Inorganic Chemistry最新文献

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Cobalt as an Anchor: Acetate and Nontrigonal Phosphorus Ligand-Assisted Hydroboration 钴作为锚:醋酸和非三角磷配体辅助氢化硼
IF 4.6 2区 化学
Inorganic Chemistry Pub Date : 2026-10-19 DOI: 10.1021/acs.inorgchem.6c03327
Pamodya P. Weerasuriya,William M. Hollingsworth,P. Raj Pokkuluri,Ethan A. Hill
{"title":"Cobalt as an Anchor: Acetate and Nontrigonal Phosphorus Ligand-Assisted Hydroboration","authors":"Pamodya P. Weerasuriya,William M. Hollingsworth,P. Raj Pokkuluri,Ethan A. Hill","doi":"10.1021/acs.inorgchem.6c03327","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03327","url":null,"abstract":"Replacing precious metals with earth-abundant alternatives remains a vital challenge in sustainable catalytic systems. Herein, the synthesis and catalytic application of a cobalt(II) acetate complex with a tridentate, dianionic urea-based ligand bearing a nontrigonal phosphorus center are reported. The Co(II) complex was fully characterized, including by single-crystal X-ray diffraction to confirm the direct coordination of the Co(II) center to the nontrigonal phosphorus. Catalytic studies reveal that this complex promotes the hydroboration of aldehydes, ketones, styrene, and phenylacetylene using pinacolborane under mild conditions. The system operates with catalyst loadings as low as 0.1 mol % for aldehydes and 0.5 mol % for ketones at room temperature and displays high selectivity toward aldehydes. Experimental and computational mechanistic studies indicate that the Co(II) center does not serve as the locus of B–H bond activation, with no evidence for catalytically active boryl or hydride species. Instead, density functional theory suggests that the strongly coordinated acetate ligand serves to activate pinacolborane during catalysis, positioning the BH group near the electrophilic phosphorus center. These findings demonstrate the potential role of ligand-centered chemistry in first-row transition-metal catalysis and open new directions for the design of cooperative ligand platforms beyond traditional metal-centered pathways.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"9 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218793","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
A Fast-Response ZnII Metal–Organic Framework Sensor toward Nitrofurazone Antibiotics and Anthrax Biomarkers in Living Cells 一种对硝基呋喃酮类抗生素和炭疽生物标志物快速响应的ni金属-有机框架传感器
IF 4.6 2区 化学
Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-02 DOI: 10.1021/acs.inorgchem.6c04001
Cheng-Cheng Qin, Man-Lian Zhang, Qinglin Chen, Xing-Kun Luan, Teng-Fei Zheng, Yongquan Wu, Sui-Jun Liu
{"title":"A Fast-Response ZnII Metal–Organic Framework Sensor toward Nitrofurazone Antibiotics and Anthrax Biomarkers in Living Cells","authors":"Cheng-Cheng Qin,&nbsp;Man-Lian Zhang,&nbsp;Qinglin Chen,&nbsp;Xing-Kun Luan,&nbsp;Teng-Fei Zheng,&nbsp;Yongquan Wu,&nbsp;Sui-Jun Liu","doi":"10.1021/acs.inorgchem.6c04001","DOIUrl":"10.1021/acs.inorgchem.6c04001","url":null,"abstract":"<p>The rapid and accurate detection of antibiotics and diseasebiomarkersis crucial for disease prevention, diagnosis, and treatment. Herein,a novel multidentate ligand containing a benzothiadiazole unit, namely,4,7-bis(1<em>H</em>-imidazol-1-yl)benzo-[2,1,3]thiadiazole(BIBT), together with 4,4′-stilbenedicaroxylic acid (H<sub>2</sub>SBCA), was employed to synthesize a new three-dimensionalseven-fold interpenetrating stable Zn<sup>II</sup> metal–organicframework (MOF) under solvothermal conditions, with the chemical formula{[Zn<sub>4</sub>(BIBT)<sub>4</sub>(SBCA)<sub>4</sub>]·DMF}<sub>n</sub> (<strong>JXUST-67</strong>, where <strong>JXUST</strong> refers toJiangxi University of Science and Technology; DMF = <em>N</em>,<em>N</em>-dimethylformamide). After immersion in aqueoussolutions at pH 2–12 for 24 h, <strong>JXUST-67</strong> remainedstructurally intact. Fluorescence sensing experiments demonstratethat <strong>JXUST-67</strong> can serve as a fast-response (≤10s) turn-off sensor for nitrofurazone (NFZ) and a turn-on sensor for2,6-pyridinedicarboxylic acid (DPA) and both analytes can be recognizedby the naked eye, achieving detection limits of 0.1378 and 0.0048μM, respectively. Furthermore, cycling tests show that <strong>JXUST-67</strong> is a reusable sensor material. More importantly, <strong>JXUST-67</strong> exhibits good biocompatibility and low cytotoxicitytoward living cells and successfully detects DPA in live cells, demonstratingsignificant potential for biosensing applications.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24437–24444"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091596","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
Solution-Gel Synthesis and In Situ Transformation of CuFeO2 and CuFe2O4 into Active Catalysts for Photothermal CO2 Conversion CuFeO2和CuFe2O4的溶液-凝胶合成及原位转化为光热CO2转化活性催化剂
IF 4.6 2区 化学
Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-06 DOI: 10.1021/acs.inorgchem.6c03652
Nele Debusschere, Hanne Broux, Naomi Billiet, Jordi Volders, Davy Deduytsche, Jolien Dendooven, Bjorn Joos, Ken Elen, Jan D’Haen, Pegie Cool, Pascal Buskens, Marlies K. Van Bael, An Hardy
{"title":"Solution-Gel Synthesis and In Situ Transformation of CuFeO2 and CuFe2O4 into Active Catalysts for Photothermal CO2 Conversion","authors":"Nele Debusschere,&nbsp;Hanne Broux,&nbsp;Naomi Billiet,&nbsp;Jordi Volders,&nbsp;Davy Deduytsche,&nbsp;Jolien Dendooven,&nbsp;Bjorn Joos,&nbsp;Ken Elen,&nbsp;Jan D’Haen,&nbsp;Pegie Cool,&nbsp;Pascal Buskens,&nbsp;Marlies K. Van Bael,&nbsp;An Hardy","doi":"10.1021/acs.inorgchem.6c03652","DOIUrl":"10.1021/acs.inorgchem.6c03652","url":null,"abstract":"<p>Thisstudy evaluates CuFeO<sub>2</sub> and CuFe<sub>2</sub>O<sub>4</sub> as promising catalysts for photothermal CO<sub>2</sub> conversionand their ability to form plasmonic Cu nanoparticles in situ. A straightforward,reproducible, aqueous citrate-based solution-gel method with highstoichiometric control was developed to synthesize both catalystsfrom the same starting materials. XRD, Raman, and ICP-OES confirmednearly phase-pure materials with appropriate bandgaps (1.13 eV forCuFeO<sub>2</sub> and 1.55 eV for CuFe<sub>2</sub>O<sub>4</sub>),determined by UV–vis spectroscopy. SEM and BET analyses showeda dense morphology for CuFeO<sub>2</sub> and a slightly more porousCuFe<sub>2</sub>O<sub>4</sub> architecture. The catalysts were testedin a photoreactor, where they selectively form CO via the reversewater–gas shift reaction. The combination of light and heatcauses exsolution of copper onto the surface. These nanoparticlesexhibit the localized surface plasmon resonance effect (LSPR), whichfacilitates CO<sub>2</sub> conversion. The CuFeO<sub>2</sub> catalystproduces 62 mmol of CO g<sub>catalyst</sub><sup>–1</sup> h<sup>–1</sup>, and CuFe<sub>2</sub>O<sub>4</sub> produces 65 mmolof CO g<sub>catalyst</sub><sup>–1</sup> h<sup>–1</sup>, both using a combination of reactor heating and catalyst illumination.The key advancements are the development of a universal aqueous solution-gelroute to structurally distinct copper iron oxides and the identificationof an in situ Cu exsolution mechanism that converts these materialsfrom pre-catalysts into active photothermal catalysts.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24343–24356"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091942","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
A Chiral-at-Metal Magnetic Complex Inside an Enantiopure Magnetic Cage Framework 对映体磁笼框架内的手性金属磁性配合物
IF 4.6 2区 化学
Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-05 DOI: 10.1021/acs.inorgchem.6c03091
Jia-Xue Chen, Feng-Lei Yang, Yu-Hao Duan, Yang Yang
{"title":"A Chiral-at-Metal Magnetic Complex Inside an Enantiopure Magnetic Cage Framework","authors":"Jia-Xue Chen,&nbsp;Feng-Lei Yang,&nbsp;Yu-Hao Duan,&nbsp;Yang Yang","doi":"10.1021/acs.inorgchem.6c03091","DOIUrl":"10.1021/acs.inorgchem.6c03091","url":null,"abstract":"<p>Theintegration of chirality and magnetism into discrete metal–organicarchitectures remains a formidable synthetic challenge, particularlywhen both the cage framework and the encapsulated complex are chiraland paramagnetic. This challenge lies in controlling the stereochemistryof both components while establishing pathways for magnetic exchangebetween their paramagnetic metal centers within a discrete host–guestassembly. In this paper, we report a new series of enantiopure paramagnetictrigonal bipyramidal Co<sup>II</sup><sub>5</sub>L<sub>6</sub> cageframeworks, which are templated by twin carbonate ions or a chiral-at-metalmagnetic [M(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]<sup>n–</sup> complex (M = Cr<sup>III</sup>, n = 3 or M = Co<sup>II</sup>, n =4) inside. The incorporation of the chiral-at-metal complex insidethe cage alters the chiroptical properties compared with the Co<sup>II</sup><sub>5</sub>L<sub>6</sub> framework encaging carbonate ions.Furthermore, the cage framework and the encapsulated chiral-at-metalcomplex exhibit significant magnetic interactions. The variation ofthe metal types in the encapsulated chiral-at-metal complex or thecage frameworks can modulate the magnetic interactions, from antiferromagnetismto ferromagnetism with different exchange strengths. This study providesa new option for the design of cage materials combining chiralityand magnetism.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24197–24205"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091541","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
Planar Dinuclear Copper-Based Hydrogen-Bonded Organic Framework with Synergy Catalysis for High-Performance Hydroboration of Alkynes 平面核铜基氢键有机骨架协同催化炔烃的高效硼化反应
IF 4.6 2区 化学
Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-05 DOI: 10.1021/acs.inorgchem.6c03384
Tianxiu He, Huaibiao Wang, ChunYe Chen, Nanyi Li, Shaoyun Shan, Tianding Hu
{"title":"Planar Dinuclear Copper-Based Hydrogen-Bonded Organic Framework with Synergy Catalysis for High-Performance Hydroboration of Alkynes","authors":"Tianxiu He,&nbsp;Huaibiao Wang,&nbsp;ChunYe Chen,&nbsp;Nanyi Li,&nbsp;Shaoyun Shan,&nbsp;Tianding Hu","doi":"10.1021/acs.inorgchem.6c03384","DOIUrl":"10.1021/acs.inorgchem.6c03384","url":null,"abstract":"<p>Dinuclearmetal synergistic catalysis (DMSC) has beenwell establishedas an effective strategy for enhancing catalytic efficiency in variousfields. However, the design of catalysts for the DMSC-enabled hydroborationof terminal alkynes has been rarely reported. Herein, we report thesynthesis of a novel copper-based hydrogen-bonded organic framework(HOF), denoted as Cu-PzDC. Benefiting from its planar dinuclear Cuunits, Cu-PzDC exhibits exceptionally high catalytic efficiency towardthe hydroboration of terminal alkynes, achieving complete conversionwithin merely 30 min at room temperature without the need of inertatmosphere. This catalytic system affords the synthetically valuableβ-(<em>E</em>)-vinylboronates with 99% selectivity anddemonstrates a broad substrate compatibility covering 29 examples.DFT calculations reveal the synergistic effect between two adjacentCu sites, which enables the simultaneous activation of boryl speciesand phenylacetylene and brings them into close proximity.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24273–24284"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091949","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
Negatively Charged Polysaccharide Stabilizes Amorphous Strontium Sulfate Precursor Phase 带负电荷的多糖稳定非晶硫酸锶前体相
IF 4.6 2区 化学
Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-07 DOI: 10.1021/acs.inorgchem.6c03428
Alejandra Coronel-Zegarra, Jefferey Baxter, Christopher T. Nelson, Jessica M. Walker, Vivian Merk
{"title":"Negatively Charged Polysaccharide Stabilizes Amorphous Strontium Sulfate Precursor Phase","authors":"Alejandra Coronel-Zegarra,&nbsp;Jefferey Baxter,&nbsp;Christopher T. Nelson,&nbsp;Jessica M. Walker,&nbsp;Vivian Merk","doi":"10.1021/acs.inorgchem.6c03428","DOIUrl":"10.1021/acs.inorgchem.6c03428","url":null,"abstract":"<p>Biomineralizationdescribes how living organisms orchestrate thesynthesis of functional inorganic materials for structural protectionor mechanical support. Mineralization under biological regulationoften involves amorphous mineral phases, such as amorphous calciumcarbonate or amorphous calcium phosphate, that lack long-range orderand transform into stable crystals over time. Unlike calcium-bearingbiominerals, little work has been dedicated toward understanding thebiomineralization of earth alkaline sulfates. To our knowledge, thisstudy is the first to unambiguously detect a transient amorphous strontiumsulfate (ASS) phase using time-resolved X-ray diffraction and TransmissionElectron Microscopy (TEM) under cryogenic conditions. Specifically,the incorporation of the negatively charged polysaccharide heparinwas found to mediate bioinspired crystallization pathways based onfundamental inorganic–organic interactions, guiding an amorphous-to-crystallinetransformation of the strontium sulfate (SrSO<sub>4</sub>) mineral.The process yielded unusual ellipsoidal SrSO<sub>4</sub> microcrystalsthat partially underwent particle–particle fusion. Nanofocusedsynchrotron wide-angle X-ray scattering and high-resolution TEM revealedmesocrystalline order from imperfect attachment of ASS nanoclusters,with crystal lattice planes exhibiting gradual tilts in orientation.The nonlinear optical properties of SrSO<sub>4</sub> crystals openintriguing avenues for solid-state optical devices used for IR-to-visiblelight conversion.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24285–24294"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091996","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
Crystal Chemistry of a Nickelate Superconductor: La/Pr Distribution, Oxygen Stoichiometry, and High-Pressure Structural Evolution in La2PrNi2O7 一种镍酸盐超导体的晶体化学:La2PrNi2O7中的La/ pr分布、氧化学计量和高压结构演变
IF 4.6 2区 化学
Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-08 DOI: 10.1021/acs.inorgchem.6c03000
Javier Gainza, Lifen Shi, Gang Wang, Ningning Wang, María Teresa Fernández-Díaz, Stanislav Savvin, Jinguang Cheng, José Antonio Alonso
{"title":"Crystal Chemistry of a Nickelate Superconductor: La/Pr Distribution, Oxygen Stoichiometry, and High-Pressure Structural Evolution in La2PrNi2O7","authors":"Javier Gainza,&nbsp;Lifen Shi,&nbsp;Gang Wang,&nbsp;Ningning Wang,&nbsp;María Teresa Fernández-Díaz,&nbsp;Stanislav Savvin,&nbsp;Jinguang Cheng,&nbsp;José Antonio Alonso","doi":"10.1021/acs.inorgchem.6c03000","DOIUrl":"10.1021/acs.inorgchem.6c03000","url":null,"abstract":"<p>We report a comprehensive structural characterizationof La<sub>2</sub>PrNi<sub>2</sub>O<sub>7</sub>, a bilayer Ruddlesden–Poppernickelate that has been described to exhibit high-temperature superconductivityunder hydrostatic pressure. Synchrotron X-ray diffraction (SXRD) dataand high-resolution neutron powder diffraction (NPD) data, collectedat ambient pressure, together with NPD data recorded under pressuresup to 8.42 GPa in a Paris–Edinburgh cell, have been analyzedby the Rietveld method in the orthorhombic <em>Amam</em> spacegroup (No. 63). This work aims at providing precise bulk structuralbenchmarks─site-selective cation distribution, oxygen stoichiometry,and the pressure evolution of the Ni–O–Ni bond geometry─thatare essential inputs for theoretical models. High-resolution NPD,which offers a strong La/Pr scattering-length contrast, yields refinedLa/Pr occupancies that suggest a slight preference of Pr for the outerrock-salt site (La2/Pr2), although the deviation from a random distributiondoes not exceed three standard deviations and is therefore not statisticallyconclusive. NPD also assesses the full oxygen stoichiometry of thespecimen under study. Under applied pressure up to 8.42 GPa (belowthe superconducting critical pressure <em>P</em><sub>c</sub> ≈ 11 GPa), the orthorhombic structure is retained with asystematic compression of all lattice parameters, a reduction of theunit-cell volume of ∼4.9%, and a progressive straighteningof the out-of-plane Ni–O–Ni bond angle. No structuralphase transition to the tetragonal <em>I4</em>/<em>mmm</em> symmetry is observed in the pressure range studied, consistent withthe superconducting onset occurring above <em>P</em><sub>c</sub> ≈ 11 GPa. Cooling to 5 K at 8.42 GPa produces no measurableadditional structural change, indicating that precursor distortionsto the superconducting state are subtle.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24175–24182"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151415","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
Decoupling the Roles of Ligand-Field and Charge-Transfer Excitations on the Photocarrier Yield in Transition-Metal Oxides: Insights from MTiO3 (M = Ni, Co, Mn) 过渡金属氧化物中配体场和电荷转移激发对光载流子产率的去耦作用:来自MTiO3 (M = Ni, Co, Mn)的见解
IF 4.6 2区 化学
Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-08 DOI: 10.1021/acs.inorgchem.6c01924
Ron Fishov, Yotam Engel, Rohit Kumar Saini, Sa’ar Shor Peled, Kumaraswamy Miriyala, Daniel A. Grave
{"title":"Decoupling the Roles of Ligand-Field and Charge-Transfer Excitations on the Photocarrier Yield in Transition-Metal Oxides: Insights from MTiO3 (M = Ni, Co, Mn)","authors":"Ron Fishov,&nbsp;Yotam Engel,&nbsp;Rohit Kumar Saini,&nbsp;Sa’ar Shor Peled,&nbsp;Kumaraswamy Miriyala,&nbsp;Daniel A. Grave","doi":"10.1021/acs.inorgchem.6c01924","DOIUrl":"10.1021/acs.inorgchem.6c01924","url":null,"abstract":"<p>Open d-shell transition-metal oxides are widely studiedas photoactivematerials for solar-energy conversion but typically exhibit low yieldsof mobile photocarriers. This inefficiency has been linked to ligand-field(LF) states that induce ultrafast relaxation, although their impactacross open d-shell oxides remains poorly understood. Here, epitaxialilmenite-type MTiO<sub>3</sub> (M = Ni, Co, Mn) thin films were stabilizedby pulsed laser deposition. In this isostructural series, the M<sup>2+</sup> cation tunes the d-electron configuration and the energeticseparation and spectral overlap of LF and charge-transfer excitations.Combined optical and time-resolved microwave conductivity measurements,benchmarked against rutile TiO<sub>2</sub> as a d<sup>0</sup> reference,together with photoelectrochemical measurements of the ilmenites,reveal reduced yield-mobility products compared to TiO<sub>2</sub>. NiTiO<sub>3</sub> and CoTiO<sub>3</sub> show measurable photoconductivityonly under UV charge-transfer excitation, whereas MnTiO<sub>3</sub>, dominated by a dense LF manifold, exhibits a negligible response.These results indicate that mobile charge-carrier generation contributingto photoelectrochemical activity originates from UV charge-transferexcitations, likely dominated by O<sup>2–</sup> → Ti<sup>4+</sup> ligand-to-metal charge-transfer (LMCT) excitation into Ti3d-derived states, while LF states primarily act as relaxation pathwaysthat do not yield mobile carriers on nanosecond time scales. Thesefindings decouple the roles of distinct optical excitations in governingphotocarrier localization in open d-shell oxides.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24103–24115"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151417","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
Fluorine-Functionalized Zr-Based Metal–Organic Framework for One-Step Methane Purification from Natural Gas 氟功能化锆基金属-有机骨架一步提纯天然气甲烷
IF 4.6 2区 化学
Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-08 DOI: 10.1021/acs.inorgchem.6c04720
Ke Zhao, Youran Li, Wen Jiang, Jiantang Li, Dongmei Wang
{"title":"Fluorine-Functionalized Zr-Based Metal–Organic Framework for One-Step Methane Purification from Natural Gas","authors":"Ke Zhao,&nbsp;Youran Li,&nbsp;Wen Jiang,&nbsp;Jiantang Li,&nbsp;Dongmei Wang","doi":"10.1021/acs.inorgchem.6c04720","DOIUrl":"10.1021/acs.inorgchem.6c04720","url":null,"abstract":"<p>Natural gas, as a clean energy source, requires the eliminationof co-occurring impurities such as C<sub>2</sub>H<sub>6</sub> andC<sub>3</sub>H<sub>8</sub> to enhance its energy utilization efficiency.Herein, by using a Zr-based MOF as a platform, we fabricated an isostructuralpair, <strong>NU-1400(−H)</strong> and fluorine-functionalized <strong>NU-1400(−F)</strong>, through rational ligand fluorination,and systematically investigated their adsorption and separation performancestoward CH<sub>4</sub>, C<sub>2</sub>H<sub>6</sub> and C<sub>3</sub>H<sub>8</sub>. This isostructural pair allows the effect of fluorinefunctionalization on the pore microenvironment and adsorption affinityto be directly evaluated. Single-component adsorption isotherms revealthat fluorine functionalization significantly improves the uptakecapacities of C<sub>2</sub>H<sub>6</sub> and C<sub>3</sub>H<sub>8</sub> (from 25.4/28.8 to 34.1/38.9 cm<sup>3</sup> g<sup>–1</sup>), while causing only marginal changes in CH<sub>4</sub> adsorption.Isosteric heat of adsorption (<em>Q</em><sub>st</sub>) analysisconfirms that <strong>NU-1400(−F)</strong> exhibits weakened affinityfor CH<sub>4</sub> (19.2 kJ mol<sup>–1</sup>) and remarkablyenhanced interaction with C<sub>3</sub>H<sub>8</sub> (47.3 kJ mol<sup>–1</sup>). Benefiting from such optimized differences in adsorptionaffinity, <strong>NU-1400(−F)</strong> achieves excellent IASTselectivity of 516 for C<sub>3</sub>H<sub>8</sub>/CH<sub>4</sub> and21 for C<sub>2</sub>H<sub>6</sub>/CH<sub>4</sub>, which are far higherthan those of pristine <strong>NU-1400(−H)</strong> (145 and 18).Dynamic breakthrough experiments and cyclic regeneration tests furthervalidate its reliable separation capability and outstanding recyclability.The rational fluorine functionalization effectively tailors the poremicroenvironment for selective heavy-hydrocarbon adsorption, making <strong>NU-1400(−F)</strong> a promising adsorbent for one-step methanepurification from natural gas. This work thus highlights a practicalpore-microenvironment engineering strategy via ligand fluorinationfor efficient light hydrocarbon/CH<sub>4</sub> separation.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24612–24619"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151419","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
Correction to “Cyclic Metallophosphines via an Unexpected Series of Metal-Mediated P–C and C–C Bond Rearrangements” 更正“通过一系列意想不到的金属介导的P-C和C-C键重排的环金属膦”
IF 4.6 2区 化学
Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-08 DOI: 10.1021/acs.inorgchem.6c04414
Mihir L Bhowmik, Md. Abdullah Al Mamun, Vladimir N. Nesterov, Jagodish C. Sarker, Shariff E. Kabir, Graeme Hogarth
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