Chemistry of Materials最新文献_第3页

Order–Disorder Transition of Supramolecular Liquid Crystalline Elastomers 超分子液晶弹性体的有序-无序转变

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-12-17 DOI: 10.1021/acs.chemmater.4c02271

Kristin L. Lewis, Jonathan D. Hoang, Michael F. Toney, Timothy J. White

{"title":"Order–Disorder Transition of Supramolecular Liquid Crystalline Elastomers","authors":"Kristin L. Lewis, Jonathan D. Hoang, Michael F. Toney, Timothy J. White","doi":"10.1021/acs.chemmater.4c02271","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02271","url":null,"abstract":"Liquid crystalline elastomers (LCEs) are soft materials which disorder upon heating through the isotropic transition temperature. The order-disorder phase transition of LCEs results in a contraction of up to ∼50% along the aligned axis. Motivated by this distinctive stimuli-response, LCEs are increasingly considered as low-density actuators. Generally, LCEs are composed entirely of covalent bonds. Recently, we have prepared LCEs with intramesogenic supramolecular bonds from dimerized oxybenzoic acid derivatives and documented distinctive thermomechanical response in these supramolecular LCEs. Here, we report a detailed investigation of phase transitions in supramolecular LCEs by systematically varying the composition to affect the strength of the intermolecular interactions in the polymer network. The order-disorder phase transition is shown to be influenced by the conformation and dissociation of supramolecular dimers. Distinctly, this report isolates and details an LCE composition which undergoes an intermediate transition to an incommensurate phase at lower temperatures than the order-disorder transition.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"19 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832827","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}

引用次数: 0

Ultralow Thermal Conductivity Approaching the Disordered Limit in Crystalline TlCuZrSe3 晶体 TlCuZrSe3 接近无序极限的超低导热率

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-12-16 DOI: 10.1021/acs.chemmater.4c03025

Rohit Kumar Rohj, Animesh Bhui, Shaili Sett, Arindam Ghosh, Kanishka Biswas, D. D. Sarma

{"title":"Ultralow Thermal Conductivity Approaching the Disordered Limit in Crystalline TlCuZrSe3","authors":"Rohit Kumar Rohj, Animesh Bhui, Shaili Sett, Arindam Ghosh, Kanishka Biswas, D. D. Sarma","doi":"10.1021/acs.chemmater.4c03025","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03025","url":null,"abstract":"A comprehensive understanding of thermal transport is crucial for many applications, including heat dissipation systems, thermal barrier coatings, and harnessing potentials of thermoelectric materials. Here, we report an ultralow thermal conductivity, κ, in a p-type layered chalcogenide, TlCuZrSe3. Our investigation reveals that the anisotropic values of κ in two perpendicular directions in this compound vary between 0.88 and 0.41 Wm–1K–1 and 1.15–0.62 Wm–1K–1, respectively, over the temperature range of 295–600 K. The low-temperature specific heat data could only be explained by considering Einstein oscillator terms in addition to the conventional Debye model-based contributions, consistent with the presence of localized Tl1+ rattlers. The unique anisotropic crystal structure of TlCuZrSe3 and the rattling of Tl1+ ions lead to the generation of low-frequency phonons. These relatively flat optical phonon modes hybridize with acoustic phonons, giving rise to strong anharmonicity and phonon scattering channels. Raman spectroscopy confirms that these low-frequency phonon modes have extremely short lifetimes (∼1 ps), explaining the ultralow κ values, approaching the disordered limit, in this highly crystalline material.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"4 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832472","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}

引用次数: 0

Stereoactive Electron Lone Pairs Facilitate Fluoride Ion Diffusion in Tetragonal BaSnF4 立体活性电子孤对促进四方 BaSnF4 中氟离子的扩散

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-12-16 DOI: 10.1021/acs.chemmater.4c02756

Xiliang Lian, Damien Dambournet, Mathieu Salanne

{"title":"Stereoactive Electron Lone Pairs Facilitate Fluoride Ion Diffusion in Tetragonal BaSnF4","authors":"Xiliang Lian, Damien Dambournet, Mathieu Salanne","doi":"10.1021/acs.chemmater.4c02756","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02756","url":null,"abstract":"Solid-state ionic conductors are of primary importance for the design of tomorrow’s batteries. In lithium- or sodium-ion-based materials, the alkali cations diffuse through three-dimensional channels consisting of interconnected tetrahedral or octahedral sites with low free energy barriers between them. Fluoride ion conductors stand out in this landscape since the materials with the highest conductivities belong to the MSnF4 family (in which M2+ is a divalent cation), whose structure is layered and characterized by double-layers of Sn2+ and M2+ cations along a given direction. Importantly, these materials display stereoactive electron lone pairs (LPs) that seemingly play an important role not only in stabilizing the Sn–Sn layer but also in modulating the fluoride ion diffusive behavior. However, despite previous experimental and simulation studies, the involvement of the LPs in the fluoride ion conduction mechanism remains to be quantitatively understood. In this work, we simulate the BaSnF4 tetragonal structure using machine learning-based molecular dynamics, in which the interaction potential is trained on density functional theory data. We investigated the role of the Sn–LP–Sn layer in lowering the diffusion energy landscape. In particular, we show how the F– ions jump across this layer and occur much more frequently than in the Ba–F–Ba one, resulting in the formation of vacancies in the Ba–Sn layers. Concurrently, the LP stereochemical activity fluctuates to accommodate the F ions jumping. In addition, the presence of the LP layer enhances the flexibility of the Sn ions, which leads to an increase in two-dimensional diffusion by several orders of magnitude. These results contribute to our understanding of the interplay between LPs and ionic diffusion, helping to explain the good performance of the material in fluoride-ion batteries.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"88 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832894","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}

引用次数: 0

Insights into the Crystal Structure and Thermoelectric Properties of the Zintl Phase Ca9Cd3+x–yMx+ySb9 (M = Cu, Zn) System 对锌相 Ca9Cd3+x-yMx+ySb9 (M = 铜、锌) 体系晶体结构和热电特性的见解

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-12-16 DOI: 10.1021/acs.chemmater.4c02740

Junsu Lee, Minkyoung Kim, Ji Hee Pi, Myung-Ho Choi, Kang Min Ok, Kyu Hyoung Lee, Tae-Soo You

{"title":"Insights into the Crystal Structure and Thermoelectric Properties of the Zintl Phase Ca9Cd3+x–yMx+ySb9 (M = Cu, Zn) System","authors":"Junsu Lee, Minkyoung Kim, Ji Hee Pi, Myung-Ho Choi, Kang Min Ok, Kyu Hyoung Lee, Tae-Soo You","doi":"10.1021/acs.chemmater.4c02740","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02740","url":null,"abstract":"Four quaternary Zintl phase solid-solutions in the Ca9Cd3+x–yMx+ySb9 (M = Cu, Zn) system were successfully synthesized, and their crystal structures were characterized by using both powder X-ray and single-crystal X-ray diffractions. All title compounds adopted the Ca9Zn3.1In0.9Sb9-type phase, featuring three-dimensional anionic frameworks composed of tetrahedral [MSb4] and tricoordinated [MSb3] moieties interconnected via vertex-sharing. Detailed structural analyses revealed that various types of partial and mixed occupations existed at the M sites, and the Zn2 site in Ca9Cd2.65(1)Zn1.84(2)Sb9 exhibited a trigonal pyramid geometry, distinct from the simple planar geometry observed in parental Ca9Zn3.1In0.9Sb9. The density of states (DOS) analyses revealed successful p-type doping in the Cu-containing compound, indicated by a shift in the Fermi level and an increase in the hole carrier concentration. Crystal orbital Hamilton population curves displayed optimized interatomic interactions between neighboring anionic elements, maintaining structural stability despite a slight increase in the DOS level. Thermoelectric property measurements were conducted for the first time on the Ca9Zn3.1In0.9Sb9-type phase. The results demonstrated that the Zn-containing compounds exhibited higher Seebeck coefficients and lower thermal conductivities, resulting in larger ZT values compared to the Cu-containing compounds. The highest ZT value of 0.70 at 775 K was observed for Ca9Cd4.05Zn0.45Sb9.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"24 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832471","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}

引用次数: 0

Epitaxial Growth of Atomic-Layer Cu on Pd Nanocatalysts for Electrochemical CO2 Reduction 用于电化学二氧化碳还原的钯纳米催化剂上原子层铜的外延生长

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-12-16 DOI: 10.1021/acs.chemmater.4c02541

Shikai Liu, Chuqiao Shi, Chaokai Xu, Haichuan Zhang, Wenqi Li, Valentín Briega-Martos, Qian He, Yimo Han, Yao Yang

{"title":"Epitaxial Growth of Atomic-Layer Cu on Pd Nanocatalysts for Electrochemical CO2 Reduction","authors":"Shikai Liu, Chuqiao Shi, Chaokai Xu, Haichuan Zhang, Wenqi Li, Valentín Briega-Martos, Qian He, Yimo Han, Yao Yang","doi":"10.1021/acs.chemmater.4c02541","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02541","url":null,"abstract":"CO2 reduction reaction (CO2RR) facilitates the sustainable synthesis of fuels and chemicals. Although copper (Cu) enables CO2-to-multicarbon product (C2+) conversion, Cu-based electrocatalysts, particularly nanocatalysts, face challenges in poor selectivity and stability owing to the highly dynamic nature of Cu atoms under reaction conditions. Core–shell structures present a promising approach to address these issues by modulating the Cu overlayer–substrate interactions with atomic-level precision. Here, we report on Pd@Cu core–shell structures with atomically thin and nanometer-thick Cu overlayers on single-crystal Pd nanocubes with {100} facets promoting the CO2-to-C2+ conversion. The microstructures and surface compositions at the atomically sharp Pd/Cu interface were investigated by atomic-scale scanning transmission electron microscopy (STEM) imaging and electron energy-loss spectroscopy (EELS). Our results reveal that atomic-layer Cu epitaxially grows on Pd and adapts to the lattice of the Pd substrate. The reaction-driven migration of atomic-layer Cu is effectively suppressed on Pd due to the strong Cu–Pd interaction. While Pd only reduces CO2 to C1 products, atomic-layer Cu on Pd can initiate the C2+ production during the CO2RR. Thick Cu overlayers (∼15 nm) on Pd further enhance the C2+ faradaic efficiency while undergoing significant structural reconstruction, with only the 2–3 nm Cu layers near the Pd surface remaining stable and resistant to Cu migration after the CO2RR. We anticipate that Pd@Cu core–shell structures with intermediate Cu shell thickness hold significant potential for enhancing C2+ selectivity while maintaining high stability of nanocatalysts for CO2 reduction to liquid fuels.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"97 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832828","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}

引用次数: 0

Noncovalent Construction of Hangman Cobalt Phthalocyanine for Enhanced Electrochemical Carbon Dioxide Reduction

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-12-16 DOI: 10.1021/acs.chemmater.4c02697

Ye Zhou, Xiaoyue Duan, Xin Xu, Poe Ei Phyu Win, Shi-Bin Ren, Jiong Wang

{"title":"Noncovalent Construction of Hangman Cobalt Phthalocyanine for Enhanced Electrochemical Carbon Dioxide Reduction","authors":"Ye Zhou, Xiaoyue Duan, Xin Xu, Poe Ei Phyu Win, Shi-Bin Ren, Jiong Wang","doi":"10.1021/acs.chemmater.4c02697","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02697","url":null,"abstract":"The hangman structure plays a critical role in determining the reaction rates of molecular CO2 electrocatalysis through constructing pendant functional groups in secondary coordination spheres of metal active sites. However, achieving hangman structures commonly requires complicated asymmetric synthesis. It is necessary to search for simple alternative strategies to develop hangman molecular electrocatalysis with realization of the concept of green chemistry. In this work, we report the synthesis of hangman molecular electrocatalysts based on the noncovalent π–π interaction between cobalt (Co) phthalocyanine nanotubes and 1-aminopyrene. It promoted the kinetics of interfacial inner and outer sphere electron transfer on the complex and chemisorption of *COOH and *CO species through interaction with both Co sites and pendant amine groups in a bridge geometry. The resultant Co sites afforded a very high turnover frequency of 4.37 s–1 at an overpotential of 0.29 V for electrochemical CO2 to CO conversion and thus afforded an industrial interest current density being steady at 350 mA cm–2.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"11 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832829","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}

引用次数: 0

Compatibility of Halide Electrolytes in Solid-State Li–S Battery Cathodes

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-12-16 DOI: 10.1021/acs.chemmater.4c02159

Shoma Yanagihara, Jan Huebner, Zheng Huang, Atsushi Inoishi, Hirofumi Akamatsu, Katsuro Hayashi, Saneyuki Ohno

{"title":"Compatibility of Halide Electrolytes in Solid-State Li–S Battery Cathodes","authors":"Shoma Yanagihara, Jan Huebner, Zheng Huang, Atsushi Inoishi, Hirofumi Akamatsu, Katsuro Hayashi, Saneyuki Ohno","doi":"10.1021/acs.chemmater.4c02159","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02159","url":null,"abstract":"The utilization of earth-abundant and high-capacity sulfur in solid-state batteries presents a promising strategy to circumvent the use of rare transition metals and enhance achievable specific energy. However, numerous challenges remain. The transport limitation within the cathode composite, particularly with sulfide electrolytes during charging, has been identified as a major degradation mechanism in solid-state Li–S batteries. This degradation is linked to electrolyte oxidation and a concomitant reduction in the effective ionic conductivity of the cathode composite. Inspired by the sufficiently high oxidation stability of halide-based electrolytes, we investigated their compatibility with solid-state Li–S batteries in this work. The electrochemical stability of halides in contact with conductive additives, the stability window of fast ion transport in the composite electrodes, and chemical compatibility with sulfur-active materials (e.g., S and Li2S), in addition to the cyclability of the halide-based composite electrodes, are explored. Three halides were employed as model electrolytes: Li3InCl6, Li3YCl6, and Li3YBr6. Despite its high oxidation stability, Li3InCl6 exhibited rapid degradation due to electrolyte reduction. The composite with Li3YCl6 lost its capacity because of chemical incompatibility, especially with Li2S, resulting in the formation of LiYS2 at the interface. In contrast, Li3YBr6 demonstrated superior performance, maintaining a capacity of 1100 mAh gS–1 for 20 cycles (normalized to the sulfur content in the cathode material). This study elucidates the degradation mechanisms of halide-based solid-state Li–S batteries and proposes potential design strategies to mitigate chemical incompatibility issues.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"244 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832469","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}

引用次数: 0

Role of Fe Impurity Reactions in the Electrochemical Properties of MgFeB2O5

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-12-16 DOI: 10.1021/acs.chemmater.4c02855

Camilla Tacconis, Sunita Dey, Carson D. McLaughlin, Moulay Tahar Sougrati, Christopher A. O’Keefe, Iuliia Mikulska, Clare P. Grey, Siân E. Dutton

{"title":"Role of Fe Impurity Reactions in the Electrochemical Properties of MgFeB2O5","authors":"Camilla Tacconis, Sunita Dey, Carson D. McLaughlin, Moulay Tahar Sougrati, Christopher A. O’Keefe, Iuliia Mikulska, Clare P. Grey, Siân E. Dutton","doi":"10.1021/acs.chemmater.4c02855","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02855","url":null,"abstract":"We investigate magnesium–iron pyroborate MgFeB2O5 as a potential cathode material for rechargeable magnesium-ion batteries. Synchrotron powder X-ray diffraction and Mössbauer spectroscopy confirm its successful synthesis and iron stabilization in the high-spin Fe(II) state. Initial electrochemical testing against a lithium metal anode yields a first charge capacity near the theoretical value (147.45 mAh·g–1), suggesting MgFeB2O5 as a promising cathode candidate. However, multimodal analyses, including scanning electron microscopy energy-dispersive X-ray (SEM-EDS) analysis, operando X-ray absorption near edge spectroscopy (XANES), and Mössbauer spectroscopy, reveal the absence of any Fe redox reactions. Instead, we propose that the source of the observed capacity involves the irreversible reaction of a small (4–7 wt%) Fe metal impurity. These findings highlight the need for diverse characterization techniques in evaluating the performance of new Mg cathode materials, since promising initial cycling may be caused by competing side reactions rather than Mg (de)intercalation.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"47 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832470","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}

引用次数: 0

Electrochemically-Formed Disordered Rock Salt ω-LixV9Mo6O40 as a Fast-Charging Li-Ion Electrode Material

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-12-13 DOI: 10.1021/acs.chemmater.4c01732

Daniel D. Robertson, Charlene Z. Salamat, David J. Pe, Helen Cumberbatch, David N. Agyeman-Budu, Johanna Nelson Weker, Sarah H. Tolbert

{"title":"Electrochemically-Formed Disordered Rock Salt ω-LixV9Mo6O40 as a Fast-Charging Li-Ion Electrode Material","authors":"Daniel D. Robertson, Charlene Z. Salamat, David J. Pe, Helen Cumberbatch, David N. Agyeman-Budu, Johanna Nelson Weker, Sarah H. Tolbert","doi":"10.1021/acs.chemmater.4c01732","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01732","url":null,"abstract":"Electrochemically-formed disordered rock salt compounds are an emerging class of Li-ion electrode materials for fast-charging energy storage. However, the specific factors that govern the formation process and the resulting charge storage performance are not well understood. Here, we characterize the transformation mechanism and charge storage properties of an electrochemically-formed disordered rock salt from V9Mo6O40 (VMO). The crystal structure of VMO has similar motifs to that of α-V2O5, a well-studied analogue, but VMO has less mechanical flexibility due to additional corner-sharing octahedra in its structure. As a result, VMO undergoes a single-step transformation pathway, which we characterize through operando X-ray diffraction, and forms an unusual highly distorted lamellar microstructure, as we show with high-resolution transmission electron microscopy. The resulting LixVMO material shows fast charging and other electrochemical characteristics and performance typical of many nanomaterials, even though the material is composed of relatively large particles.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"56 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816126","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}

引用次数: 0

Understanding Water Enhancement of CO2 Adsorption in Zeolite Cs–RHO

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2024-12-13 DOI: 10.1021/acs.chemmater.4c02496

Hwangho Lee, Kun-Lin Wu, Dan Xie, Le Xu, Alexander Okrut, Stacey I. Zones, Ambarish Kulkarni, Alexander Katz

{"title":"Understanding Water Enhancement of CO2 Adsorption in Zeolite Cs–RHO","authors":"Hwangho Lee, Kun-Lin Wu, Dan Xie, Le Xu, Alexander Okrut, Stacey I. Zones, Ambarish Kulkarni, Alexander Katz","doi":"10.1021/acs.chemmater.4c02496","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02496","url":null,"abstract":"Structural characterization of humid CO2 adsorbed in Cs–RHO zeolite was achieved with computationally guided Rietveld refinement, and elucidates the extraordinary enhancement in CO2 adsorption under wet compared with dry conditions in this zeolite. Our data encompass Rietveld refinement, IR spectroscopy, and molecular simulations, and demonstrate a cooperative effect of water (pulling Cs+ cations) and CO2 (pushing Cs+ cations) in translocating Cs+ cations away from initial positions in the center of the double eight-membered ring (D8R). This translocation is crucial for unblocking the small-pore RHO framework for CO2 transport as well as exposing thermodynamically controlled selective sites that can adsorb CO2 under our humid conditions. Our data emphasize the essentialness of cooperativity in that neither water nor CO2 achieve this unblocking on their own at 5% relative humidity and 30 °C. These results also demonstrate the importance of multidentate interactions between CO2 and cations through the D8R, as well as framework oxygen atoms of the D8R, as a key motif in water-resilient CO2 bonding sites in zeolites, along with additional, weaker interactions with other cations in the alpha cage.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"29 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816128","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}

引用次数: 0