ConspectusTraditional metal nanoparticles have been widely utilized as heterogeneous catalysts in both fundamental scientific research and industrial applications. Their catalytic performances are commonly statistical and represent averaged results from all of the nanoparticles due to their inherent size polydispersity and structure heterogeneity. Recently, metal clusters (1-2 nm) with precise compositions and well-defined structures have provided opportunities to precisely correlate the catalytic properties with the structure and composition of the clusters at the atomic level. Specifically, the distinct metal core, interface, and surface structures of these clusters render them ideal for exploring the contributions of the surface/interface/core of cluster-based catalysts to catalytic properties.In this Account, we introduce the correlation of the catalytic properties of clusters with their ligand, interface, and metal kernel, ultimately mapping out the key factors that dictate the catalytic activity and selectivity. We first preview atomically precise clusters and the structural characteristics of the surface, interface, and kernel. Then, we emphasize the modulation of catalytic properties of cluster catalysts through the ligand, interface, and core. (i) Surface ligand: An efficient surface modification via ligand exchange is able to not only remarkably enhance the catalytic activity but also effectively modulate the product selectivity. (ii) Metal-ligand interface and cluster-cluster interface: The metal-ligand interface can enable the catalytic sites to directly control the whole catalytic process through the synergy between the metal atom and the ligand. Additionally, the interfaces between the clusters and their surrounding environment can cooperatively tailor the catalytic activity and selectivity. (iii) Metal core: The one-atom variation in the cluster kernel composition can effectively tune the overall electronic structures of clusters, thereby indirectly improving their catalytic activities. Furthermore, the central atom within an open core can also act as the active site to directly participate in and facilitate the catalytic reaction. Ultimately, looking to the future of catalysis science, there are still many challenges, but atomically precise metal clusters deserve more future efforts to unravel fundamental catalysis. Therefore, we offer several perspectives on the future research of precise catalysis using atomically precise cluster catalysts. We anticipate that this Account can provide fundamental insight into the unique contributions of the surface/interface/core of heterogeneous catalysts to their overall catalytic performances. By learning these fundamental principles, we will ultimately be able to design high-performance catalysts for a variety of catalytic processes.

ConspectusImproved plastic waste management strategies are required to combat the rapid accumulation of postconsumer waste in landfills and the environment. Unfortunately, mechanical recycling currently accounts for only 10% of plastic recovery and is limited by product downcycling, highlighting the need for more effective chemical alternatives. Ironically, the robust mechanochemical properties that make plastics so useful also make them difficult to process at the end of their lifetime. Unlike polyolefins, made up of C-C bonds, polyurethanes contain reactive C-O and C-N bonds that make them amenable to chemical degradation. Chemical recycling of polyurethanes toward their molecular building units can be driven using a variety of chemical reagents, including acids, amines, glycols, and water. Acidolysis has shown particular promise as an effective and sustainable method for polyurethane closed-loop recycling. However, the mechanistic and fundamental chemical principles governing this process remain elusive.In this Account, we detail our mechanistic and kinetic studies of polyurethane foam acidolysis. By systematically varying the carboxylic acid reagent, we highlight the impact of the acid transport phase, acid structure, and acid electronics on the rate, product distribution, and rate-limiting regimes of polyurethane depolymerization. We suggest design rules that can be used to predict and explain how new reagents will impact the rate and products of polyurethane acidolysis. From these design rules, we suggest a promising choice of acid for the efficient and facile recovery of polyol, the major building block used in polyurethane synthesis. We conclude by recognizing the remaining challenges related to polyurethane chemical recycling, largely related to making this process more economically feasible.

ConspectusChemical manufacturing is dominated by color changes that offer quantifiable insights into a huge variety of transformations. Yet, despite the vast array of chemical phenomena we experience by eye, few reaction monitoring tools are designed to measure what we see. This Account describes our journey developing computer vision to turn any camera into a chemistry-agnostic reaction monitoring tool able to transform everyday visual observations into quantitative kinetic data. Chemists routinely record color changes, precipitation, and mixing patterns without systematically leveraging this information. Our work emerged from an idea inspired by early career resource constraints: if visual changes can be described qualitatively, they can be quantified digitally, and cheaply. This insight, catalyzed by Raspberry Pi camera experiments and a serendipitous industrial need, led us to develop computer vision methods that enable bulk process monitoring across scales. Central to our contributions is the development of Kineticolor, a software platform converting video recordings into time-resolved kinetic information. Beyond color averaging, we developed spatially resolved analyses, providing time-resolved texture metrics to reveal mixing phenomena, even in small scale applications where the temptation is often to ignore mixing effects. Crucially, our methods are scale-agnostic, meaning identical algorithms apply from microscale wells to industrial reactors. Our industry-focused collaborations have highlighted computer vision's complementary role in process monitoring: while molecular techniques provide chemical identity, noninvasive visual methods capture bulk phenomena missed by point measurements. Our work serves modern automation laboratories looking for their next complementary data stream, as well as enabling accessible monitoring using standard cameras for resource-constrained environments. If chemists observe visual changes in laboratory notebooks, computer vision can quantify those tacit insights. The principle is simple: if you can see it, these methods can measure it.

ConspectusThe direct oxidation of methane, which is the main component of natural gas, shale gas, methane clathrates, and biogas, to value-added products is an economically attractive and environmentally friendly alternative to strongly endothermic methane steam reforming to synthesis gas (CO/H2). Among the different routes, the oxidative coupling of methane (OCM) to ethylene/ethane (C2-hydrocarbons) is the most promising one. A key limiting factor is insufficiently high selectivity to C2-hydrocarbons due to their overoxidation to carbon oxides (COx) at industrially relevant degrees of methane conversion. Although it is generally agreed that both selective and unselective reactions are initiated by oxygen species on the surface of catalysts, the kind, role, and origin of these species remain elusive, which hampers the tailored design of catalysts.In this Account, we summarize our recent progress in understanding how product selectivity in the OCM reaction can be tuned by controlling the type of oxygen species through catalyst composition or reaction conditions. The combination of in situ time- and temperature-resolved catalyst characterization with transient kinetic methods, i.e., temporal analysis of products (TAP) and steady-state isotopic transient kinetic analysis (SSITKA), has been proven to be effective for understanding the origin and role of oxygen species involved in selective and unselective pathways. We also present strategies for regulating the concentrations of selective and unselective oxygen species. For the Mn-M(M = Na, K, Rb, or Cs)2WO4 system, the electronegativity of the alkali metal was found to influence the ability of the catalysts to form selective oxygen species from gas-phase oxygen. The binding strength of atomic oxygen species is a key parameter for hindering the oxidation of methane to COx over Gd2O3-based catalysts. This property can be adjusted by using a metal oxide promoter. The nature and concentration of different oxygen species can also be controlled through the use of steam or an alternative oxidizing agent, N2O, and by performing the OCM reaction in a chemical looping mode, i.e., by alternating between CH4- and air-containing feeds. Using steam in the latter option enabled us to largely enhance the productivity of C2-hydrocarbons, thus making this technology more attractive for large-scale applications. The knowledge summarized in this Account is expected to present insights for further studies in the development of selective catalysts for various alkane oxidation reactions and in the optimization of reactor operation.

ConspectusElectrochemical technologies represent a transformative frontier for environmental remediation, offering unparalleled advantages such as precise redox control, seamless integration with renewable energy, and chemical-free operation. However, their practical implementation in water and wastewater treatment remains constrained by inefficient mass transport, poor utilization of catalytic sites under dilute conditions, and persistent challenges in energy consumption and overall system sustainability. These limitations are particularly pronounced when treating trace contaminants or pursuing selective transformation pathways. In this Account, we summarize our recent efforts to overcome these hurdles through the development of single atom-based electrified membrane (SAEM). By integrating atomically dispersed catalytic sites into flow-through and electrically conductive membrane architectures, we have successfully coupled atomic-level active-site engineering with device-level transport intensification.We first outline the construction principles of SAEM, highlighting how coordination environment, defect engineering, and membrane architecture collectively govern catalytic stability and site accessibility. We then examine how flow-through operation fundamentally alters transport regimes by suppressing diffusion limitations that dominate conventional flow-by and batch electrochemical systems. Building on these concepts, we discuss representative reaction systems in which SAEM exhibit clear advantages, including peroxymonosulfate activation for micropollutant degradation, in situ production of reactive oxygen species from oxygen reduction reaction for wastewater treatment, and electrocatalytic nitrate reduction for nitrogen transformation. Finally, we assess the stability, scalability, and sustainability of SAEM from a system-level perspective. Rather than focusing solely on catalytic metrics, we emphasize circularity and life-cycle considerations. This analysis underscores that the long-term viability of this platform depends on its performance as a durable, modular, and resource-efficient device within realistic treatment infrastructure.Overall, this Account positions SAEM as a platform for integrating catalysis, separation, and environmental sustainability withinelectrochemistry, offering guiding principles for the development of advanced electrochemical technologies that are both scientifically rigorous and practically relevant.

ConspectusAlongside societal development, large-scale urgent public health crises, routine food safety concerns and persistent environmental pollution have emerged as increasingly prominent challenges, prompting growing demands for rapid and reliable chemical and biological detection. Among various sensing technologies, luminescent sensing has attracted considerable attention due to its instant response, operational simplicity, and easily visualized readouts. In this context, metal-organic frameworks (MOFs) have attracted considerable interest as heterogeneous luminescent sensing materials owing to their inherent porosity, highly structural designability, and tunable photophysical properties.Based on these advantages, numerous MOF-based luminescent sensing materials have been developed recently. However, most of these rely on highly coupled multifunctional designs, in which all functional sites are incorporated within a single framework component. Such coupled architectures introduce significant complexity in ligand and framework synthesis, obscure mechanistic insight, and require bespoke material development along with extensive screening processes. These limitations restrict scalable fabrication, constrain rational design, and impede the translation in practical applications.To address the challenges associated with tightly coupled multifunctional MOF components, the concept of "function decoupling" was introduced as a pathway for the rational design and construction of sensing materials. In this approach, luminescence and recognition sites are independently introduced, optimized, and assembled within the framework. Such function decoupling into discrete components simplifies synthesis, reduces redundant trial-and-error optimization, and enhances design modularity, enabling the establishment of clear structure-function relationships.Furthermore, beyond the initial concept of function decoupling, a "modular platform" strategy is further developed, in which the decoupled functional centers are packaged as interchangeable modules and incorporated into pre-engineered MOF scaffolds with reserved insertion sites. These modules can encode spectral and energy-level matching, coordination bonding, or supramolecular interactions, allowing the platform to be programmably customized for analytes with diverse structures and properties. By selectively inserting and matching the appropriate functional modules, this approach redefines MOFs from single-purpose sensing materials into adaptable, programmable platforms, enabling broader analytical applicability, while substantially reducing the synthetic complexity, matching effort, cost, and development time.In summary, this Account traces the evolution from traditional, highly coupled MOF architectures to function decoupled centers, and further to modular platforms. First, the function decoupling strategy, in which the luminescence and recognition centers are sequentially introduced, reduces the synthetic complexity and extensive screening and matching challenges associated with conventional designs. Based on this, decoupled interchangeable functional modules are further packaged and incorporated into pre-engineered MOFs, enabling platform-based, customizable sensing, and providing a generalizable methodology for designing practical luminescent sensing materials. Collectively, this strategy establishes a rational and scalable design paradigm that bridges fundamental structure-function understanding with practical deployment and is expected to accelerate the development of next-generation programmable sensing systems across diverse analytical and real-world applications.

ConspectusTwisted graphene nanoribbons (tw-GNRs), exemplified by helical perylene diimide (hPDI) oligomers and polymers, represent a versatile platform for next-generation organic electronics. Their distinctive architecture features a fused, twisted backbone that simultaneously introduces void space for ion transport while maintaining high electronic conductivity along the graphitic core. This Account details the development of these materials, underpinned by a defect-free polymerization-cyclization synthesis based on perylene tetraester precursors. This robust synthetic route enables the creation of ribbons up to 120 nm long with precise control over molecular length, edge chemistry, and backbone helicity, allowing for a systematic investigation of structure-property relationships.Leveraging this unique combination of properties, we address key challenges in energy storage, bioelectronics, and chiroptics. In the context of energy storage, we discuss how intermediate-length ribbons strike a structural "sweet spot" that balances the trade-off between electrode insolubility and ion permeability, facilitating ultrafast charging kinetics in lithium and magnesium batteries. Furthermore, we demonstrate how introducing cruciform hinges into the backbone creates an amorphous morphology that resolves the critical "conductivity-hydrophilicity-insolubility" trade-off, enabling high-performance aqueous sodium-ion batteries. In bioelectronics, we describe how modifying the ribbon edges with hydrophilic chains enables high performance and ultrastable n-type organic mixed ionic-electronic conductors (OMIECs) capable of high-fidelity neural recording. Finally, we explore the chiroptical properties of these ribbons, explaining how remote chiral side chains can dynamically induce long-range helical order in the backbone. This structural control allows the materials to function as room-temperature spin filters via the chiral-induced spin selectivity (CISS) effect.Collectively, these studies illustrate how precise molecular engineering can unlock new functionalities, ranging from dual ion-electron conduction to spin-selective transport, defining a versatile platform for next-generation organic electronics.