Chemistry of Materials最新文献

{"title":"Engineering of a Coupled Nanocomposite as a High-Performance Protonic Ceramic Fuel Cell Cathode","authors":"Liang Han, Jiawei Zhang, Minda Zou, Yuchen Zhang, Hongkui Zheng, Ryo Kitamura, Yanfei Cai, Talia Marie Sebastian, Ted Burye, Dong Ding, Zeyu Zhao, Kai He, Jianhua Tong","doi":"10.1021/acs.chemmater.4c02386","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02386","url":null,"abstract":"The lack of high-performance cathode catalysts is a salient issue that bedeviled the commercialization of protonic ceramic fuel cells (PCFCs). Here, we report a remarkable electrocatalytic activity and stability enhancement of cathode electrodes by engineering a coupled nanocomposite. The as-prepared Pr_0.3(Ba_0.5Sr_0.5)_0.7Co_0.8Fe_0.2O_3−δ nanocomposite possesses a bulk cubic phase on which homogeneous and intimate orthorhombic PrCo_0.5Fe_0.5O_3−δ nanoparticles are uniformly decorated. X-ray diffraction and Raman spectroscopy reveal the excellent thermal stability of the nanocomposite. It achieves a high peak power density of 1.02 W cm^–2 based on protonic electrolytes at 600 °C. No noticeable structural degradation is observed over ∼210 h at 550 °C according to scanning electron microscopy analysis. This work demonstrates an effective strategy to boost the performance of perovskite oxides for PCFCs via nanocomposite engineering. It may apply to other catalyst designs and discoveries, such as for batteries, electrolyzers, and membrane reactors.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142579965","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}

{"title":"Machine-Learning-Driven Predictive 3D Ramified Foam Fabrication and Mechanistic Understanding","authors":"Yifei Liu, Donglei Emma Fan","doi":"10.1021/acs.chemmater.4c01790","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01790","url":null,"abstract":"Hierarchical nanosuperstructures, ubiquitously found in nature, present dually enhanced mass transport and interfacial chemical reactions due to their unique 3D cascading features. Their man-made counterparts have demonstrated meritorious benefits toward electrocatalysis, flexible supercapacitors, and water disinfection. However, fabricating 3D superstructures with accurate structural characteristics remains exhaustive and challenging due to a multitude of variables in both experimental conditions and structural features. In this work, we explore three machine learning (ML) methods─linear regression, neural network regression, and Gaussian process regression─and, for the first time, realize accurate predictive fabrication of designed 3D microbranched foams by using a small training data set. Our findings demonstrate an advantageous accuracy of Gaussian process regression of over 87% across all benchmarks. We also effectively unravel the weighted roles of various experimental conditions, shedding light on the synthetic mechanisms. Overall, this work represents a new advance in the ML-enabled predictive fabrication of complex structures and materials with mechanistic elucidation.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574306","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}

{"title":"Machine-Learning-Driven Predictive 3D Ramified Foam Fabrication and Mechanistic Understanding","authors":"Yifei Liu,&nbsp; and ,&nbsp;Donglei Emma Fan*,&nbsp;","doi":"10.1021/acs.chemmater.4c0179010.1021/acs.chemmater.4c01790","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01790https://doi.org/10.1021/acs.chemmater.4c01790","url":null,"abstract":"<p >Hierarchical nanosuperstructures, ubiquitously found in nature, present dually enhanced mass transport and interfacial chemical reactions due to their unique 3D cascading features. Their man-made counterparts have demonstrated meritorious benefits toward electrocatalysis, flexible supercapacitors, and water disinfection. However, fabricating 3D superstructures with accurate structural characteristics remains exhaustive and challenging due to a multitude of variables in both experimental conditions and structural features. In this work, we explore three machine learning (ML) methods─linear regression, neural network regression, and Gaussian process regression─and, for the first time, realize accurate predictive fabrication of designed 3D microbranched foams by using a small training data set. Our findings demonstrate an advantageous accuracy of Gaussian process regression of over 87% across all benchmarks. We also effectively unravel the weighted roles of various experimental conditions, shedding light on the synthetic mechanisms. Overall, this work represents a new advance in the ML-enabled predictive fabrication of complex structures and materials with mechanistic elucidation.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142607995","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}

{"title":"Investigating the Influence of Transition Metal Substitution in Lithium Argyrodites on Structure, Transport, and Solid-State Battery Performance","authors":"Johannes Hartel,&nbsp;Ananya Banik,&nbsp;Md Yusuf Ali,&nbsp;Bianca Helm,&nbsp;Kyra Strotmann,&nbsp;Vasiliki Faka,&nbsp;Oliver Maus,&nbsp;Cheng Li,&nbsp;Hartmut Wiggers and Wolfgang G. Zeier*,&nbsp;","doi":"10.1021/acs.chemmater.4c0228110.1021/acs.chemmater.4c02281","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02281https://doi.org/10.1021/acs.chemmater.4c02281","url":null,"abstract":"<p >Lithium argyrodites have gained significant attention as candidates for solid electrolytes in solid-state batteries due to their superior ionic conductivities and favorable mechanical properties. However, during charging, oxidative decomposition reactions occur at the interface between the solid electrolyte and cathode active material, which impede cell performance. In this study, transition metal substitution of the solid electrolyte is investigated with the intention of tuning the composition of the cathode electrolyte interphase (CEI) and thereby improving the cycling performance. Hence, the Li_{5.5–2<i>x</i>}Zn<i>_x</i>PS_4.5Cl_1.5 (0 ≤ <i>x</i> ≤ 0.15) and Li_{6–2<i>x</i>}Zn<i>_x</i>PS₅Br (0 ≤ <i>x</i> ≤ 0.15) substitution series are investigated to elucidate how substitution affects structure, Li⁺ transport, and the performance of the materials as catholytes in solid-state batteries. Corefinement of the neutron and powder X-ray diffraction data unveils the occupation of Li⁺ positions by Zn²⁺. This leads to blocking of Li⁺ transport pathways within the Li⁺ cages causing a decrease of ionic conductivities along with increasing activation energies for Li⁺ transport. By using a combination of cycling experiments, impedance spectroscopy and X-ray photoelectron spectroscopy, the composition of the CEI and the state-of-charge dependence of the CEI growth when using Li_{5.5–2<i>x</i>}Zn<i>_x</i>PS_4.5Cl_1.5|NCM-83 composites was investigated in half-cells, revealing that Zn²⁺ substitution leads to faster decomposition kinetics and affects the CEI composition. Overall, this work explores the influence of Li⁺ substitution by Zn²⁺ on structure and transport in lithium argyrodites and the potential of transition metal substitutions as means to tune the kinetics of CEI growth, the CEI composition, and thereby cell performance.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608151","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}

{"title":"Microscopic Mechanisms of Reaction-Coupled Acid Diffusion in Chemically Amplified Photoresists","authors":"Zilin Wang, Hong Du, Hanshen Xin, Jie Xue, Jianhua Zhang, Haoyuan Li","doi":"10.1021/acs.chemmater.4c02731","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02731","url":null,"abstract":"Diffusion in photoresists is a fundamental process that significantly impacts micro-nano manufacturing. However, it often intertwines with chemical reactions, leading to intricate kinetics that compounds our comprehension. Here, we successfully applied all-atom molecular dynamics simulations to simultaneously describe the diffusion of acids and the deprotection reactions they catalyze in extreme ultraviolet photoresists, which are critical materials for high-resolution patterning. The results show that acids hop between binding sites with the aid of the other species present in photoresists, akin to observations of ion transport in organic electrolytes. The deprotection reactions enable acids to overcome spatially prohibitive barriers. These chemical reactions also create local free volume, facilitating the motion of the organic matrix and consequently promoting acid movement. We show that by simultaneously describing diffusion and chemical reactions, atomic-level simulations can reproduce the features of experimental reaction dynamics, highlighting the potential of molecular modeling in advancing photoresist design. These insights broaden our understanding of diffusion in organic solids and serve as a theoretical reference in the development of photoresists for higher performances.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142563227","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}

{"title":"Microscopic Mechanisms of Reaction-Coupled Acid Diffusion in Chemically Amplified Photoresists","authors":"Zilin Wang,&nbsp;Hong Du,&nbsp;Hanshen Xin,&nbsp;Jie Xue,&nbsp;Jianhua Zhang and Haoyuan Li*,&nbsp;","doi":"10.1021/acs.chemmater.4c0273110.1021/acs.chemmater.4c02731","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02731https://doi.org/10.1021/acs.chemmater.4c02731","url":null,"abstract":"<p >Diffusion in photoresists is a fundamental process that significantly impacts micro-nano manufacturing. However, it often intertwines with chemical reactions, leading to intricate kinetics that compounds our comprehension. Here, we successfully applied all-atom molecular dynamics simulations to simultaneously describe the diffusion of acids and the deprotection reactions they catalyze in extreme ultraviolet photoresists, which are critical materials for high-resolution patterning. The results show that acids hop between binding sites with the aid of the other species present in photoresists, akin to observations of ion transport in organic electrolytes. The deprotection reactions enable acids to overcome spatially prohibitive barriers. These chemical reactions also create local free volume, facilitating the motion of the organic matrix and consequently promoting acid movement. We show that by simultaneously describing diffusion and chemical reactions, atomic-level simulations can reproduce the features of experimental reaction dynamics, highlighting the potential of molecular modeling in advancing photoresist design. These insights broaden our understanding of diffusion in organic solids and serve as a theoretical reference in the development of photoresists for higher performances.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608142","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}

{"title":"Investigating the Influence of Transition Metal Substitution in Lithium Argyrodites on Structure, Transport, and Solid-State Battery Performance","authors":"Johannes Hartel, Ananya Banik, Md Yusuf Ali, Bianca Helm, Kyra Strotmann, Vasiliki Faka, Oliver Maus, Cheng Li, Hartmut Wiggers, Wolfgang G. Zeier","doi":"10.1021/acs.chemmater.4c02281","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02281","url":null,"abstract":"Lithium argyrodites have gained significant attention as candidates for solid electrolytes in solid-state batteries due to their superior ionic conductivities and favorable mechanical properties. However, during charging, oxidative decomposition reactions occur at the interface between the solid electrolyte and cathode active material, which impede cell performance. In this study, transition metal substitution of the solid electrolyte is investigated with the intention of tuning the composition of the cathode electrolyte interphase (CEI) and thereby improving the cycling performance. Hence, the Li_{5.5–2<i>x</i>}Zn<i>_x</i>PS_4.5Cl_1.5 (0 ≤ <i>x</i> ≤ 0.15) and Li_{6–2<i>x</i>}Zn<i>_x</i>PS₅Br (0 ≤ <i>x</i> ≤ 0.15) substitution series are investigated to elucidate how substitution affects structure, Li⁺ transport, and the performance of the materials as catholytes in solid-state batteries. Corefinement of the neutron and powder X-ray diffraction data unveils the occupation of Li⁺ positions by Zn²⁺. This leads to blocking of Li⁺ transport pathways within the Li⁺ cages causing a decrease of ionic conductivities along with increasing activation energies for Li⁺ transport. By using a combination of cycling experiments, impedance spectroscopy and X-ray photoelectron spectroscopy, the composition of the CEI and the state-of-charge dependence of the CEI growth when using Li_{5.5–2<i>x</i>}Zn<i>_x</i>PS_4.5Cl_1.5|NCM-83 composites was investigated in half-cells, revealing that Zn²⁺ substitution leads to faster decomposition kinetics and affects the CEI composition. Overall, this work explores the influence of Li⁺ substitution by Zn²⁺ on structure and transport in lithium argyrodites and the potential of transition metal substitutions as means to tune the kinetics of CEI growth, the CEI composition, and thereby cell performance.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142563226","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}

{"title":"Highly Stable Bismuth-Based Layered Oxides Modified by Phytic Acid for Anhydrous and Water-Assisted Proton Conductivity","authors":"Bo Hu, Qing Fang, Bailing Liu, Jianxin Ma, Qingbo An, Hong-Ying Zang, Yang-Guang Li, Haiming Xie, Zhong-Min Su","doi":"10.1021/acs.chemmater.4c02267","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02267","url":null,"abstract":"Proton-conducting materials serving as key components in various electrochemical and energy conversion devices have attracted a great deal of attention. The creation of superior proton-conducting materials in a wide temperature range under both humidified and anhydrous conditions is of great significance for practical applications. In this paper, we develop a coprecipitation synthesis approach for a new proton-conducting nanocomposite, [Bi₂O₂]H_<i>x</i>-PA_0.28, which consists of a layered framework with [Bi₂O₂]²⁺ and phytic acid (C₆H₁₈O₂₄P₆, abbreviated as PA) existing as interlayer-embedded charge-balancing anions. Infrared spectroscopy (FTIR), solid-state NMR, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) suggest that oxygen atoms on the surface of the [Bi₂O₂]²⁺ layer bridge the uncoordinated oxygen atoms on the phosphate group to form a strong hydrogen bonding network. This leads to a water-assisted proton conductivity of 1.76 × 10^–2 S cm^–1 at 90 °C under 98% RH and even a stable anhydrous proton conductivity of 5.24 × 10^–3 S cm^–1 at 150 °C. Isotope effect tests have verified the selective transmission of hydrogen ions by the composite electrolyte materials. [Bi₂O₂]H_<i>x</i>-PA_0.28 as electrolyte was further assembled into an ion-selective electrode for the recognition of hydrogen ions. Furthermore, open circuit potential time (OCPT) testing further confirms that solid-state electrolytes composed of [Bi₂O₂]H_<i>x</i>-PA_0.28 exhibit a good electrochemical stability. This work broadens the possibilities for the development of solid-state proton conductors in a wide temperature range, even under anhydrous conditions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562353","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}

{"title":"Selective Hydrogenation of α,β-Unsaturated Aldehydes Over Intermetallic Compounds─A Critical Review","authors":"Paweł Adamski, Hongjun Zhang, Simer Kaur, Xiao Chen, Changhai Liang, Marc Armbrüster","doi":"10.1021/acs.chemmater.4c02648","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02648","url":null,"abstract":"The selective hydrogenation of α,β-unsaturated aldehydes is a complex reaction. Of industrial interest is the thermodynamically unfavored hydrogenation of the carbonyl group, which is a prerequisite for the synthesis of pharmaceuticals and fragrances. Several strategies to enhance the selectivity using intermetallic compounds have been proposed, which are summarized and critically assessed concerning discrepancies between the reports in literature. Analysis shows that strategies enabling vertical adsorption of α,β-unsaturated aldehydes via the carbonyl group yield high selectivities to unsaturated alcohols. The frequently reported influence of charge transfer, which involves the presence of an intermetallic compound with high electronegativity difference of the constituent elements, does not correlate reliably with selectivity. Evaluation of the literature reveals that often a number of different influence factors might be responsible for enhanced selectivity, which are frequently hard to disentangle.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562155","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}

{"title":"Highly Stable Bismuth-Based Layered Oxides Modified by Phytic Acid for Anhydrous and Water-Assisted Proton Conductivity","authors":"Bo Hu,&nbsp;Qing Fang,&nbsp;Bailing Liu*,&nbsp;Jianxin Ma,&nbsp;Qingbo An,&nbsp;Hong-Ying Zang*,&nbsp;Yang-Guang Li*,&nbsp;Haiming Xie and Zhong-Min Su,&nbsp;","doi":"10.1021/acs.chemmater.4c0226710.1021/acs.chemmater.4c02267","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02267https://doi.org/10.1021/acs.chemmater.4c02267","url":null,"abstract":"<p >Proton-conducting materials serving as key components in various electrochemical and energy conversion devices have attracted a great deal of attention. The creation of superior proton-conducting materials in a wide temperature range under both humidified and anhydrous conditions is of great significance for practical applications. In this paper, we develop a coprecipitation synthesis approach for a new proton-conducting nanocomposite, [Bi₂O₂]H_<i>x</i>-PA_0.28, which consists of a layered framework with [Bi₂O₂]²⁺ and phytic acid (C₆H₁₈O₂₄P₆, abbreviated as PA) existing as interlayer-embedded charge-balancing anions. Infrared spectroscopy (FTIR), solid-state NMR, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) suggest that oxygen atoms on the surface of the [Bi₂O₂]²⁺ layer bridge the uncoordinated oxygen atoms on the phosphate group to form a strong hydrogen bonding network. This leads to a water-assisted proton conductivity of 1.76 × 10^–2 S cm^–1 at 90 °C under 98% RH and even a stable anhydrous proton conductivity of 5.24 × 10^–3 S cm^–1 at 150 °C. Isotope effect tests have verified the selective transmission of hydrogen ions by the composite electrolyte materials. [Bi₂O₂]H_<i>x</i>-PA_0.28 as electrolyte was further assembled into an ion-selective electrode for the recognition of hydrogen ions. Furthermore, open circuit potential time (OCPT) testing further confirms that solid-state electrolytes composed of [Bi₂O₂]H_<i>x</i>-PA_0.28 exhibit a good electrochemical stability. This work broadens the possibilities for the development of solid-state proton conductors in a wide temperature range, even under anhydrous conditions.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608589","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}