Chemical Reviews最新文献

Gas-phaseand multiphase reactions of free radicals playpivotalroles in tropospheric chemistry. Recent studies indicate that photoinducedmultiphase reactions serve as a potential source of free radicalsrather than a traditional sink. To accurately evaluate their environmentalimpacts, this Review provides a comprehensive overview of radicalmultiphase chemistry on key photoactive components. By systematicallyreviewing the multiphase generation of photoinduced free radicals,we first provide insights into the underlying multiphase reactionmechanisms and kinetics. Subsequently, the synergistic reactions amongphotoreactive components and the mutual feedback mechanism betweenshort-lived and persistent free radicals are illustrated, therebyrevealing their complex interactions on environmental microinterfaces.Then, the effects of multiphase radical chemistry on primary particleaging and secondary particle formation and growth are described indetail. Finally, we critically examine existing challenges and inaccuraciesin the exploration of radical multiphase chemistry, highlighting theurgent need for the comprehensive quantification of photoinduced surfaceoxidation capacity, along with the scientific evaluation of theirhealth risks and climatic effects. The aim of this work is to identifythe missing source of atmospheric radicals, thereby facilitating theevaluation of their environmental impacts and illuminating futuredirections for particle-emission reduction.

High-loading single-atom catalysts (SACs) have recentlyemergedas a frontier in electrochemical catalysis because of their completeactive-site utilization, tunable coordination environment, and atomicallydefined structure. While it is widely recognized that the single-atomicsite in SACs often presents extraordinary catalytic performance, theirlimited metal content and low active-site density still hinder large-scaleimplementation in practical electrochemical reactors. Overcoming thislimitation requires the development of strategies to achieve highmetal loading while preserving atomic dispersion and stability underoperational conditions. In this Review, we comprehensively summarizerecent advances in the synthesis of high-loading SACs, the state-of-the-artcharacterization techniques used to probe their atomic and electronicstructures, and their applications in advanced electrochemical systems,such as CO₂ electrolyzers, fuel cells, and zinc–airbatteries. We critically analyze representative breakthroughs thatbridge the gap between atomic-scale loading control and commercial-levelperformance, elucidating the correlations among metal loading, electronicstructure modulation, and catalytic activity. Then, we offer perspectiveson rational design strategies and emerging opportunities for integratinghigh-loading SACs into next-generation electrocatalytic reactors,with the aim of accelerating their transition from laboratory researchto industrial deployment.

Thermally activated delayed fluorescence (TADF) in coinagemetalnanoclusters (CMNCs) has introduced new paradigms in the design ofoptoelectronic materials, uniting atomic precision with tunable quantumand photophysical properties. This review provides a critical andcomprehensive analysis of TADF mechanisms in gold, silver, copper,and doped/alloy nanoclusters, emphasizing quantum confinement, strongspin–orbit coupling, and engineered singlet–tripletenergy gaps that enable efficient reverse intersystem crossing andhigh photoluminescence quantum yields. Recent advances in TADF-activeCMNCs are highlighted, including ligand architecture, core composition,supramolecular assembly, and heterometallic doping, which collectivelyafford unprecedented control over emission color, dynamics, and stability.Comparative perspectives versus organic and metal–organic TADFemitters are presented, underscoring the distinctive advantages andongoing challenges of CMNCs. Current and emerging applications inOLEDs, X-ray scintillation, chiral photonics, and bioimaging are discussed,along with future research directions and critical barriers to therealization of CMNCs in next-generation optoelectronic devices.

Electrochemical energy conversion underpins the sustainableproductionof fuels and chemicals, with efficiency and selectivity governed byreactions at electrified solid–liquid interfaces. In supportedelectrocatalysts, metal–support interactions (MSIs) shape howcatalytic states form and persist under polarization. Yet a predictivedescription of MSI remains elusive. The as-prepared contact may reconstructunder operating conditions. Activity shifts, morphology, and chargeredistribution do not uniquely identify the current-carrying ensemble.These limitations motivate this review, which separates interfacialstructure, chemical bonding, and collective adhesion before relatingthem to catalytic function. The framework spans single atoms, clusters,nanoparticles, core–shell architectures, and reconstructedinterphases. We assess how atomic-resolution imaging, operando characterization, and potential-aware calculations constrain modelsof the working interface and relate them to electrocatalytic performance.Together, these analyses show that MSI effects depend on the workinginterfacial state and its reaction environment. Predictive designtherefore requires balancing interfacial stabilization with the active-siteaccessibility and structural adaptability needed for turnover.