Modulated transition metal-oxygen covalency in the octahedral sites of CoFe layered double hydroxides with vanadium
Yibin Yang1, Yingqing Ou2, Yang Yang2
1Chongqing Key Laboratory of Soft Condensed Matter Physics and Smart Materials, College of Physics, Chongqing University, Chongqing 400030, China. xiaopeng@cqu.edu.cn.
Abstract:
The development of efficient and stable non-noble-metal electrocatalytic materials for the oxygen evolution reaction (OER) is a huge and important challenge at present. Herein, we report the prominent enhancement of OER activity via doping vanadium into CoFe-based layered double hydroxide (LDH) electrocatalysts. Electrochemical characterization shows that the Co2Fe0.5V0.5 LDH grown on carbon papers (CPs) has an enormous electrochemical surface area (ECSA) and exhibits the smallest overpotential of 242 mV at 10 mA cm-2, which only requires a small Tafel slope of 41.4 mV dec-1 in 1 M KOH solution. The X-ray photoelectron spectroscopy (XPS) peak position of Co, Fe and O moves slightly to higher binding energy, elucidating the improved covalency of the metal-oxygen bond after V doping. DFT+U simulation indicates that the outstanding electrocatalytic activity of Co2Fe0.5V0.5 could be ascribed to the increased metal-oxygen covalency in LDH after V element doping, and facilitates the charge-transfer from oxygen to the metal. This finely tuned strategy by V doping into the CoFe-based LDH matrix can adjust the covalency of metal-oxygen bridges and enhance its electrocatalytic activity for the OER. In this work, we also present a general method to study various highly efficient metal hydroxide catalysts for the OER.
Related Concept Videos
02:58Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
02:42Valence Bond Theory
02:58Properties of Transition Metals
03:02Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
02:44Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
01:23Properties of Organometallic Compounds