Chemistry of Materials最新文献

{"title":"Au-Acyclic Diaminocarbene-Linked Homochiral Covalent Organic Frameworks: Synthesis and Asymmetric Catalytic Application","authors":"Ying Dong, Chuan-Fen Yin, Jing-Lan Kan, Chun-Run Chang, Jian-Ping Ma, Jian-Biao Liu, Yu-Bin Dong","doi":"10.1021/acs.chemmater.4c02884","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02884","url":null,"abstract":"Chiral covalent organic framework (CCOF)-based heterogeneous catalysts are the new hot topic in asymmetric catalysis. The chiral metal-acyclic diaminocarbene complexes (M-ADCs), on the other hand, make up a powerful class of homogeneous catalysts for various asymmetric organic transformations. The integration of chiral M-ADCs with COFs into a single platform will undoubtedly lead to a new breed of heterogeneous asymmetric catalysts. Here, we report the synthesis of Au-ADC-linked CCOFs via a metal-mediated nucleophilic addition approach. This research not only provides a new type of COF linkage but also affords a new kind of heterogeneous catalysts for asymmetric catalysis.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"11 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880258","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":"Frustrated Magnetism in a Gyroidal Metal–Organic Framework Magnet","authors":"Shusaku Imajo, Hajime Ishikawa, Koichi Kindo, Kazuya Nakashima, Rie Suizu, Kunio Awaga","doi":"10.1021/acs.chemmater.4c02578","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02578","url":null,"abstract":"Metal–organic frameworks (MOFs) present a diverse chemical platform, leading to innovative breakthroughs in functional materials due to their controllable properties. In recent years, significant progress has been made in the realm of MOF magnets, with a primary emphasis on developing new molecule-based magnets for various applications. Nevertheless, the potential of MOFs as a platform for understanding quantum magnetism is still cultivating. Herein, based on detailed high-magnetic-field experiments on single crystals of Co(II)-oxalate gyroidal MOF, we revealed the competition of multiple quantum magnetic states. Although such phase competition is typically observed in geometrically frustrated magnets, the gyroidal structure does not inherently induce geometric frustration for spins. We propose that in this system, the emergence of bond-dependent anisotropic interactions and tilting of the local trigonal axis lead to the observed competition. This finding unveils the potential of MOF magnets as a novel source of quantum magnetism.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"28 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880261","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":"Topological Semimetal KAlGe with Novel Electronic Instability","authors":"Toshiya Ikenobe, Takahiro Yamada, Jun-ichi Yamaura, Tamio Oguchi, Ryutaro Okuma, Daigorou Hirai, Hajime Sagayama, Yoshihiko Okamoto, Zenji Hiroi","doi":"10.1021/acs.chemmater.4c02284","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02284","url":null,"abstract":"Compounds with an anti-PbFCl structure exhibit a variety of electronic instabilities and intriguing physical properties. NaAlSi and NaAlGe are similar topological nodal-line semimetals, but they have distinct properties. NaAlSi is a superconductor at 6.8 K, whereas NaAlGe is an insulator with a pseudogap of approximately 100 K. Using the potassium–indium flux method, we succeeded in synthesizing a single crystal of KAlGe, a new anti-PbFCl compound. First-principles electronic structure calculations reveal that KAlGe is isoelectronic with NaAlSi and NaAlGe. KAlGe undergoes a metal-to-metal transition at 89 K and exhibits no superconductivity above 1.8 K. The low-temperature phase has significantly lower carrier density and extremely high mobility, similar to Dirac electron systems. Furthermore, X-ray diffraction experiments show a structural change that breaks the fourfold symmetry during the phase transition. Electron–phonon interactions may be responsible for superconductivity in NaAlSi, whereas excitonic electron–hole interactions are thought to play an important role in KAlGe and possibly NaAlGe. Our findings demonstrate that fascinating physics lies within the compound family.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"137 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880259","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":"Rapid Synthesis of a Green Emitting Phosphor by Sulfidation of Intermetallic EuAl2 and its Use in a Hybrid Material","authors":"Elias C. J. Gießelmann, Stefan Engel, Svenja Pohl, Max Briesenick, Lukas P. Rüthing, Cedric Kloos, Aylin Koldemir, Lars Schumacher, Joshua Wiethölter, Jörn Schmedt auf der Günne, Guido Kickelbick, Oliver Janka","doi":"10.1021/acs.chemmater.4c02093","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02093","url":null,"abstract":"Ternary sulfides are usually synthesized from the binary sulfidic precursors at elevated temperatures using prolonged reaction times and sometimes H₂S atmosphere to remove residual oxygen. The direct synthesis from the elements is usually hampered by the highly exothermic reaction vaporizing the sulfur. One way to suppress this exothermic reaction is to use a prereacted metallic precursor. In this work, the well-defined and crystalline intermetallic compounds CaAl₂, SrAl₂, and EuAl₂ have been reacted with elemental sulfur in less than 24 h at 1173 K achieving phase pure samples of CaAl₂S₄, SrAl₂S₄, and EuAl₂S₄, according to powder X-ray diffraction. While the first two are extremely sensitive to moisture, the latter is air and moisture stable and could therefore be characterized with respect to its magnetic and luminescent properties as well as by ¹⁵¹Eu Mössbauer spectroscopy. All methods clearly confirm the divalent oxidation state of the Eu atoms. Since CaAl₂S₄ and SrAl₂S₄ are diamagnetic materials, we have investigated these by ²⁷Al solid state MAS NMR to verify the crystal structure and gain further information about the local Al environment. Subsequently, three polysiloxane-polysilsesquioxane-based materials with phenyl, naphthyl, and phenanthrenyl groups were used as a water impermeable material to embed powdered EuAl₂S₄ and investigate the luminescent properties of the resulting hybrid material.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"32 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874147","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":"Heteroatom-Induced Fractal Growth for Hierarchical Zeolites","authors":"Yilun Ding, Yihan Ye, Dengyun Miao, Haodi Wang, Jingyao Feng, Jiaqi Qu, Yongzhi Zhao, Ziquan Chen, Peng Zhang, Runsheng Yu, Xingzhong Cao, Xiulian Pan, Xinhe Bao","doi":"10.1021/acs.chemmater.4c01850","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01850","url":null,"abstract":"Hierarchical zeolites have been demonstrated to be advantageous in catalysis and adsorption applications due to facilitated diffusion without degrading its molecule sieving function. However, the direct synthesis of hierarchical zeolites in one step is still challenging. Herein, we report a simple one-step synthesis of single-crystalline hierarchical zeolites by fractal growth induced by the strong adsorption of heteroatom metal species on the initially formed crystals. This method is feasible in the presence of a variety of metal species (M–OH), which can develop a stronger hydrogen bond with Si–OH in comparison to that among Si–OH themselves, such as Ti, Sn, Ga, Nb, and V. Furthermore, the method is versatile as substantiated with several common zeolites, including ZSM-5, TS-1, and ZSM-11. Such a hierarchical zeolite exhibits significantly enhanced activity in polyethylene pyrolysis and a remarkably prolonged lifetime in methanol conversion to hydrocarbons due to facilitated diffusion.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"48 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874065","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":"Mechanical and Electronic Properties of Bulk and Surface Li6PS5Cl Argyrodite: First-Principles Insights on Li-Filament Resistance","authors":"Gregory Pustorino, Harsh Jagad, Wenzao Li, Min Feng, Matteo Poma, Jeonghyun Ko, Priya Johari, Yue Qi","doi":"10.1021/acs.chemmater.4c02577","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02577","url":null,"abstract":"Different Li-filament growth patterns have been experimentally observed in numerous solid electrolytes (SEs) with high ionic conductivity such as garnet Li₇La₃Zr₂O₁₂ (LLZO) and argyrodite Li₆PS₅Cl (LPSC). Herein, we probed the mechanical and electronic properties of LPSC, using density functional theory calculations, and compared with other SEs to determine the relevant descriptors for predicting Li-filament resistance. LPSC has a complicated structure that can incorporate S^2–/Cl^– inversion and has Li⁺ distributed among two Wyckoff sites (24g and 48h). A representative bulk structure that incorporates both phenomena was determined via systematic structure sampling. The lowest energy bulk structures had a majority of Li⁺ in 48h sites after relaxation, agreeing with experimental studies. The Young’s modulus and shear modulus of bulk LPSC are low, ∼10–30 GPa, and the fracture energy of cleaving along the (100)-Li₂S-deficient surface is also low, 0.20 J/m², suggesting poor mechanical resistance to filament growth. The crack surfaces and pore surfaces in LPSC have a similar bandgap and excess electron distribution compared to bulk LPSC, suggesting that these internal defects will not trap electrons to reduce Li⁺ to Li-metal. Thus, LPSC is likely to experience “dry” cracks, with a mechanical crack opening up first, followed by a Li-filament filling the crack. This is opposite to LLZO, which has a high fracture energy and experiences electron localization at internal defects (e.g., crack surfaces, pore surfaces, and grain boundaries). LLZO has been experimentally observed to suffer “wet” cracks.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"112 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867607","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":"Electrochemical Chlorozincate Anion Intercalation into Layered Carbon Materials for the Cathodes of Aqueous Zinc Metal Secondary Batteries","authors":"Akane Inoo, Junichi Inamoto, Koji Nakanishi, So Fujinami, Yoshiaki Matsuo","doi":"10.1021/acs.chemmater.4c02551","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02551","url":null,"abstract":"Aqueous zinc metal secondary batteries (ZSBs) are expected to be next-generation secondary batteries, and it is important to explore cathode materials and electrolyte solutions that exhibit excellent electrochemical properties for their practical use. In this study, we employed a layered carbon material named graphene-like graphite (GLG) as a cathode active material and a concentrated aqueous zinc chloride solution as an electrolyte solution, and its electrochemical anion intercalation reaction was investigated. As a result, GLG obtained at 300 °C of thermal treatment (GLG300) exhibited lower anion intercalation potential and better Coulombic efficiency in ZnCl₂·2.33H₂O compared to graphite and GLG obtained at 700 °C. X-ray diffraction measurement suggested that GLG300 formed a stage-1 intercalation compound at 1.8 V vs Zn²⁺/Zn, and extended X-ray absorption fine structure analysis revealed that the intercalated anion was hydrated [ZnCl₄]^2–. The initial discharge capacity of GLG300 was approximately 170 mAh g^–1 in the potential range of 0.5–2.2 V with a current density of 20 mA g^–1. The charge–discharge cycling test showed that GLG300 had good reversibility, the discharge capacity remained above 110 mAh g^–1, and the Coulombic efficiency approached nearly 100% at the 50th cycle. These results demonstrated that the system using GLG300 and concentrated aqueous zinc chloride solution exhibits excellent cathode properties as aqueous ZSBs and showed great promise for their future practical use.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"19 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858097","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":"Enriching Unsaturated Coordination for High-Performance Chromium Oxide Catalysts","authors":"Mingxin Lv, Qiang Li, Fan Xue, Zhiguo Li, Peixi Zhang, Longlong Fan, Jianrong Zeng, Mengshi Li, Yufei He, Dianqing Li, Qiheng Li, Xin Chen, Kun Lin, Jinxia Deng, Xianran Xing","doi":"10.1021/acs.chemmater.4c02260","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02260","url":null,"abstract":"Chromium oxide catalysts are a type of industrial catalyst that is commonly utilized in heterogeneous catalytic processes. Their outstanding catalytic activity is accomplished through the efficient interception of unsaturated coordination and favored surface aggregation. However, the increase of surficial unsaturated coordination and its structural characterization continues to challenge the limitations of chemical synthesis and atomic decoding of nanocatalysts. In this study, a thermal shock method was employed to intercept a significant number of unsaturated coordination and high-valence chromium species in CrO_<i>x</i>-based nanocatalysts. The transformation of nearest-neighbor symmetry from octahedral to tetrahedral was discovered to be centered on the surface of the nanoparticle through the atomic recognition of chromium species using the pair distribution function (PDF) and reverse Monte Carlo (RMC). The catalytic efficacy of symbolic catalytic reactions, such as the dehydrogenation of propane, toluene oxidation, and benzyl alcohol oxidation, is enhanced by the precise synthesis of the surficial active sites. Our results demonstrate a convenient chemical synthesis method that preserves the metastable structure of oxide catalysts under thermal shock. The atomic structural understanding also offers an intuitional experimental model for the study of reaction mechanisms.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849823","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":"Polymorphs of NASICON-Type Na3Sc2(PO4)3/Eu2+ Phosphors Analyzed by Single Crystal Structure Determination and Molecular Dynamics Simulations","authors":"Mizuki Watanabe, Masato Iwaki, Atsushi Itadani, Tadashi Ishigaki, Kazuyoshi Uematsu, Kenji Toda, Mineo Sato","doi":"10.1021/acs.chemmater.4c01778","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01778","url":null,"abstract":"This study aimed to determine the site assignment of Eu²⁺ in the Na₃Sc₂(PO₄)₃/Eu²⁺ (NSP/Eu²⁺) host lattice for phosphors with NASICON-type frameworks. For this purpose, molecular dynamics (MD) simulations, in which an adiabatic shell method based on crystal structure refinement data for polymorphs of NSP, was employed and verified to be effective. Precise crystal structure analysis of good-quality single crystals indicated the presence of three types of phases: a γ phase assigned to the <i>R</i>3̅<i>c</i> space group [γ(trig)-NSP] reported previously, a monoclinic phase assigned to the <i>I</i>2/<i>a</i> space group [α(mono)-NSP], and another monoclinic phase assigned to the <i>C</i>2/<i>c</i> space group [γ(mono)-NSP]. In the MD simulations of α(mono)-NSP with two crystallographically independent Na sites, Na⁺ ion hopping between the sites frequently occurred. However, the MD simulations of the cells with one type of Na⁺ ion partially replaced by an Eu²⁺ ion and vacancy showed that the Eu²⁺ ions were preferentially located at a distorted octahedral site, and Na⁺ ion hopping did not occur. The α(mono)-NSP-phase Eu²⁺-doped phosphors obtained via a conventional solid-state reaction method exhibited intense blue luminescence, which was assigned to the Eu²⁺ d–f transition, under irradiation at 370 nm, whereas the intensity of the light emitted by the (trig)-phase phosphors was lower. The luminescence and thermal quenching of the α(mono)-NSP phase phosphors was improved when K⁺ ions were substituted at Na⁺ ion sites. The quantum yields were significantly improved compared to those of NSP/Eu²⁺, being almost comparable with those of a commercial BaMgAl₁₀O₁₇/Eu²⁺ (BAM) phosphor. The luminescence properties of NSP/Eu²⁺ are discussed based on the crystal structure refinement and MD simulation results.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"24 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858099","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":"Bayesian Optimization-Assisted Engineering of Formate Dehydrogenase Encapsulation in Multivariate Zeolitic Imidazolate Framework","authors":"Weibin Liang, Sisi Zheng, Ying Shu, Jun Huang","doi":"10.1021/acs.chemmater.4c02816","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02816","url":null,"abstract":"Engineering of multivariate zeolitic imidazolate frameworks (mZIFs) offers substantial potential for optimizing enzyme encapsulation by enhancing encapsulation efficiency (EE), enzyme loading capacity (<i>P</i>_loading), retained enzymatic activity (REA), and protection. However, this area remains underexplored. In this study, we rationally employed three imidazole-based ligands with distinct functionalities─HeIM (2-ethylimidazole), HTz (1,2,4-triazole), and HIM (1-(2-hydroxyethyl)imidazole)─to fine-tune hydrophobicity and defect simultaneously within FDH@mZIF (FDH = formate dehydrogenase). Leveraging an iterative Bayesian optimization-assisted training-design-synthesis-measurement workflow, we efficiently identified F190 as the best FDH@mZIF, achieving EE = 89.3%, REA = 14.9%, and <i>P</i>_loading = 30.3 wt%. This establishes F190 as the leading FDH-based biocatalyst in the literature. The optimal FDH-mZIF interactions in F190 were reflected by minimal structural perturbation of encapsulated FDH, as evidenced by the ATR-FTIR and fluorescence studies. Additionally, F190 can effectively safeguard the encapsulated FDH against thermal and proteolytic degradation and catalyze CO₂-to-formate conversion while maintaining activity for at least five cycles without significant activity loss.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"24 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858061","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}