The oxygen evolution reaction (OER) is known as the efficiency-limiting step for the electrochemical cleavage of water mainly due to the large overpotentials commonly used materials on the anode side cause. Since Ni-Fe oxides reduce overpotentials occurring in the OER dramatically they are regarded as anode materials of choice for the electrocatalytically driven water-splitting reaction. We herewith show that a straightforward surface modification carried out with AISI 304, a general purpose austenitic stainless steel, very likely, based upon a dissolution mechanism, to result in the formation of an ultra-thin layer consisting of Ni, Fe oxide with a purity > 99%. The Ni enriched thin layer firmly attached to the steel substrate is responsible for the unusual highly efficient anodic conversion of water into oxygen as demonstrated by the low overpotential of 212 mV at 12 mA/cm 2 current density in 1 M KOH, 269.2 mV at 10 mA/cm 2 current density in 0.1 M KOH respectively. The Ni, Fe-oxide layer formed on the steel creates a stable outer sphere, and the surface oxidized steel samples proved to be inert against longer operating times (> 150 ks) in alkaline medium. In addition Faradaic efficiency measurements performed through chronopotentiometry revealed a charge to oxygen
Janus type Water-Splitting Catalysts have attracted highest attention as a tool of choice for solar to fuel conversion. AISI Ni 42 steel was upon harsh anodization converted in a bifunctional electrocatalyst. Oxygen evolution reaction-(OER) and hydrogen evolution reaction (HER) are highly efficiently and steadfast catalyzed at pH 7, 13, 14, 14.6 (OER) respectively at pH 0, 1, 13, 14, 14.6 (HER). The current density taken from long-term OER measurements in pH 7 buffer solution upon the electro activated steel at 491 mV overpotential (η) was around 4 times higher (4 mA/cm 2 ) in comparison with recently developed OER electrocatalysts. The very strong voltagecurrent behavior of the catalyst shown in OER polarization experiments at both pH 7 and at pH 13 were even superior to those known for IrO 2 -RuO 2 . No degradation of the catalyst was detected even when conditions close to standard industrial operations were applied to the catalyst. A stable Ni-, Fe-oxide based passivating layer sufficiently protected the bare metal for further oxidation. Quantitative charge to oxygen-(OER) and charge to hydrogen (HER) conversion was confirmed. High resolution XPS spectra showed that most likely γ−NiO(OH) and FeO(OH) are the catalytic active OER and NiO is the catalytic active HER species.
We fabricated NiFe 2 O 4 thin films on MgAl 2 O 4 (001) substrates by reactive dc magnetron co-sputtering in a pure oxygen atmosphere at different substrate temperatures. The film properties were investigated by various techniques with a focus on their structure, surface topography, magnetic characteristics, and transport properties. Structural analysis revealed a good crystallization with epitaxial growth and low roughness and a similar quality as in films grown by pulsed laser deposition. Electrical conductivity measurements showed high room temperature resistivity (12 Ωm), but low activation energy, indicating an extrinsic transport mechanism. A band gap of about 1.55 eV was found by optical spectroscopy. Detailed x-ray spectroscopy studies confirmed the samples to be ferrimagnetic with fully compensated Fe moments. By comparison with multiplet calculations of the spectra we found that the cation valencies are to a large extent Ni 2+ and Fe 3+ .
In spite of the drastic oil price collapse in the second half of 2014 resulting in a price below 30 $/barrel in January 2016 1 , the exploration of promising renewable energy sources for the Abstract: Water splitting allows the storage of solar energy into chemical bonds (H 2 +O 2 ) and will help to implement the urgently needed replacement of limited available fossil fuels. Particularly in neutral environment electrochemically initiated water splitting suffers from low efficiency due to high overpotentials (η) caused by the anode. Electro-activation of X20CoCrWMo10-9, a Co-based tool steel resulted in a new composite material (X20CoCrWMo10-9//Co 3 O 4 ) that catalyzes the anode half-cell reaction of water electrolysis with a so far-, unequalled effectiveness. The current density achieved with this new anode in pH 7 corrected 0.1 M phosphate buffer is over a wide range of η around 10 times higher compared to recently developed, up-to-date electrocatalysts and represents the benchmark performance advanced catalysts show in regimes that support water splitting significantly better than pH 7 medium. X20CoCrWMo10-9//Co 3 O 4 exhibited electrocatalyticproperties not only at pH 7, but also at pH 13, which is much superior to the ones of IrO 2 -RuO 2 , single-phase Co 3 O 4 -or Fe/Ni-based catalysts. Both XPS and FT-IR experiments unmasked Co 3 O 4 as the dominating compound on the surface of the X20CoCrWMo10-9//Co 3 O 4 composite. Upon a comprehensive dual beam FIB-SEM (focused ion beam-scanning electron microscopy) study we could show that the new composite does not exhibit a classical substrate-layer structure due to the intrinsic formation of the Co-enriched outer zone. This structural particularity is basically responsible for the outstanding electrocatalytic OER performance.2 future is one of the significant challenges for scientists and engineers concerned with energy issues research. Splitting of water into hydrogen and oxygen by exploiting solar energy transforms water to an inexhaustible and environmental friendly fuel source 2,3,4,5,6,7,8,9 .Electrocatalytically initiated hydrogen-and oxygen formation from water is considered an important realization of this solar to fuel conversion route 10,11,12 but is typically hampered by the high overpotentials oxygen evolution on the anode side goes with 13,14 . This is particularly true when the electrochemical cleavage of more or less untreated water is intended-; hence, when the splitting procedure is carried out at neutral pH value. 17,18,19,20,21,22,23,24 . Scheme 1 gives some idea of the position of current heterogeneous catalysts in terms of their efficiency regarding OER in neutral regime. The significant improvement of the voltage-current behavior can be taken from both-, the non-steady state ( Figure 1a) as well as the steady state polarization (Figure 1b) experiments. Results OER properties in neutral mediumThe CV of sample Co-300 shows along the entire curve substantially stronger current to voltage ratio than the CV of sample Co and reached, at the upper...
We present a study of the electronic structure of oxygen-deficient ferrites SrFeO x (x = 2.46, 2.52, 2.68, and 2.82) by means of X-ray photoelectron, X-ray emission, and X-ray absorption spectroscopies. From the Fe 3s photoelectron splitting, the magnetic moments are estimated. It is found that the doped holes are localized in both Fe 3d and O 2p states. The valence band structure is analyzed. It is shown that the band gap decreases with the increase of oxygen concentration.
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