Science China Chemistry最新文献

Emerging solar photothermal technologies demonstrate significant potential for addressing global freshwater and energy shortages, as well as for treating offshore oil spills. However, simultaneously optimizing hydrophilic and hydrophobic sites at material interfaces to balance the specific functions of efficient water evaporation, anti-saline fouling, and resistance to oily contaminants is a significant challenge. Herein, inspired by the dual properties of “hydrophobic gliding and hydrophilic moisture retention” observed in water strider legs, the competitive assembly of hydrophilic polyoxometalates and hydrophobic oleic acid anions with polyaniline cations is selected for fabricating an innovative heteropoly blue-polyaniline-oleic acid shell-encapsulated melamine foam evaporator (3D MF@HPB-PAn_x-OA). Under electrostatic repulsion, hydrophilic HPB and hydrophobic OA respectively bind to the inner and outer sides of PAn, forming a unique spatially segregated structure. Hydrophilic HPB enhances evaporation performance by serving as an in-situ photothermal evaporation site. The hydrophobic armor layer enhances surface self-cleaning properties and the ability to treat oily substances. By leveraging its unique structural design and excellent mechanical stability, MF@HPB-PAn₁₀-OA accomplished zero-liquid-discharge seawater treatment at an evaporation rate of 3.70 kg m⁻² h⁻¹ and achieved a recovery rate as high as 3.11 × 10⁴ kg m⁻³ h⁻¹ in highly challenging crude oil treatment scenarios.

Nanogap-induced surface-enhanced Raman spectroscopy (SERS) represents an advanced platform for ultrasensitive, non-destructive molecular detection. But the detection sensitivity and reproducibility are compromised because only 0.1%–1% of the target molecules can reach the Raman-enhanced hotspots within the nanogap. Optical tweezers (OT) can capture particles into the nanogaps to achieve stable amplification of SERS signals, thus expanding the utility of plasmonic nanogaps for SERS applications. However, the combined nanogap-induced SERS and optical tweezers approach remains fraught with challenges, particularly regarding the complexity of molecular trapping within the nanogaps by optical forces. In this review, we outline recent developments in the construction of plasmonic nanogaps for enhancing SERS detection and OT-based molecular manipulation. Building on an analysis of the fundamental physics of optical trapping, we highlight key strategies to boost the combined SERS and optical tweezers approach bridged by plasmonic nanogaps. Our focus encompasses mechanisms, structural configurations, and capture modalities, with particular emphasis on the construction of static and dynamic nanogaps and on plasmonic optical trapping methodologies. Finally, we discuss current challenges and prospects to stimulate further progress in this promising field.

Direct deracemization of racemates presents an ideal access to acquire highly enantioenriched molecules. Research in photocatalytic deracemization, since its first demonstration in 2018, has been advancing steadily and witnessed explosive growth in 2025, becoming a more diverse and active field. This review comprehensively summarizes recent advances in photocatalytic deracemization by categorizing the catalytic systems employed, including organocatalysis, metal catalysis, biocatalysis, or cooperative strategies, with a focus on their evolution and mechanisms. The diversification of catalytic systems has advanced the understanding of photochemical stereocontrol and offered useful guidance for the development of novel catalysts and the optimization of reaction systems. Moreover, these advances have laid a solid foundation for the preparation of valuable chiral compounds, enabling their broader application in pharmaceutical development and materials science.

This study introduces a nitrite-driven hydrochemical regulation strategy to reconfigure the ligand environment of ruthenium (Ru), transforming it from heterogeneous species into a uniform and stable anionic complex, [Ru(NO)(NO₂)_x(OH)_5−x]²⁻. This transformation significantly enhances the homogeneity and reactivity of Ru, enabling highly efficient separation from high-level liquid waste (HLLW) using a pyridine-based resin. Combined density functional theory (DFT) and X-ray absorption fine structure (XAFS) analyses identified the dominant complex as [Ru(NO)(NO₂)_2.2(ONO)_1.8(OH)]²⁻. To counteract the inherent instability of the nitrite-nitric acid system, a silicon-based composite adsorbent (N3/SiO₂) was developed, providing protective barriers against deterioration. Under optimized conditions, the adsorbent achieved a maximum capacity of 69.20 mg/g at 298 K—a 65% improvement over conventional systems. Adsorption and desorption mechanisms were elucidated, and a reusable ion-exchange-complexation cycle was proposed. This work offers an innovative strategy for Ru separation in HLLW, with strong potential for industrial scale-up applications.

Phthalocyanine-based metal-organic frameworks (Pc-MOFs) are rapidly emerging as a distinctive subclass of coordination materials with unique optoelectronic features and structural versatility. Their extended π-conjugation, capacity for metalation, and stability under operational conditions make them attractive for applications where conventional MOFs have often shown limitations. In this review, we provide a comprehensive overview of the current state of Pc-MOF chemistry, with emphasis on their synthetic design, structural diversity, and functional integration. Then, we examine their most relevant applications across three main areas: (1) Sensing. Pc-MOFs have enabled chemiresistive, electrochemical, and photoelectrochemical devices with enhanced sensitivity, selectivity, and low detection limits. (2) Catalysis. Studies in CO₂ valorization and oxygen electrocatalysis demonstrate that Pc-MOFs can achieve competitive performance by exploiting their electronic structure and redox-active centers, although the scope of explored reactions remains relatively limited. (3) Energy storage. The use of Pc-MOFs in supercapacitors and batteries has revealed promising charge-storage capacities, high cycling stability, and mechanical flexibility, pointing to their suitability for next-generation electrochemical devices. While Pc-MOFs still represent an emerging field with relatively few examples compared to other functional MOFs, the available evidence underlines their vast potential. The combination of phthalocyanine linkers with reticular chemistry offers unprecedented opportunities for rational material design. We foresee that continued progress in synthetic diversification and integration strategies will unlock their applicability not only in sensing, catalysis, and energy, but also in broader areas such as biomedicine, environmental remediation, and optoelectronics, in the upcoming years.

The construction of Cu(I) nanoclusters based on polyoxometalates initially encounters significant obstacles, particularly with respect to achieving crystallization within complex reaction systems. The synthesis of novel nanoclusters with enhanced functional performance poses an even greater challenge. In this study, four polyoxotungstate (POT)-constructed Cu(I) nanocluster-based assembly crystals are reported. Single-crystal X-ray diffraction analyses reveal that POT units preferentially coordinate on the periphery of the Cu(I) nanoclusters, promoting the formation of one-dimensional (1D) or two-dimensional (2D) architectures while preserving the structural integrity of the POT precursors. Notably, the 2D assemblies exhibit superior photothermal properties among the synthesized structures. Comprehensive experimental and theoretical investigations indicate that POTs exert a pronounced influence on the charge transfer processes within these assemblies. Moreover, the catalytic activities of the nanoclusters were systematically assessed in the context of the electrochemical nitrate reduction reaction (NO₃RR). Remarkably, the 1D alkynyl Cu(I) nanocluster assemblies derived from an antimony-containing POT precursor demonstrated a substantially enhanced ammonia yield and Faradaic efficiency (FE), achieving an NH₃ production rate of 0.82 mmol h⁻¹ cm⁻² and a maximum FE of 93.51% under optimal applied potentials. These findings collectively reveal that both the photothermal and electrocatalytic performances of W–Cu nanocluster-assembled crystals are closely correlated with their distinct crystal and electronic structures.

In supramolecular chemistry, macrocycle-based host-guest chemistry is of central importance, as it enables the selective recognition and reversible binding of guest molecules within well-defined host cavities through noncovalent interactions. Traditional research has mainly focused on solution-phase host-guest systems. However, in recent years, solid-state host-guest chemistry has attracted increasing attention due to its distinct advantages in constructing solid-state functional materials. This review systematically summarizes recent advances in the solid-state host-guest chemistry of pillararenes, with a particular focus on the resulting supramolecular confinement effects. Pillararenes were a class of macrocyclic hosts featuring rigid, electron-rich cavities, tunable rim functionalities, and symmetrical architectures, which have emerged as versatile platforms for constructing solid-state host-guest systems. Depending on guest size and binding mode, pillararenes can form diverse solid-state assemblies, including 1:1 inclusion complexes, 2:1 nanocapsules, linear supramolecular polymers, exo-wall binding architectures, and variable-stoichiometry systems. The confinement of guest molecules within pillararene-based crystalline frameworks not only restricts their molecular motion and conformation but also dictates their spatial arrangement, thereby giving rise to emergent physicochemical properties. These obtained solid-state host-guest systems have been successfully exploited in a wide range of applications, including optical materials, selective adsorptive separation, and structural determination. Finally, the remaining challenges and future prospects are discussed to guide further development in this field. We hope that this review will inspire researchers to explore the full potential of macrocycle-based solid-state host-guest systems and stimulate the design of next-generation functional materials harnessing the unique supramolecular confinement effects from macrocycles.

Atropisomers have attracted growing interest in synthetic and medicinal chemistry. Nevertheless, transient atropisomeric intermediates are often overlooked in catalytic asymmetric synthesis, and the chirality transfer processes mediated by these species have thus not been systematically explored or thoroughly studied. The catalytic enantioselective synthesis via a transient axial chirality transfer strategy effectively overcomes the reliance of traditional methods on pre-synthesized chiral substrates. By virtue of the precise stereinduction by chiral catalysts to generate transient axial chirality relays, it enables the efficient conversion of racemic or prochiral precursors into chiral functional molecules. This review focuses on metal-catalyzed enantioselective reaction pathways for the transfer of transient atropisomer axial chirality to central chirality and/or axial chirality. Through a systematic overview of the latest advances, current challenges, and future perspectives, this review is intended to offer comprehensive guidance and fresh perspectives for researchers in related fields, and to foster the development and application of novel chirality transfer strategies in asymmetric catalysis.

Engineering geometric asymmetry in molecular architectures offers a powerful strategy for boosting third-order nonlinear optical (NLO) responses, yet such approaches have not been reported for metal-oxo clusters. Here, we synthesized three iron-oxo clusters [Fe₇(μ₄-O)₄(FcDCA)₆] (Fe₇OC), [Fe₆Ca(μ₄-O)₄(FcDCA)₆] (Fe₆CaOC), and [Fe₆Na(μ₃-O)₄(FcDCA)₆] (Fe₆NaOC) (ferrocene dicarboxylic acid = H₂FcDCA) with spatially distorted cluster cores via a heterometal incorporation strategy. Single-crystal X-ray diffraction analysis reveals incorporation of heterometal Ca or Na ions induces severe tetrahedral-core distortion through bond elongation, leading to breaking spatial symmetry in the geometric structure of the cluster core. Spectroscopy and Z-scan measurements demonstrated that the symmetry breaking of these geometric structures in the Fe-oxo clusters results in a narrowed optical band gap and a substantially increased third-order nonlinear absorption coefficient (β). Theoretical calculations indicate that the introduction of heterometals lowered the band gap of Fe-oxo clusters, enhanced the nonlinear hyperpolarizability, and improved the third-order NLO performance. Furthermore, the metal-oxo cluster-based polymer liquid crystal device prepared by mixing Fe₆NaOC clusters with nematic liquid crystals not only has high transmittance and electro-optical switch characteristics, but also has stronger optical limiting performance. This work not only develops new high-performance NLO metal-oxo cluster materials with geometric symmetry engineering, but also establishes metal-oxo cluster-based electro-optical smart devices for nonlinear optical limiting applications.