Precision Metal Nanoclusters Meet Proteins: Crafting Next-Gen Hybrid Materials.

Metal nanoclusters (NCs), owing to their atomic precision and unique molecule-like properties, have gained widespread attention for applications ranging from catalysis to bioimaging. In recent years, proteins, with their hierarchical structures and diverse functionalities, have emerged as good candidates for functionalizing metal NCs, rendering metal NC-protein conjugates with combined and even synergistically enhanced properties featured by both components. In this Perspective, we explore key questions regarding why proteins serve as complementary partners for metal NCs, the methodologies available for conjugating proteins with metal NCs, and the characterization techniques necessary to elucidate the structures and interactions within this emerging bionano system.

Beyond Polymerization: In Situ Coupled Fluorination Enables More Stable Interfaces for Solid-State Lithium Batteries.

In situ polymerization strategies hold great promise for enhancing the physical interfacial stability in solid-state batteries, yet (electro)chemical degradation of polymerized interfaces, especially at high voltages, remains a critical challenge. Herein, we find interphase engineering is crucial for the polymerization process and polymer stability and pioneer an in situ polymerization-fluorination (Poly-FR) strategy to create durable interfaces with excellent physical and (electro)chemical stabilities, achieved by designing a bifunctional initiator for both polymerization and on-surface lithium donor reactions. The integrated in situ fluorination converts LiCO impurities on LiNiCoMnO (NCM811) surfaces into LiF-rich interphases, effectively inhibiting the aggressive (de)lithiation intermediates and protecting the interface from underlying chemical degradation, thereby surpassing the stability limitations of polymerization alone.

Promoting in-situ stability of hydroxide exchange membranes by thermally conductive network for durable water electrolysis.

Hydroxide exchange membrane (HEM) water electrolysis is promising for green hydrogen production due to its low cost and excellent performance. However, HEM often has insufficient stability in strong alkaline solutions, particularly under in-situ electrolysis operation conditions, hindering its commercialization. In this study, we discover that the in-situ stability of HEM is primarily impaired by the locally accumulated heat in HEM due to its low thermal conductivity.

Photocatalytic upcycling of polylactic acid to alanine by sulfur vacancy-rich cadmium sulfide.

Photocatalytic conversion has emerged as a promising strategy for harnessing renewable solar energy in the valorization of plastic waste. However, research on the photocatalytic transformation of plastics into valuable nitrogen-containing chemicals remains limited. In this study, we present a visible-light-driven pathway for the conversion of polylactic acid (PLA) into alanine under mild conditions.

Unraveling the Stoichiometric Interactions and Synergism between Ligand-Protected Gold Nanoparticles and Proteins.

Nanomaterials that engage in well-defined and tunable interactions with proteins are pivotal for the development of advanced applications. Achieving a precise molecular-level understanding of nano-bio interactions is essential for establishing these interactions. However, such an understanding remains challenging and elusive.

Enhancing CO Oversaturation in the Confined Water Enables Superior Gas Selectivity of 2D Membranes.

Due to the global demands on carbon neutralization, CO separation membranes, particularly those based on two-dimensional (2D) materials, have attracted increasing attention. However, recent works have focused on the chemical decoration of membranes to realize the selective transport, leading to the compromised stability in the presence of moisture. Herein, we develop a series of 2D capillaries based on layered double hydroxide (LDH), graphene oxide, and vermiculite to enhance the oversaturation of CO in the confined water for promoting the membrane permselectivity.

New Molecular Photoswitch Based on the Conformational Transition of Phenothiazine Derivatives and Corresponding Triplet Emission Properties.

Molecular photoswitch research has drawn much attention in the last century owing to its great potential in the development of smart materials. However, photoswitches suitable for constructing light-responsive luminescent materials remain limited, especially those involving triplet-state phosphorescence. Herein, we designed a novel molecular photoswitch based on the conformation transition of phenothiazine derivatives, minimizing steric hindrance (-CH > -Cl > -F) to regulate the conformation transition process while introducing a cyanobenzene acceptor to promote phosphorescence emission potential.

Identifying the Bifunctional Mechanism in Alkaline Water Electrolysis by Lewis Pairs at the Single-Atom Scale.

The bifunctional mechanism, involving multiactive compositions to simultaneously dissociate water molecules and optimize intermediate adsorption, has been widely used in the design of catalysts to boost water electrolysis for sustainable hydrogen energy production but remains debatable due to difficulties in accurately identifying the reaction process. Here, we proposed the concept of well-defined Lewis pairs in single-atom catalysts, with a unique acid-base nature, to comprehensively understand the exact role of multiactive compositions in an alkaline hydrogen evolution reaction. By facilely adjusting active moieties, the induced synergistic effect between Lewis pairs (M-P/S/Cr pairs, M = Ru, Ir, Pt) can significantly facilitate the cleavage of the H-OH bond and accelerate the removal of intermediates, thereby switching the rate-determining step from the Volmer step to the Heyrovsky step.

Confining Phosphoric Acid in Quaternized COF Channels for Ultra-Stable and Fast Anhydrous Proton Transport.

Phosphoric acid (HPO) doping is a widely employed strategy to facilitate anhydrous proton transport in high-temperature proton exchange membrane fuel cells (HT-PEMFCs). However, significant HPO leaching during long-term operation poses critical challenges to maintaining membrane stability and proton conductivity. Herein, HPO is incorporated into positively charged nanochannels of quaternized covalent organic framework membranes (QACOFMs), leveraging strong electrostatic interactions and confinement effects to achieve exceptional HPO retention under hydration conditions.

Janus graphene nanoribbons with localized states on a single zigzag edge.

Topological design of π electrons in zigzag-edged graphene nanoribbons (ZGNRs) leads to a wealth of magnetic quantum phenomena and exotic quantum phases. Symmetric ZGNRs typically show antiferromagnetically coupled spin-ordered edge states. Eliminating cross-edge magnetic coupling in ZGNRs not only enables the realization of a class of ferromagnetic quantum spin chains, enabling the exploration of quantum spin physics and entanglement of multiple qubits in the one-dimensional limit, but also establishes a long-sought-after carbon-based ferromagnetic transport channel, pivotal for ultimate scaling of GNR-based quantum electronics.

Cationic Magnetically Active Nitrogen-Doped Polycyclic Aromatic Hydrocarbon with Record Low Band Gap.

Polycyclic aromatic hydrocarbons (PAHs) have attracted significant interest in material chemistry, particularly if they own extremely low band gaps and magnetic properties. However, challenges remain regarding the synthetic accessibility and energy saturation issues. In this study, we introduce NR-11, which consists of eleven aromatic rings in its main conjugation and is separately doped with two electron-rich nitrogen atoms.

Sustainable aviation fuel (SAF) from lignin: Pathways, catalysts, and challenges.

The aviation industry plays a crucial role in global trade and cultural exchange, but it faces significant challenges due to high production cost and environmental impacts. To achieve carbon neutrality, promoting the development of sustainable aviation fuel (SAF) is essential, with projections indicating that 65% of emissions reductions in the aviation industry by 2050 will come from the use of SAF. Lignin, as an abundant renewable resource, has great potential for conversion into aviation fuel components.

Chemical looping synthesis of amines from N via iron nitride as a mediator.

Amines are commonly synthesized through the amination of organooxygenates using ammonia, frequently involving the use of noble metal catalysts. In this study, we present an alternative route to make amines using iron nitride (FeN) as the nitrogen source. Without any additional catalyst, FeN reacts with a range of alcohols at 250 °C under 1 or 10 bar H to produce amines as major products.

Molecular Design of Positively Charged 3D Covalent-Organic Framework Membranes for Li/Mg Separation.

3D covalent-organic framework (3D COF) membranes have unique features such as smaller pore sizes and more interconnected networks compared with 2D COF counterparts. However, the complicated and unmanageable fabrication hinders their rapid development. Molecular simulation, which can efficiently explore the structure-performance relationship of membranes, holds great promise in accelerating the development of 3D COF membranes.

Navigating the transitional window for organic semiconductor single crystals towards practical integration: from materials, crystallization, and technologies to real-world applications.

Organic semiconductor single crystals (OSSCs), which possess the inherent merits of long-range order, low defect density, high mobility, structural tunability and good flexibility, have garnered significant attention in the organic optoelectronic community. Past decades have witnessed the explosive growth of OSSCs. Despite numerous conceptual demonstrations, OSSCs remain in the early stages of implementation for applications that require high integration and multifunctionality.

Ion Hydration Enables Generality in Asymmetric Catalysis: Desymmetrization to P-Stereogenic Triarylphosphine Derivatives.

Asymmetric synthesis relies on seamless transmission of stereochemical information from a chiral reagent/catalyst to a prochiral substrate. The disruption by substrates' structural changes presents a hurdle in innovating generality-oriented asymmetric catalysis. Here, we report a strategy for substrate adaptability by exploiting a fundamental physicochemical phenomenon-ion hydration, in developing remote desymmetrization to access P-stereogenic triarylphosphine oxides and sulfides.

HClO-Activated Near-Infrared Chemiluminescent Probes with a Malononitrile Group for In-Vivo Imaging.

Chemiluminescence (CL) imaging has emerged as a powerful approach to molecular imaging that allows exceptional sensitivity with virtually no background interference because of its unique capacity to emit photons without an external excitation source. Despite its high potential, the application of this nascent technique faces challenges because the current chemiluminescent agents have limited reactive sites, require complex synthesis, are insufficiently bright, and lack near-infrared emission. Herein, a series of HClO-activated chemiluminescent probes that exhibit robust near-infrared emission are studied.

Stabilizing Electron Transport of 2D Materials.

2D materials are promising candidates for beyond-Si electronic devices. However, their stability is a key bottleneck in their industrial applications. The instability of 2D materials is mainly attributed to their intrinsic susceptibility to O and HO-particularly to reactive oxygen species (ROS), which have strong oxidizing properties.

Photocatalytic Partial Water Oxidation Promoted by a Hydrogen Acceptor-Hydroxyl Mediator Couple.

Hydrogen peroxide (HO) is an important chemical in synthetic chemistry with huge demands. Photocatalytic synthesis of HO via oxygen reduction and water oxidation reactions (ORR and WOR) is considered as a promising and desirable solution for on-site applications. However, the efficiency of such a process is low due to the poor solubility of molecular oxygen and the rapid reverse reaction of hydroxyl radicals (OH) with hydrogen atoms (H).

Trace Metal Impurities Induce Differences in Lithium-Sulfur Batteries.

Carbon nanotubes (CNTs) with exceptional conductivity have been widely adopted in lithium-sulfur (Li-S) batteries. While trace metal impurities in CNTs have demonstrated electrocatalytic activity in various catalytic processes, their influence on sulfur electrocatalysis in Li-S batteries has been largely overlooked. Herein, we reveal that the trace metal impurities content in CNTs significantly improves the specific capacity and cycling performance of Li-S batteries by analyzing both our own results and previous literature with CNTs as the sulfur hosts.

Ligand-Mediated Surface Reaction for Achieving Pure 2D Phase Passivation in High-Efficiency Perovskite Solar Cells.

The surface passivation with the heterostructure of the 2D/3D stack has been widely used for boosting the efficiency of n-i-p perovskite solar cells (PSCs). However, the disordered quantum well width distribution of 2D perovskites leads to energy landscape inhomogeneity and crystalline instability, which limits the further development of n-i-p PSCs. Here, a versatile approach, ligand-mediated surface passivation, was developed to produce a phase-pure 2D perovskite passivation layer with a homogeneous energy landscape by dual-ligand codeposition.

Iridium-Catalyzed Enantioconvergent Construction of Piperidines and Tetrahydroisoquinolines from Racemic 1,5-Diols.

We report herein a one-step synthesis of valuable enantioenriched piperidines and tetrahydroisoquinolines from readily available racemic 1,5-diols. Key to the success is the development of new iridacycle catalysts that enable efficient redox-neutral construction of two C-N bonds between diols and amines in an enantioconvergent fashion. Mechanistic studies identified an intriguing preferential oxidation of secondary versus primary alcohol in the diol substrate by the iridacycle catalyst, which set a challenging intermolecular amination of aryl-alkyl-substituted alcohol as the enantiodetermining step for this catalytic -heterocycle synthesis.

Synthesis of Single-Crystal Two-Dimensional Covalent Organic Frameworks and Uncovering Their Hidden Structural Features by Three-Dimensional Electron Diffraction.

Two-dimensional covalent organic frameworks (2D COFs) are formed by the polycondensation of geometrically specific monomers to grow covalently connected 2D polygonal polymers over the - plane and supramolecular polymerization and/or crystallization of 2D sheets along the direction to constitute layer architectures. Despite various efforts, the synthesis of single-crystal 2D COFs remains a challenging goal. Here, we report the synthesis of single-crystal 2D COFs, by taking the representative imine-linked TPB-DMTP-COF as an example, to reveal the key synthetic parameters that control the crystallization of 2D COFs.

Boosting C Alcohols Selectivity and Activity in High-Current CO Electroreduction using Synergistic Cu/Zn Co-Catalysts.

The electrosynthesis of multi-carbon (C) alcohols, specifically ethanol and n-propanol through CO electroreduction (CORR) in HO, presents a sustainable pathway for intermittent renewable energy storage and a low-carbon economy. However, achieving high selectivity for alcohol production at industrial current densities is kinetically hampered by side reactions such as ethylene generation and hydrogen evolution reaction, which result from competing adsorption of *CO and *H. In this study, we developed a Cu/Zn alloy catalyst to simultaneously enhance the activity and selectivity for alcohol production by increasing CO capture capacity and enriching active hydrogen on Cu sites.

In Situ Welding Ionic Conductive Breakpoints for Highly Reversible All-Solid-State Lithium-Sulfur Batteries.

Poly(ethylene oxide) (PEO)-based solid-state lithium-sulfur batteries (SSLSBs) have garnered considerable interest owing to their impressive energy density and high safety. However, the dissolved lithium polysulfide (LiPS) together with sluggish reaction kinetics disrupts the electrolyte network, bringing about ionic conductive breakpoints and severely limiting battery performance. To cure this, we propose an in situ welding strategy by introducing phosphorus pentasulfide (PS) as the welding filler into PEO-based solid cathodes.