Pub Date : 2025-04-08DOI: 10.1021/acs.chemmater.5c0011110.1021/acs.chemmater.5c00111
Annalise E. Maughan*, Eric S. Toberer* and Alexandra Zevalkink*,
{"title":"Integrating Large Language Models into the Chemistry and Materials Science Laboratory Curricula","authors":"Annalise E. Maughan*, Eric S. Toberer* and Alexandra Zevalkink*, ","doi":"10.1021/acs.chemmater.5c0011110.1021/acs.chemmater.5c00111","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00111https://doi.org/10.1021/acs.chemmater.5c00111","url":null,"abstract":"","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 7","pages":"2389–2394 2389–2394"},"PeriodicalIF":7.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143790248","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-04DOI: 10.1021/acs.chemmater.5c00163
Shruti Iyer, Nicholas E. Jackson
Future soft materials and polymer chemistries will require innovative nonpetroleum sourcing pathways. While leveraging microbial metabolites derived from biological feedstocks possesses high potential in many avenues of chemical development, the applicability of this paradigm to the specifics of soft materials chemistry is unclear. Here, we construct a chemical reaction network based on databases of common microbial metabolites and the USPTO reaction set to examine what is possible in the chemical space of metabolite-derived chemistries of relevance to soft materials. We observe that the accessible chemical space of our chemical reaction network possesses strong microbe-specific chemical diversity and that this space saturates rapidly within three synthetic steps applied to the original microbial metabolites. Importantly, we show that the chemical space accessible from metabolite precursors possesses significant overlap with existing petrochemical building blocks, known and proposed synthetically feasible polymer monomers, and the chemical space of common organic semiconductors and redox active materials. The biases induced by the metabolite and reaction databases that parametrize our reaction network are analyzed as a function of chemical functional groups, and pathways toward broader sets of chemistries and reactions are outlined. This work introduces a computational framework for soft materials discovery with the potential to accelerate the identification of soft materials relevant to metabolic engineering targets and nonpetroleum sourcing pathways for existing soft materials.
{"title":"In Silico Exploration of Metabolite-Derived Soft Materials Using a Chemical Reaction Network","authors":"Shruti Iyer, Nicholas E. Jackson","doi":"10.1021/acs.chemmater.5c00163","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00163","url":null,"abstract":"Future soft materials and polymer chemistries will require innovative nonpetroleum sourcing pathways. While leveraging microbial metabolites derived from biological feedstocks possesses high potential in many avenues of chemical development, the applicability of this paradigm to the specifics of soft materials chemistry is unclear. Here, we construct a chemical reaction network based on databases of common microbial metabolites and the USPTO reaction set to examine what is possible in the chemical space of metabolite-derived chemistries of relevance to soft materials. We observe that the accessible chemical space of our chemical reaction network possesses strong microbe-specific chemical diversity and that this space saturates rapidly within three synthetic steps applied to the original microbial metabolites. Importantly, we show that the chemical space accessible from metabolite precursors possesses significant overlap with existing petrochemical building blocks, known and proposed synthetically feasible polymer monomers, and the chemical space of common organic semiconductors and redox active materials. The biases induced by the metabolite and reaction databases that parametrize our reaction network are analyzed as a function of chemical functional groups, and pathways toward broader sets of chemistries and reactions are outlined. This work introduces a computational framework for soft materials discovery with the potential to accelerate the identification of soft materials relevant to metabolic engineering targets and nonpetroleum sourcing pathways for existing soft materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"20 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776013","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-04DOI: 10.1021/acs.chemmater.4c03477
Fabian Pieck, Ralf Tonner-Zech
Area-selective atomic layer deposition (AS-ALD) has emerged as a transformative technique in nanotechnology, enabling the precise deposition of materials on designated substrates while preventing unwanted growth on adjacent surfaces. This capability is critical for applications in microelectronics, catalysis, and energy technologies. Computational methods, particularly density functional theory (DFT), are indispensable for uncovering the mechanisms underlying AS-ALD, providing insights into surface interactions, selectivity mechanisms, and precursor design. This review introduces the theoretical background of computational techniques applied to AS-ALD and provides a detailed overview of their applications. Special emphasis is placed on the use of ab initio methods to explore surface chemistry, optimize precursor and inhibitor properties, and improve selectivity. A comprehensive overview of the literature is given with an analysis of research questions targeted, and methods used. By consolidating the state of knowledge and identifying future challenges, this work aims to guide researchers in further leveraging computational approaches to drive innovations in AS-ALD processes.
{"title":"Computational Ab Initio Approaches for Area-Selective Atomic Layer Deposition: Methods, Status, and Perspectives","authors":"Fabian Pieck, Ralf Tonner-Zech","doi":"10.1021/acs.chemmater.4c03477","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03477","url":null,"abstract":"Area-selective atomic layer deposition (AS-ALD) has emerged as a transformative technique in nanotechnology, enabling the precise deposition of materials on designated substrates while preventing unwanted growth on adjacent surfaces. This capability is critical for applications in microelectronics, catalysis, and energy technologies. Computational methods, particularly density functional theory (DFT), are indispensable for uncovering the mechanisms underlying AS-ALD, providing insights into surface interactions, selectivity mechanisms, and precursor design. This review introduces the theoretical background of computational techniques applied to AS-ALD and provides a detailed overview of their applications. Special emphasis is placed on the use of <i>ab initio</i> methods to explore surface chemistry, optimize precursor and inhibitor properties, and improve selectivity. A comprehensive overview of the literature is given with an analysis of research questions targeted, and methods used. By consolidating the state of knowledge and identifying future challenges, this work aims to guide researchers in further leveraging computational approaches to drive innovations in AS-ALD processes.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"89 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776012","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-04DOI: 10.1021/acs.chemmater.5c00287
Henglong Li, Pengheng Li, Min Lin, Xing Zhu
The design of oxygen carriers is essential for the chemical looping partial oxidation of methane (CL-POM) in syngas production. LaFeO3 is a promising oxygen storage material, but the impact of its morphology on the reaction characteristics and mechanisms in CL-POM remains unclear. Herein, we synthesized and characterized LaFeO3 samples with diverse morphologies (cube, porous microsphere, irregular nanoparticle, and polyhedron) to explore how morphology governs crystal plane exposure, oxygen vacancy formation, and oxygen migration. Results showed that cubic LaFeO3 not only achieved outstanding oxygen storage capacity (4.18 mmol/g), 2.5 times that of the other three samples combined (1.64 mmol/g), but also demonstrated superior methane reactivity with good low-temperature activity (initial reaction temperature of 500 °C) and the highest methane conversion (78.26% at 750 °C). This impressive performance is due to the synergy between oxygen vacancies and the (110) crystal plane, which optimizes oxygen release and enhances methane adsorption and dissociation. DFT calculations further confirmed that the (110) plane has lower energy barriers for reaction processes than the (100) plane, and more oxygen vacancies enhance reactivity and oxygen migration. This work underscores the pivotal role of LaFeO3 morphology in advancing the design of oxygen storage materials and a redox catalyst.
{"title":"Effects of LaFeO3 Morphology on Oxygen Species and Chemical Looping Partial Oxidation of Methane","authors":"Henglong Li, Pengheng Li, Min Lin, Xing Zhu","doi":"10.1021/acs.chemmater.5c00287","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00287","url":null,"abstract":"The design of oxygen carriers is essential for the chemical looping partial oxidation of methane (CL-POM) in syngas production. LaFeO<sub>3</sub> is a promising oxygen storage material, but the impact of its morphology on the reaction characteristics and mechanisms in CL-POM remains unclear. Herein, we synthesized and characterized LaFeO<sub>3</sub> samples with diverse morphologies (cube, porous microsphere, irregular nanoparticle, and polyhedron) to explore how morphology governs crystal plane exposure, oxygen vacancy formation, and oxygen migration. Results showed that cubic LaFeO<sub>3</sub> not only achieved outstanding oxygen storage capacity (4.18 mmol/g), 2.5 times that of the other three samples combined (1.64 mmol/g), but also demonstrated superior methane reactivity with good low-temperature activity (initial reaction temperature of 500 °C) and the highest methane conversion (78.26% at 750 °C). This impressive performance is due to the synergy between oxygen vacancies and the (110) crystal plane, which optimizes oxygen release and enhances methane adsorption and dissociation. DFT calculations further confirmed that the (110) plane has lower energy barriers for reaction processes than the (100) plane, and more oxygen vacancies enhance reactivity and oxygen migration. This work underscores the pivotal role of LaFeO<sub>3</sub> morphology in advancing the design of oxygen storage materials and a redox catalyst.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"47 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776014","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-04DOI: 10.1021/acs.chemmater.4c03274
Elena Castagnotto, Stefano Alberti, Marta Campolucci, Pietro Manfrinetti, Maurizio Ferretti, Federico Locardi
Cadmium zinc sulfide pigments (CdxZn1–xS) have been extensively used in art and industry for their bright colors. However, concerns exist over their long-term chemical stability. Due to their semiconductive properties under light exposure, these compounds may trigger photocatalytic processes that can lead to degradation issues in artworks. This study aims to replicate and compare the historical wet and dry synthesis of CdxZn1–xS pigments and investigate their photocatalytic behavior, specifically their reactivity and ion leaching predispositions. Using adapted historical methods, we synthesized a series of CdxZn1–xS pigments and fully characterized them using a range of analytical techniques. Their photocatalytic activity was evaluated against methylene blue dye under simulated sunlight, alongside a concomitant assessment of metal ion leaching. These experiments provide valuable insights into the historical pigments photocatalytic behavior, proposing key indicators of pigment reactivity in real artworks and demonstrating the origin of the inherent instability of historically synthesized pigments, particularly those made via wet methods. Under solar simulation, cubic nanosized pigments with 20% and 40% zinc content exhibit the highest degradation activity. This process is accompanied by the leaching of Cd2+ and Zn2+ ions, which may contribute to the formation of undesirable secondary products. The same pigments exhibited ion leaching even in the dark, although at significantly lower levels.
{"title":"Photocorrosion Stability of CdxZn1–xS Yellow-Orange Pigments","authors":"Elena Castagnotto, Stefano Alberti, Marta Campolucci, Pietro Manfrinetti, Maurizio Ferretti, Federico Locardi","doi":"10.1021/acs.chemmater.4c03274","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03274","url":null,"abstract":"Cadmium zinc sulfide pigments (Cd<sub><i>x</i></sub>Zn<sub>1–<i>x</i></sub>S) have been extensively used in art and industry for their bright colors. However, concerns exist over their long-term chemical stability. Due to their semiconductive properties under light exposure, these compounds may trigger photocatalytic processes that can lead to degradation issues in artworks. This study aims to replicate and compare the historical wet and dry synthesis of Cd<sub><i>x</i></sub>Zn<sub>1–<i>x</i></sub>S pigments and investigate their photocatalytic behavior, specifically their reactivity and ion leaching predispositions. Using adapted historical methods, we synthesized a series of Cd<sub><i>x</i></sub>Zn<sub>1–<i>x</i></sub>S pigments and fully characterized them using a range of analytical techniques. Their photocatalytic activity was evaluated against methylene blue dye under simulated sunlight, alongside a concomitant assessment of metal ion leaching. These experiments provide valuable insights into the historical pigments photocatalytic behavior, proposing key indicators of pigment reactivity in real artworks and demonstrating the origin of the inherent instability of historically synthesized pigments, particularly those made via wet methods. Under solar simulation, cubic nanosized pigments with 20% and 40% zinc content exhibit the highest degradation activity. This process is accompanied by the leaching of Cd<sup>2+</sup> and Zn<sup>2+</sup> ions, which may contribute to the formation of undesirable secondary products. The same pigments exhibited ion leaching even in the dark, although at significantly lower levels.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"18 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782897","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1021/acs.chemmater.5c00248
Xiang Zhang, Mingfei Xu, Zhi Kai Ng, Robert Vajtai, Edwin Hang Tong Teo, Yuji Zhao, Pulickel M. Ajayan
Diamond, with its extraordinary physical and electrical properties, has emerged as a transformative material for next-generation electronics. Its ultrawide bandgap, superior thermal conductivity, high carrier mobility, and excellent mechanical characteristics uniquely position it to address the limitations of traditional semiconductor materials. However, realizing the full potential of diamond in electronic applications requires overcoming significant challenges in its synthesis scalability, defect and dislocation control, and advanced device fabrication. In this Perspective, we discuss strategies and recent advancements in the synthesis of single-crystalline diamond in wafer scales as well as the reduction of defects and dislocations. The development of new diamond morphologies is also reviewed, underscoring their potential to modify properties and broaden application domains. Furthermore, we highlight the progress in engineering diamond-based electronic devices, particularly, field-effect transistors (FETs). Innovations in surface conductivity optimization and the realization of stable, normally off-device operation have enhanced the performance and reliability of diamond devices. Key areas for future research are proposed throughout, offering insights into the opportunities and challenges that remain in diamond synthesis and harnessing diamond’s full potential for next-generation electronic applications.
{"title":"Diamond: Recent Progress in Synthesis and Its Potential in Electronics","authors":"Xiang Zhang, Mingfei Xu, Zhi Kai Ng, Robert Vajtai, Edwin Hang Tong Teo, Yuji Zhao, Pulickel M. Ajayan","doi":"10.1021/acs.chemmater.5c00248","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00248","url":null,"abstract":"Diamond, with its extraordinary physical and electrical properties, has emerged as a transformative material for next-generation electronics. Its ultrawide bandgap, superior thermal conductivity, high carrier mobility, and excellent mechanical characteristics uniquely position it to address the limitations of traditional semiconductor materials. However, realizing the full potential of diamond in electronic applications requires overcoming significant challenges in its synthesis scalability, defect and dislocation control, and advanced device fabrication. In this Perspective, we discuss strategies and recent advancements in the synthesis of single-crystalline diamond in wafer scales as well as the reduction of defects and dislocations. The development of new diamond morphologies is also reviewed, underscoring their potential to modify properties and broaden application domains. Furthermore, we highlight the progress in engineering diamond-based electronic devices, particularly, field-effect transistors (FETs). Innovations in surface conductivity optimization and the realization of stable, normally off-device operation have enhanced the performance and reliability of diamond devices. Key areas for future research are proposed throughout, offering insights into the opportunities and challenges that remain in diamond synthesis and harnessing diamond’s full potential for next-generation electronic applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"16 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1021/acs.chemmater.4c03429
Philipp Groppe, Valentin Müller, Johannes Will, Xin Zhou, Kailun Zhang, Michael S. Moritz, Christian Papp, Jörg Libuda, Tanja Retzer, Erdmann Spiecker, Julien Bachmann, Karl Mandel, Susanne Wintzheimer
The controlled assembly of supraparticles by using spray-drying enables the synthesis of nanoporous materials. Changing the size of the constituent nanoparticles or their agglomeration states provides access to a diverse range of pore frameworks. This turns supraparticles into ideal scaffolds in heterogeneous catalysis. The combination of supraparticles with atomic layer deposition (ALD) as a surface functionalization technique offers excellent control over the deposition of a functional material and its distribution over the scaffold on the nanoscale. This work reports the combination of SiO2 supraparticles as tunable scaffolds and their loading with a platinum-based ALD catalyst. The deliberate adjustment of the scaffold pore framework via spray-drying and its effect on the catalyst deposition are highlighted. Furthermore, varying numbers of Pt ALD cycles are applied to explore the capability of the combination approach with respect to catalyst loading and Pt efficiency. High-resolution electron microscopy reveals ultrasmall Pt clusters deposited on the supraparticles after the very first ALD cycle. Using the hydrogenation of 4-nitrophenol as a demonstration, the impact of the pore framework and the Pt deposition variation in ALD on the catalytic functionality is investigated.
{"title":"Atomic Layer Deposition on Spray-Dried Supraparticles to Rationally Design Catalysts with Ultralow Noble Metal Loadings","authors":"Philipp Groppe, Valentin Müller, Johannes Will, Xin Zhou, Kailun Zhang, Michael S. Moritz, Christian Papp, Jörg Libuda, Tanja Retzer, Erdmann Spiecker, Julien Bachmann, Karl Mandel, Susanne Wintzheimer","doi":"10.1021/acs.chemmater.4c03429","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03429","url":null,"abstract":"The controlled assembly of supraparticles by using spray-drying enables the synthesis of nanoporous materials. Changing the size of the constituent nanoparticles or their agglomeration states provides access to a diverse range of pore frameworks. This turns supraparticles into ideal scaffolds in heterogeneous catalysis. The combination of supraparticles with atomic layer deposition (ALD) as a surface functionalization technique offers excellent control over the deposition of a functional material and its distribution over the scaffold on the nanoscale. This work reports the combination of SiO<sub>2</sub> supraparticles as tunable scaffolds and their loading with a platinum-based ALD catalyst. The deliberate adjustment of the scaffold pore framework via spray-drying and its effect on the catalyst deposition are highlighted. Furthermore, varying numbers of Pt ALD cycles are applied to explore the capability of the combination approach with respect to catalyst loading and Pt efficiency. High-resolution electron microscopy reveals ultrasmall Pt clusters deposited on the supraparticles after the very first ALD cycle. Using the hydrogenation of 4-nitrophenol as a demonstration, the impact of the pore framework and the Pt deposition variation in ALD on the catalytic functionality is investigated.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"32 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766525","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The general aspects in the formation mechanism of mesoporous architecture during the dealumination of zeolites are not fully elucidated owing to their complexity, wherein the creation of dealuminated species and pore structural change can occur in diverse ways. In particular, there is still a lack of direct evidence of intermediate states of the mesopore formation, i.e., the detailed location, precise structure, and behavior of the dealuminated species. Herein, integrated techniques of recently developed high-resolution, low-accelerating-voltage field-emission scanning electron microscope (FE-SEM) and energy-dispersive X-ray spectroscopy (EDS) enable direct observation and comparative investigation of the structural and compositional evolution inside zeolite Y with a wide range of Si/Al ratios realized by sequential dealumination. A systematic FE-SEM observation in the cross-section of zeolite Y (fabricated by Ar-BIB milling) revealed that steaming and calcination created a complex local structure in submicrometer-scale regions with bright contrast originating from high-density Al-rich amorphous components. Results of Ar physisorption analyses suggested that steaming and calcination force to eject Al atoms from the zeolite Y framework and create mesopores in it, but this extra-framework Al (EFAl) does not fill micro- and mesopores, which strictly contradicts the previous mechanism. Local condensation of the EFAl leads to a partial collapse of the framework, which transforms into segregated Al-rich amorphous aluminosilicate regions. Further removal of segregated amorphous aluminosilicate via acid leaching significantly led to the additional formation of mesopores. Especially with regard to the internal structure, our concept of the direct visualization approach can be effectively used as a versatile technique to unveil the detailed features of dealuminated species correlated with step-by-step mesopore formation in the dealumination of zeolites.
{"title":"Direct Visualization of the Dealumination Process on Zeolite Y: How Was the Mesoporous Architecture Formed?","authors":"Yoshihiro Kamimura, Tetsuya Kodaira, Hiroki Yamada, Norihito Hiyoshi, Akira Endo","doi":"10.1021/acs.chemmater.4c03233","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03233","url":null,"abstract":"The general aspects in the formation mechanism of mesoporous architecture during the dealumination of zeolites are not fully elucidated owing to their complexity, wherein the creation of dealuminated species and pore structural change can occur in diverse ways. In particular, there is still a lack of direct evidence of intermediate states of the mesopore formation, i.e., the detailed location, precise structure, and behavior of the dealuminated species. Herein, integrated techniques of recently developed high-resolution, low-accelerating-voltage field-emission scanning electron microscope (FE-SEM) and energy-dispersive X-ray spectroscopy (EDS) enable direct observation and comparative investigation of the structural and compositional evolution inside zeolite Y with a wide range of Si/Al ratios realized by sequential dealumination. A systematic FE-SEM observation in the cross-section of zeolite Y (fabricated by Ar-BIB milling) revealed that steaming and calcination created a complex local structure in submicrometer-scale regions with bright contrast originating from high-density Al-rich amorphous components. Results of Ar physisorption analyses suggested that steaming and calcination force to eject Al atoms from the zeolite Y framework and create mesopores in it, but this extra-framework Al (EFAl) does not fill micro- and mesopores, which strictly contradicts the previous mechanism. Local condensation of the EFAl leads to a partial collapse of the framework, which transforms into segregated Al-rich amorphous aluminosilicate regions. Further removal of segregated amorphous aluminosilicate via acid leaching significantly led to the additional formation of mesopores. Especially with regard to the internal structure, our concept of the direct visualization approach can be effectively used as a versatile technique to unveil the detailed features of dealuminated species correlated with step-by-step mesopore formation in the dealumination of zeolites.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"6 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776016","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1021/acs.chemmater.5c00206
Emily Milan, James A. Quirk, Kenjiro Hashi, John Cattermull, Andrew L. Goodwin, James A. Dawson, Mauro Pasta
In this paper, we build on previous work to characterize a phase with stoichiometry Li3(OH)2Br existing between ∼225 and ∼275 °C in the LiBr-LiOH phase diagram. Diffraction studies indicate that the phase takes a hexagonal unit cell, and theoretical modeling is used to suggest a possible crystal structure. Nuclear magnetic resonance spectroscopy and electrochemical impedance spectroscopy measurements demonstrate excellent lithium-ion dynamics in this phase, with an ionic conductivity of 0.12 S cm–1 at 250 °C. Initial attempts to stabilize this phase at room temperature through quenching were not successful. Instead, a metastable state demonstrating poor ionic conductivity is found to form. This is an important consideration for the synthesis of Li2OHBr solid-state electrolytes (also found in the LiBr-LiOH phase diagram) which are synthesized by cooling through phase fields containing Li3(OH)2Br, and are hence susceptible to these impurities.
{"title":"Filling the Gaps in the LiBr-LiOH Phase Diagram: A Study on the High-Temperature Li3(OH)2Br Phase","authors":"Emily Milan, James A. Quirk, Kenjiro Hashi, John Cattermull, Andrew L. Goodwin, James A. Dawson, Mauro Pasta","doi":"10.1021/acs.chemmater.5c00206","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00206","url":null,"abstract":"In this paper, we build on previous work to characterize a phase with stoichiometry Li<sub>3</sub>(OH)<sub>2</sub>Br existing between ∼225 and ∼275 °C in the LiBr-LiOH phase diagram. Diffraction studies indicate that the phase takes a hexagonal unit cell, and theoretical modeling is used to suggest a possible crystal structure. Nuclear magnetic resonance spectroscopy and electrochemical impedance spectroscopy measurements demonstrate excellent lithium-ion dynamics in this phase, with an ionic conductivity of 0.12 S cm<sup>–1</sup> at 250 °C. Initial attempts to stabilize this phase at room temperature through quenching were not successful. Instead, a metastable state demonstrating poor ionic conductivity is found to form. This is an important consideration for the synthesis of Li<sub>2</sub>OHBr solid-state electrolytes (also found in the LiBr-LiOH phase diagram) which are synthesized by cooling through phase fields containing Li<sub>3</sub>(OH)<sub>2</sub>Br, and are hence susceptible to these impurities.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"216 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776018","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1021/acs.chemmater.4c02450
Stefanie M. Müller, Benjamin R. Nelson, Rita Höller, Christoph Waly, Alexander Jelinek, Bruce E. Kirkpatrick, Sean P. Keyser, Christoph Naderer, Dmitry Sivun, Jaroslaw Jacak, Kristi S. Anseth, Christopher N. Bowman, Sandra Schlögl, Thomas Griesser
Photopolymerization-driven additive manufacturing (AM) is a well-established technique to generate polymeric 3D structures with both high resolution and formation in complex geometries. Recent approaches focus on AM techniques that enable multiproperty architectures using wavelength orthogonal photochemistry. Herein, a dual-cure, single-vat resin was developed, based on the radical photopolymerization of a thiol-methacrylate monomer system containing covalently bound chalcone moieties as dimerizable cross-linkers. Thermo-mechanical properties were spatially and systematically controlled via the wavelength-selective [2 + 2] cycloaddition reaction of the chalcone groups. Reaction kinetics were studied with infrared and ultraviolet–visible spectroscopy to ensure sequence-dependent λ-orthogonality during the two-stage illumination process. 3D-structures were fabricated by dynamic light processing (DLP), imprinting, and two-photon lithography (TPL). In particular, the ability to excite both the radical photoinitiator and the chalcone groups separately with TPL in high spatial resolution enabled the production of multifunctional microstructures and represents a versatile concept for the fabrication of soft active devices along various length scales.
{"title":"Chalcones as Wavelength-Selective Cross-Linkers: Multimaterial Additive Manufacturing of Macro- and Microscopic Soft Active Devices","authors":"Stefanie M. Müller, Benjamin R. Nelson, Rita Höller, Christoph Waly, Alexander Jelinek, Bruce E. Kirkpatrick, Sean P. Keyser, Christoph Naderer, Dmitry Sivun, Jaroslaw Jacak, Kristi S. Anseth, Christopher N. Bowman, Sandra Schlögl, Thomas Griesser","doi":"10.1021/acs.chemmater.4c02450","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02450","url":null,"abstract":"Photopolymerization-driven additive manufacturing (AM) is a well-established technique to generate polymeric 3D structures with both high resolution and formation in complex geometries. Recent approaches focus on AM techniques that enable multiproperty architectures using wavelength orthogonal photochemistry. Herein, a dual-cure, single-vat resin was developed, based on the radical photopolymerization of a thiol-methacrylate monomer system containing covalently bound chalcone moieties as dimerizable cross-linkers. Thermo-mechanical properties were spatially and systematically controlled via the wavelength-selective [2 + 2] cycloaddition reaction of the chalcone groups. Reaction kinetics were studied with infrared and ultraviolet–visible spectroscopy to ensure sequence-dependent λ-orthogonality during the two-stage illumination process. 3D-structures were fabricated by dynamic light processing (DLP), imprinting, and two-photon lithography (TPL). In particular, the ability to excite both the radical photoinitiator and the chalcone groups separately with TPL in high spatial resolution enabled the production of multifunctional microstructures and represents a versatile concept for the fabrication of soft active devices along various length scales.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"22 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776015","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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