am9b13666_si_001.pdf (1.62 MB)
Modulation of Phosphorene for Optimal Hydrogen Evolution Reaction
journal contribution
posted on 2019-10-04, 12:34 authored by Jiang Lu, Xue Zhang, Danni Liu, Na Yang, Hao Huang, Shaowei Jin, Jiahong Wang, Paul K. Chu, Xue-Feng YuEconomical
and highly effective catalysts are crucial to the electrocatalytic
hydrogen evolution reaction (HER), and few-layer black phosphorus
(phosphorene) is a promising candidate because of the high carrier
mobility, large specific surface area, and tunable physicochemical
characteristics. However, the HER activity of phosphorene is limited
by the weak hydrogen adsorption ability on the basal plane. In this
work, optimal active sites are created to modulate the electronic
structure of phosphorene to improve the HER activity and the effectiveness
is investigated theoretically by density-functional theory calculation
and verified experimentally. The edges and defects affect the electronic
density of states, and a linear relationship between the HER activity
and lowest unoccupied states (εLUS) is discovered.
The medium εLUS value corresponds to the suitable
hydrogen adsorption strength. Experiments are designed and performed
to verify the prediction, and our results show that a smaller phosphorene
moiety with more edges and defects exhibits better HER activity and
surface doping with metal adatoms improves the catalytic performance.
The results suggest that modified phosphorene has large potential
in efficient HER and provides a convenient standard to explore ideal
electrocatalysts.