Intermetallic Cobalt Indium Nanoparticles as Oxygen Evolution Reaction Precatalyst: A Non-Leaching p-Block Element.

Merely all transition-metal-based materials reconstruct into similar oxyhydroxides during the electrocatalytic oxygen evolution reaction (OER), severely limiting the options for a tailored OER catalyst design. In such reconstructions, initial constituent p-block elements take a sacrificial role and leach into the electrolyte as oxyanions, thereby losing the ability to tune the catalyst's properties systematically. From a thermodynamic point of view, indium is expected to behave differently and should remain in the solid phase under alkaline OER conditions. However, the structural behavior of transition metal indium phases during the OER remains unexplored. Herein, are synthesized intermetallic cobalt indium (CoIn3) nanoparticles and revealed by in situ X-ray absorption spectroscopy and scanning transmission microscopy that they undergo phase segregation to cobalt oxyhydroxide and indium hydroxide. The obtained cobalt oxyhydroxide outperforms a metallic-cobalt-derived one due to more accessible active sites. The observed phase segregation shows that indium behaves distinctively differently from most p-block elements and remains at the electrode surface, where it can form lasting interfaces with the active metal oxo phases.

Degradation of Phenol via an Advanced Oxidation Process (AOP) with Immobilized Commercial Titanium Dioxide (TiO2) Photocatalysts.

Four commercial titanium dioxide (TiO2) photocatalysts, namely P25, P90, PC105, and PC500, were immobilized onto steel plates using a sol-gel binder and investigated for phenol degradation under 365 nm UV-LED irradiation. High-performance liquid chromatography (HPLC) and total organic carbon (TOC) analyses were performed to study the impact of three types of oxygen sources (air, dispersed synthetic air, and hydrogen peroxide) on the photocatalytic performance. The photocatalyst films were stable and there were significant differences in their performance. The best result was obtained with the P90/UV/H2O2 system with 100% degradation and about 70% mineralization within 3 h of irradiation. The operating conditions varied, showing that water quality is crucial for the performance. A wastewater treatment plant was developed based on the lab-scale results and water treatment costs were estimated for two cases of irradiation: UV-LED (about 600 EUR/m3) and sunlight (about 60 EUR/m3). The data show the high potential of immobilized photocatalysts for pollutant degradation under advanced oxidation process (AOP) conditions, but there is still a need for optimization to further reduce treatment costs.

Evolution of Carbonate-Intercalated γ-NiOOH from a Molecularly Derived Nickel Sulfide (Pre)Catalyst for Efficient Water and Selective Organic Oxidation.

The development of a competent (pre)catalyst for the oxygen evolution reaction (OER) to produce green hydrogen is critical for a carbon-neutral economy. In this aspect, the low-temperature, single-source precursor (SSP) method allows the formation of highly efficient OER electrocatalysts, with better control over their structural and electronic properties. Herein, a transition metal (TM) based chalcogenide material, nickel sulfide (NiS), is prepared from a novel molecular complex [NiII (PyHS)4 ][OTf]2 (1) and utilized as a (pre)catalyst for OER. The NiS (pre)catalyst requires an overpotential of only 255 mV to reach the benchmark current density of 10 mA cm-2 and shows 63 h of chronopotentiometry (CP) stability along with over 95% Faradaic efficiency in 1 m KOH. Several ex situ measurements and quasi in situ Raman spectroscopy uncover that NiS irreversibly transformed to a carbonate-intercalated γ-NiOOH phase under the alkaline OER conditions, which serves as the actual active structure for the OER. Additionally, this in situ formed active phase successfully catalyzes the selective oxidation of alcohol, aldehyde, and amine-based organic substrates to value-added chemicals, with high efficiencies.

Perspective on intermetallics towards efficient electrocatalytic water-splitting.

Intermetallic compounds exhibit attractive electronic, physical, and chemical properties, especially in terms of a high density of active sites and enhanced conductivity, making them an ideal class of materials for electrocatalytic applications. Nevertheless, widespread use of intermetallics for such applications is often limited by the complex energy-intensive processes yielding larger particles with decreased surface areas. In this regard, alternative synthetic strategies are now being explored to realize intermetallics with distinct crystal structures, morphology, and chemical composition to achieve high performance and as robust electrode materials. In this perspective, we focus on the recent advances and progress of intermetallics for the reaction of electrochemical water-splitting. We first introduce fundamental principles and the evaluation parameters of water-splitting. Then, we emphasize the various synthetic methodologies adapted for intermetallics and subsequently, discuss their catalytic activities for water-splitting. In particular, importance has been paid to the chemical stability and the structural transformation of the intermetallics as well as their active structure determination under operating water-splitting conditions. Finally, we describe the challenges and future opportunities to develop novel high-performance and stable intermetallic compounds that can hold the key to more green and sustainable economy and rise beyond the horizon of water-splitting application.

Combination of Highly Efficient Electrocatalytic Water Oxidation with Selective Oxygenation of Organic Substrates using Manganese Borophosphates.

One of the key catalytic reactions for life on earth, the oxidation of water to molecular oxygen, occurs in the oxygen-evolving complex of the photosystem II (PSII) mediated by a manganese-containing cluster. Considerable efforts in this research area embrace the development of efficient artificial manganese-based catalysts for the oxygen evolution reaction (OER). Using artificial OER catalysts for selective oxygenation of organic substrates to produce value-added chemicals is a worthwhile objective. However, unsatisfying catalytic performance and poor stability have been a fundamental bottleneck in the field of artificial PSII analogs. Herein, for the first time, a manganese-based anode material is developed and paired up for combining electrocatalytic water oxidation and selective oxygenations of organics delivering the highest efficiency reported to date. This can be achieved by employing helical manganese borophosphates, representing a new class of materials. The uniquely high catalytic activity and durability (over 5 months) of the latter precursors in alkaline media are attributed to its unexpected surface transformation into an amorphous MnOx phase with a birnessite-like short-range order and surface-stabilized MnIII sites under extended electrical bias, as unequivocally demonstrated by a combination of in situ Raman and quasi in situ X-ray absorption spectroscopy as well as ex situ methods.

Boosting Water Oxidation through In Situ Electroconversion of Manganese Gallide: An Intermetallic Precursor Approach.

For the first time, the manganese gallide (MnGa4 ) served as an intermetallic precursor, which upon in situ electroconversion in alkaline media produced high-performance and long-term-stable MnOx -based electrocatalysts for water oxidation. Unexpectedly, its electrocorrosion (with the concomitant loss of Ga) leads simultaneously to three crystalline types of MnOx minerals with distinct structures and induced defects: birnessite δ-MnO2 , feitknechtite ß-MnOOH, and hausmannite α-Mn3 O4 . The abundance and intrinsic stabilization of MnIII /MnIV active sites in the three MnOx phases explains the superior efficiency and durability of the system for electrocatalytic water oxidation. After electrophoretic deposition of the MnGa4 precursor on conductive nickel foam (NF), a low overpotential of 291 mV, comparable to that of precious-metal-based catalysts, could be achieved at a current density of 10 mA cm-2 with a durability of more than five days.

Boosting Electrocatalytic Hydrogen Evolution Activity with a NiPt3@NiS Heteronanostructure Evolved from a Molecular Nickel-Platinum Precursor.

A facile synthetic route to NiPt3@NiS heteronanostructures is reported, starting from a subsulfido bridged heterobimetallic nickel-platinum molecular precursor. Notably, the NiPt3@NiS on nickel foam displayed merely an overpotential of 12 mV at -10 mA cm-2, which is substantially lower than that of Pt or NiS, synthesized through a similar approach and represents the most active hydrogen evolution reaction (HER) electrocatalysts yet reported in alkaline solutions. NiPt3@NiS electrodes demonstrated an unceasing HER stability over 8 days, which is well over those reported for Pt-based catalysts signifying a capability of scaled hydrogen production.

Structurally Ordered Intermetallic Cobalt Stannide Nanocrystals for High-Performance Electrocatalytic Overall Water-Splitting.

The synthesis of structurally ordered non-noble intermetallic cobalt stannide (CoSn2 ) nanocrystals and their utilization for high-performance electrocatalytic overall water-splitting is presented. The structurally and electronically beneficial properties of the tetragonal CoSn2 exhibit a considerably low overpotential for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) on fluorine-doped tin oxide (FTO) and Ni foam (NF). Loss of Sn from the crystal lattices and oxidation of Co under strongly alkaline conditions furnishes highly disordered amorphous active CoOx (H), the catalytically active structure for OER. The Co0 atoms in the CoSn2 act as active sites for HER and the presence of Sn provides efficient electrical conductivity. This intermetallic phase is a novel type of cost-effective and competitive bifunctional electrocatalysts and predestinated for overall water-splitting devices: A two-electrode electrolyzer with CoSn2 on NF delivers a cell voltage of merely 1.55 V at 10 mA cm-2 maintaining long-term stability.

Facile Formation of Nanostructured Manganese Oxide Films as High-Performance Catalysts for the Oxygen Evolution Reaction.

The development of inexpensive, earth abundant, and bioinspired oxygen evolution electrocatalysts that are easily accessible and scalable is a principal requirement with regard to the feasibility of water splitting for large-scale chemical energy storage. A unique, versatile, and scalable approach has been developed to fabricate manganese oxide films from single layers to multilayers with a controlled thickness and high reproducibility. The produced MnOx films are composed of small nanostructures that are assembled closely in the form of porous sponge-like layers. The films were investigated for the electrochemical oxygen evolution reaction in alkaline media and demonstrate a remarkable activity as well as a superior stability of over 60 h. To elucidate the catalytically active species, as well as the striking structural characteristics, the films were further examined in depth by using SEM, TEM, and X-ray photoelectron spectroscopy, as well as quasi in situ extended X-ray absorption fine structure and X-ray absorption near edge structure analysis. The MnOx catalyst films excel because of a favorably high fraction of Mn3+ ions that are retained even after operation at oxidizing potentials. Upon exposure to oxidizing potentials in strongly alkaline aqueous electrolyte, the catalyst material maintains its structural integrity at the nanostructural, morphological, and atomic level.

High Electromagnetic Field Enhancement of TiO2 Nanotube Electrodes.

We present the fabrication of TiO2 nanotube electrodes with high biocompatibility and extraordinary spectroscopic properties. Intense surface-enhanced resonance Raman signals of the heme unit of the redox enzyme Cytochrome b5 were observed upon covalent immobilization of the protein matrix on the TiO2 surface, revealing overall preserved structural integrity and redox behavior. The enhancement factor could be rationally controlled by varying the electrode annealing temperature, reaching a record maximum value of over 70 at 475 °C. For the first time, such high values are reported for non-directly surface-interacting probes, for which the involvement of charge-transfer processes in signal amplification can be excluded. The origin of the surface enhancement is exclusively attributed to enhanced localized electric fields resulting from the specific optical properties of the nanotubular geometry of the electrode.

A Molecular Approach to Manganese Nitride Acting as a High Performance Electrocatalyst in the Oxygen Evolution Reaction.

The scalable synthesis of phase-pure crystalline manganese nitride (Mn3 N2 ) from a molecular precursor is reported. It acts as a superiorly active and durable electrocatalyst in the oxygen evolution reaction (OER) from water under alkaline conditions. While electrophoretically deposited Mn3 N2 on fluorine tin oxide (FTO) requires an overpotential of 390 mV, the latter is substantially decreased to merely 270 mV on nickel foam (NF) at a current density of 10 mA cm-2 with a durability of weeks. The high performance of this material is due to the rapid transformation of manganese sites at the surface of Mn3 N2 into an amorphous active MnOx overlayer under operation conditions intimately connected with metallic Mn3 N2 , which increases the charge transfer from the active catalyst surface to the electrode substrates and thus outperforms the electrocatalytic activity in comparison to solely MnOx -based OER catalysts.

From a Molecular 2Fe-2Se Precursor to a Highly Efficient Iron Diselenide Electrocatalyst for Overall Water Splitting.

A highly active FeSe2 electrocatalyst for durable overall water splitting was prepared from a molecular 2Fe-2Se precursor. The as-synthesized FeSe2 was electrophoretically deposited on nickel foam and applied to the oxygen and hydrogen evolution reactions (OER and HER, respectively) in alkaline media. When used as an oxygen-evolution electrode, a low 245 mV overpotential was achieved at a current density of 10 mA cm-2 , representing outstanding catalytic activity and stability because of Fe(OH)2 /FeOOH active sites formed at the surface of FeSe2 . Remarkably, the system is also favorable for the HER. Moreover, an overall water-splitting setup was fabricated using a two-electrode cell, which displayed a low cell voltage and high stability. In summary, the first iron selenide material is reported that can be used as a bifunctional electrocatalyst for the OER and HER, as well as overall water splitting.