Bridging the Catalytic Turnover Gap Between Single-Atom Iron Nanozymes and Natural Enzymes by Engineering the First and Second Shell Coordination.

Single-atom nanozymes (SAzymes) constitute a promising category of enzyme-mimicking materials with outstanding catalytic performance. The performance of SAzymes improves through modification of the coordination environments around the metal center. However, the catalytic turnover rates of SAzymes, which are key measures of the effectiveness of active site modifications, remain lower than those of natural enzymes, especially in peroxidase-reactions. Here, the first and second shell coordination tuning strategy that yields SAzymes with structures and activities analogous to those of natural enzymes is reported. The optimized SAzyme exhibits a turnover rate of 52.7 s-1 and a catalytic efficiency of 6.97 × 105 M-1 s-1. A computational study reveals that axial S-ligands induce an alternative reaction mechanism, and SO2- functional groups provide hydrogen bonds to reduce the activation energy. In addition, SAzyme shows superior anti-tumor ability in vitro and in vivo. These results demonstrate the validity of coordination engineering strategies and the carcinostatic potential of SAzymes.

Hexaazatriphenylene-Based Two-Dimensional Conductive Covalent Organic Framework with Anisotropic Charge Transfer.

The development of covalent organic frameworks (COFs) with efficient charge transport is of immense interest for applications in optoelectronic devices. To enhance COF charge transport properties, electroactive building blocks and dopants can be used to induce extended conduction channels. However, understanding their intricate interplay remains challenging. We designed and synthesized a tailor-made COF structure with electroactive hexaazatriphenylene (HAT) core units and planar dioxin (D) linkages, denoted as HD-COF. With the support of theoretical calculations, we found that the HAT units in the HD-COF induce strong, eclipsed π-π stacking. The unique stacking of HAT units and the weak in-plane conjugation of dioxin linkages leads to efficient anisotropic charge transport. We fabricated HD-COF films to minimize the grain boundary effect of bulk COFs, which resulted in enhanced conductivity. As a result, the HD-COF films showed an electrical conductivity as high as 1.25 S cm-1 after doping with tris(4-bromophenyl)ammoniumyl hexachloroantimonate.

Cooperative Electronic Structure Modulator of Fe Single-Atom Electrocatalyst for High Energy and Long Cycle Li-S Pouch Cell.

High-energy and long cycle lithium-sulfur (Li-S) pouch cells are limited by the insufficient capacities and stabilities of their cathodes under practical electrolyte/sulfur (E/S), electrolyte/capacity (E/C), and negative/positive (N/P) ratios. Herein, an advanced cathode comprising highly active Fe single-atom catalysts (SACs) is reported to form 320.2 W h kg-1 multistacked Li-S pouch cells with total capacity of ≈1 A h level, satisfying low E/S (3.0), E/C (2.8), and N/P (2.3) ratios and high sulfur loadings (8.4 mg cm-2 ). The high-activity Fe SAC is designed by manipulating its local environments using electron-exchangeable binding (EEB) sites. Introducing EEB sites comprising two different types of S species, namely, thiophene-like-S (-S) and oxidized-S (-SO2 ), adjacent to Fe SACs promotes the kinetics of the Li2 S redox reaction by providing additional binding sites and modulating the Fe d-orbital levels via electron exchange with Fe. The -S donates the electrons to the Fe SACs, whereas -SO2 withdraws electrons from the Fe SACs. Thus, the Fe d-orbital energy level can be modulated by the different -SO2 /-S ratios of the EEB site, controlling the electron donating/withdrawing characteristics. This desirable electrocatalysis is maximized by the intimate contact of the Fe SACs with the S species, which are confined together in porous carbon.

A Versatile Strategy for Achieving Fast-Charging Batteries via Interfacial Engineering: Pseudocapacitive Potassium Storage without Nanostructuring.

The rapid transport of alkali ions in electrodes is a long-time dream for fast-charging batteries. Though electrode nanostructuring has increased the rate-capability, its practical use is limited because of the low tap density and severe irreversible reactions. Therefore, development of a strategy to design fast-charging micron-sized electrodes without nanostructuring is of significant importance. Herein, a simple and versatile strategy to accelerate the alkali ion diffusion behavior in micron-sized electrode is reported. It is demonstrated that the diffusion rate of K+ ions is significantly improved at the hetero-interface between orthorhombic Nb2 O5 (001) and monoclinic MoO2 (110) planes. Lattice distortion at the hetero-interface generates an inner space large enough for the facile transport of K+ ions, and electron localization near oxygen-vacant sites further enhances the ion diffusion behavior. As a result, the interfacial-engineered micron-sized anode material achieves an outstanding rate capability in potassium-ion batteries (KIBs), even higher than nanostructured orthorhombic Nb2 O5  which is famous for fast-charging electrodes. This is the first study to develop an intercalation pseudocapacitive micron-sized anode without nanostructuring for fast-charging and high volumetric energy density KIBs. More interestingly, this strategy is not limited to K+ ion, but also applicable to Li+ ion, implying the versatility of interfacial engineering for alkali ion batteries.

Surface Roughening Strategy for Highly Efficient Bifunctional Electrocatalyst: Combination of Atomic Layer Deposition and Anion Exchange Reaction.

Electrocatalytic water splitting, which is an interface-dominated process, can be significantly accelerated by increasing the number of front-line surface active sites (NA ) of the electrocatalyst. In this study, a unique method is used for increasing the NA by converting the smooth ultrathin atomic-layer-deposited nanoshells of the electrocatalysts into nano-roughened active shell layers using a controlled anion-exchange reaction (AER). The coarse thin nanoshells present abundant surface active sites, which are generated owing to the inherent unit-cell volume mismatch induced during the AER. Consequently, the nano-roughened electrodes accelerate the sluggish water reaction kinetics and lower the overpotentials required for the hydrogen and oxygen evolution reactions. In addition, the electronic modulation induced by the nanoshell layer at the core-nanoshell interface amplifies the local electron density, as confirmed using electrochemical analysis data and density functional theory calculations. Because of the integrity of the composite electrodes during water-splitting half-cell reactions, their durability for industrial seawater electrolysis is evaluated. The results indicate that their electrochemical activity does not change significantly after 10 days of continuous overall water splitting.

Catalyst- and Solvent-Free Synthesis of a Chemically Stable Aza-Bridged Bis(phenanthroline) Macrocycle-Linked Covalent Organic Framework.

Developing new linkage-based covalent organic frameworks (COFs) is one of the major topics in reticular chemistry. Electrically conductive COFs have enabled applications in energy storage and electrochemical catalysis, which are not feasible using insulating COFs. Despite significant advances, the construction of chemically stable conductive COFs by the formation of new linkages remains relatively unexplored and challenging. Here we report the solvent- and catalyst-free synthesis of a two-dimensional aza-bridged bis(phenanthroline) macrocycle-linked COF (ABBPM-COF) from the thermally induced poly-condensation of a tri-topic monomer and ammonia gas. The ABBPM-COF structure was elucidated using multiple techniques, including X-ray diffraction analysis combined with structural simulation, revealing its crystalline nature with an ABC stacking mode. Further experiments demonstrated its excellent chemical stability in acid/base solutions. Electrical-conductivity measurements showed that the insulating ABBPM-COF becomes a semiconducting material after exposure to iodine vapor.

High-Efficiency Anion-Exchange Membrane Water Electrolyzer Enabled by Ternary Layered Double Hydroxide Anode.

Developing high-efficiency and low-cost oxygen-evolving electrodes in anion exchange membrane (AEM) water electrolysis technology is one of the major challenges. Herein, it is demonstrated that the surface corrosion of a conventional Ni foam electrode in the presence of Fe3+ and V3+ cations can transform it into an electrode with a high catalytic performance for oxygen evolution reaction (OER). The corroded electrode consists of a ternary NiFeV layered double hydroxide (LDH) nanosheet array supported on the Ni foam surface. This NiFeV LDH electrode achieves an OER current density of 100 mA cm-2 at an overpotential of 272 mV in 1 m KOH, outperforming the IrO2 catalyst by 180 mV. Density functional theory calculations reveal that the unique structure and the presence of vanadium in NiFeV LDH play a key role in achieving improved OER activity. When coupled with a commercial Pt/C cathode catalyst, the resulting AEM water electrolyzer achieves a cell current density as high as 2.1 A cm-2 at a voltage of only 1.8 Vcell in 1 m KOH, which is similar to the performance of the proton exchange membrane water electrolyzer obtained from the IrO2 and Pt/C catalysts pair.

Design principles of noble metal-free electrocatalysts for hydrogen production in alkaline media: combining theory and experiment.

Water electrolysis is a promising solution to convert renewable energy sources to hydrogen as a high-energy-density energy carrier. Although alkaline conditions extend the scope of electrocatalysts beyond precious metal-based materials to earth-abundant materials, the sluggish kinetics of cathodic and anodic reactions (hydrogen and oxygen evolution reactions, respectively) impede the development of practical electrocatalysts that do not use precious metals. This review discusses the rational design of efficient electrocatalysts by exploiting the understanding of alkaline hydrogen evolution reaction and oxygen evolution reaction mechanisms and of the electron structure-activity relationship, as achieved by combining experimental and computational approaches. The enhancement of water splitting not only deals with intrinsic catalytic activity but also includes the aspect of electrical conductivity and stability. Future perspectives to increase the synergy between theory and experiment are also proposed.

Tailoring Binding Abilities by Incorporating Oxophilic Transition Metals on 3D Nanostructured Ni Arrays for Accelerated Alkaline Hydrogen Evolution Reaction.

Developing efficient and inexpensive electrocatalysts for the hydrogen evolution reaction (HER) in alkaline water electrolysis plays a key role for renewable hydrogen energy technology. The slow reaction kinetics of HER in alkaline solutions, however, has hampered advances in high-performance hydrogen production. Herein, we investigated the trends in HER activity with respect to the binding energies of Ni-based thin film catalysts by incorporating a series of oxophilic transition metal atoms. It was found that the doping of oxophilic atoms enables the modulation of binding abilities of hydrogen and hydroxyl ions on the Ni surfaces, leading to the first establishment of a volcano relation between OH-binding energies and alkaline HER activities. In particular, Cr-incorporated Ni catalyst shows optimized OH-binding as well as H-binding energies for facilitating water dissociation and improving HER activity in alkaline media. Further enhancement of catalytic performance was achieved by introducing an array of three-dimensional (3D) Ni nanohelixes (NHs) that provide abundant surface active sites and effective channels for charge transfer and mass transport. The Cr dopants incorporated into the Ni NHs accelerate the dissociative adsorption process of water, resulting in remarkably enhanced catalytic activities in alkaline medium. Our approach can provide a rational design strategy and experimental methodology toward efficient bimetallic electrocatalysts for alkaline HER using earth-abundant elements.