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A large variety of nickel‐based catalysts has been investigated for the oxygen evolution reaction (OER) in alkaline media. However, their reported activity, as well as Tafel slope values, vary greatly. To understand this variation, we studied electrodeposited Ni80Fe20OOH catalysts with different loadings at varying rotation rates, hydroxide concentrations, with or without sonication. We show that, at low current density (<5 mA cm−2), the Tafel slope value is ≈30 mV dec−1 for Ni80Fe20OOH. At higher polarization, the Tafel slope continuously increases and is dependent on rotation rate, loading, hydroxide concentration and sonication. These Tafel slope values are convoluted by non‐kinetic effects, such as bubbles, potential‐dependent changes in ohmic resistance and (internal) OH− gradients. As best practise, we suggest that Tafel slopes should be plotted vs. current or potential. In such a plot, it can be appreciated if there is a kinetic Tafel slope or if the observed Tafel slope is influenced by non‐kinetic effects. [ABSTRACT FROM AUTHOR]

Electrochemical water splitting is a promising means to produce eco‐friendly hydrogen fuels. Inspired by the Mn4CaO5 cluster in nature, substantial works have been performed to develop efficient manganese (Mn)‐based heterogeneous catalysts. Despite improvements in catalytic activity, the underlying mechanism of the oxygen evolution reaction (OER) is not completely elucidated owing to the lack of direct spectroscopic evidence for the active Mn‐oxo moieties. We identify water oxidation intermediates on the surface of Mn3O4 nanoparticles (NPs) in the OER at neutral pH by in situ Raman spectroscopy. A potential‐dependent Raman peak was detected at 760 cm−1 and assigned to the active MnIV=O species generated during water oxidation. Isotope‐labeling experiments combined with scavenger experiments confirmed the generation of surface terminal MnIV=O intermediates in the Mn‐oxide NPs. This study provides an insight into the design of systems for the observation of reaction intermediates. [ABSTRACT FROM AUTHOR]

Scalable and facile synthesis of highly active alkaline hydrogen evolution reaction catalysts was demonstrated by controlling the microstructures of Al–Ni alloys and making porous foam and powder. The microstructures were carefully controlled in the binary alloys and the subsequent selective etching resulted in highly active catalysts, which are comparable to conventional Pt-based catalysts. Large-scale coating of a dealloyed Al–Ni alloy powder was also demonstrated, showing the practical applicability of this method. [ABSTRACT FROM AUTHOR]

As the demand for energy has dramatically increased in the past decade, electrochemical water splitting has been regarded as an attractive approach to produce renewable hydrogen energy. However, large overpotentials of oxygen‐evolving reaction (OER) is a key bottleneck for practical application. Thus, water‐oxidizing electrocatalysts with low cost and high efficiency should be developed. Here, 5 nm‐sized Mn3O4 nanoparticles (NPs) are synthesized by a hydrothermal method, which is appropriate for large‐scale production. To further improve their performance, various 3d transition metal elements are successfully doped in Mn3O4 NPs. Ni‐doped Mn3O4 NPs exhibit the highest efficiency among the Mn3O4 NPs doped with various elements. Based on structural analysis, the Ni‐doping process leads to the lattice distortion of their tetragonal spinel structure and it strongly correlates with the enhancement of OER activity. The overpotential at the current density of 10 mA cm–2 is 524 and 458 mV for pristine and 5 at% doped Mn3O4 NPs under neutral condition. The heteroatom‐doping process in sub‐10 nm‐sized nanocatalysts is expected to be a promising methodology to induce distorted structure related to active species. Thus, it can be effective to improve catalytic performance of various heterogeneous nano‐catalysts. [ABSTRACT FROM AUTHOR]

Electrochemical water splitting is one of the ways to produce environmentally‐friendly hydrogen energy. Transition‐metal (TM)‐based catalysts have been attracting attention due to their low cost and abundance, but their insufficient activity still remains a challenge. Here, 4 nm Mn3O4 nanoparticles (NPs) are successfully synthesized and their electrochemical behavior is investigated. Using electrokinetic analyses, an identical water oxidizing mechanism is demonstrated between the 4 and 8 nm Mn3O4 NPs. In addition, it is confirmed that the overall increase in the active surface area is strongly correlated with the superb catalytic activity of the 4 nm Mn3O4 NPs. To further enhance the oxygen evolution reaction (OER) performance, Ni foam substrate is introduced to maximize the entire number of the NPs participating in OER. The 4 nm Mn3O4/Ni foam electrode exhibits outstanding electrocatalytic activity for OER with overpotential of 395 mV at a current density of 10 mA cm−2 under neutral conditions (0.5 m PBS, pH 7). [ABSTRACT FROM AUTHOR]

Electrochemical water splitting is one of the most important ways to produce hydrogen fuel for an environmentally friendly energy system. Low‐cost and efficient electrocatalysts for oxygen evolution reaction (OER) have been studied to overcome the sluggish kinetics of OER, which is considered to be a bottleneck that affects the overall efficiency of water splitting. However, the atomic‐level understanding and control of the catalyst surface still remains elusive. Here, we show that methylamine treatment of manganese oxide nanoparticles can effectively control their surface charge and enhance their OER catalytic activity under neutral condition. Methylamine treatment can reduce the overpotential for OER by nearly 100 mV at the current density 5 mA cm−2. Through spectroscopic studies, potentiometric titration, and zeta potential analysis, we discovered that methylamine does not exist on the surface after methylamine treatment but deprotonates the surface of nanoparticles and induce additional negative charge on the surface. Surprisingly, treatment with not only methylamine but other amines can also improve the OER performance and the catalytic activity of the amine treated nanoparticles is influenced by the pKa values of amines. Underwater stars: After methylamine treatment of OH− ligand exchanged Mn3O4 nanoparticles, oxygen evolving reaction performance is significantly enhanced. Detailed mechanistic study reveals that methylamine deprotonates the surface and generates additional negative charges on the surface. The catalytic performance could also be enhanced with different amines and the decrease in overpotential is associated with pKa of amines. [ABSTRACT FROM AUTHOR]

The electrochemical reduction of carbon dioxide (CO 2 ) to produce fuels and chemicals has garnered significant attention. However, achieving control over the selectivity of the resulting products remains a challenging task, particularly within molecular systems. In this study, we employed a molecular silver complex immobilized on graphitized mesoporous carbon (GMC) as a catalyst for converting CO 2 into CO, achieving an impressive selectivity of over 90% at -1.05 V vs RHE. Notably, the newly formed silver nanoparticles emerged as the active sites responsible for this high CO selectivity rather than the molecular system. Intriguingly, the introduction of copper ions into the restructured Ag-nanoparticle-decorated carbon altered the product selectivity. At -1.1 V vs RHE in 0.1 M KCl, we achieved a high C2 selectivity of 75%. Furthermore, not only the Ag-Cu bimetallic nanoparticle but also the small-sized Ag-Cu nanocluster decorated over GMC was proposed as active sites during catalytic reactions. Our straightforward approach offers valuable insights for fine-tuning the product selectivity of immobilized molecular systems, extending beyond C1 products.

The evolution of electrogenerated gas bubbles during water electrolysis can significantly hamper the overall process efficiency. Promoting the departure of electrochemically generated bubbles during (water) electrolysis is therefore beneficial. For a single bubble, a departure from the electrode surface occurs when buoyancy wins over the downward-acting forces (e.g., contact, Marangoni, and electric forces). In this work, the dynamics of a pair of H 2 bubbles produced during the hydrogen evolution reaction in 0.5 M H 2 SO 4 using a dual platinum microelectrode system is systematically studied by varying the electrode distance and the cathodic potential. By combining high-speed imaging and electrochemical analysis, we demonstrate the importance of bubble-bubble interactions in the departure process. We show that bubble coalescence may lead to substantially earlier bubble departure as compared to buoyancy effects alone, resulting in considerably higher reaction rates at a constant potential. However, due to continued mass input and conservation of momentum, repeated coalescence events with bubbles close to the electrode may drive departed bubbles back to the surface beyond a critical current, which increases with the electrode spacing. The latter leads to the resumption of bubble growth near the electrode surface, followed by buoyancy-driven departure. While less favorable at small electrode spacing, this configuration proves to be very beneficial at larger separations, increasing the mean current up to 2.4 times compared to a single electrode under the conditions explored in this study.

The water oxidation reaction, the most important reaction for hydrogen production and other sustainable chemistry, is efficiently catalyzed by the Mn 4 CaO 5 cluster in biological photosystem II. However, synthetic Mn-based heterogeneous electrocatalysts exhibit inferior catalytic activity at neutral pH under mild conditions. Symmetry-broken Mn atoms and their cooperative mechanism through efficient oxidative charge accumulation in biological clusters are important lessons but synthesis strategies for heterogeneous electrocatalysts have not been successfully developed. Here, we report a crystallographically distorted Mn-oxide nanocatalyst, in which Ir atoms break the space group symmetry from I 4 1 / amd to P1. Tetrahedral Mn(II) in spinel is partially replaced by Ir, surprisingly resulting in an unprecedented crystal structure. We analyzed the distorted crystal structure of manganese oxide using TEM and investigated how the charge accumulation of Mn atoms is facilitated by the presence of a small amount of Ir.

The electrochemical chlorine evolution reaction (CER) is one of the most important electrochemical reactions. Typically, iridium (Ir)- or ruthenium (Ru)-based mixed metal oxides have been used as electrocatalysts for the CER due to their high activities and durabilities. However, the scarcity of Ir and Ru has indicated the need to develop alternative earth-abundant transition-metal-based CER catalysts. In this study, we report a Co 3 O 4 nanoparticle (NP) catalyst synthesized by a hydrothermal method. Furthermore, Ru was successfully incorporated into the Co 3 O 4 NPs (Ru x Co 3- x O 4 NPs) for further improvement of catalytic performance in chlorine generation. Electrokinetic analyses combined with in situ X-ray absorption near-edge structure (XANES) results suggested an identical CER mechanism for the Co 3 O 4 NPs and Ru x Co 3- x O 4 NPs. Various characterization techniques demonstrated that the homogeneous substitution of Ru 4+ ions into the Co 3+ octahedral sites enhanced the structural disorder and changed the electronic state of Co 3 O 4 , resulting in additional exposed active sites. Remarkably, the Ru 0.09 Co 2.91 O 4 NP electrode exhibited outstanding stability for more than 150 h even at a high current density of 500 mA/cm 2 , which shows its commercial viability for active chlorine generation., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Photocatalysis is an easily configurable and cost-effective technology for the conversion of solar energy into chemical energy. Recently, increasing attention has been given to metal halide perovskite (MHP) photocatalysts because of the development of stabilization strategies for MHPs under reaction conditions. From this perspective, we first describe several substantial breakthroughs in the photocatalytic application of MHPs. Performance trends in the solar fuel production applications of MHPs, including photocatalytic H 2 generation and photocatalytic CO 2 reduction reactions, are then described. Recent developments to extend the use of MHPs to various photocatalytic organic transformations are also highlighted. Finally, we propose several scientific challenges for the practical implications of MHPs for solar fuel production and various photoreactions.

The development of efficient water-oxidizing electrocatalysts is a key issue for achieving high performance in the overall water electrolysis technique. However, the complexity of multiple electron transfer processes and large activation energies have been regarded as major bottlenecks for efficient water electrolysis. Thus, complete electrochemical processes, including electron transport, charge accumulation, and chemical bond formation/dissociation, need to be analyzed for establishing a design rule for film-type electrocatalysts. In light of this, complex capacitance analysis is an effective tool for investigating the charge accumulation and dissipation processes of film-type electrocatalysts. Here, we conduct complex capacitance analysis for the Mn 3 O 4 nanocatalyst, which exhibits superb catalytic activity for water oxidation under neutral conditions. Charge was accumulated on the catalyst surface by the change in Mn valence between Mn(II) and Mn(IV) prior to the rate-determining O-O bond forming step. Furthermore, we newly propose the dissipation ratio ( D ) for understanding the energy balance between charge accumulation and charge consumption for chemical O-O bond formation. From this analysis, we reveal the potential- and thickness-dependent contribution of the charge accumulation process on the overall catalytic efficiency. We think that an understanding of complex capacitance analysis could be an effective methodology for investigating the charge accumulation process on the surface of general film-type electrocatalysts., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Identification of the surface structure of nanoparticles is important for understanding the catalytic mechanism and improving the properties of the particles. Here, we provide a detailed description of the coordination modes of ethylenediaminetetraacetate (EDTA) on Mn 3 O 4 nanoparticles at the atomic level, as obtained by advanced electron paramagnetic resonance (EPR) spectroscopy. Binding of EDTA to Mn 3 O 4 leads to dramatic changes in the EPR spectrum, with a 5-fold increase in the axial zero-field splitting parameter of Mn(II). This indicates significant changes in the coordination environment of the Mn(II) site; hence, the binding of EDTA causes a profound change in the electronic structure of the manganese site. Furthermore, the electron spin echo envelope modulation results reveal that two 14 N atoms of EDTA are directly coordinated to the Mn site and a water molecule is coordinated to the surface of the nanoparticles. An Fourier transform infrared spectroscopy study shows that the Ca(II) ion is coordinated to the carboxylic ligands via the pseudobridging mode. The EPR spectroscopic results provide an atomic picture of surface-modified Mn 3 O 4 nanoparticles for the first time. These results can enhance our understanding of the rational design of catalysts, for example, for the water oxidation reaction.

A highly efficient CO 2 electrolysis system could be created by introducing biomass oxidation as an alternative anodic reaction to the sluggish oxygen evolution reaction in a CO 2 -saturated and near-neutral electrolyte. Here, we successfully demonstrate anodic biomass oxidation by synthesizing 5 nm nickel oxide nanoparticles (NiO NPs). NiO NPs show a unique electrocatalytic activity for 5-hydroxymethylfurfural (HMF) oxidation under near-neutral conditions, exhibiting an anodic current onset (1 mA cm -2 ) at 1.524 V versus the reversible hydrogen electrode and a total Faradaic efficiency of ≤70%. Electrokinetic and in situ ultraviolet-visible spectroscopic analyses suggest that a redox active nickel hydroxide species is formed on the surface of NiO electrocatalysts during HMF oxidation, and this oxidation of Ni(II) hydroxide to Ni(III) oxyhydroxide could be the rate-determining step. This mechanistic study of biomass oxidation in a CO 2 -saturated electrolyte provides insight into constructing a highly efficient system for the paired electrolysis of CO 2 reduction and biomass oxidation.

The reaction mechanism of electrochemical chloride oxidation at neutral pH is different from that at acidic pH, in which a commercial chlor-alkali process has been developed. Different proton concentrations and accelerated hydrolysis of the generated chlorine into hypochlorous acid at high pH can change the electrokinetics and stability of reaction intermediates. We have investigated a unique reaction mechanism of Co 3 O 4 nanoparticles for chloride oxidation at neutral pH. In contrast with water oxidation, the valency of cobalt was not changed during chloride oxidation. Interestingly, a new intermediate of Co-Cl was captured spectroscopically, distinct from the reaction intermediate at acidic pH. In addition, Co 3 O 4 nanoparticles exhibited high selectivity for active chlorine generation at neutral pH, comparable to commercially available RuO 2 -based catalysts. We believe that this study provides insight into designing efficient electrocatalysts for active chlorine generation at neutral pH, which can be practically applied to electrochemical water treatment coupled to hydrogen production.

Functional graffiti of nanoparticles onto target surface is an important issue in the development of nanodevices. A general strategy has been introduced here to decorate chemically diverse substrates with gold nanoparticles (AuNPs) in the form of a close-packed single layer by using an omni-adhesive protein of α-synuclein (αS) as conjugated with the particles. Since the adsorption was highly sensitive to pH, the amino acid sequence of αS exposed from the conjugates and its conformationally disordered state capable of exhibiting structural plasticity are considered to be responsible for the single-layer coating over diverse surfaces. Merited by the simple solution-based adsorption procedure, the particles have been imprinted to various geometric shapes in 2-D and physically inaccessible surfaces of 3-D objects. The αS-encapsulated AuNPs to form a high-density single-layer coat has been employed in the development of nonvolatile memory, fule-cell, solar-cell, and cell-culture platform, where the outlying αS has played versatile roles such as a dielectric layer for charge retention, a sacrificial layer to expose AuNPs for chemical catalysis, a reaction center for silicification, and biointerface for cell attachment, respectively. Multiple utilizations of the αS-based hybrid NPs, therefore, could offer great versatility to fabricate a variety of NP-integrated advanced materials which would serve as an indispensable component for widespread applications of high-performance nanodevices.

Nature designs circulatory systems with hierarchically organized networks of gradually tapered channels ranging from micrometer to nanometer in diameter. In most hard tissues in biological systems, fluid, gases, nutrients and wastes are constantly exchanged through such networks. Here, we developed a biologically inspired, hierarchically organized structure in ceramic to achieve effective permeation with minimum void region, using fabrication methods that create a long-range, highly interconnected nanochannel system in a ceramic biomaterial. This design of a synthetic model-material was implemented through a novel pressurized sintering process formulated to induce a gradual tapering in channel diameter based on pressure-dependent polymer agglomeration. The resulting system allows long-range, efficient transport of fluid and nutrients into sites and interfaces that conventional fluid conduction cannot reach without external force. We demonstrate the ability of mammalian bone-forming cells placed at the distal transport termination of the nanochannel system to proliferate in a manner dependent solely upon the supply of media by the self-powering nanochannels. This approach mimics the significant contribution that nanochannel transport plays in maintaining living hard tissues by providing nutrient supply that facilitates cell growth and differentiation, and thereby makes the ceramic composite "alive".