Regulating the reactivity of black phosphorus via protective chemistry

Xiao Liu; Liangping Xiao; Jian Weng; Qingchi Xu; Wanli Li; Chunhui Zhao; Jun Xu; Yanli Zhao

doi:10.1126/sciadv.abb4359

Regulating the reactivity of black phosphorus via protective chemistry

Sci Adv. 2020 Nov 11;6(46):eabb4359. doi: 10.1126/sciadv.abb4359. Print 2020 Nov.

Authors

Xiao Liu^{1

2

3}, Liangping Xiao⁴, Jian Weng³, Qingchi Xu^{1

2}, Wanli Li³, Chunhui Zhao³, Jun Xu^{5

2

6}, Yanli Zhao⁷

Affiliations

¹ Department of Physics, Research Institute for Biomimetics and Soft Matter, Fujian Provincial Key Laboratory for Soft Functional Materials, Xiamen University, Xiamen 361005, China.
² Shenzhen Research Institute of Xiamen University, Shenzhen 518057, China.
³ Department of Biomaterials, College of Materials, Xiamen University, Xiamen 361005, China.
⁴ State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
⁵ Department of Physics, Research Institute for Biomimetics and Soft Matter, Fujian Provincial Key Laboratory for Soft Functional Materials, Xiamen University, Xiamen 361005, China. [email protected] [email protected].
⁶ Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University , 21 Nanyang Link, 637371, Singapore.
⁷ Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University , 21 Nanyang Link, 637371, Singapore. [email protected] [email protected].

Abstract

Rationally regulating the reactivity of molecules or functional groups is common in organic chemistry, both in laboratory and industry synthesis. This concept can be applied to inorganic nanomaterials, particularly two-dimensional black phosphorus (BP) nanosheets. The high reactivity of few-layer (even monolayer) BP is expected to be "shut down" when not required and to be resumed upon application. Here, we demonstrate a protective chemistry-based methodology for regulating BP reactivity. The protective step initiates from binding Al³⁺ with lone pair electrons from P to decrease the electron density on the BP surface, and ends with an oxygen/water-resistant layer through the self-assembly of hydrophobic 1,2-benzenedithiol (BDT) on BP/Al³⁺ This protective step yields a stabilized BP with low reactivity. Deprotection of the obtained BP/Al³⁺/BDT is achieved by chelator treatment, which removes Al³⁺ and BDT from the BP surface. The deprotective process recovers the electron density of BP and thus restores the reactivity of BP.

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