Chemistry of Materials最新文献

{"title":"Para-Fluoro-Thiol Reaction: Powerful Tool for the Versatile Functionalization of Microporous Materials","authors":"Benhur Mekonnen, Delphine Flahaut, Abdel Khoukh, Laurent Perrier, Christelle Miqueu, Antoine Bousquet, Joachim Allouche, David Grégoire","doi":"10.1021/acs.chemmater.4c02441","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02441","url":null,"abstract":"Hyper-cross-linked polystyrene-like polymers (HCPs) represent a cost-effective, highly stable, and scalable class of porous materials with significant potential for environmental remediation, catalysis, gas storage, and separation applications. Herein, we demonstrate that the introduction of pentafluorostyrene in the precursor HCP formulation and the subsequent para-fluoro-thiol reaction is an efficient and energy-saving strategy to functionalize these materials. The important quantity of thiol compounds available in the market offers a wide variety of chemical functions accessible for microporous materials and tailors the properties of HCPs to the specific sorption application. In this study, the proportion of the three building blocks used in the polymerization is first optimized to obtain HCPs exhibiting high microporosity, large Brunauer–Emmett–Teller surface areas, and pore volumes independent of the incorporated functional groups (hexyl, alcohol, amine, or sulfonate). The efficiency and versatility of the para-fluoro-thiol coupling reaction are then demonstrated. Finally, the HCPs′ CO₂ adsorption capacity was accessed, as an analyte example, using a manometric setup. At ambient pressure, uptake capacity is predominantly governed by surface chemistry alongside textural properties, while at higher pressure, the uptake capacity is correlated with pore volume, with a probable influence of the swelling of the material upon adsorption.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"114 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849741","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":"Ionic Transport Properties and Additive Effect of Lithium Polysulfides in Binary Conducting Poly(ethylene oxide)-Based Copolymer Electrolytes","authors":"Ernest Ahiavi, Jihen Talbi, Trang N. T. Phan, Priscillia Soudant, Fabrice Cousin, Renaud Bouchet, Didier Devaux","doi":"10.1021/acs.chemmater.4c02594","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02594","url":null,"abstract":"Despite the high impact lithium–sulfur (Li–S) batteries can bring in terms of specific energy and battery lifetime, their full advantage has not yet been realized due to inherent issues associated with this technology. The intermediate polysulfide products produced in the positive electrode during discharge dissolve and diffuse in the electrolyte, leading to capacity fading and low Coulombic efficiency. A promising solution to this issue is the use of a solid polymer electrolyte that combines the advantages of an ion-conducting poly(ethylene oxide) (PEO) phase and a mechanically reinforced phase, such as polystyrene (PS), that can suppress the nonuniform electrodeposition of Li onto Li metal. In this work, the possibility of using PS–PEO–PS triblock copolymer as an electrolyte or binder in a Li–S battery was investigated by characterizing the thermodynamical, morphological, and ionic transport properties of lithium polysulfides species (Li₂S_<i>x</i>, with <i>x</i> = 4 and 8). Thermodynamic results showed that the long-chain lithium polysulfide (Li₂S₈) is more soluble in the copolymers compared to the short-chain polysulfide (Li₂S₄). Meanwhile, the addition of Li₂S₄ and Li₂S₈ in the mesostructured block copolymer influences both the phase transition (lamellar or hexagonal) and the domain spacing in a fashion similar to the conventional LiTFSI salt. In terms of ionic transport, the mobility of the polysulfides (S₄^2– and S₈^2–) in the copolymers is reduced compared to the TFSI^– anion, and the cationic transference number remains in the range of 0.5 compared to 0.15 for LiTFSI. To move toward the application, the introduction of Li₂S₄ into the block copolymer electrolyte is also used as an additive in the presence of LiTFSI salt, resulting in a very low interfacial resistance with the Li metal electrode. The results of these investigations would guide the design of solid polymer electrolytes for application in Li–S batteries.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"25 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858101","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":"Generalized Assembly of Semiconductor–Molecule Superlattices","authors":"Duncan A. Peterson, Tyler W. Farnsworth, Adam H. Woomer, Zachary S. Fishman, Sydney H. Shapiro, Rebecca C. Radomsky, Emily A. Barron, Jonathan R. Thompson, Scott C. Warren","doi":"10.1021/acs.chemmater.4c02165","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02165","url":null,"abstract":"The synthesis of structurally precise materials that combine diverse building blocks will accelerate the development of artificial solids for electronics, energy, and medicine. Here, we utilize simulation to identify how organic molecules can self-assemble with 2D materials into periodic superlattices with alternating layers of molecules and 2D monolayers. We experimentally demonstrate the generalizability of this mechanism by applying it to 2D semiconductors and various organic molecules or polymers. The resulting superlattices have unique and well-defined lattice constants that depend on the dimensions of the organic species. We are able to design superlattices with a wide variety of molecules (photoresponsive, chelating, light-emitting moieties), suggesting that the self-assembly does not depend on any specific chemical interaction and yet can accommodate chemically diverse functional groups. We also observe that the 2D materials within the superlattices (MoS₂, WSe₂) remain quantum-confined, even though the superlattice retains excellent electrical conductivity. This introduction of a mechanism and its experimental realization yield a general design strategy for a large class of quantum-confined, molecule–2D hybrid materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"23 7 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849742","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":"Surface Modulation Insights of High-Performing Ni–Fe Nitride Fuel Cell and Electrolyzer Electrocatalysts","authors":"Joesene Soto, Qihao Li, Zixiao Shi, Andrés Molina Villarino, David Muller, Héctor D. Abruña","doi":"10.1021/acs.chemmater.4c02245","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02245","url":null,"abstract":"Catalysis has been crucial in advancing and commercializing energy conversion technologies. It is essential to identify abundant, active, and stable materials to enable the reliable and cost-efficient use of catalysts in renewable technologies, such as fuel cells (FCs) and electrolyzers. Suitable candidates, such as nonprecious metals, can be found in first-row transition metals, where materials such as bimetallics, metal oxides, and metal nitrides can be readily synthesized. Recently, these materials have exhibited high activity toward the oxygen reduction (ORR) and oxygen evolution (OER) reactions in alkaline media, which, in turn, were related to promising performance in FCs and electrolyzers. However, most of these studies have not gone beyond half-cell reactions. In this study, we explored the synthesis of a metal nitride, Ni₃FeN, and its application as an electrocatalyst for ORR and OER. We developed procedures for the synthesis of Ni₃FeN nanocrystals with different carbon loadings using a one-step ammonolysis route. We show that the pristine structure of the material encompasses a nitride core and an oxide shell with a thickness of a few nanometers. However, the bulk electronic structure is mainly dominated by the Ni₃FeN phase. The nitride exhibited an impressive and stable ORR performance in 1 M KOH favoring the 4 e^– pathway. The material exhibited a slight decrease in <i>E</i>_1/2 of 10 mV (from 0.85 to 0.84 V vs RHE) during a prolonged (100 K) accelerated stress test (AST). The AST degradation at ORR potentials indicates that the catalyst aggregates into larger nanoparticles, forming a Ni@NiFeOx structure. After tests at OER potentials, the catalyst breaks into smaller nanoparticles and mainly favors the NiFeOx structure. MEA testing of the Ni₃FeN ORR catalyst in a hydrogen-fueled alkaline exchange membrane fuel cell (AEMFC) yielded a peak power density of ca. 700 mW/cm²; among the highest reported for nitride and NiFe-based materials. We believe that this work could enable the use of NiFe-based materials as viable, inexpensive alternatives for fuel cell applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"94 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849751","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":"Role of Molecular Orientation: Comparison of Nitrogenous Aromatic Small Molecule Inhibitors for Area-Selective Atomic Layer Deposition","authors":"Alexander Shearer, Fabian Pieck, Josiah Yarbrough, Andreas Werbrouck, Ralf Tonner-Zech, Stacey F. Bent","doi":"10.1021/acs.chemmater.4c02231","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02231","url":null,"abstract":"Area-selective atomic layer deposition (AS-ALD) shows great potential for meeting the stringent demands of the semiconductor industry for precision nanopatterning. Small molecule inhibitors (SMIs) have recently proven to be a promising, industry-compatible means of achieving AS-ALD. In this work, we compare three nitrogenous aromatic SMIs – aniline, pyrrole, and pyridine – for their ability to block Al₂O₃ ALD on copper with (CuO_<i>x</i>) and without (Cu) a native oxide. We find that pyrrole and aniline perform much better as inhibitors than pyridine does. Furthermore, when redosed on copper before every ALD cycle in an ABC scheme, pyrrole and aniline provide outstanding inhibition, facilitating the selective deposition of over 11 nm of Al₂O₃ on an SiO₂ growth surface in the presence of Cu with 99.9% selectivity. By combining both theory and experiment, we provide new understanding of the mechanisms by which selectivity is prolonged and lost. First, we show that whereas pyrrole and aniline adsorb in a planar bonding orientation, pyridine binds upright at the copper surface, and we propose that the upright molecular orientation is the origin of the ineffective inhibition of pyridine. Second, we find that the CuO_<i>x</i> surface is inherently more reactive than the Cu surface, leading to an eventual loss of selectivity, despite the redosing of the inhibitor. Finally, we observe that redosing of aniline protects the copper surface from undesired oxidation, whereas the redosing of pyridine does not. As such, we posit that a likely benefit of redosing is preventing oxidation and thus reducing reactive site formation during ALD. Through this work, we demonstrate the capability of nitrogenous aromatics to serve as SMIs for AS-ALD, and we contribute insights regarding the role of molecular orientation on inhibition and the impact of ALD process parameters on selectivity.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"23 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849743","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":"A Cellular Automaton Simulation for Predicting Phase Evolution in Solid-State Reactions","authors":"Max C. Gallant, Matthew J. McDermott, Bryant Li, Kristin A. Persson","doi":"10.1021/acs.chemmater.4c02301","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02301","url":null,"abstract":"New computational tools for solid-state synthesis recipe design are needed in order to accelerate the experimental realization of novel functional materials proposed by high-throughput materials discovery workflows. This work contributes a cellular automaton simulation framework for predicting the time-dependent evolution of intermediate and product phases during solid-state reactions as a function of precursor choice and amount, reaction atmosphere, and heating profile. The simulation captures the effects of reactant particle spatial distribution, particle melting, and reaction atmosphere. Reaction rates based on rudimentary kinetics are estimated using density functional theory data from the Materials Project and machine learning estimators for the melting point and the vibrational entropy component of the Gibbs free energy. The resulting simulation framework allows for the prediction of the likely outcome of a reaction recipe before any experiments are performed. We analyze five experimental solid-state recipes for BaTiO₃, CaZrN₂, and YMnO₃ found in the literature to illustrate the performance of the model in capturing reaction selectivity and reaction pathways as a function of temperature and precursor choice. This simulation framework offers an easier way to optimize existing recipes, aid in the identification of intermediates, and design effective recipes for yet unrealized inorganic solids <i>in silico</i>.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"47 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841735","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":"Exploring Ionic Transport Mechanisms in Solid Conductors: A Dual Perspective on Static Structural Properties and Anion Dynamics","authors":"Haijin Ni, Lei Gao, Jinlong Zhu, Dubin Huang, Wen Yin, Ruqiang Zou, Changping Li, Songbai Han","doi":"10.1021/acs.chemmater.4c02478","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02478","url":null,"abstract":"Solid Li-ion conductors require high ionic conductivity to ensure rapid Li⁺ transport within solid-state batteries, necessitating a thorough examination of the relationship between the structure and Li⁺ transport mechanisms. Factors such as crystal symmetries, anion electronegativity, and Li-anion bond lengths are critical in influencing the ionic conductivities of solid conductors. Furthermore, the relationship between Li⁺ transport and the dynamic behavior of anions, particularly through mechanisms such as the paddle-wheel effect, highlights the complexity of ionic transport in solid conductors. In this study, we focus on investigating the antiperovskite-type ionic conductor Li₂OHX (X = Cl or Br), which integrates various static structural features with dynamic anion behavior, to delve deeper into the structure–function relationship. Employing Rietveld refinement on neutron powder diffraction, maximum entropy method analysis, and ab initio molecular dynamics simulations, our findings reveal that Li⁺ transport is influenced not only by static structural properties like space groups, anion electronegativity, Li vacancies, and Li–O bond lengths but also, and more crucially, by the dynamics of OH^– anions. These insights highlight the pivotal role of anion dynamics and offer foundational guidelines for designing solid ionic conductors.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"54 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841736","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":"Modulation of Optical and Electronic Properties in InP Quantum Dots through Residual Halide Ions at the Heterostructural Interface","authors":"Hyun-Min Kim, Goo Min Park, Donghyeok Shin, Seong Min Park, Yuri Kim, Yang-Hee Kim, Yongwoo Kim, Kyoungwon Park, Chae Woo Ryu, Heesun Yang","doi":"10.1021/acs.chemmater.4c02784","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02784","url":null,"abstract":"This study explores the role of residual halide ions (Cl, Br, and I) in modulating the optical and electronic properties of heterostructured InP quantum dots (QDs) with ZnSe/ZnS double shells. By synthesizing halide-containing InP cores using aminophosphine chemistry, we investigate the impact of surface halides on the energy levels of red-, amber-, and green-emissive InP QDs. X-ray photoelectron and ultraviolet photoelectron spectroscopic analyses confirm the presence of halides on the InP core surface, which induces surface dipole and shift energy levels. Our findings reveal that the interfacial Cl and Br ions cause significant alterations in the conduction and valence band energy levels, resulting in band gap reduction and a photoluminescence (PL) red shift in the heterostructured QDs. These effects are the most pronounced for Cl-containing red-emissive QDs, while green-emissive QDs with I ions exhibit negligible changes. These results provide new insights into how surface halide ligands at the core–shell interface influence the optical performance of InP-based heterostructures, offering potential pathways for tuning the properties of QDs for advanced optoelectronic applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"50 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832895","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":"Intercalation-Induced Topotactic Phase Transformation of Tungsten Disulfide Crystals","authors":"A. K. M. Manjur Hossain, Joseph McBride, Masoumeh Mahmoudi Gahrouei, Sabin Gautam, Jefferson A. Carter, Piumi Indrachapa Samarawickrama, John F. Ackerman, Laura Rita de Sousa Oliveira, Jinke Tang, Jifa Tian, Brian M. Leonard","doi":"10.1021/acs.chemmater.4c02160","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02160","url":null,"abstract":"Recent research has demonstrated the potential for topological superconductivity, anisotropic Majorana bound states, optical nonlinearity, and enhanced electrochemical activity for transition metal dichalcogenides (TMDs) with a 2M structure. These unique TMD compounds exhibit metastability and, upon heating, undergo a transition to the thermodynamically stable 2H phase. The 2M phase is commonly made at high temperatures using traditional solid-state methods, and this metastability further complicates the growth of large 2M WS₂ crystals. Herein, a novel synthetic method was developed, focusing on a molten salt reaction to synthesize large 2H crystals and then inducing transformation to the 2M phase through intercalation and thermal treatment. The 2H crystals were intercalated via a room-temperature sodium naphthalenide solution, producing a previously unreported Na-intercalated 2H WS₂ phase. Thermal heating was required to facilitate the phase transition to the intercalated 2M crystal structure. This phase transition was studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), electron dispersive X-ray spectroscopy (EDS), and Raman spectroscopy, which confirmed the synthesis of the intercalated 2M phase. Upon deintercalation, crystal and powder samples showed superconductivity with a <i>T</i>_c of 8.6–8.7 K, similar to previously reported values. The generality of this process was further demonstrated using alkali metal triethyl borohydride to intercalate 2H WS₂ and produced the desired 2M phase. This novel synthetic method has broad implications for discovering metastable phases in other TMD families and layered materials. Separation of the intercalation and phase transition also has the potential to allow for large-scale synthesis of this technologically important phase with greater control over each step of the reaction.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"43 2 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832826","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":"Order–Disorder Transition of Supramolecular Liquid Crystalline Elastomers","authors":"Kristin L. Lewis, Jonathan D. Hoang, Michael F. Toney, Timothy J. White","doi":"10.1021/acs.chemmater.4c02271","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02271","url":null,"abstract":"Liquid crystalline elastomers (LCEs) are soft materials which disorder upon heating through the isotropic transition temperature. The order-disorder phase transition of LCEs results in a contraction of up to ∼50% along the aligned axis. Motivated by this distinctive stimuli-response, LCEs are increasingly considered as low-density actuators. Generally, LCEs are composed entirely of covalent bonds. Recently, we have prepared LCEs with intramesogenic supramolecular bonds from dimerized oxybenzoic acid derivatives and documented distinctive thermomechanical response in these supramolecular LCEs. Here, we report a detailed investigation of phase transitions in supramolecular LCEs by systematically varying the composition to affect the strength of the intermolecular interactions in the polymer network. The order-disorder phase transition is shown to be influenced by the conformation and dissociation of supramolecular dimers. Distinctly, this report isolates and details an LCE composition which undergoes an intermediate transition to an incommensurate phase at lower temperatures than the order-disorder transition.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"19 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832827","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}