| 1. |
- Kwong, Wai Ling, et al.
(författare)
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Cationic Vacancy Defects in Iron Phosphide : A Promising Route toward Efficient and Stable Hydrogen Evolution by Electrochemical Water Splitting
- 2017
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Ingår i: ChemSusChem. - : Wiley-Blackwell. - 1864-5631 .- 1864-564X. ; 10:22, s. 4544-4551
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Tidskriftsartikel (refereegranskat)abstract
- Engineering the electronic properties of transition metal phosphides has shown great effectiveness in improving their intrinsic catalytic activity for the hydrogen evolution reaction (HER) in water splitting applications. Herein, we report for the first time, the creation of Fe vacancies as an approach to modulate the electronic structure of iron phosphide (FeP). The Fe vacancies were produced by chemical leaching of Mg that was introduced into FeP as "sacrificial dopant". The obtained Fe-vacancy-rich FeP nanoparticulate films, which were deposited on Ti foil, show excellent HER activity compared to pristine FeP and Mg-doped FeP, achieving a current density of 10 mAcm(-2) at overpotentials of 108 mV in 1 m KOH and 65 mV in 0.5 m H2SO4, with a near-100% Faradaic efficiency. Our theoretical and experimental analyses reveal that the improved HER activity originates from the presence of Fe vacancies, which lead to a synergistic modulation of the structural and electronic properties that result in a near-optimal hydrogen adsorption free energy and enhanced proton trapping. The success in catalytic improvement through the introduction of cationic vacancy defects has not only demonstrated the potential of Fe-vacancy-rich FeP as highly efficient, earth abundant HER catalyst, but also opens up an exciting pathway for activating other promising catalysts for electrochemical water splitting.
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| 2. |
- Kwong, Wai Ling, et al.
(författare)
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Scalable Two-Step Synthesis of Nickel Iron Phosphide Electrodes for Stable and Efficient Electrocatalytic Hydrogen Evolution
- 2017
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 121:1, s. 284-292
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Tidskriftsartikel (refereegranskat)abstract
- The development of efficient, durable, and inexpensive hydrogen evolution electrodes remains a key challenge for realizing a sustainable H-2 fuel production via electrocatalytic water splitting. Herein, nickel-iron phosphide porous films with precisely controlled metal content were synthesized on Ti foil using a simple and scalable two-step strategy of spray-pyrolysis deposition followed by low-temperature phosphidation. The nickel-iron phosphide of an optimized Ni:Fe ratio of 1:4 demonstrated excellent overall catalytic activity for hydrogen evolution reaction (HER) in 0.5 M H2SO4, achieving current densities of -10 and -30 mA cm(-2) at overpoteritials of 101 and 123 mV, respectively, with a Tafel slope of 43 mV dec(-1). Detailed analysis obtained by X-ray diffraction, electron microscopy, electrochemistry, and X-ray photoelectron spectroscopy revealed that the superior overall HER activity of nickel iron phosphide as compared to nickel phosphide and iron phosphide was a combined effect of differences in the morphology (real surface area) and the intrinsic catalytic properties (electronic structure). Together with a long-term stability and a near-100% Faradaic efficiency, the nickel-iron phosphide electrodes produced in this study provide blueprints for large-scale H-2 production.
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| 3. |
- Melder, Jens, et al.
(författare)
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Electrocatalytic Water Oxidation by MnOx/C : In Situ Catalyst Formation, Carbon Substrate Variations, and Direct O2/CO2 Monitoring by Membrane-Inlet Mass Spectrometry
- 2017
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Ingår i: ChemSusChem. - : John Wiley & Sons. - 1864-5631 .- 1864-564X. ; 10:22, s. 4491-4502
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Tidskriftsartikel (refereegranskat)abstract
- Layers of amorphous manganese oxides were directly formed on the surfaces of different carbon materials by exposing the carbon to aqueous solutions of permanganate (MnO4- ) followed by sintering at 100-400 °C. During electrochemical measurements in neutral aqueous buffer, nearly all of the MnOx /C electrodes show significant oxidation currents at potentials relevant for the oxygen evolution reaction (OER). However, by combining electrolysis with product detection by using mass spectrometry, it was found that these currents were only strictly linked to water oxidation if MnOx was deposited on graphitic carbon materials (faradaic O2 yields >90 %). On the contrary, supports containing sp3 -C were found to be unsuitable as the OER is accompanied by carbon corrosion to CO2 . Thus, choosing the "right" carbon material is crucial for the preparation of stable and efficient MnOx /C anodes for water oxidation catalysis. For MnOx on graphitic substrates, current densities of >1 mA cm-2 at η=540 mV could be maintained for at least 16 h of continuous operation at pH 7 (very good values for electrodes containing only abundant elements such as C, O, and Mn) and post-operando measurements proved the integrity of both the catalyst coating and the underlying carbon at OER conditions.
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