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Atomic layer deposition of Co₃O₄ nanocrystals on N-doped electrospun carbon nanofibers for oxygen reduction and oxygen evolution reactions.

ABSTRACT: The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are considered as the two crucial reactions in key renewable-energy technologies including fuel cells and water splitting. Despite promising research progress in the preparation of various non-noble metal based electrocatalysts, it is still highly challenging but desirable to develop novel fabrication strategies to synthesize highly active and cost-effective ORR/OER bifunctional electrocatalysts in a precisely controlled manner. Herein, we report atomic layer deposition (ALD) of highly monodisperse Co₃O₄ nanocrystals of different sizes on N-doped electrospun carbon nanofibers (nCNFs) as high performance bifunctional catalysts (Co@nCNFs) for the ORR and OER. Co@nCNFs (with an average Co₃O₄ particle size of ∼3 nm) show high ORR performance exhibiting an onset potential of 0.87 V with a low Tafel slope of 119 mV dec^-1 approaching that of commercial Pt/C. Similarly, the Co@nCNF electrocatalyst showed remarkable catalytic activity in the OER. The turnover frequency (TOF) value determined at an overpotential of 550 mV for the Co@nCNFs is ∼0.14 s^-1 which is ca. 3 and ca. 15-fold higher than those of bulk Co (∼0.05 s^-1) and the standard state-of-the-art IrO _x (0.0089 s^-1) catalyst, respectively. This work will open new possibilities for fabrication of inexpensive non-noble metal materials in highly controlled manner for applications as bifunctional ORR/OER electrocatalysis.

SUBMITTER: Khalily MA

PROVIDER: S-EPMC9473253 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Atomic layer deposition of Co<sub>3</sub>O<sub>4</sub> nanocrystals on N-doped electrospun carbon nanofibers for oxygen reduction and oxygen evolution reactions.

Khalily Mohammad Aref MA Patil Bhushan B Yilmaz Eda E Uyar Tamer T

Nanoscale advances 20181226 3

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are considered as the two crucial reactions in key renewable-energy technologies including fuel cells and water splitting. Despite promising research progress in the preparation of various non-noble metal based electrocatalysts, it is still highly challenging but desirable to develop novel fabrication strategies to synthesize highly active and cost-effective ORR/OER bifunctional electrocatalysts in a precisely controlled man ...[more]

PMID: 36133191

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Project description:Atomic layer deposition (ALD) of alumina using trimethylaluminum (TMA) has technological importance in microelectronics. This process has demonstrated a high potential in applications of protective coatings on Cu surfaces for control of diffusion of Cu in Cu2S films in photovoltaic devices and sintering of Cu-based nanoparticles in liquid phase hydrogenation reactions. With this motivation in mind, the reaction between TMA and oxygen was investigated on Cu(111) and Cu2O/Cu(111) surfaces. TMA did not adsorb on the Cu(111) surface, a result consistent with density functional theory (DFT) calculations predicting that TMA adsorption and decomposition are thermodynamically unfavorable on pure Cu(111). On the other hand, TMA readily adsorbed on the Cu2O/Cu(111) surface at 473 K resulting in the reduction of some surface Cu(1+) to metallic copper (Cu(0)) and the formation of a copper aluminate, most likely CuAlO2. The reaction is limited by the amount of surface oxygen. After the first TMA half-cycle on Cu2O/Cu(111), two-dimensional (2D) islands of the aluminate were observed on the surface by scanning tunneling microscopy (STM). According to DFT calculations, TMA decomposed completely on Cu2O/Cu(111). High-resolution electron energy loss spectroscopy (HREELS) was used to distinguish between tetrahedrally (Altet) and octahedrally (Aloct) coordinated Al(3+) in surface adlayers. TMA dosing produced an aluminum oxide film, which contained more octahedrally coordinated Al(3+) (Altet/Aloct HREELS peak area ratio ? 0.3) than did dosing O2 (Altet/Aloct HREELS peak area ratio ? 0.5). After the first ALD cycle, TMA reacted with both Cu2O and aluminum oxide surfaces in the absence of hydroxyl groups until film closure by the fourth ALD cycle. Then, TMA continued to react with surface Al-O, forming stoichiometric Al2O3. O2 half-cycles at 623 K were more effective for carbon removal than O2 half-cycles at 473 K or water half-cycles at 623 K. The growth rate was approximately 3-4 Å/cycle for TMA+O2 ALD (O2 half-cycles at 623 K). No preferential growth of Al2O3 on the steps of Cu(111) was observed. According to STM, Al2O3 grows homogeneously on Cu(111) terraces.

Dataset Information

Atomic layer deposition of Co₃O₄ nanocrystals on N-doped electrospun carbon nanofibers for oxygen reduction and oxygen evolution reactions.

Publications

Atomic layer deposition of Co<sub>3</sub>O<sub>4</sub> nanocrystals on N-doped electrospun carbon nanofibers for oxygen reduction and oxygen evolution reactions.

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Dataset Information

Atomic layer deposition of Co3O4 nanocrystals on N-doped electrospun carbon nanofibers for oxygen reduction and oxygen evolution reactions.

Publications

Atomic layer deposition of Co<sub>3</sub>O<sub>4</sub> nanocrystals on N-doped electrospun carbon nanofibers for oxygen reduction and oxygen evolution reactions.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Atomic layer deposition of Co₃O₄ nanocrystals on N-doped electrospun carbon nanofibers for oxygen reduction and oxygen evolution reactions.