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      Phosphorized polyoxometalate-etched iron-hydroxide porous nanotubes for efficient electrocatalytic oxygen evolution

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          Abstract

          FeOOH/FePO x porous nanotubes were prepared with polyoxometalates for high-performance electrocatalytic OER, affording a low overpotential of 230 mV.

          Abstract

          Splitting water into H 2 and O 2 attracts significant attention to meet the increasing need for energy. As the oxygen evolution reaction (OER) constitutes the bottleneck in water splitting, the development of efficient OER catalysts is highly desirable. As a potential electrocatalyst for this reaction, we demonstrate herein a facile two-step method to synthesize FeOOH/FePO x porous nanotubes, which involve the phosphorization of β-FeOOH nanotubes that are hydrothermally prepared with the assistance of polyoxometalates (POMs). The acidity of POMs readily modulates the pore size and surface area of the nanotubes. Benefitting from the porous and hollow feature to expose multiple active sites, the FeOOH/FePO x porous nanotubes can be used as a high-performance electrocatalyst, which offers an overpotential of 230 mV at a current density of 10 mA cm −2 with extraordinary stability in 300 h operation. Its superior performance exceeds that of the commercial catalyst (IrO 2, 275 mV) under the same conditions and those of most reported Fe catalysts.

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          Most cited references52

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          Transition Metal Oxides as Electrocatalysts for the Oxygen Evolution Reaction in Alkaline Solutions: An Application-Inspired Renaissance

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            Mechanistic studies of the oxygen evolution reaction by a cobalt-phosphate catalyst at neutral pH.

            The mechanism of the oxygen evolution reaction (OER) by catalysts prepared by electrodepositions from Co(2+) solutions in phosphate electrolytes (Co-Pi) was studied at neutral pH by electrokinetic and (18)O isotope experiments. Low-potential electrodepositions enabled the controlled preparation of ultrathin Co-Pi catalyst films (<100 nm) that could be studied kinetically in the absence of mass transport and charge transport limitations to the OER. The Co-Pi catalysts exhibit a Tafel slope approximately equal to 2.3 × RT/F for the production of oxygen from water in neutral solutions. The electrochemical rate law exhibits an inverse first order dependence on proton activity and a zeroth order dependence on phosphate for [Pi] ≥ 0.03 M. In the absence of phosphate buffer, the Tafel slope is increased ∼3-fold and the overall activity is greatly diminished. Together, these electrokinetic studies suggest a mechanism involving a rapid, one electron, one proton equilibrium between Co(III)-OH and Co(IV)-O in which a phosphate species is the proton acceptor, followed by a chemical turnover-limiting process involving oxygen-oxygen bond coupling.
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              Filling the oxygen vacancies in Co3O4 with phosphorus: an ultra-efficient electrocatalyst for overall water splitting

              It is of essential importance to design an electrocatalyst with excellent performance for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting. It is of essential importance to design an electrocatalyst with excellent performance for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting. Co 3 O 4 has been developed as a highly efficient OER electrocatalyst, but it has almost no activity for HER. In a previous study, it has been demonstrated that the formation of oxygen vacancies (V O ) in Co 3 O 4 can significantly enhance the OER activity. However, the stability of V O needs to be considered, especially under the highly oxidizing conditions of the OER process. It is a big challenge to stabilize the V O in Co 3 O 4 while reserving the excellent activity. Filling the oxygen vacancies with heteroatoms in the V O -rich Co 3 O 4 may be a smart strategy to stabilize the V O by compensating the coordination numbers and obtain an even surprising activity due to the modification of electronic properties by heteroatoms. Herein, we successfully transformed V O -rich Co 3 O 4 into an HER-OER electrocatalyst by filling the in situ formed V O in Co 3 O 4 with phosphorus (P-Co 3 O 4 ) by treating Co 3 O 4 with Ar plasma in the presence of a P precursor. The relatively lower coordination numbers in V O -Co 3 O 4 than those in pristine Co 3 O 4 were evidenced by X-ray adsorption spectroscopy, indicating that the oxygen vacancies were created after Ar plasma etching. On the other hand, the relatively higher coordination numbers in P-Co 3 O 4 than those in V O -Co 3 O 4 and nearly same coordination number as that in pristine Co 3 O 4 strongly suggest the efficient filling of P in the vacancies by treatment with Ar plasma in the presence of a P precursor. The Co–O bonds in Co 3 O 4 consist of octahedral Co 3+ (O h )–O and tetrahedral Co 2+ (T d )–O (Oh, octahedral coordination by six oxygen atoms and T d , tetrahedral coordination by four oxygen atoms). More Co 3+ (O h )–O are broken when oxygen vacancies are formed in V O -Co 3 O 4 , and more electrons enter the octahedral Co 3d orbital than those entering the tetrahedral Co 3d orbital. Then, with the filling of P in the vacancy site, electrons are transferred out of the Co 3d states, and more Co 2+ (T d ) than Co 3+ (O h ) are left in P-Co 3 O 4 . These results suggest that the favored catalytic ability of P-Co 3 O 4 is dominated by the Co 2+ (T d ) site. P-Co 3 O 4 shows superior electrocatalytic activities for HER and OER (among the best non-precious metal catalysts). Owing to its superior efficiency, P-Co 3 O 4 can directly catalyze overall water splitting with excellent performance. The theoretical calculations illustrated that the improved electrical conductivity and intermediate binding by P-filling contributed significantly to the enhanced HER and OER activity of Co 3 O 4 .
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                Author and article information

                Journal
                JMCAET
                Journal of Materials Chemistry A
                J. Mater. Chem. A
                Royal Society of Chemistry (RSC)
                2050-7488
                2050-7496
                December 4 2018
                2018
                : 6
                : 47
                : 24479-24485
                Affiliations
                [1 ]Institute for New Energy Materials and Low Carbon Technologies
                [2 ]School of Material Science & Engineering
                [3 ]Tianjin University of Technology
                [4 ]Tianjin 300384
                [5 ]People's Republic of China
                [6 ]Tianjin Key Laboratory of Organic Solar Cells and Photochemical Conversion
                [7 ]School of Chemistry and Chemical Engineering
                Article
                10.1039/C8TA09240K
                bafa808d-aba8-4e71-bc23-d8af75525b5e
                © 2018

                http://rsc.li/journals-terms-of-use

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