RAFT合成的MoS2-PAN纳米片：高效光保护性能与宽谱激光防护

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本研究论文发表在《无机化学通讯》(J.Mater.Chem.C)上，2017年5期，编号11920-11926。该研究关注了二硫化钼(MoS2)纳米片与聚乙酸乙烯酯(Polyacrylonitrile, PAN)之间通过共价键连接的新型合成及其在宽光谱范围内的激光防护性能。研究人员采用可逆加成-断裂链转移(RAFT)聚合方法现场制备了高溶解性的MoS2-PAN复合材料。与纯MoS2和MoS2/PAN混合物相比，MoS2-PAN衍生物在溶液及聚甲基丙烯酸甲酯(PPMA)基质中的光学限止响应表现出显著的优势。在可见光和近红外范围内，这种改性后的材料显示出更强的光学性能。经过200°C氮气环境下4小时的热处理后，MoS2-PAN/PMMA薄膜的非线性光学响应和光学限止性能得到了显著增强。未经处理的样品，其在532nm和1064nm波长下的非线性系数分别为10^15 cm/GW·cm和534 cm/GW·cm，而经过热处理后的MoS2-PAN/PMMA薄膜，这些数值分别提升至1151 cm/GW·cm和699 cm/GW·cm。这项研究的重要性在于它揭示了通过共价修饰的方式，可以显著提高MoS2纳米片的光学性能，使其在激光防护应用中有潜在的应用价值。莫氏二硫化物因其独特的二维结构和光吸收特性，一直以来都是光电材料领域的研究热点。通过与PAN结合，不仅可以提高其溶解性和稳定性，还能够扩展其在可见光和近红外光谱区域的光学响应，这对于设计高性能的防辐射、防热保护层或光学开关等应用具有重要意义。因此，这项工作对于开发新型纳米复合材料以及优化其在光电器件和激光防护方面的性能具有重要指导作用。

11920 | J. Mater. Chem. C, 2017, 5, 11920--11926 This journal is

The Royal Society of Chemistry 2017

Cite this: J. Mater. Chem. C, 2017,

5, 11920

MoS

nanosheets covalently functionalized with

polyacrylonitrile: synthesis and broadband laser

protection performance

Makai Shi,

Ningning Dong,

Nan He,

Yan Wan,

Hongxia Cheng,

Mengru Han,

Jun Wang *

and Yu Chen *

Highly soluble polyacrylonitrile (PAN)-covalently grafted MoS

nanosheets (MoS

–PAN) were synthesized

in situ through reversible addition fragmentation chain transfer (RAFT) polymerization. In comparison

with MoS

and the MoS

/PAN blends, whether in solution or in a PMMA matrix, the MoS

–PAN-based

samples show superior optical limiting response in the visible and near-infrared ranges. After annealing

at 200 1CinN

for 4 hours, the annealed MoS

–PAN/PMMA film exhibits significantly enhanced

nonlinear optical and optical limiting responses when compared to the non-annealed MoS

–PAN/PMMA

film. The observed nonlinear coe fficients of the MoS

–PAN/PMMAfilmarechangedfrom1015cmGW

1

532 nm and 534 cm GW

1

at 1064 nm before annealing to 1151 cm GW

1

at532nmand699cmGW

1

1064 nm after annealing. The limiting thresholds were also decreased from 1.98 J cm

1

at 532 nm and

3.60 J cm

1

at 1064 nm before annealing to 1.56 J cm

1

at 532 nm and 2.67 J cm

1

at 1064 nm after

annealing.

Introduction

With the fast development of laser technology, lasers have been

more and more widely used in the military field. Some are

designed to destroy the missiles, unmanned planes, optoelectronic/

optical facilities and other targets, while others are used to

permanently disable humans by blinding. During the past few

decades, therefore, significant eﬀorts have been made in the

design and preparation of state-of-the-art optical limiting (OL)

materials.

1–14

Some representative OL materials for laser protection,

including phthalocyanines, carbon-based nanomaterials, por-

phyrins, inorganic nanomaterials, mixed metal complexes, and

polymers, have been widely reported. To achieve simultaneous

protection against both pulsed and continuous wave (cw) or

quasi-cw lasers, the ideal OL materials, which can exhibit high

transmittance for low intensity light (e.g., ambient light and/or

natural light), while strongly attenuating intense laser beams,

should be designed for multimechanistic function (reverse

saturable absorption (RSA) behavior at the high-energy end of

the visible; two photon absorption (TPA) or multi-photon

absorption (MPA) behavior at the low-energy end of the visible;

and nonlinear scattering (NLS) behavior in the visible near-

infrared region).

As an encouraging broadband saturable absorber,

the

ultrafast nonlinear optical (NLO) performances of two-dimensional

molybdenum disulfide (MoS

) and its derivatives have attracted

significant attention.

6,15–21

By using the Z-scan technique with a

nanosecond pulsed laser, Dong et al. observed the OL effect of

MoS

nanosheets at both 532 and 1064 nm, with the OL

thresholds of 11.16 J cm

2

at 532 nm and 19 J cm

2

1064 nm.

The limiting mechanism for the former is assigned

to the combined effect of both NLS and saturable absorption

(SA), while the latter mainly corresponds to NSL. The few-layer

MoS

nanosheets doped into the poly(methylmethacrylate)

(PMMA) matrix were also found to exhibit low limiting differential

transmittance values of 2% and 3% at 532 and 1064 nm,

respectively.

Very recently, we used a ‘‘grafting from’’ approach

to synthesize highly soluble poly(N-vinylcarbazole) (PVK) chemically

modified MoS

nanosheets (MoS

-PVK).

6,18

This is the first example

of MoS

nanosheets covalently functionalized with a polymer. As

expected, both the solution of MoS

-PVK in DMF and the MoS

-PVK/

PMMA film show good OL responses when compared to MoS

and

MoS

/PVK blends. In this work, we used a similar method to

in situ synthesize new polyacrylonitrile (PAN)-covalently grafted

Key Laboratory for Advanced Materials, Institute of Applied Chemistry,

School of Chemistry and Molecular Engineering, East China University of Science

and Technology 130 Meilong Road, Shanghai 200237, China.

E-mail: chentangyu@yahoo.com

Key Laboratory of Materials for High-Power Laser, Shanghai Institute of Optics

and Fine Mechanics, CAS, Shanghai 201800, China. E-mail: jwang@siom.ac.cn

State Key Laboratory of High Field Laser Physics, Shanghai Institute of Optics and

Fine Mechanics, CAS, Shanghai 201800, China

Beijing No. 13 Middle School, 27 Niuying Str., Xicheng District, Beijing 1 00009,

China

Received 26th August 2017,

Accepted 30th October 2017

DOI: 10.1039/c7tc03900j

rsc.li/materials-c

Journal of

Materials Chemistry C

PAPER

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