Pub Date : 2025-10-06DOI: 10.1021/accountsmr.4c00401
Yoonjae Park, Rohit Rana, Daniel Chabeda, Eran Rabani, David T. Limmer
Lead halide perovskites have been extensively studied as a class of materials with unique optoelectronic properties. A fundamental aspect that governs optical and electronic behaviors within these materials is the intricate coupling between charges and their surrounding lattice. Unravelling the role of charge-lattice interactions in the optoelectronic properties in lead halide perovskites is necessary to understand their photophysics. Unlike traditional semiconductors where a harmonic approximation often suffices to capture lattice fluctuations, lead halide perovskites have a significant anharmonicity attributed to the rocking and tilting motions of the inorganic framework. Thus, while there is broad consensus on the importance of the structural deformations and polar fluctuations on the behavior of charge carriers and quasiparticles, the strongly anharmonic nature of these fluctuations and their strong interactions render theoretical descriptions of lead halide perovskites challenging. In this Account, we review our recent efforts to understand how the soft, polar lattice of this class of materials alters their excited state properties. We highlight the influence of the lattice on static properties by examining the quasiparticle binding energies and fine structure. With perovskite nanocrystals, we discuss how incorporating lattice distortion is essential for accurately defining the exciton fine structure. By considering lattices across various dimensionalities, we are able to illustrate that the energetics of excitons and their complexes are significantly modulated by polaron formation. Beyond energetics, we also delve into how the lattice impacts the dynamic properties of quasi-particles. The mobilities of charge carriers are studied with various charge-lattice coupling models, and the recombination rate calculation demonstrates the molecular origin on the peculiar feature in the lifetime of charge carriers in these materials. In addition, we address how lattice vibrations themselves relax upon excitation from charge-lattice coupling. Throughout, these examples are aimed at characterizing the interplay between lattice fluctuations and optoelectronic properties of lead halide perovskites and are reviewed in the context of the effective models we have built and the novel theoretical methods we have developed to understand bulk crystalline materials, as well as nanostructures and lower dimensionality lattices. By integrating theoretical advances with experimental observations, the perspective we detail in this Account provides a comprehensive picture that serves as both design principles for optoelectronic materials and a set of theoretical tools to study them when charge-lattice interactions are important. These insights may further guide the development of next-generation optoelectronic devices with improved efficiency and stability while also inspiring new research directions to explore emerging quantum phenomena in these materials.
{"title":"Theoretical Insights into the Role of Lattice Fluctuations on the Excited Behavior of Lead Halide Perovskites","authors":"Yoonjae Park, Rohit Rana, Daniel Chabeda, Eran Rabani, David T. Limmer","doi":"10.1021/accountsmr.4c00401","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00401","url":null,"abstract":"Lead halide perovskites have been extensively studied as a class of materials with unique optoelectronic properties. A fundamental aspect that governs optical and electronic behaviors within these materials is the intricate coupling between charges and their surrounding lattice. Unravelling the role of charge-lattice interactions in the optoelectronic properties in lead halide perovskites is necessary to understand their photophysics. Unlike traditional semiconductors where a harmonic approximation often suffices to capture lattice fluctuations, lead halide perovskites have a significant anharmonicity attributed to the rocking and tilting motions of the inorganic framework. Thus, while there is broad consensus on the importance of the structural deformations and polar fluctuations on the behavior of charge carriers and quasiparticles, the strongly anharmonic nature of these fluctuations and their strong interactions render theoretical descriptions of lead halide perovskites challenging. In this Account, we review our recent efforts to understand how the soft, polar lattice of this class of materials alters their excited state properties. We highlight the influence of the lattice on static properties by examining the quasiparticle binding energies and fine structure. With perovskite nanocrystals, we discuss how incorporating lattice distortion is essential for accurately defining the exciton fine structure. By considering lattices across various dimensionalities, we are able to illustrate that the energetics of excitons and their complexes are significantly modulated by polaron formation. Beyond energetics, we also delve into how the lattice impacts the dynamic properties of quasi-particles. The mobilities of charge carriers are studied with various charge-lattice coupling models, and the recombination rate calculation demonstrates the molecular origin on the peculiar feature in the lifetime of charge carriers in these materials. In addition, we address how lattice vibrations themselves relax upon excitation from charge-lattice coupling. Throughout, these examples are aimed at characterizing the interplay between lattice fluctuations and optoelectronic properties of lead halide perovskites and are reviewed in the context of the effective models we have built and the novel theoretical methods we have developed to understand bulk crystalline materials, as well as nanostructures and lower dimensionality lattices. By integrating theoretical advances with experimental observations, the perspective we detail in this Account provides a comprehensive picture that serves as both design principles for optoelectronic materials and a set of theoretical tools to study them when charge-lattice interactions are important. These insights may further guide the development of next-generation optoelectronic devices with improved efficiency and stability while also inspiring new research directions to explore emerging quantum phenomena in these materials.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"209 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145236032","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-24DOI: 10.1021/accountsmr.5c00185
Shuangjun Li, Yan Xie, Shuai Deng, Xiangzhou Yuan
Plastic pollution and climate change are interconnected global environmental challenges. Conventional methods (incineration and landfills) exacerbate these issues by emitting greenhouse gases and releasing micro/nanoplastics. To simultaneously address these two critical environmental issues, we upcycle plastic waste into porous carbon materials, enabling high-performance postcombustion CO2 capture in a transformative and practical manner. This strategy tackles environmental pollution, aligns with circular economy principles, and supports several of UN Sustainable Development Goals (SDGs). We conduct systematic studies, including experimental validations, numerical simulations, and machine learning (ML)-empowered optimizations, to provide detailed guidelines for upcycling plastic waste into porous carbons with high-performance CO2 capture.
{"title":"Machine Learning-Empowered Plastic-Derived Porous Carbons for High-Performance CO2 Capture","authors":"Shuangjun Li, Yan Xie, Shuai Deng, Xiangzhou Yuan","doi":"10.1021/accountsmr.5c00185","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00185","url":null,"abstract":"Plastic pollution and climate change are interconnected global environmental challenges. Conventional methods (incineration and landfills) exacerbate these issues by emitting greenhouse gases and releasing micro/nanoplastics. To simultaneously address these two critical environmental issues, we upcycle plastic waste into porous carbon materials, enabling high-performance postcombustion CO<sub>2</sub> capture in a transformative and practical manner. This strategy tackles environmental pollution, aligns with circular economy principles, and supports several of UN Sustainable Development Goals (SDGs). We conduct systematic studies, including experimental validations, numerical simulations, and machine learning (ML)-empowered optimizations, to provide detailed guidelines for upcycling plastic waste into porous carbons with high-performance CO<sub>2</sub> capture.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127465","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-02eCollection Date: 2025-10-24DOI: 10.1021/accountsmr.5c00172
Bindu Kalleshappa, Martin Pumera
{"title":"Single-Atom Engineering in Room-Temperature Sodium-Sulfur Batteries.","authors":"Bindu Kalleshappa, Martin Pumera","doi":"10.1021/accountsmr.5c00172","DOIUrl":"10.1021/accountsmr.5c00172","url":null,"abstract":"","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 10","pages":"1172-1176"},"PeriodicalIF":14.7,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12560075/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145403024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
<p><p>This Account presents surface electrochemical nanopatterning as a powerful and underexplored strategy for engineering the electronic and functional properties of electrochemically active materials. By enabling precise, localized manipulation of electronic states at the micro- and nanoscale, this technique offers a unique pathway to unlock and control intrinsic material properties. These capabilities open new frontiers in materials science, with implications ranging from catalysis to the fabrication of advanced, multifunctional devices. Traditional lithographic techniques, such as photolithography, electron beam lithography, and nanoimprinting, mainly focus on shaping surface topography. In contrast, electrochemical nanopatterning introduces a fundamentally different approach: it modifies the material itself. By changing oxidation states, creating or healing defects, and tuning surface chemistry, this method allows for direct control of material properties. Consequently, it greatly expands the range of applications, enabling the development of materials with customized electronic and functional features. This Account focuses specifically on stamp-assisted electrochemical lithography (ECL), a versatile and scalable technique. We start by outlining the fundamental principles of ECL, including the electrochemical processes that drive it, namely oxidation, reduction, and defect generation. Next, we trace its historical development and highlight its advantages over traditional nanofabrication methods, particularly in terms of simplicity, cost-effectiveness, and compatibility with a wide range of materials. Through a curated selection of case studies, we demonstrate how ECL can be used to (i) generate and tune electronic properties, (ii) impart various functional behaviors, and (iii) achieve spatially controlled defect engineering, especially in semiconductors. Crucially, the ability to fabricate large-area samples has allowed us to harness size-dependent properties that were previously inaccessible in electrochemical nanolithography performed via scanning probe techniques, such e catalysis and the in situ fabrication of nanoclusters. These findings dramatically expand the scientific and technological potential of ECL, opening new avenues for innovation and application. The example cases were selected for their relevance to current challenges in materials science and emerging technologies. Notable applications include in situ healing in resistive switching devices, the development of critical-element-free catalysts, and the direct fabrication of active components within devices. Many of these studies were pioneering at the time of publication and have only recently gained broader recognition due to the growing interest in sustainable, low-cost, and scalable nanofabrication techniques. We emphasize ECL's unique capabilities in enabling regenerable resistive switching, spatially selective nanoembedding of functional nanoparticles, and creating funct
{"title":"Generation and Tuning of Semiconductor Electronic and Functional Properties through Electrochemical Patterning.","authors":"Denis Gentili, Edoardo Chini, Massimiliano Cavallini","doi":"10.1021/accountsmr.5c00104","DOIUrl":"10.1021/accountsmr.5c00104","url":null,"abstract":"<p><p>This Account presents surface electrochemical nanopatterning as a powerful and underexplored strategy for engineering the electronic and functional properties of electrochemically active materials. By enabling precise, localized manipulation of electronic states at the micro- and nanoscale, this technique offers a unique pathway to unlock and control intrinsic material properties. These capabilities open new frontiers in materials science, with implications ranging from catalysis to the fabrication of advanced, multifunctional devices. Traditional lithographic techniques, such as photolithography, electron beam lithography, and nanoimprinting, mainly focus on shaping surface topography. In contrast, electrochemical nanopatterning introduces a fundamentally different approach: it modifies the material itself. By changing oxidation states, creating or healing defects, and tuning surface chemistry, this method allows for direct control of material properties. Consequently, it greatly expands the range of applications, enabling the development of materials with customized electronic and functional features. This Account focuses specifically on stamp-assisted electrochemical lithography (ECL), a versatile and scalable technique. We start by outlining the fundamental principles of ECL, including the electrochemical processes that drive it, namely oxidation, reduction, and defect generation. Next, we trace its historical development and highlight its advantages over traditional nanofabrication methods, particularly in terms of simplicity, cost-effectiveness, and compatibility with a wide range of materials. Through a curated selection of case studies, we demonstrate how ECL can be used to (i) generate and tune electronic properties, (ii) impart various functional behaviors, and (iii) achieve spatially controlled defect engineering, especially in semiconductors. Crucially, the ability to fabricate large-area samples has allowed us to harness size-dependent properties that were previously inaccessible in electrochemical nanolithography performed via scanning probe techniques, such e catalysis and the in situ fabrication of nanoclusters. These findings dramatically expand the scientific and technological potential of ECL, opening new avenues for innovation and application. The example cases were selected for their relevance to current challenges in materials science and emerging technologies. Notable applications include in situ healing in resistive switching devices, the development of critical-element-free catalysts, and the direct fabrication of active components within devices. Many of these studies were pioneering at the time of publication and have only recently gained broader recognition due to the growing interest in sustainable, low-cost, and scalable nanofabrication techniques. We emphasize ECL's unique capabilities in enabling regenerable resistive switching, spatially selective nanoembedding of functional nanoparticles, and creating funct","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 9","pages":"1094-1104"},"PeriodicalIF":14.7,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12481725/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145208537","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-29DOI: 10.1021/accountsmr.5c00087
Simon Sau Yin Law*, Ali D. Malay and Keiji Numata*,
<p >Peptides and proteins, though both composed of amino acids, differ significantly in their structural and functional complexity. Peptides are generally shorter chains of amino acids and typically adopt simple secondary structures, such as α-helices or β-sheets. However, they rarely develop the intricate tertiary and quaternary structures that are characteristic of proteins. Proteins, which consist of longer polypeptide chains, exhibit complex folding patterns stabilized by various interactions, including hydrogen bonds, disulfide linkages, and hydrophobic interactions. This structural complexity allows proteins to perform highly specialized biological functions, such as enzymatic catalysis, signal transduction, and structural support.</p><p >Both peptides and proteins have the ability to undergo self-assembly, forming higher-order structures through noncovalent interactions such as hydrogen bonding, electrostatic forces, and hydrophobic interactions. In particular, peptide functional assemblies also serve various roles, such as drug delivery, biosensors, intracellular modulation, and structural scaffolds. Depending on their sequence, they can exhibit antioxidant, antimicrobial, receptor-targeting, or enzyme-inhibitory properties. Peptides also play a crucial role in developing biomaterials like hydrogels and nanomaterials for various applications in both biomedical and engineering fields. Researchers have explored the design of peptide-based hydrogels, nanoparticles, and scaffolds that can mimic extracellular matrices, facilitating cell growth and tissue regeneration. The combination of peptides with other biomaterials has also led to innovative solutions for controlled drug release and antimicrobial coatings.</p><p >In proteins, self-assembly is crucial for biological function, as exemplified by the formation of multiprotein complexes. These complexes are essential for many biological processes, including structural scaffolds, cellular signaling and immune responses. Among structural protein assemblies, silk has gained significant attention due to its exceptional mechanical properties, biocompatibility, and sustainability. Silk fibers adopt a hierarchical structure comprising crystalline β-sheet domains interspersed with amorphous regions. This unique arrangement imparts superior strength, elasticity, and toughness, making silk a versatile material for a wide range of applications. Traditionally used in textiles, silk has recently emerged as a promising biomaterial building block in the medical field. Its ability to form various material formats, including fibers, films, and hydrogels, has enabled advancements in drug delivery, wound healing, and regenerative medicine.</p><p >The expanding field of recombinant silk and peptide engineering holds tremendous promise for sustainable bioengineering and biomaterial development. Advances in synthetic biology and genetic engineering have enabled the mass production of silk-inspired proteins and funct
{"title":"From Peptides to Silk-Inspired Proteins: Self-Assembling Systems for Functional Biomaterials","authors":"Simon Sau Yin Law*, Ali D. Malay and Keiji Numata*, ","doi":"10.1021/accountsmr.5c00087","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00087","url":null,"abstract":"<p >Peptides and proteins, though both composed of amino acids, differ significantly in their structural and functional complexity. Peptides are generally shorter chains of amino acids and typically adopt simple secondary structures, such as α-helices or β-sheets. However, they rarely develop the intricate tertiary and quaternary structures that are characteristic of proteins. Proteins, which consist of longer polypeptide chains, exhibit complex folding patterns stabilized by various interactions, including hydrogen bonds, disulfide linkages, and hydrophobic interactions. This structural complexity allows proteins to perform highly specialized biological functions, such as enzymatic catalysis, signal transduction, and structural support.</p><p >Both peptides and proteins have the ability to undergo self-assembly, forming higher-order structures through noncovalent interactions such as hydrogen bonding, electrostatic forces, and hydrophobic interactions. In particular, peptide functional assemblies also serve various roles, such as drug delivery, biosensors, intracellular modulation, and structural scaffolds. Depending on their sequence, they can exhibit antioxidant, antimicrobial, receptor-targeting, or enzyme-inhibitory properties. Peptides also play a crucial role in developing biomaterials like hydrogels and nanomaterials for various applications in both biomedical and engineering fields. Researchers have explored the design of peptide-based hydrogels, nanoparticles, and scaffolds that can mimic extracellular matrices, facilitating cell growth and tissue regeneration. The combination of peptides with other biomaterials has also led to innovative solutions for controlled drug release and antimicrobial coatings.</p><p >In proteins, self-assembly is crucial for biological function, as exemplified by the formation of multiprotein complexes. These complexes are essential for many biological processes, including structural scaffolds, cellular signaling and immune responses. Among structural protein assemblies, silk has gained significant attention due to its exceptional mechanical properties, biocompatibility, and sustainability. Silk fibers adopt a hierarchical structure comprising crystalline β-sheet domains interspersed with amorphous regions. This unique arrangement imparts superior strength, elasticity, and toughness, making silk a versatile material for a wide range of applications. Traditionally used in textiles, silk has recently emerged as a promising biomaterial building block in the medical field. Its ability to form various material formats, including fibers, films, and hydrogels, has enabled advancements in drug delivery, wound healing, and regenerative medicine.</p><p >The expanding field of recombinant silk and peptide engineering holds tremendous promise for sustainable bioengineering and biomaterial development. Advances in synthetic biology and genetic engineering have enabled the mass production of silk-inspired proteins and funct","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 8","pages":"964–978"},"PeriodicalIF":14.7,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/accountsmr.5c00087","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144885248","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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