Accounts of materials research最新文献

{"title":"Design Strategies, Properties, and Applications toward Cycloarenes and Heterocycloarenes","authors":"Jiangyu Zhu, Rong Zhang, Dongyue An, Yuanhe Gu, Xuefeng Lu, Yunqi Liu","doi":"10.1021/accountsmr.5c00041","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00041","url":null,"abstract":"Cycloarenes, fully benzene-annelated macrocyclic systems with inward-facing carbon–hydrogen bonds, serve as ideal models for defects in graphene, offering great application potential in organic electronics, supramolecular chemistry, and optics. They offer an attractive combination of synthesis challenge, aesthetic appeal, fundamental problems, and potential applications. Initially, the most typical cycloarene, kekulene, was expected to provide a crucial experimental test to determine whether π-electrons are delocalized over the entire molecule or delocalized at the benzenoid rings. This question has captivated synthetic chemists for decades. After numerous failed attempts, Staab and Diederich achieved the first conclusive synthesis of kekulene in 1978. The deshielded inner protons in the <sup>1</sup>H NMR spectrum conclusively demonstrated that the π-electrons in cycloarenes are delocalized at individual benzenoid rings. However, owing to limited synthetic methods, complex reaction routes, and poor solubility of the final products, progress in cycloarene research has been slow. Over the next four decades, only a few contracted or expanded kekulene homologues were reported. Nevertheless, the changes in their chemical structure bring some exciting physicochemical properties. The enlargement of the central ring of kekulene induces a transition from a planar to a saddle-shaped structure, further influencing its electronic and optical properties and unlocking unexpected applications in supramolecular chemistry. Therefore, developing new rational synthetic methods to controllably synthesize structurally diverse cycloarenes is crucial. With the continuous development of synthetic science, in recent years, some functional cycloarenes and heteroatom-embedded heterocycloarenes have been reported. Owing to their unique topological structures, well-defined cavities, and large cyclic conjugated systems, these (hetero)cycloarenes have been applied in fields such as supramolecular chemistry, organic field-effect transistors, and solar cells. However, the limited understanding of the structure–property relationship in (hetero)cycloarenes poses a formidable challenge to their custom synthesis for specific functions. Herein, we review our efforts in the design, synthesis, and applications of cycloarenes and heterocycloarenes. First, we summarize four representative synthetic methods for cycloarenes. Subsequently, we present a comprehensive overview of three molecular design strategies: π-extension, heteroatom embedding, and acceptor moiety insertion, to achieve the molecular structure diversity of cycloarenes. Then, we highlight their synthetic methods, geometries, fundamental optoelectronic properties, and unique applications in ultranarrowband emission, organic transistor devices, and supramolecular chemistry. We also delve into the intrinsic correlations among structures, properties, and applications of these cycloarenes and heterocycloarenes. Finally, we envis","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"183 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713782","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}

{"title":"Nanospace Engineering of Metal–Organic Frameworks for Adsorptive Gas Separation","authors":"Lingshan Gong, Shyam Chand Pal, Yingxiang Ye* and Shengqian Ma*, ","doi":"10.1021/accountsmr.5c0000610.1021/accountsmr.5c00006","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00006https://doi.org/10.1021/accountsmr.5c00006","url":null,"abstract":"<p >Gas separation is a critical process in the industrial production of chemicals, polymers, plastics, and fuels, which traditionally rely on energy-intensive cryogenic distillation techniques. In contrast, adsorptive separation using porous materials has emerged as a promising alternative, presenting substantial potential for energy savings and improved operational efficiency. Among these materials, metal–organic frameworks (MOFs) have garnered considerable attention due to their unique structural and functional characteristics. MOFs are a class of crystalline porous materials constructed from inorganic metal ions or clusters connected by organic linkers through strong coordination bonds. Their precisely engineered architectures create well-defined nanoscale spaces capable of selectively trapping guest molecules. In contrast to traditional porous materials such as zeolites and activated carbons, emerging MOFs not only demonstrate exceptional capabilities for pore regulation and interior modification through nanospace engineering but also hold great promise as a superior platform for the development of high-performance functional materials. By virtue of the isoreticular principle and building unit assembly strategies in MOF chemistry, precise adjustments to pore structures─including pore size, shape, and surface chemistry─can be readily achieved, making them well-suited for addressing the separation of intractable industrial gas mixtures, particularly those with similar sizes and physicochemical properties.</p><p >This Account presents a comprehensive overview of our recent advancements in high-performance gas separation through nanospace engineering within porous MOFs. First, by strategically immobilizing open metal sites (e.g., Ag<sup>+</sup>) in the pore surface, the functionalized PAF-1-SO<sub>3</sub>Ag demonstrates enhanced ethylene uptake capacity while maintaining exceptional structural stability under humid conditions. Furthermore, pore surface modification with low-polarity groups (e.g., −CH<sub>3</sub>, −CF<sub>3</sub>), as demonstrated in Ni(TMBDC)(DABCO)<sub>0.5</sub>, leads to enhanced C<sub>2</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>4</sub> separation performance. To achieve strong guest molecule binding, we engineered novel ″nanotrap″ binding sites that synergistically integrate oppositely adjacent open metal sites and dense alkyl groups, as exemplified by the Cu-ATC framework. Remarkably, Cu-ATC achieves efficient separation of several challenging gas mixtures, including acetylene/carbon dioxide (C<sub>2</sub>H<sub>2</sub>/CO<sub>2</sub>), xenon/krypton (Xe/Kr), and methane/nitrogen (CH<sub>4</sub>/N<sub>2</sub>). These innovations have resulted in the development of MOF materials with exceptional separation performance, tailored for specific industrial applications such as light hydrocarbon purification, rare gas separation, and coalbed methane enrichment. Our work not only advances the fundamental understanding of structure–prope","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 4","pages":"499–511 499–511"},"PeriodicalIF":14.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867407","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}

{"title":"Engineering Peptide Self-Assembly: Modulating Noncovalent Interactions for Biomedical Applications","authors":"Yaoting Li, Huanfen Lu, Liheng Lu and Huaimin Wang*, ","doi":"10.1021/accountsmr.4c0039110.1021/accountsmr.4c00391","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00391https://doi.org/10.1021/accountsmr.4c00391","url":null,"abstract":"<p >Controlling self-assembled peptide nanostructures has emerged as a significant area of research, offering versatile tools for developing functional materials for various applications. This Account emphasizes the essential role of noncovalent interactions, particularly in peptide-based materials. Key forces, such as aromatic stacking and hydrogen bonding, are crucial for promoting molecular aggregation and stabilizing supramolecular structures. Numerous studies demonstrate how these interactions influence the phase transitions and the morphology of self-assembled structures. Recent advances in computational methodologies, including molecular dynamics simulations and machine learning, have significantly enhanced our understanding of self-assembly processes. These tools enable researchers to predict how molecular properties, such as hydrophobicity, charge distribution, and aromaticity, affect assembly behavior. Simulations uncover the energetic landscapes governing peptide aggregation, providing insights into the kinetic pathways and thermodynamic stabilities. Meanwhile, machine learning facilitates the rapid screening of peptide libraries, identifying sequences with optimal self-assembly characteristics, and accelerating material design with tailored functionalities.</p><p >Beyond their structural and physicochemical properties, self-assembled peptide nanostructures hold immense potential in biological applications due to their versatility and biocompatibility. By manipulating molecular interactions, researchers have engineered responsive systems that interact with cellular environments to elicit specific biological responses. These peptide nanostructures can mimic extracellular matrices, facilitating cell adhesion, proliferation, and differentiation. They also show promise in modulating immune responses, recruiting immune cells, and regulating signaling pathways, making them valuable tools in immunotherapy and regenerative medicine. Moreover, their ability to disrupt bacterial membranes positions them as innovative alternatives to conventional antibiotics, addressing the urgent need for solutions to antimicrobial resistance.</p><p >Despite its promise, peptide self-assembly faces several challenges. The assembly process is highly sensitive to environmental conditions, such as pH, temperature, and ionic strength, leading to variability in the morphology and properties. Furthermore, peptide aggregation can result in heterogeneous and poorly defined assemblies, complicating the reproducibility and scalability. Designing peptides with predictable self-assembly behavior remains a significant hurdle. Looking ahead, integrating computational predictions with experimental validations will be crucial in discovering novel peptide sequences with tailored self-assembly properties. Machine learning, combined with high-throughput screening techniques, will enable the rapid identification of optimal peptide sequences. In situ characterization tools, such as ","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 4","pages":"447–461 447–461"},"PeriodicalIF":14.0,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867533","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}

{"title":"Engineering Peptide Self-Assembly: Modulating Noncovalent Interactions for Biomedical Applications","authors":"Yaoting Li, Huanfen Lu, Liheng Lu, Huaimin Wang","doi":"10.1021/accountsmr.4c00391","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00391","url":null,"abstract":"Controlling self-assembled peptide nanostructures has emerged as a significant area of research, offering versatile tools for developing functional materials for various applications. This Account emphasizes the essential role of noncovalent interactions, particularly in peptide-based materials. Key forces, such as aromatic stacking and hydrogen bonding, are crucial for promoting molecular aggregation and stabilizing supramolecular structures. Numerous studies demonstrate how these interactions influence the phase transitions and the morphology of self-assembled structures. Recent advances in computational methodologies, including molecular dynamics simulations and machine learning, have significantly enhanced our understanding of self-assembly processes. These tools enable researchers to predict how molecular properties, such as hydrophobicity, charge distribution, and aromaticity, affect assembly behavior. Simulations uncover the energetic landscapes governing peptide aggregation, providing insights into the kinetic pathways and thermodynamic stabilities. Meanwhile, machine learning facilitates the rapid screening of peptide libraries, identifying sequences with optimal self-assembly characteristics, and accelerating material design with tailored functionalities.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"42 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635764","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}

{"title":"Polymer–Nanoparticle Composite Films with Ultrahigh Nanoparticle Loadings Using Capillarity-Based Techniques","authors":"Baekmin Q. Kim, Uiseok Hwang, Hong Huy Tran and Daeyeon Lee*, ","doi":"10.1021/accountsmr.4c0038710.1021/accountsmr.4c00387","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00387https://doi.org/10.1021/accountsmr.4c00387","url":null,"abstract":"<p >Polymer–nanoparticle (NP) composites with ultrahigh loadings (more than 50 vol %) of NPs possess exceptional mechanical, transport, and physical properties, making them valuable for various applications. However, producing such polymer–NP composites poses significant challenges due to difficulties associated with mixing and dispersing high fractions of NPs in polymers. A promising approach to overcome these challenges involves infiltrating a polymer into the interstitial pores of a disordered NP packing, resulting in a polymer-infiltrated NP film (PINF). Recently, versatile capillarity-driven techniques have emerged, successfully enabling the production of PINFs. These capillarity-driven techniques allow for the fabrication of homogeneous (fully infiltrated), nanoporous (partially infiltrated), and heterostructured PINFs. Infiltrating polymers into stiff but brittle NP packings increases their toughness, attributed to the formation of polymer bridges between adjacent NPs or interchain entanglements. The physical confinement of polymer within the interstitial pore also enhances thermal stability and heat transfer of PINFs. Additionally, the tunable nanoporosity and heterostructures of PINFs lead to unique optical properties suitable for various practical applications.</p><p >In this Account, we present recent advances and progress in capillarity-based techniques for the fabrication of PINFs and provide a summary of our latest finding on the infiltration process and the properties of PINFs which we have obtained after the publication of our 2021 review paper. We also discuss the stability of the resulting PINFs and demonstrate some practical applications. We conclude the Account by outlining the fundamental research and application directions for the future.</p><p >In Section 2, we detail capillarity-driven techniques to infiltrate a polymer into a disordered packing of NPs, specifically capillary rise infiltration (CaRI), solvent-driven infiltration of polymer (SIP), and leaching-enabled CaRI (LeCaRI). The CaRI and SIP techniques involve thermal and solvent vapor annealing processes, respectively, while the LeCaRI technique is performed at room temperature without any solvent. For each technique, factors influencing the extent and dynamics of polymer infiltration, including nanoconfinement and polymer–NP surface interactions, are explained. In Section 3, we focus on the mechanical properties and thermal/photo degradation behaviors of the PINFs, which are closely linked to their stability, and explain how nanoconfinement and polymer–NP surface interactions affect these properties. We show that kinetics of infiltration and the properties of PINFs have nontrivial and at times counterintuitive dependence on the extent of nanoconfinement and the interaction strengths between polymers and NPs. In Section 4, we explore some practical applications of PINFs, demonstrating their multifunctionality in areas such as antireflection coatings and antifouling","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 4","pages":"512–522 512–522"},"PeriodicalIF":14.0,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867532","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}

{"title":"Polymer–Nanoparticle Composite Films with Ultrahigh Nanoparticle Loadings Using Capillarity-Based Techniques","authors":"Baekmin Q. Kim, Uiseok Hwang, Hong Huy Tran, Daeyeon Lee","doi":"10.1021/accountsmr.4c00387","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00387","url":null,"abstract":"Polymer–nanoparticle (NP) composites with ultrahigh loadings (more than 50 vol %) of NPs possess exceptional mechanical, transport, and physical properties, making them valuable for various applications. However, producing such polymer–NP composites poses significant challenges due to difficulties associated with mixing and dispersing high fractions of NPs in polymers. A promising approach to overcome these challenges involves infiltrating a polymer into the interstitial pores of a disordered NP packing, resulting in a polymer-infiltrated NP film (PINF). Recently, versatile capillarity-driven techniques have emerged, successfully enabling the production of PINFs. These capillarity-driven techniques allow for the fabrication of homogeneous (fully infiltrated), nanoporous (partially infiltrated), and heterostructured PINFs. Infiltrating polymers into stiff but brittle NP packings increases their toughness, attributed to the formation of polymer bridges between adjacent NPs or interchain entanglements. The physical confinement of polymer within the interstitial pore also enhances thermal stability and heat transfer of PINFs. Additionally, the tunable nanoporosity and heterostructures of PINFs lead to unique optical properties suitable for various practical applications.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"89 3 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143627706","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}

{"title":"Emerging Electrochemical Catalysis on {001}-Facet and Defect-Engineered TiO2 for Water Purification","authors":"Ai-Yong Zhang, Chang Liu, Han-Qing Yu","doi":"10.1021/accountsmr.4c00377","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00377","url":null,"abstract":"Electrochemical water purification and pollutant monitoring have garnered significant attention due to their unique technical advantages. The pursuit of safe, efficient, and economically viable catalysts remains a critical priority. Titanium dioxide (TiO₂), a prototypical transition-metal oxide with substantial industrial importance, is widely recognized as a benchmark catalyst for photochemical reactions. However, its practical application is limited by restricted light absorption and rapid photocarrier recombination. Recently, TiO₂ has emerged as a promising candidate in electrochemical catalysis, particularly in the fields of energy and environmental science. Its atomic and electronic structures can be precisely engineered through advanced techniques such as nanoscale morphology control, polar-facet engineering, guest-metal doping, and structural-defect modulation. This review examines recent advancements in TiO₂-based electrochemical applications, with a focus on water purification and pollutant monitoring.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"69 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618905","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}

{"title":"Emerging Electrochemical Catalysis on {001}-Facet and Defect-Engineered TiO2 for Water Purification","authors":"Ai-Yong Zhang, Chang Liu and Han-Qing Yu*, ","doi":"10.1021/accountsmr.4c0037710.1021/accountsmr.4c00377","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00377https://doi.org/10.1021/accountsmr.4c00377","url":null,"abstract":"<p >Electrochemical water purification and pollutant monitoring have garnered significant attention due to their unique technical advantages. The pursuit of safe, efficient, and economically viable catalysts remains a critical priority. Titanium dioxide (TiO<sub>2</sub>), a prototypical transition-metal oxide with substantial industrial importance, is widely recognized as a benchmark catalyst for photochemical reactions. However, its practical application is limited by restricted light absorption and rapid photocarrier recombination. Recently, TiO<sub>2</sub> has emerged as a promising candidate in electrochemical catalysis, particularly in the fields of energy and environmental science. Its atomic and electronic structures can be precisely engineered through advanced techniques such as nanoscale morphology control, polar-facet engineering, guest-metal doping, and structural-defect modulation. This review examines recent advancements in TiO<sub>2</sub>-based electrochemical applications, with a focus on water purification and pollutant monitoring.</p><p >In this Account, we present our efforts to harness facet- and defect-engineered TiO<sub>2</sub> as electrochemical catalysts for water purification, addressing critical challenges such as low conductivity and poor reactivity. Initially, we demonstrate that facet-engineered TiO<sub>2</sub>, specifically designed to expose the high-energy {001} polar facet, facilitates the dissociation of both pollutant and water molecules. This significantly lowers energy barriers and enhances anodic reactions through both direct and indirect pathways, thereby markedly improving water purification efficiency. Furthermore, the dual photochemical and electrochemical functionalities of a single {001}-tailored TiO<sub>2</sub> electrode enable synergistic UV-light-assisted electrochemical catalysis under low bias conditions, achieving superior energy efficiency and resistance to electrode fouling. Next, we explore the catalytic potential of defect-engineered TiO<sub>2</sub> (TiO<sub>2–<i>x</i></sub>), highlighting the role of titanium (≡Ti<sup>3+</sup>) and oxygen vacancies (O<sub>v</sub>) in boosting electrochemical water purification. Surface and subsurface defects, characterized by localized atomic disorder and structural distortions, serve as active sites that drive beneficial structural transformations, enriched electronic distribution, enhanced spin–spin correlations, and polaron hopping mechanisms, all of which contribute to improved cathodic reduction. To stabilize these reactive sites under anodic polarization, we propose a practical visible-light-assisted electrochemical catalysis strategy. This approach leverages mild non-band-gap excitation pathways mediated by defect sub-bands, providing enhanced stability and catalytic efficiency. Finally, we identify the challenges associated with the application of self-engineered TiO<sub>2</sub> in electrochemical water purification and outline directions for future re","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 4","pages":"422–433 422–433"},"PeriodicalIF":14.0,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867531","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}

{"title":"Bismuth-Catalyzed Electrochemical Carbon Dioxide Reduction to Formic Acid: Material Innovation and Reactor Design","authors":"Yuqing Luo, Junmei Chen, Na Han and Yanguang Li*, ","doi":"10.1021/accountsmr.4c0038610.1021/accountsmr.4c00386","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00386https://doi.org/10.1021/accountsmr.4c00386","url":null,"abstract":"<p >Electrochemical CO<sub>2</sub> reduction reaction (eCO<sub>2</sub>RR) has gained increasing attention as a promising strategy to mitigate the negative impacts of CO<sub>2</sub> emission while simultaneously producing valuable chemicals or fuels. By converting CO<sub>2</sub> into energy-rich products using renewable electricity, eCO<sub>2</sub>RR provides a sustainable approach to reducing the carbon footprint and promoting a circular carbon economy. Among different reduction products, the formic acid (or formate) is particularly attractive due to its economic viability and diverse industrial applications, making it a key focus for both research and industrial adoption.</p><p >Bismuth (Bi)-based electrocatalysts have emerged as promising candidates for eCO<sub>2</sub>RR to formic acid, by virtue of their nontoxicity, low cost, high abundance and exceptional selectivity for the two-electron pathway. These characteristics allow Bi-based catalysts to effectively suppress competing reactions and maximize formic acid production. In this Account, we discuss our contributions, along with those of others, to advancing the field of Bi-based materials for formic acid/formate production, focusing on both the fundamental understanding of their unique catalytic properties and innovative strategies employed to enhance their performances.</p><p >One of our significant contributions lies in the development of advanced nanostructures that enhance the catalytic activity of Bi-based materials. By tailoring the size and morphology of Bi nanostructures, we have demonstrated improvements in active site density and reaction kinetics, leading to higher formic acid/formate selectivity and productivity. We have also explored the design of three-dimensional architectures, which provide enhanced mass transport and reduce diffusion limitations, thereby improving the overall efficiency of the catalytic process. Furthermore, works on defect engineering have revealed how modifying the electronic properties of Bi can optimize its binding affinity for key intermediates, significantly enhancing its catalytic performance.</p><p >In addition to material innovations, recent research has contributed to the advancement of reactor designs that enable efficient and scalable eCO<sub>2</sub>RR systems. We have optimized flow cells to ensure continuous operation with high mass transport efficiency, making them suitable for industrial production. Furthermore, studies on membrane electrode assemblies (MEAs) have integrated Bi-based catalysts into compact and energy-efficient systems, furthering enhancing the practical applicability of eCO<sub>2</sub>RR. Solid-electrolyte systems have also been explored to simplify system configurations, improve stability and enable the production of pure formic acid. These efforts reflect the commitment of the community to bridging the gap between laboratory-scale research and industrial-scale implementation.</p><p >Despite the significant progress achieve","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 4","pages":"462–472 462–472"},"PeriodicalIF":14.0,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867539","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}

{"title":"Bismuth-Catalyzed Electrochemical Carbon Dioxide Reduction to Formic Acid: Material Innovation and Reactor Design","authors":"Yuqing Luo, Junmei Chen, Na Han, Yanguang Li","doi":"10.1021/accountsmr.4c00386","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00386","url":null,"abstract":"Electrochemical CO₂ reduction reaction (eCO₂RR) has gained increasing attention as a promising strategy to mitigate the negative impacts of CO₂ emission while simultaneously producing valuable chemicals or fuels. By converting CO₂ into energy-rich products using renewable electricity, eCO₂RR provides a sustainable approach to reducing the carbon footprint and promoting a circular carbon economy. Among different reduction products, the formic acid (or formate) is particularly attractive due to its economic viability and diverse industrial applications, making it a key focus for both research and industrial adoption.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"30 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569851","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}