Inorganic Chemistry最新文献_第2页

Mechanochemical Synthesis of MgV2O4: Reactivity Pathways Driven by Milling Energy and Precursors. 机械化学合成MgV2O4：由磨矿能和前驱体驱动的反应途径。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-10-02 DOI: 10.1021/acs.inorgchem.5c03095

Anna Michaely,Hong Chen,Oliver Clemens,Maxim Neuberger,Christopher W M Kay,Robert Haberkorn,Guido Kickelbick

{"title":"Mechanochemical Synthesis of MgV2O4: Reactivity Pathways Driven by Milling Energy and Precursors.","authors":"Anna Michaely,Hong Chen,Oliver Clemens,Maxim Neuberger,Christopher W M Kay,Robert Haberkorn,Guido Kickelbick","doi":"10.1021/acs.inorgchem.5c03095","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03095","url":null,"abstract":"Magnesium spinels such as MgAl2O4 and MgFe2O4 have been widely explored for energy storage and sensing applications, but MgV2O4 remains relatively unexplored despite its promising potential, e.g., as a battery electrode material. In this study, we report the first mechanochemical synthesis of MgV2O4 at room temperature using either MgO or Mg with various vanadium oxides as reactants. Directed by thermodynamic calculations on a DFT level, only the self-sustaining reaction between V2O5 and Mg led to MgV2O4 within 20 min of milling, along with MgO as a side product. With increasing rotational speed, an earlier reaction ignition after a few minutes of milling, smaller crystallite sizes in the nanometer range, and increased strain in MgV2O4 were observed. In addition, harsh milling conditions induce increasing nonstoichiometry in both phases, leading to a magnesium-rich spinel and a vanadium-containing rock salt phase, as supported by X-ray diffraction and electron paramagnetic resonance measurements. Acid washing after synthesis removed MgO, and electrochemical impedance spectroscopy showed that milder grinding conditions increased the conductivity of MgV2O4 due to the smaller number of defects.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145204062","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Coexisting Displacive and Order-Disorder Lattice Instabilities in the Antiferroelectric Titanite CaTiSiO5. 反铁电钛矿CaTiSiO5中共存的位移和有序无序晶格不稳定性。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-10-02 DOI: 10.1021/acs.inorgchem.5c02798

Akitoshi Nakano,Toshiya Uohashi,Ayako Taguchi,Hiroki Moriwake,Hiroki Taniguchi

引用次数: 0

CAU-63, an Ultramicroporous Al-MOF with a Honeycomb-Shaped 2D IBU. 具有蜂窝状二维IBU的超微孔Al-MOF。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-10-02 DOI: 10.1021/acs.inorgchem.5c03315

Lasse Wegner,Diletta Morelli Venturi,Evgeniia Ikonnikova,Kai Hetze,Jennifer Theissen,Elien Derveaux,Martin Oschatz,Tom Willhammar,Norbert Stock

{"title":"CAU-63, an Ultramicroporous Al-MOF with a Honeycomb-Shaped 2D IBU.","authors":"Lasse Wegner,Diletta Morelli Venturi,Evgeniia Ikonnikova,Kai Hetze,Jennifer Theissen,Elien Derveaux,Martin Oschatz,Tom Willhammar,Norbert Stock","doi":"10.1021/acs.inorgchem.5c03315","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03315","url":null,"abstract":"The hydrothermal synthesis of the new aluminum metal-organic framework (Al-MOF) CAU-63 [Al7(OH)12O3(2,4-HPydc)3] and two new Al coordination polymers (CPs) Al-Pydc-CP1 [Al2(OH)5(2,4-HPydc)] and Al-Pydc-CP2 [Al(OH)(H2O)(2,4-Pydc)] linked by anions of lutidinic acid (pyridine-2,4-dicarboxylic acid, 2,4-H2Pydc) is reported. High-throughput investigations of the Al3+/2,4-H2Pydc/NaOH/H2O system were carried out to determine the fields of formation. An increase of the molar ratio of metal to linker was found to be the key parameter for the formation of higher condensed inorganic building units (IBU), changing from dimeric to one- and two-dimensional structures. The crystal structures were determined by 3D electron diffraction with subsequent Rietveld refinement against powder X-ray diffraction data. The pyridine nitrogen atoms of the linker molecules coordinate to aluminum ions in all three compounds, resulting in crystal structures deviating from the typically observed MIL-53 and CAU-10 type frameworks. The coordination polymers Al-Pydc-CP1 and Al-Pydc-CP2 contain edge-sharing Al-O/N polyhedra leading to dimeric and helical IBUs, while in CAU-63, tetrameric [Al4O14N2] units are bridged by Al3+ ions, leading to a honeycomb Al-O-N network with organic moieties interconnecting the layers. This linkage results in channel-like ultramicropores, which are accessible to H2O and NH3 molecules but too small to adsorb N2 and even CO2.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Luminescent Coordination Polymer with Ultrasensitive "Turn-On" Hg2+ Sensing Ability and Its Portable Hydrogel Test Kit. 具有超灵敏“开启”Hg2+传感能力的发光配位聚合物及其便携式水凝胶检测试剂盒。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-10-01 DOI: 10.1021/acs.inorgchem.5c03549

Jinfang Zhang,Shuaixing Wang,Jiamin Wang,Dejing Yin,Chi Zhang

{"title":"Luminescent Coordination Polymer with Ultrasensitive \"Turn-On\" Hg2+ Sensing Ability and Its Portable Hydrogel Test Kit.","authors":"Jinfang Zhang,Shuaixing Wang,Jiamin Wang,Dejing Yin,Chi Zhang","doi":"10.1021/acs.inorgchem.5c03549","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03549","url":null,"abstract":"Hg2+ has serious effects on ecosystems and human health. Thus, it is very important to develop simple and efficient methods to detect Hg2+. A luminescent coordination polymer (LCP) [Cd(L)(1-NA)2(H2O)·(L)(H2O)0.5]n (1) was constructed by 5,5'-((9H-fluoren-9-ylidene)-methylene)dipyrimidine (L) and 1-naphthoic acid (1-NA) with rigid groups. 1 demonstrates a 1-D wave-like chain structure. Its fluorene and naphthalene groups from adjacent chains exist in π-π interaction. 1 has excellent water, pH, and thermal stability. It exhibits very rare and ultrahigh sensitive \"turn-on\" Hg2+ sensing ability. Its detection limit toward Hg2+ is extremely low (8.86 × 10-8 M). Particularly, the fluorescence intensity of the water suspension of 1 (2.5 mL, 0.05 mg mL-1) can be rapidly enhanced by approximately 80 times after only adding Hg2+ solution (200 μL, 1 mmol). Accordingly, 1 shows the lowest LOD and the highest emission enhancement in all LCP-based \"turn-on\" Hg2+ sensors. Furthermore, 1 was immobilized in a hydrogel to fabricate a portable test kit to realize the convenient, fast, and quantitative Hg2+ detection. This study provides an excellent sensor material and the first on-site platform for environmental monitoring of Hg2+.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203895","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enhanced NOx Catalytic Reduction by NH3 over Polymeric Sulfur Species in CeO2 via Tailoring Ce-O Bonds. 通过调整Ce-O键，NH3在CeO2中聚合硫种上增强NOx催化还原。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-10-01 DOI: 10.1021/acs.inorgchem.5c03976

Zehui Huang,Ziyi Fan,Zirui Yu,Ruihua Wang,Jingfang Sun,Xiuwen Wang,Weixin Zou,Lin Dong

{"title":"Enhanced NOx Catalytic Reduction by NH3 over Polymeric Sulfur Species in CeO2 via Tailoring Ce-O Bonds.","authors":"Zehui Huang,Ziyi Fan,Zirui Yu,Ruihua Wang,Jingfang Sun,Xiuwen Wang,Weixin Zou,Lin Dong","doi":"10.1021/acs.inorgchem.5c03976","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03976","url":null,"abstract":"Sulfate-modified CeO2 is one of the effective routes to improving the performance of NH3-SCR; however, tailoring sulfur species and their effect on the Ce-O bond and NOx removal remains challenging. Herein, we rationally designed an excellent sulfate-modified ceria-based NH3-SCR catalyst by tuning the sulfate species to tailor chemical bonds in CeO2. NOx conversion was dramatically enhanced from 40% (conventional sulfuric acid impregnated CeO2-S catalyst) to 100% of the synthesized CeO2-TDC at 250 °C. By using Ce L3-edge XANES with various characterizations and density functional theory calculations, it was found that, in addition to the sulfate species in CeO2-S and CeO2-TDC, the polymeric state sulfate was also observed in CeO2-TDC, which redistributed the electron density between Ce sulfate and reduced the Ce-O bond length. Moreover, the reaction processes of NH3 to NH4+/*NH2 and NO to monodentate nitrate were more facilitated on CeO2-TDC via the synergistic interactions of rich Lewis acidic Ce4+, Brønsted acidic S-OH, and enhanced redox, thus achieving the Langmuir-Hinshelwood (L-H) and Eley-Rideal (E-R) pathways, whereas only the E-R mechanism was on the conventional CeO2-S. This work provides a novel strategy for designing highly efficient sulfate-modified NH3-SCR catalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"74 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145204063","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

From Nanocrystals to Nanowires: The Control of Cs2AgBiBr6 Morphology by Cesium Oleate. 从纳米晶到纳米线：油酸铯对Cs2AgBiBr6形态的控制。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-10-01 DOI: 10.1021/acs.inorgchem.5c03596

Zhuolu Li,Yi Wu,Zhangwei Guo,Jiaxin Rui,Zhaogang Teng,Song Wang,Kai Pan

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Adsorption of Radioiodine Species by a Microporous Rare-Earth-Organic Framework. 微孔稀土有机骨架对放射性碘的吸附研究。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-10-01 DOI: 10.1021/acs.inorgchem.5c03724

Siyuan Cheng,Tingrui Xu,Junfeng Qian,Huangjie Lu,Zhi-Hui Zhang,Ming-Yang He,Qun Chen

{"title":"Adsorption of Radioiodine Species by a Microporous Rare-Earth-Organic Framework.","authors":"Siyuan Cheng,Tingrui Xu,Junfeng Qian,Huangjie Lu,Zhi-Hui Zhang,Ming-Yang He,Qun Chen","doi":"10.1021/acs.inorgchem.5c03724","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03724","url":null,"abstract":"Rare-earth-organic frameworks (REOFs) have been extensively investigated as promising adsorbents for radioactive nuclides, owing to the diverse coordination environments and robust bonding structures of rare-earth ions and the tunable large-pore architectures of frameworks. Herein, a yttrium-based REOF (Y-NH2-BTB) featuring microporous and hierarchical channels (pore volume of 0.2625 cm3 g-1) is reported as an efficient platform for capturing radioactive iodine vapor─a highly radiotoxic fission product released during nuclear fuel reprocessing. A maximum adsorption capacity of 1238 mg g-1 was achieved via vapor diffusion experiments. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations identified the preferred adsorption sites of iodine within the microporous structure. The high uptake capacity is primarily attributed to halogen bonding and charge-transfer interactions between the I3- species and the NH2-functionalized ligand in addition to the structural confinement offered by the microporous channels. Furthermore, cyclic adsorption tests demonstrated the excellent reusability of Y-NH2-BTB. This study highlights the potential of microporous REOFs for radioactive species separation, combining high adsorption capacity with excellent recyclability through the use of a lighter rare-earth element.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"102 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Energy-Saving Hydrogen Production from Electrocatalytic Oxidation of Urea in Seawater over Mixed-Linker Mn1-xCox Metal-Organic Frameworks with Open Metal Sites. 开放金属位Mn1-xCox金属-有机混合骨架电催化氧化海水尿素节能制氢研究

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-10-01 DOI: 10.1021/acs.inorgchem.5c03912

Soheila Sanati,Reza Abazari,Jafar Shariati,Zhifang Guo,Peter C Junk,Alexander M Kirillov,Jinjie Qian

{"title":"Energy-Saving Hydrogen Production from Electrocatalytic Oxidation of Urea in Seawater over Mixed-Linker Mn1-xCox Metal-Organic Frameworks with Open Metal Sites.","authors":"Soheila Sanati,Reza Abazari,Jafar Shariati,Zhifang Guo,Peter C Junk,Alexander M Kirillov,Jinjie Qian","doi":"10.1021/acs.inorgchem.5c03912","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03912","url":null,"abstract":"Seawater electrolysis offers a sustainable and cost-effective solution for hydrogen production, addressing both the energy crisis and global warming. Herein, a new Co(II)-based metal-organic framework [Co3(μ4-oba)2(μ3-pca)2(DMF)2]n·nDMF (Co-MUM-5) with the sql topology was assembled from two types of linkers, namely, 4,4'-oxybis(benzoic acid) (H2oba) and 4-pyridinecarboxylic acid (Hpca). A series of bimetallic derivatives of Co-MUM-5 (Mn1-xCox-MUM-5) was synthesized, aiming at the development of new electrocatalytic materials for the urea oxidation reaction (UOR) and the oxygen evolution reaction (OER). Exceptionally low potentials of 1.62 V (391 mV overpotential) and 1.87 V (640 mV overpotential) were shown by Mn0.15Co0.85-MUM-5 at 10 and 100 mA cm-2 current densities in the OER. Following the addition of 1 M KOH + 0.5 M NaCl + 0.33 M urea, Mn0.15Co0.85-MUM-5 also revealed low UOR potentials of 1.40 and 1.51 V at 10 and 100 mA cm-2, respectively; these values are considerably reduced (by 220 mV) compared to the OER. Evaluation of hydrogen production using water containing urea showed that only a 1.51 V cell voltage is required for the Mn0.15Co0.85-MUM-5 electrode to yield the current density of 10 mA cm-2. This study highlights the application of bimetallic MOFs with open metal sites as promising electrocatalysts in UOR, and their use in energy conversion systems.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203574","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Photodecarboxylation of the Siderophore Aerobactin with the Lewis Acidic Metal Ions Fe(III), Ga(III), and Ti(IV). 铁载体有氧肌动蛋白与刘易斯酸性金属离子Fe(III), Ga（III）和Ti（IV）的光脱羧作用。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-10-01 DOI: 10.1021/acs.inorgchem.5c02471

Edith K Amason,Thomas C Brunold,Eszter Boros

{"title":"Photodecarboxylation of the Siderophore Aerobactin with the Lewis Acidic Metal Ions Fe(III), Ga(III), and Ti(IV).","authors":"Edith K Amason,Thomas C Brunold,Eszter Boros","doi":"10.1021/acs.inorgchem.5c02471","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02471","url":null,"abstract":"The class of α-hydroxy carboxylic acid-containing ferric siderophore natural products undergo photochemical modification by decarboxylation. To date, there is only limited mechanistic understanding of the metal-ion-mediated photodegradation of photoactive siderophores. This study investigates the photoreactivity of the α-hydroxy carboxylic acid-containing siderophore aerobactin (AB) and the corresponding Ga3+ and Ti4+ metal complexes in direct comparison with their Fe3+-bound counterpart. Using UV-vis and nuclear magnetic resonance (NMR) spectroscopy, complemented by time-dependent density functional theory (TD-DFT) calculations, we demonstrate that ligand-to-metal charge transfer (LMCT)-driven photocleavage of aerobactin-metal complexes is feasible beyond Fe3+. We show that photoirradiation at shorter wavelengths of [Ga(AB)]3- and [Ti(AB)]2- results in decarboxylative photocleavage at two distinct sites. While [Fe(AB)]3- exhibits distinct reactivity upon photoexcitation from 254 to 575 nm, producing C-C bond cleavage to release CO2 and form the corresponding tautomer, the analogous [Ti(AB)]2- complex can be selectively exited. Lower energy excitation of [Ti(AB)]2- within the LMCT band centered at 295 nm induces decarboxylation in direct homology with the parent ferric complex, whereas secondary decarboxylation of the lysine carboxylate is observed using short wavelength irradiation of [Ga(AB)]3- and [Ti(AB)]2-. These experimental results, supported by TD-DFT findings, reveal that the coordinating hydroxamate groups, rather than the α-hydroxy carboxylate, are the source of efficient LMCT excitation and radical formation, challenging previous assumptions about aerobactin's photochemical decarboxylation mechanism. We provide a mechanistic framework for siderophore-mediated photochemistry and highlight its applicability to xenometal ions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194550","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Thermally Activated and Nonactivated Excited State Decay of [Cr(dgpy)2]3. [Cr(dgpy)2]的热激活与非激活激发态衰变

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-10-01 DOI: 10.1021/acs.inorgchem.5c03668

Steven Sittel,Robert Naumann,Christoph Förster,Maximilian E Huber,Jennifer Meyer,Katja Heinze

引用次数: 0