Browsing by Subject "Hydrogen evolution"

Now showing 1 - 4 of 4

Open Access
Cobalt borophosphate on nickel foam as an electrocatalyst for water splitting
(Elsevier BV, 2022-06-10) Ülker, E.; Akbari, Sina Sadigh; Karadas, Ferdi
One of the most critical steps in the transition to carbon-free energy systems is sustainable hydrogen evolution from water. In this research, a cobalt borophosphate crystalline compound consisting of phosphate and borate anions was synthesized with a solid-state reaction. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and X-ray Photoelectron (XPS) was employed to investigate the structure, composition, and morphology of Co3BPO7. Electrocatalytic performances of the catalyst towards oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) have been investigated on nickel foam (NF) electrode in 1.0 M KOH (pH 13.6) by linear sweep voltammetry, chronopotentiometry, cyclic voltammetry, and electrochemical impedance spectroscopy. For OER, the catalyst exhibits an overpotential of 230 mV at 10 mA cm−2 with a Tafel slope of 130 mV dec−1, which is comparable to that of the benchmark RuO2 electrocatalyst, and 220 mV overpotential for a current density of 10 mA cm−2 with a Tafel slope of 147 mV dec−1 for HER process. Long-term chronoamperometry and multiple cyclic voltammetric experiments indicate the catalyst is stable throughout both HER and OER processes. Electrochemical experiments and characterization studies performed on the pristine and post-catalytic electrode indicate that the catalyst is robust under alkaline electrocatalytic conditions (pH 13.6).
Open Access
A cyanide-based coordination polymer for hydrogen evolution electrocatalysis
(Springer New York LLC, 2018) Alsaç, Elif Pınar; Ülker, E.; Nune, Satya Vijaya Kumar; Karadaş, Ferdi
Abstract: Research on H2 production has recently been directed to the development of cost-efficient and robust heterogeneous catalysts for hydrogen evolution reaction (HER). Given the promising catalytic activities of several cobalt-based systems and the robustness of Prussian blue analogues in harsh catalytic processes including water oxidation, a Co-Co Prussian blue analogue was investigated as a HER catalyst for the first time. Co-Co Prussian Blue modified fluorine doped tin oxide (FTO) electrode demonstrated a significant HER activity with an onset overpotential of 257 mV, a Tafel slope of 80 mV dec−1, and a turnover frequency of 0.090 s−1 at an overpotential of 250 mV. Comparative XPS, Infrared, and XRD studies performed on pristine and post-catalytic electrodes confirm the stability of the catalyst.
Open Access
Electrocatalytic hydrogen evolution with cobalt–poly (4-vinylpyridine) metallopolymers
(Springer Netherlands, 2018) Kap, Zeynep; Ülker, Emine; Nune, Satya Vijaya Kuma; Karadaş, Ferdi
Abstract: A facile synthetic pathway using poly(4-vinylpyridine) as a polypyridyl platform is reported for the formation of a metallopolymer. Electrochemical studies indicate that the metallopolymer acts as an efficient H2 evolution catalyst similar to cobalt polypyridyl complexes. It is also observed that the metallopolymer is transformed to cobalt particles when a cathodic potential is applied in the presence of an acid. Electrochemical measurements indicate that an FTO electrode coated with these cobalt particles also acts as an efficient hydrogen evolution catalyst. Approximately 80 µmoles of H2 gas can be collected during 2 h of electrolysis at − 1.5 V (vs. Fc+/0) in the presence of 60 mM of acetic acid. A comprehensive study of the electrochemical and electrocatalytic behavior of cobalt-poly(4-vinylpyridine) is discussed in detail. Graphical Abstract: Poly(4-vinylpyridine) as a precursor for electrodeposited cobalt particles: a cobalt coat derived by a metallopolymer acts as an efficient H2 evolution catalyst. It can transform to a cobalt coat when a potential above − 1.1 V is applied in acid medium. Exchange current density of 10−2.67 mA cm−2 was observed from the Co-coat at − 1.5 V (vs. Fc+/0).
Open Access
The pursuit of an ideal coordination environment of the catalytic site for water splitting
(2022-07) Ahmad, Aliyu Aremu
The construction of catalysts from cheap materials and exquisite tuning of the coordination environment of the active site is pivotal to the development of a highly active sustainable water-splitting catalyst. Although recent years have seen tremendous growth in the application of Prussian Blue Analogues (PBAs) as non-noble catalysts for water splitting, the effect of the structural coordination of the active sites on the activity of a Prussian blue (PB) catalyst is yet to be explored. Herein, using two simple synthetic strategies, we show that manipulating the coordination environment of the catalytic sites affects the morphology, electronic properties, and eventually the catalytic activity of PBAs. Moreover, this study mimics natural photosynthesis by using solar light as an energy source. First, we demonstrate that the water oxidation activity and stability of a Co–Fe PBA can be tuned by coordinating bidentate capping ligands to the catalytic cobalt sites. Structural characterization studies reveal that the ligand decorated structures are of relatively lower dimensionality and they retained their network structures even after photocatalysis. Photocatalytic water oxidation studies indicate that coordination of one equivalent ligand group to the catalytic cobalt sites (CoL–Fe) results in an enhancement of about 50 times in upper-bound turnover frequency (TOF), while coordination of two equivalent ligand groups to the catalytic cobalt sites (CoL2–Fe) lead to an inactivity, which is attributed to the lack of coordination of water molecules to the catalytic sites. In addition, computational studies support experimental observation by showing that bidentate pyridyl groups enhance the susceptibility of the rate-determining Co(IV)-oxo species to the nucleophilic water attack during the critical O−O bond formation. We found in the second study that the replacement of [Fe(CN)6]3− unit with a square planar [Ni(CN)4]2− building block drastically changes the electronic environment and catalytic properties by converting the PB structure from 3D to a 2D layered structure, and we utilized it for the first time for photocatalytic hydrogen evolution reaction. We synthesized a 2D cyanide-coordination compound [Co–Ni] and performed a complete structural and morphological characterization that fully supports our synthetic claim. Relying on its exposed facets, layered morphology, and abundant surface-active sites, [Co–Ni] can efficiently convert water and sunlight to H2 in the presence of a ruthenium photosensitizer with an optimal evolution rate of 30,029 μmol g−1 h −1, greatly exceeding that of 3D PBA frameworks and top-ranked catalysts operating under the same condition. Furthermore, [Co–Ni] retains its structural integrity throughout a 6-hour photocatalytic cycle, which is confirmed by XPS, XRD and Infrared analysis. Overall, these two strategies signify the importance of the coordination environment of the active sites in exploiting structure/morphology and optimizing the activity of the catalyst.