Latest ArticlesDeveloping catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction (OER) is crucial for advancing overall water splitting (OWS) systems. In this study, we synthesized the electrode material Ce-NiCo-LDHs@SnO2/NF through a two-step hydrothermal reaction, where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO2 layer. Ce doping adjusts the internal electronic distribution of NiCo-LDHs, while the introduction of the SnO2 layer enhances electron transfer capability. Together, these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism (LOM). Consequently, Ce-NiCo-LDHs@SnO2/NF exhibits high level electrochemical performance in OER, requiring only 234 mV overpotential to achieve a current density of 10 mA/cm2, with a Tafel slope of just 27.39 mV/dec. When paired with Pt/C/NF, an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 mA/cm2. Furthermore, the catalyst demonstrates stability for 100 h during the OWS stability test. This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO2 layer.
Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes. Herein, we report the construction of ultrasmall gold nanocluster-based nanoassemblies (Dp-AuNCs@Fe2+) through the coordination of Fe2+ ions by a dopa-containing peptidomimetic ligand (DpCDp). This nanoarchitecture simultaneously integrates catalytically active gold cores and redox-active Fe2+ centers, bridged by DpCDp to facilitate directional electron transfer. Comprehensive spectroscopic and kinetic analyses reveal that DpCDp promotes efficient charge migration from the Au core to surface-bound Fe2+, significantly enhancing H2O2-mediated peroxidase-like activity. Compared to bare Dp-AuNCs, Dp-AuNCs@Fe2+ display a 4.3-fold improvement in detection sensitivity, a 6.7-fold increase in catalytic efficiency, and markedly stronger hydroxyl radical generation. Mechanistically, this activity stems from a synergistic triad: direct H2O2 oxidation at gold surfaces, radical generation at Fe2+ sites, and DpCDp-facilitated electron shuttling. This work presents a robust strategy for nanozyme enhancement via electronic and structural co-engineering, offering valuable insights for the future design of bioinspired catalytic systems.
Conversion of ammonia into hydrogen, a crucial pathway for the hydrogen economy, is severely constrained by the intricacy of the required equipment and the low efficiency. Herein, Pd@PtNiCoRuIr core-shell mesoporous bifunctional electrocatalysts were fabricated via a one-step wet-chemical reduction approach. By utilizing the limiting effect of triblock copolymers, gradient distribution control of six metal elements (Pd core and Pt/Ni/Co/Ru/Ir high-entropy alloys shell) was achieved, where the high-entropy alloy shell forms high-density active sites through lattice distortion effect. With the help of lattice distortion and mesoporous-confinement-enabled interfacial coupling effects, Pd@PtNiCoRuIr catalyst exhibited exceptional bifunctional performance in alkaline media: A low hydrogen evolution reaction (HER) overpotential of 30.5 mV at 10 mA/cm2 and a high ammonia oxidation reaction (AOR) peak current density of 19.6 mA/cm2 at 0.7 V vs. RHE, representing a 3.83-fold enhancement over commercial Pt/C. Moreover, a rechargeable Zn-NH3 battery system was constructed and achieved 92.3% Faradaic efficiency (FE) for NH3-to-H2 conversion with outstanding stability at 16 mA/cm2, thereby providing an innovative solution for efficient ammonia decomposition-based hydrogen production.
Radical cycloaddition reactions (RCRs) are highly effective methods for constructing complex carbo- and heterocycles, which are frequently encountered in natural products that exhibit intriguing biological properties and hold significant potential for applications in medicinal chemistry. Radical-mediated cycloaddition strategies, which recycle radical character, are particularly appealing because they require only a catalytic amount of reagent and promise reactions with theoretically high atom economy. This review focuses on recent developments and synthetic applications in RCRs, with an emphasis on visible light-induced radical photocycloaddition reactions (RPCRs), transition metal-catalyzed approaches, and small molecule-catalyzed methods. By highlighting some outstanding innovations and addressing current challenges, this review aims to identify potential areas for improvement. These advancements will provide more efficient pathways for the synthesis of natural product molecules and offer valuable insights for the development of new synthetic methodologies.
Interlocked covalent organic cages have aesthetic skeletons endowed with structural and topological complexity. Their self-assembly provides a unique possibility to mimic the hierarchical self-assembly of biomacromolecules. In recent years, significant progresses in interlocked covalent organic cages have been witnessed. Different topological structures have been fabricated via various non-template induced methods, and diverse weak interactions are demonstrated to play critical roles in guiding the formation of interlocked structures. Therefore, this article systematically summarizes the recent advances in interlocked covalent organic cages, especially their design, synthesis, and self-assembly properties. Depending on different types of chemical reactions, irreversible and reversible reactions are separately introduced. In each section, proper monomer selection, critical topology design, key driving forces as well as detailed interlocked mechanisms for the formation of interlocked structures, and their self-assembly behaviors in single crystals are discussed detailedly. Finally, the challenge and future development of interlocked covalent organic cages are briefly prospected.
Developing advanced electrocatalysts to convert CO2 into liquid fuels such as C2H5OH is critical for utilizing intermittent renewable energy. The formation of C2H5OH, however, is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts. In this work, an alkanethiol-modified Cu2O nanowire array (OTT-Cu2O) was constructed with asymmetric Cu sites consisting of paired Cu–O and Cu–S motifs to overcome previous limitations of C2H5OH electrosynthesis via CO2RR pathway. This catalyst achieves a high Faradaic efficiency of 45% for CO2-to-C2H5OH conversion at 300 mA/cm2, representing a more than two-fold enhancement over the Cu2O electrode. Mechanistic investigations reveal that the Cu–S site exhibits distinct C-binding capability that stabilizes key intermediates (*OCH2 and *CO), in contrast to the O-affinitive Cu–O site. The asymmetric S–Cu–O configuration promotes thermodynamically favorable asymmetric C–C coupling between *CO and *OCH2, forming the critical CO–OCH2 intermediate and facilitating C2H5OH production, as opposed to symmetric O–Cu–O sites that mainly generate HCOOH. This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO2 reduction to C2H5OH and provides fundamental insight into the reaction mechanism.
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science. Multi-nuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mono-nuclear catalysts, but which substantially involve multi-step, tedious, and difficult synthesis. Herein, this study reports an intriguing approach to construct multi-nuclear catalysts for the milestone α-diimine nickel catalysts using an oligomeric strategy. A polymerizable norbornene unit is incorporated into the α-diimine ligand backbone, leading to the formation of the monomeric nickel catalyst Ni1 and its corresponding oligomeric nickel catalysts (Ni3 and Ni5) with varying degrees of polymerization (DP = 3 and 5). Notably, the oligomeric catalyst Ni5 was facilely scaled up (50 g-level), showed enhanced thermal stability, exhibited 4.6 times higher activity, and yielded polyethylene elastomer with a 379% increased molecular weight in ethylene polymerization, compared to the monomeric catalyst Ni1. Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent. The kilogram-scale polyethylene, produced using Ni5 in a 20 L reactor, presented a highly branched all-hydrocarbon structure, which demonstrated typical elastic properties (tensile strength: 4 MPa, elastic recovery: SR = 72%) along with great processability (MFI = 3.0 g/10 min), insulating characteristics (volume resistivity = 2 × 1016 Ω/m), and hydrophobicity (water vapor permeability: 0.03 g/m2/day), suggesting potentially practical applications.
Achieving high energy densities for all-solid-state lithium batteries is restricted by the poor high voltage stability of solid electrolytes. Herein, F-doping strategy is successfully employed on Li3InCl6 to obtain enhanced voltage stability and electrode compatability towards bare LiNi0.7Mn0.2Co0.1O2 at high voltages. The optimized Li3InCl5.5F0.5 electrolyte exhibits a decreased conductivity of 1.00 mS/cm, a wider voltage window, and improved electrochemical performance in solid-state batteries when cycled at upper cut-off voltages of 4.5 and 4.8 V (vs. Li+/Li0). The generation of more stable LiInF4 phase in the cathode mixture of Li3InCl5.5F0.5-based battery ensures superior electrochemical performances compared to the Li3InCl6-based battery. The former battery exhibits a higher discharge capacity of 218.9 mAh/g and coulombic efficiency of 86.7% for the first cycle, and retains 80.0% of its original value after 100 cycles when cycled in the range of 3.0–4.5 V (vs. Li+/Li0). In contrast, the Li3InCl6-based battery exhibits lower capacities and faster degradation under the same conditions due to the formation of InCl3 phase with poor electrochemical stability. This work facilitates the advancement of high energy density solid-state battery technologies by utilizing high-voltage cathodes.
Conductive hydrogel membranes with nanofluids channels represent one of the most promising capacitive electrodes due to their rapid kinetics of ion transport. The construction of these unique structures always requires new self-assembly behaviors with different building blocks, intriguing phenomena of colloidal chemistry. In this work, by delicately balancing the electrostatic repulsions between 2D inorganic nanosheets and the electrostatic adsorption with cations, we develop a general strategy to fabricate stable free-standing 1T molybdenum disulphide (MoS2) hydrogel membranes with abundant fluidic channels. Given the interpenetrating ionic transport network, the MoS2 hydrogel membranes exhibit a high-level capacitive performance 1.34 F/cm2 at an ultrahigh mass loading of 11.2 mg/cm2. Furthermore, the interlayer spacing of MoS2 in the hydrogel membranes can be controlled with ångström-scale precision using different cations, which can promote further fundamental studies and potential applications of the transition-metal dichalcogenides hydrogel membranes.
Spin-orbit coupling (SOC) plays a vital role in determining the ground state and forming novel electronic states of matter where heavy elements are involved. Here, the prototypical perovskite iridate oxide SrIrO3 is investigated to gain more insights into the SOC effect in the modification of electronic structure and corresponding magnetic and electrical properties. The high pressure metastable orthorhombic SrIrO3 is successfully stabilized by physical and chemical pressures, in which the chemical pressure is induced by Ru doping in Ir site and Mg substitution of Sr position. Detailed structural, magnetic, electrical characterizations and density functional theory (DFT) calculations reveal that the substitution of Ru for Ir renders an enhanced metallic characteristic, while the introduction of Mg into Sr site results in an insulating state with 10.1% negative magnetoresistance at 10 K under 7 T. Theoretical calculations indicate that Ru doping can weaken the SOC effect, leading to the decrease of orbital energy difference between J1/2 and J3/2, which is favorable for electron transport. On the contrary, Mg doping can enhance the SOC effect, inducing a metal-insulator-transition (MIT). The electronic phase transition is further revealed by DFT calculations, confirming that the strong SOC and electron-electron interactions can lead to the emergence of insulating state. These findings underline the intricate correlations between lattice degrees of freedom and SOC in determining the ground state, which effectively stimulate the physical pressure between like structures by chemical compression.
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