Bandgap- and Local Field-Dependent Photoactivity of Ag/Black Phosphorus Nanohybrids
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- 作者：Wanying Lei ; Tingting Zhang ; Ping Liu ; José A. Rodriguez ; Gang Liu ; Minghua Liu
- 刊名：ACS Catalysis
- 出版年：2016
- 出版时间：December 2, 2016
- 年：2016
- 卷：6
- 期：12
- 页码：8009-8020
- 全文大小：822K
- ISSN：2155-5435
文摘
Black phosphorus (BP) is the most exciting post-graphene layered nanomaterial that serendipitously bridges the 2D materials gap between semimetallic graphene and large bandgap transition-metal dichalcogenides in terms of high charge-carrier mobility and tunable direct bandgap, yet research into BP-based solar to chemical energy conversion is still in its infancy. Herein, a novel hybrid photocatalyst with Ag nanoparticles supported on BP nanosheets is prepared using a chemical reduction approach. Spin-polarized density functional theory (DFT) calculations show that Ag nanoparticles are stabilized on BP by covalent bonds at the Ag/BP interface and Ag−Ag interactions. In the visible-light photocatalysis of rhodamine B by Ag/BP plasmonic nanohybrids, a significant rise in photoactivity compared with pristine BP nanosheets is observed either by decreasing BP layer thickness or increasing Ag particle size, with the greatest enhancement being up to ∼20-fold. By virtue of finite-difference time domain (FDTD) simulations and photocurrent measurements, we give insights into the enhanced photocatalytic performance of Ag/BP nanohybrids, including the effects of BP layer thickness and Ag particle size. In comparison with BP, Ag/BP nanohybrids present intense local field amplification at the perimeter of Ag NPs, which is increased by either decreasing the BP layer thickness from multiple to few layers or increasing the Ag particle size from 20 to 40 nm. Additionally, when the BP layer thickness is decreased from multiple to few layers, the bandgap becomes favorable to generate more strongly oxidative holes in the proximity of the Ag/BP interface to enhance photoactivity. Our findings illustrate a synergy between locally enhanced electric fields and BP bandgap, in which BP layer thickness and Ag particle size can be independently tuned to enhance photoactivity. This study may open a new avenue for further exploiting BP-based plasmonic nanostructures in photocatalysis, photodetectors, and photovoltaics.