Chemical Reviews最新文献

All-inorganic perovskites have gained significant attention in recent years due to their superior thermal and environmental stability compared to their organic–inorganic hybrid counterparts. These materials, typically represented by CsPbX₃, exhibit excellent optoelectronic properties such as high absorption coefficients, suitable bandgaps, and long carrier diffusion lengths, making them promising candidates for next-generation photovoltaic applications. This review provides a comprehensive overview of the structural characteristics, phase behavior, and optoelectronic properties of inorganic perovskites. Various fabrication techniques, including solution processing, vacuum deposition, and hybrid approaches, are discussed with respect to their influence on film quality and device performance. Key issues, including phase instability and defect formation, are discussed, together with recent advances in composition engineering, additive optimization, and interfacial modification. In addition, the environmental and health concerns associated with lead usage have driven the development of lead-free alternatives, such as bismuth-, tin-, or antimony-based perovskites. This review also summarizes progress in the fabrication of large-area and flexible IPSCs and explores their potential applications under extreme environmental conditions. Finally, the remaining challenges and future opportunities for advancing high-performance all-inorganic perovskite photovoltaics are highlighted.

Polyhedral oligomeric silsesquioxanes (POSS) and ionic liquids (ILs) have emerged as highly promising components for the design of advanced hybrid materials. The integration of ILs onto the POSS core has led to the development of a novel class of materials known as POSS-based ILs (POSS-ILs), which synergistically combine the thermal and mechanical stability of POSS with the tunable physicochemical properties of ILs. Despite their great potential, a detailed and unified review covering the synthesis, properties, and multifunctional applications of POSS-ILs remains limited. This review therefore presents a thorough discussion of their synthetic approaches such as direct functionalization, IL grafting, and sol–gel techniques alongside their distinctive physicochemical features, including high thermal and mechanical stability, ionic conductivity, viscosity control, tunability, solubility, and chemical resistance. Furthermore, the roles of POSS-ILs in catalysis, energy storage and conversion, smart materials, analytical applications, and wastewater treatment are systematically explored. The review also highlights current challenges related to structure–property relationships and multifunctionality, while outlining future perspectives for optimizing POSS-ILs as sustainable, high-performance materials. Overall, this review aims to serve as a comprehensive resource for researchers across materials science, nanotechnology, and environmental chemistry, supporting the continued innovation and application of POSS-ILs in next-generation functional systems.

The photoelectric conversion process has traditionally been dominated by studies on light intensity, while the role of polarization remains an emerging and underexplored frontier. Despite the growing number of mechanisms and material architectures demonstrating polarization-sensitive photoelectric responses, a systematic framework to unify these findings is still lacking. This review establishes a comprehensive structure based on the photoelectric conversion pathway, spanning from multidimensional light-field parameters (including intensity, polarization angle, degree of polarization, and ellipticity) to electronic degrees of freedom (charge, momentum, spin, and valley) and ultimately to multidimensional electrical outputs (absorption scalars, current vectors). Leveraging symmetry analysis, we categorize polarization-sensitive photoelectric responses into scalar and vector photocurrent contributions, systematically examining material structures that exhibit the requisite symmetries. Special attention is given to oblique incidence illumination, which modulates symmetry and induces polarization-dependent effects. Finally, we outline the future research directions.

Semiartificial photosynthesis presents an attractive route to overcome limitations of natural photosynthesis for sustainable chemicals production. Synthetic materials are combined with biological molecules, forming biohybrid systems, that provide unique opportunities to innovate new solar-to-chemical pathways. There are further advantages if the biohybrids confine specific processes to different spatial locations. Such behavior is a defining feature of natural photosynthesis and it is mimicked in the photocatalytic biohybrid vesicles discussed in this Review. A nonleaky membrane comprised of amphiphilic molecules defines the wall of the reactor vesicle. Light-driven directional transfer of electrons and/or ions across the vesicle membrane generates an (electro)chemical gradient, a form of energy storage, that is subsequently harnessed for chemical synthesis. In such systems, nonproductive backreactions are avoided, reactants can be concentrated to favor their conversion, and reaction intermediates can be channeled through the desired pathway. This Review introduces natural photosynthesis and vesicles as biohybrid reaction containers. Different approaches to achieving light-driven charge transfer across vesicle membranes are reviewed, and state-of-the-art strategies for delivering light-driven chemical production are systematically summarized for this interdisciplinary field. Finally, key scientific problems and bottlenecks to the development of photocatalytic biohybrid vesicles are defined to provide insights for driving forward future research.

Cyclic hemiboronic acids are boron-containing heterocycles composed of one exocyclic boranol (B–OH) group, one endocyclic B–C bond, and one endocyclic B–heteroatom (O or N) bond. Compared to their open-form congeners, boronic acids, they are largely underexplored. Inspired by the recent success of the benzoxaborole ring system in drug discovery, highlighted by the approved products tavaborole and crisaborole, the last two decades have seen a continuous rise in interest toward other classes of nonaromatic and pseudoaromatic hemiboronic heterocycles. These boroheterocycles have been employed in various applications including organocatalysis, bioconjugation, drug discovery, as synthetic intermediates in natural product synthesis, and as components of new dynamic materials. This article brings together, using a structure-based organization, a comprehensive review of the current knowledge of these unique compounds. Preparative methods, structural characteristics, and important physical properties such as the open-closed equilibrium, acidity (pK_a), and molecular interactions are discussed and compared between different structural subtypes. Ring size and the nature of heteroatoms within the ring often exert dramatic differences in acidity, reactivity, and aromatic character of the heterocycle, which in turn enable their methodical application.

The rapid advancement of wearable electronics over the recent decadal span has positioned it as a cornerstone of scientific innovation and everyday life, bridging applications from fitness tracking to advanced medical diagnostics. These technologies enable real-time physiological monitoring, personalized healthcare, and precision medicine, yet their progress is hindered by the limitations of conventional fabrication methods, which struggle to accommodate unconventional nanomaterials and the escalating complexity of wearable devices. This review addresses this gap by spotlighting cutting-edge micro/nanofabrication techniques and novel nanomaterials poised to redefine wearable electronics. We systematically examine breakthroughs in sensing nanomaterials across dimensional architectures, while highlighting innovative printing methodologies that enable scalable, cost-effective, and geometrically tailored fabrication of flexible, high-performance devices. By analyzing these advances, we explore their transformative applications in wearable biochemical, biophysical, electrophysiological, and multimodal electronics, underscoring their potential to elevate device performance and user experience universally. Finally, we critically evaluate the advantages, persistent challenges, and prospects of these micro/nanofabrication strategies, offering insights to guide next-generation wearable electronics. This review aims to catalyze interdisciplinary innovation, fostering the integration of these techniques into diverse applications and accelerating the evolution of wearable electronics.

As the most accessible and abundant renewable resource on earth, lignocellulosic biomass mainly consists of cellulose, hemicelluloses, and lignin with a small amount of protein, pectin, minerals, and extractives (e.g., tannins, lipids, and resins). Lignocellulosic biomass has gained extensive attention in industry and research owing to its renewability, availability, and low cost. However, achieving efficient fractionation of lignocellulose components and all-component utilization in a green and cost-effective manner remains a challenge dueto biomass recalcitrance. Deep eutectic solvents (DESs) have received considerable attention because they are biocompatible, inexpensive, biodegradable, have low toxicity, and are easy to prepare and recycle; these characteristics strongly depend on individual components involved in DESs preparation. This review systematically summarizes recent progress in the fractionation of carbohydrates (cellulose and hemicelluloses) and lignin from biomass using DESs, with particular emphasis on the effects of DES types and pretreatment parameters on fractionation efficiency. The subsequent conversion and upgrading of the DES-fractionated products (i.e., carbohydrates and lignin) are comprehensively analyzed. Finally, the challenges and future prospects of lignocellulose biomass fractionation using DESs are proposed in view of the existing limitations. This review provides an in-depth understanding of lignocellulose biomass fractionation during DESs processing, offering insights to improve current pretreatment methods and/or to explore new pretreatment methods aimed at mitigating the global energy crisis.

Leveraging base metal catalysis to transform small organic molecules by forging X–N bonds (X = C, N, P, S) through nitrene transfer reactions (NTRs) renders a robust and sustainable paradigm shift for preparing valuable amine building blocks. Over the last four decades, 3d metal-catalyzed NTRs have received significant attention in the field of organic synthesis. This review will thoroughly discuss the manipulation of various complexes of base metals, such as Mn, Fe, Co, Ni, and Cu, to control the reaction pathways for X–N bond formation using different nitrene precursors. This review will encompass exemplary, pioneering, and pertinent synthesis in this area and will comprehensively elucidate the mechanistic rationale behind each 3d metals. The reactivity, regioselectivity, chemoselectivity and enantioselectivity of those novel base-metal catalysts are an inevitable part of this discussion. We will also address the inherent limitations and potential opportunities within this specific field of study.