Transition-metal (oxy)hydroxides with an abundance of redox metal sites are important for the development of electrochromic devices, rechargeable metal−air batteries, pseudo-capacitors, and industrial electrolyzers. The robust charging reversibility of the redox metal sites ensures long-term durability of the devices but remains unachieved and usually ignored. Here, we use in situ UV−vis and Raman spectroscopies to track the redox states of a nickel hydroxide Ni(OH) 2 model catalyst for the oxygen evolution reaction (OER) during its lifetime in strong alkaline media. We show that at 200 mAcm −2 in the 1.0 M KOH electrolyte, the reversible redox states of the catalytically active Ni sites gradually disappear when the catalyst converts into an irreversible and inactive phase. We found that after deactivation, the complete reduction of such oxidized Ni sites can not be achieved until a very negative reduction potential around 0.1 V RHE was applied owing to the structural amorphization/disordering of the layered Ni(OH) 2 catalyst. Our results suggest that the deactivated and unreduced Ni sites hardly re-hydrate/re-hydroxylate and thus obstruct the OER process. These findings provide direct evidence for elucidation of the origin of the oxygen evolution decay and contribute to a reference to extend the lifetime of 2D-layered transition-metal hydroxide catalysts by stabilizing the reversible redox metal sites.
Controllable atmospheric pressure CVD has been optimized to grow transition metal dichalcogenide MoSe2 with tunable morphology at 750 °C on a silicon substrate with a native oxide layer of 250 nm.
A substantial effort is devoted to the development of efficient electrolyzers made of earth-abundant elements for low-temperature industrial-scale water electrolysis. However, a large current density leads to the decline of the reaction kinetics that result from the decrease of local pH, the irreversible redox states of active metal sites, and the structure and composition collapse. Currently, the transition metal layered double hydroxides (LDHs) are proven as efficient alkaline oxygen evolution catalysts and demonstrate promising current density, generally at the scale of 10 mA cm–2 for the potential solar-driven catalysis concerning 10% solar-to-fuels efficiency. However, there is very limited progress in understanding the activity and stability degradation mechanism of LDHs at high current density, for instance above 100 mA cm–2. Here we introduce the current advances in achieving activity enhancement by tuning the composition, structure, and morphology of LDHs and present the degradation mechanism during the electrolysis under oxidative alkaline environments, long-term operation, and voltage fluctuations. Finally, we present the state-of-the-art approaches to stabilize the overall performance of LDHs for water oxidation and provide an outlook in this field.
Substantial progress has been made in the photoelectrochemical (PEC) field to understand the photoelectrode behavior, semiconductor‐electrolyte interface, and photocorrosion, enabling new photoelectrode architectures with higher photocurrent, reduced photovoltage losses, and longer lifetime. Nevertheless, for practical PEC applications additional efforts are still needed to optimize all components of the photoelectrodes, including the light absorbing semiconductors, the layers for charge extraction, charge transfer, corrosion protection, and catalysis. In this regard, atomic layer deposition (ALD) offers new opportunities due to the monolayer‐by‐monolayer deposition approach, allowing preparation of conformal films with precisely controlled thickness and composition. As the ALD instruments are becoming widely accessible, this review aims to make an overview of the applications for photoelectrodes fabrication. The deposition of semiconductors onto flat and nano‐textured substrates, the deposition of ultrathin interlayers to ease charge transport by energy band alignment and surface states passivation, the deposition of corrosion protection layers, and finally, the possibilities for high catalyst dispersion is presented.
Amorphous coatings formed with mono-, di-, and tetra-phosphonic acids on barium hexaferrite (BHF) nanoplatelets using various synthesis conditions. The coatings, synthesized in water with di-or tetra-phosphonic acids, were thicker than that could be expected from the ligand size and the surface coverage, as determined by thermogravimetric analysis. Here, we propose a mechanism for coating formation based on direct evidence of the surface dissolution/precipitation of the BHF nanoplatelets. The partial dissolution of the nanoplatelets was observed with atomic-resolution scanning transmission electron microscopy, and the released Fe(III) ions were detected with energy-dispersive Xray spectroscopy and electron energy loss spectroscopy in amorphous coating. The strong chemical interaction between the surface Fe(III) ions with phosphonic ligands induces the dissolution of BHF nanoplatelets and the consequent precipitation of the Fe(III)-phosphonates that assemble into a porous coating. The so-obtained porous nanomagnets are highly responsive to a very weak magnetic field (in the order of Earth's magnetic field) at room temperature, which is a major advantage over the classic mesoporous nanomaterials and metal−organo-phosphonic frameworks with only a weak magnetic response at a few kelvins. The combination of porosity with the intrinsic magneto-crystalline anisotropy of BHF can be exploited, for example, as sorbents for heavy metals from contaminated water.
This study presents a method for high temperature stabilization of amorphous alumina. The strain‐induced stabilization is obtained by dispersion of rigid globular polycarbosilane macromolecules within an alumina matrix. The alumina matrix remains amorphous even at 1200 °C. This study confirms the chemical composition of the coating with an advanced chemical depth‐profile analysis and shows its nanostructure by transmission electron microscopy. Based on this amorphous nanocomposite, a new facile and inexpensive coating for mechanical protection of glass surfaces is further developed. The nanocomposite coating is characterized by a full optical transparency and exceptional tribological characteristics. The wear resistance exceeds that of the current advanced ion‐exchanged boroaluminosilicate glass by a factor of 25–35 whereas its scratch resistance is exceeded by more than an order of magnitude.
Strategies to generate high-valence metal species capable of oxidizing water often employ composition and coordination tuning of oxide-based catalysts, where strong covalent interactions with metal sites are crucial. However, it remains unexplored whether a relatively weak “non-bonding” interaction between ligands and oxides can mediate the electronic states of metal sites in oxides. Here we present an unusual non-covalent phenanthroline-CoO2 interaction that substantially elevates the population of Co4+ sites for improved water oxidation. We find that phenanthroline only coordinates with Co2+ forming soluble Co(phenanthroline)2(OH)2 complex in alkaline electrolytes, which can be deposited as amorphous CoOxHy film containing non-bonding phenanthroline upon oxidation of Co2+ to Co3+/4+. This in situ deposited catalyst demonstrates a low overpotential of 216 mV at 10 mA cm−2 and sustainable activity over 1600 h with Faradaic efficiency above 97%. Density functional theory calculations reveal that the presence of phenanthroline can stabilize CoO2 through the non-covalent interaction and generate polaron-like electronic states at the Co-Co center.
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