Journal
ACS CATALYSIS
Volume 9, Issue 2, Pages 1489-1502Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.8b04502
Keywords
Al-doping; dealloying; solid-vapor sulfurization; hydrogen evolution reaction; electrocatalysis; DFT calculation
Categories
Funding
- National Natural Science Foundation of China [21878201]
- Natural Science Foundation of Shanxi Province [201801D121059]
- Program for the Outstanding Innovative Teams of Higher Learning Institutions of Shanxi OIT
- Special/Youth Foundation of Taiyuan University of Technology [1205-04020203/SC18100330]
- Program for Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization [201705D111002]
- Shanxi Scholarship Council of China [2017-034]
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Foreign atom doping is known to not only modify the electronic structure but also improve the intrinsic activity of catalysts. Herein, we fabricate three-dimensional (3D) self-supporting nanoporous cobalt-aluminum intermetallic (np-Co(Al)) through dealloying of Al90Co10 master alloy to in situ introduce Al element into the precursor. The intrinsic Al dopant is determined to be insensitive to S vapor but beneficial to generate numerous Al-doped CoS2 nanowires (Al-CoS2 NA/Vs) when they were subjected to solid vapor sulfurization treatment. The density functional theory (DFT) calculations evidence that spontaneous Al-doping in CoS2 crystal could enhance the hybridization between Co d-orbital and S p-orbital near the Fermi level. On the one hand, the Co-sites are more active than that of the S-sites, and the intermediate hydrogen (H*) adsorption free energy (Delta G(H)*) of Al-CoS2 is only -0.16 eV when adsorbed on the bridge site of Co. On the other hand, the embedded Al can not only facilitate the activity improvement of Co-sites but also greatly activate the inert S-sites in CoS2. An overpotential as small as 86 and 191 mV to reach 10 and 100 mA cm(-2) H-2-evolving current, a small Tafel slope of 62.47 mV dec(-1), and long-term operational stability are achieved on the AI doped CoS2 catalyst. This finding opens up an easily accessible in situ doping route via alloying-dealloying followed by inheritance to nanoporous earth-abundant chalcogenide electrocatalyst for regulating their physicochemical and electrochemical properties, accelerating the development of high performance H-2-evolving electrode for electrochemical hydrogen production.
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