

[0060] Embodiment 2: An example of the application of a novel RAFT reagent based on black phosphorus in polymerization according to the present invention, under an inert gas atmosphere, DDAT-BP, 9 vinyl carbazole (compound 7), azobisisobutyl Nitrile (compound 8) (molar ratio: compound 7: compound 8 = 150: 1) in dry tetrahydrofuran solvent (1-5ml), heat reaction for about 1-12 hours, after the reaction is completed drop into methanol to precipitate the product, pump Filter and wash to obtain BP-PVK; compound 7, compound 8, and the result formula of BP-PVK are as follows:

[0061]

[0062]

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Abstract

The invention belongs to a method for preparing a novel reversible additive-fragment transfer (RAFT) reagent based on black phosphorus, and the method includes the steps that a RAFT reagent containingcarboxyl groups in molecules is grafted onto BP nano sheets by covalent modification, and the RAFT reagent based on black phosphorus is obtained. The preparation method is applicable to various RAFTreagents with carboxyl groups in the molecules and can be effectively applied to a series of RAFT polymerized monomers, a platform for the modification of black phosphorus nano sheets is provided; meanwhile the polymer modified black phosphorus nano sheet material by the material in the preparation method has outstanding solubility and charge transfer properties compared with pure black phosphorusnano sheets, so that the polymer modified black phosphorus nano sheet material has a wide application prospect in photoelectric devices. The preparation method is applicable to the RAFT reagents containing carboxyl groups in molecules such as s-1-dodecyl-s'-(a,a'-dimethyl-a''-acetoxy) tristhiocarbonate (DDAT), 4-cyano-4-[(dodecyl thiocarbonyl) thioalkyl]valeric acid, 4-cyano-4-(phenylthioformyl)valeric acid, S-(thiobenzoyl) thioacetic acid.

Description

technical field [0001] The invention belongs to the technical field of the preparation of black phosphorus materials and the covalent grafting of RAFT polymerization initiators through covalent modification, so as to more conveniently carry out polymerization modification on the surface of black phosphorus nanosheets. Phosphorus nanosheets can be modified by covalent grafting of RAFT reagents and black phosphorus nanosheets. Background technique [0002] In the past decade, breakthroughs have been made in the development of two-dimensional materials. This type of material with a thickness of only one or a few layers of atoms has become an important tool for exploring fundamental quantum physics due to its extremely small thickness and weak interlayer interactions. As well as excellent materials for exploring the size effect of semiconductor materials. The two-dimensional materials that have received the most attention are graphene and transition metal dichalcogenides. Graph...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F126/12C08F120/14C08F2/38
CPCC08F2/38C08F120/14C08F126/12C08F2438/03
Inventor 张斌顾敏超甘帆樊菲陈彧
Owner EAST CHINA UNIV OF SCI & TECH
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