Pub Date : 2024-12-13DOI: 10.1021/acs.chemmater.4c02496
Hwangho Lee, Kun-Lin Wu, Dan Xie, Le Xu, Alexander Okrut, Stacey I. Zones, Ambarish Kulkarni, Alexander Katz
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.
{"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 CO<sub>2</sub> adsorbed in Cs–RHO zeolite was achieved with computationally guided Rietveld refinement, and elucidates the extraordinary enhancement in CO<sub>2</sub> 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<sup>+</sup> cations) and CO<sub>2</sub> (pushing Cs<sup>+</sup> cations) in translocating Cs<sup>+</sup> 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 CO<sub>2</sub> transport as well as exposing thermodynamically controlled selective sites that can adsorb CO<sub>2</sub> under our humid conditions. Our data emphasize the essentialness of cooperativity in that neither water nor CO<sub>2</sub> achieve this unblocking on their own at 5% relative humidity and 30 °C. These results also demonstrate the importance of multidentate interactions between CO<sub>2</sub> and cations through the D8R, as well as framework oxygen atoms of the D8R, as a key motif in water-resilient CO<sub>2</sub> 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}
Pub Date : 2024-12-13DOI: 10.1021/acs.chemmater.4c02294
Harpriya Minhas, Milan Kumar Jena, Rahul Kumar Sharma, Biswarup Pathak
Stereochemically active lone pairs (SCALPs) are pivotal in influencing the lattice thermal conductivity (κL), representing a critical aspect in formulating strategies for achieving high thermoelectric performance. Despite the transformative potential of the material genome paradigm for screening materials with tailored properties, accurately describing SCALPs in terms of performance indicators remains a challenge. In this machine learning (ML) study, we introduce specialized chemical bonding descriptors that capture the empirical hidden influence of SCALP and chemical bonding hierarchies in pnictogen chalcogenide materials. The ML model, trained with screened data sets from the Open Quantum Materials Database, the Materials Project, and experimental reports, achieved a significant reduction in test error scores by using chemical bonding descriptors over conventional features in predicting κL values for pnictogen chalcogenides. We predict five materials, MnTl2As2S5, Ba2As2Se5, Bi14Te13S8, AgCu2PbBiS4, and Tl2SnAs2S6, exhibiting ultralow κL values of ≤0.40 W m–1 K–1 at room temperature. Additionally, we specified the precise ranges for ionicity, hybridization, number mismatch, and polarizability required for ultralow κL for 245 newly predicted materials. Our data-driven approach not only identifies promising candidates with ultralow κL but also reveals new avenues for the design of pnictogen-based thermoelectric materials, emphasizing the crucial influence of lone pairs and hybridization.
{"title":"Insights into Thermal Conductivity of Pnictogen Chalcogenides: Machine Learning Stereochemically Active Lone Pairs and Hybridization","authors":"Harpriya Minhas, Milan Kumar Jena, Rahul Kumar Sharma, Biswarup Pathak","doi":"10.1021/acs.chemmater.4c02294","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02294","url":null,"abstract":"Stereochemically active lone pairs (SCALPs) are pivotal in influencing the lattice thermal conductivity (κ<sub>L</sub>), representing a critical aspect in formulating strategies for achieving high thermoelectric performance. Despite the transformative potential of the material genome paradigm for screening materials with tailored properties, accurately describing SCALPs in terms of performance indicators remains a challenge. In this machine learning (ML) study, we introduce specialized chemical bonding descriptors that capture the empirical hidden influence of SCALP and chemical bonding hierarchies in pnictogen chalcogenide materials. The ML model, trained with screened data sets from the Open Quantum Materials Database, the Materials Project, and experimental reports, achieved a significant reduction in test error scores by using chemical bonding descriptors over conventional features in predicting κ<sub>L</sub> values for pnictogen chalcogenides. We predict five materials, MnTl<sub>2</sub>As<sub>2</sub>S<sub>5</sub>, Ba<sub>2</sub>As<sub>2</sub>Se<sub>5</sub>, Bi<sub>14</sub>Te<sub>13</sub>S<sub>8</sub>, AgCu<sub>2</sub>PbBiS<sub>4</sub>, and Tl<sub>2</sub>SnAs<sub>2</sub>S<sub>6</sub>, exhibiting ultralow κ<sub>L</sub> values of ≤0.40 W m<sup>–1</sup> K<sup>–1</sup> at room temperature. Additionally, we specified the precise ranges for ionicity, hybridization, number mismatch, and polarizability required for ultralow κ<sub>L</sub> for 245 newly predicted materials. Our data-driven approach not only identifies promising candidates with ultralow κ<sub>L</sub> but also reveals new avenues for the design of pnictogen-based thermoelectric materials, emphasizing the crucial influence of lone pairs and hybridization.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"22 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816127","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 : 2024-12-12DOI: 10.1021/acs.chemmater.4c01795
Karlie Bach, Eduard Garrido Ribó, Jacob S. Hirschi, Zhiwei Mao, Makenzie T. Nord, Lev N. Zakharov, Konstantinos A. Goulas, Tim J. Zuehlsdorff, May Nyman
Materials chemists play a strategic role in achieving ambitious global climate goals, including removing legacy CO2 via direct air capture (DAC). Innovating diverse DAC materials will enable their effective use in varying conditions and improve our understanding of CO2 capture mechanisms. In our current contribution, we have synthesized a family of homoleptic alkali tetraperoxotitanate materials (generally formulated A4Ti(O2)4, A = Li, Na, or K) and studied their DAC reactivity. Synthesis was achieved with inexpensive reagents and >90% yields. We present the first single-crystal X-ray structures (five total) of A4Ti(O2)4 compounds along with supplemental bulk characterization and computation. We compare their DAC behavior in simple ambient benchtop experiments, determining CO2 uptake by combustion analysis of postcapture materials. The K analogue exhibited the most rapid and high-capacity DAC, 8.17 mmol CO2/g sorbent, translating to nearly 3 mol CO2 per mole Ti and reaching near maximum capacity in under 10 days. The Li and Na analogues exhibit delayed reactivity along with high DAC capacity (6.66 and 8.18 mmol of CO2/g sorbent, respectively). Characterization of the DAC products via scanning electron microscopy shows phase separation of alkali-rich and Ti-rich regions in core–shell morphologies for the Na and Li analogues; this is discussed with respect to the role of titanium vs alkali in DAC. On the other hand, no phase separation was observed for the K analogue. In situ monitoring detailed the early-stage CO2 capture behavior of the K analogue, reaching ∼50% of maximum capacity within 1 h. The differentiating behavior of the K analogue is attributed to its unique composition, containing four H2O2 lattice molecules in addition to the four O2– peroxide anions bonded to TiIV. While H2O2 (aq) alone does not exhibit CO2 chemisorption, the basic environment of the A4Ti(O2)4 lattice activates its rapid DAC, inspiring the future exploration of peroxosolvate materials for DAC.
{"title":"Tetraperoxotitanates for High-Capacity Direct Air Capture of Carbon Dioxide","authors":"Karlie Bach, Eduard Garrido Ribó, Jacob S. Hirschi, Zhiwei Mao, Makenzie T. Nord, Lev N. Zakharov, Konstantinos A. Goulas, Tim J. Zuehlsdorff, May Nyman","doi":"10.1021/acs.chemmater.4c01795","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01795","url":null,"abstract":"Materials chemists play a strategic role in achieving ambitious global climate goals, including removing legacy CO<sub>2</sub> via direct air capture (DAC). Innovating diverse DAC materials will enable their effective use in varying conditions and improve our understanding of CO<sub>2</sub> capture mechanisms. In our current contribution, we have synthesized a family of homoleptic alkali tetraperoxotitanate materials (generally formulated A<sub>4</sub>Ti(O<sub>2</sub>)<sub>4</sub>, A = Li, Na, or K) and studied their DAC reactivity. Synthesis was achieved with inexpensive reagents and >90% yields. We present the first single-crystal X-ray structures (five total) of A<sub>4</sub>Ti(O<sub>2</sub>)<sub>4</sub> compounds along with supplemental bulk characterization and computation. We compare their DAC behavior in simple ambient benchtop experiments, determining CO<sub>2</sub> uptake by combustion analysis of postcapture materials. The K analogue exhibited the most rapid and high-capacity DAC, 8.17 mmol CO<sub>2</sub>/g sorbent, translating to nearly 3 mol CO<sub>2</sub> per mole Ti and reaching near maximum capacity in under 10 days. The Li and Na analogues exhibit delayed reactivity along with high DAC capacity (6.66 and 8.18 mmol of CO<sub>2</sub>/g sorbent, respectively). Characterization of the DAC products via scanning electron microscopy shows phase separation of alkali-rich and Ti-rich regions in core–shell morphologies for the Na and Li analogues; this is discussed with respect to the role of titanium vs alkali in DAC. On the other hand, no phase separation was observed for the K analogue. In situ monitoring detailed the early-stage CO<sub>2</sub> capture behavior of the K analogue, reaching ∼50% of maximum capacity within 1 h. The differentiating behavior of the K analogue is attributed to its unique composition, containing four H<sub>2</sub>O<sub>2</sub> lattice molecules in addition to the four O<sub>2</sub><sup>–</sup> peroxide anions bonded to Ti<sup>IV</sup>. While H<sub>2</sub>O<sub>2</sub> (aq) alone does not exhibit CO<sub>2</sub> chemisorption, the basic environment of the A<sub>4</sub>Ti(O<sub>2</sub>)<sub>4</sub> lattice activates its rapid DAC, inspiring the future exploration of peroxosolvate materials for DAC.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"8 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809186","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 : 2024-12-12DOI: 10.1021/acs.chemmater.4c02575
Rongyu Zhang, Yongjun Zhou, Shifeng Xu, Liyan Wang, Dan Xu, Wenbo Li, Xing Meng, Xu Yang, Yi Zeng, Fei Du
Developing high-performance solid-state electrolytes (SSEs) is of great significance for addressing the foundational scientific issues of K-ion batteries and accelerating their transition to practical applications. The complex experimental explorations are time-consuming and labor-intensive, and the technical barriers in phase synthesis have hindered the development speed of potassium SSEs. In this study, we studied the effect of Cl-doping on the K-ion diffusion rate of K3SbS4 via deep molecular dynamics. To reduce the quantum fluctuation phenomena during the simulation process, we simulated a system composed of approximately 3400 atoms for 500 ps and averaged the results over five runs. The results of the MD simulation show that Cl doping can induce the generation of potassium vacancies, and a small amount of doping can convert K3SbS4 from an ionic insulator to a superionic conductor with an ionic conductivity of 14.8 mS/cm at 300 K. The cubic K3–xSbS4–xClx is a promising candidate for potassium SSEs for K-ions.
{"title":"Cl-Doped Cubic K3SbS4 as a Solid-State Electrolyte for K-Ion Batteries with Ultrafast Ionic Conductivity","authors":"Rongyu Zhang, Yongjun Zhou, Shifeng Xu, Liyan Wang, Dan Xu, Wenbo Li, Xing Meng, Xu Yang, Yi Zeng, Fei Du","doi":"10.1021/acs.chemmater.4c02575","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02575","url":null,"abstract":"Developing high-performance solid-state electrolytes (SSEs) is of great significance for addressing the foundational scientific issues of K-ion batteries and accelerating their transition to practical applications. The complex experimental explorations are time-consuming and labor-intensive, and the technical barriers in phase synthesis have hindered the development speed of potassium SSEs. In this study, we studied the effect of Cl-doping on the K-ion diffusion rate of K<sub>3</sub>SbS<sub>4</sub> via deep molecular dynamics. To reduce the quantum fluctuation phenomena during the simulation process, we simulated a system composed of approximately 3400 atoms for 500 ps and averaged the results over five runs. The results of the MD simulation show that Cl doping can induce the generation of potassium vacancies, and a small amount of doping can convert K<sub>3</sub>SbS<sub>4</sub> from an ionic insulator to a superionic conductor with an ionic conductivity of 14.8 mS/cm at 300 K. The cubic K<sub>3–<i>x</i></sub>SbS<sub>4–<i>x</i></sub>Cl<sub><i>x</i></sub> is a promising candidate for potassium SSEs for K-ions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"91 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816130","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}
In titanium dioxide (TiO2), oxygen vacancies- and cation interstitials-related functionalities have widely been studied in various fields, such as catalysis, sensors, and electronic devices. Anatase Nb-doped TiO2, a promising transparent conducting oxide material, shows a reversible metal–insulator transition by annealing in an oxidizing and reducing atmosphere. Theoretical and experimental studies have proposed that interstitial oxygen is key to this behavior. However, the chemical state of interstitial oxygen and its impact on the crystal lattice, which governs the electrical conduction mechanism, have not been elusive for over a decade. Herein, we reveal that superoxo-type (M–OO–) interstitial oxygen hinders electrical conductivity. Polarized X-ray absorption spectroscopy is combined with multimodal experiments, such as X-ray diffraction, Raman spectroscopy, and electrical transport measurements. The results show that the superoxo-type interstitial oxygens introduced in the vicinity of the dopant Nb ions trap conduction electrons. Furthermore, the interstitial oxygens induce off-centered [NbO6] and rutile-like [TiO6] octahedral distortions, potentially reducing carrier mobility. This study showcases the potential for expanding the oxygen-related functionalities of oxide materials from transparent conductors to battery materials, catalysts, and oxygen conductors.
{"title":"Elucidating the Role of Interstitial Oxygen in Transparent Conducting Anatase TiO2 by Polarized X-ray Absorption Spectroscopy Study","authors":"Tomohito Sudare, Ryota Shimizu, Naoomi Yamada, Yumie Miura, Reiichi Ueda, Ryo Nakayama, Shigeru Kobayashi, Kentaro Kaneko, Taro Hitosugi","doi":"10.1021/acs.chemmater.4c02896","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02896","url":null,"abstract":"In titanium dioxide (TiO<sub>2</sub>), oxygen vacancies- and cation interstitials-related functionalities have widely been studied in various fields, such as catalysis, sensors, and electronic devices. Anatase Nb-doped TiO<sub>2</sub>, a promising transparent conducting oxide material, shows a reversible metal–insulator transition by annealing in an oxidizing and reducing atmosphere. Theoretical and experimental studies have proposed that interstitial oxygen is key to this behavior. However, the chemical state of interstitial oxygen and its impact on the crystal lattice, which governs the electrical conduction mechanism, have not been elusive for over a decade. Herein, we reveal that superoxo-type (M–OO<sup>–</sup>) interstitial oxygen hinders electrical conductivity. Polarized X-ray absorption spectroscopy is combined with multimodal experiments, such as X-ray diffraction, Raman spectroscopy, and electrical transport measurements. The results show that the superoxo-type interstitial oxygens introduced in the vicinity of the dopant Nb ions trap conduction electrons. Furthermore, the interstitial oxygens induce off-centered [NbO<sub>6</sub>] and rutile-like [TiO<sub>6</sub>] octahedral distortions, potentially reducing carrier mobility. This study showcases the potential for expanding the oxygen-related functionalities of oxide materials from transparent conductors to battery materials, catalysts, and oxygen conductors.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"15 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805129","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 : 2024-12-11DOI: 10.1021/acs.chemmater.4c02374
Debolina Deb, Gopalakrishnan Sai Gautam
Na-ion batteries (NIBs) are increasingly considered as a viable alternative to Li-ion batteries due to the abundance, low cost, and thermal stability of Na-based systems. To improve the practical utilization of NIBs in applications, it is important to boost the energy and power densities of the electrodes being used by the discovery of novel candidate materials. Thus, we explore the chemical space of transition metal-containing oxyfluorides (TMOFs) that adopt a perovskite structure as possible NIB electrodes. Our choice of the perovskite structure is motivated by the “large” cationic tunnels that can accommodate Na+, while the chemistry of TMOFs is motivated by the high electronegativity and inductive effect of F–, which can possibly lead to higher voltages. We use density functional theory-based calculations to estimate the ground state polymorphs, average Na (de)intercalation voltages, thermodynamic stabilities, and Na+ mobility on two distinct sets of compositions: the F-rich NaxMOF2 and the O-rich Na1+xMO2F, where x = 0–1 and M = Ti, V, Cr, Mn, Fe, Co, or Ni. Upon identifying the ground state polymorphs in the charged compositions (i.e., MOF2 and NaMO2F), we show that F-rich perovskites exhibit higher average voltages compared to those of the O-rich perovskites. Also, we find six stable/metastable perovskites in the F-rich space, while all the O-rich perovskites (except NaTiO2F) are unstable. Finally, our Na-ion mobility calculations indicate that TiOF2–NaTiOF2, VOF2–NaVOF2, CrOF2, and NaMnOF2 can be promising compositions, albeit with challenges to be resolved, for experimental exploration as NIB cathodes. These oxyfluoride compositions can be promising if used primarily in a strained electrode configuration and/or in thin film batteries. Our computational approach and findings provide insights into developing practical NIBs involving fluorine-containing intercalation frameworks.
{"title":"Exploration of Oxyfluoride Frameworks as Na-ion Cathodes","authors":"Debolina Deb, Gopalakrishnan Sai Gautam","doi":"10.1021/acs.chemmater.4c02374","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02374","url":null,"abstract":"Na-ion batteries (NIBs) are increasingly considered as a viable alternative to Li-ion batteries due to the abundance, low cost, and thermal stability of Na-based systems. To improve the practical utilization of NIBs in applications, it is important to boost the energy and power densities of the electrodes being used by the discovery of novel candidate materials. Thus, we explore the chemical space of transition metal-containing oxyfluorides (TMOFs) that adopt a perovskite structure as possible NIB electrodes. Our choice of the perovskite structure is motivated by the “large” cationic tunnels that can accommodate Na<sup>+</sup>, while the chemistry of TMOFs is motivated by the high electronegativity and inductive effect of F<sup>–</sup>, which can possibly lead to higher voltages. We use density functional theory-based calculations to estimate the ground state polymorphs, average Na (de)intercalation voltages, thermodynamic stabilities, and Na<sup>+</sup> mobility on two distinct sets of compositions: the F-rich Na<sub><i>x</i></sub>MOF<sub>2</sub> and the O-rich Na<sub>1+<i>x</i></sub>MO<sub>2</sub>F, where <i>x</i> = 0–1 and M = Ti, V, Cr, Mn, Fe, Co, or Ni. Upon identifying the ground state polymorphs in the charged compositions (i.e., MOF<sub>2</sub> and NaMO<sub>2</sub>F), we show that F-rich perovskites exhibit higher average voltages compared to those of the O-rich perovskites. Also, we find six stable/metastable perovskites in the F-rich space, while all the O-rich perovskites (except NaTiO<sub>2</sub>F) are unstable. Finally, our Na-ion mobility calculations indicate that TiOF<sub>2</sub>–NaTiOF<sub>2</sub>, VOF<sub>2</sub>–NaVOF<sub>2</sub>, CrOF<sub>2</sub>, and NaMnOF<sub>2</sub> can be promising compositions, albeit with challenges to be resolved, for experimental exploration as NIB cathodes. These oxyfluoride compositions can be promising if used primarily in a strained electrode configuration and/or in thin film batteries. Our computational approach and findings provide insights into developing practical NIBs involving fluorine-containing intercalation frameworks.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"90 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809187","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}
AgBiS2 nanocrystals (NCs), composed of nontoxic, earth-abundant materials and exhibiting an exceptionally high absorption coefficient from visible to near-infrared (>105 cm–1), hold promise for photovoltaics but have lack of photoluminescence (PL) due to intrinsic nonradiative recombination and challenging shell growth. In this study, we reported a facile wet-chemical approach for the epitaxial growth of ZnS shell on AgBiS2 NCs, which triggered the observation of PL emission in the near-infrared (764 nm). Since high quality of the core is critical for epitaxial shell growth, we first obtained rock-salt structured AgBiS2 NCs with high crystallinity, nearly spherical shape and monodisperse size distribution (<6%) via a dual-ligand approach reacting Ag–Bi oleate with elemental sulfur in oleylamine. Next, a zincblende ZnS shell with a low-lattice mismatch of 4.9% was grown on as-prepared AgBiS2 NCs via a highly reactive zinc (Zn(acac)2) precursor that led to a higher photoluminescence quantum yield (PLQY) of 15.3%, in comparison with a relatively low reactivity precursor (Zn(ac)2) resulting in reduced PLQY. The emission from AgBiS2 NCs with ultrastrong absorption, facilitated by shell growth, can open up new possibilities in lighting, display, and bioimaging.
{"title":"Emergence of Near-Infrared Photoluminescence via ZnS Shell Growth on the AgBiS2 Nanocrystals","authors":"Asim Onal, Tarik Safa Kaya, Önder Metin, Sedat Nizamoglu","doi":"10.1021/acs.chemmater.4c02406","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02406","url":null,"abstract":"AgBiS<sub>2</sub> nanocrystals (NCs), composed of nontoxic, earth-abundant materials and exhibiting an exceptionally high absorption coefficient from visible to near-infrared (>10<sup>5</sup> cm<sup>–1</sup>), hold promise for photovoltaics but have lack of photoluminescence (PL) due to intrinsic nonradiative recombination and challenging shell growth. In this study, we reported a facile wet-chemical approach for the epitaxial growth of ZnS shell on AgBiS<sub>2</sub> NCs, which triggered the observation of PL emission in the near-infrared (764 nm). Since high quality of the core is critical for epitaxial shell growth, we first obtained rock-salt structured AgBiS<sub>2</sub> NCs with high crystallinity, nearly spherical shape and monodisperse size distribution (<6%) via a dual-ligand approach reacting Ag–Bi oleate with elemental sulfur in oleylamine. Next, a zincblende ZnS shell with a low-lattice mismatch of 4.9% was grown on as-prepared AgBiS<sub>2</sub> NCs via a highly reactive zinc (Zn(acac)<sub>2</sub>) precursor that led to a higher photoluminescence quantum yield (PLQY) of 15.3%, in comparison with a relatively low reactivity precursor (Zn(ac)<sub>2</sub>) resulting in reduced PLQY. The emission from AgBiS<sub>2</sub> NCs with ultrastrong absorption, facilitated by shell growth, can open up new possibilities in lighting, display, and bioimaging.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"28 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809188","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 : 2024-12-11DOI: 10.1021/acs.chemmater.4c02897
Lucas Fine, Rasmus Lavén, Zefeng Wei, Tatsuya Tsumori, Hiroshi Kageyama, Ryoichi Kajimoto, Mónica Jimenéz-Ruiz, Michael Marek Koza, Maths Karlsson
We report results on the configuration and vibrational dynamics of hydride ions (H–) in the novel mixed-anion, nitride-hydride, catalyst Ca3CrN3H by means of variable temperature inelastic neutron scattering experiments, harmonic phonon calculations, and machine-learning molecular dynamics calculations. The combined analyses of experimental and theoretical data show that the vibrational dynamics of H– are manifested as a broad, asymmetric vibrational band between 80 and 130 meV. These vibrational dynamics are generally anharmonic in nature and polarized along the crystallographic c axis, and their dispersive character reveals significant interactions between neighboring H– in the material. We find that most H– are surrounded by two other H– and that the H– sites of the studied sample have an occupancy of at least 95%. We argue that this high H– occupancy may be related to the material’s high efficiency as a catalyst for ammonia synthesis.
{"title":"Configuration and Dynamics of Hydride Ions in the Nitride-Hydride Catalyst Ca3CrN3H","authors":"Lucas Fine, Rasmus Lavén, Zefeng Wei, Tatsuya Tsumori, Hiroshi Kageyama, Ryoichi Kajimoto, Mónica Jimenéz-Ruiz, Michael Marek Koza, Maths Karlsson","doi":"10.1021/acs.chemmater.4c02897","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02897","url":null,"abstract":"We report results on the configuration and vibrational dynamics of hydride ions (H<sup>–</sup>) in the novel mixed-anion, nitride-hydride, catalyst Ca<sub>3</sub>CrN<sub>3</sub>H by means of variable temperature inelastic neutron scattering experiments, harmonic phonon calculations, and machine-learning molecular dynamics calculations. The combined analyses of experimental and theoretical data show that the vibrational dynamics of H<sup>–</sup> are manifested as a broad, asymmetric vibrational band between 80 and 130 meV. These vibrational dynamics are generally anharmonic in nature and polarized along the crystallographic <i>c</i> axis, and their dispersive character reveals significant interactions between neighboring H<sup>–</sup> in the material. We find that most H<sup>–</sup> are surrounded by two other H<sup>–</sup> and that the H<sup>–</sup> sites of the studied sample have an occupancy of at least 95%. We argue that this high H<sup>–</sup> occupancy may be related to the material’s high efficiency as a catalyst for ammonia synthesis.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"27 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809189","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 : 2024-12-10DOI: 10.1021/acs.chemmater.4c02081
Juan A. Santana, David Bugallo, Andrew Mirea, Tessa D. Tucker, David Alfredo Gonzalez-Narvaez, Alejandra Rosario-Crespo, Yalexander Sanchez-Navarro, Gabriela Marrero-Hernandez, Kevin Rosa-Dieppa, Andrea Garcia-Ramos, Rajeev Kumar Rai, Eric A. Stach, Steven J. May, Andrew M. Rappe
In this study, we explore how the orientation of oxygen vacancy channels (OVCs) in SrFeO2.5 and SrCoO2.5 thin films is influenced by the metal–oxygen bonds in their octahedral and tetrahedral coordination environments. Using density-functional theory (DFT) calculations, we found that energy changes due to applied strain are driven primarily by the octahedral Fe–O bonds in SrFeO2.5, leading to a strain-induced transition between perpendicular and parallel OVCs relative to the substrate. In contrast, the tetrahedral Co–O bonds in SrCoO2.5 primarily drive energy changes due to applied strain, resulting in a parallel OVC orientation regardless of the strain state. These computational findings are supported by experimental results obtained through molecular beam epitaxy (MBE) synthesis, X-ray diffraction (XRD), and scanning transmission electron microscopy (STEM) analysis. Our research underscores the critical role of metal–oxygen coordination environments in predicting and tailoring the properties of strained complex oxide thin films, providing a comprehensive understanding of the mechanisms governing vacancy ordering in brownmillerite structures.
{"title":"Octahedral and Tetrahedral Coordination Influences the Ordering of Oxygen Vacancy Channels in SrCoO2.5 and SrFeO2.5 Thin Films","authors":"Juan A. Santana, David Bugallo, Andrew Mirea, Tessa D. Tucker, David Alfredo Gonzalez-Narvaez, Alejandra Rosario-Crespo, Yalexander Sanchez-Navarro, Gabriela Marrero-Hernandez, Kevin Rosa-Dieppa, Andrea Garcia-Ramos, Rajeev Kumar Rai, Eric A. Stach, Steven J. May, Andrew M. Rappe","doi":"10.1021/acs.chemmater.4c02081","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02081","url":null,"abstract":"In this study, we explore how the orientation of oxygen vacancy channels (OVCs) in SrFeO<sub>2.5</sub> and SrCoO<sub>2.5</sub> thin films is influenced by the metal–oxygen bonds in their octahedral and tetrahedral coordination environments. Using density-functional theory (DFT) calculations, we found that energy changes due to applied strain are driven primarily by the octahedral Fe–O bonds in SrFeO<sub>2.5</sub>, leading to a strain-induced transition between perpendicular and parallel OVCs relative to the substrate. In contrast, the tetrahedral Co–O bonds in SrCoO<sub>2.5</sub> primarily drive energy changes due to applied strain, resulting in a parallel OVC orientation regardless of the strain state. These computational findings are supported by experimental results obtained through molecular beam epitaxy (MBE) synthesis, X-ray diffraction (XRD), and scanning transmission electron microscopy (STEM) analysis. Our research underscores the critical role of metal–oxygen coordination environments in predicting and tailoring the properties of strained complex oxide thin films, providing a comprehensive understanding of the mechanisms governing vacancy ordering in brownmillerite structures.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"13 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805130","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 : 2024-12-10DOI: 10.1021/acs.chemmater.4c02900
Iuliia Neumann, Iuliia Kosolapova, Bertold Rasche
Perovskite-derived tungsten bronzes are formed from tungsten oxide by electrochemical intercalation of all alkali metals from aqueous solutions. In two steps, we yield two different polymorphs, where the first step is reversible and the second step is irreversible. The electrochemical approach affords precise control of the composition, while ex situ X-ray diffraction and particularly in situ X-ray diffraction allow the analysis of the atomic structure. For the heavy alkali metals, rubidium and cesium, the in situ synchrotron X-ray diffraction experiments reveal in sum four new structures and their formation process. The irreversible deintercalation step yields at room temperature, the α-WO3 phase, a tungsten oxide polymorph which is thermodynamically only stable above 1073 K. Finally, analyzing the full alkali metal series allows us to conclude that the symmetry and structure of the formed bronzes are dictated by the electron count on the tungsten oxide network and the size of the ions plays a negligible role.
{"title":"Discovering Perovskite-Derived Tungsten Bronzes from In Situ Diffraction of Electrochemical Rubidium and Cesium Intercalation","authors":"Iuliia Neumann, Iuliia Kosolapova, Bertold Rasche","doi":"10.1021/acs.chemmater.4c02900","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02900","url":null,"abstract":"Perovskite-derived tungsten bronzes are formed from tungsten oxide by electrochemical intercalation of all alkali metals from aqueous solutions. In two steps, we yield two different polymorphs, where the first step is reversible and the second step is irreversible. The electrochemical approach affords precise control of the composition, while ex situ X-ray diffraction and particularly in situ X-ray diffraction allow the analysis of the atomic structure. For the heavy alkali metals, rubidium and cesium, the in situ synchrotron X-ray diffraction experiments reveal in sum four new structures and their formation process. The irreversible deintercalation step yields at room temperature, the α-WO<sub>3</sub> phase, a tungsten oxide polymorph which is thermodynamically only stable above 1073 K. Finally, analyzing the full alkali metal series allows us to conclude that the symmetry and structure of the formed bronzes are dictated by the electron count on the tungsten oxide network and the size of the ions plays a negligible role.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797735","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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