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Heterostructured composite of NiFe-LDH nanosheets with Ti4O7 for oxygen evolution reaction
Authors:K.B. Ibrahim  W.-N. Su  M.-C. Tsai  A.W. Kahsay  S.A. Chala  M.K. Birhanu  J.-F. Lee  B.J. Hwang
Affiliation:1. Nano-electrochemistry Laboratory, Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei 106, Taiwan;2. Nano-electrochemistry Laboratory, Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei, 106, Taiwan;3. National Synchrotron Radiation Research Center, Hsin-Chu, 300, Taiwan
Abstract:Developing oxygen evolution reaction (OER) electrocatalyst based on earth-abundant materials holds great promise for ascertaining water-splitting to surmount its deprived kinetics. In this regard, NiFe-LDH (layered double hydroxide) receives considerable attention owing to their layered structure. However, they still suffer from poor electronic conductivity and structural stability. We combined NiFe-LDH nanosheets with Magnéli phase Ti4O7 into a heterostructured composite. A series of analyses reveal that decorating Ti4O7 facilitates charge transfer to enhance the conductivity of NiFe-LDH-Ti4O7. During electrochemical measurement, Ni2+ is transformed to metastable Ni3+ (Ni (OH)→ NiOOH) before the OER onset potential. Thus, the presence of Ni3+ as the main active sites could improve the chemisorption of OH? to facilitate OER. As a result, the NiFe-LDH-Ti4O7 catalyst delivers as low as onset potential (1.43 V). Combining the holey structure (NiFe-LDH and Ti4O7) and the defect engineering generated on NiFe-LDH-Ti4O7 as a synergistic effect improves the OER performance. The inclusion of Ti4O7 in the composite leads to more vacancy sites, as evidenced by the extended X-ray absorption fine structure (EXAFS) analysis. The obtained defective structure with a low coordination environment would improve the electronic conductivity and facilitate the adsorption process of H2O onto metal cations, thereby increasing the intrinsic catalytic activity of NiOOH. The strong coupling of NiFe-LDH and Ti4O7 also increases the stability, and the heterostructured composite helps maintain the structural robustness of the LDH.
Keywords:Layered double hydroxides  Charge transfer effect  Structural deformation  Oxide support  Defects
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