Chemical Society Reviews最新文献

This tutorial serves as an accessible introduction for researchers and students interested in the multifaceted chemistry of formaldehyde and its potential in shaping a more sustainable future. We explore its roles in renewable energy storage in the form of liquid organic hydrogen carriers (LOHCs) and renewable fuels, as well as carbon capture, utilization and storage (CCUS), and biomass valorisation. Furthermore, the relevance of these applications to several United Nations Sustainable Development Goals (UNSDGs 6, 7, 9, 12, and 13) is examined. Beyond the energy and environmental aspects, we discuss the use of formaldehyde and related surrogates in synthetic chemistry, focusing on innovative catalytic strategies to make use of this versatile and abundant C1 building block. Given formaldehyde's central role as an intermediate in both synthetic and biological C1-H₂ reaction networks, the tutorial additionally offers discussion points on related small molecules, including methane, methanol, formic acid, CO, and CO₂.

Photocatalytic decarboxylation of carboxylic acids or their redox active esters has become an important strategy in organic chemistry. Using catalytic amounts of metal-based or organic photocatalysts, normally under visible light irradiation, these substrates generate carbon centered radicals, which have been applied to a broad range of C–C and C–heteroatom bond forming reactions. Addition reaction to electron-deficient alkenes, hydroalkylation of unsaturated C–C bonds and addition to C–heteroatom multiple bonds have been extensively studied. Cross-coupling reactions such as arylation, alkylation, allylation, vinylation, alkynylation, acylation, cyanation and C–H functionalization reactions are also successfully performed. In the case of C–heteroatom bond forming reactions, C–halogen, C–oxygen, C–sulfur, C–nitrogen, C–phosphorus, C–boron and C–silicon are fundamental functionalization processes. Hydro- and deuterodecarboxylation reactions allow the substitution of the carboxylic group by a hydrogen or a deuterium atom regioselectively. Finally, decarboxylative elimination reactions, such as olefination reactions for the synthesis of alkenes and decarboxylative C–C bond cleavage of cyclic carboxylic acids, give 1,n-dicarbonyl compounds. These photoredox transformations, a renaissance in organic chemistry, starting from readily accessible carboxylic acids widely available in Nature and the pharma industry with a great structural diversity occur under mild and simple reaction conditions with excellent efficiency and clean energy input.

Stimuli-activatable covalent labeling probes have emerged as powerful tools for targeted biomolecule labeling, addressing the limitations of conventional covalent probes, such as off-target reactivity, limited spatiotemporal control, and low signal-to-background ratios. These probes remain inert under physiological conditions but are selectively activated by specific endogenous or exogenous stimuli—such as enzymes, reactive oxygen species, light, ultrasound, or X-ray irradiation—initiating a cascade of stimulus-activation-covalent ligation. This mechanism enables precise, on-demand covalent conjugation to target biomolecules, improving labeling specificity, enhancing probe retention at pathological sites, and reducing interference with healthy tissues. Recent advances in molecular design, including enzymatic or light-mediated proximity labeling, have expanded their applications in protein profiling, interaction mapping, cell–cell communication analysis, and in vivo imaging. This review provides a comprehensive overview of the design principles, activation strategies focusing on enzymatic and photochemical triggers, and key biomedical applications, while critically assessing challenges related to stability, pharmacokinetics, and clinical translation. By integrating chemical probe engineering with translational research, we highlight the transformative potential of stimuli-activatable covalent labeling probes for protein profiling, disease diagnosis, therapeutic monitoring, and real-time visualization of biological processes.

Conventional sensor systems suffer from an inherent limitation in delivering direct visual feedback during the physical-to-electrical signal transduction process, creating a cognitive disconnect between users and functional device interactions. This challenge can be addressed through the development of visualised flexible tactile sensing platforms that embed real-time sensory feedback into interactive interfaces via electrochromic visualisation. This review systematically examines advancements in multimodal integration strategies, particularly the convergence of diverse sensing modalities (e.g. pressure, sweat, temperature, and humidity sensing) with dynamically responsive electrochromic display units. It dissects the material innovations, structural engineering, and mechanistic principles underpinning individual module performance. It also rigorously analyses advanced alignment protocols for heterointegrated systems and critical challenges. The evolution from discrete flexible sensors to multifunctional visualization platforms represents a shift toward interdisciplinary convergence.

The essence of catalysis lies in the transfer of electrons, driving the cleavage and formation of chemical bonds. Understanding the fundamental attributes of electrons is essential for improving the efficiency of catalytic processes. This tutorial review provides a systematic and accessible framework, integrating electron fundamentals and dynamics across diverse catalytic scenarios. We begin by summarizing the foundational principles of electron behavior, including free electrons, molecular orbital theory for molecular systems, and crystal field splitting theory in catalyst materials. Next, we elucidate the basic principles governing key catalytic processes: the Arrhenius equation in thermocatalysis, band structure theory and electron–hole recombination in photocatalysis, electronic structures of active sites and adsorption mechanisms in electrocatalysis, and the piezoelectric effect in mechanocatalysis. Building on this foundation, a universal framework for understanding electron transfer dynamics across surfaces and within bulk materials is proposed. Subsequently, we examine current material engineering strategies, categorizing them based on the fundamental parameters, including charge, orbital, lattice, and spin. Finally, we highlight emerging opportunities, with a particular focus on the underexplored potential of electron spin and the integration of interdisciplinary approaches for advancing energy technologies. By presenting a clear physical perspective and an organized knowledge base, this work is expected to bridge the gap between fundamental physics and chemical reactions, fostering interdisciplinary collaboration and driving innovations in energy solutions.

Since the 2000s, so-called scaling relations have been recognised as a limiting factor in electrocatalysis. Overcoming these constraints is essential to advance energy conversion technologies such as electrolysers, fuel cells, and metal–air batteries. This review presents key concepts, tools, and manipulation strategies required to deal with the scaling relations in oxygen electrocatalysis, chosen as a representative case. Special attention is given to the catalyst's geometry as an emerging central variable in electrocatalysis – one whose influence is only beginning to be systematically understood. Building on geometric and chemical grounds, this review offers a structured tutorial for the theory-driven design of electrocatalysts the deliberate manipulation of scaling relations.

Efficient oxygen reduction reaction (ORR) catalysts are pivotal for advancing clean energy technologies, such as fuel cells and metal–air batteries. Metalloporphyrins and metallocorroles, inspired by biological systems, represent promising molecular catalysts for the ORR due to their tunable structures and redox properties. This review systematically explores recent progress made in developing metalloporphyrin- and metallocorrole-based catalysts for the ORR, spanning from fundamental molecular design to advanced material engineering. We first introduce the fundamentals of the ORR and its significance. The discussion then delves into molecular catalysis, covering both homogeneous and heterogeneous catalytic systems. For heterogeneous systems, in addition to directly loading molecular catalysts on electrode materials through physical adsorption, we discuss covalent grafting of molecular catalysts on carbon supports (e.g., carbon nanotubes, graphene, and carbon black) and other support materials (e.g., metal oxides and gold electrodes). Moreover, the other focus of this review is placed on elucidating structure–property relationships, particularly on analyzing the effect of substituents, trans axial ligands, proton relay groups, electrostatic effects, and binuclear structures on the ORR mechanism and performance. Furthermore, the integration of these molecular catalysts into structured porous materials, including metal–organic frameworks (MOFs), covalent-organic frameworks (COFs), and porous organic polymers (POPs), is discussed, highlighting how material design enhances catalytic activity, stability, and electron/proton transport. Finally, this review summarizes key achievements, identifies current challenges, and offers perspectives on future research directions for developing next-generation, high-performance ORR catalysts based on metalloporphyrins and metallocorroles. This work aims to provide valuable insights for the rational design of efficient and durable metalloporphyrin- and metallocorrole-based ORR catalysts and for the development of molecule-based functional materials for the future application of molecular electrocatalysis.

Intelligent chemiresistive gas sensing platforms are emerging as pivotal technologies for addressing global challenges such as climate change, urbanization, and public health crises. As core components of modern sensing systems, these platforms demonstrate immense potential in environmental monitoring, industrial safety, and medical diagnostics. Chemiresistive gas sensors, with their high sensitivity, rapid response, low power consumption, and miniaturization capabilities, serve as a key enabler for next-generation intelligent gas sensing. However, critical challenges remain in selectivity, long-term stability, energy efficiency, and scalable manufacturing. Recent advancements in materials science, including the development of novel materials such as metal–organic frameworks, two-dimensional transition metal dichalcogenides, and MXenes, has expanded design possibilities for sensors. Meanwhile, progress in artificial intelligence and the Internet of Things have significantly enhanced chemiresistive sensors, where machine learning algorithms improve selectivity, dynamically compensate for environmental interference, and facilitate distributed data training to optimize performance. This review systematically examines the design strategies, emerging applications, and current challenges of intelligent chemiresistive gas sensing platforms, with a focus on their multidimensional evolution from material innovation to cognitive decision-making. Furthermore, it explores future directions in environmental sustainability and interdisciplinary research. By integrating hardware–software co-design, advanced signal processing, and energy management strategies, intelligent chemiresistive gas sensing platforms are poised to transition from standalone detection to integrated system functionality, laying the foundation for responsive sensing ecosystems.