Chemistry of Materials最新文献

{"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 (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.","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}

{"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 (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.","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}

{"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}

{"title":"Multimodal Machine Learning for Materials Science: Discovery of Novel Li-Ion Solid Electrolytes","authors":"Shuo Wang,&nbsp;Sheng Gong,&nbsp;Thorben Böger,&nbsp;Jon A. Newnham,&nbsp;Daniele Vivona,&nbsp;Muy Sokseiha,&nbsp;Kiarash Gordiz,&nbsp;Abhishek Aggarwal,&nbsp;Taishan Zhu,&nbsp;Wolfgang G. Zeier,&nbsp;Jeffrey C. Grossman* and Yang Shao-Horn*,&nbsp;","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}

{"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 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.","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}

{"title":"Correction to “Crystalline Antimony Selenide Thin Films for Optoelectronics through Photonic Curing”","authors":"Udari Wijesinghe, William D. Tetlow, Pietro Maiello, Nicole Fleck, Graeme O’Dowd, Neil S. Beattie, Giulia Longo, Oliver S. Hutter","doi":"10.1021/acs.chemmater.4c02495","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02495","url":null,"abstract":"In the original article of <cite><i>Chem. Mater.</i></cite> <span>2024</span>, <em>36</em>, <i>12</i>, 6027–6037, an oversight occurred whereby an important reference (reference 13 in the original text) was cited but not properly discussed. The authors offer their apologies for this oversight. The reference provides important and valuable methodological information using photonic curing, and it was therefore taken as inspiration. In fact, the article <cite><i>Chem.\u0000Mater.</i></cite> <span>2024</span>, <em>36</em>, <i>12</i>, 6027–6037 follows a similar methodology to the one reported in reference 13, even if applied to a different material system. On page 6027, after the sentence citing reference 13, the above reference should be cited again with an additional sentence reading “The current work follows a methodology similar to the work from Xu et al.¹³” On page 6031 after the sentence “Furthermore, a shorter discharge of the lamp delivers a higher current density in the UV range, which explains why overconverted films are easily obtained (i.e., the Xe lamp spectrum depends on the current density)”, the following sentence should be added: “Longer pulse lengths also work better on perovskites.¹³ which suggests that long pulse lengths could be beneficial for other light-absorbing photovoltaic materials.” <b>Impact of the Addition</b>: This addition does not affect the conclusions of the original article in any way. This article has not yet been cited by other publications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"259 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142752901","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhancing Lithium Ion Conduction in LLZO-Based Solid Electrolytes through Anion Doping for Advanced Energy Storage: Insights from Molecular Dynamics Simulations","authors":"Cristina Lopez-Puga, Jincheng Du","doi":"10.1021/acs.chemmater.4c02506","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02506","url":null,"abstract":"Solid-state electrolytes (SSEs) have emerged as promising alternatives to traditional liquid electrolytes due to their enhanced safety, higher stability and energy density in energy storage applications. Among SSEs, cubic Li₇La₃Zr₂O₁₂ (LLZO) is considered particularly promising, offering high lithium ion conductivity, high chemical stability to metal anode and a wide electrochemical stability window. Nevertheless, the cubic phase converts to a less conductive tetragonal phase during cooling in pure LLZO. Doping is one of most effective methods to stabilize the cubic LLZO at lower temperatures and improve the ion conductivity. While there is extensive research on cation site substitutions, studies on anion doping are very limited. We have investigated the effects of fluorine doping on the phase stability and ion conductivity of LLZO, exploring fluorine concentrations ranging from 1 to 10% across a wide temperature range of 300–1400 K using molecular dynamics (MD) simulations based on polarizable shell model potentials. Our results indicate that 3% fluorine doping achieves the highest diffusion coefficient (3.69 × 10^–7 cm² s^–1) at room temperature, while the lowest activation energy (∼0.22 eV) also occurs at around 3% doping, which is in good agreement with experimental observations. Doping at 1% was found to be insufficient to stabilize the cubic phase, while high fluorine concentrations (&gt;4%) inhibited ion migration pathways due to stronger electrostatic interactions between point defects <i>V</i>_Li^′ and <i>F</i>_O^•. Defect formation energies were also calculated to study defect formation and interactions and their effect on lithium ion conduction. Lithium ion diffusion pathways and mechanisms are also explored by using trajectories from MD simulations. This study provides insights into the optimization of fluorine-doped LLZO, suggesting that moderate doping levels (around 3%) offer a balance between phase stability and ionic conductivity.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"69 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142752903","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhancing Lithium Ion Conduction in LLZO-Based Solid Electrolytes through Anion Doping for Advanced Energy Storage: Insights from Molecular Dynamics Simulations","authors":"Cristina Lopez-Puga,&nbsp; and ,&nbsp;Jincheng Du*,&nbsp;","doi":"10.1021/acs.chemmater.4c0250610.1021/acs.chemmater.4c02506","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02506https://doi.org/10.1021/acs.chemmater.4c02506","url":null,"abstract":"<p >Solid-state electrolytes (SSEs) have emerged as promising alternatives to traditional liquid electrolytes due to their enhanced safety, higher stability and energy density in energy storage applications. Among SSEs, cubic Li₇La₃Zr₂O₁₂ (LLZO) is considered particularly promising, offering high lithium ion conductivity, high chemical stability to metal anode and a wide electrochemical stability window. Nevertheless, the cubic phase converts to a less conductive tetragonal phase during cooling in pure LLZO. Doping is one of most effective methods to stabilize the cubic LLZO at lower temperatures and improve the ion conductivity. While there is extensive research on cation site substitutions, studies on anion doping are very limited. We have investigated the effects of fluorine doping on the phase stability and ion conductivity of LLZO, exploring fluorine concentrations ranging from 1 to 10% across a wide temperature range of 300–1400 K using molecular dynamics (MD) simulations based on polarizable shell model potentials. Our results indicate that 3% fluorine doping achieves the highest diffusion coefficient (3.69 × 10^–7 cm² s^–1) at room temperature, while the lowest activation energy (∼0.22 eV) also occurs at around 3% doping, which is in good agreement with experimental observations. Doping at 1% was found to be insufficient to stabilize the cubic phase, while high fluorine concentrations (&gt;4%) inhibited ion migration pathways due to stronger electrostatic interactions between point defects <i>V</i>_Li^′ and <i>F</i>_O^•. Defect formation energies were also calculated to study defect formation and interactions and their effect on lithium ion conduction. Lithium ion diffusion pathways and mechanisms are also explored by using trajectories from MD simulations. This study provides insights into the optimization of fluorine-doped LLZO, suggesting that moderate doping levels (around 3%) offer a balance between phase stability and ionic conductivity.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 23","pages":"11570–11582 11570–11582"},"PeriodicalIF":7.2,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850760","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to “Crystalline Antimony Selenide Thin Films for Optoelectronics through Photonic Curing”","authors":"Udari Wijesinghe,&nbsp;William D. Tetlow,&nbsp;Pietro Maiello,&nbsp;Nicole Fleck,&nbsp;Graeme O’Dowd,&nbsp;Neil S. Beattie,&nbsp;Giulia Longo* and Oliver S. Hutter*,&nbsp;","doi":"10.1021/acs.chemmater.4c0249510.1021/acs.chemmater.4c02495","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02495https://doi.org/10.1021/acs.chemmater.4c02495","url":null,"abstract":"","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 23","pages":"11717 11717"},"PeriodicalIF":7.2,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c02495","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850772","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tetracyanoanthracenediacenaphthalimides as n-Type Organic Semiconductors: Control of Molecular Orientation","authors":"Ying-Hsuan Liu,&nbsp;Pegah Ghamari,&nbsp;Meng Wei,&nbsp;Cory Ruchlin,&nbsp;Daling Cui,&nbsp;Federico Rosei and Dmytro F. Perepichka*,&nbsp;","doi":"10.1021/acs.chemmater.4c0265310.1021/acs.chemmater.4c02653","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02653https://doi.org/10.1021/acs.chemmater.4c02653","url":null,"abstract":"<p >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.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 23","pages":"11618–11627 11618–11627"},"PeriodicalIF":7.2,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142844021","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}