Chemical Society Reviews最新文献

Biomass conversion into fuels and chemicals holds great promise for sustainable development, yet its efficient valorization remains hindered by the intrinsic complexity of polymeric structures and oxygen-rich functionalities. While thermocatalysis specializes in depolymerization and electrocatalysis enables precise redox control, both face fundamental limitations when used alone. Thermoelectric catalysis has recently emerged as a transformative strategy to resolve this trade-off by synergistically integrating thermal and electrical energy. More than a simple integration of techniques, this strategy represents a paradigm shift in catalyst design: from creating static, heat-tolerant materials to engineering adaptive, field-responsive systems. In this framework, temperature is reimagined as a precision tool for modulating electronic structure and driving in situ catalyst evolution. This tutorial review systematically builds on this concept, starting from mechanistic fundamentals and a comparison of cascade and coupled architectures to highlight different design logics. We then present a multi-scale electrode design roadmap: from atomic-scale active sites to mesoscale transport control and intrinsically responsive materials, showcasing how these strategies can unlock energy-efficient pathways for the concurrent production of value-added chemicals and hydrogen. The review concludes by outlining critical challenges for industrial relevance, including control of fluid flow and heat/mass transfer in non-Newtonian electrolyte suspensions, the operational stability and durability of thermoelectrocatalytic reactors, and process integration and evaluation.

The halogen bond (XB) is a directional noncovalent interaction formed between a halogen atom acting as an electrophilic site and a Lewis base. In recent years, it has shown great potential in the design of functional chiral systems. Due to its tunable interaction strength and pronounced directionality, the XB is becoming a powerful tool for constructing and controlling chirality at both molecular and supramolecular levels. In functional chiral systems, XBs are widely employed to induce, amplify, and transfer chirality, primarily arising from the directionally anisotropic electronic distribution on the surfaces of iodine, bromine, or chlorine atoms. This strategy enables precise construction and stereocontrol of chiral molecular assemblies, asymmetric catalysts, and chiroptical materials. In this review, we first discuss the fundamental properties of XBs and introduce several unconventional types of XBs to stimulate readers' interest. Subsequently, we summarize the latest research progress in XB-based crystal engineering, chiral recognition and separation, chiroptical materials, and supramolecular assemblies. Various XB-mediated asymmetric catalytic systems are also examined, with particular attention paid to their reaction mechanisms and catalyst design strategies. Undoubtedly, living organisms are multilevel chiral systems-from individual protein molecules to large and complex biological structures-thus, this review also explores the potential roles of XBs in biological and biomimetic systems. Finally, we provide a summary and outlook on the current research status, existing challenges, and future opportunities of XBs in functional chiral systems. Through these discussions, this review aims to inspire further exploration of XBs in chiral systems, opening new avenues for supramolecular chemistry, asymmetric synthesis, catalysis, and the development of advanced chiroptical materials.

The emergence of additive manufacturing techniques offers more opportunities for fabricating complex structures with designed properties that are challenging to achieve using traditional manufacturing methods. Micro-/nano-scale metastructures are among the most promising applications of additive manufacturing and are composed of meta-atoms at the subwavelength scale with artificial design, which enables the creation of materials and structures with tailored and programmable properties that go beyond the limitations of their natural and traditional counterparts. This review depicts the thriving intersection of state-of-the-art additive manufacturing and micro-/nano-scale metastructures, such as metamaterials, metasurfaces, etc., aiming to provide a comprehensive overview of current achievements and explore future potential. An array of additive manufacturing techniques are discussed, such as electrohydrodynamic printing, two-photon lithography, and aerosol jet printing, which are reshaping the fabrication of metastructures with unprecedented structural design and functional diversity. Furthermore, the selection of the materials based on fabrication principles and device functions is considered. The diverse applications based on different metastructures are highlighted. Finally, this review is concluded by discussing the current challenges and giving future perspectives.

Liquid-phase heterogeneous catalysis underpins numerous chemical manufacturing processes, ranging from essential products to renewable energy sources, such as hydrogen. Despite the differences in reactor setups and the driving forces between thermos- and electro-catalysis, it is commonly overlooked that the two disciplines are fundamentally governed by the same underlying fundamentals. In this tutorial review, we explore the similarities between electro- and thermocatalysis and introduce how electrochemical methodologies can be applied to characterize thermocatalysis to gain both fundamental and experimental insights. Here, we discuss the recent discovery of Cooperative Redox Enhancement (CORE), a phenomenon whereby selectivity differences for two electrochemical half reactions on two physically separated but electrochemically connected dissimilar metal catalyst particles lead to acceleration of the overall catalytic rate. This approach suggests a new paradigm for the design of heterogeneous catalysis.

In complex reaction systems such as energy conversion and environmental catalysis, the traditional "structure-performance" relationship framework centered around active sites is gradually revealing limitations, such as insufficient regulation dimensions and rigid reaction pathways. In recent years, curvature engineering and spin degree of freedom regulation have emerged as new paradigms for structural and electronic dimension control, showing potential to break through the limitations of conventional catalytic pathway selectivity and reaction rates. Although previous studies have reported catalytic responses to strain induced by curvature and spin-polarization effects, the intrinsic coupling mechanism between the two remains underexplored and lacks systematic summarization and theoretical unification. This review proposes a "curvature-spin-catalytic dynamics triple coupling frontier mechanism", aiming to elucidate how non-uniform geometric perturbations at the nanoscale collaboratively drive electronic structure reconstruction, spin state transitions, and reaction barrier adjustments. The physical origins, microscopic pathways, and experimental characterization related to this coupling mechanism are integrated across scales. Beginning with lattice distortion-induced d-orbital reorganization and crystal field regulation, the discussion extends to enhanced orbital-spin coupling, spin-filtered electron transfer, and pathway differentiation, further connecting to dynamic feedback, self-regulating active platform construction, and multi-physical field responsive regulation. This review also summarizes key advances in related in situ characterization techniques, first-principles simulation systems, and multi-field coupling configurations. This review not only fills the gap in the catalysis field regarding the triple coupling mechanism of structure-electron-reaction pathways, but also provides a paradigm framework and cross-scenario guidance for the development of next-generation programmable and responsive catalytic systems.

The escalating global burden of diseases-including cancer, neurodegenerative, and cardiovascular disorders-poses severe threats to human health and social development. The inherent limitations of conventional diagnostic, imaging, and therapeutic modalities have driven the rapid evolution of nanomedicine, particularly nanotheranostics, which integrates diagnostic and therapeutic functionalities within a single nanoplatform for enhanced precision and safety. Despite remarkable advances in nanotechnology and materials science over recent decades, challenges such as the biological complexity of living systems, incomplete understanding of nano-bio interactions, inefficiencies in nanoparticle synthesis, and limited clinical translation continue to hinder progress. The recent convergence of nanomedicine with artificial intelligence (AI) and computational sciences has opened transformative opportunities to overcome these obstacles. AI-empowered algorithms, including machine learning, deep learning, and generative models, are increasingly being applied to optimize nanoparticle design and synthesis, predict nano-bio interactions, and improve diagnostic and therapeutic efficacy. These approaches not only accelerate materials discovery but also enable data-driven, adaptive nanotheranostic systems capable of autonomous optimization across disease contexts. This review systematically summarizes the current landscape of AI-powered nanomedicine, highlighting advances in nanoparticle design, synthesis, and the development of AI-guided diagnostic and therapeutic nanoplatforms. It further discusses applications in bioimaging, targeted therapy, and clinical translation, while identifying existing challenges and future perspectives in establishing next-generation AI-empowered nanotheranostics. Ultimately, the integration of artificial intelligence and nanotechnology is expected to revolutionize precision medicine by bridging the gap between fundamental nanoscience and clinical implementation, paving the way toward intelligent, personalized healthcare.

Halide perovskites are widely recognized for optoelectronic devices such as photodetectors, photovoltaics, and light emitting diodes. Crucially, their unique characteristic as a mixed ionic-electronic semiconductor has recently positioned them as a highly promising material for neuromorphic computing, which necessitates a dedicated review of this rapidly emerging field. This comprehensive review first correlates the relationship between the perovskite's crystal structure and its resulting optoelectronic and ionic properties, which underpins memristor functionality. We then systematically discuss the figure of merit, operating mechanisms, and characterization techniques for halide perovskite memristors. After critically reviewing the state-of-the-art devices, we analyze the critical gap between lab-scale systems and real-world applications, specifically tackling the challenges of crossbar array implementation and discussing various neuromorphic applications. Finally, we detail an outlook, highlighting persistent hurdles like endurance and stability as well as identifying key research directions, such as high-throughput experimentation and customizing devices based on the necessary trade-off between response time, energy, and retention to realize practical, next-generation neuromorphic hardware.

Phototheranostics has emerged as an important branch of oncology, relying on multiple dissipation pathways of the excited state energy of phototheranostic agents to achieve disease diagnosis and therapy. However, the fixed excited-state energy dissipation pathways of conventional phototheranostic agents lead to inherent competition among diagnostic and therapeutic functions, ultimately compromising their efficacies in heterogeneous and dynamic tumor microenvironments (TMEs). The use of smart switchable phototheranostic platforms, which can dynamically redistribute photoenergy on demand to best fit the changed TMEs, has emerged as a transformative strategy to overcome this limitation. Their photo-functions could be smartly switched or adapted to maximize multimodal imaging and therapeutic performance. This review provides a comprehensive overview of the recent advancements in organic-based smart switchable phototheranostics, systematically categorizing them into five distinct design paradigms: (1) caging/uncaging molecular engineering, (2) dynamic assembly/disassembly, (3) manipulation of intramolecular motions, (4) photo-controlled molecular isomerization, and (5) metal-ion-involved redox-state transition. For each strategy, we elucidate the fundamental working principles and highlight representative examples that demonstrate tailored applications in adaptive phototheranostics. Finally, we discuss the prevailing challenges and future perspectives of these smart switching phototheranostic technologies. This review aims to inspire interdisciplinary research efforts for advancing precision oncology.

Artificial cells capable of mimicking metabolism represent a rapidly evolving frontier in synthetic biology. These systems integrate enzymes to reconstruct essential metabolic pathways, enabling the study of cellular processes in simplified yet controllable environments. This review provides a comprehensive overview of the advantages and limitations of various artificial cells for metabolic mimicry based on their physical properties. The major strategies for energy generation, including organelle encapsulation, photosynthetic phosphorylation, and nanomaterial-assisted ATP synthesis, are summarized. Anabolic processes such as carbon fixation, lipid biosynthesis, and protein expression are discussed in detail, along with representative examples of catabolic pathways involved in carbon and nitrogen metabolism. We highlight the emerging applications of metabolically functional artificial cells in biosensing and disease diagnosis. By bridging the fundamental principles and practical applications, this review aims to provide valuable insights into the design and deployment of artificial metabolic systems, paving the way for next-generation synthetic biological tools.