Electrocatalytic Water Oxidation with α-[Fe(mcp)(OTf)2] and Analogues.
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ABSTRACT: The complex α-[Fe(mcp)(OTf)2] (mcp = N,N'-dimethyl-N,N'-bis(pyridin-2-ylmethyl)-cyclohexane-1,2-diamine and OTf = trifluoromethanesulfonate anion) was reported in 2011 by some of us as an active water oxidation (WO) catalyst in the presence of sacrificial oxidants. However, because chemical oxidants are likely to take part in the reaction mechanism, mechanistic electrochemical studies are critical in establishing to what extent previous studies with sacrificial reagents have actually been meaningful. In this study, the complex α-[Fe(mcp)(OTf)2] and its analogues were investigated electrochemically under both acidic and neutral conditions. All the systems under investigation proved to be electrochemically active toward the WO reaction, with no major differences in activity despite the structural changes. Our findings show that WO-catalyzed by mcp-iron complexes proceeds via homogeneous species, whereas the analogous manganese complex forms a heterogeneous deposit on the electrode surface. Mechanistic studies show that the reaction proceeds with a different rate-determining step (rds) than what was previously proposed in the presence of chemical oxidants. Moreover, the different kinetic isotope effect (KIE) values obtained electrochemically at pH 7 (KIE ∼ 10) and at pH 1 (KIE = 1) show that the reaction conditions have a remarkable effect on the rds and on the mechanism. We suggest a proton-coupled electron transfer (PCET) as the rds under neutral conditions, whereas at pH 1 the rds is most likely an electron transfer (ET).
Project description:This paper describes a simple, low-temperature, and environmentally friendly aqueous route for the layer-by-layer nanometric growth of crystalline α-Fe2O3. The formation mechanism involves alternative sequences of the electrostatic adsorption of Fe2+ ions on the surface and the subsequent onsite oxidation to Fe3+. A combination analysis of X-ray diffraction, scanning electron microscopy, UV-Vis spectroscopy, and X-ray photoelectron spectroscopy revealed that α-Fe2O3 is directly formed without post-growth annealing via designed chemical reactions with a growth rate of ca. 1.7 nm per deposition cycle. The obtained α-Fe2O3 layer exhibits electrocatalytic activity for water oxidation and, at the same time, insignificant photo-electrocatalytic response, indicating its defective nature. The electrocatalytic activity was tailored by annealing up to 500 °C in air, where thermal diffusion of Sn4+ into the α-Fe2O3 lattice from the substrate probably provides an increased electrical conductivity. The subsequent surface-modification with Ni(OH)2 lowers the overpotential (250 mV at 0.5 mA cm-2) in a 1 M KOH solution. These findings open direct growth pathways to functional metal oxide nanolayers via liquid phase atomic layer deposition.
Project description:Electrocatalytic water oxidation is a rate-determining step in the water splitting reaction. Here, we report one single atom W6+ doped Ni(OH)2 nanosheet sample (w-Ni(OH)2) with an outstanding oxygen evolution reaction (OER) performance that is, in a 1 M KOH medium, an overpotential of 237 mV is obtained reaching a current density of 10 mA/cm2. Moreover, at high current density of 80 mA/cm2, the overpotential value is 267 mV. The corresponding Tafel slope is measured to be 33 mV/dec. The d0 W6+ atom with a low spin-state has more outermost vacant orbitals, resulting in more water and OH- groups being adsorbed on the exposed W sites of the Ni(OH)2 nanosheet. Density functional theory (DFT) calculations confirm that the O radical and O-O coupling are both generated at the same site of W6+. This work demonstrates that W6+ doping can promote the electrocatalytic water oxidation activity of Ni(OH)2 with the highest performance.
Project description:We report excellent electrocatalytic performance by AlFe2B2 in the oxygen-evolution reaction (OER). The inexpensive catalytic material, prepared simply by arc-melting followed by ball-milling, exhibits high stability and sustained catalytic performance under alkaline conditions. The overpotential value of 0.24 V observed at the current density of 10 mA cm-2 remained constant for at least 10 days. Electron microscopy and electron energy loss spectroscopy performed on the initial ball-milled material and on the material activated under electrocatalytic conditions suggest that the catalytic mechanism involves partial leaching of Al from the layered structure of AlFe2B2 and the formation of Fe3O4 nanoclusters on the exposed [Fe2B2] layers. Thus, the AlFe2B2 structure serves as a robust supporting material and, more importantly, as a pre-catalyst to the in situ formed active electrocatalytic sites. Comparative electrochemical measurements demonstrate that the electrocatalytic performance of the AlFe2B2-supported Fe3O4 nanoclusters substantially exceeds the results obtained with unsupported nanoparticles of Fe3O4, FeB, or such benchmark OER catalysts as IrO2 or RuO2. The excellent catalytic performance and long-term stability of this system suggests that AlFe2B2 can serve as a promising and inexpensive OER electrocatalyst.
Project description:In this study, the photoelectrochemical behavior of electrodeposited FeNiOOH/Fe2O3/graphene nanohybrid electrodes is investigated, which has precisely controlled structure and composition. The photoelectrode assembly is designed in a bioinspired manner where each component has its own function: Fe2O3 is responsible for the absorption of light, the graphene framework for proper charge carrier transport, while the FeNiOOH overlayer for facile water oxidation. The effect of each component on the photoelectrochemical behavior is studied by linear sweep photovoltammetry, incident photon-to-charge carrier conversion efficiency measurements, and long-term photoelectrolysis. 2.6 times higher photocurrents are obtained for the best-performing FeNiOOH/Fe2O3/graphene system compared to its pristine Fe2O3 counterpart. Transient absorption spectroscopy measurements reveal an increased hole-lifetime in the case of the Fe2O3/graphene samples. Long-term photoelectrolysis measurements in combination with Raman spectroscopy, however, prove that the underlying nanocarbon framework is corroded by the photogenerated holes. This issue is tackled by the electrodeposition of a thin FeNiOOH overlayer, which rapidly accepts the photogenerated holes from Fe2O3, thus eliminating the pathway leading to the corrosion of graphene.
Project description:Developing a cost-effective, efficient, and stable oxygen evolution reaction (OER) catalyst is of great importance for sustainable energy conversion and storage. In this study, we report a facile one-step fabrication of cationic surfactant-assisted Prussian blue analogues (PBAs) Mx[Fe(CN)5CH3C6H4NH2]∙yC19H34NBr abbreviated as SF[Fe-Tol-M] (where SF = N-tridecyl-3-methylpyridinium bromide and M = Mn, Co and Ni) as efficient heterogeneous OER electrocatalysts. The electrocatalysts have been characterized by Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX) analysis, and X-ray photoelectron spectroscopy (XPS). In the presence of cationic surfactant (SF), PBAs-based electrodes showed enhanced redox current, high surface area and robust stability compared to the recently reported PBAs. SF[Fe-Tol-Co] hybrid catalyst shows superior electrochemical OER activity with a much lower over-potential (610 mV) to attain the current density of 10 mA cm-2 with the Tafel slope value of 103 mV·dec-1 than that for SF[Fe-Tol-Ni] and SF[Fe-Tol-Mn]. Moreover, the electrochemical impedance spectroscopy (EIS) unveiled that SF[Fe-Tol-Co] exhibits smaller charge transfer resistance, which results in a faster kinetics towards OER. Furthermore, SF[Fe-Tol-Co] offered excellent stability for continues oxygen production over extended reaction time. This work provides a surface assisted facile electrode fabrication approach for developing binder-free OER electrocatalysts for efficient water oxidation.
Project description:Effectively regulating and promoting the charge separation and transfer of photoanodes is a key and challenging aspect of photoelectrochemical (PEC) water oxidation. Herein, a Ti-doped hematite photoanode with a CoFe-LDH cocatalyst loaded on the surface was prepared through a series of processes, including hydrothermal treatment, annealing and electrodeposition. The prepared CoFe-LDH/Ti:α-Fe2O3 photoanode exhibited an outstanding photocurrent density of 3.06 mA/cm2 at 1.23 VRHE, which is five times higher than that of α-Fe2O3 alone. CoFe-LDH modification and Ti doping on hematite can boost the surface charge transfer efficiency, which is mainly attributed to the interface interaction between CoFe-LDH and Ti:α-Fe2O3. Furthermore, we investigated the role of Ti doping in enhancing the PEC performance of CoFe-LDH/Ti:α-Fe2O3. A series of characterizations and theoretical calculations revealed that, in addition to improving the electronic conductivity of the bulk material, Ti doping also further enhances the interface coupling of CoFe-LDH/α-Fe2O3 and finely regulates the interfacial electronic structure. These changes promote the rapid extraction of holes from hematite and facilitate charge separation and transfer. The informative findings presented in this work provide valuable insights for the design and construction of hematite photoanodes, offering guidance for achieving excellent performance in photoelectrochemical (PEC) water oxidation.
Project description:Chemical and structural changes preceding electrocatalysis obfuscate the nature of the active state of electrocatalysts for the oxygen evolution reaction (OER), which calls for model systems to gain systematic insight. We investigated the effect of bulk oxidation on the overpotential of ink-casted LiMn2 O4 electrodes by a rotating ring-disk electrode (RRDE) setup and X-ray absorption spectroscopy (XAS) at the K shell core level of manganese ions (Mn-K edge). The cyclic voltammogram of the RRDE disk shows pronounced redox peaks in lithium hydroxide electrolytes with pH between 12 and 13.5, which we assign to bulk manganese redox based on XAS. The onset of the OER is pH-dependent on the scale of the reversible hydrogen electrode (RHE) with a Nernst slope of -40(4) mV/pH at -5 μA monitored at the RRDE ring. To connect this trend to catalyst changes, we develop a simple model for delithiation of LiMn2 O4 in LiOH electrolytes, which gives the same Nernst slope of delithiation as our experimental data, i. e., 116(25) mV/pH. From this data, we construct an ERHE -pH diagram that illustrates robustness of LiMn2 O4 against oxidation above pH 13.5 as also verified by XAS. We conclude that manganese oxidation is the origin of the increase of the OER overpotential at pH lower than 14 and also of the pH dependence on the RHE scale. Our work highlights that vulnerability to transition metal redox may lead to increased overpotentials, which is important for the design of stable electrocatalysts.
Project description:As inspired by the Mn4CaO5 oxygen evolution center in nature, Mn-based electrocatalysts have received overwhelming attention for water oxidation. However, the understanding of the detailed reaction mechanism has been a long-standing problem. Herein, homologous KMnPO4 and KMnPO4•H2O with 4-coordinated and 6-coordinated Mn centers, respectively, are prepared. The two catalysts constitute an ideal platform to study the structure-performance correlation. The presence of Mn(III), Mn(IV), and Mn(V) intermediate species are identified during water oxidation. The Mn(V)=O species is demonstrated to be the substance for O-O bond formation. In KMnPO4•H2O, the Mn coordination structure did not change significantly during water oxidation. In KMnPO4, the Mn coordination structure changed from 4-coordinated [MnO4] to 5-coordinated [MnO5] motif, which displays a triangular biconical configuration. The structure flexibility of [MnO5] is thermodynamically favored in retaining Mn(III)-OH and generating Mn(V)=O. The Mn(V)=O species is at equilibrium with Mn(IV)=O, the concentration of which determines the intrinsic activity of water oxidation. This study provides a clear picture of water oxidation mechanism on Mn-based systems.
Project description:Water splitting is thermodynamically uphill reaction, hence it cannot occur easily, and also highly complicated and challenging reaction in chemistry. In electrocatalytic water splitting, the combination of oxygen and hydrogen evolution reactions produces highly clean and sustainable hydrogen energy and which attracts research communities. Also, fabrication of highly active and low cost materials for water splitting is a major challenge. Therefore, in the present study, γ-Fe2O3 nanowires were fabricated from highly available and cost-effective iron plate without any chemical modifications/doping onto the surface of the working electrode with high current density. The fabricated nanowires achieved the current density of 10 mA/cm2 at 1.88 V vs. RHE with the scan rate of 50 mV/sec. Stability measurements of the fabricated Fe2O3 nanowires were monitored up to 3275 sec with the current density of 9.6 mA/cm2 at a constant potential of 1.7 V vs. RHE and scan rate of 50 mV/sec.
Project description:Targeted improvement of the low efficiency of water oxidation during the oxygen evolution reaction (OER) is severely hindered by insufficient knowledge of the electrocatalytic mechanism on heterogeneous surfaces. We chose LiMn2 O4 as a model system for mechanistic investigations as it shares the cubane structure with the active site of photosystem II and the valence of Mn3.5+ with the dark-stable S1 state in the mechanism of natural photosynthesis. The investigated LiMn2 O4 nanoparticles are electrochemically stable in NaOH electrolytes and show respectable activity in any of the main metrics. At low overpotential, the key mechanistic parameters of Tafel slope, Nernst slope, and reaction order have constant values on the RHE scale of 62(1) mV dec-1 , 1(1) mV pH-1 , -0.04(2), respectively. These values are interpreted in the context of the well-studied mechanism of natural photosynthesis. The uncovered difference in the reaction sequence is important for the design of efficient bio-inspired electrocatalysts.