Laser modification-induced NiCo2O4-δ with high exterior Ni3+/Ni2+ ratio and substantial oxygen vacancies for electrocatalysis. (20th February 2019)

• Record Type: Journal Article
• Authors: Liu, Ying; Liu, Pu; Qin, Wei; Wu, Xiaoju; Yang, Guowei
• Is Part Of: Electrochimica acta. Volume 297(2019)
• Page Start: 623
• Page End: 632
• Publication Date: 2019-02-20
• Subjects: NiCo2O4-δ -- Pulse laser ablation -- Octahedral site -- Oxygen vacancy -- Electrocatalysis; Electrochemistry -- Periodicals; Electrochemistry, Industrial -- Periodicals; 541.37
• DOI: 10.1016/j.electacta.2018.11.111
• Languages: English
• ISSNs: 0013-4686

Abstract

Abstract: To explore the surface state of electrocatalysts, herein we developed a surface laser modification (pulsed laser ablation, PLA) approach for the fabrication of NiCo2 O4-δ with substantial inner oxygen vacancies (Vo ·· ) and higher exterior Ni 3+ /Ni 2+ ratio. The separated NiCo2 O4 nanoplates were transformed to cross-linked NiCo2 O4-δ nanostructure through PLA strategy. As compare with the primordial NiCo2 O4 produce, the laser-modificated NiCo2 O4-δ exhibits higher capacitance, lower overpotential and better electrocatalytic performance. The first-principles calculation proves that the additional energy level is introduced between the valence band and conduction band of L-NiCo2 O4-δ . The additional energy level not only benefits the hopping of electrons, but also inhibits the recombination of electron-hole pairs. The X-ray photoelectron spectrum (XPS) confirms that the active sites of the electrocatalytic reaction are Vo ··, suggesting that the electron structure of catalyst could be adjusted by PLA. The high electrocatalytic activity of laser-modificated NiCo2 O4-δ could be ascribed to the synergistic effect of increased number of inner Vo ··, higher electrochemically active surface area, and dominated Nioct . Our findings might inspire new thoughts on the tuning the surface state and electronic structure of electrocatalyst. Highlights: L-NiCo2 O4-δ provides an inter-connected carrier transfer multi-channel, showing good electrocatalytic performance. PLA introduces high exterior Ni 3+ /Ni 2+ ratio and abundant Vo ·· at the surface of L-NiCo2 O4-δ . The Ni 3+ ions in octahedral site occupy a leading role in electrocatalysis.