Inorganic Chemistry Frontiers最新文献

{"title":"Z-Scheme Ba2AgIO6/C3N4 Heterojunction Enabling Efficient Visible-Light Photocatalytic H2O2 Production via Direct One-Step Two-Electron O2 Reduction Reaction","authors":"Kexin Yang, Zhijia Song, XiaoXiao Fu, Wei Yan, Tao Zhang, Yiwei Hua, Haixin Lin, Qin Kuang, Zhaoxiong Xie","doi":"10.1039/d5qi01052g","DOIUrl":"https://doi.org/10.1039/d5qi01052g","url":null,"abstract":"The photocatalytic direct one-step two-electron (2e-) oxygen reduction reaction (ORR) holds great potential in efficient H2O2 synthesis. However, it is still a significant challenge to design photocatalysts for achieving high-efficiency H2O2 production via this direct one-step 2e- ORR pathway. To address this, we have constructed a Z-scheme BAIO/C3N4 heterojunction by in situ growing Ba2AgIO6 (BAIO) on the surface of C3N4 nanosheets. Under visible light irradiation, the optimal sample, with a BAIO:C3N4 mass ratio of 1:1.5, exhibited a remarkable H2O2 yield of up to 535.9 μmol g-1 h-1, which is 8.8 times higher than that of pure C3N4. This enhancement is attributed to the improved charge separation and migration efficiency facilitated by the enhanced internal electric field (IEF) in BAIO/C3N4 heterojunction. Furthermore, the heterojunction altered the O2 adsorption configuration to the Yeager-type, promoting a more efficient and selective direct one-step 2e- ORR for H2O2 production. This study highlights the importance of regulating the reaction pathway to enhance photocatalytic H2O2 production activity and offers a new insight for designing highly active photocatalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"71 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144611256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The complexation and solvent extraction properties of a phenanthroline diamide extractant for trivalent actinide and lanthanide ions","authors":"Emma M Archer, Felipe A. Pereiro, Jocelyn M. Riley, Jacob P. Brannon, Elizabeth B. Flynn, J. Connor Gilhula, Brittany Huffman, Jessica A Jackson, Julia G. Knapp, Brian Long, Harris E. Mason, Monica S. Mullis, Stosh Anthony Kozimor, Jenifer Shafer, Shane Galley","doi":"10.1039/d5qi01056j","DOIUrl":"https://doi.org/10.1039/d5qi01056j","url":null,"abstract":"Characterization of trivalent actinide (An(III)) chemistry with nitrogen and oxygen donor (<em>N,O</em>-donor) extractants is relevant to closing the nuclear fuel cycle. In general the extraction of transplutonium actinides has not been extensively explored, but is essential to fundamental chemical understanding and separation schemes. A popular <em>N,O</em>-donor extractant, phenanthroline diamide (DAPhen), has incurred interest for <em>f</em>-element separations due to numerous positive qualities as an extractant. DAPhen ligands are stable in molar concentrated acids and have a pre-organized binding mode that encourages faster complexation. Additionally, the amide moieties can be functionalized to tune interactions between metals and ligands. In this work, solvent extraction experiments were completed using a derivative of the DAPhen extractant in nitrobenzene that revealed selectivity for multiple An(III) (An = Am, Cm, Bk, Cf) metals in comparison to Eu(III). The extraction of all surveyed An(III) cations was effective. Surprisingly, the degree to which each An(III) cation was extracted was not periodic. Extraction was most effective for Am(III), intermediate for Cf(III) and Bk(III), and lowest for Cm(III). To provide additional insight into the extraction process, we characterized the corrdiantion chemistry between Am(III) and numerous Ln(III) cations (Pr(III), Nd(III), Tb(III), Lu(III)) with TEtDAPhen. Lanthanide speciation and stability constants were measured using UV-Visible spectroscopy for multiple Ln(III) metals (Nd(III), Eu(III), Gd(III)). Those experiments showed increasing stability constants from Nd(III) – Gd(III) and that the metal-to-ligand stoichiometry was one-to-one. Consistent with that interpretation were single crystal X-ray crystallography studies on M(TEtDAPhen)(NO<small>₃</small>)<small>₃</small> complexes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"29 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144611254","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Advancing photocatalysis through efficient fabrication of morphology-engineered photonic crystals","authors":"Yukai Chen, Qinglian Tan, Yiyi Ji, Dan Wang, Rulin Dong, Baoying Dai","doi":"10.1039/d5qi01087j","DOIUrl":"https://doi.org/10.1039/d5qi01087j","url":null,"abstract":"Enhancing photocatalytic efficiency remains a key research focus and challenge due to limitations like narrow light absorption ranges and rapid recombination of photogenerated carriers. Photonic crystals offer promising solutions through their unique PBG characteristics, photon localization effects, and slow light properties. Unlike previous studies emphasizing photocatalytic material optimization, this work investigates multi-dimensional photonic crystal structures and their mechanisms in controlling light propagation. Preparation methods such as self-assembly and template techniques are discussed, particularly highlighting strategies for creating morphologically unique photonic crystals. The study further explores how photonic crystals expand light absorption spectra, enhance light utilization efficiency, and facilitate carrier separation. These mechanisms not only provide theoretical guidance for boosting photocatalytic reaction activity but also establish new design principles for high-performance photocatalysts. This review may advance the application potential of photocatalytic technology by addressing fundamental challenges through structural innovation and light–matter interaction regulation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"37 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144611313","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Simultaneously enhanced mechanical and thermoelectric performance of Ag9GaSe6 argyrodites via tailoring chemical compositions","authors":"Siqi Lin, Zhenyu Lai, Shoumei Liu, Linlin Guo, Yanjiao Li, Shiyun Wang, Hezhu Shao, Min Jin","doi":"10.1039/d5qi01166c","DOIUrl":"https://doi.org/10.1039/d5qi01166c","url":null,"abstract":"Argyrodite materials with ion diffusion (Ag+, Cu+, and Li+) and inherently low thermal conductivity have attracted significant interest as promising candidates for thermoelectric and solid-state battery applications. Empirically, poor mechanical performance often accompanies such low thermal conductivity, but the mechanical properties of argyrodite compounds have rarely been reported, especially for high-performance argyrodite Ag9GaSe6. In this work, we reveal the inferior hardness and elastic modulus of argyrodite Ag9GaSe6 through experimental measurements and theoretical calculations, primarily attributed to the presence of a large number of weak chemical bonds. To enhance the mechanical properties, Mn atoms were introduced to partially substitute either the rigid Ga sites or the highly diffusive Ag sites, forming composition of Ag9Ga1-xMnxSe6 (0≤x≤0.1) and Ag9-yMnyGaSe6 (0≤y≤0.2). As a result, the doped samples exhibited approximately 38% higher hardness (2.3 GPa) and 44% higher elastic modulus (30.1 GPa) compared to pristine Ag9GaSe6. In addition, the slightly optimized carrier concentration, along with the preservation of low thermal conductivity, contributed to enhanced average zT values as high as 0.9 for Mn-doped Ag9GaSe6. This work demonstrates an effective strategy for simultaneously improving both mechanical and thermoelectric performance in argyrodite materials for thermoelectric applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"44 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144603703","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Strategic synthesis and near-infrared photothermal conversion of unique single/double trefoil knots and [2]catenane assemblies","authors":"Xiaoyan Lu, Yao He, Jian-Xin Yang, Wen-Jie Liu, Min-Le Han, Francisco Aznárez Pemán, Li-Long Dang, Lufang Ma","doi":"10.1039/d5qi01399b","DOIUrl":"https://doi.org/10.1039/d5qi01399b","url":null,"abstract":"The rare molecular structures and application possibilities in a variety of fields has attracted the attention to molecular knots and catenanes in recent years. However, their selective synthesis remains a major challenge. Herein, a new diimidazole-based flexible ligand precursor L1 possessing two phenyl conjugated groups and two methylene moieties has been synthesized. In addition, five half-sandwich-based building units (B1-B5) featuring different sizes and functional groups were selected to combine with compound L1 for generating different molecular knots and catenanes, by following a classical coordination-driven self-assembly strategy. Thus, one double trefoil knot, two trefoil knots, one D-type [2]catenane and one metallamacrocycle have been isolated in remarkable yields. Interestingly, the D-shaped [2]catenane 2 could be converted into metallamacrocycle 1 upon light irradiation and introduction of Cl⁻ ions. The formation of all the indicated structures has been unequivocally confirmed by single-crystal X-ray diffraction analysis, NMR spectroscopy and ESI-TOF-MS. Photothermal conversion studies showed that the double trefoil knot 5 exhibits remarkable photothermal conversion efficiency in near-infrared (NIR) experiments (31.32% - 40.28%), which can be attributed to its unique topological structure and π-π stacking interactions. Electron paramagnetic resonance (EPR) experiments fully confirmed the recorded results.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"21 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Divergent Deazotation and Nitrene Group Transfer Pathways at Cobalt Phospha-Triazene Species","authors":"Kunwoo Lee, Seji Kim, Yunho Lee","doi":"10.1039/d5qi01338k","DOIUrl":"https://doi.org/10.1039/d5qi01338k","url":null,"abstract":"Metal-nitrenes are critical intermediates in the incorporation of nitrogen functional groups, and a better understanding of the mechanism of their formation from the corresponding organoazide adducts is highly desirable. In this work, we demonstrate a new mode of organoazide deazotation at a phosphide-containing (PPP)Co scaffold. A dimeric cobalt species reacts with organoazides to furnish the corresponding cobalt(II) phosphazido complexes via selective [2+3] cycloaddition. This metal-ligand cooperative (MLC) transformation involves P–P bond cleavage along with Co–N<small>_𝛼</small> and P–N<small>_γ</small> bond formation, revealing that the Co-phosphide site acts as an anchoring site for organoazide binding. The reduced Co(I) phosphazido complexes react with electrophiles such as B(C<small>₆</small>F<small>₅</small>)<small>₃</small> and methylating reagents at the N<small>_γ</small> position to give the respective borane adduct and methyl species. The electrophilic functionalization of such anchored organoazide moieties leads to a significantly less delocalized azide moiety and elongation of the N<small>_β</small>–N<small>_γ</small> distance, rendering it susceptible toward thermolytic N<small>_β</small>–N<small>_γ</small> bond cleavage. The resulting nitrene moiety reacts with the phosphide moiety or with exogenous nitriles to form the respective iminophosphide or phospha-amidinate species. Such reactivity provides a new mode of organoazide activation distinct from previous studies that primarily feature N<small>_𝛼</small>–N<small>_β</small> bond cleavage.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"109 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594711","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Extraordinarily Enhanced Rate and Stability of Ni-Rich Cathodes through MXene Coating","authors":"Hang Yang, Zi Xuan Wu, Guihong Mao, Yang Li, Tengyu Yao, Duo Chen, Laifa Shen","doi":"10.1039/d5qi00662g","DOIUrl":"https://doi.org/10.1039/d5qi00662g","url":null,"abstract":"Ni-rich layered cathodes play a crucial role in achieving high energy density in lithium-ion batteries, primarily due to their substantial theoretical capacity. However, Ni-rich layered cathodes suffer from structural degradation, severe side reactions, and limited cycle life, particularly under conditions of high operating voltage. This study introduces an innovative interfacial engineering strategy employing two-dimensional transition metal carbide (MXene) nanosheets as conformal surface modifiers to significantly improve the structural and electrochemical stability of high-nickel layered oxide cathode materials The modifying layer enhances the charge and ion transport of the interface for the cathode material, effectively promoting the rate performances. Moreover, the induced cathode electrolyte interphase (CEI) can mitigate the attack of HF by preference adsorption of PF5 on MXene, which substantially improve the cycling stability especially at high operating voltage. As a result, the modified material shows excellent electrochemical performance with 96.75% capacity retention at 4.5V after 100 cycles at 1C, which is higher than bare NCM90 of 76.09%. In addition, the rate capability is also enhanced by this coating engineering, which endows the cathode with high capacity of 142 mAh g⁻¹ at 10C, superior to the 110.6 mAh g⁻¹ of bare NCM90. This work provides a new reference for constructing stable high-energy-density Ni-rich layered cathode with MXene materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594708","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Inorganic Chemist’s Guide to Actinide Radiation Chemistry: A Review","authors":"Tori Forbes, Samantha Kruse, Sarah K. Scherrer, Gregory Peter Holmbeck, Jay A Laverne","doi":"10.1039/d5qi00975h","DOIUrl":"https://doi.org/10.1039/d5qi00975h","url":null,"abstract":"This review aims to provide an overview of the current state of ionizing radiation chemistry with respect to the actinide elements, thorium through californium. Despite the inherent radioactivity of the actinides, only a few studies explore the effects of ionizing radiation on their redox chemistry and surrounding environment. This fundamental knowledge gap, coupled with the current renaissance in actinide-based technologies such as nuclear power, space exploration, and medicine, underscores the importance of research in this interdisciplinary area. This review will focus on the interactions between reactive species formed by radiolysis with actinides and their complexes, offering an inorganic chemist’s perspective on research in radiation chemistry. In addition, a thorough discussion of our current understanding of radiation-induced changes in actinide speciation in both aqueous solution and the solid-state will be provided, focusing on changes in oxidation state distribution, complexation, and secondary coordination effects within inorganic materials. Finally, this review will discuss challenges and opportunities for inorganic chemists to explore this unique intersection of fields.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A ruthenium carbolong skeleton with ten carbon atoms","authors":"Jiaomei Guo, Zhengyu Lu, Wenhao Zhou, Qingde Zhuo, Dafa Chen, Haiping Xia","doi":"10.1039/d5qi01141h","DOIUrl":"https://doi.org/10.1039/d5qi01141h","url":null,"abstract":"Carbolong complexes, constituting a fundamental class of metallaaromatics, include metallapentalynes and metallapentalenes. While third-row transition metal-based carbolong skeletons exhibit carbon counts spanning 7-12 and 15, those derived from other metals exhibit carbon numbers limited to a narrower range of 7-9. Here, we report the synthesis of a series of ruthenium 10C-carbolong complexes through a [8C+2C] strategy via alkyne insertion into a ruthenium 8C-carbolong complex. These complexes show broad UV-Vis absorptions, and their aromaticity has been revealed by both experimental data and theoretical calculations. This work achieves the longest carbolong skeleton based on a non-third-row transition metal, expanding the structural diversity of carbolong chemistry.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594709","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Vanadates inhibit non-small cell lung cancer through modulation of ferroptosis mediated by the CBS-CPS1 axis","authors":"Tianxiang Su, Xiaofen Zhang, Yuanyuan Sun, Xing Chen, Meiling Tian, Dan Yan, Yi Zhao, Bingjie Han","doi":"10.1039/d5qi01088h","DOIUrl":"https://doi.org/10.1039/d5qi01088h","url":null,"abstract":"Lung cancer remains the leading cause of cancer mortality, where intrinsic and acquired resistance to cisplatin-based chemotherapy constitutes a major therapeutic challenge in non-small cell lung cancer (NSCLC). Previous studies suggested that vanadium might represent a promising platinum-alternative therapeutic strategy for NSCLC through a unique chemical reaction pattern, though the regulatory networks remain incompletely characterized. Integrated pharmacological screening with cell death pathway inhibitors and transcriptomic profiling revealed that vanadium compounds suppress NSCLC progression by triggering ferroptosis, a process governed by cystathionine β-synthetase (CBS)-mediated regulatory mechanisms. CBS knockdown promoted intracellular Fe<small>²⁺</small> accumulation, elevated lipid ROS levels, and increased MDA content, ultimately leading to the inhibition of cell growth and proliferation both <em>in vitro</em> and <em>in vivo</em>. Conversely, ICP-MS analysis revealed that CBS overexpression substantially decreased cellular iron uptake. The CBS-specific inhibitor AOAA demonstrated potent synergistic effects with vanadates in suppressing NSCLC cell growth. Furthermore, CoIP-MS identified CPS1 as a potential direct interacting protein of CBS. Remarkably, CPS1 complementation in shCBS NSCLC cells attenuated the key indicators of ferroptosis while restoring cell growth and proliferation. Collectively, our study systematically elucidated the underlying mechanisms by which vanadates inhibit NSCLC progression and defined the functional significance of the CBS-CPS1 axis, providing novel therapeutic insights for advancing vanadium-based metallodrugs in clinical oncology.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"32 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}