The Supporting Information is available free of charge at http://pubs.acs.org/doi/10.1021/accountsmr.2c00221. Discussion on the activation of CuO cathode by Bi-based additive inclusions (Supplementary Note 1), challenges of MZIB cathodes (Supplementary Note 2) and meeting the challenge of developing highly reversible Zn anodes (Supplementary Note 3), AZB cathode mechanism schematic, SEM and TEM images, electronic mapping images and ex situ data, galvanostatic (curve/cycling) data for AZB/MZIBs, Zn anode printing schematic, performance data for AZBs/MZIBs and optic microscopy images (PDF) Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACS website may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machine-readable form or any other form without permission from the American Chemical Society. For permission to reproduce, republish and redistribute this material, requesters must process their own requests via the RightsLink permission system. Information about how to use the RightsLink permission system can be found at http://pubs.acs.org/page/copyright/permissions.html.

Flow battery (FB) is nowadays one of the most suited energy storage technologies for large-scale stationary energy storage, which plays a vital role in accelerating the wide deployment of renewable energies. FBs achieve the energy conversion by reversible redox reactions of flowing active species at the positive and negative sides. An ion conducting membrane (ICM) is necessary to separate the anolyte and catholyte, while conducting charge-balanced ions to form a complete electric circuit simultaneously. However, the commonly used commercial perfluorinated sulfonated ion exchange membranes suffer from low selectivity and high cost. The widely studied nonfluorinated ion exchange membranes have poor chemical stability. Most importantly, these membranes are confronted with a trade-off between selectivity and conductivity. That has motivated researchers to explore novel membrane materials with innovative design. Among them, porous membranes based on the “ion sieving conducting” mechanism instead of the “ion exchange conducting” mechanism from traditional ion exchange membranes were put forward, upon which very impressive progress has been achieved in recent years. Different from ion exchange membranes, the porous ICMs can separate active species from charge-balanced ions by pore size exclusion. As a result, by controlling the pore structures, porous membranes can break up the selectivity and conductivity trade-off.

Two-dimensional (2D) semiconducting materials are poised to revolutionize ultrathin, high-performance optoelectronic devices. In particular, transition-metal dichalcogenides (TMDs) are well-suited for applications requiring robust and stable materials such as electrocatalytic, photocatalytic, and photo-electrochemical devices. One of the most compelling assets of these materials is the ability to produce and process 2D TMDs in the nanosheet form using solution-based (SB) exfoliation methods. Compared to other methods, SB techniques are typically inexpensive, efficient, and more suitable for scale-up and industrial implementation. In acknowledgment of the importance of this area, much work has been done to develop various SB methods starting from the exfoliation of bulk crystalline TMD materials to the chemical modification of final devices consisting of thin films of semiconducting 2D TMD nanosheets. However, not all SB methods are equally compatible or interchangeable, and they result in very diverse material and device properties. Therefore, the aim of this Account is to provide an overview of the developed SB techniques that can serve as a guide for assembling high-performance thin films of 2D TMDs. We start by introducing the most popular methods for producing 2D TMDs using liquid-phase exfoliation (LPE), discussing their working mechanisms as well as their advantages and disadvantages. Notably we highlight a recently developed LPE technique using electro-intercalation that draws on the advantages of previously presented methods. Next, we discuss processing the as-produced 2D TMD nanosheets via SB separating techniques designed for size and morphology selection while also presenting the ongoing challenges in this area. We then examine SB methods for processing the selected 2D nanomaterial dispersions into semiconducting thin films. Various methods are compared and contrasted, and special attention is paid to a recently developed method that carefully deposits 2D TMD nanoflakes with preferential alignment and has been shown scalable to the meter-squared size range. Finally, we explore strategies for increasing the optoelectronic performance of the TMD films via device engineering and defect management. We scrutinize these post-treatments based on the final device application, which are explicitly discussed. In all of the discussed processes we present the most promising SB techniques giving critical analysis and insight from experience. While we provide our own “best practices”, we stress the use of adaptability and critical thinking when designing specifically tailored procedures. By providing examples of different uses and measured improvements in one comprehensive guide, we hope to simplify process-development and aid researchers in making their own unique photoactive 2D “puzzles”.

Figure 1. Cell-based biohybrid microrobots. Biohybrid robots incorporate adoptive cell transfers and particles. They are organized into two categories: (a) cells used as particle delivery vehicles and (b) particles used as cell delivery vehicles. An example of (a) is shown with a macrophage coated with nanosponge metal-phenolic network particles for treating metastatic cancer. Scale bar, 10 μm. Reproduced with permission from ref (6). Copyright 2023 The Authors. An example of (b) is shown with a helical microparticle for carrying mesenchymal stem cells. Scale bars, 40 μm. Reproduced with permission from ref (7). Copyright 2019 The Authors. C. Wyatt Shields, IV, is currently an Assistant Professor in the Department of Chemical and Biological Engineering at the University of Colorado (CU) Boulder. He obtained his Ph.D. from Duke University in 2016 and subsequently performed postdoctoral research at NC State University and Harvard University. Since joining the faculty at CU Boulder, he has received several research awards, including the NSF CAREER award, the ONR YIP award, and the NIH R35 MIRA. In 2022, he was named a Packard Fellow in Science and Engineering and a Pew Scholar in the Biomedical Sciences. The Shields lab is focused on developing field-responsive and active particle systems as vehicles for next-generation biosensing and drug delivery. C.W.S. acknowledges support from the National Institutes of Health (NIH R35GM147455 and R21CA267608) and the National Science Foundation (NSF) through a CAREER grant (CBET 2143419). C.W.S. is a Pew Scholar in the Biomedical Sciences, supported by the Pew Charitable Trusts. He would also like to thank the Packard Foundation for their support. This article references 25 other publications. This article has not yet been cited by other publications. Figure 1. Cell-based biohybrid microrobots. Biohybrid robots incorporate adoptive cell transfers and particles. They are organized into two categories: (a) cells used as particle delivery vehicles and (b) particles used as cell delivery vehicles. An example of (a) is shown with a macrophage coated with nanosponge metal-phenolic network particles for treating metastatic cancer. Scale bar, 10 μm. Reproduced with permission from ref (6). Copyright 2023 The Authors. An example of (b) is shown with a helical microparticle for carrying mesenchymal stem cells. Scale bars, 40 μm. Reproduced with permission from ref (7). Copyright 2019 The Authors. This article references 25 other publications.

Salinity-gradient energy represents a widespread, clean, environmentally friendly, and sustainable source of renewable energy, which has attracted great attention in the past years. To harness this energy, interdisciplinary efforts from chemistry, materials science, environmental science, and nanotechnology have been made to develop efficient and low-cost approaches and materials for energy conversion. Conventional reverse electrodialysis (RED) systems are generally based on ion-exchange membranes, which usually suffer from ineffective mass transport, high membrane resistance, limited pore size, and concentration polarization, resulting in low output power density and poor energy-conversion efficiency. As one promising material, nanofluidic channels with their unique transport properties, which can be attributed to nanoconfinement effect, enable high-performance reverse electrodialysis to efficiently harvest salinity-gradient energy. Due to the unique porous architectures, three-dimensional (3D) nanoporous membranes demonstrate great potential for harvesting salinity-gradient power. It is generally known that the porous membranes can be prepared by many methods; however, there are some shortcomings such as high costs, poor ion conductance, and fragility limiting the practical application. Several simple and versatile approaches to low-cost fabrication of 3D nanoporous membranes have been developed in recent years. For example, self-assembly provides an effective route of constructing functional materials and organizing them into 3D architectures. In this Account, we mainly review our recent progress in the design and fabrication of bioinspired 3D nanoporous membranes for salinity-gradient energy harvesting. First, we give a brief introduction to bioinspired nanochannel membranes (BNMs) with diverse structural dimensions, and nanofluidic channel membranes may lead to technological breakthroughs and thus act as an emerging platform for harvesting salinity-gradient energy. Subsequently, we discuss the typical preparation approaches for bioinspired 3D nanoporous membranes. To tackle the bottlenecks of the conventional membrane-based power generator and extrapolate single-channel devices to macroscopic materials, our group have developed a series of 3D nanoporous membranes for power generation via various simple and versatile methods. We highlight the design and fabrication of several types of 3D nanoporous membranes, i.e., heterogeneous and homogeneous membranes, with tunable surface charge and porosity. The proof-of-concept demonstration of bioinspired 3D porous membranes shows that these nanofluidic platforms have the potential to overcome the selectivity-permeability trade-off and have impressive osmotic-energy-harvesting performance. Specifically, the scale-up Janus 3D porous membranes maintained high selectivity and rectified current in a hypersaline environment, which benefitted effective energy conversion and high output power density when seawater and river water were mixed. Finally, we give an outlook for future challenges and perspectives on the development of 3D nanofluidics for salinity-gradient energy conversion. We expect that this Account will spark further efforts on the development of bioinspired 3D nanoporous membranes for large-scale (typical side length of more than 10 cm) energy conversion and new opportunities for the applications in water desalination, dialysis, and ionic circuitries.

Janus films have attracted widespread interest due to their asymmetric structure and unique physical and/or chemical properties, demonstrating broad and blooming potentials in mechanical sensing, soft actuation, energy management, advanced separation, energy conversion and storage, etc. Among them, based on the unique features of carbon nanomaterials, extensive efforts have been dedicated to exploiting carbon-based Janus films for high-performance electronic skins, soft actuators, and their integration for smart robotics. Drawing inspiration from nature, biological skins can actively perceive external physical/chemical stimuli and further perform specific motion behaviors. However, there still remain challenges of guided structural design principles, an alternative combination of multifunctions, and advanced synergetic applications. Specifically, their intrinsic properties and related device performances are strongly determined by the functional components’ coupling, surface wettability, and controllability of the interface structures. The asymmetric combination of carbon nanomaterials and functional polymers in controllable manners can facilitate the design of high-performance sensing, actuation, and integrated devices, enabling the development of smart soft robotics. Therefore, it is highly desired to summarize this research area of carbon-based Janus functional films for sensing, actuating, and integration as well as to have a deep understanding of the relationship between interfacial structures and their performance for directing future development.

Supported metal catalyst, has been one of the most important systems in the field of heterogeneous catalysis. The great complexity of both the compositions and structures of such supported metal catalysts provides a great degree of freedom for tuning their catalytic properties, which has essentially triggered the explosive growth in research on design and control active metals’ surface structures for decades. An ideal metal catalyst theoretically features maximum active sites and optimal intrinsic reactivity to facilitate a desired chemical reaction. Inspired by the catalytic concepts brought by natural enzymes and homogeneous catalysis, the fabrication of heterogeneous catalysts with atomically dispersed metal atoms has attracted much attention and been extensively explored in recent years.

Iron corrosion product, commonly known as rust, forms from the chemical reaction between iron and oxygen in the presence of water. It is a heterogeneous solid-state material composed of multiple phases and is ubiquitous throughout the universe. Sixteen distinct phases of iron corrosion product exist naturally under different temperature, pH, and pressure. Rust species such as hematite (α- Fe2O3), maghemite (γ-Fe2O3), goethite (α-FeOOH), and lepidocrocite (γ- FeOOH), first documented ca. 800 BCE, make up the solid-state chemical family composed of iron oxides, oxyhydroxides, and hydroxides. On an anthropogenic scale, rust represents a persistent problem to all manner of engineering and industrial pursuits. Corrosion is gradual and nondiscriminatory, affecting iron structures of all shapes and sizes from bridges and buildings to pipelines and wires that necessitates considerable spending on rust prevention and removal techniques. The infamous “Rust Belt” is colloquially used to describe regions of the United States characterized by sharp industrial decline and evokes images of derelict steel factories rusted over from decades of disuse. Therefore, iron corrosion product is commonly regarded as a symptom of deterioration and a physical manifestation of neglect in the eyes of the public. Yet, invaluable scientific potential exists within this “waste” material.

Figure 1. (a) Guidelines for the construction of HTP physical fields; region I represents energy density, region II represents the power of energy input, and region III represents an insulated space without external energy input. (b) General strategy for providing faster PHT physical fields. (c) Typical time-dependent temperature profile during HTP. (d) Characteristics of HTP in the synthesis of kinetically controlled products being trapped at various local minima relative to the thermodynamic product located at the global minimum in terms of the total free energy. Reproduced with permission from ref (16). Copyright 2021 American Chemical Society. (e) Space-time scales for a heterogeneous catalytic process. The light red represents the process of chemical dynamics on the catalyst, the light green region represents the molecular reaction process, and the light blue region represents the transport processes of the reactants. Reproduced with permission from ref (17). Copyright 2015 John Wiley & Sons, Inc. (f) Synthesis of intermediate and metastable structures by using pulsed heating methods. (g) Time-temperature transformation diagram showing the kinetic formation of metallic glass, high entropy alloy, and phase-separated structures, respectively, as a function of cooling rate. Reproduced with permission from ref (10). Copyright 2018 The Authors. Figure 2. (a) Typical space-time scales for different heating methods and fundamental processes occurs during materials synthesis. (b) Size-controlled synthesis of Pt-based materials by tuning the duration of HTP, a faster heating/cooling rate and a shorter HTP generate smaller particles. (b1) Pt foil. Reproduced with permission from ref (19). Copyright 2018 The Authors. (b2) Pt NPs. Reproduced with permission from ref (20). Copyright 2020 American Chemical Society. (b3) Pt clusters. Reproduced with permission from ref (21). Copyright 2020 John Wiley & Sons, Inc. (b4) Pt SAs. Reproduced with permission from ref (22). Copyright 2019 The Author(s). (c) Composition-controlled synthesis of high-entropy materials; the rapid cooling process enabled a homogeneous mixture of various elements into one particle while preventing phase separation. (c1) Schematic of the high-entropy mixing in a face-centered cubic lattice. Multiple elements will occupy the same lattice site randomly to form a high-entropy structure such as a high-entropy alloy. Reproduced with permission from ref (14). Copyright 2022 The Authors. (c2) Schematic of a HEA nanoparticle. Reproduced with permission from ref (14). Copyright 2022 The Authors. (c3) Schematic of an HEO nanoparticle. Reproduced with permission from ref (25). Copyright 2021 The Author(s). (c4) Schematic of an HEC nanoparticle. (d) Phase-controlled synthesis of molybdenum carbide materials by tuning the peak temperature of HTP. Reproduced with permission from ref (27). Copyright 2022, The Author(s). (d1) β-Mo2C, (d2) α-MoC1–x, (d3) η-MoC1–x. (e) Morphology-controlled synthesis of Si nanostructures; graphene interlayer confined (e1) Si NPs. Reproduced with permission from ref (28). Copyright 2016, The Author(s). (e2) Si NWs. Reproduced with permission from ref (29). Copyright 2021 John Wiley & Sons, Inc. Figure 3. (a) Prevalent and laboratory-achievable energy ranges of thermal energy, electrical energy, and light energy; electrical and light energy can drive chemical reactions with ΔG > 0 while thermal energy cannot. (b) Typical time scales involved in various pulsed heating methods. (c) Construction of laser-triggered HTP by various types of photothermal mechanisms in carbonaceous materials, semiconductor materials, and plasmonic metal materials such as Au, Ag, Cu, etc. Reprinted with permission from ref (32). Copyright 2019 Royal Society of Chemistry. (d) Excitation and relaxation of surface plasmons, as well as the corresponding three main effects, including the enhanced electromagnetic near field, excited carriers (e– refers to electron and h+ is hole) and local heating. Reprinted with permission from ref (34). Copyright 2023 Springer Nature Limited. The utilization of operando characterization and data-driven computational analysis for establishing the synthesis–structure–performance relationship. The significance of advanced characterization under realistic operando HTP conditions and high-throughput computational analysis is increasingly recognized as it provides a scientific basis for the development of innovative solid catalyst materials, chemical processes, or systems. This approach is expected to address the limitations of empirical schemes and effectively satisfies multiple catalytic performance objectives. The comprehensive comprehension of the multifield coupling effect toward the synthesis of solid catalysts by pulsed heating. The generate and application of HTP in the preparation of solid catalysts are typically accompanied by the presence of various physical fields, including electrical, magnetic, and optical fields. However, the extent to which these fields can impact the synthesis of solid catalysts remains largely unknown. Controllable synthesis of designed solid catalysts through the implementation of programmable pulsed heating methods. The development of programmable pulsed heating techniques with high levels of temporal and spatial accuracy is imperative in expediting the shift from traditional trial-and-error methodologies toward novel paradigms for the development of exceptional and sustainable solid catalysts. Scalable and cost-effective synthesis of function-specific solid catalyst materials by automated and continuous pulsed heating approach. In forthcoming times, it is imperative to prioritize the large-scale manufacturing of sophisticated solid catalysts by pulsed heating strategy, which satisfies the criteria of industrial catalytic applications, namely high-performance and low cost. Ye-Chuang Han received his Ph.D. degree from Xiamen University in 2022 under the supervision of Prof. Zhong-Qun Tian. He is now a postdoctoral fellow at Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province under the supervision of Prof. Zhong-Qun Tian. His work focuses on synthetic chemistry under extreme environments. Pei-Yu Cao received her B.S. degree from Hubei University in 2023. She is currently a M.S. student at Xiamen University under the supervision of Prof. Zhong-Qun Tian. Her work focuses on ultrafast materials synthesis and processing. Zhong-Qun Tian received his B.S. degree at Xiamen University in 1982 and his Ph.D. degree under the supervision of Prof. Martin Fleischmann at the University of Southampton in 1987. He has been a full Professor of Chemistry at Xiamen University since 1991. He is a Member of the Chinese Academy of Sciences and the Elected President of the International Society of Electrochemistry. Currently, his main research interests include surface enhanced Raman spectroscopy, spectroelectrochemistry, nanochemistry, plasmonics, catalyzed molecular assembly, and synthetic chemistry under extreme environments. We sincerely thank Prof. Yanan Chen from Tianjin University and Prof. Yonggang Yao from Huazhong University of Science and Technology for their insightful discussions. This work was supported by the China Postdoctoral Science Foundation (2022M722646), the National Natural Science Foundation of China (21991130), and the National Key Research and Development Program of China (2021YFA1201502). This article references 34 other publications. This article has not yet been cited by other publications. Figure 1. (a) Guidelines for the construction of HTP physical fields; region I represents energy density, region II represents the power of energy input, and region III represents an insulated space without external energy input. (b) General strategy for providing faster PHT physical fields. (c) Typical time-dependent temperature profile during HTP. (d) Characteristics of HTP in the synthesis of kinetically controlled products being trapped at various local minima relative to the thermodynamic product located at the global minimum in terms of the total free energy. Reproduced with permission from ref (16). Copyright 2021 American Chemical Society. (e) Space-time scales for a heterogeneous catalytic process. The light red represents the process of chemical dynamics on the catalyst, the light green region represents the molecular reaction process, and the light blue region represents the transport processes of the reactants. Reproduced with permission from ref (17). Copyright 2015 John Wiley & Sons, Inc. (f) Synthesis of intermediate and metastable structures by using pulsed heating methods. (g) Time-temperature transformation diagram showing the kinetic formation of metallic glass, high entropy alloy, and phase-separated structures, respectively, as a function of cooling rate. Reproduced with permission from ref (10). Copyright 2018 The Authors. Figure 2. (a) Typical space-time scales for different heating methods and fundamental processes occurs during materials synthesis. (b) Size-controlled synthesis of Pt-based materials by tuning the duration of HTP, a faster heating/cooling rate and a shorter HTP generate smaller particles. (b1) Pt foil. Reproduced with permission from ref (19). Copyright 2018 The Authors. (b2) Pt NPs. Reproduced with permission from ref (20). Copyright 2020 American Chemical Society. (b3) Pt clusters. Reproduced with permission from ref (21). Copyright 2020 John Wiley & Sons, Inc. (b4) Pt SAs. Reproduced with permission from ref (22). Copyright 2019 The Author(s). (c) Composition-controlled synthesis of high-entropy materials; the rapid cooling process enabled a homogeneous mixture of various elements into one particle while preventing phase separation. (c1) Schematic of the high-entropy mixing in a face-centered cubic lattice. Multiple elements will occupy the same lattice site randomly to form a high-entropy structure such as a high-entropy alloy. Reproduced with permission from ref (14). Copyright 2022 The Authors. (c2) Schematic of a HEA nanoparticle. Reproduced with permission from ref (14). Copyright 2022 The Authors. (c3) Schematic of an HEO nanoparticle. Reproduced with permission from ref (25). Copyright 2021 The Author(s). (c4) Schematic of an HEC nanoparticle. (d) Phase-controlled synthesis of molybdenum carbide materials by tuning the peak temperature of HTP. Reproduced with permission from ref (27). Copyright 2022, The Author(s). (d1) β-Mo2C, (d2) α-MoC1–x, (d3) η-MoC1–x. (e) Morphology-controlled synthesis of Si nanostructures; graphene interlayer confined (e1) Si NPs. Reproduced with permission from ref (28). Copyright 2016, The Author(s). (e2) Si NWs. Reproduced with permission from ref (29). Copyright 2021 John Wiley & Sons, Inc. Figure 3. (a) Prevalent and laboratory-achievable energy ranges of thermal energy, electrical energy, and light energy; electrical and light energy can drive chemical reactions with ΔG > 0 while thermal energy cannot. (b) Typical time scales involved in various pulsed heating methods. (c) Construction of laser-triggered HTP by various types of photothermal mechanisms in carbonaceous materials, semiconductor materials, and plasmonic metal materials such as Au, Ag, Cu, etc. Reprinted with permission from ref (32). Copyright 2019 Royal Society of Chemistry. (d) Excitation and relaxation of surface plasmons, as well as the corresponding three main effects, including the enhanced electromagnetic near field, excited carriers (e– refers to electron and h+ is hole) and local heating. Reprinted with permission from ref (34). Copyright 2023 Springer Nature Limited. This article references 34 other publications.

This article has not yet been cited by other publications.

In heterogeneous catalysis, the long-standing challenge is to achieve extremely high activity and chemoselectivity in liquid-phase organic transformations comparable to that of homogeneous or enzymatic processes. Single-atom catalysts (SACs) with atomically precise coordination are developed with the objectives to mimic the homogeneous pathways but face stability issues due to metal leaching or clustering. Additionally, the practical application of SACs in chemical production is hampered by the lack of standard preparation protocols and low conversion using laboratory batch reactors.

Photocatalysis technology has gained extensive attention in the past few decades due to its potential to alleviate or solve energy and environmental contamination problems. The development and design of new photocatalytic semiconductor materials with high catalytic activity has become a research hotspot in this field. In recent years, inorganic ultrathin two-dimensional (2D) semiconductor photocatalysts have shown excellent performance in photocatalytic applications due to their high specific surface area, clear atomic structure, unique electronic structure, intrinsic quantum confined electrons, and high atomic exposure ratio. When the thickness of the bulk semiconductor is decreased to the atomic level, its local atomic structure changes prominently. This is a major reason why the atomic thin 2D materials could show improved inherent properties and produce new properties that are not available in the corresponding bulk semiconductors. Furthermore, compared with the bulk photocatalysts, the surface electronic structure of inorganic ultrathin 2D materials is more sensitive and thus could be regulated more easily by surface and interfacial modification methods, leading to great optimization of photocatalytic properties. Therefore, inorganic ultrathin 2D materials not only provide an ideal reaction model for clearly revealing the relationships between surface/interface structure characteristics and photocatalytic performance but also bring new opportunities for the development of efficient catalysts to resolve energy crises and environmental problems.

Figure 1. Schematic presentation of different (A) noncovalent interactions and (B) liquid droplets discussed in this Viewpoint. The figure was created with Biorender.com. Figure 2. Potential applications of liquid droplets, such as (1) drug delivery systems, (2) diagnostic tools, (3) immunomodulating scaffolds, (4) neurodegenerative disease model, and (5) in vitro model for drug discovery. The figure is created with Biorender.com. L. Su acknowledges the Dutch Research Council (NWO, Rolling Grant 2022) for financial support. L. Su acknowledges Prof. Matthias Barz and Dr. Shikha Dhiman for discussion. This article references 12 other publications. This article has not yet been cited by other publications. Figure 1. Schematic presentation of different (A) noncovalent interactions and (B) liquid droplets discussed in this Viewpoint. The figure was created with Biorender.com. Figure 2. Potential applications of liquid droplets, such as (1) drug delivery systems, (2) diagnostic tools, (3) immunomodulating scaffolds, (4) neurodegenerative disease model, and (5) in vitro model for drug discovery. The figure is created with Biorender.com. This article references 12 other publications.

Figure 1. (A) Different emulsions (w/o, o/w, o/o, and multi-) stabilized by small molecule or polymeric surfactants. (B) Cartoon with routes of polymerization to produce of foams (open/closed cell), capsules, and armored particles. Figure 2. Modification of graphene oxide (GO) by reaction with primary alkyl amines to give nanosheets of different wettability for stabilization of nonaqueous emulsions. Functionalization of GO with hexyl amine gives nanosheets dispersible in DMF and capable of stabilizing octane-in-DMF o/o emulsions (left). Functionalization of GO with octadecyl amine gives nanosheets dispersible in octane and capable of stabilizing DMF-in-octane o/o emulsions (right). Optical microscope images reproduced with permission from ref (40). Copyright 2017 American Chemical Society. Figure 3. Examples of the performance of composite structures produced from Pickering emulsions: (A) Capsules of ionic liquid (IL) and their performance in uptake of CO2: (i) comparison of capacity of still IL, agitated IL, and encapsulated IL, (ii) time for equilibration of CO2 uptake for agitated IL and encapsulated IL, and (iii) CO2 uptake and release profiles for capsules with core of task specific IL. (3Ai-3Aii) reproduced with permission from ref (22). Copyright 2019 American Chemical Society. (3Aiii) reproduced with permission from ref (46). Copyright 2019 American Chemical Society. (B) Capsules with core of salt hydrate phase change material (PCM): (i) optical microscopy image of capsules when heated about the melting point of the PCM, (ii) DSC curve of bulk PCM, and (iii) DSC trace of encapsulated PCM. Reproduced from ref (48) with permission. Copyright 2022 Elsevier. (C) Capsules with a shell that contains hindered urea bonds: (i) optical microscopy image of as prepared capsules, (ii) SEM image of capsules after shell fusion, and (iii) optical microscopy image of the emulsion formed after destruction of shells. Reproduced with permission from ref (50). Copyright 2022 American Chemical Society. Emily Pentzer is an associate professor in the Department of Chemistry and Department of Materials Science & Engineering at Texas A&M University, with a courtesy appointment in the Department of Chemical Engineering. She received her B.S. in Chemistry from Butler University (2005) and PhD in Chemistry from Northwestern University (2010), then performed postdoctoral research at UMass Amherst in Polymer Science and Engineering. She started her independent career at Case Western Reserve University and moved her group to Texas A&M in 2019. The Pentzer Lab’s research focuses on developing new polymeric materials and assemblies as a route to understand structure–property–application relationships and access functions not possible with current state-of-the-art systems. Dr. Pentzer was named an ACS WCC Rising Star and Texas A&M Presidential Impact Fellow. She currently serves as an associate editor for the RSC journal Polymer Chemistry and is editor in chief of RSC Applied Polymers. Eliandreina Cruz Barrios received her B.S. in Chemistry (2008) from University of Carabobo, M.S. in Chemistry (2014), with focus on colloidal and interface science, from Venezuelan Institute of Scientific Research, and PhD in Chemistry (2022) from Texas Christian University; she is currently a Postdoctoral Researcher at Texas A&M University under the supervision of Dr. Emily Pentzer. Her research focuses on microencapsulation strategies using multiple emulsions. Nicholas Starvaggi received his B.S. in chemistry and biochemistry from Mount St. Mary’s University in 2021. He is currently pursuing his PhD in Chemistry in the Pentzer lab at Texas A&M University, where he is an NSF graduate research fellow. His research interests focus on functionalized soft materials and microencapsulation strategies. E.P. acknowledges NSF DMR #2103182. E. C. B. acknowledges DEEE0009155 for funding. N.S. is supported by NSF GRFP #2139772. This article references 52 other publications. This article has not yet been cited by other publications. Figure 1. (A) Different emulsions (w/o, o/w, o/o, and multi-) stabilized by small molecule or polymeric surfactants. (B) Cartoon with routes of polymerization to produce of foams (open/closed cell), capsules, and armored particles. Figure 2. Modification of graphene oxide (GO) by reaction with primary alkyl amines to give nanosheets of different wettability for stabilization of nonaqueous emulsions. Functionalization of GO with hexyl amine gives nanosheets dispersible in DMF and capable of stabilizing octane-in-DMF o/o emulsions (left). Functionalization of GO with octadecyl amine gives nanosheets dispersible in octane and capable of stabilizing DMF-in-octane o/o emulsions (right). Optical microscope images reproduced with permission from ref (40). Copyright 2017 American Chemical Society. Figure 3. Examples of the performance of composite structures produced from Pickering emulsions: (A) Capsules of ionic liquid (IL) and their performance in uptake of CO2: (i) comparison of capacity of still IL, agitated IL, and encapsulated IL, (ii) time for equilibration of CO2 uptake for agitated IL and encapsulated IL, and (iii) CO2 uptake and release profiles for capsules with core of task specific IL. (3Ai-3Aii) reproduced with permission from ref (22). Copyright 2019 American Chemical Society. (3Aiii) reproduced with permission from ref (46). Copyright 2019 American Chemical Society. (B) Capsules with core of salt hydrate phase change material (PCM): (i) optical microscopy image of capsules when heated about the melting point of the PCM, (ii) DSC curve of bulk PCM, and (iii) DSC trace of encapsulated PCM. Reproduced from ref (48) with permission. Copyright 2022 Elsevier. (C) Capsules with a shell that contains hindered urea bonds: (i) optical microscopy image of as prepared capsules, (ii) SEM image of capsules after shell fusion, and (iii) optical microscopy image of the emulsion formed after destruction of shells. Reproduced with permission from ref (50). Copyright 2022 American Chemical Society. This article references 52 other publications.

Solar–thermal energy storage (STES) is an effective and attractive avenue to overcome the intermittency of solar radiation and boost the power density for a variety of thermal related applications. Benefiting from high fusion enthalpy, narrow storage temperature ranges, and relatively low expansion coefficients, solid–liquid phase change materials (PCMs) have been viewed as one of the promising candidates for large-capacity STES. Organic and inorganic PCMs, however, generally suffer from poor solar absorption, slow thermal diffusion, and leakage problems, which seriously limit their direct STES applications. Preparing composites through compounding functional fillers with PCMs has been investigated as the mainstream route to enhance their thermophysical properties, but optimizing the charging, storage, and discharging performances of PCM systems remains a grand challenge. Most often, improved STES performances were achieved at the sacrifice of reduced energy storage capacity. Simultaneous enhancement of STES performances has been viable in recent years through fabricating PCM composites with lightly loaded functional fillers and tailoring their heat diffusion and solid–liquid phase change kinetics.

Interventional fluorescence imaging has gradually developed into a promising imaging strategy for the diagnosis of diseases in clinic. This strategy could benefit interventional targeted treatment because of the clear display of microstructures at the margins and boundaries. There are some stranded crucial issues in clinical application: (i) fast clearance of fluorescence probes; (ii) light instability and photobleaching; and (iii) residual and microsatellite lesions. The development of superstable homogeneous intermixed formulation technology (SHIFT) can solve the aforementioned clinical problems for precision hepatectomy. Interventional fluorescence imaging based on SHIFT-prepared product has some advantages such as (i) strong stability, (ii) greatly extending imageable time window, and (iii) precisely visualizing microsatellite lesions. In this Account, we overview our current progress in interventional fluorescence imaging based on SHIFT method for surgical resection following long-lasting embolization conversion. To greatly realize interventional fluorescence imaging, we summarize clinical and preclinical application of interventional fluorescence imaging in a transarterial delivery system. Indeed, compared with conventional fluorescence imaging, interventional fluorescence imaging possesses non-negligible strengths on improved intensity in target location and step-down systemic toxicity. Unfortunately, a challenging issue is that immobile fluorescence performance is difficult to maintain after long-time embolization, resulting in a failed hepatectomy. On this basis, associated with our previous research, SHIFT was proposed and developed. Thus, we detailedly introduce and account the development and preponderance of SHIFT on interventional fluorescence imaging. Predictably, after lengthy embolization, its lightful fluorescence was still observable in tumor targets of a clinical trial. To regulate the fluorescence rendering of microsatellite lesion, SHIFT combining with pure nanoprobes (nanoICG) occurs, namely SHIFT nanoICG, and we dwell on its performance in transarterial invasive surgical navigation and its clinical application under interventional fluorescence imaging compared with conventional indocyanine green (ICG) formulations. Amazingly, the SHIFT nanoICG brings us an extraordinary imaging consequence for deep-seated tumor tissues and imperceptible microsatellite lesions. Finally, we offer perspectives on the future tendency of interventional imaging-guided SHIFT products in clinical translation such as chemoembolization, radioembolization, and immunotherapy. Actually, these directions have been underway for some time, and even relative products are already applied for clinical trials, exhibiting effective therapeutic outcomes. Our green high-performance SHIFT products are concentrated on meeting clinical needs and solving clinical problems, breaking through the cure limitations of patients with advanced diseases. Thus, the discovery offers insight into the development and superiority of SHIFT products under interventional fluorescence imaging and simultaneously provides a new view on the development of clinically pragmatic products.

The electrochemical conversion of sunlight by photoelectrochemical cells (PECs) is based on semiconductor electrodes that are interfaced with a liquid electrolyte. This approach is highly promising, first, because it can be employed for the generation of a chemical fuel (e.g., H2) to store solar energy that can be used on-demand to generate electricity when the sun is not available. Second, it can be seen as a concept reminiscent of photosynthesis, where CO2 is converted into a valuable feedstock by solar energy. Thus, photoelectrochemical cells are sometimes referred to as “artificial leaves”. Silicon, being the main semiconductor in the electronics and photovoltaic sector, is a prime candidate to be used as the light absorber and the substrate for building photoelectrochemical cells. However, Si alone has “poor-to-no photoelectrochemical performance”. This is caused by its weak electrocatalytic activity for cathodic reactions (namely, the hydrogen evolution reaction (HER), the CO2 reduction reaction (CDRR), and the N2 reduction reaction) and by its deactivation in the anodic regime, prohibiting its use for the oxygen evolution reaction (OER). This latter reaction is essential for supplying electrons to generate a solar fuel. Due to these problems, layers that both protect and are catalytically active are typically employed on Si photoelectrodes but require rather sophisticated manufacturing processes (e.g., atomic layer or electron beam deposition), which hinders research and innovation in this field. Nevertheless, our group and others have demonstrated that these layers are not always required and that highly active and stable Si-based photoelectrodes can be manufactured using simple wet processes, such as drop casting, electroless deposition, or aqueous electrodeposition. In this Account, we first introduce the topic and the possible structures that can be easily obtained starting from commercial Si wafers. Then, we discuss strategies that have been employed to manufacture photocathodes based on p-type Si. Among these, we describe Si photocathodes coated with metal, inorganic compounds such as metal sulfides, and more original constructs, such as those based on macromolecules composed of a catalytic Mo3S4 core and a polyoxometallate macrocycle. Also, we discuss the elaboration and the advantages of Si photocathodes obtained by grafting organometallic catalysts which are promising candidates for reaching excellent selectivity for the CDRR. Then, the manufacturing of photoanodes based on n-Si is reviewed with an emphasis on those prepared by electrodeposition of a transition metal such as Ni and Fe. The effect of the catalyst morphology, density, and Si structuration is discussed, and future developments are proposed.

Polypeptides, as the synthetic analogues of natural proteins, are an important class of biopolymers that are widely studied and used in various biomedical applications. However, the preparation of polypeptide materials from the polymerization of N-carboxyanhydride (NCA) is limited by various side reactions and stringent polymerization conditions. Recently, we report the cooperative covalent polymerization (CCP) of NCA in solvents with low polarity and weak hydrogen-bonding ability (e.g., dichloromethane or chloroform). The polymerization exhibits characteristic two-stage kinetics, which is significantly accelerated compared with conventional polymerization under identical conditions. In this Account, we review our recent studies on the CCP, with the focus on the acceleration mechanism, the kinetic modeling, and the use of fast kinetics for the efficient preparation of polypeptide materials.

Electrochromic devices (ECDs) can reversibly regulate their optical properties (transmittance, reflectance, and color) via internal ion migration under applied voltage, thus exhibiting advantages such as controllable switching, high contrast ratio between bleached and colored states, and low power consumption. Based on these features, ECDs have been studied in the fields of photothermal modulation, dynamic display, energy storage, and camouflage. Recently, remarkable breakthroughs have been made in ECDs with respect to the contrast ratio, coloration efficiency, cycle stability, and scale-up fabrication. Nevertheless, the response speed, which is related to the efficiency and power consumption of devices, especially in application scenarios with strict requirements on switching rate, remains a major restricting parameter.

Tremendous progress in nanomaterial and nanotechnology has been made in recent years, which greatly contributes to the development of inorganic nanoparticles (NPs) as luminescent probes in diverse biomedical applications. In particular, these luminescent nanoprobes are widely employed for sensitive assays of biomarkers like disease markers. Generally, the luminescent bioassay technologies mainly rely on conventional molecular probes such as lanthanide (Ln3+) chelates or organic dyes, which suffer from inferior photochemical stability, low photobleaching, potential long-term toxicity, or high background noise. In contrast, Ln3+-doped NPs possess distinct physicochemical properties including better photostability, lower toxicity, and superior optical properties like long photoluminescent (PL) lifetime, narrow emission band, and tunable spectral range from the ultraviolet to the second near-infrared (NIR-II), which make them extremely ideal as luminescent nanoprobes. As such, enormous research enthusiasm has been invested in this fascinating field of Ln3+-doped luminescent nanoprobes in recent years. Accordingly, background-free luminescent bioassays with high signal-to-noise have been achieved by employing Ln3+-doped NPs on the basis of their downshifting luminescence (DSL) with a long PL lifetime, NIR-II luminescence with long-wavelength emissions, or upconverting luminescence (UCL) upon NIR excitation. However, there are still key challenges for Ln3+-doped nanoprobes owing to their low brightness and quantum yield, which restrict their biomedical applications. During the past decade, we have explored efficient approaches for the synthesis and design of highly efficient Ln3+-doped nanoprobes toward ultrasensitive luminescent bioassay of disease markers.