Pub Date : 2026-01-23DOI: 10.1021/acs.chemmater.5c02589
Najat Maher Aldaqqa, Dinesh Shetty
Capacitive deionization (CDI) has emerged as a promising electrochemical technology for water desalination and ion recovery owing to its low energy consumption, modularity, and operational simplicity. However, the performance of conventional carbon-based electrodes remains constrained by inherent limitations in selectivity, stability, and redox activity. Covalent organic frameworks (COFs), crystalline, porous polymers composed of light elements and customizable linkers, offer a unique opportunity to engineer next-generation electrode materials with molecular precision. In this Perspective, we highlight recent advances in the rational design, functionalization, and hybridization of COF-based materials for CDI applications. We focus on three emerging categories: (i) cathodic COFs for enhanced sodium ion uptake in water desalination; (ii) cathodic COFs for selective recovery of metal ions from complex mixtures; and (iii) anodic COFs with redox-active moieties tailored for selective anion removal. Beyond summarizing these developments, we discuss key challenges in integrating COF chemistry into practical CDI systems, including intrinsic conductivity, scalable synthesis, cost-effectiveness, and long-term cyclic stability. COFs can serve as versatile and architecturally tunable platforms for CDI electrodes, enabling selective and energy-efficient operation with a potential relevance to sustainable resource recovery.
{"title":"Redesigning Covalent Organic Framework Electrodes for Capacitive Deionization: A Step Forward in Electrochemical Desalination and Resource Recovery","authors":"Najat Maher Aldaqqa, Dinesh Shetty","doi":"10.1021/acs.chemmater.5c02589","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02589","url":null,"abstract":"Capacitive deionization (CDI) has emerged as a promising electrochemical technology for water desalination and ion recovery owing to its low energy consumption, modularity, and operational simplicity. However, the performance of conventional carbon-based electrodes remains constrained by inherent limitations in selectivity, stability, and redox activity. Covalent organic frameworks (COFs), crystalline, porous polymers composed of light elements and customizable linkers, offer a unique opportunity to engineer next-generation electrode materials with molecular precision. In this Perspective, we highlight recent advances in the rational design, functionalization, and hybridization of COF-based materials for CDI applications. We focus on three emerging categories: (i) cathodic COFs for enhanced sodium ion uptake in water desalination; (ii) cathodic COFs for selective recovery of metal ions from complex mixtures; and (iii) anodic COFs with redox-active moieties tailored for selective anion removal. Beyond summarizing these developments, we discuss key challenges in integrating COF chemistry into practical CDI systems, including intrinsic conductivity, scalable synthesis, cost-effectiveness, and long-term cyclic stability. COFs can serve as versatile and architecturally tunable platforms for CDI electrodes, enabling selective and energy-efficient operation with a potential relevance to sustainable resource recovery.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"44 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043087","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 : 2026-01-22DOI: 10.1021/acs.chemmater.5c02061
Doreen C. Beyer, Kristina Spektor, Roman Lucrezi, Pedro Nunes Ferreira, Christoph Heil, Shrikant Bhat, Robert Farla, Volodymyr Baran, Martin Aaskov Karlsen, Martin Etter, Vanessa Stephan, Martin Boerner, Christopher Owen, Andrew J. Morris, Holger Kohlmann, Ulrich Häussermann
High-pressure forms of LiX (X = Si or Ge) that adopt the simple tetragonal P4/mmm CuAu structure were synthesized by reacting stoichiometric Li12Si7/5Si mixtures and by transforming I41/a-LiGe (MgGa structure) at ∼12.5 GPa and 410 and 265 °C, respectively. P4/mmm-LiGe was recovered in quantitative yield as a metastable phase at ambient pressure, whereas P4/mmm-LiSi was partially converted into a hitherto unknown, kinetically more stable polymorph. The structures of the P4/mmm phases consist of alternately stacked square planar nets of X (dSi–Si = 2.595 Å, and dGe–Ge = 2.761 Å) and Li atoms. Density functional theory (DFT)-based electronic structure calculations reveal pronounced polarity, Li0.83+Si0.83– and Li0.84+Ge0.84–, together with strong covalent bonding between X atoms. Electron–phonon coupling calculations within the Migdal–Eliashberg framework predict superconducting transition temperatures of ∼7 K for P4/mmm-LiGe and ∼6 K for P4/mmm-LiSi. For LiGe, magnetic susceptibility measurements show a sharp diamagnetic transition at 6.3 K, in support of the theoretical result.
{"title":"Superconducting High-Pressure Forms of LiSi and LiGe Featuring Square Planar Nets","authors":"Doreen C. Beyer, Kristina Spektor, Roman Lucrezi, Pedro Nunes Ferreira, Christoph Heil, Shrikant Bhat, Robert Farla, Volodymyr Baran, Martin Aaskov Karlsen, Martin Etter, Vanessa Stephan, Martin Boerner, Christopher Owen, Andrew J. Morris, Holger Kohlmann, Ulrich Häussermann","doi":"10.1021/acs.chemmater.5c02061","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02061","url":null,"abstract":"High-pressure forms of LiX (X = Si or Ge) that adopt the simple tetragonal <i>P</i>4/<i>mmm</i> CuAu structure were synthesized by reacting stoichiometric Li<sub>12</sub>Si<sub>7</sub>/5Si mixtures and by transforming <i>I</i>4<sub>1</sub>/<i>a</i>-LiGe (MgGa structure) at ∼12.5 GPa and 410 and 265 °C, respectively. <i>P</i>4/<i>mmm</i>-LiGe was recovered in quantitative yield as a metastable phase at ambient pressure, whereas <i>P</i>4/<i>mmm</i>-LiSi was partially converted into a hitherto unknown, kinetically more stable polymorph. The structures of the <i>P</i>4/<i>mmm</i> phases consist of alternately stacked square planar nets of X (<i>d</i><sub>Si–Si</sub> = 2.595 Å, and <i>d</i><sub>Ge–Ge</sub> = 2.761 Å) and Li atoms. Density functional theory (DFT)-based electronic structure calculations reveal pronounced polarity, Li<sup>0.83+</sup>Si<sup>0.83–</sup> and Li<sup>0.84+</sup>Ge<sup>0.84–</sup>, together with strong covalent bonding between X atoms. Electron–phonon coupling calculations within the Migdal–Eliashberg framework predict superconducting transition temperatures of ∼7 K for <i>P</i>4/<i>mmm</i>-LiGe and ∼6 K for <i>P</i>4/<i>mmm</i>-LiSi. For LiGe, magnetic susceptibility measurements show a sharp diamagnetic transition at 6.3 K, in support of the theoretical result.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"39 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022080","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 : 2026-01-22DOI: 10.1021/acs.chemmater.5c02710
Maria Wróblewska, Angela Pak, Elif Ertekin, Eric S. Toberer, Kamil M. Ciesielski
XYZ half-Heusler phases are often described as an XZ rocksalt sublattice with an interstitial Y atom. However, transport properties across a solid solution between rocksalt and half-Heusler structures have not previously been studied. In this article, we demonstrate the exceptional tolerance of Ni vacancies in ErNixSb, resulting in a complete alloy in the ErSb-ErNiSb space. Thermoelectric characterization demonstrates a continuous electronic transition associated with the gradual collapse of the band gap with Ni removal. The carrier concentration increases by 3 orders of magnitude, and the Seebeck coefficient decreases from 260 μV/K to <5 μV/K. Speed-of-sound measurements indicate that removal of Ni softens the lattice, consistent with the breakdown of the covalent Ni–Sb sublattice. For compositions depleted in nickel, the combination of low speed of sound coupled with Ni vacancies strongly hampers the propagation of phonons. The ability to tune physical properties across this alloy space opens new material design strategies across topics explored with half-Heusler phases: thermoelectricity, superconductivity, and nontrivial topology.
{"title":"Continuous Alloying between Rocksalt and Half-Heusler Structures Drives Metal–Semiconductor Transition in ErNixSb","authors":"Maria Wróblewska, Angela Pak, Elif Ertekin, Eric S. Toberer, Kamil M. Ciesielski","doi":"10.1021/acs.chemmater.5c02710","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02710","url":null,"abstract":"<i>XYZ</i> half-Heusler phases are often described as an <i>XZ</i> rocksalt sublattice with an interstitial <i>Y</i> atom. However, transport properties across a solid solution between rocksalt and half-Heusler structures have not previously been studied. In this article, we demonstrate the exceptional tolerance of Ni vacancies in ErNi<sub><i>x</i></sub>Sb, resulting in a complete alloy in the ErSb-ErNiSb space. Thermoelectric characterization demonstrates a continuous electronic transition associated with the gradual collapse of the band gap with Ni removal. The carrier concentration increases by 3 orders of magnitude, and the Seebeck coefficient decreases from 260 μV/K to <5 μV/K. Speed-of-sound measurements indicate that removal of Ni softens the lattice, consistent with the breakdown of the covalent Ni–Sb sublattice. For compositions depleted in nickel, the combination of low speed of sound coupled with Ni vacancies strongly hampers the propagation of phonons. The ability to tune physical properties across this alloy space opens new material design strategies across topics explored with half-Heusler phases: thermoelectricity, superconductivity, and nontrivial topology.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"96 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022084","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}
Covalent organic frameworks (COFs) are promising materials for CO2 adsorption owing to their tunable porosity and modular functionality. The detailed atomic-scale understanding of CO2 adsorption has yet to be achieved. Here, we report a systematic study on halogenated N,N,N′,N′-tetraphenyl-1,4-phenylenediamine (Wurster, W)-anthracene (A) COFs (W-A-X, X = H, Cl, Br, I) designed to isolate the effect of halogen atoms on CO2 sorption behavior. All halogen-functionalized COFs exhibit significantly higher CO2 uptake and increased isosteric heats of adsorption compared to the W-A-H COF. To elucidate the origin of this enhanced affinity, density functional theory (DFT) calculations were performed on molecular fragments and, for the first time, on extended COF frameworks, enabling direct insight into host–guest interactions within the lattice. In W-A-H, CO2 binds primarily via N(δ–)···C(δ+) interactions at the imine linkage, whereas halogenated derivatives introduce additional adsorption sites through σ-holes, localized regions of positive electrostatic potential on halogen atoms, allowing X−σ(δ+)···O(δ–) interactions with CO2. The interaction strength follows the trend I > Br > Cl, consistent with halogen polarizability. These findings demonstrate σ-hole-mediated adsorption in COFs and establish halogenation as a powerful molecular design strategy to tune host–guest electrostatics for enhanced CO2 uptake.
{"title":"Single-Atom Halogen Substitution in Covalent Organic Frameworks Enables σ-Hole-Driven CO2 Adsorption","authors":"Klaudija Paliušytė, Kuangjie Liu, Kornel Roztocki, Shuo Sun, Hendrik Zipse, Jenny Schneider","doi":"10.1021/acs.chemmater.5c03215","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03215","url":null,"abstract":"Covalent organic frameworks (COFs) are promising materials for CO<sub>2</sub> adsorption owing to their tunable porosity and modular functionality. The detailed atomic-scale understanding of CO<sub>2</sub> adsorption has yet to be achieved. Here, we report a systematic study on halogenated <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-tetraphenyl-1,4-phenylenediamine (Wurster, W)-anthracene (A) COFs (W-A-X, X = H, Cl, Br, I) designed to isolate the effect of halogen atoms on CO<sub>2</sub> sorption behavior. All halogen-functionalized COFs exhibit significantly higher CO<sub>2</sub> uptake and increased isosteric heats of adsorption compared to the W-A-H COF. To elucidate the origin of this enhanced affinity, density functional theory (DFT) calculations were performed on molecular fragments and, for the first time, on extended COF frameworks, enabling direct insight into host–guest interactions within the lattice. In W-A-H, CO<sub>2</sub> binds primarily via N(δ<sup>–</sup>)···C(δ<sup>+</sup>) interactions at the imine linkage, whereas halogenated derivatives introduce additional adsorption sites through σ-holes, localized regions of positive electrostatic potential on halogen atoms, allowing X−σ(δ<sup>+</sup>)···O(δ<sup>–</sup>) interactions with CO<sub>2</sub>. The interaction strength follows the trend I > Br > Cl, consistent with halogen polarizability. These findings demonstrate σ-hole-mediated adsorption in COFs and establish halogenation as a powerful molecular design strategy to tune host–guest electrostatics for enhanced CO<sub>2</sub> uptake.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"93 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022085","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 : 2026-01-22DOI: 10.1021/acs.chemmater.5c02530
Jyoti Sinha, Nicholas M. Carroll, Marleen van der Veen, Laura Nyns, Gregory N. Parsons, Annelies Delabie
Area-selective deposition (ASD) shows promise for tackling nanofabrication challenges for advanced nanoelectronic devices. Understanding the proximity effects during ASD in nanopatterns is important to ensure atomic scale precision of deposition. This work reveals and analyzes proximity effects during GeTe ASD by atomic layer deposition (ALD) with the well-known dechlorosilylation chemistry and an aminosilane inhibitor. The proximity of the TiN growth and the trimethylsilyl-terminated SiO2 nongrowth area in a line-pattern with 35 nm critical dimension leads to an altered GeTe thickness profile and a higher selectivity compared to the nonpatterned SiO2 substrate. The GeTe film on the TiN growth area shows a well-controlled, inverted U-shaped profile, different than conformal deposition typical for ALD. The ASD process in a passivated trench is mimicked using a previously developed stochastic lattice growth model, and the model results indicate that the observed edge profile is consistent with electrostatic interactions between the Te precursor’s Si(CH3)3 ligands on the growth surface and the trimethylsilyl-groups present on the adjacent vertical passivated SiO2 nongrowth surface. The selectivity increase is attributed to diffusion-mediated migration of adspecies from the nongrowth to the growth area. We conclude that this ASD process is influenced by the proximity of growth and nongrowth surfaces by processes that go beyond the well-known self-limiting surface reactions of ALD. This work opens opportunities to tune the thickness profiles during ALD in nanopatterns beyond conformal deposition by the substrate and deposition conditions. The insights into the mechanisms of proximity effects are relevant to enable atomic-scale precision in ASD for various materials and applications in nanofabrication, including nanoelectronic device fabrication by ALD and by other deposition techniques.
{"title":"Proximity Effects during GeTe Area-Selective Deposition by Atomic Layer Deposition: Nanopattern Induced Thickness Profile Alteration","authors":"Jyoti Sinha, Nicholas M. Carroll, Marleen van der Veen, Laura Nyns, Gregory N. Parsons, Annelies Delabie","doi":"10.1021/acs.chemmater.5c02530","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02530","url":null,"abstract":"Area-selective deposition (ASD) shows promise for tackling nanofabrication challenges for advanced nanoelectronic devices. Understanding the proximity effects during ASD in nanopatterns is important to ensure atomic scale precision of deposition. This work reveals and analyzes proximity effects during GeTe ASD by atomic layer deposition (ALD) with the well-known dechlorosilylation chemistry and an aminosilane inhibitor. The proximity of the TiN growth and the trimethylsilyl-terminated SiO<sub>2</sub> nongrowth area in a line-pattern with 35 nm critical dimension leads to an altered GeTe thickness profile and a higher selectivity compared to the nonpatterned SiO<sub>2</sub> substrate. The GeTe film on the TiN growth area shows a well-controlled, inverted U-shaped profile, different than conformal deposition typical for ALD. The ASD process in a passivated trench is mimicked using a previously developed stochastic lattice growth model, and the model results indicate that the observed edge profile is consistent with electrostatic interactions between the Te precursor’s Si(CH<sub>3</sub>)<sub>3</sub> ligands on the growth surface and the trimethylsilyl-groups present on the adjacent vertical passivated SiO<sub>2</sub> nongrowth surface. The selectivity increase is attributed to diffusion-mediated migration of adspecies from the nongrowth to the growth area. We conclude that this ASD process is influenced by the proximity of growth and nongrowth surfaces by processes that go beyond the well-known self-limiting surface reactions of ALD. This work opens opportunities to tune the thickness profiles during ALD in nanopatterns beyond conformal deposition by the substrate and deposition conditions. The insights into the mechanisms of proximity effects are relevant to enable atomic-scale precision in ASD for various materials and applications in nanofabrication, including nanoelectronic device fabrication by ALD and by other deposition techniques.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"13 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022081","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}
Sulfide-based all-solid-state lithium metal batteries are considered promising next-generation energy storage devices owing to their safety and high energy densities. However, short-circuiting caused by Li dendrite growth hinders their practical applications. Hence, developing solid electrolytes that have high reduction tolerance and ionic conductivity is essential to avoid cell failure. In this study, Li3PS4–xOx·LiF glass-ceramic electrolytes were synthesized by partially substituting S with O to improve reduction tolerance. The oxygen-substituted Li3PS3.8O0.2·LiF glass precipitated a high-temperature α-Li3PS4 analog phase through crystallization via a conventional slow heating–cooling process, without requiring rapid heating–cooling. The Li3PS3.8O0.2·LiF glass-ceramic electrolyte exhibited a high conductivity of 1.3 × 10–3 S cm–1 at room temperature. Furthermore, a reaction layer was hardly observed at the Li metal interface after cycling, suggesting that the Li3PS3.8O0.2·LiF glass-ceramic electrolyte has excellent reduction tolerance. These findings emphasize the critical role of achieving both high reduction tolerance and high ionic conductivity in designing solid electrolytes for Li metal batteries.
基于硫化物的全固态锂金属电池因其安全性和高能量密度被认为是有前途的下一代储能设备。然而，锂枝晶生长引起的短路阻碍了它们的实际应用。因此，开发具有高还原耐受性和离子电导率的固体电解质对于避免电池失效至关重要。在本研究中，通过用O部分取代S来合成Li3PS4-xOx·LiF玻璃陶瓷电解质，以提高还原性。氧取代li3ps3.80 o0.2·LiF玻璃不需要快速加热冷却，通过传统的慢速加热冷却过程结晶，析出高温α-Li3PS4模拟相。li3ps3.80 o0.2·LiF玻璃陶瓷电解质在室温下具有1.3 × 10-3 S cm-1的高电导率。此外，循环后在锂金属界面几乎没有观察到反应层，表明li3ps3.80 o0.2·LiF玻璃陶瓷电解质具有优异的耐还原性。这些发现强调了在设计锂金属电池固体电解质时，实现高还原容限和高离子电导率的关键作用。
{"title":"Oxygen- and Fluorine-Doped Li3PS4 Glass-Ceramic Electrolytes Compatible with Lithium Metal Electrodes for All-Solid-State Batteries","authors":"Taichi Asakura, Ryo Izawa, Sotaro Sato, Takuya Kimura, Chie Hotehama, Hiroe Kowada, Kota Motohashi, Atsushi Sakuda, Masahiro Tatsumisago, Akitoshi Hayashi","doi":"10.1021/acs.chemmater.5c02634","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02634","url":null,"abstract":"Sulfide-based all-solid-state lithium metal batteries are considered promising next-generation energy storage devices owing to their safety and high energy densities. However, short-circuiting caused by Li dendrite growth hinders their practical applications. Hence, developing solid electrolytes that have high reduction tolerance and ionic conductivity is essential to avoid cell failure. In this study, Li<sub>3</sub>PS<sub>4–<i>x</i></sub>O<sub><i>x</i></sub>·LiF glass-ceramic electrolytes were synthesized by partially substituting S with O to improve reduction tolerance. The oxygen-substituted Li<sub>3</sub>PS<sub>3.8</sub>O<sub>0.2</sub>·LiF glass precipitated a high-temperature α-Li<sub>3</sub>PS<sub>4</sub> analog phase through crystallization via a conventional slow heating–cooling process, without requiring rapid heating–cooling. The Li<sub>3</sub>PS<sub>3.8</sub>O<sub>0.2</sub>·LiF glass-ceramic electrolyte exhibited a high conductivity of 1.3 × 10<sup>–3</sup> S cm<sup>–1</sup> at room temperature. Furthermore, a reaction layer was hardly observed at the Li metal interface after cycling, suggesting that the Li<sub>3</sub>PS<sub>3.8</sub>O<sub>0.2</sub>·LiF glass-ceramic electrolyte has excellent reduction tolerance. These findings emphasize the critical role of achieving both high reduction tolerance and high ionic conductivity in designing solid electrolytes for Li metal batteries.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"258 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022082","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 : 2026-01-21DOI: 10.1021/acs.chemmater.5c02752
Xu Mu, Pengpeng Wang, Shanshan Chen
(Photo)electrocatalysis-driven artificial photosynthesis using water as an electron donor provides a sustainable approach for solar fuel production, in which three elementary reaction steps including diffusion–adsorption, catalytic conversion, and desorption–diffusion can collectively contribute to the overall conversion efficiency. Based on the mainline of these three steps, in this review, surface engineering is summarized and illustrated to modulate the (photo)electrodes toward the target reaction-oriented direction for the promoted artificial photosynthesis. Specifically, the following three aspects are elucidated in detail: (1) the regulation of the diffusion–adsorption process via surface hydrophobic modification and the optimization of electronic structure/vacancy; (2) the alternation of catalytic conversion from two aspects including both the improvement of target reactions and suppression of side and reverse reactions; (3) the modulation of the desorption–diffusion process through superhydrophobic interface construction. In addition, challenges and perspectives in this field are also analyzed and discussed. It is expected that this review can deepen the understanding of the (photo)electrocatalytic reaction mechanism and contribute to the effective design and construction of (photo)electrodes for promoted artificial photosynthesis.
{"title":"Reaction-Oriented Surface Engineering over (Photo)electrodes toward Promoted Artificial Photosynthesis","authors":"Xu Mu, Pengpeng Wang, Shanshan Chen","doi":"10.1021/acs.chemmater.5c02752","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02752","url":null,"abstract":"(Photo)electrocatalysis-driven artificial photosynthesis using water as an electron donor provides a sustainable approach for solar fuel production, in which three elementary reaction steps including diffusion–adsorption, catalytic conversion, and desorption–diffusion can collectively contribute to the overall conversion efficiency. Based on the mainline of these three steps, in this review, surface engineering is summarized and illustrated to modulate the (photo)electrodes toward the target reaction-oriented direction for the promoted artificial photosynthesis. Specifically, the following three aspects are elucidated in detail: (1) the regulation of the diffusion–adsorption process via surface hydrophobic modification and the optimization of electronic structure/vacancy; (2) the alternation of catalytic conversion from two aspects including both the improvement of target reactions and suppression of side and reverse reactions; (3) the modulation of the desorption–diffusion process through superhydrophobic interface construction. In addition, challenges and perspectives in this field are also analyzed and discussed. It is expected that this review can deepen the understanding of the (photo)electrocatalytic reaction mechanism and contribute to the effective design and construction of (photo)electrodes for promoted artificial photosynthesis.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"30 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005697","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 : 2026-01-21DOI: 10.1021/acs.chemmater.5c02800
Sarah A. Englehart, Mason C. Lawrence, Russell M. Main, Ross S. Forgan, Barry A. Blight
Fluoride anions (F–) are commonly found in everyday items and are known to have positive medicinal uses. Despite their importance, overconsumption can lead to dental and skeletal fluorosis, among other health issues. In pursuit of a more effective method to detect trace amounts of anions in aqueous media, we synthesized two triarylborane-functionalized lanthanide metal–organic frameworks (LnBMOFs) to act as solid-state luminescent sensors. The LnBMOFs, EuBMOF and TbBMOF, use europium and terbium, respectively, as these metal ions display strong luminescent properties. The electrophilic nature of the triarylborane ligand makes it an ideal candidate for sensing high affinity F–, while also providing steric bulk to enhance the selectivity and stability of the LnBMOFs. We further demonstrate that LnBMOFs are capable of sensing other small anions including CN– and OH– but also a wider scope of anions including PO43–, SO42–, NO3–, and Cl–, while maintaining a high degree of sensitivity. The structural design of these LnBMOFs provides a turn-on/off effect with some anions, where the luminescence is regenerated and maintains stability through several cycles upon washing with water.
{"title":"Regenerable Luminescent Triarylborane Lanthanide Metal–Organic Frameworks as Solid-State Sensors","authors":"Sarah A. Englehart, Mason C. Lawrence, Russell M. Main, Ross S. Forgan, Barry A. Blight","doi":"10.1021/acs.chemmater.5c02800","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02800","url":null,"abstract":"Fluoride anions (F<sup>–</sup>) are commonly found in everyday items and are known to have positive medicinal uses. Despite their importance, overconsumption can lead to dental and skeletal fluorosis, among other health issues. In pursuit of a more effective method to detect trace amounts of anions in aqueous media, we synthesized two triarylborane-functionalized lanthanide metal–organic frameworks (LnBMOFs) to act as solid-state luminescent sensors. The LnBMOFs, <b>EuBMOF</b> and <b>TbBMOF</b>, use europium and terbium, respectively, as these metal ions display strong luminescent properties. The electrophilic nature of the triarylborane ligand makes it an ideal candidate for sensing high affinity F<sup>–</sup>, while also providing steric bulk to enhance the selectivity and stability of the LnBMOFs. We further demonstrate that LnBMOFs are capable of sensing other small anions including CN<sup>–</sup> and OH<sup>–</sup> but also a wider scope of anions including PO<sub>4</sub><sup>3–</sup>, SO<sub>4</sub><sup>2–</sup>, NO<sub>3</sub><sup>–</sup>, and Cl<sup>–</sup>, while maintaining a high degree of sensitivity. The structural design of these LnBMOFs provides a turn-on/off effect with some anions, where the luminescence is regenerated and maintains stability through several cycles upon washing with water.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"68 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005936","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 : 2026-01-21DOI: 10.1021/acs.chemmater.5c03306
Nobutaka Shioya, Fabian Gasser, Nina Strasser, Egbert Zojer, Roland Resel, Josef Simbrunner, Takeshi Hasegawa
Organic compounds have the potential to form distinct crystal structures on a substrate surface. These are typically referred to as thin-film and monolayer phases. The properties of these phases are often key for developing high-performance devices. Nevertheless, many thin-film-specific phases remain unidentified, and the known bulk phase is instead used as a structural model to discuss structure–property relationships also in thin films. For example, the polymorphism of dinaphtho[2,3-b:2’,3′-f]thieno[3,2-b]thiophene (DNTT) has long been overlooked, even though this compound is widely used as a benchmark material for organic thin-film transistors. For a comprehensive understanding of polymorphic transitions in organic semiconductors, the present study investigates the thickness-dependent structural changes in DNTT vapor-deposited films using high-resolution infrared Brewster-angle transmission spectroscopy, grazing incidence X-ray diffraction, and density functional theory calculations. This multimodal approach identifies three different crystal structures depending on the film thickness: the monolayer phase, the thin-film phase, and the bulk phase. Furthermore, the structure solutions of the monolayer phase and candidate structures of the thin-film phase are obtained. This study not only provides an overall model for the thin-film growth of organic semiconductors but also discusses a powerful combination of analytical and modeling techniques for identifying unknown thin-film phases of organic materials.
{"title":"From Monolayer to Bulk: Thin-Film-Specific Polymorphic Transitions of a Molecular Semiconductor","authors":"Nobutaka Shioya, Fabian Gasser, Nina Strasser, Egbert Zojer, Roland Resel, Josef Simbrunner, Takeshi Hasegawa","doi":"10.1021/acs.chemmater.5c03306","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03306","url":null,"abstract":"Organic compounds have the potential to form distinct crystal structures on a substrate surface. These are typically referred to as thin-film and monolayer phases. The properties of these phases are often key for developing high-performance devices. Nevertheless, many thin-film-specific phases remain unidentified, and the known bulk phase is instead used as a structural model to discuss structure–property relationships also in thin films. For example, the polymorphism of dinaphtho[2,3-<i>b</i>:2’,3′-<i>f</i>]thieno[3,2-<i>b</i>]thiophene (DNTT) has long been overlooked, even though this compound is widely used as a benchmark material for organic thin-film transistors. For a comprehensive understanding of polymorphic transitions in organic semiconductors, the present study investigates the thickness-dependent structural changes in DNTT vapor-deposited films using high-resolution infrared Brewster-angle transmission spectroscopy, grazing incidence X-ray diffraction, and density functional theory calculations. This multimodal approach identifies three different crystal structures depending on the film thickness: the monolayer phase, the thin-film phase, and the bulk phase. Furthermore, the structure solutions of the monolayer phase and candidate structures of the thin-film phase are obtained. This study not only provides an overall model for the thin-film growth of organic semiconductors but also discusses a powerful combination of analytical and modeling techniques for identifying unknown thin-film phases of organic materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"101 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005698","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 : 2026-01-20DOI: 10.1021/acs.chemmater.5c02772
Shengliang Wu, Zhongyu Li, Glib V. Baryshnikov, Man Zhang, Boru Jiang, Liangliang Zhu
Stimuli-responsive luminescent materials have attracted considerable interest due to their high sensitivity and fast response. However, most reported systems exhibit limited shifts in luminescence wavelength and intensity upon external stimulation, restricting their practical applications. Herein, we synthesized an ortho-pyridylphenol derivative bearing a para-position pyrene group, which displays multistage luminescence photoconversion from blue to red and finally to green. Theoretical and experimental investigations revealed that this primary-color luminescence conversion is mainly induced by the interaction of intermolecular hydrogen bonding and π-π stacking triggered by solvents or light, with photoinduced excited-state proton transfer being crucial for the red emission. Based on this multicolor luminescence property, we constructed a white-light-emitting system from a unimolecular Platform. This unique multistage three-primary-color luminescence conversion can be anticipated to exhibit broad application prospects, such as data security and protection.
{"title":"A Unimolecular Platform Enabling Three-Primary-Color Luminescent Photoconversion","authors":"Shengliang Wu, Zhongyu Li, Glib V. Baryshnikov, Man Zhang, Boru Jiang, Liangliang Zhu","doi":"10.1021/acs.chemmater.5c02772","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02772","url":null,"abstract":"Stimuli-responsive luminescent materials have attracted considerable interest due to their high sensitivity and fast response. However, most reported systems exhibit limited shifts in luminescence wavelength and intensity upon external stimulation, restricting their practical applications. Herein, we synthesized an ortho-pyridylphenol derivative bearing a para-position pyrene group, which displays multistage luminescence photoconversion from blue to red and finally to green. Theoretical and experimental investigations revealed that this primary-color luminescence conversion is mainly induced by the interaction of intermolecular hydrogen bonding and π-π stacking triggered by solvents or light, with photoinduced excited-state proton transfer being crucial for the red emission. Based on this multicolor luminescence property, we constructed a white-light-emitting system from a unimolecular Platform. This unique multistage three-primary-color luminescence conversion can be anticipated to exhibit broad application prospects, such as data security and protection.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"59 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146000639","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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