ABSTRACT
Transition metal-carbon hybrids have been proposed as efficient electrocatalysts for hydrogen evolution reaction (HER) in acidic media. Herein, effective HER electrocatalysts based on metal-carbon composites are prepared by controlled pyrolysis of resin containing a variety of heavy metals. For the first time, Cr2 O3 nanoparticles of 3-6 nm in diameter homogeneously dispersed in the resulting porous carbon framework (Cr-C hybrid) is synthesized as efficient HER electrocatalyst. Electrochemical measurements show that Cr-C hybrids display a high HER activity with an onset potential of -49 mV (vs reversible hydrogen electrode), a Tafel slope of 90 mV dec(-1) , a large catalytic current density of 10 mA cm(-2) at -123 mV, and the prominent electrochemical durability. X-ray photoelectron spectroscopic measurements confirm that electron transfer occurs from Cr2 O3 into carbon, which is consistent with the reported metal@carbon systems. The obtained correlation between metals and HER activities may be exploited as a rational guideline in the design and engineering of HER electrocatalysts.
ABSTRACT
Advanced materials for electrocatalytic water splitting are central to renewable energy research. In this work, MoS2 nanosheets supported on porous metallic MoO2 (MoS2/MoO2) were produced by sulfuration treatments of porous and highly conductive MoO2 for the hydrogen evolution reaction. Porous MoO2 with one-dimensional channel-like structures was prepared by calcination at elevated temperatures using phosphomolybdic acid as the precursor and mesoporous silica (SBA-15) as the template, and the subsequent hydrothermal treatment in the presence of thioacetamide led to the transformation of the top layers to MoS2 forming MoS2/MoO2 composites. Electrochemical studies showed that the obtained composites exhibited excellent electrocatalytic activity for HER with an onset potential of -104 mV (vs. RHE), a large current density (10 mA cm(-2) at -0.24 V), a small Tafel slope of 76.1 mV dec(-1) and robust electrochemical durability. The performance might be ascribed to the high electrical conductivity and porous structures of MoO2 with one-dimensional channels of 3 to 4 nm in diameter that allowed for fast charge transport and collection.
ABSTRACT
Advanced materials for electrocatalytic water splitting are central to renewable energy research. In this work, three-dimensional (3D) hierarchical frameworks based on the self-assembly of MoS2 nanosheets on graphene oxide were produced via a simple one-step hydrothermal process. The structures of the resulting 3D frameworks were characterized by using a variety of microscopic and spectroscopic tools, including scanning and transmission electron microscopies, X-ray diffraction, X-ray photoelectron spectroscopy, and Raman scattering. Importantly, the three-dimensional MoS2/graphene frameworks might be used directly as working electrodes which exhibited apparent and stable electrocatalytic activity in hydrogen evolution reaction (HER), as manifested by a large cathodic current density with a small overpotential of -107 mV (-121 mV when loaded on a glassy-carbon electrode) and a Tafel slope of 86.3 mV/dec (46.3 mV/dec when loaded on a glassy-carbon electrode). The remarkable performance might be ascribed to the good mechanical strength and high electrical conductivity of the 3D frameworks for fast charge transport and collection, where graphene oxide provided abundant nucleation sites for MoS2 deposition and oxygen incorporation led to the formation of defect-rich MoS2 nanosheets with active sites for HER.
