Chemistry of Materials最新文献

{"title":"Configuration Engineering of Plasmonic-Metal/Semiconductor Nanohybrids for Solar Fuel Production†","authors":"Tianyi Yang,&nbsp;Binbin Lu,&nbsp;Yong Zuo and Jianfeng Huang*,&nbsp;","doi":"10.1021/acs.chemmater.4c0317010.1021/acs.chemmater.4c03170","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03170https://doi.org/10.1021/acs.chemmater.4c03170","url":null,"abstract":"<p >Solar fuel production, which primarily focuses on harnessing solar energy to convert CO₂ into fuels or produce H₂ through water splitting, holds transformative potential for addressing global energy demands and environmental challenges. However, several obstacles still need to be overcome, particularly concerning the efficiency and scalability of solar fuel systems. Plasmonic-metal/semiconductor nanohybrids (PSNs) represent a cutting-edge class of photocatalysts designed to overcome current efficiency bottlenecks by merging the unique localized surface plasmon resonance (LSPR) properties of plasmonic metals with the catalytic efficiency of semiconductors, thereby enhancing the overall efficiency of light-driven solar-to-fuel conversion. Precise regulation of PSN structures is essential for guiding the extraction and flow of energy and charge carriers within the nanohybrids, which ultimately determines their photocatalytic performance. In this perspective, we aim to highlight the direct impact that the configuration of these nanohybrids has on the efficiency of solar fuel production through various triggered plasmonic energy transfer mechanisms. To this end, we begin with a brief introduction to the basic plasmonic effects and fundamental energy transfer mechanisms between plasmonic metals and semiconductors. We then provide representative examples of how PSNs with five categories of engineered configurations (namely, core–shell, yolk–shell, Janus/heterodimer/dumbbell, core–satellite, and other hierarchical structures) enhance solar fuel production through three primary mechanisms: plasmon-induced resonance energy transfer, light absorption/trapping, and hot electron injection. We conclude this Perspective by outlining the remaining challenges and research directions in this field.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 5","pages":"1685–1715 1685–1715"},"PeriodicalIF":7.2,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143590593","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":"Guidelines for the Selection of Scintillators for Indirect Photon-Counting X-ray Detectors","authors":"J. Jasper van Blaaderen*,&nbsp;Casper van Aarle,&nbsp;David Leibold,&nbsp;Pieter Dorenbos and Dennis R. Schaart*,&nbsp;","doi":"10.1021/acs.chemmater.4c0343710.1021/acs.chemmater.4c03437","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03437https://doi.org/10.1021/acs.chemmater.4c03437","url":null,"abstract":"<p >X-ray photon-counting detectors (PCDs) are a rapidly developing technology. Current PCDs used in medical imaging are based on CdTe, CZT, or Si semiconductor detectors, which directly convert X-ray photons into electrical pulses. An alternative approach is to combine ultrafast scintillators with silicon photomultipliers (SiPMs). Here, an overview is presented of different classes of scintillators, with the aim of assessing their potential application in scintillator-SiPM based indirect X-ray PCDs. To this end, three figures of merit (FOMs) are defined: the pulse intensity, the pulse duration, and the pulse quality. These FOMs quantify how characteristics such as light yield, pulse shape, and energy resolution affect the suitability of scintillators for application in indirect PCDs. These FOMs are based on emissive characteristics; a fourth FOM (ρZ_<i>eff</i>^3.5) is used to also take stopping power into account. Other important properties for the selection process include low self-absorption, low after-glow, possibility to produce sub-mm pitch pixel arrays, and cost-effectiveness. It is shown that material classes with promising emission properties are Ce³⁺- or Pr³⁺-doped materials, near band gap exciton emitters, plastics, and core–valence materials. Possible shortcomings of each of these groups, e.g., suboptimal emission wavelength, nonproportionality, and density, are discussed. Additionally, the engineering approach of quenching the scintillator emission, resulting in a targeted shortening of the decay time, and the possibility of codoping are explored. When selecting and/or engineering a material, it is important to consider not only the characteristics of the scintillator but also relevant SiPM properties, such as recharge time and photodetection efficiency.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 5","pages":"1716–1740 1716–1740"},"PeriodicalIF":7.2,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c03437","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143590597","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":"Guidelines for the Selection of Scintillators for Indirect Photon-Counting X-ray Detectors","authors":"J. Jasper van Blaaderen, Casper van Aarle, David Leibold, Pieter Dorenbos, Dennis R. Schaart","doi":"10.1021/acs.chemmater.4c03437","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03437","url":null,"abstract":"X-ray photon-counting detectors (PCDs) are a rapidly developing technology. Current PCDs used in medical imaging are based on CdTe, CZT, or Si semiconductor detectors, which directly convert X-ray photons into electrical pulses. An alternative approach is to combine ultrafast scintillators with silicon photomultipliers (SiPMs). Here, an overview is presented of different classes of scintillators, with the aim of assessing their potential application in scintillator-SiPM based indirect X-ray PCDs. To this end, three figures of merit (FOMs) are defined: the pulse intensity, the pulse duration, and the pulse quality. These FOMs quantify how characteristics such as light yield, pulse shape, and energy resolution affect the suitability of scintillators for application in indirect PCDs. These FOMs are based on emissive characteristics; a fourth FOM (ρZ_<i>eff</i>^3.5) is used to also take stopping power into account. Other important properties for the selection process include low self-absorption, low after-glow, possibility to produce sub-mm pitch pixel arrays, and cost-effectiveness. It is shown that material classes with promising emission properties are Ce³⁺- or Pr³⁺-doped materials, near band gap exciton emitters, plastics, and core–valence materials. Possible shortcomings of each of these groups, e.g., suboptimal emission wavelength, nonproportionality, and density, are discussed. Additionally, the engineering approach of quenching the scintillator emission, resulting in a targeted shortening of the decay time, and the possibility of codoping are explored. When selecting and/or engineering a material, it is important to consider not only the characteristics of the scintillator but also relevant SiPM properties, such as recharge time and photodetection efficiency.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"210 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495738","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":"Configuration Engineering of Plasmonic-Metal/Semiconductor Nanohybrids for Solar Fuel Production†","authors":"Tianyi Yang, Binbin Lu, Yong Zuo, Jianfeng Huang","doi":"10.1021/acs.chemmater.4c03170","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03170","url":null,"abstract":"Solar fuel production, which primarily focuses on harnessing solar energy to convert CO₂ into fuels or produce H₂ through water splitting, holds transformative potential for addressing global energy demands and environmental challenges. However, several obstacles still need to be overcome, particularly concerning the efficiency and scalability of solar fuel systems. Plasmonic-metal/semiconductor nanohybrids (PSNs) represent a cutting-edge class of photocatalysts designed to overcome current efficiency bottlenecks by merging the unique localized surface plasmon resonance (LSPR) properties of plasmonic metals with the catalytic efficiency of semiconductors, thereby enhancing the overall efficiency of light-driven solar-to-fuel conversion. Precise regulation of PSN structures is essential for guiding the extraction and flow of energy and charge carriers within the nanohybrids, which ultimately determines their photocatalytic performance. In this perspective, we aim to highlight the direct impact that the configuration of these nanohybrids has on the efficiency of solar fuel production through various triggered plasmonic energy transfer mechanisms. To this end, we begin with a brief introduction to the basic plasmonic effects and fundamental energy transfer mechanisms between plasmonic metals and semiconductors. We then provide representative examples of how PSNs with five categories of engineered configurations (namely, core–shell, yolk–shell, Janus/heterodimer/dumbbell, core–satellite, and other hierarchical structures) enhance solar fuel production through three primary mechanisms: plasmon-induced resonance energy transfer, light absorption/trapping, and hot electron injection. We conclude this Perspective by outlining the remaining challenges and research directions in this field.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"6 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495902","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":"Tuning the Metal-Free Room Temperature Phosphorescence of Fluorene-Based Chromophores through Side-Group Molecular Engineering","authors":"Maxime Rémond, Hee Jung Kim, Yanghyun Auh, Kwang Keat Leong, Jinbo Kim, Hwandong Jang, Yongnam Ahn, Kiyoung Chang, Eunkyoung Kim","doi":"10.1021/acs.chemmater.4c03482","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03482","url":null,"abstract":"A series of bromofluorene-based metal-free dyes (<b>BrFX</b>) exhibiting room-temperature phosphorescence (<b>RTP</b>) were synthesized via a scalable two-step process in high yields from the linkage of 2-bromofluorene (<b>BrF</b>) through a ketone with different side group (<b>X</b>). Structural analysis of <b>BrFX</b> revealed that the ketone group was well conjugated with the fluorene group but less conjugated with the <b>X</b> side group. The nature of the <b>X</b> side group played a crucial role in fine-tuning emission maxima of <b>BrFX</b>. Moreover, incorporating aromatic side groups having low triplet energy effectively red-shifted RTP and increased its lifetime. Theoretical calculations using density functional theory revealed that the highest occupied molecular orbital was localized on the fluorene core, supporting these experimental observations. <b>BrFX</b> showed strong phosphorescence in diverse amorphous semiconducting hosts with quantum yields up to 65%, enabling their application in light-emitting electrochemical cells. These findings underscore the success of converting <b>BrFH</b> into its ketone analogs, <b>BrFX</b>, as an effective strategy to enhance both phosphorescence and electroluminescence, representing a notable advancement in <b>RTP</b> molecule design.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"49 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495904","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":"Chemistry of Materials Highlights Colloidal Semiconductor Nanocrystals","authors":"Paul D. Goring,&nbsp; and ,&nbsp;Sara E. Skrabalak*,&nbsp;","doi":"10.1021/acs.chemmater.5c0018310.1021/acs.chemmater.5c00183","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00183https://doi.org/10.1021/acs.chemmater.5c00183","url":null,"abstract":"","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 4","pages":"1335–1336 1335–1336"},"PeriodicalIF":7.2,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143478237","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":"First-Principles Statistical Mechanics Study of Magnetic Fluctuations and Order–Disorder in the Spinel LiNi0.5Mn1.5O4 Cathode","authors":"Graciela E. García Ponte, Sesha Sai Behara, Euan N. Bassey, Raphaële J. Clément, Anton Van der Ven","doi":"10.1021/acs.chemmater.4c02772","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02772","url":null,"abstract":"While significant magnetic interactions exist in lithium transition metal oxides, commonly used as Li-ion cathodes, the interplay between magnetic couplings, disorder, and redox processes remains poorly understood. In this work, we focus on the high-voltage spinel LiNi_0.5Mn_1.5O₄ (LNMO) cathode as a model system on which to apply a computational framework that uses first principles-based statistical mechanics methods to predict the finite temperature magnetic properties of materials and provide insights into the complex interplay between magnetic and chemical degrees of freedom. Density functional theory calculations on multiple distinct Ni–Mn orderings within the LNMO system, including the ordered ground-state structure (space group <i>P</i>4₃32), reveal a preference for a ferrimagnetic arrangement of the Ni and Mn sublattices due to strong antiferromagnetic superexchange interactions between neighboring Mn⁴⁺ and Ni²⁺ ions and ferromagnetic Mn–Mn and Ni–Ni couplings, as revealed by magnetic cluster expansions. These results are consistent with qualitative predictions using the Goodenough-Kanamori-Anderson rules. Simulations of the finite temperature magnetic properties of LNMO are conducted using Metropolis Monte Carlo. We find that a “semiclassical” Monte Carlo sampling method based on the Heisenberg Hamiltonian accurately predicts experimental magnetic transition temperatures observed in magnetometry measurements. This study highlights the importance of a robust computational toolkit that accurately captures the complex chemomagnetic interactions and predicts finite temperature magnetic behavior to help analyze experimental magnetic and magnetic resonance spectroscopy data acquired <i>ex situ</i> and <i>operando</i>.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"32 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486599","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":"The Future of Colloidal Semiconductor Nanocrystals","authors":"Raffaella Buonsanti*,&nbsp; and ,&nbsp;Brandi Cossairt*,&nbsp;","doi":"10.1021/acs.chemmater.5c0002310.1021/acs.chemmater.5c00023","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00023https://doi.org/10.1021/acs.chemmater.5c00023","url":null,"abstract":"","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 4","pages":"1333–1334 1333–1334"},"PeriodicalIF":7.2,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143478249","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":"Tuning the Metal-Free Room Temperature Phosphorescence of Fluorene-Based Chromophores through Side-Group Molecular Engineering","authors":"Maxime Rémond,&nbsp;Hee Jung Kim,&nbsp;Yanghyun Auh,&nbsp;Kwang Keat Leong,&nbsp;Jinbo Kim,&nbsp;Hwandong Jang,&nbsp;Yongnam Ahn,&nbsp;Kiyoung Chang and Eunkyoung Kim*,&nbsp;","doi":"10.1021/acs.chemmater.4c0348210.1021/acs.chemmater.4c03482","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03482https://doi.org/10.1021/acs.chemmater.4c03482","url":null,"abstract":"<p >A series of bromofluorene-based metal-free dyes (<b>BrFX</b>) exhibiting room-temperature phosphorescence (<b>RTP</b>) were synthesized via a scalable two-step process in high yields from the linkage of 2-bromofluorene (<b>BrF</b>) through a ketone with different side group (<b>X</b>). Structural analysis of <b>BrFX</b> revealed that the ketone group was well conjugated with the fluorene group but less conjugated with the <b>X</b> side group. The nature of the <b>X</b> side group played a crucial role in fine-tuning emission maxima of <b>BrFX</b>. Moreover, incorporating aromatic side groups having low triplet energy effectively red-shifted RTP and increased its lifetime. Theoretical calculations using density functional theory revealed that the highest occupied molecular orbital was localized on the fluorene core, supporting these experimental observations. <b>BrFX</b> showed strong phosphorescence in diverse amorphous semiconducting hosts with quantum yields up to 65%, enabling their application in light-emitting electrochemical cells. These findings underscore the success of converting <b>BrFH</b> into its ketone analogs, <b>BrFX</b>, as an effective strategy to enhance both phosphorescence and electroluminescence, representing a notable advancement in <b>RTP</b> molecule design.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 5","pages":"1995–2007 1995–2007"},"PeriodicalIF":7.2,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143590871","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":"First-Principles Statistical Mechanics Study of Magnetic Fluctuations and Order–Disorder in the Spinel LiNi0.5Mn1.5O4 Cathode","authors":"Graciela E. García Ponte,&nbsp;Sesha Sai Behara,&nbsp;Euan N. Bassey,&nbsp;Raphaële J. Clément* and Anton Van der Ven*,&nbsp;","doi":"10.1021/acs.chemmater.4c0277210.1021/acs.chemmater.4c02772","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02772https://doi.org/10.1021/acs.chemmater.4c02772","url":null,"abstract":"<p >While significant magnetic interactions exist in lithium transition metal oxides, commonly used as Li-ion cathodes, the interplay between magnetic couplings, disorder, and redox processes remains poorly understood. In this work, we focus on the high-voltage spinel LiNi_0.5Mn_1.5O₄ (LNMO) cathode as a model system on which to apply a computational framework that uses first principles-based statistical mechanics methods to predict the finite temperature magnetic properties of materials and provide insights into the complex interplay between magnetic and chemical degrees of freedom. Density functional theory calculations on multiple distinct Ni–Mn orderings within the LNMO system, including the ordered ground-state structure (space group <i>P</i>4₃32), reveal a preference for a ferrimagnetic arrangement of the Ni and Mn sublattices due to strong antiferromagnetic superexchange interactions between neighboring Mn⁴⁺ and Ni²⁺ ions and ferromagnetic Mn–Mn and Ni–Ni couplings, as revealed by magnetic cluster expansions. These results are consistent with qualitative predictions using the Goodenough-Kanamori-Anderson rules. Simulations of the finite temperature magnetic properties of LNMO are conducted using Metropolis Monte Carlo. We find that a “semiclassical” Monte Carlo sampling method based on the Heisenberg Hamiltonian accurately predicts experimental magnetic transition temperatures observed in magnetometry measurements. This study highlights the importance of a robust computational toolkit that accurately captures the complex chemomagnetic interactions and predicts finite temperature magnetic behavior to help analyze experimental magnetic and magnetic resonance spectroscopy data acquired <i>ex situ</i> and <i>operando</i>.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 5","pages":"1835–1846 1835–1846"},"PeriodicalIF":7.2,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c02772","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143590485","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}