摘要
在大气环境下,寡层黑磷(简称为磷烯)很容易被氧化,因此阻碍了其在光催化太阳能转换领域的应用.相关的一些保护方法,比如在磷烯表面引入保护层、表面配位、P–C共价官能化等方法可以维持磷烯的稳定性,使其免受氧化降解,可是这些方法对磷烯的催化活性位点造成了堵塞,因此不可避免地降低了其光催化活性.在本项工作中,我们开发了一种在磷烯表面引入P–H共价键的策略,表面P–H共价键的引入既能维持磷烯在大气环境下的稳定性,又能实现高效光催化分解水产H_(2).相关实验和DFT计算表明,磷烯表面约5 mol%的磷原子参与了P–H共价键的形成,在热力学和动力学两方面同时抑制了磷烯的氧化反应.磷烯的表面氢化策略有希望促进磷烯在光催化领域的实际应用.
The facile oxidation of few-layer black phosphorus(i.e., phosphorene) in the atmospheric environment is a major hurdle for its applications in photocatalytic solarenergy conversion. The introduction of protective layers, such as a surface capping layer, surface coordination, and P–C covalent functionalization, can protect phosphorene from oxidative degradation but inevitably decreases its photocatalytic performance due to the blockage of catalytic active sites. Herein, we develop a hydrogenation approach via the introduction of P–H covalent bonds on the surface of phosphorene(i.e., phosphorene-H) to inhibit the oxidation of phosphorene-H without sacrificing the original photocatalytic H_(2) evolution performance. Experiments and density functional theory calculations demonstrate that about 5 mol% of phosphorus atoms in phosphorene-H are involved in forming P–H covalent bonds, hindering the reaction between O_(2) and phosphorene-H in terms of thermodynamics and kinetics.This hydrogenation strategy is envisaged to augment the prospect of phosphorene in the field of photocatalysis.
作者
石睿
康雷
白晓娟
陈勇
Rui Shi;Lei Kang;Xiaojuan Bai;Yong Chen(Key Laboratory of Photochemical Conversion and Optoelectronic Materials&CAS-HKU Joint Laboratory on New Materials,Technical Institute of Physics and Chemistry,Chinese Academy of Sciences,Beijing 100190,China;Key Laboratory of Functional Crystals and Laser Technology,Technical Institute of Physics and Chemistry,Chinese Academy of Sciences,Beijing 100190,China;Key Laboratory of Urban Stormwater system and Water Environment,Beijing Engineering Research Center of Sustainable Urban Sewage System Construction and Risk Control,Beijing University of Civil Engineering and Architecture,Beijing 100044,China;University of Chinese Academy of Sciences,Beijing 100190,China)
基金
the financial support from the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17000000)
the National Natural Science Foundation of China (21773275 and 21971250)
the financial support from K.C. Wong Education Foundation and the CAS-Croucher Funding Scheme for Joint Laboratories。