Manipulating chemical bonding in a solid is crucial for controlling and realizing desirable properties. We have recently demonstrated that replacing the M3+ cation of Bi2MO4Cl, which contains triple-fluorite slabs, from Y3+ to a larger cation (La3+, Bi3+) induces tensile strain in the Bi–O square net, resulting in Bi–O bond cleavage to form double- and single-chain structures, respectively. In this study, we synthesized a solid solution of Bi2(La1–xBix)O4Cl with almost uniform tensile strain, revealing an unexpected tetragonal (T) phase (0.15 ≤ x ≤ 0.35), along with an additional monoclinic single-chain phase (0.425 ≤ x ≤ 0.475). The emergence of the T phase with the elongated in-plane axis likely arises from the competition between the single and double chain structures. The T phase exhibits a narrower bandgap of 2.2 eV (vs Bi2YO4Cl), ascribed to the presence of Bi in the inner sublayer. Furthermore, the T phase undergoes a reentrant transition upon heating via the single-chain phase, forming a high-temperature tetragonal (T′) phase with partial Bi–O bond cleavage due to spatial and thermal fluctuations of the outer Bi cations. This study emphasizes the role of uniform tensile strain in promoting phase competition in triple fluorite layered systems, resulting in complex phase transitions under external stimuli. Controlling such delicate balance offers a pathway to engineering of physical properties of functional materials, such as visible-light photocatalysts.
{"title":"Emergence of Tetragonal Phase and Reentrant Transition in Tensile-Strained Bi2(La1–xBix)O4Cl Solid Solution","authors":"Artem Gabov, Daichi Kato, Takamasa Tsukamoto, Yosuke Matsuzaki, Naoji Kakudou, Akinori Saeki, Hajime Suzuki, Ryu Abe, Koji Fujita, Smagul Zh Karazhanov, Hiroshi Kageyama","doi":"10.1021/acs.chemmater.4c02834","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02834","url":null,"abstract":"Manipulating chemical bonding in a solid is crucial for controlling and realizing desirable properties. We have recently demonstrated that replacing the M<sup>3+</sup> cation of Bi<sub>2</sub>MO<sub>4</sub>Cl, which contains triple-fluorite slabs, from Y<sup>3+</sup> to a larger cation (La<sup>3+</sup>, Bi<sup>3+</sup>) induces tensile strain in the Bi–O square net, resulting in Bi–O bond cleavage to form double- and single-chain structures, respectively. In this study, we synthesized a solid solution of Bi<sub>2</sub>(La<sub>1–<i>x</i></sub>Bi<sub><i>x</i></sub>)O<sub>4</sub>Cl with almost uniform tensile strain, revealing an unexpected tetragonal (T) phase (0.15 ≤ <i>x</i> ≤ 0.35), along with an additional monoclinic single-chain phase (0.425 ≤ <i>x</i> ≤ 0.475). The emergence of the T phase with the elongated in-plane axis likely arises from the competition between the single and double chain structures. The T phase exhibits a narrower bandgap of 2.2 eV (vs Bi<sub>2</sub>YO<sub>4</sub>Cl), ascribed to the presence of Bi in the inner sublayer. Furthermore, the T phase undergoes a reentrant transition upon heating via the single-chain phase, forming a high-temperature tetragonal (T′) phase with partial Bi–O bond cleavage due to spatial and thermal fluctuations of the outer Bi cations. This study emphasizes the role of uniform tensile strain in promoting phase competition in triple fluorite layered systems, resulting in complex phase transitions under external stimuli. Controlling such delicate balance offers a pathway to engineering of physical properties of functional materials, such as visible-light photocatalysts.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"25 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142887167","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 : 2024-12-24DOI: 10.1021/acs.chemmater.4c01804
Lila Laundry-Mottiar, Thilini Malsha Suduwella, Waruni G. K. Senanayake, Matthew J. Turnbull, Antoine Juneau, Ekrupe Kaur, Mark D. Aloisio, Thiago M. Guimarães Selva, Jeffrey D. Henderson, Heng-Yong Nie, Mark Biesinger, James J. Noel, Yolanda S. Hedberg, Cathleen M. Crudden, Janine Mauzeroll
Although the functionalization of noble metals with N-heterocyclic carbenes (NHCs) is well-known, the interactions of these versatile ligands with common alloys are not. Herein, we present an immersion-deposition approach that enables the modification of mild steel (MiS) with diisopropylbenzimidazolium hydrogen carbonate (iPrNHC·H2CO3). The NHC-modified surface was characterized by X-ray photoelectron spectroscopy, angle-resolved X-ray photoelectron spectroscopy, atomic force microscopy-based infrared spectroscopy, time-of-flight secondary ion mass spectrometry, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. These experimental methods provide support for the functionalization of mild steel with iPrNHC and for the reduction of surface oxide by the carbene. Electrochemical analyses and salt immersion tests were also performed and they showed that the NHC coating increases the corrosion resistance of MiS. This study demonstrates that immersion deposition is a viable method for the modification of mild steel surfaces with N-heterocyclic carbenes and shows the potential for mitigating corrosion.
{"title":"N-Heterocyclic Carbene Overlayers on Mild Steel","authors":"Lila Laundry-Mottiar, Thilini Malsha Suduwella, Waruni G. K. Senanayake, Matthew J. Turnbull, Antoine Juneau, Ekrupe Kaur, Mark D. Aloisio, Thiago M. Guimarães Selva, Jeffrey D. Henderson, Heng-Yong Nie, Mark Biesinger, James J. Noel, Yolanda S. Hedberg, Cathleen M. Crudden, Janine Mauzeroll","doi":"10.1021/acs.chemmater.4c01804","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01804","url":null,"abstract":"Although the functionalization of noble metals with N-heterocyclic carbenes (NHCs) is well-known, the interactions of these versatile ligands with common alloys are not. Herein, we present an immersion-deposition approach that enables the modification of mild steel (MiS) with diisopropylbenzimidazolium hydrogen carbonate (<sup><b>iPr</b></sup><b>NHC</b>·<b>H</b><sub><b>2</b></sub><b>CO</b><sub><b>3</b></sub>). The NHC-modified surface was characterized by X-ray photoelectron spectroscopy, angle-resolved X-ray photoelectron spectroscopy, atomic force microscopy-based infrared spectroscopy, time-of-flight secondary ion mass spectrometry, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. These experimental methods provide support for the functionalization of mild steel with <sup><b>iPr</b></sup><b>NHC</b> and for the reduction of surface oxide by the carbene. Electrochemical analyses and salt immersion tests were also performed and they showed that the NHC coating increases the corrosion resistance of MiS. This study demonstrates that immersion deposition is a viable method for the modification of mild steel surfaces with N-heterocyclic carbenes and shows the potential for mitigating corrosion.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"70 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142884467","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}
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.
{"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}
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.
{"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}
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.
{"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}
Pub Date : 2024-12-23DOI: 10.1021/acs.chemmater.4c02093
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
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.
{"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 H<sub>2</sub>S 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 CaAl<sub>2</sub>, SrAl<sub>2</sub>, and EuAl<sub>2</sub> have been reacted with elemental sulfur in less than 24 h at 1173 K achieving phase pure samples of CaAl<sub>2</sub>S<sub>4</sub>, SrAl<sub>2</sub>S<sub>4</sub>, and EuAl<sub>2</sub>S<sub>4</sub>, 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 <sup>151</sup>Eu Mössbauer spectroscopy. All methods clearly confirm the divalent oxidation state of the Eu atoms. Since CaAl<sub>2</sub>S<sub>4</sub> and SrAl<sub>2</sub>S<sub>4</sub> are diamagnetic materials, we have investigated these by <sup>27</sup>Al 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 EuAl<sub>2</sub>S<sub>4</sub> 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}
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.
{"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}
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 S2–/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.
{"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 Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> (LLZO) and argyrodite Li<sub>6</sub>PS<sub>5</sub>Cl (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<sup>2–</sup>/Cl<sup>–</sup> inversion and has Li<sup>+</sup> 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<sup>+</sup> 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)-Li<sub>2</sub>S-deficient surface is also low, 0.20 J/m<sup>2</sup>, 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<sup>+</sup> 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}
Pub Date : 2024-12-20DOI: 10.1021/acs.chemmater.4c02551
Akane Inoo, Junichi Inamoto, Koji Nakanishi, So Fujinami, Yoshiaki Matsuo
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.
{"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 ZnCl<sub>2</sub>·2.33H<sub>2</sub>O 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 Zn<sup>2+</sup>/Zn, and extended X-ray absorption fine structure analysis revealed that the intercalated anion was hydrated [ZnCl<sub>4</sub>]<sup>2–</sup>. The initial discharge capacity of GLG300 was approximately 170 mAh g<sup>–1</sup> in the potential range of 0.5–2.2 V with a current density of 20 mA g<sup>–1</sup>. The charge–discharge cycling test showed that GLG300 had good reversibility, the discharge capacity remained above 110 mAh g<sup>–1</sup>, 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}
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 CrOx-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.
{"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<sub><i>x</i></sub>-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}
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