title: Hollow Cobalt-Based Bimetallic Sulfide Polyhedra for Efficient All-pH-Value Electrochemical and Photocatalytic Hydrogen Evolution.
abstract: The development of highly active, universal, and stable inexpensive electrocatalysts/cocatalysts for hydrogen evolution reaction (HER) by morphology and structure modulations remains a great challenge. Herein, a simple self-template strategy was developed to synthesize hollow Co-based bimetallic sulfide (MxCo3-xS4, M = Zn, Ni, and Cu) polyhedra with superior HER activity and stability. Homogenous bimetallic metal-organic frameworks are transformed to hollow bimetallic sulfides by solvothermal sulfidation and thermal annealing. Electrochemical measurements and density functional theory computations show that the combination of hollow structure and homoincorporation of a second metal significantly enhances the HER activity of Co3S4. Specifically, the homogeneous doping in Co3S4 lattice optimizes the Gibbs free energy for H* adsorption and improves the electrical conductivity. Impressively, hollow Zn0.30Co2.70S4 exhibits electrocatalytic HER activity better than most of the reported nobel-metal-free electrocatalysts over a wide pH range, with overpotentials of 80, 90, and 85 mV at 10 mA cm(-2) and 129, 144, and 136 mV at 100 mA cm(-2) in 0.5 M H2SO4, 0.1 M phosphate buffer, and 1 M KOH, respectively. It also exhibits photocatalytic HER activity comparable to that of Pt cocatalyst when working with organic photosensitizer (Eosin Y) or semiconductors (TiO2 and C3N4). Furthermore, this catalyst shows excellent stability in the electrochemical and photocatalytic reactions. The strategy developed here, i.e., homogeneous doping and self-templated hollow structure, provides a way to synthesize transition metal sulfides for catalysis and energy conversion.
authors.affiliation: Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University , Tianjin 300072, China.|Collaborative Innovative Center of Chemical Science and Engineering (Tianjin) , Tianjin 300072, China.
authors.forename: Zhen-Feng
authors.initials: ZF
authors.lastname: Huang
authors.affiliation: Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University , Tianjin 300072, China.|Collaborative Innovative Center of Chemical Science and Engineering (Tianjin) , Tianjin 300072, China.
authors.forename: Jiajia
authors.initials: J
authors.lastname: Song
authors.affiliation: Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University , Tianjin 300072, China.|Collaborative Innovative Center of Chemical Science and Engineering (Tianjin) , Tianjin 300072, China.
authors.forename: Ke
authors.initials: K
authors.lastname: Li
authors.affiliation: Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University , Tianjin 300072, China.|Collaborative Innovative Center of Chemical Science and Engineering (Tianjin) , Tianjin 300072, China.|Department of Physics, The University Of Lahore , Punjab 54600, Pakistan.
authors.forename: Muhammad
authors.initials: M
authors.lastname: Tahir
authors.affiliation: Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University , Tianjin 300072, China.|Collaborative Innovative Center of Chemical Science and Engineering (Tianjin) , Tianjin 300072, China.
authors.forename: Yu-Tong
authors.initials: YT
authors.lastname: Wang
authors.affiliation: Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University , Tianjin 300072, China.|Collaborative Innovative Center of Chemical Science and Engineering (Tianjin) , Tianjin 300072, China.
authors.forename: Lun
authors.initials: L
authors.lastname: Pan
authors.affiliation: Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University , Tianjin 300072, China.|Collaborative Innovative Center of Chemical Science and Engineering (Tianjin) , Tianjin 300072, China.
authors.forename: Li
authors.initials: L
authors.lastname: Wang
authors.affiliation: Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University , Tianjin 300072, China.|Collaborative Innovative Center of Chemical Science and Engineering (Tianjin) , Tianjin 300072, China.
authors.forename: Xiangwen
authors.initials: X
authors.lastname: Zhang
authors.affiliation: Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University , Tianjin 300072, China.|Collaborative Innovative Center of Chemical Science and Engineering (Tianjin) , Tianjin 300072, China.
authors.forename: Ji-Jun
authors.initials: JJ
authors.lastname: Zou