Two-dimensional nanostructures of non-layered ternary thiospinels and their bifunctional electrocatalytic properties for oxygen reduction and evolution: the case of CuCo2S4 nanosheets
Zhao, SL (Zhao, Shulin)[ 1 ] ; Wang, Y (Wang, Yu)[ 1 ] ; Zhang, QH (Zhang, Qinghua)[ 2,3 ] ; Li, YF (Li, Yafei)[ 1 ] ; Gu, L (Gu, Lin)[ 2 ] ; Dai, ZH (Dai, Zhihui)[ 1 ] ; Liu, SL (Liu, Suli)[ 1 ] ; Lan, YQ (Lan, Ya-Qian)[ 1 ] ; Han, M (Han, Min)[ 1 ]*（韩敏）; Bao, JC (Bao, Jianchun)[ 1 ]*（包建春）
[ 1 ] Nanjing Normal Univ, Sch Chem & Mat Sci, Jiangsu Key Lab Biofunct Mat, Nanjing 210023, Jiangsu, Peoples R China
[ 2 ] Chinese Acad Sci, Inst Phys, Beijing Natl Lab Condensed Matter Phys, Beijing 100190, Peoples R China
[ 3 ] Tsinghua Univ, Dept Mat Sci & Engn, Beijing 100084, Peoples R China
INORGANIC CHEMISTRY FRONTIERS,Sep. 2016,3(12),1501-1509
Two-dimensional (2D) transition metal chalcogenide nanostructures exhibit unique electronic, optoelectronic and mechanical properties, showing great potential for innovation of future electronics, renewable energy, sensing, and catalysis fields. Despite achieving great progress, fabricating 2D nanostructures of non-layered ternary thiospinels remains a great challenge, and their bifunctional electrocatalytic properties toward both oxygen reduction and evolution reactions (ORR and OER) have not been explored. In this paper, 2D nanostructures of an earth-abundant non-layered ternary thiospinel compound - CuCo2S4 nanosheets (NSs) - with their (111), (022) and (004) planes mainly exposed, are synthesized via a "leveling metal activity and structure-directed one-pot sulfurization" strategy. The electrocatalytic tests in alkaline solution show that such CuCo2S4 NSs can efficiently catalyze both the ORR and OER, whose bifunctional catalytic properties are superior to binary metal sulfide nanostructures, Pt/C, CuCo2S4 nanoparticles, and recently reported some bifunctional oxygen-electrode catalysts (e.g. CoxSy@C-1000, N-doped G/CNTs, Co3O4/NBGHSs, CoFe2O4, Cox Mn3-xO4, MnOx, NiCo2S4 hollow spheres, NiCo2S4@N/S-rGO, etc.). Combined with spin-polarized density functional theory computations based on a computational hydrogen electrode model, their excellent bifunctional catalytic properties originate from the presence of the two special facets, (022) and (004), which have different preferences in terms of the ORR/OER. This work not only enriches the current 2D material family but also paves the way for rational design of advanced multifunctional 2D electrocatalysts for use in renewable energy fields.