Pub Date : 2024-10-22DOI: 10.1021/acs.chemmater.4c02118
Md Abdullah Al Muhit, Sean C. Wechsler, Zachary J. L. Bare, CJ Sturgill, Navindra Keerthisinghe, Matthias A. Grasser, Gregory Morrison, Christopher Sutton, Morgan Stefik, Hans-Conrad zur Loye
The demand for fast charging requires high-performance battery materials with improved ionic transport. Wadsley–Roth (WR) structures have garnered attention, where the combination of blocks and shear planes addresses ionic and electronic conductivity, respectively. An improved understanding of structure–property relationships could lead to higher-performance materials. Herein, we report the first single-crystal structures of Nb12MoO33 and Ta12MoO33 that are consistent with other (3 × 4 × ∞) WR phases. The lithiation of Ta12MoO33 is reported to enable an isostructural comparison with Nb12MoO33. These two compounds have similar unit cell volumes and atomic radii, where the Ta12MoO33 unit cell is 0.2 vol % smaller. Despite the similarities in structure, the lithiation capacities, voltage windows, C rate-dependent capacities, and ionic diffusivities are distinctly different. These experimental trends align well with density functional theory calculations showing (1) a lower activation energy for Li transport within Ta12MoO33 consistent with its measured 1.5–4.9-fold higher diffusion coefficients (lithiation) and (2) an ∼25% greater measured lithiation stoichiometry for Nb12MoO33, which is attributed to the calculated smaller octahedral distortions (compared to Ta12MoO33). These findings reveal that smaller channels in Ta12MoO33 stabilize the transition state with 5-fold coordination, which both decreases the activation energy for diffusion and limits the extent of lithiation. Such structure–property trends help in the search for next-generation battery materials.
{"title":"Comparison of Lithium Diffusion in Isostructural Ta12MoO33 and Nb12MoO33: Experimental and Computational Insights from Single Crystals","authors":"Md Abdullah Al Muhit, Sean C. Wechsler, Zachary J. L. Bare, CJ Sturgill, Navindra Keerthisinghe, Matthias A. Grasser, Gregory Morrison, Christopher Sutton, Morgan Stefik, Hans-Conrad zur Loye","doi":"10.1021/acs.chemmater.4c02118","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02118","url":null,"abstract":"The demand for fast charging requires high-performance battery materials with improved ionic transport. Wadsley–Roth (WR) structures have garnered attention, where the combination of blocks and shear planes addresses ionic and electronic conductivity, respectively. An improved understanding of structure–property relationships could lead to higher-performance materials. Herein, we report the first single-crystal structures of Nb<sub>12</sub>MoO<sub>33</sub> and Ta<sub>12</sub>MoO<sub>33</sub> that are consistent with other (3 × 4 × ∞) WR phases. The lithiation of Ta<sub>12</sub>MoO<sub>33</sub> is reported to enable an isostructural comparison with Nb<sub>12</sub>MoO<sub>33</sub>. These two compounds have similar unit cell volumes and atomic radii, where the Ta<sub>12</sub>MoO<sub>33</sub> unit cell is 0.2 vol % smaller. Despite the similarities in structure, the lithiation capacities, voltage windows, C rate-dependent capacities, and ionic diffusivities are distinctly different. These experimental trends align well with density functional theory calculations showing (1) a lower activation energy for Li transport within Ta<sub>12</sub>MoO<sub>33</sub> consistent with its measured 1.5–4.9-fold higher diffusion coefficients (lithiation) and (2) an ∼25% greater measured lithiation stoichiometry for Nb<sub>12</sub>MoO<sub>33</sub>, which is attributed to the calculated smaller octahedral distortions (compared to Ta<sub>12</sub>MoO<sub>33</sub>). These findings reveal that smaller channels in Ta<sub>12</sub>MoO<sub>33</sub> stabilize the transition state with 5-fold coordination, which both decreases the activation energy for diffusion and limits the extent of lithiation. Such structure–property trends help in the search for next-generation battery materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486481","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 : 2024-10-22DOI: 10.1021/acs.chemmater.4c02128
Pan Wang, Jiawei Lin, Zhu Guo, Lingling Mao
Hybrid supramolecular trimetallic halides with a double-shell clathrate structure belong to a type of functional material with complex compositions and wide tunability. The double-shell structure is generally composed of a crown ether molecule sandwiched between different metal halide units. Here, we synthesize six new hybrid trimetallic halides and their solid solutions with the general formula [(A18C6)3MX4][BX4] (where A = K+, Rb+, Cs+; M = Mn2+ or Mn1–xZnx2+; B = In3+; X = Cl– or Br–), abbreviated as A-M-X. Through the structural analysis of the crystal structure and characterizations of the optical properties of these materials, we have found a direct correlation between the photoluminescence quantum yield (PLQY) and the suitability of the coordination between the A-site metal and the crown ether. Specifically, as the radius of the alkali metal increases (from K to Rb), the PLQY decreases due to poorer suitability. The suitability of the coordination has been analyzed in detail by quantifying the structural parameters (i.e., A–O bond distance, O–A–O bond angle, and distance from A metal to the crown ether center). This trend has been further confirmed via two independent systems using solid solutions through M-site alloying and comparing the chloride and bromide analogs. Surprisingly, a selective coordination mode has surfaced when alloying on the A-site, where the larger alkali metal preferentially coordinates with the connected crown ether instead of the isolated one. This effective approach leads to a wide range of tunability of the PLQY from 21.7 to 95.2% within the total 12 materials. Through further analysis, we have found that the substitution of the A-site metal from K to Cs increases the Mn–X distance, which weakens the crystal field strength of Mn and aligns with the observed trend in PLQY. Our work has further expanded the material space of hybrid trimetallic double-shell clathrates and provides determining insights into controlling the structure and PLQY.
{"title":"Impact of Alkali Metal Coordination on the Photoluminescence Quantum Efficiency Trend in Hybrid Supramolecular Trimetallic Halides","authors":"Pan Wang, Jiawei Lin, Zhu Guo, Lingling Mao","doi":"10.1021/acs.chemmater.4c02128","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02128","url":null,"abstract":"Hybrid supramolecular trimetallic halides with a double-shell clathrate structure belong to a type of functional material with complex compositions and wide tunability. The double-shell structure is generally composed of a crown ether molecule sandwiched between different metal halide units. Here, we synthesize six new hybrid trimetallic halides and their solid solutions with the general formula [(<i>A</i>18C6)<sub>3</sub><i>MX</i><sub>4</sub>][<i>BX</i><sub>4</sub>] (where <i>A</i> = K<sup>+</sup>, Rb<sup>+</sup>, Cs<sup>+</sup>; M = Mn<sup>2+</sup> or Mn<sub>1–<i>x</i></sub>Zn<sub><i>x</i><sup>2+</sup></sub>; <i>B</i> = In<sup>3+</sup>; <i>X</i> = Cl<sup>–</sup> or Br<sup>–</sup>), abbreviated as <i>A</i>-<i>M</i>-<i>X</i>. Through the structural analysis of the crystal structure and characterizations of the optical properties of these materials, we have found a direct correlation between the photoluminescence quantum yield (PLQY) and the suitability of the coordination between the <i>A</i>-site metal and the crown ether. Specifically, as the radius of the alkali metal increases (from K to Rb), the PLQY decreases due to poorer suitability. The suitability of the coordination has been analyzed in detail by quantifying the structural parameters (i.e., <i>A</i>–O bond distance, O–<i>A</i>–O bond angle, and distance from <i>A</i> metal to the crown ether center). This trend has been further confirmed via two independent systems using solid solutions through <i>M</i>-site alloying and comparing the chloride and bromide analogs. Surprisingly, a selective coordination mode has surfaced when alloying on the A-site, where the larger alkali metal preferentially coordinates with the connected crown ether instead of the isolated one. This effective approach leads to a wide range of tunability of the PLQY from 21.7 to 95.2% within the total 12 materials. Through further analysis, we have found that the substitution of the <i>A</i>-site metal from K to Cs increases the Mn–<i>X</i> distance, which weakens the crystal field strength of Mn and aligns with the observed trend in PLQY. Our work has further expanded the material space of hybrid trimetallic double-shell clathrates and provides determining insights into controlling the structure and PLQY.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487135","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 : 2024-10-19DOI: 10.1021/acs.chemmater.4c02091
Nikolaos Chalmpes, Iosif Tantis, Ahmed Wasel Alsmaeil, Athanasios B. Bourlinos, Emmanuel P. Giannelis
We report the first synthesis of metal nanoparticles and supported metal nanoparticles on carbon by using hypergolic reactions. Specifically, we report the synthesis of noble metal nanoparticles (Pt, Ag, and Au) using sodium hydride (NaH) as both an ignition trigger and a reducing agent for the corresponding metal salt precursors. In addition, we report the one-step, in situ synthesis of Pt nanoparticles supported on carbon by adding sucrose as the carbon source. The hypergolically synthesized nanoparticles display elliptical morphology and are more crystalline compared with those conventionally synthesized in solution using sodium borohydride (NaBH4). When tested as electrocatalysts, the hypergolic Pt nanoparticles exhibit more than 2 times higher specific electrochemical active surface area (ECSA) and a higher half-wave potential (E1/2) of 0.94 V vs the reversible hydrogen electrode (RHE) compared to the conventionally synthesized ones. In addition, the electrocatalyst based on the in situ synthesized carbon that was decorated with the Pt nanoparticles synthesized hypergolically outperforms an analogous, state of the art, commercial PtC system. For example, the former shows an attractive E1/2 (0.94 V) compared with 0.9 V for the commercial PtC. Accelerated durability tests (ADT) in an alkaline environment add another advantage. After 10 000 cycles, the hypergolically synthesized system shows a smaller reduction of E1/2 and less degradation compared to the commercial PtC (10 mV compared to ∼30 mV). The work described here represents the first reported synthesis using hypergolic reactions of metal nanoparticles as well as supported metal nanoparticles. The properties of the resulting electrocatalysts demonstrate the versatility and promise of the new approach in materials synthesis and open new avenues for further investigation as electrocatalysts.
{"title":"Design, Synthesis, and Evaluation of Noble Metal Nanoparticles and In Situ-Decorated Carbon-Supported Nanoparticle Electrocatalysts Using Hypergolic Reactions","authors":"Nikolaos Chalmpes, Iosif Tantis, Ahmed Wasel Alsmaeil, Athanasios B. Bourlinos, Emmanuel P. Giannelis","doi":"10.1021/acs.chemmater.4c02091","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02091","url":null,"abstract":"We report the first synthesis of metal nanoparticles and supported metal nanoparticles on carbon by using hypergolic reactions. Specifically, we report the synthesis of noble metal nanoparticles (Pt, Ag, and Au) using sodium hydride (NaH) as both an ignition trigger and a reducing agent for the corresponding metal salt precursors. In addition, we report the one-step, in situ synthesis of Pt nanoparticles supported on carbon by adding sucrose as the carbon source. The hypergolically synthesized nanoparticles display elliptical morphology and are more crystalline compared with those conventionally synthesized in solution using sodium borohydride (NaBH<sub>4</sub>). When tested as electrocatalysts, the hypergolic Pt nanoparticles exhibit more than 2 times higher specific electrochemical active surface area (ECSA) and a higher half-wave potential (<i>E</i><sub>1/2</sub>) of 0.94 V vs the reversible hydrogen electrode (RHE) compared to the conventionally synthesized ones. In addition, the electrocatalyst based on the in situ synthesized carbon that was decorated with the Pt nanoparticles synthesized hypergolically outperforms an analogous, state of the art, commercial PtC system. For example, the former shows an attractive <i>E</i><sub>1/2</sub> (0.94 V) compared with 0.9 V for the commercial PtC. Accelerated durability tests (ADT) in an alkaline environment add another advantage. After 10 000 cycles, the hypergolically synthesized system shows a smaller reduction of <i>E</i><sub>1/2</sub> and less degradation compared to the commercial PtC (10 mV compared to ∼30 mV). The work described here represents the first reported synthesis using hypergolic reactions of metal nanoparticles as well as supported metal nanoparticles. The properties of the resulting electrocatalysts demonstrate the versatility and promise of the new approach in materials synthesis and open new avenues for further investigation as electrocatalysts.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449947","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 : 2024-10-19DOI: 10.1021/acs.chemmater.4c02083
Jonathan Schimmels, Willa Mihalyi-Koch, Chris R. Roy, Kyana M. Sanders, John C. Wright, Song Jin
Hybrid organic–inorganic metal halides provide a diverse parameter space in which the optoelectronic properties can be tuned through the composition. The compositional tunability extends to the metal site, which can be expanded from single valent metals (e.g., Pb2+) to multivalent metals (e.g., Ag+ and Bi3+), and the dimension (2D, 1D, or 0D). However, a deeper understanding of how the organic cations template these metal halide structures is needed. Here, we synthesize and study the structures of a series of new layered and low-dimensional metal (Pb, Ag, and Bi) halides templated by the halogenated aryl spacer cations 2-chlorobenzylammonium (2ClBZ) and 3-chloro-2-fluorobenzylammonium (3Cl2FBZ). We report new lead perovskites, (3Cl2FBZ)2PbBr4, (2ClBZ)3PbI5, and (3Cl2FBZ)2PbI4, and compare them to their silver and/or bismuth analogs (2ClBZ)4AgBiBr8, (3Cl2FBZ)4AgBiBr8, (2ClBZ)3Bi2I9, and (3Cl2FBZ)4Bi2I10. In all structures, the halogen-substituted cations result in 2D or “pseudo-2D” layering, but the different halogen substituents introduce different distortions (tilting, octahedral distortion) and dimensional reduction to 1D or 0D depending on the metal and halide compositions. Optical absorption measurements reveal the bandgaps are tunable through metal sites, dimension, and cations to different extents. Furthermore, the 1D (3Cl2FBZ)4Bi2I10 crystallizes in the noncentrosymmetric space group Cmc21 and exhibits second-harmonic generation (SHG). The organic–inorganic interactions and resultant structural distortions examined here provide insights toward the engineering of noncentrosymmetry and dimensional control in hybrid metal halide perovskites.
{"title":"Layered and Low-Dimensional Lead, Silver, and Bismuth Halide Perovskites Directed by Halogen-Substituted Spacer Cations","authors":"Jonathan Schimmels, Willa Mihalyi-Koch, Chris R. Roy, Kyana M. Sanders, John C. Wright, Song Jin","doi":"10.1021/acs.chemmater.4c02083","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02083","url":null,"abstract":"Hybrid organic–inorganic metal halides provide a diverse parameter space in which the optoelectronic properties can be tuned through the composition. The compositional tunability extends to the metal site, which can be expanded from single valent metals (<i>e.g</i>., Pb<sup>2+</sup>) to multivalent metals (<i>e.g</i>., Ag<sup>+</sup> and Bi<sup>3+</sup>), and the dimension (2D, 1D, or 0D). However, a deeper understanding of how the organic cations template these metal halide structures is needed. Here, we synthesize and study the structures of a series of new layered and low-dimensional metal (Pb, Ag, and Bi) halides templated by the halogenated aryl spacer cations 2-chlorobenzylammonium (2ClBZ) and 3-chloro-2-fluorobenzylammonium (3Cl2FBZ). We report new lead perovskites, (3Cl2FBZ)<sub>2</sub>PbBr<sub>4</sub>, (2ClBZ)<sub>3</sub>PbI<sub>5</sub>, and (3Cl2FBZ)<sub>2</sub>PbI<sub>4</sub>, and compare them to their silver and/or bismuth analogs (2ClBZ)<sub>4</sub>AgBiBr<sub>8</sub>, (3Cl2FBZ)<sub>4</sub>AgBiBr<sub>8</sub>, (2ClBZ)<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub>, and (3Cl2FBZ)<sub>4</sub>Bi<sub>2</sub>I<sub>10</sub>. In all structures, the halogen-substituted cations result in 2D or “pseudo-2D” layering, but the different halogen substituents introduce different distortions (tilting, octahedral distortion) and dimensional reduction to 1D or 0D depending on the metal and halide compositions. Optical absorption measurements reveal the bandgaps are tunable through metal sites, dimension, and cations to different extents. Furthermore, the 1D (3Cl2FBZ)<sub>4</sub>Bi<sub>2</sub>I<sub>10</sub> crystallizes in the noncentrosymmetric space group <i>Cmc</i>2<sub>1</sub> and exhibits second-harmonic generation (SHG). The organic–inorganic interactions and resultant structural distortions examined here provide insights toward the engineering of noncentrosymmetry and dimensional control in hybrid metal halide perovskites.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449894","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 : 2024-10-18DOI: 10.1021/acs.chemmater.4c02365
Samantha Harvey, Jonathan M. DeStefano, Jiun-Haw Chu, Daniel R. Gamelin, Brandi M. Cossairt
The ongoing development and eventual implementation of magnetic nanocrystals in devices requires not only syntheses that can bring bulk compositions down to the nanoscale but also a deep understanding of their formation such that size, morphology, and composition can be finely tuned. Chromium chalcogenide spinels are a class of materials that epitomize this dilemma; their unique magnetic and magneto-optical properties make them promising for applications in spintronics, data storage, and quantum information sciences, but only a few compositions have been synthesized as colloidal nanocrystals. Furthermore, these few existing reports lack mechanistic understanding and demonstrate little control over the physical characteristics of the final products. Here, we set forth to understand the synthesis of CuCr2Se4 nanocrystals by examining how the structure, composition, and magnetic properties evolve over the course of the reaction. We find that the material proceeds through binary copper selenide nanocrystal intermediates followed by Cr incorporation via diffusion. This process results in polycrystalline CuCr2Se4 nanocrystals that do not exhibit magnetic ordering until Cu incorporation modifies their stoichiometry and defects are annealed, which takes approximately 40 min at 340 °C to achieve. The resulting CuCr2Se4 nanocrystals show a strongly enhanced magnetic circular dichroism signal at the bulk plasma frequency of ℏωpl ∼ 1.0 eV with a field dependence that reflects magnetization of the Cr3+ spin sublattice. These results highlight the possibility of solution processing strong near-IR magneto-optical materials for future device integration.
{"title":"Understanding the Formation of Colloidal Ferrimagnetic CuCr2Se4 Nanocrystals with Strong Room-Temperature Magnetic Circular Dichroism","authors":"Samantha Harvey, Jonathan M. DeStefano, Jiun-Haw Chu, Daniel R. Gamelin, Brandi M. Cossairt","doi":"10.1021/acs.chemmater.4c02365","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02365","url":null,"abstract":"The ongoing development and eventual implementation of magnetic nanocrystals in devices requires not only syntheses that can bring bulk compositions down to the nanoscale but also a deep understanding of their formation such that size, morphology, and composition can be finely tuned. Chromium chalcogenide spinels are a class of materials that epitomize this dilemma; their unique magnetic and magneto-optical properties make them promising for applications in spintronics, data storage, and quantum information sciences, but only a few compositions have been synthesized as colloidal nanocrystals. Furthermore, these few existing reports lack mechanistic understanding and demonstrate little control over the physical characteristics of the final products. Here, we set forth to understand the synthesis of CuCr<sub>2</sub>Se<sub>4</sub> nanocrystals by examining how the structure, composition, and magnetic properties evolve over the course of the reaction. We find that the material proceeds through binary copper selenide nanocrystal intermediates followed by Cr incorporation via diffusion. This process results in polycrystalline CuCr<sub>2</sub>Se<sub>4</sub> nanocrystals that do not exhibit magnetic ordering until Cu incorporation modifies their stoichiometry and defects are annealed, which takes approximately 40 min at 340 °C to achieve. The resulting CuCr<sub>2</sub>Se<sub>4</sub> nanocrystals show a strongly enhanced magnetic circular dichroism signal at the bulk plasma frequency of <i>ℏ</i>ω<sub>pl</sub> ∼ 1.0 eV with a field dependence that reflects magnetization of the Cr<sup>3+</sup> spin sublattice. These results highlight the possibility of solution processing strong near-IR magneto-optical materials for future device integration.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449948","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}
Conducting polymer hydrogels have been considered as promising materials for flexible sensors. The integrated performances of ultrasoftness, high deformation, mechanical robustness, conformal adhesion, and high sensitivity are of great importance for their applications in wearable sensors but still remains challenging. Herein, a highly deformable conducting polymer hydrogel with ultrasoftness, tear resistance, and self-adhesiveness is fabricated by incorporating poly(3, 4-ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS) and silk sericin (SS) into a covalently cross-linked polyacrylamide (PAM) network. Owing to abundant noncovalent interactions among the folded SS chains, PAM chains, and PEDOT:PSS, the obtained hydrogel shows a low modulus (10.3 kPa), ultrastretchability (>2000%), particularly large biaxial strain (an areal strain of 1700%), high toughness (tearing energy of 2.5 kJ/m2), and good conformal adhesion. As a result, this hydrogel demonstrates superior strain-sensitivity (gauge factor = 13.8) in a broad strain range (2000%) and excellent sensing reproducibility. The hydrogel-based wearable sensor can be used for accurately monitoring large and tiny human movements in real time and serves as bioelectrodes for precise gathering of electrocardiography and electromyography signals, showing great potential for applications in flexible sensing devices.
{"title":"Ultrasoft Conducting Polymer Hydrogels with Large Biaxial Strain and Conformal Adhesion for Sensitive Flexible Sensors","authors":"Xiaojiao Shi, Linli Xu, Qiuli Xu, Na Li, Xinyu Li, Yubin Zhang, Zhihui Qin, Tifeng Jiao","doi":"10.1021/acs.chemmater.4c01909","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01909","url":null,"abstract":"Conducting polymer hydrogels have been considered as promising materials for flexible sensors. The integrated performances of ultrasoftness, high deformation, mechanical robustness, conformal adhesion, and high sensitivity are of great importance for their applications in wearable sensors but still remains challenging. Herein, a highly deformable conducting polymer hydrogel with ultrasoftness, tear resistance, and self-adhesiveness is fabricated by incorporating poly(3, 4-ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS) and silk sericin (SS) into a covalently cross-linked polyacrylamide (PAM) network. Owing to abundant noncovalent interactions among the folded SS chains, PAM chains, and PEDOT:PSS, the obtained hydrogel shows a low modulus (10.3 kPa), ultrastretchability (>2000%), particularly large biaxial strain (an areal strain of 1700%), high toughness (tearing energy of 2.5 kJ/m<sup>2</sup>), and good conformal adhesion. As a result, this hydrogel demonstrates superior strain-sensitivity (gauge factor = 13.8) in a broad strain range (2000%) and excellent sensing reproducibility. The hydrogel-based wearable sensor can be used for accurately monitoring large and tiny human movements in real time and serves as bioelectrodes for precise gathering of electrocardiography and electromyography signals, showing great potential for applications in flexible sensing devices.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448648","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 : 2024-10-18DOI: 10.1021/acs.chemmater.4c02251
Xiang-Jing Kong, Ming-Ming Xu, Tao He, Lin-Hua Xie, Yu-Hui Liu, Xin Zhang, Hao-Tian Wang, Jian-Rong Li
Tailoring a MOF with suitable pore windows for the sieving C3H6/C3H8 separation is attractive but challenging, where controlling the local framework flexibility by introducing functionality provides a solution. In this work, four isoreticular ultramicroporous Zn–triazolate–dicarboxylate frameworks, Zn-ATZ-IP(R) (R = −F, −OH, −NH2, and −CH3) (HATZ = 3-amino-1,2,4-triazole; H2IP-R = R group functionalized isophthalic acid) with variable pore apertures, were targeted as platforms to study the effect of functional groups on their separation performance. Single-component adsorption isotherms uncovered the potential of Zn-ATZ-IP(OH)-a with hydroxyl groups as a sieving adsorbent. Single X-ray diffraction (SXRD) measurements revealed that strong intraframework hydrogen bonds hinder the free torsion of ATZ– ligand in Zn-ATZ-IP(OH)-a, defining rigid pore windows that admit C3H6 while exclude C3H8, whereas other groups give adaptive larger pores that allow both C3H6 and C3H8 in. Further, in situ XRD measurements suggested that temperature alters the strength of hydrogen bonds, making Zn-ATZ-IP(OH)-a ideal for room-temperature sieving of C3H6/C3H8. This work highlights the superiority of customizing sieving pores sustained by hydrogen bonds, which advances the rational design of smart adsorbents for energy-efficient light hydrocarbon separations.
{"title":"Hydrogen Bonds Defined Pore Windows Enable Sieving Separation of Propylene from Propane in an Ultramicroporous Metal–Organic Framework","authors":"Xiang-Jing Kong, Ming-Ming Xu, Tao He, Lin-Hua Xie, Yu-Hui Liu, Xin Zhang, Hao-Tian Wang, Jian-Rong Li","doi":"10.1021/acs.chemmater.4c02251","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02251","url":null,"abstract":"Tailoring a MOF with suitable pore windows for the sieving C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub> separation is attractive but challenging, where controlling the local framework flexibility by introducing functionality provides a solution. In this work, four isoreticular ultramicroporous Zn–triazolate–dicarboxylate frameworks, <b>Zn-ATZ-IP(R)</b> (R = −F, −OH, −NH<sub>2</sub>, and −CH<sub>3</sub>) (HATZ = 3-amino-1,2,4-triazole; H<sub>2</sub>IP-R = R group functionalized isophthalic acid) with variable pore apertures, were targeted as platforms to study the effect of functional groups on their separation performance. Single-component adsorption isotherms uncovered the potential of <b>Zn-ATZ-IP(OH)-a</b> with hydroxyl groups as a sieving adsorbent. Single X-ray diffraction (SXRD) measurements revealed that strong intraframework hydrogen bonds hinder the free torsion of ATZ<sup>–</sup> ligand in <b>Zn-ATZ-IP(OH)-a</b>, defining rigid pore windows that admit C<sub>3</sub>H<sub>6</sub> while exclude C<sub>3</sub>H<sub>8</sub>, whereas other groups give adaptive larger pores that allow both C<sub>3</sub>H<sub>6</sub> and C<sub>3</sub>H<sub>8</sub> in. Further, <i>in situ</i> XRD measurements suggested that temperature alters the strength of hydrogen bonds, making <b>Zn-ATZ-IP(OH)-a</b> ideal for room-temperature sieving of C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub>. This work highlights the superiority of customizing sieving pores sustained by hydrogen bonds, which advances the rational design of smart adsorbents for energy-efficient light hydrocarbon separations.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448642","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 : 2024-10-18DOI: 10.1021/acs.chemmater.3c03002
Songsheng Tao, Jonas Billet, Jonathan De Roo, Simon J. L. Billinge
A detailed workflow is presented for applying attenuated crystal modeling (ACM) of atomic pair distribution functions from TiO2 nanoparticles to understand the structure and morphology of the nanoparticles. We use small-box modeling approaches with the diffpy-CMIsoftware program. The modeling reveals that all synthesis conditions yield nanoparticles with a majority bronze phase and a minority anatase phase, with the synthesis temperature affecting the proportion of impurity phase and the size of the nanoparticles. The fast, straightforward, and reliable workflow is widely applicable for modeling PDFs of most inorganic nanoparticles as long as hypothesized ACM models are available, providing a helpful guide for researchers to analyze the structure of nanoparticles from PDF data.
本文介绍了应用二氧化钛纳米粒子原子对分布函数衰减晶体建模 (ACM) 来了解纳米粒子结构和形态的详细工作流程。我们使用 diffpy-CMI 软件程序进行小盒子建模。建模结果表明，所有合成条件下得到的纳米粒子都是青铜相占大多数，锐钛矿相占少数，合成温度会影响杂质相的比例和纳米粒子的尺寸。只要有假定的 ACM 模型，该快速、直接、可靠的工作流程可广泛应用于大多数无机纳米粒子的 PDF 建模，为研究人员从 PDF 数据分析纳米粒子结构提供了有益的指导。
{"title":"Rapid Modeling of the Local Structure of Metal Oxide Nanoparticles from PDF Data: A Case Study Using TiO2 Nanoparticles","authors":"Songsheng Tao, Jonas Billet, Jonathan De Roo, Simon J. L. Billinge","doi":"10.1021/acs.chemmater.3c03002","DOIUrl":"https://doi.org/10.1021/acs.chemmater.3c03002","url":null,"abstract":"A detailed workflow is presented for applying attenuated crystal modeling (ACM) of atomic pair distribution functions from TiO<sub>2</sub> nanoparticles to understand the structure and morphology of the nanoparticles. We use small-box modeling approaches with the diffpy<span>-CMI</span>software program. The modeling reveals that all synthesis conditions yield nanoparticles with a majority bronze phase and a minority anatase phase, with the synthesis temperature affecting the proportion of impurity phase and the size of the nanoparticles. The fast, straightforward, and reliable workflow is widely applicable for modeling PDFs of most inorganic nanoparticles as long as hypothesized ACM models are available, providing a helpful guide for researchers to analyze the structure of nanoparticles from PDF data.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448643","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 : 2024-10-17DOI: 10.1021/acs.chemmater.4c01557
Lance M. Wheeler, Thanh Luan Phan, Michelle A. Smeaton, Swagata Acharya, Shruti Hariyani, Marlena E. Alexander, Miranda I. Gonzalez, Elisa M. Miller, David W. Mulder, Sarbajit Banerjee, Katherine L. Jungjohann, Andrew J. Ferguson, Jeffrey L. Blackburn
Vanadium oxides are widely tunable materials, with many thermodynamically stable phases suitable for applications spanning catalysis to neuromorphic computing. The stability of vanadium in a range of oxidation states enables mixed-valence polymorphs of kinetically accessible metastable materials. Low-temperature synthetic routes to, and the properties of, these metastable materials are poorly understood and may unlock new optoelectronic and magnetic functionalities for expanded applications. In this work, we demonstrate topochemical reduction of α-V2O5 to produce metastable vanadium oxide phases with tunable oxygen vacancies (>6%) and simultaneous substitutional tin incorporation (>3.5%). The chemistry is carried out at low temperature (65 °C) with solution-phase SnCl2, where Sn2+ is oxidized to Sn4+ as V5+ sites are reduced to V4+ during oxygen vacancy formation. Despite high oxygen vacancy and tin concentrations, the transformations are topochemical in that the symmetry of the parent crystal remains intact, although the unit cell expands. Band structure calculations show that these vacancies contribute electrons to the lattice, whereas substitutional tin contributes holes, yielding a compensation doping effect and control over the electronic properties. The SnCl2 redox chemistry is effective on both solution-processed V2O5 nanoparticle inks and mesoporous films cast from untreated inks, enabling versatile routes toward functional films with tunable optical and electronic properties. The electrical conductance rises concomitantly with the SnCl2 concentration and treatment time, indicating a net increase in density of free electrons in the host lattice. This work provides a valuable demonstration of kinetic tailoring of electronic properties of vanadium–oxygen systems through top-down chemical manipulation from known thermodynamic phases.
{"title":"Tuning Optical and Electrical Properties of Vanadium Oxide with Topochemical Reduction and Substitutional Tin","authors":"Lance M. Wheeler, Thanh Luan Phan, Michelle A. Smeaton, Swagata Acharya, Shruti Hariyani, Marlena E. Alexander, Miranda I. Gonzalez, Elisa M. Miller, David W. Mulder, Sarbajit Banerjee, Katherine L. Jungjohann, Andrew J. Ferguson, Jeffrey L. Blackburn","doi":"10.1021/acs.chemmater.4c01557","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01557","url":null,"abstract":"Vanadium oxides are widely tunable materials, with many thermodynamically stable phases suitable for applications spanning catalysis to neuromorphic computing. The stability of vanadium in a range of oxidation states enables mixed-valence polymorphs of kinetically accessible metastable materials. Low-temperature synthetic routes to, and the properties of, these metastable materials are poorly understood and may unlock new optoelectronic and magnetic functionalities for expanded applications. In this work, we demonstrate topochemical reduction of α-V<sub>2</sub>O<sub>5</sub> to produce metastable vanadium oxide phases with tunable oxygen vacancies (>6%) and simultaneous substitutional tin incorporation (>3.5%). The chemistry is carried out at low temperature (65 °C) with solution-phase SnCl<sub>2</sub>, where Sn<sup>2+</sup> is oxidized to Sn<sup>4+</sup> as V<sup>5+</sup> sites are reduced to V<sup>4+</sup> during oxygen vacancy formation. Despite high oxygen vacancy and tin concentrations, the transformations are topochemical in that the symmetry of the parent crystal remains intact, although the unit cell expands. Band structure calculations show that these vacancies contribute electrons to the lattice, whereas substitutional tin contributes holes, yielding a compensation doping effect and control over the electronic properties. The SnCl<sub>2</sub> redox chemistry is effective on both solution-processed V<sub>2</sub>O<sub>5</sub> nanoparticle inks and mesoporous films cast from untreated inks, enabling versatile routes toward functional films with tunable optical and electronic properties. The electrical conductance rises concomitantly with the SnCl<sub>2</sub> concentration and treatment time, indicating a net increase in density of free electrons in the host lattice. This work provides a valuable demonstration of kinetic tailoring of electronic properties of vanadium–oxygen systems through top-down chemical manipulation from known thermodynamic phases.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444423","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}
Ti-containing silica-based catalysts are widely used for various organic oxidation reactions. Recently, increasing attention has been paid to the catalytic role of dinuclear (SiO)3Ti–O–Ti(OSi)3 sites in titanosilicate zeolite TS-1. A promising experimental approach for elucidating the active sites is to use model compounds with dinuclear Ti sites. In this study, we report the synthesis and catalytic properties of a μ-oxo-bridged dinuclear titanosiloxane compound with a (SiO)3Ti–O–Ti(OSi)3 site. A Ti-containing cage siloxane compound (iBu7Si7O12)TiOiPr (mononuclear Ti-polyhedral oligomeric silsesquioxane (POSS)) is prepared by the reaction of incompletely condensed POSS with titanium tetraisopropoxide. Then, it is converted to the dinuclear species (iBu7Si7O12)2Ti2(μ-O) (dinuclear Ti-POSS) by the simple hydrolytic condensation of the TiOiPr groups. The addition of H2O2 to dinuclear Ti-POSS leads to the formation of a bishydroperoxo complex, as revealed by Ti K-edge X-ray absorption fine structure analysis. Dinuclear Ti-POSS possesses high catalytic activity in the cyclohexene epoxidation reaction, indicating that the (SiO)3Ti–O–Ti(OSi)3 sites can function as efficient catalytically active sites. These findings contribute to the comprehension of the catalytic properties exhibited by dinuclear titanium sites within titanosilicate zeolite catalysts.
含钛的硅基催化剂被广泛用于各种有机氧化反应。最近，人们越来越关注钛硅酸盐沸石 TS-1 中双核 (SiO)3Ti-O-Ti(OSi)3 位点的催化作用。利用具有双核 Ti 位点的模型化合物来阐明活性位点是一种很有前景的实验方法。在本研究中，我们报告了一种具有 (SiO)3Ti-O-Ti(OSi)3 位点的μ-氧桥双核钛硅氧烷化合物的合成和催化特性。一种含钛笼状硅氧烷化合物（iBu7Si7O12）TiOiPr（单核钛-多面体低聚硅倍半氧烷（POSS））是通过未完全缩合的 POSS 与四异丙醇钛反应制备的。然后，通过 TiOiPr 基团的简单水解缩合，将其转化为双核物种 (iBu7Si7O12)2Ti2(μ-O)（双核 Ti-POSS）。Ti K 边 X 射线吸收精细结构分析表明，在双核 Ti-POSS 中加入 H2O2 会形成双氢过氧复合物。双核 Ti-POSS 在环己烯环氧化反应中具有很高的催化活性，这表明 (SiO)3Ti-O-Ti(OSi)3 位点可作为高效的催化活性位点。这些发现有助于理解钛硅酸盐沸石催化剂中的双核钛位点所表现出的催化特性。
{"title":"Simple Molecular Synthetic Approach to Dinuclear Titanium Sites in Ti-Containing Silica-Based Catalysts","authors":"Takuya Hikino, Yuka Kawakubo, Takamichi Matsuno, Seiji Yamazoe, Kazuyuki Kuroda, Atsushi Shimojima","doi":"10.1021/acs.chemmater.4c01454","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01454","url":null,"abstract":"Ti-containing silica-based catalysts are widely used for various organic oxidation reactions. Recently, increasing attention has been paid to the catalytic role of dinuclear (SiO)<sub>3</sub>Ti–O–Ti(OSi)<sub>3</sub> sites in titanosilicate zeolite TS-1. A promising experimental approach for elucidating the active sites is to use model compounds with dinuclear Ti sites. In this study, we report the synthesis and catalytic properties of a μ-oxo-bridged dinuclear titanosiloxane compound with a (SiO)<sub>3</sub>Ti–O–Ti(OSi)<sub>3</sub> site. A Ti-containing cage siloxane compound (<sup><i>i</i></sup>Bu<sub>7</sub>Si<sub>7</sub>O<sub>12</sub>)TiO<sup><i>i</i></sup>Pr (mononuclear Ti-polyhedral oligomeric silsesquioxane (POSS)) is prepared by the reaction of incompletely condensed POSS with titanium tetraisopropoxide. Then, it is converted to the dinuclear species (<sup><i>i</i></sup>Bu<sub>7</sub>Si<sub>7</sub>O<sub>12</sub>)<sub>2</sub>Ti<sub>2</sub>(μ-O) (dinuclear Ti-POSS) by the simple hydrolytic condensation of the TiO<sup><i>i</i></sup>Pr groups. The addition of H<sub>2</sub>O<sub>2</sub> to dinuclear Ti-POSS leads to the formation of a bishydroperoxo complex, as revealed by Ti K-edge X-ray absorption fine structure analysis. Dinuclear Ti-POSS possesses high catalytic activity in the cyclohexene epoxidation reaction, indicating that the (SiO)<sub>3</sub>Ti–O–Ti(OSi)<sub>3</sub> sites can function as efficient catalytically active sites. These findings contribute to the comprehension of the catalytic properties exhibited by dinuclear titanium sites within titanosilicate zeolite catalysts.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444422","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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