Inorganic Chemistry最新文献

{"title":"Enhanced Photocatalytic O2 Evolution over Layered Perovskite Oxyiodide Ba2Bi3Nb2O11I through Flux Synthesis and Surface Modifications","authors":"Reiya Takahashi, Makoto Ogawa, Hajime Suzuki, Osamu Tomita, Akinobu Nakada, Shunsuke Nozawa, Akinori Saeki, Ryu Abe","doi":"10.1021/acs.inorgchem.5c00803","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00803","url":null,"abstract":"Sillén–Aurivillius oxyiodides, particularly Ba₂Bi₃Nb₂O₁₁I with double-perovskite layers, are promising photocatalysts for visible-light-driven water splitting due to their excellent light absorption and carrier transport properties. However, efforts to enhance their photocatalytic performance through advancements in synthesis methods or surface modifications remain limited. Here, we report the flux synthesis of Ba₂Bi₃Nb₂O₁₁I and the optimization of cocatalyst loading. Single-phase Ba₂Bi₃Nb₂O₁₁I was successfully synthesized using molten alkali iodide salts under appropriate reaction conditions. The heating rate during the synthesis significantly influenced crystallinity and carrier lifetime, as shown by time-resolved microwave conductivity measurements. By optimizing the reaction conditions to enhance crystallinity (prolong carrier lifetime), the flux-synthesized sample exhibited a higher sacrificial O₂ evolution rate than that prepared via the conventional solid-state reaction. Furthermore, precise control over the loading conditions of the iron–ruthenium oxide cocatalyst ((Fe,Ru)O<i>_<i>x</i></i>) significantly enhanced nonsacrificial O₂ evolution from an aqueous Fe³⁺ solution. Electrochemical analysis revealed that the tuned loading conditions enhanced the catalytic activity of the (Fe,Ru)O<i>_<i>x</i></i> cocatalyst for both water oxidation and Fe³⁺ reduction. Finally, Z-scheme water splitting using the optimized (Fe,Ru)O<i>_<i>x</i></i>-loaded Ba₂Bi₃Nb₂O₁₁I photocatalyst showed superior efficiency than that using the previously reported unoptimized sample. This study provides valuable insights into enhancing the O₂ evolution activity of oxyiodide photocatalysts for water-splitting applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"42 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876288","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}

{"title":"Exploring the Coordination Chemistry and Potential Applications of PC3PA-Based Lanthanide Complexes: Synthesis, Solution Structure, Luminescence, and Relaxation Properties","authors":"Loëza Collobert, Lucile Bridou, Zoltán Garda, Olivier Maury, Éva Tóth, Carlos Platas-Iglesias, Raphaël Tripier, Maryline Beyler","doi":"10.1021/acs.inorgchem.5c01318","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01318","url":null,"abstract":"The novel ligand H₃<b>PC3PA</b> was synthesized from pyclen and methyl-6-(bromomethyl)picolinate with 82% overall yield, and its rare-earth complexes (La, Eu, Gd, Tb, Lu, Y) were isolated and characterized by HR-MS and analytical HPLC. Solution ¹H and ¹³C NMR studies of the diamagnetic [Lu(<b>PC3PA</b>)] and [Y(<b>PC3PA</b>)] chelates evidenced non-coordination of the picolinate moiety at the <i>N</i>₆ position to the metal. The ¹H NMR spectrum of [Lu(<b>PC3PA</b>)] showed diastereotopic CH₂ signals corresponding to a single, rigid isomer in solution, while [Y(<b>PC3PA</b>)] displayed sharp signals at higher temperatures, and diffusion-ordered NMR spectroscopy (DOSY) confirmed a single monomer species. [Eu(<b>PC3PA</b>)] and [Tb(<b>PC3PA</b>)] in water showed broad absorption bands at 269 nm due to the picolinate chromophore. [Eu(<b>PC3PA</b>)] displays red emission with a splitting of the ⁷F_J manifold characteristic of a low-symmetry coordination environment, while [Tb(<b>PC3PA</b>)] shows typical ⁵D₄–⁷F_J transitions of Tb³⁺. Emission lifetimes confirmed monohydration of both complexes, in accordance with a non-coordinating picolinate pendant. The relaxivity of [Gd(<b>PC3PA</b>)], <i>r</i>_1p = 3.97 mM^–1 s^–1 (20 MHz, 298 K), is comparable to that of commercial MRI contrast agents. The dissociation half-life of [Gd(<b>PC3PA</b>)] (22 min at pH 1, 25 °C) is short in comparison to that of analogous complexes, evidencing that the non-coordinating picolinate accelerates proton-assisted dissociation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"40 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876289","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}

{"title":"Insight into Oxidative Desulfurization Mechanism from the Interaction between Different Facets of TiO2 and V Single Atom or V2O5 Cluster","authors":"Peng Zheng, Zitao Zhu, Chengkun Xiao, Gang Wang","doi":"10.1021/acs.inorgchem.4c05395","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05395","url":null,"abstract":"This research was devoted to investigating the oxidative desulfurization (ODS) reaction of thiophene over V₁–TiO₂ and V₂O₅–TiO₂ surfaces through density functional theory calculations. The calculation results showed that V single atoms and V₂O₅ clusters exhibited significantly different binding energies and charge transfer characteristics over the different TiO₂ facets. The density of states and orbital interaction analyses further revealed that V single atoms exhibited a more pronounced advantage in adsorbing and activating the O₂ molecules compared to the V₂O₅ clusters, which was primarily attributed to their unique electronic structure and coordination environment. Based on the calculation results, the V single atoms exhibited the highest catalytic activity in the formation of sulfoxide over the TiO₂ (101) facet. Additionally, this work found that the extra oxygen (O_ext) species also played a key role in reducing the reaction barriers and promoting the formation of sulfoxides, with O_ext species directly contributing to the V₂O₅-catalyzed thiophene ODS reaction. The O_ext species also promoted the continuous conversion of sulfoxides to sulfones. Comprehensive analysis indicated that there was a significant synergistic effect between V single atoms and V₂O₅ clusters, which collectively promoted the effective ODS process of thiophene.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876263","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}

{"title":"Au-Acyclic Diaminocarbene-Linked Porphyrin Covalent Organic Framework as a Cascade Catalyst for Photocatalytic Sulfide Oxidation and Intermolecular Nucleophilic Addition","authors":"Qiao-Qiao Sun, Guo-Tai Li, Yi-Ming Chen, Jing-Lan Kan, Jian-Ping Ma, Ying Dong, Yu-Bin Dong","doi":"10.1021/acs.inorgchem.5c00789","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00789","url":null,"abstract":"The design and synthesis of a multifunctional covalent organic framework (COF) for various applications have been considered a big challenge. Herein, we report the construction of a novel porphyrin-based Au-acyclic diaminocarbene (Au-ADC)-linked COF (abbreviated as <b>Au-ADC-Por-COF</b>) via a metal-mediated nucleophilic addition reaction. The resultant multifunctional <b>Au-ADC-Por-COF</b> revealed an outstanding performance in a cascade catalyzing photocatalytic sulfide oxidation under visible-light irradiation and intermolecular nucleophilic addition. This research might open a new way for the design of advanced materials with unprecedented structures and catalytic activities.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"71 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872375","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}

{"title":"Molten Salt Synthesis of Single-Crystalline Sr2MgSi2O7: Eu2+, Dy3+ Nanoplates: Breaking the Afterglow-Size Trade-off","authors":"Lang Pei, Yingqiang Yu, Zhanfeng Ma, Xusheng Wang, Qinan Mao, Jiasong Zhong","doi":"10.1021/acs.inorgchem.5c00555","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00555","url":null,"abstract":"Sr₂MgSi₂O₇/Eu²⁺, Dy³⁺ (SMSED) phosphors show promise for persistent luminescence applications due to their long afterglow and robust chemical stability. However, a trade-off exists between achieving precise size and shape control of SMSED and maintaining prolonged afterglow intensity and duration during synthesis. Herein, we unveil a molten-salt method that successfully produces uniform single-crystalline plate-like SMSED for the first time. This synthesis significantly reduces both the sintering temperature and time compared to the classic solid–state reaction (SSR) method. Owing to the nanoplates structure, uniform size distribution, and single-crystal nature, the resulting SMSED exhibited excellent afterglow performance and thermal stability, with a sustained blue afterglow exceeding 24 h and retaining &gt;70% of its initial luminescence up to 523 K, outperforming most reported SMSED phosphors. These remarkable properties underscore the considerable potential of SMSED nanoplates for applications in fingerprint detection. This work unlocks a new synthetic frontier for achieving the controllable synthesis of SMSED phosphors, paving the way for future optimizations aimed at the development of advanced persistent luminescent phosphors.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"257 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872374","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}

{"title":"The Inhibited Dehydration Polycondensation Tendency of a Titanocene Aqua Complex Attributed to the Formation of Hydrogen Bonds Between the Ligand Water and Py-NO: Mechanism and Application","authors":"Lei Fan, Xiao Zhang, Shunan Zhao, Huaming Sun, Weiqiang Zhang, Yajun Jian, Ziwei Gao","doi":"10.1021/acs.inorgchem.5c00338","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00338","url":null,"abstract":"Titanocene aqua complexes (<b>TACs</b>) demonstrate versatile activities that critically depend on maintaining their molecular integrity in aqueous media. However, the strong oxophilicity of Ti(IV) centers renders these complexes prone to undesirable dehydration-condensation reactions, which severely compromise their structural stability. To address this challenge, we developed a simple yet effective strategy for dramatically stabilizing <b>TACs</b> in aqueous environments through the introduction of pyridine-N-oxides (<b>Py-NOs</b>) as auxiliary ligands. Comprehensive mechanistic investigations, including spectroscopic analyses and DFT calculations, reveal that the enhanced stability originates primarily from the formation of intermolecular hydrogen bonds between <b>TACs</b> and <b>Py-NOs</b>. These interactions effectively suppress Ti(IV)-mediated hydrolysis pathways while preserving the complexes’ functionality.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872373","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}

{"title":"Borate Salts of Aluminum-Alkyl Cations Stabilized by P-, O-, and C-Donors: Synthesis, Characterization and Application as Cocatalysts","authors":"Gaia Urciuoli, Antonio Vittoria, Francesco Zaccaria, Cristiano Zuccaccia, Roberta Cipullo, Peter H. M. Budzelaar, Leonardo Tensi, Christian Ehm, Alceo Macchioni, Vincenzo Busico","doi":"10.1021/acs.inorgchem.5c00906","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00906","url":null,"abstract":"Well-defined Al-alkyl borate (AAB) salts {[<i>i</i>Bu₂(<b>L</b>)Al]₂(μ-H)}⁺[B(C₆F₅)₄]⁻ (<b>AlHAl_L</b>) with <b>L</b> = N-donor ligands have been recently reported as promising “complete” cocatalysts for olefin polymerization. Herein, we explore structural variations of <b>AlHAl_L</b> going beyond the class of N-donors like the prototypical <i>N,N</i>-dimethyl aniline (<b>DMA</b>). Thirteen P-, O-, and C-donor ligands were screened, allowing isolation of AAB salts with mono- and bidentate phosphines, alkyl-, aryl-, and silyl-ethers, and a N-heterocyclic carbene. Except for the diphosphine with the longest spacer between the P atoms [bis(diphenylphosphino)hexane, <b>DPPH</b>], all donors gave well-defined tetracoordinate or tricoordinate molecular species, which were characterized in solution (NMR) and solid state (XRD), and tested as cocatalyst in ethylene/1-hexene copolymerization with an <i>ansa</i>-zirconocene catalyst [<i>rac</i>-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂]. The vast majority of novel AAB salts provided active catalytic systems, further demonstrating the broad tunability of these species. Consistent with previous studies, variability in productivity upon <b>L</b> variation is primarily related to the efficiency of precatalyst activation, determining the fraction of Zr active sites. Variations in polymer molecular weight and comonomer incorporation observed with some P-, O- and C-donor ligands indicate that also interactions between the <b>L</b> donors and the Zr active species might be relevant in determining catalytic performance in some cases.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"48 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866414","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}

{"title":"Self-Supported NiCo2S4@Ce-NiFe LDH/CeO2 Nanoarrays for Electrochemical Water Splitting","authors":"Jun Yu, Nannan Zhang, Jie Li, Huiyu Sun, Xinyu Gu, Zhengying Wu, Tianpeng Liu, Yukou Du","doi":"10.1021/acs.inorgchem.5c00289","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00289","url":null,"abstract":"The design of high-performance OER catalysts is crucial for efficient electrochemical water splitting (EWS). Herein, a NiCo₂S₄@Ce-NiFe LDH/CeO₂ heterostructure nanoarray electrocatalyst with abundant oxygen defect sites is reported. The introduction of Ce species activates the lattice oxygen in the oxyhydroxides, inducing the transformation of the catalytic mechanism toward the lattice oxygen oxidation mechanism (LOM) pathway, bypassing the thermodynamic limitation of the adsorbate evolution mechanism (AEM), and strengthening the intrinsic activity of the material. Moreover, the reversible transitions between different oxidation states of Ce species and the high oxygen storage capacity of CeO₂ regulate the adsorption behavior of the reaction intermediates, allowing it to be easier for the material to enrich the oxygen-containing intermediates, thereby improving the adsorption kinetics. Accordingly, NiCo₂S₄@Ce-NiFe LDH/CeO₂ exhibits remarkable OER performance (η₅₀ = 226 mV, η₁₀₀ = 244 mV) and brilliant stability. Additionally, the presence of the CeO₂ protective layer inhibits the impact of Cl^– and other pollutants in seawater, which enables NiCo₂S₄@Ce-NiFe LDH/CeO₂ to perform satisfactorily in seawater electrolysis, as well. This study offers a fresh perspective on the design of defect-rich OER catalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"21 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866416","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}

{"title":"An Electrochemical Strategy for Chalcogenation of closo-Dodecaborate (B12H12)2– Anion","authors":"Tyler A. Kerr, Yessica A. Nelson, Nicholas A. Bernier, Alexander M. Spokoyny","doi":"10.1021/acs.inorgchem.5c00469","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00469","url":null,"abstract":"Advancements in thermal neutron generation technologies within clinical environments have led to a renewed interest in developing boron-containing compounds for boron neutron capture therapy (BNCT). Previous syntheses of several key boron cluster-based therapeutics with clinical relevance are low-yielding and have complicated workup procedures. Using electrolytic methods, we report the <i>in situ</i> oxidation of pseudohalides, [SCN]⁻ and [SeCN]⁻, to synthesize pseudohalogenated products, B₁₂H₁₁YCN^2– (Y = S or Se). Further, these compounds can be reduced to their respective thiol or selenol, [B₁₂H₁₁SH]^2– (BSH) or [B₁₂H₁₁SeH]^2– (BSeH), which are exceedingly nucleophilic and able to form zwitterionic sulfonium and selenonium compounds using alkyl-based electrophiles. The newly reported preparation of BSH and BSeH provides an efficient and convenient route to the preparation of key chalcogenated boron cluster building blocks for the biomedical and materials science communities.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872376","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}

{"title":"From Orthorhombic Cu8GeS6 to Cubic Cu6HgGeS6: Second-Harmonic Generation and Photocurrent Responses","authors":"Qiu-Yang Du, Shan-Shan Han, Wen-Dong Yao, Xu-Bin Ni, Wenfeng Zhou, Wenlong Liu, Sheng-Ping Guo","doi":"10.1021/acs.inorgchem.5c01375","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01375","url":null,"abstract":"A new noncentrosymmetric sulfide, Cu₆HgGeS₆ (CHGS), has been successfully synthesized via a heterovalent substitution strategy based on argyrodite-type Cu₈GeS₆ (CGS). Benefiting from the substitution of Cu⁺ with Hg²⁺ cation, the structure changes from orthorhombic <i>Pmn</i>2₁ to cubic <i>P</i>2₁3. CHGS exhibits obvious nonlinear optical (NLO) activity, while CGS not. The combination of theoretical calculation and structure analysis indicates that the introduction of Hg²⁺ ions leads to a structural transformation, in which the trigonal pyramid [CuS₃] units provide the main contribution to the NLO performance to a certain extent. Additionally, CHGS exhibits a relatively large photocurrent response (2.5 <i>μ</i>A/cm²) among chalcogenides. This case of heterovalent substitution induced structural transformation and enhanced NLO properties provides a good example to design new NLO materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872377","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}