Pub Date : 2024-12-03DOI: 10.1021/acs.chemmater.4c02146
Alessia Provino, Thomas J. Emge, David Walker, Corey E. Frank, Suguru Yoshida, Venkatraman Gopalan, Mark Croft, Zheng Deng, Changqing Jin, Pietro Manfrinetti, Martha Greenblatt
Two new compounds, Zn2FeSbO6 and Zn2MnSbO6, have been synthesized under high-pressure and high-temperature conditions. The synthesis, single-crystal and powder X-ray diffraction, X-ray absorption near-edge spectroscopy (XANES), optical second harmonic generation (SHG), and magnetic and heat capacity measurements were carried out for both compounds and are described. The lattice parameters are a = 5.17754(6) Å and c = 13.80045(16) Å for Zn2FeSbO6 and a = 5.1889(10) Å and c = 14.0418(3) Å for Zn2MnSbO6. Single-crystal X-ray diffraction analyses indicate that Zn2FeSbO6 consists of a cocrystal of superimposed Ni3TeO6 (NTO) and ordered ilmenite (OIL) components with a ratio of approximately 2:1 and Zn2MnSbO6 contains two nearly identical, but noncrystallographically related, OIL components in a ratio of approximately 6:1. XANES analysis shows Fe3+ and Mn3+ as formal oxidation states for Fe and Mn cations, respectively, for these A2BB′O6 compounds. SHG measurements for Zn2MnSbO6 indicate that it is noncentrosymmetric and confirm the polar R3 (no. 146) space group strongly implied by single-crystal reflection data. The magnetic measurements reveal spin-glass behavior with antiferromagnetic (AFM) interactions in both compounds and a frustration factor (f) being significantly larger for Zn2MnSbO6 (f ≈ 20) compared to Zn2FeSbO6 (f ≈ 7). While Zn2FeSbO6 exhibits AFM ordering at a Néel temperature (TN) of 9 K, Zn2MnSbO6 shows magnetic ordering around 4 K. Additionally, the negative Curie–Weiss temperatures for both compounds corroborate the presence of AFM exchange interactions.
{"title":"Zn2MnSbO6 and Zn2FeSbO6: Two New Polar High-Pressure Ordered Corundum-Type Compounds","authors":"Alessia Provino, Thomas J. Emge, David Walker, Corey E. Frank, Suguru Yoshida, Venkatraman Gopalan, Mark Croft, Zheng Deng, Changqing Jin, Pietro Manfrinetti, Martha Greenblatt","doi":"10.1021/acs.chemmater.4c02146","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02146","url":null,"abstract":"Two new compounds, Zn<sub>2</sub>FeSbO<sub>6</sub> and Zn<sub>2</sub>MnSbO<sub>6</sub>, have been synthesized under high-pressure and high-temperature conditions. The synthesis, single-crystal and powder X-ray diffraction, X-ray absorption near-edge spectroscopy (XANES), optical second harmonic generation (SHG), and magnetic and heat capacity measurements were carried out for both compounds and are described. The lattice parameters are <i>a</i> = 5.17754(6) Å and <i>c</i> = 13.80045(16) Å for Zn<sub>2</sub>FeSbO<sub>6</sub> and <i>a</i> = 5.1889(10) Å and <i>c</i> = 14.0418(3) Å for Zn<sub>2</sub>MnSbO<sub>6</sub>. Single-crystal X-ray diffraction analyses indicate that Zn<sub>2</sub>FeSbO<sub>6</sub> consists of a cocrystal of superimposed Ni<sub>3</sub>TeO<sub>6</sub> (NTO) and ordered ilmenite (OIL) components with a ratio of approximately 2:1 and Zn<sub>2</sub>MnSbO<sub>6</sub> contains two nearly identical, but noncrystallographically related, OIL components in a ratio of approximately 6:1. XANES analysis shows Fe<sup>3+</sup> and Mn<sup>3+</sup> as formal oxidation states for Fe and Mn cations, respectively, for these A<sub>2</sub>BB′O<sub>6</sub> compounds. SHG measurements for Zn<sub>2</sub>MnSbO<sub>6</sub> indicate that it is noncentrosymmetric and confirm the polar <i>R</i>3 (no. 146) space group strongly implied by single-crystal reflection data. The magnetic measurements reveal spin-glass behavior with antiferromagnetic (AFM) interactions in both compounds and a frustration factor (<i>f</i>) being significantly larger for Zn<sub>2</sub>MnSbO<sub>6</sub> (<i>f</i> ≈ 20) compared to Zn<sub>2</sub>FeSbO<sub>6</sub> (<i>f</i> ≈ 7). While Zn<sub>2</sub>FeSbO<sub>6</sub> exhibits AFM ordering at a Néel temperature (<i>T</i><sub>N</sub>) of 9 K, Zn<sub>2</sub>MnSbO<sub>6</sub> shows magnetic ordering around 4 K. Additionally, the negative Curie–Weiss temperatures for both compounds corroborate the presence of AFM exchange interactions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"13 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760523","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 : 2024-12-03DOI: 10.1021/acs.chemmater.4c02422
Monika Schied, Hanna Pazniak, Florian Brette, Paolo Lacovig, Michael Paris, Florent Boucher, Silvano Lizzit, Vincent Mauchamp, Rosanna Larciprete
Two-dimensional transition metal carbides or nitrides, so-called MXenes, hold the prospect of a proactive emergence as innovative catalysts and device components owing to the specific qualities gained from the chemical species that functionalize the layers. Tuning the nature and the number of the surface terminations becomes the key factor for the effective use of MXenes in technology. This study explores the capability of H atoms to modify the surface composition of Ti3C2Tx flakes. While exposing the sample at room temperature to H atoms, the change of its surface chemical state is followed by synchrotron radiation X-ray photoelectron spectroscopy. It turns out that halogen terminations are progressively and substantially removed. In parallel, the O terminations are partially converted into OH groups, the O/OH ratio being possibly controlled by the OH–OH repulsion. The dramatic surface composition change leaves the valence state of the Ti atoms almost unchanged. Density functional theory simulations of the valence band spectra for different Ti3C2Tx model systems identify all spectral features and model the change of the electronic properties around the Fermi level. Heating the hydrogenated sample to 400 K removes the OH groups, leaving the MXene surface deprived of most of the pristine terminations, thus giving way to new, application-oriented functionalization.
{"title":"Reactivity of Ti3C2Tx MXene with Atomic Hydrogen: Tuning of Surface Terminations by Halogen Removal and Reversible O to OH Conversion","authors":"Monika Schied, Hanna Pazniak, Florian Brette, Paolo Lacovig, Michael Paris, Florent Boucher, Silvano Lizzit, Vincent Mauchamp, Rosanna Larciprete","doi":"10.1021/acs.chemmater.4c02422","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02422","url":null,"abstract":"Two-dimensional transition metal carbides or nitrides, so-called MXenes, hold the prospect of a proactive emergence as innovative catalysts and device components owing to the specific qualities gained from the chemical species that functionalize the layers. Tuning the nature and the number of the surface terminations becomes the key factor for the effective use of MXenes in technology. This study explores the capability of H atoms to modify the surface composition of Ti<sub>3</sub>C<sub>2</sub>T<sub><i>x</i></sub> flakes. While exposing the sample at room temperature to H atoms, the change of its surface chemical state is followed by synchrotron radiation X-ray photoelectron spectroscopy. It turns out that halogen terminations are progressively and substantially removed. In parallel, the O terminations are partially converted into OH groups, the O/OH ratio being possibly controlled by the OH–OH repulsion. The dramatic surface composition change leaves the valence state of the Ti atoms almost unchanged. Density functional theory simulations of the valence band spectra for different Ti<sub>3</sub>C<sub>2</sub>T<sub><i>x</i></sub> model systems identify all spectral features and model the change of the electronic properties around the Fermi level. Heating the hydrogenated sample to 400 K removes the OH groups, leaving the MXene surface deprived of most of the pristine terminations, thus giving way to new, application-oriented functionalization.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"74 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760521","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 : 2024-12-03DOI: 10.1021/acs.chemmater.4c02592
Tongxin Zhou, Arulmonic Britto Seethalakshmi, Divakar Arumugam, Lihua Zhang, A. M. Milinda Abeykoon, Gihan Kwon, Daniel Olds, Xiaowei Teng
Vanadium-based oxides are intriguing electrode materials in aqueous electrochemical systems owing to their low cost and high theoretical capacity for alkali storage, especially lithium (Li) ions. However, a sequence of phase transformations and irreversible structure distortion upon Li-ion intercalation causes structural instability and has been a lingering problem for vanadium oxide electrodes. Here, we investigate lithium vanadate (Li–V3O8) for aqueous Li-ion intercalation and deintercalation processes. Unlike its crystalline V2O5 polymorph, Li–V3O8 retains monophasic lithiation, which is attributed to its disordered crystalline nature and large interplanar distance. Importantly, we show a unique and reversible sequence of disorder-to-order structural transition induced by the extent of lithiation, which indicates sequential interlayer and intralayer lithiation process, and vice versa in delithiation process, supported by electrokinetic analysis, in situ X-ray diffraction (XRD), and Debye scattering simulations. The absence of distortive phase transitions and multilithiation pathways facilitates Li-ion diffusion across the vanadate electrode materials to improve storage capacity. This work opens a new dimension for vanadium-based disordered oxides, accelerating the development of low-cost, aqueous electrochemical systems.
{"title":"Reversible Disorder-to-Order Transition Induced by Aqueous Lithiation in Vanadate Electrode Materials","authors":"Tongxin Zhou, Arulmonic Britto Seethalakshmi, Divakar Arumugam, Lihua Zhang, A. M. Milinda Abeykoon, Gihan Kwon, Daniel Olds, Xiaowei Teng","doi":"10.1021/acs.chemmater.4c02592","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02592","url":null,"abstract":"Vanadium-based oxides are intriguing electrode materials in aqueous electrochemical systems owing to their low cost and high theoretical capacity for alkali storage, especially lithium (Li) ions. However, a sequence of phase transformations and irreversible structure distortion upon Li-ion intercalation causes structural instability and has been a lingering problem for vanadium oxide electrodes. Here, we investigate lithium vanadate (Li–V<sub>3</sub>O<sub>8</sub>) for aqueous Li-ion intercalation and deintercalation processes. Unlike its crystalline V<sub>2</sub>O<sub>5</sub> polymorph, Li–V<sub>3</sub>O<sub>8</sub> retains monophasic lithiation, which is attributed to its disordered crystalline nature and large interplanar distance. Importantly, we show a unique and reversible sequence of disorder-to-order structural transition induced by the extent of lithiation, which indicates sequential interlayer and intralayer lithiation process, and <i>vice versa</i> in delithiation process, supported by electrokinetic analysis, <i>in situ</i> X-ray diffraction (XRD), and Debye scattering simulations. The absence of distortive phase transitions and multilithiation pathways facilitates Li-ion diffusion across the vanadate electrode materials to improve storage capacity. This work opens a new dimension for vanadium-based disordered oxides, accelerating the development of low-cost, aqueous electrochemical systems.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"13 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760531","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 : 2024-12-03DOI: 10.1021/acs.chemmater.4c02887
Jiarong Lv, Gangji Yi, Xuan Zou, Hongkun Liu, Xiangyu Han, Ling Huang, Hongmei Zeng, Zhien Lin, Guohong Zou
Birefringent crystals with significant optical anisotropy have played a pivotal role in laser technology and scientific research by modulating and controlling light polarization. In this study, we have successfully synthesized three new birefringent materials with mixed-valence antimony, namely, KSb3O6, RbSb3O6, and α-Sb2O4, through the introduction of Sb3+ with stereochemically active lone pairs (SCALP) to the total oxygen system using a high-temperature solution method. To the best of our knowledge, K/RbSb3O6 represents the first alkali metal mixed-valence Sb-based oxide. Interestingly, despite their similar sandwich structure, these materials exhibit vastly different levels of birefringence (almost 10 times difference). It is worth noting that α-Sb2O4 demonstrates the largest experimental birefringence (0.201 at 546 nm) among non-π-conjugated Sb-based oxides to date, which can be attributed to the synergistic effect of SCALP group distortion and arrangement. These findings hold valuable implications for guiding future efforts in designing and synthesizing large birefringent materials.
{"title":"Birefringence Disparity Induced by Synergistic Effects of Stereochemically Active Lone Pairs","authors":"Jiarong Lv, Gangji Yi, Xuan Zou, Hongkun Liu, Xiangyu Han, Ling Huang, Hongmei Zeng, Zhien Lin, Guohong Zou","doi":"10.1021/acs.chemmater.4c02887","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02887","url":null,"abstract":"Birefringent crystals with significant optical anisotropy have played a pivotal role in laser technology and scientific research by modulating and controlling light polarization. In this study, we have successfully synthesized three new birefringent materials with mixed-valence antimony, namely, KSb<sub>3</sub>O<sub>6</sub>, RbSb<sub>3</sub>O<sub>6</sub>, and α-Sb<sub>2</sub>O<sub>4</sub>, through the introduction of Sb<sup>3+</sup> with stereochemically active lone pairs (SCALP) to the total oxygen system using a high-temperature solution method. To the best of our knowledge, K/RbSb<sub>3</sub>O<sub>6</sub> represents the first alkali metal mixed-valence Sb-based oxide. Interestingly, despite their similar sandwich structure, these materials exhibit vastly different levels of birefringence (almost 10 times difference). It is worth noting that α-Sb<sub>2</sub>O<sub>4</sub> demonstrates the largest experimental birefringence (0.201 at 546 nm) among non-π-conjugated Sb-based oxides to date, which can be attributed to the synergistic effect of SCALP group distortion and arrangement. These findings hold valuable implications for guiding future efforts in designing and synthesizing large birefringent materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"215 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142763908","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}
Oxychalcogenides have become notable contenders for infrared nonlinear optical (IR NLO) applications because of their diverse heteroanionic functional motifs. However, while the main group elements are well-explored for these motifs, transition elements have been less studied and lack high-performance materials. To address this gap, we investigated a series of noncentrosymmetric [Ba4(Ba6S)][(VOxS4–x)6] (space group: P63), the first V-based salt-inclusion oxychalcogenides demonstrating phase-matched IR-NLO properties. We achieved this by cation–anion module cosubstitution in the centrosymmetric structure of [Ba4(Ba6Cl2)][(VO4)6] (space group: P63/m). The novel [Ba4(Ba6S)][(VOxS4–x)6] features isolated heteroanionic [VOxS4–x]3– units, charge-balanced Ba2+ cations, and a one-dimensional cationic chain of [Ba6S]10+ octahedral units. Moreover, [Ba4(Ba6S)][(VO3S)6] exhibits notable properties including a high second-harmonic-generation intensity (1.33 × AgGaS2@2900 nm), a substantial laser-induced damage threshold (7.65 × AgGaS2), a broad IR cutoff edge (up to 11.2 μm), and significant birefringence for phase matching (Δn = 0.073@2900 nm). Structural analysis and DFT calculations demonstrate that the configuration of the [VO3S]3– units enhances NLO properties and increases structural anisotropy. Our findings suggest that V-based salt-inclusion oxychalcogenides are a promising class for IR-NLO applications and highlight cation–anion module cosubstitution as an effective approach for creating high-performance heteroanionic NLO crystals.
{"title":"Balanced IR Nonlinear Optical Performance Achieved by Cation–Anion Module Cosubstitution in V-Based Salt-Inclusion Oxychalcogenides","authors":"Mao-Yin Ran, Sheng-Hua Zhou, Bing-Xuan Li, Xin-Tao Wu, Hua Lin, Qi-Long Zhu","doi":"10.1021/acs.chemmater.4c02779","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02779","url":null,"abstract":"Oxychalcogenides have become notable contenders for infrared nonlinear optical (IR NLO) applications because of their diverse heteroanionic functional motifs. However, while the main group elements are well-explored for these motifs, transition elements have been less studied and lack high-performance materials. To address this gap, we investigated a series of noncentrosymmetric [Ba<sub>4</sub>(Ba<sub>6</sub>S)][(VO<sub><i>x</i></sub>S<sub>4–<i>x</i></sub>)<sub>6</sub>] (space group: <i>P</i>6<sub>3</sub>), the first V-based salt-inclusion oxychalcogenides demonstrating phase-matched IR-NLO properties. We achieved this by cation–anion module cosubstitution in the centrosymmetric structure of [Ba<sub>4</sub>(Ba<sub>6</sub>Cl<sub>2</sub>)][(VO<sub>4</sub>)<sub>6</sub>] (space group: <i>P</i>6<sub>3</sub>/<i>m</i>). The novel [Ba<sub>4</sub>(Ba<sub>6</sub>S)][(VO<sub><i>x</i></sub>S<sub>4–<i>x</i></sub>)<sub>6</sub>] features isolated heteroanionic [VO<sub><i>x</i></sub>S<sub>4–<i>x</i></sub>]<sup>3–</sup> units, charge-balanced Ba<sup>2+</sup> cations, and a one-dimensional cationic chain of [Ba<sub>6</sub>S]<sup>10+</sup> octahedral units. Moreover, [Ba<sub>4</sub>(Ba<sub>6</sub>S)][(VO<sub>3</sub>S)<sub>6</sub>] exhibits notable properties including a high second-harmonic-generation intensity (1.33 × AgGaS<sub>2</sub>@2900 nm), a substantial laser-induced damage threshold (7.65 × AgGaS<sub>2</sub>), a broad IR cutoff edge (up to 11.2 μm), and significant birefringence for phase matching (Δ<i>n</i> = 0.073@2900 nm). Structural analysis and DFT calculations demonstrate that the configuration of the [VO<sub>3</sub>S]<sup>3–</sup> units enhances NLO properties and increases structural anisotropy. Our findings suggest that V-based salt-inclusion oxychalcogenides are a promising class for IR-NLO applications and highlight cation–anion module cosubstitution as an effective approach for creating high-performance heteroanionic NLO crystals.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"18 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760522","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 : 2024-12-03DOI: 10.1021/acs.chemmater.4c02109
Noa Azaria, Danielle Schweke, Lee Shelly, Shmuel Hayun
Ceria (CeO2) and doped ceria are well known for their catalytic surfaces that are active in various oxidation/reduction processes such as hydrogen production through thermochemical water splitting and three-way catalyst in combustion engines. Doping ceria with trivalent cations is expected to increase the concentration of oxygen vacancies due to charge compensation, but its effect on oxygen mobility or adsorption is not straightforward and depends on the specific trivalent element considered. In this study, we explore the effect of La addition on the bulk and surface properties of ceria by combining bulk (X-ray diffraction, thermogravimetry analysis, differential scanning calorimetry, and temperature-programmed desorption) and surface-sensitive techniques (X-ray photoelectron spectroscopy and water adsorption calorimetry). Three nanosized compositions of ceria doped with La were synthesized (at 5, 10, and 15% La3+) and thoroughly characterized. Compared with undoped ceria, the solid solutions obtained exhibited enhanced thermal stability. The solid solutions preserved their fluorite structure up to 1200 °C and exhibited a significantly reduced coarsening compared to pure ceria. The enhanced stability is attributed to the segregation of La to the surface. Doping of ceria with La led to an increase in the oxygen storage capacity, with the effect increasing with the increasing concentration of La. This increase was attributed to increased oxygen mobility with increasing La concentration. The addition of a small concentration of La (5%) leads to a significant increase in the amount of water adsorbed compared to pure ceria. Notably, water adsorption led to an enrichment of La on the surface, most pronounced for the highest La content, probably as the result of La diffusion from the subsurface to the surface. The heat of adsorption isotherms exhibits an unusual behavior, pointing to the need for further theoretical work.
{"title":"Effect of La Addition to Ceria on the Oxygen Storage Capacity and the Energetics of Water Adsorption","authors":"Noa Azaria, Danielle Schweke, Lee Shelly, Shmuel Hayun","doi":"10.1021/acs.chemmater.4c02109","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02109","url":null,"abstract":"Ceria (CeO<sub>2</sub>) and doped ceria are well known for their catalytic surfaces that are active in various oxidation/reduction processes such as hydrogen production through thermochemical water splitting and three-way catalyst in combustion engines. Doping ceria with trivalent cations is expected to increase the concentration of oxygen vacancies due to charge compensation, but its effect on oxygen mobility or adsorption is not straightforward and depends on the specific trivalent element considered. In this study, we explore the effect of La addition on the bulk and surface properties of ceria by combining bulk (X-ray diffraction, thermogravimetry analysis, differential scanning calorimetry, and temperature-programmed desorption) and surface-sensitive techniques (X-ray photoelectron spectroscopy and water adsorption calorimetry). Three nanosized compositions of ceria doped with La were synthesized (at 5, 10, and 15% La<sup>3+</sup>) and thoroughly characterized. Compared with undoped ceria, the solid solutions obtained exhibited enhanced thermal stability. The solid solutions preserved their fluorite structure up to 1200 °C and exhibited a significantly reduced coarsening compared to pure ceria. The enhanced stability is attributed to the segregation of La to the surface. Doping of ceria with La led to an increase in the oxygen storage capacity, with the effect increasing with the increasing concentration of La. This increase was attributed to increased oxygen mobility with increasing La concentration. The addition of a small concentration of La (5%) leads to a significant increase in the amount of water adsorbed compared to pure ceria. Notably, water adsorption led to an enrichment of La on the surface, most pronounced for the highest La content, probably as the result of La diffusion from the subsurface to the surface. The heat of adsorption isotherms exhibits an unusual behavior, pointing to the need for further theoretical work.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"262 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142763911","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 : 2024-12-02DOI: 10.1021/acs.chemmater.4c02190
Prasad V. Sarma, Boris V. Kramar, Lihaokun Chen, Sayantan Sasmal, Nicholas P. Weingartz, Jiawei Huang, James B. Mitchell, Minkyoung Kwak, Lin X. Chen, Shannon W. Boettcher
The local electric field strength is thought to affect the rate of water dissociation (WD) in bipolar membranes (BPMs) at the catalyst–nanoparticle surfaces. Here, we study core–shell nanoparticles, where the core is metallic, semiconducting, or insulating, to understand this effect. The nanoparticle cores were coated with a WD catalyst layer (TiO2 or HfO2) via atomic layer deposition (ALD), and the morphology was imaged with transmission electron microscopy. Irrespective of the core material, these core–shell catalysts displayed comparable WD overpotentials at optimal mass loading, despite the hypothesized differences in the electric field strength across the catalyst particle suggested by continuum electrostatic simulations. Substantial atomic interdiffusion between the core and shell was ruled out by X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and diffuse reflectance optical measurements. However, the optimal mass loading of catalyst was roughly 1 order of magnitude higher for the conductive and high dielectric core materials than for the low dielectric insulating cores. These findings are consistent with the hypothesis that electric field screening within the core material focuses the electric field drop between particles such that larger film thicknesses can be tolerated. Collectively, these data support the idea that it is the local electric field at the molecular level that controls proton-transfer rates and that the metal core/dielectric-shell constructs introduced here modulate that field. Further materials and synthetic design may enable optimization of the electric field strength across the proton-transfer trajectory at the material surface.
{"title":"Local Electric Field Effects on Water Dissociation in Bipolar Membranes Studied Using Core–Shell Catalysts","authors":"Prasad V. Sarma, Boris V. Kramar, Lihaokun Chen, Sayantan Sasmal, Nicholas P. Weingartz, Jiawei Huang, James B. Mitchell, Minkyoung Kwak, Lin X. Chen, Shannon W. Boettcher","doi":"10.1021/acs.chemmater.4c02190","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02190","url":null,"abstract":"The local electric field strength is thought to affect the rate of water dissociation (WD) in bipolar membranes (BPMs) at the catalyst–nanoparticle surfaces. Here, we study core–shell nanoparticles, where the core is metallic, semiconducting, or insulating, to understand this effect. The nanoparticle cores were coated with a WD catalyst layer (TiO<sub>2</sub> or HfO<sub>2</sub>) via atomic layer deposition (ALD), and the morphology was imaged with transmission electron microscopy. Irrespective of the core material, these core–shell catalysts displayed comparable WD overpotentials at optimal mass loading, despite the hypothesized differences in the electric field strength across the catalyst particle suggested by continuum electrostatic simulations. Substantial atomic interdiffusion between the core and shell was ruled out by X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and diffuse reflectance optical measurements. However, the optimal mass loading of catalyst was roughly 1 order of magnitude higher for the conductive and high dielectric core materials than for the low dielectric insulating cores. These findings are consistent with the hypothesis that electric field screening within the core material focuses the electric field drop between particles such that larger film thicknesses can be tolerated. Collectively, these data support the idea that it is the local electric field at the molecular level that controls proton-transfer rates and that the metal core/dielectric-shell constructs introduced here modulate that field. Further materials and synthetic design may enable optimization of the electric field strength across the proton-transfer trajectory at the material surface.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"26 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760524","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 : 2024-11-29DOI: 10.1021/acs.chemmater.4c02257
Shuo Wang, Sheng Gong, Thorben Böger, Jon A. Newnham, Daniele Vivona, Muy Sokseiha, Kiarash Gordiz, Abhishek Aggarwal, Taishan Zhu, Wolfgang G. Zeier, Jeffrey C. Grossman, Yang Shao-Horn
The widespread adoption of multimodal machine learning (ML) models such as GPT-4 and Gemini has revolutionized various research domains, including computer vision and natural language processing. However, their implementation in materials informatics remains underexplored, despite the availability of diverse modalities in materials data. This study introduces an approach to multimodal machine learning in materials science via composition-structure bimodal learning and proposes the COmposition-Structure Bimodal Network (COSNet). The COSNet demonstrates significantly improved performance in predicting a variety of material properties, such as lithium-ion conductivity in solid electrolytes, band gap, refractive index, and formation enthalpy. This research highlights the critical importance of representation alignment in multimodal learning for materials science, enabling knowledge transfer between modalities and avoiding biased or divergent learning. Furthermore, we present an integrated paradigm that combines multimodal learning, transfer learning, ensemble methods, and atomic simulation to facilitate the discovery of novel superionic conductors.
{"title":"Multimodal Machine Learning for Materials Science: Discovery of Novel Li-Ion Solid Electrolytes","authors":"Shuo Wang, Sheng Gong, Thorben Böger, Jon A. Newnham, Daniele Vivona, Muy Sokseiha, Kiarash Gordiz, Abhishek Aggarwal, Taishan Zhu, Wolfgang G. Zeier, Jeffrey C. Grossman, Yang Shao-Horn","doi":"10.1021/acs.chemmater.4c02257","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02257","url":null,"abstract":"The widespread adoption of multimodal machine learning (ML) models such as GPT-4 and Gemini has revolutionized various research domains, including computer vision and natural language processing. However, their implementation in materials informatics remains underexplored, despite the availability of diverse modalities in materials data. This study introduces an approach to multimodal machine learning in materials science via composition-structure bimodal learning and proposes the COmposition-Structure Bimodal Network (COSNet). The COSNet demonstrates significantly improved performance in predicting a variety of material properties, such as lithium-ion conductivity in solid electrolytes, band gap, refractive index, and formation enthalpy. This research highlights the critical importance of representation alignment in multimodal learning for materials science, enabling knowledge transfer between modalities and avoiding biased or divergent learning. Furthermore, we present an integrated paradigm that combines multimodal learning, transfer learning, ensemble methods, and atomic simulation to facilitate the discovery of novel superionic conductors.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"25 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142752900","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 : 2024-11-29DOI: 10.1021/acs.chemmater.4c0225710.1021/acs.chemmater.4c02257
Shuo Wang, Sheng Gong, Thorben Böger, Jon A. Newnham, Daniele Vivona, Muy Sokseiha, Kiarash Gordiz, Abhishek Aggarwal, Taishan Zhu, Wolfgang G. Zeier, Jeffrey C. Grossman* and Yang Shao-Horn*,
The widespread adoption of multimodal machine learning (ML) models such as GPT-4 and Gemini has revolutionized various research domains, including computer vision and natural language processing. However, their implementation in materials informatics remains underexplored, despite the availability of diverse modalities in materials data. This study introduces an approach to multimodal machine learning in materials science via composition-structure bimodal learning and proposes the COmposition-Structure Bimodal Network (COSNet). The COSNet demonstrates significantly improved performance in predicting a variety of material properties, such as lithium-ion conductivity in solid electrolytes, band gap, refractive index, and formation enthalpy. This research highlights the critical importance of representation alignment in multimodal learning for materials science, enabling knowledge transfer between modalities and avoiding biased or divergent learning. Furthermore, we present an integrated paradigm that combines multimodal learning, transfer learning, ensemble methods, and atomic simulation to facilitate the discovery of novel superionic conductors.
{"title":"Multimodal Machine Learning for Materials Science: Discovery of Novel Li-Ion Solid Electrolytes","authors":"Shuo Wang, Sheng Gong, Thorben Böger, Jon A. Newnham, Daniele Vivona, Muy Sokseiha, Kiarash Gordiz, Abhishek Aggarwal, Taishan Zhu, Wolfgang G. Zeier, Jeffrey C. Grossman* and Yang Shao-Horn*, ","doi":"10.1021/acs.chemmater.4c0225710.1021/acs.chemmater.4c02257","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02257https://doi.org/10.1021/acs.chemmater.4c02257","url":null,"abstract":"<p >The widespread adoption of multimodal machine learning (ML) models such as GPT-4 and Gemini has revolutionized various research domains, including computer vision and natural language processing. However, their implementation in materials informatics remains underexplored, despite the availability of diverse modalities in materials data. This study introduces an approach to multimodal machine learning in materials science via composition-structure bimodal learning and proposes the COmposition-Structure Bimodal Network (COSNet). The COSNet demonstrates significantly improved performance in predicting a variety of material properties, such as lithium-ion conductivity in solid electrolytes, band gap, refractive index, and formation enthalpy. This research highlights the critical importance of representation alignment in multimodal learning for materials science, enabling knowledge transfer between modalities and avoiding biased or divergent learning. Furthermore, we present an integrated paradigm that combines multimodal learning, transfer learning, ensemble methods, and atomic simulation to facilitate the discovery of novel superionic conductors.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 23","pages":"11541–11550 11541–11550"},"PeriodicalIF":7.2,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142844020","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}
We investigated tetracyanoanthracenediacenaphthalimides (TCDADIs) as n-type organic semiconductors (OSCs) and assessed their molecular self-assembly in forming monolayers and thin films using optical absorption spectroscopy, scanning tunneling microscopy (STM), atomic force microscopy (AFM), and grazing incidence wide-angle X-ray scattering (GIWAXS). The absorption spectra, along with quantitative GIWAXS analysis, reveal the influence of molecular structure (alkyl chain length) and film processing conditions (annealing temperature and spin-coating speed) on the orientation of TCDADI molecules in films. Our findings indicate that increasing the spin-coating speed and annealing temperatures causes a transition from a mixed phase to a predominantly edge-on molecular orientation. This transition significantly enhances the electron mobility, from 0.01 to 0.05 cm2 V–1 s–1 for TCDADI-C16 and from 0.13 to 0.20 cm2 V–1 s–1 for TCDADI-C24. In addition, we highlight the potential of TCDADIs for photodetector applications, showing a photoresponse gain of over 2000 under white light.
{"title":"Tetracyanoanthracenediacenaphthalimides as n-Type Organic Semiconductors: Control of Molecular Orientation","authors":"Ying-Hsuan Liu, Pegah Ghamari, Meng Wei, Cory Ruchlin, Daling Cui, Federico Rosei, Dmytro F. Perepichka","doi":"10.1021/acs.chemmater.4c02653","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02653","url":null,"abstract":"We investigated tetracyanoanthracenediacenaphthalimides (TCDADIs) as n-type organic semiconductors (OSCs) and assessed their molecular self-assembly in forming monolayers and thin films using optical absorption spectroscopy, scanning tunneling microscopy (STM), atomic force microscopy (AFM), and grazing incidence wide-angle X-ray scattering (GIWAXS). The absorption spectra, along with quantitative GIWAXS analysis, reveal the influence of molecular structure (alkyl chain length) and film processing conditions (annealing temperature and spin-coating speed) on the orientation of TCDADI molecules in films. Our findings indicate that increasing the spin-coating speed and annealing temperatures causes a transition from a mixed phase to a predominantly edge-on molecular orientation. This transition significantly enhances the electron mobility, from 0.01 to 0.05 cm<sup>2</sup> V<sup>–1</sup> s<sup>–1</sup> for TCDADI-C16 and from 0.13 to 0.20 cm<sup>2</sup> V<sup>–1</sup> s<sup>–1</sup> for TCDADI-C24. In addition, we highlight the potential of TCDADIs for photodetector applications, showing a photoresponse gain of over 2000 under white light.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142752904","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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