This study explores the influence of Fe ion incorporation on the oxygen-evolution reaction (OER) in alkaline media, utilizing CuO-based materials. Instead of developing an efficient and stable OER catalyst, this research investigates two distinct CuO variants: one with Fe ions adhered to the surface and another with Fe ions integrated into the CuO lattice. By employing a variety of analytical techniques, the study demonstrates that the CuO variant with surface-bound Fe ions (referred to as compound 1) exhibits significantly enhanced OER performance compared to the variant with internally embedded Fe ions (referred to as compound 2).
View Article and Find Full Text PDFThis study investigated the dynamic changes in NiFe (hydr)oxide and identified the role of high-valent Fe in the oxygen-evolution reaction (OER) within alkaline media via in situ techniques. Several high-valent Fe ions were found to remain considerably stable in the absence of potential in NiFe (hydr)oxide, even 96 hours after the OER. For Ni hydroxide treated with Fe ions, where Fe sites are introduced onto the surface of Ni hydroxide, no Fe species were detected at the rate-determining step (RDS).
View Article and Find Full Text PDFThe oxygen evolution reaction (OER) in alkaline media is crucial for energy conversion technologies, and Fe-based catalysts have garnered significant attention for their efficacy. In this study, we provide an investigation of Fe-based catalysts under OER conditions using some techniques. Our findings reveal minimal structural alterations in the bulk FeHO framework during OER, indicating that the bulk structure remains largely intact.
View Article and Find Full Text PDFDeveloping Mn-based water-oxidation reaction (WOR) catalysts is key for renewable energy storage, utilizing Mn's abundance, cost-effectiveness, and natural role. Cerium(IV) ammonium nitrate (CAN) has been widely utilized as a sacrificial oxidant in the exploration of WOR catalysts. In this study, advanced techniques, such as X-ray absorption spectroscopy (XAS), in situ Raman spectroscopy, and in situ electron paramagnetic resonance (EPR), to delve into the WOR facilitated by CAN and birnessite were employed.
View Article and Find Full Text PDFTungsten disulfide (WS), a promising electrocatalyst made from readily available materials, demonstrates significant effectiveness in the hydrogen-evolution reaction (HER). The study conducts a thorough investigation using various analytical methods such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS), X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR), and in situ Raman spectroscopy. These techniques have uncovered changes in the WS particle structure during HER.
View Article and Find Full Text PDFThis study focuses on the oxygen-evolution reaction (OER) activity comparison between two forms of NiFe (hydr)oxides: compound , where Fe ions are applied on the surface of nickel (hydr)oxide, and compound , with Fe ions incorporated into the structural matrix of nickel (hydr)oxide. The observed exponential link between Coulombic energy and the total charge of the system points to a direct proportionality between the potential and the concentration of oxidized nickel ions (e.g.
View Article and Find Full Text PDFThe progress made in natural language processing (NLP) and large language models (LLMs), such as generative pre-trained transformers, (GPT) has provided exciting opportunities for enhancing research across various fields. Within the realm of catalysis studies, GPT-driven models present valuable support in expediting the exploration and comprehension of catalytic processes. This research underscores the significance of ChatGPT in catalysis research, emphasizing its prowess as a valuable tool for furthering scientific inquiries.
View Article and Find Full Text PDFRecently, Ni molecular catalysis has been extensively applied in oxygenation reactions. This work is underpinned by the characterization techniques and the discovered instability of the Ni-bipyridine/phenanthroline system, which results in Ni (hydr)oxide production under oxidative conditions. The practical applications of this mechanism by employing a prepared Ni (hydr)oxide-based electrode specifically in the oxygenation of sulfides, achieving noteworthy yields in contrast to noncatalyst control experiments, are explored.
View Article and Find Full Text PDFThe oxygen-evolution reaction (OER) is a bottleneck in water splitting, which is a critical process for energy storage. In this study, the electrochemistry of Pb in the absence or presence of KFeO, as a soluble Fe source, is examined at pH ≈ 13. Our findings indicate that Pb exhibits limited catalytic activity for the OER under alkaline conditions.
View Article and Find Full Text PDFAlthough nickel (hydr)oxides in the absence of other metal ions are conventionally deemed inefficient catalysts for the oxygen-evolution reaction (OER) under alkaline conditions, this study reveals that nickel oxyhydroxide displays an OER activity at the associated peak for Ni(II) to Ni(III) oxidation postcharge accumulation. This occurs with only 90-120 mV overpotentials (at a low current density) and a Tafel slope of 297 mV/decade in a 0.10 M KOH solution.
View Article and Find Full Text PDFLarge-scale solar-driven water splitting is a way to store energy, but it requires the development of practical and durable oxygen evolution reaction (OER) catalysts. The present paper aims to investigate the mechanism of the OER, local pH, high-valent metal ions, limitations, conversions, and details during the OER in the presence of FeNi foam using in situ surface-enhanced Raman spectroscopy. This research also explores the use of in situ surface-enhanced Raman spectroscopy for detecting species on foam surfaces during the OER.
View Article and Find Full Text PDFAn efficient and durable oxygen evolution reaction (OER) catalyst is necessary for the water-splitting process toward energy conversion. The OER through water oxidation reactions could provide electrons for HO, CO, and N reduction and produce valuable compounds. Herein, the FeNi (1:1 Ni/Fe) alloy as foam, after anodizing at 50 V in a two-electrode system in KOH solution (1.
View Article and Find Full Text PDFSolar fuel production by photosynthetic systems strongly relies on developing efficient and stable oxygen-evolution catalysts (OECs). Cerium(IV) ammonium nitrate (CAN) has been the most commonly used sacrificial oxidant to investigate OECs. Although many metal oxides have been extensively investigated as OECs in the presence of CAN, mechanistic studies were rarely reported.
View Article and Find Full Text PDFCerium(IV) ammonium nitrate (CAN) has been extensively used as a sacrificial oxidant to study water-oxidation catalysts (WOCs). Although nickel hydroxide has been extensively investigated as WOCs, the water-oxidation reaction (WOR) and mechanistic studies in the presence of CAN and nickel hydroxide were rarely performed. Herein, using in situ Raman spectroscopy, in situ X-ray absorption spectroscopy, and in situ electron paramagnetic resonance spectroscopy, WOR in the presence of CAN and β-Ni(OH) was investigated.
View Article and Find Full Text PDFMetal complexes are extensively explored as catalysts for oxidation reactions; molecular-based mechanisms are usually proposed for such reactions. However, the roles of the decomposition products of these materials in the catalytic process have yet to be considered for these reactions. Herein, the cyclohexene oxidation in the presence of manganese(III) 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine chloride tetrakis(methochloride) (1) in a heterogeneous system via loading the complex on an SBA-15 substrate is performed as a study case.
View Article and Find Full Text PDFRecently, copper(II) complexes have been extensively investigated as oxygen-evolution reaction (OER) catalysts through a water-oxidation reaction. Herein, new findings regarding OER in the presence of a Cu(II) complex with 6,6'-dihydroxy-2,2'-bipyridine ligand are reported. Using scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction, Raman spectroscopy, in situ visible microscopy, in situ visible spectroelectrochemistry, X-ray absorption spectroscopy, and electrochemistry, it is hypothesized that the film formed on the electrode's surface in the presence of this complex causes an appropriated matrix to produce Cu (hydr)oxide.
View Article and Find Full Text PDFArtificial photosynthesis, an umbrella term, is a chemical process that biomimetics natural photosynthesis. In natural photosynthesis, electrons from the water-oxidation reaction are used for carbon dioxide reduction. Herein, we report the reducion of aldehydes and ketones to corresponding alcohols in a simple undivided cell.
View Article and Find Full Text PDFThe excitation-emission fluorescence spectroscopy combined with three-way analysis was applied for discriminating the pure BSA and BSA/FeO(OAc)ClO (Fe) using unsupervised classification methods. Herein, the interaction of bovine serum albumin (BSA) and Fe clusters as an artificial enzyme is studied by extracting the intrinsic excitation-emission (EEM) fluorescence of BSA. The conformation of BSA changes with pH, temperature, and Fe concentration.
View Article and Find Full Text PDFWater-oxidation reaction (WOR) catalysts are critical for energy conversion. WOR is a four-electron oxidation and sluggish reaction. WOR needs a high thermodynamic driving force; it is also a kinetically slow reaction.
View Article and Find Full Text PDFIn the context of energy storage, the oxygen-evolution reaction (OER, 2HO → O + 4H + 4e) through the water-oxidation reaction is a thermodynamically uphill reaction in overall water splitting. In recent years, copper(II) coordination compounds have been extensively used for the OER. However, challenges remain in finding the mechanism of the OER in the presence of these metal coordination compounds.
View Article and Find Full Text PDFThe oxygen evolution reaction (OER) can provide electrons for reducing water, carbon dioxide, and ammonia. On the other hand, copper compounds are among the most interesting OER catalysts. In this study, water oxidation of a Cu foil in the presence of KFeO, a soluble Fe source, under alkaline conditions (pH ≈ 13) is investigated using electrochemical methods, X-ray diffraction, X-ray photoelectron spectroscopy, in situ visible spectroelectrochemistry, Raman spectroscopy, and scanning electron microscopy.
View Article and Find Full Text PDFMetal-organic frameworks (MOFs) are extensively investigated as catalysts in the oxygen-evolution reaction (OER). A Ni-Fe MOF with 2,5-dihydroxy terephthalate as a linker has been claimed to be among the most efficient catalysts for the oxygen-evolution reaction (OER) under alkaline conditions. Herein, the MOF stability under the OER was reinvestigated by electrochemical methods, X-ray diffraction, X-ray absorption spectroscopy, energy-dispersive spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy, nuclear magnetic resonance, operando visible spectroscopy, electrospray ionization mass spectroscopy, and Raman spectroscopy.
View Article and Find Full Text PDFThe design of molecular-based catalysts for oxygen-evolution reaction (OER) requires more investigations for the true catalyst to be found. First-row transition metal complexes are extensively investigated for OER, but the role of these metal complexes as a true catalyst is doubtful. Some doubts have been expressed about the role of first-row transition metal complexes for OER at high overpotentials (η > 450).
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