Accounts of materials research最新文献

{"title":"Thermally Drawn Semiconductor Fibers: Fabrication Strategies and Applications","authors":"Zhixun Wang,  and , Lei Wei*, ","doi":"10.1021/accountsmr.4c0013210.1021/accountsmr.4c00132","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00132https://doi.org/10.1021/accountsmr.4c00132","url":null,"abstract":"<p >Wearable electronics enable seamless incorporation of electronics into our daily lives. Consumer-grade wearables, such as smart rings, bands, and watches, have gained popularity in recent years due to their capacity to offer consistent and dependable data collection and assistance for daily activities. Moreover, wearable electronics are emerging in professional medical services, such as continuous glucose monitoring and minimally invasive thrombectomy, to aid healthcare professionals in diagnosing and treating. In addition, the proliferation of the Internet of Things (IoT) has further fueled the demand for wearable electronics, as they are the critical components for an IoT system to support the sharing and analysis of data across multiple devices and platforms. The market for wearable electronics predictably continues to expand in the future. Semiconductors are crucial components of wearable electronics, and especially in fiber form factor, they enable monolithic fiber electronics and smart textiles. Several techniques are developed for fabricating inorganic semiconductor fibers, such as the Czochralski growth method, micropulling-down process, and thermal drawing technique. Thermal drawing of semiconductor fibers is a technique in which semiconductor materials are supported by glassy cladding materials and heated into fluid melts, with the combination drawn to fiber dimensions. Among the various fabrication methods, the thermal drawing technique has the advantages of a high yield rate, feasible integration of multiple materials, the capability of achieving designable sophisticated structures, and an extended single-strand fiber length. The as-drawn semiconductor fibers may serve as the building blocks of wearable electronics directly or subject to postprocessing procedures for on-demand alteration of dimension, geometry, or phase structure before employment. Research efforts within the fundamental understanding of fluid dynamics, rheology, and molecular structure evolution seek to improve the performance and quality of thermally drawn semiconductor fibers such as conductivity, bandgap, electron mobility, thermal stability, and mechanical strength. In this Account, we systematically recapitulate our efforts in developing semiconductor fibers and their application in wearable electronics, including diodes, sensors, energy harvesters, and more. We begin by introducing the three primary thermal drawing methods, highlighting the unique features of each. Next, postprocessing methods to further alter the materials, structures, and geometries of semiconductor fibers are discussed. We then discuss the various devices and applications and conclude with an examination of current challenges and our perspectives on future research directions. This Account aims to inspire further research efforts to expand the scope of fiber materials, the design of in-fiber structures, and configurations of device assembly to achieve widespread adoption of semiconduct","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 11","pages":"1366–1376 1366–1376"},"PeriodicalIF":14.0,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691365","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":"Stabilization of Superionic Copper Selenide Based Thermoelectric Materials","authors":"Jincheng Yu, Haihua Hu, Hua-Lu Zhuang, Hezhang Li and Jing-Feng Li*, ","doi":"10.1021/accountsmr.4c0022910.1021/accountsmr.4c00229","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00229https://doi.org/10.1021/accountsmr.4c00229","url":null,"abstract":"<p >Thermoelectric (TE) technology enables the direct conversion between heat and electricity, thereby contributing to the alleviation of the prevailing energy crisis and the mitigation of environmental concerns. Bismuth telluride-based TE materials have been commercially utilized, while they are mainly applied to solid-state cooling rather than energy harvesting. Superionic conductors including copper chalcogenides and silver chalcogenides are rendered as promising TE candidates for power generation due to their superior thermoelectric figure of merit (<i>ZT</i>) at middle or high temperatures; the liquid-like behavior of ions aligns these systems with the concept of phonon-liquid electron-crystal (PLEC). Although the mobile ions are beneficial to enhancing the electrical transport and phonon scattering, their directional migration driven by an electric field or temperature gradient can result in the unintended deposition of metals, which can impair both the TE properties and the service stability of the materials. Therefore, it is imperative to identify stabilized liquid-like TE materials that can withstand current strike and high temperature.</p><p >In this Account, we select copper selenide as a model superionic TE material to elucidate the origins of excellent TE performance, liquid-like behaviors, and instability at high temperatures. First, the unique electrical and transport properties are analyzed based on the electronic band structure and spectral lattice thermal conductivity calculated using the Density Functional Theory (DFT). Second, the microstructures are evaluated based on the data collected from advanced electron microscopes to understand the characteristics of highly active Cu ions. Third, we summarize the reasons for the Cu instability under different circumstances, as well as several effective strategies toward enhanced stability, including defect engineering, interface engineering, and chemical bond engineering. In particular, these strategies are well implemented by applicable routes, such as manipulation of cation vacancies, establishment of internal electric field, voltage division, interfacial trapping, ion confinement, and phase separation; the advantages and disadvantages of each strategy are clearly presented. Most importantly, we reveal the underlying modulation mechanisms for each route and highlight their core concept, i.e., control of potential barriers during the activation or motion process of ions, which helps us to master and popularize these strategies for practical use. Finally, we raise additional concerns regarding the trade-off between stability enhancement and liquid-like feature as well as the loss of volatile elements, and then point out the meaningful directions for future studies. We hope that our work will help to draw attention to the potential for enhancing the stability of superionic conductors and anticipate that the proposed approaches will facilitate the development of stabilized liquid-like TE","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 11","pages":"1428–1439 1428–1439"},"PeriodicalIF":14.0,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691396","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":"Stabilization of Superionic Copper Selenide Based Thermoelectric Materials","authors":"Jincheng Yu, Haihua Hu, Hua-Lu Zhuang, Hezhang Li, Jing-Feng Li","doi":"10.1021/accountsmr.4c00229","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00229","url":null,"abstract":"Thermoelectric (TE) technology enables the direct conversion between heat and electricity, thereby contributing to the alleviation of the prevailing energy crisis and the mitigation of environmental concerns. Bismuth telluride-based TE materials have been commercially utilized, while they are mainly applied to solid-state cooling rather than energy harvesting. Superionic conductors including copper chalcogenides and silver chalcogenides are rendered as promising TE candidates for power generation due to their superior thermoelectric figure of merit (<i>ZT</i>) at middle or high temperatures; the liquid-like behavior of ions aligns these systems with the concept of phonon-liquid electron-crystal (PLEC). Although the mobile ions are beneficial to enhancing the electrical transport and phonon scattering, their directional migration driven by an electric field or temperature gradient can result in the unintended deposition of metals, which can impair both the TE properties and the service stability of the materials. Therefore, it is imperative to identify stabilized liquid-like TE materials that can withstand current strike and high temperature.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317723","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":"The Design of Transition Metal Sulfide Cathodes for High-Performance Magnesium-Ion Batteries","authors":"Jianbiao Wang,&nbsp; and ,&nbsp;Zhi Wei Seh*,&nbsp;","doi":"10.1021/accountsmr.4c0018110.1021/accountsmr.4c00181","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00181https://doi.org/10.1021/accountsmr.4c00181","url":null,"abstract":"&lt;p &gt;Despite the widespread use of lithium-ion battery (LIB) technology, conventional LIB suffer from severe limitations (e.g., low energy density, flammable electrolytes) that have prompted much research interest for alternative battery technologies. To overcome the limitations of lithium-ion batteries, magnesium-ion batteries (MIBs) have been proposed as promising alternative energy storage devices, with advantages of high volumetric energy density, high safety, low cost, and environmental benignity. However, the high charge density of Mg&lt;sup&gt;2+&lt;/sup&gt; in MIBs leads to sluggish electrochemical kinetics, owing to the strong electrostatic interactions between the host material and Mg&lt;sup&gt;2+&lt;/sup&gt;. To mitigate this problem, transition metal sulfides (TMS) have been proposed as a solution and intensively researched as cathodes in MIBs, given that the soft features of sulfur can weaken undesirable electrostatic interactions (the low charge density of sulfur and high theoretical capacity). Nevertheless, TMS suffer from large volume variation, poor electronic conductivity as well as detrimental side reactions that all lead to degraded cycling performance. To this end, many solutions have been proposed to resolve these issues.&lt;/p&gt;&lt;p &gt;Herein, we present the latest research on the design of nanostructured TMS (e.g., NiS&lt;sub&gt;2&lt;/sub&gt;, FeS&lt;sub&gt;2&lt;/sub&gt;, and Co&lt;sub&gt;3&lt;/sub&gt;S&lt;sub&gt;4&lt;/sub&gt;/CoS&lt;sub&gt;2&lt;/sub&gt;) and their electrochemical storage performances when used as cathodes in MIBs. We highlight and discuss important findings that include: (1) different synthetic methods for preparing TMS nanostructures, (2) nanostructures (hollow and hierarchical spheres) effectively alleviating the volume variation in the insertion/extraction of Mg&lt;sup&gt;2+&lt;/sup&gt;, (3) sulfur anions enhancing the electrochemical properties, (4) the TMS cathode having a shuttle effect in the electrochemical process that can be retarded by well-designed crystalline structures. (5) density functional theoretical calculations and ab initio molecular dynamics being extensively used to support the experimental results to guide the design of high-performing TMS cathodes, and (6) advanced characterization technologies (e.g., cryogenic transmission electron microscopy, X-ray absorption spectroscopy) being effective tools to investigate the dynamic evolution of TMS cathodes during the discharge/charge process. Moreover, we also evaluate other conventional strategies for designing TMS cathodes. To advance the realization of MIBs as an energy system, recent studies of MIBs in pouch cells are reviewed and discussed with reference to the challenges faced in industrial-scale production. To satisfy increasing demand for cathodes with high energy densities, we demonstrate our prospect in machine learning-driven TMS-based cathode research, given that machine learning is highly suited for discovering new materials and reducing the time taken for developing a technology from the laboratory to commercialization.&lt;/p&gt;&lt;p &gt;","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 11","pages":"1329–1339 1329–1339"},"PeriodicalIF":14.0,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691397","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":"The Design of Transition Metal Sulfide Cathodes for High-Performance Magnesium-Ion Batteries","authors":"Jianbiao Wang, Zhi Wei Seh","doi":"10.1021/accountsmr.4c00181","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00181","url":null,"abstract":"Despite the widespread use of lithium-ion battery (LIB) technology, conventional LIB suffer from severe limitations (e.g., low energy density, flammable electrolytes) that have prompted much research interest for alternative battery technologies. To overcome the limitations of lithium-ion batteries, magnesium-ion batteries (MIBs) have been proposed as promising alternative energy storage devices, with advantages of high volumetric energy density, high safety, low cost, and environmental benignity. However, the high charge density of Mg²⁺ in MIBs leads to sluggish electrochemical kinetics, owing to the strong electrostatic interactions between the host material and Mg²⁺. To mitigate this problem, transition metal sulfides (TMS) have been proposed as a solution and intensively researched as cathodes in MIBs, given that the soft features of sulfur can weaken undesirable electrostatic interactions (the low charge density of sulfur and high theoretical capacity). Nevertheless, TMS suffer from large volume variation, poor electronic conductivity as well as detrimental side reactions that all lead to degraded cycling performance. To this end, many solutions have been proposed to resolve these issues.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"23 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317786","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":"Beyond Drug Delivery: Metal–Organic Framework-Derived Nanosystems for Bone Regeneration under Complicated Pathological Microenvironments","authors":"Yue Zhao, Yuan Xiong, Yanli Zhao","doi":"10.1021/accountsmr.3c00263","DOIUrl":"https://doi.org/10.1021/accountsmr.3c00263","url":null,"abstract":"The development of tactics to effectively manage various bone illnesses, including bone abnormalities, bone infections, fractures, osteoarthritis, osteoporosis, and malignancies, has become a significant public health concern for achieving optimal bone repair outcomes. Conventionally, bisphosphonates and monoclonal antibody medications have shown partial clinical efficacy in bone regeneration. However, issues such as medication resistance, life-threatening off-target side effects, and poor bioavailability continue to affect the majority of patients. Additionally, surgical interventions like subchondral bone microfracture, lavage, debridement, and shaving are primarily effective for minor bone defects. For severe bone defects, the gold standard treatment involves implanting autologous or allogeneic bone grafts. Nevertheless, these grafts come with challenges, such as donor site complications, immune rejection, infections, and limited tissue availability.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"25 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142275757","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":"Intriguing Facets of Solution Processable Cross-Linked Porous Organic Polymers","authors":"Madhurima Sarkar, Suprabhat Sarkar, Monisha Saha, Khushi Luvani, Abhijit Patra","doi":"10.1021/accountsmr.4c00197","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00197","url":null,"abstract":"Porous organic polymers (POPs) are organic networks distinguished by their highly cross-linked structures and their intrinsic porosity. The growing emphasis on POPs is driven by their exceptional hydrothermal stability and diverse application prospects. However, traditional metal-catalyzed high-temperature reactions using rigid building units yield POPs in insoluble powder form, posing challenges for processing into different shapes for device integration and optoelectronic applications. The successful fabrication of a soluble porous organic polymer relies on the employment of specific design strategies and reaction conditions to restrict the molecular weight and extensive cross-linking. In recent decades, researchers have been actively exploring various design strategies, such as limiting molecular weight through hyperbranching and employing controlled polymer growth strategies, to produce solution processable amorphous porous organic polymers. However, targeted synthesis for specific applications remains underdeveloped, justifying the need for an in-depth deliberation of currently available strategies and possible future avenues. In this context, this Account highlights the advancements in the field of solution processable amorphous cross-linked porous organic polymers (SCPOPs), describing diverse design strategies and function-led applications. In order to address the challenges associated with the solution processing of amorphous cross-linked POPs, our research group has focused on fine-tuning the noncovalent interactions among the molecular building blocks, the key to achieving both porosity and solubility in the resultant porous polymer. Following this principle, we introduce long alkyl chains as flexible groups in the monomer and comonomer units that offer a high degree of rotational freedom and a substantial twist angle. This approach facilitates alleviation of the pronounced π–π stacking interaction and extensive cross-linking, thereby enhancing the solubility of the porous polymer. As a result, the facile interaction between the analytes and inefficiently packed polymer chains with aromatic building units in SCPOPs opens the scope for fluorescence-based nitroaromatic sensing in solution. Further, a stable dispersion of fluorescent porous polymer nanoparticles could be an attractive platform for analyte detection in water with enhanced sensitivity. The porous nature of the fluorescent SCPOPs enables the encapsulation of diverse dye molecules, and controlling the energy transfer efficiency from polymer to dyes results in fluorescence tuning, leading to the emission of white light in solution, nanoparticles, gel, and a thin transparent film. Furthermore, we demonstrate that incorporating alternate donor–acceptor units into the cross-linked polymer leads to the optimum band positions for light-driven redox reactions, such as photooxidation of benzylamine and hydrogen evolution. We investigated a biphasic catalysis route employing solution-p","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"13 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142237292","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":"Intriguing Facets of Solution Processable Cross-Linked Porous Organic Polymers","authors":"Madhurima Sarkar,&nbsp;Suprabhat Sarkar,&nbsp;Monisha Saha,&nbsp;Khushi Luvani and Abhijit Patra*,&nbsp;","doi":"10.1021/accountsmr.4c0019710.1021/accountsmr.4c00197","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00197https://doi.org/10.1021/accountsmr.4c00197","url":null,"abstract":"&lt;p &gt;Porous organic polymers (POPs) are organic networks distinguished by their highly cross-linked structures and their intrinsic porosity. The growing emphasis on POPs is driven by their exceptional hydrothermal stability and diverse application prospects. However, traditional metal-catalyzed high-temperature reactions using rigid building units yield POPs in insoluble powder form, posing challenges for processing into different shapes for device integration and optoelectronic applications. The successful fabrication of a soluble porous organic polymer relies on the employment of specific design strategies and reaction conditions to restrict the molecular weight and extensive cross-linking. In recent decades, researchers have been actively exploring various design strategies, such as limiting molecular weight through hyperbranching and employing controlled polymer growth strategies, to produce solution processable amorphous porous organic polymers. However, targeted synthesis for specific applications remains underdeveloped, justifying the need for an in-depth deliberation of currently available strategies and possible future avenues. In this context, this Account highlights the advancements in the field of solution processable amorphous cross-linked porous organic polymers (SCPOPs), describing diverse design strategies and function-led applications. In order to address the challenges associated with the solution processing of amorphous cross-linked POPs, our research group has focused on fine-tuning the noncovalent interactions among the molecular building blocks, the key to achieving both porosity and solubility in the resultant porous polymer. Following this principle, we introduce long alkyl chains as flexible groups in the monomer and comonomer units that offer a high degree of rotational freedom and a substantial twist angle. This approach facilitates alleviation of the pronounced π–π stacking interaction and extensive cross-linking, thereby enhancing the solubility of the porous polymer. As a result, the facile interaction between the analytes and inefficiently packed polymer chains with aromatic building units in SCPOPs opens the scope for fluorescence-based nitroaromatic sensing in solution. Further, a stable dispersion of fluorescent porous polymer nanoparticles could be an attractive platform for analyte detection in water with enhanced sensitivity. The porous nature of the fluorescent SCPOPs enables the encapsulation of diverse dye molecules, and controlling the energy transfer efficiency from polymer to dyes results in fluorescence tuning, leading to the emission of white light in solution, nanoparticles, gel, and a thin transparent film. Furthermore, we demonstrate that incorporating alternate donor–acceptor units into the cross-linked polymer leads to the optimum band positions for light-driven redox reactions, such as photooxidation of benzylamine and hydrogen evolution. We investigated a biphasic catalysis route employing soluti","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 11","pages":"1353–1365 1353–1365"},"PeriodicalIF":14.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691378","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":"From Understanding of Catalyst Functioning toward Controlling Selectivity in CO2 Hydrogenation to Higher Hydrocarbons over Fe-Based Catalysts","authors":"Qingxin Yang*,&nbsp; and ,&nbsp;Evgenii V. Kondratenko*,&nbsp;","doi":"10.1021/accountsmr.4c0016010.1021/accountsmr.4c00160","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00160https://doi.org/10.1021/accountsmr.4c00160","url":null,"abstract":"&lt;p &gt;The conversion of carbon dioxide (CO&lt;sub&gt;2&lt;/sub&gt;) with hydrogen (H&lt;sub&gt;2&lt;/sub&gt;), generated by renewable energy sources, into value-added products is a promising approach to meet future demands for sustainable development. In this context, the hydrogenation of CO&lt;sub&gt;2&lt;/sub&gt; (CO&lt;sub&gt;2&lt;/sub&gt;-FTS) to higher hydrocarbons (C&lt;sub&gt;2+&lt;/sub&gt;), lower olefins, and fuels should be mentioned in particular. These products are used in our daily lives but are currently produced by energy-intensive and CO&lt;sub&gt;2&lt;/sub&gt;-emitting oil-based cracking processes. The environmental compatibility and abundance of iron (Fe) used in CO&lt;sub&gt;2&lt;/sub&gt;-FTS catalysts are also relevant to sustainable development. The CO&lt;sub&gt;2&lt;/sub&gt;-FTS reaction was inspired by the experience accumulated in long-term research on Fischer–Tropsch synthesis with CO (CO-FTS). A simple grafting of catalyst formulations and reaction mechanisms from CO-FTS to CO&lt;sub&gt;2&lt;/sub&gt;-FTS has, however, been proven unsatisfactory, likely due to differences in surface adsorbates, chemical potentials of CO and CO&lt;sub&gt;2&lt;/sub&gt;, and H&lt;sub&gt;2&lt;/sub&gt;O partial pressure. These characteristics affect both the catalyst structure and the reaction pathways. Consequently, CO&lt;sub&gt;2&lt;/sub&gt;-FTS provides higher CH&lt;sub&gt;4&lt;/sub&gt; selectivity but lower C&lt;sub&gt;2+&lt;/sub&gt;-selectivity than does CO-FTS, which appeals to fundamental research to hinder CH&lt;sub&gt;4&lt;/sub&gt; formation.&lt;/p&gt;&lt;p &gt;In this Account, our recent progress in identifying descriptors for purposeful catalyst design is highlighted. Different from the trial-and-error methods and chemist’s intuition strategies commonly used for catalyst design, our initial efforts were devoted to a meta-analysis of literature data to identify catalyst property–performance relationships in CO&lt;sub&gt;2&lt;/sub&gt;-FTS. The resulting hypotheses were experimentally validated and provided the basis for catalyst development. Our other distinguishing strategy is spatially resolved analyses of reaction-induced catalyst restructuring and reaction kinetics. As the catalyst composition changes downstream of the catalyst bed, it is critical to consider the respective profiles to establish proper correlations between the working catalyst phase and species and the kinetics of the formation of selective and unselective reaction products. The importance of in situ characterization studies for understanding reaction-induced catalyst restructuring is especially highlighted. We also demonstrate the power of transient kinetic methods, i.e., temporal analysis of products (TAP) and steady-state isotopic transient kinetic analysis (SSITKA), to identify the mechanism and microkinetics of the activation of CO&lt;sub&gt;2&lt;/sub&gt;, CO, and H&lt;sub&gt;2&lt;/sub&gt; that characterize the efficiency of iron carbides for CO&lt;sub&gt;2&lt;/sub&gt; hydrogenation. The SSITKA method is also instrumental in quantifying the abundance and lifetime of surface intermediates, leading to CO or CH&lt;sub&gt;4&lt;/sub&gt;. The global network of product formation is further established by analyzing","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 11","pages":"1314–1328 1314–1328"},"PeriodicalIF":14.0,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/accountsmr.4c00160","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691377","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}

{"title":"From Understanding of Catalyst Functioning toward Controlling Selectivity in CO2 Hydrogenation to Higher Hydrocarbons over Fe-Based Catalysts","authors":"Qingxin Yang, Evgenii V. Kondratenko","doi":"10.1021/accountsmr.4c00160","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00160","url":null,"abstract":"The conversion of carbon dioxide (CO₂) with hydrogen (H₂), generated by renewable energy sources, into value-added products is a promising approach to meet future demands for sustainable development. In this context, the hydrogenation of CO₂ (CO₂-FTS) to higher hydrocarbons (C₂₊), lower olefins, and fuels should be mentioned in particular. These products are used in our daily lives but are currently produced by energy-intensive and CO₂-emitting oil-based cracking processes. The environmental compatibility and abundance of iron (Fe) used in CO₂-FTS catalysts are also relevant to sustainable development. The CO₂-FTS reaction was inspired by the experience accumulated in long-term research on Fischer–Tropsch synthesis with CO (CO-FTS). A simple grafting of catalyst formulations and reaction mechanisms from CO-FTS to CO₂-FTS has, however, been proven unsatisfactory, likely due to differences in surface adsorbates, chemical potentials of CO and CO₂, and H₂O partial pressure. These characteristics affect both the catalyst structure and the reaction pathways. Consequently, CO₂-FTS provides higher CH₄ selectivity but lower C₂₊-selectivity than does CO-FTS, which appeals to fundamental research to hinder CH₄ formation.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"7 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235485","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}