Chemistry of Materials最新文献

{"title":"Ordered Cationic Mixing in a 1D Organic–Inorganic Hybrid","authors":"Megan A. Cassingham, Sujeewa N. S. Lamahewage, Yang G. Goh, Alexander G. Squires, Aamani Ponnekanti, Sarah Karabadjakyan, Anna Wapner, Peter I. Djurovich, David O. Scanlon, Aaron J. Rossini, Mark E. Thompson, Brent C. Melot","doi":"10.1021/acs.chemmater.4c02364","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02364","url":null,"abstract":"Hybrid metal halides are a remarkably dynamic family of materials that offer a flexible platform for exploring the novel crystal chemistry that emerges at the intersection of organic and inorganic solids. Herein, we report the discovery of a hybrid that contains two molecules effectively adopting isostructural geometry, (1-NA)PbI₃ and (1-MQ)PbI₃, and our attempts to create solid solutions of the two beyond the 1:1 ratio. Single-crystal X-ray diffraction, combined with solid-state NMR measurements, clearly show that despite having nearly identical steric geometry, the only mixed phase attained was the composition (1-MQ)(1-NA)Pb₂I₆, which exhibits a high degree of order between the two molecules. We propose that this ordering is primarily driven by local molecular dipoles, which ultimately creates a band structure in the blended phase that is highly characteristic of the end members, with little sign of rehybridization between the organic or inorganic components.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"101 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695191","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 “Controlling Thickness of Aurivillius Phase Perovskite Nanosheets Obtained by Delaminating Bi2SrNan–2NbnO3n+3 (n = 2–5) Layered Crystal”","authors":"Keisuke Awaya, Kazuto Hatakeyama, Shintaro Ida","doi":"10.1021/acs.chemmater.5c00609","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00609","url":null,"abstract":"This article has not yet been cited by other publications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"125 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703526","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":"Three-Dimensional Covalent Organic Frameworks Containing Diverse Nitrogen Sites for Gold Adsorption","authors":"Ke Li, Douchao Mei, Yin-sheng Liu, Bing Yan","doi":"10.1021/acs.chemmater.4c03404","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03404","url":null,"abstract":"As the study progresses, it becomes more significant to explore the effect of specific active sites in covalent organic frameworks (COFs) on the gold adsorption process. Meanwhile, emerging 3D COFs are potential candidates for the adsorption of gold due to their rich pore and cage structures. In this work, to study the effect of the introduction and position of aromatic Ns on the gold capture, we synthesized three 3D COFs which have good selectivity, immunity to interference, reproducibility, and the potential to recover gold from e-waste. Compared to the COF containing only imine bonds as a blank, the introduction of triazine and pyridine rings resulted in a higher maximum adsorption capacity (2081 mg/g) and a faster adsorption rate (within 10 min), respectively. Theoretical calculations show that the presence of the triazine ring enhances the reduction of Au³⁺ by COF, while the synergistic effect of pyridine N and imine bonding shortens the adsorption time of gold. This work reveals the great potential of 3D COFs for gold adsorption and the roles played by the different types of aromatic Ns on gold capture, providing a reference for enhancing the adsorption performance of 3D COFs on gold.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"34 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695190","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":"Patterning Technology: From Supporting Role to Main Player in Materials Chemistry","authors":"Han-Bo-Ram Lee","doi":"10.1021/acs.chemmater.5c00419","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00419","url":null,"abstract":"Published as part of <i>Chemistry of Materials</i> special issue “Precision Patterning”. I recall, when I traveled to Italy, how comfortable I felt browsing items on the shelves of a grocery store (see Figure 1). The neatly and periodically arranged cans and pasta boxes exhibited a satisfying symmetry, adhering to a certain pattern. Like many other scientists, I appreciate symmetry and predictability. Generally, in science and engineering, patterning technology has not received as much attention as other fields, for example those that investigate novel materials’ properties or demonstrate new applications. Instead, patterning technology has often been considered as a type of advance in measurement and device fabrication processes. For instance, the interesting properties and new applications of graphene, which originate from its unique dimensions and atomic structure, attract more interest than the fabrication methods using patterning technology for measurements and demonstrations of graphene’s potential usefulness. Nevertheless, patterning is considered a key technology for commercialization and materials device fabrication. In other words, patterning is akin to arranging pasta sauce cans on shelves in an attractive manner to increase sales rather than changing their taste directly. However, as patterns become smaller, denser, and more complex on a large scale, patterning is evolving into a major player in future research and development. Fundamentally, the purposes of patterning in science and technology can be categorized as follows: 1) to obtain novel properties from interactions within periodic structures and 2) to fabricate repeated structures or devices with a desired level of integration within a given area or space. The first purpose tends to attract interest from scientists, as periodic patterns exhibit fascinating physical properties through their interactions with environmental inputs such as photons and electrons. Plasmonics, for instance, exemplifies the significance of patterning technology (see Fan et al., DOI: 10.1021/acs.chemmater.4c00134). Surface plasmons with periodic quantum dot patterns show great potential for various applications, including sensors, photovoltaics, photocatalysts, and lasers (see Sen et al., DOI: 10.1021/acs.chemmater.4c01090. Additionally, crystalline metal–organic frameworks (MOFs) exhibit novel catalytic properties due to their porosity and periodicity (see Patel et al., DOI: 10.1021/acs.chemmater.4c01137).<named-content content-type=\"anchor\" r type=\"simple\"></named-content> The second purpose is important from a manufacturing perspective, as many production processes rely on patterning technology to optimize time, resources, and operational efficiency. As integrated electronic device technology advances, patterning has become an indispensable tool for increasing integration levels, thereby enhancing capacity, speed, and resolution. For example, the number of pixels on a display screen is determined by ","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"35 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695193","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":"Patterning Technology: From Supporting Role to Main Player in Materials Chemistry","authors":"Han-Bo-Ram Lee*, ","doi":"10.1021/acs.chemmater.5c0041910.1021/acs.chemmater.5c00419","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00419https://doi.org/10.1021/acs.chemmater.5c00419","url":null,"abstract":"","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2071–2072 2071–2072"},"PeriodicalIF":7.2,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678748","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":"Symmetry over Chemistry: Harmonic Generation of Low-Dimensional Alkali Chalcopnictates RbMP2S6 (M = Sb, Bi)","authors":"Benjamin M. Oxley, Jong-Hoon Lim, Kyeong-Hyeon Lee, Jeong-Bin Cho, Saugata Sarker, Jadupati Nag, Michael J. Waters, James M. Rondinelli, Venkatraman Gopalan, Joon I. Jang, Mercouri G. Kanatzidis","doi":"10.1021/acs.chemmater.5c00140","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00140","url":null,"abstract":"We have discovered RbSbP₂S₆ and β-RbBiP₂S₆, two alkali chalcopnictates that crystallize as one-dimensional chains. These near-isostructural analogs differ primarily in the coordination environment of the central metal: Sb has a coordination number (CN) of 4, while Bi exhibits a CN of 5. Notably, β-RbBiP₂S₆ is another form of a Rb/Bi/P/S compound with a 1126 stoichiometry. The β-phase, detailed in this work, is synthesized via direct combination, whereas the previously reported α-phase forms through a reactive Rb/Bi salt flux. The α- and β-phases also differ primarily by the Bi coordination sphere: α-phase Bi CN = 7; β-phase Bi CN = 5. RbSbP₂S₆ and β-RbBiP₂S₆ are both semiconductors. RbSbP₂S₆ has a bandgap of 2.68 eV while β-RbBiP₂S₆ has a bandgap of 2.06 eV. Neither material is congruently melting, but both have successfully been grown into large single crystals via slow cooling of the melt. Nonlinear optical (NLO) results in powder samples show that the symmetry breaking, which leads to lower dimensionality, also leads to significantly lower second harmonic generation (SHG) intensity (∼0.1x AgGaSe₂ for β-RbBiP₂S₆ vs ∼12x AgGaS₂ for α-RbBiP₂S₆). Third Harmonic Generation (THG) in powder samples show similar intensities (∼0.3x AgGaSe₂ for β-RbBiP₂S₆ and ∼0.1x AgGaSe₂ for RbSbP₂S₆). These are corroborated by single crystal SHG results for β-RbBiP₂S₆ (∼0.5x AgGaSe₂). The nonzero NLO coefficients <i>d</i>₁₄, <i>d</i>₂₅, and <i>d</i>₃₆ at 1550 nm fundamental wavelength are measured to be 9.5 ± 2.4, 17.2 ± 3.2, and 3.6 ± 2.3 pm/V, respectively. β-RbBiP₂S₆ has a comparable laser-induced damage threshold (LIDT) to AgGaSe₂ while RbSbP₂S₆ has a LIDT approximately 3x that of β-RbBiP₂S₆ attributed to its higher bandgap.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"27 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666651","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":"In Situ Heterostructure Formation of NaSbS2 and Na2Sb4S7 for Efficient Photogenerated Charge Separation","authors":"Edita Joseph, Vaishnav Raveendran, S. Charis Caroline, Sudip K. Batabyal","doi":"10.1021/acs.chemmater.4c03281","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03281","url":null,"abstract":"Sodium antimony sulfide is a recently discovered alkali metal chalcogenide that has gained considerable attention due to its enhanced efficiency, nontoxicity, and low cost as a photoabsorber. This material exists in various phases, such as NaSbS₂, NaSbS, Na₃SbS₄, and Na₂Sb₄S₇, and can be obtained only by annealing at high temperatures. However, here, we report the controlled formation of two different phases of sodium antimony sulfide, NaSbS₂, and a heterostructure of NaSbS₂/Na₂Sb₄S₇ achieved in a single successive ionic layer adsorption and reaction (SILAR) cycle without annealing procedures. Both phases were formed in two distinct colors, namely, orange (NaSbS₂) and brown (Na₂Sb₄S₇/NaSbS₂), and were found to be two different materials with different electronic properties. The band gaps for both phases were calculated to be 2.0 and 1.6 eV, which lies in the ideal band gap region for a solar absorber. Two photodetectors were fabricated, where both phases acted as the active layers with fluorine-doped tin oxide (FTO) and carbon as the other two electrodes. Both devices produced an outstanding photocurrent and photovoltage under zero-bias conditions, proving to work as excellent self-powered photodetectors. The devices were tested under 455, 525, 632 nm, and white light-emitting diode (LED) light illumination. The rise and fall times under light irradiation were as rapid as 380 and 480 ms for the NaSbS₂ device and 370 and 420 ms for the Na₂Sb₄S₇/NaSbS₂ device, respectively. The responsivity and detectivity for both the photodetectors at low intensities were found to be 0.89 and 3.5 mA/W and 8.8 × 10⁹ and 4.7 × 10¹⁰ Jones, respectively.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"183 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666649","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":"Thiol–Ene Click Chemistry for Functionalizing Silica-Overcoated Gold Nanorods","authors":"Melanie M. Ghelardini, Chuanzhen Zhou, Birgit Urban, Martin Müller, Joseph B. Tracy","doi":"10.1021/acs.chemmater.4c02625","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02625","url":null,"abstract":"Gold nanorods (GNRs) coated with SiO₂ are functionalized through thermally initiated free-radical thiol–ene click reactions, which couple vinyl groups on the SiO₂ surface with thiols to form thioethers. This method of functionalization is developed as an alternative approach to thiolate functionalization of the gold surface. GNRs are synthesized using cetyltrimethylammonium bromide (CTAB), which is challenging to displace with thiols in high yield. In this work, a shell of SiO₂ is instead deposited on the outer surface of the GNRs, which also maintains colloidal stability. A reaction with a vinyl silane then prepares the outer surface of the SiO₂ shells for subsequent thiol–ene click reactions with five thiols that are selected to represent variations in structure and functional groups, including aliphatic and aromatic structures and acids and bases, demonstrating the versatility of the reaction. The SiO₂ shell is initially 17 nm thick and further grows to 20 nm when functionalized with vinyl groups. Deposition of vinyl groups and the formation of thioethers are confirmed by Fourier-transform infrared (FTIR) spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS). While FTIR spectroscopy is well-known for characterizing the surface of nanoparticles, ToF-SIMS has been applied less for this purpose and strongly complements analysis by FTIR spectroscopy.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"56 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672499","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":"Boosting the Thermoelectric Properties of Textured BiSbSe3 via Versatile CuI Compositing","authors":"Xiaowei Shi, Quanwei Jiang, Yu Yan, Zhen Tian, Erkuo Yang, Jianbo Zhu, Huijun Kang, Enyu Guo, Zongning Chen, Fengkai Guo, Rongchun Chen, Tongmin Wang","doi":"10.1021/acs.chemmater.5c00195","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00195","url":null,"abstract":"Tellurium-free BiSbSe₃ has emerged as a promising candidate for medium-temperature n-type thermoelectric (TE) materials, which is attributed to its low lattice thermal conductivity and high performance-cost ratio. However, the intrinsically poor electrical properties restrict the enhancement of TE properties. Herein, the versatile CuI is introduced into BiSbSe₃. The synergistic effects of iodine substituting for selenium and copper occupying the intercalation position collectively increase the carrier concentration. Concurrently, microstructure analysis results reveal that multiscale defects such as dislocations, (Bi,Sb)SeI nanoprecipitates, elemental segregation, and subgrain boundaries are introduced into BiSbSe₃ via CuI compositing, which enhances the multifrequency phonon scattering. Ultimately, benefiting from the trade-off between the power factor and thermal conductivity, BiSbSe₃+0.02CuI parallel to the hot-pressing direction attains an excellent <i>ZT</i> value of ∼ 0.64 at 673 K, representing approximately a 12-fold improvement over that of pristine BiSbSe₃. These results demonstrate a viable compositing strategy for designing high-performance BiSbSe₃ materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"56 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666668","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":"High-Pressure Phase Transition of Metastable Wurtzite-Like CuInSe2 Nanocrystals","authors":"Shinhyo Bang, Juejing Liu, Bipeng Wang, Carlos Mora Perez, Ting-Ran Liu, Kyle D. Crans, Zhaohong Sun, Andrew Strzelecki, Oleg V. Prezhdo, Yu-Tsun Shao, Xiaofeng Guo, Richard L. Brutchey","doi":"10.1021/acs.chemmater.5c00152","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00152","url":null,"abstract":"Ternary I–III–VI₂ semiconductors, such as CuInSe₂, exhibit diverse polymorphs with unique structural characteristics and optoelectronic properties. This study investigates the pressure-induced phase transitions of metastable wurtzite-like CuInSe₂ nanocrystals. Using a combination of synchrotron X-ray diffraction, pair distribution function analysis, and density functional theory calculations, we reveal a transition from cation-ordered wurtzite-like (<i>Pmc</i>2₁) to cation-disordered NaCl-like (<i>Fm</i>3̅<i>m</i>) structures at 7.7 GPa. The cation-disordered NaCl-like phase persists upon decompression. Bulk modulus calculations highlight size-dependent deviations from bulk material behavior. These findings deepen our understanding of phase stability in colloidal I–III–VI₂ semiconductor nanocrystals, with implications for tailoring functional materials under extreme conditions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"12 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666650","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}