Inorganic Chemistry Frontiers最新文献

{"title":"Kernel-Differentiated Fusion Strategy Redefines Critical Size Thresholds in Giant Twinned-FCC RS-AuNCs: Unlocking Size Adaptability and Birth of Metallicity","authors":"Youqiong Fang, Pu Wang, Yong Pei, lin xiong","doi":"10.1039/d5qi00976f","DOIUrl":"https://doi.org/10.1039/d5qi00976f","url":null,"abstract":"Thiolate-protected gold nanoclusters (RS-AuNCs) have emerged as an ideal research system for unveiling intrinsic structure-property correlations due to their atomically precise structural tunability. This study addresses the structural absence and configuration stability controversies of face-centered cubic (FCC)-configured RS-AuNCs in the large-size regime of 102-191 gold atoms by establishing an innovative theoretical analysis framework. Through density functional theory (DFT) calculations, we successfully predicted for the first time a twinned-FCC Au127(SR)48 structure with C2 symmetry (Au127-x), which exhibits a remarkably small energy difference of merely 0.03 eV compared to the lowest-energy Dh configuration (Au127-w). This discovery strongly confirms the thermodynamic feasibility of FCC configurations in the 102-144 atom range. By integrating the ‘kernel-differentiated fusion’ growth mechanism with the ‘divide-and-protected’ assembly strategy, we systematically constructed three large-sized FCC cluster models: Au164(SR)60, Au182(SR)66 and Au188(SR)66. The calculated average formation energies (Eave) validate the exceptional structural stability of these clusters. Strikingly divergent evolution patterns in HOMO-LUMO gaps are observed between shell-structured and cubic FCC-type RS-AuNCs across varying sizes, unambiguously demonstrating configuration-governed electronic structure modulation. More crucially, UV-Vis absorption spectra unveil emergent metallic signatures in both Au182(SR)66 and Au188(SR)66 clusters, thereby fundamentally redefining the critical size threshold for incipient metallicity in FCC-type RS-AuNCs. Breaking through traditional theoretical frameworks centered on ‘size-configuration preference’, this research first elucidates the potential stability of FCC-configured RS-AuNCs within controversial size ranges. It not only addresses the existing size gap in structural models of large RS-AuNCs but also establishes a novel configuration design paradigm based on a ‘kernel-differentiated fusion’ strategy.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"43 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144237838","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":"Enhanced Symmetric Lithium-Ion Batteries: Utilizing Polyhedron Structures Constructed from Ultrafine Li2FeSiO4/C Nanoparticles as Dual-Function Cathode and Anode","authors":"Xueting Wang, Yakun Tang, Wenjie Ma, Yue Zhang, Sen Dong, Yushen Zhou, Chun-Mei Ma, Lang Liu","doi":"10.1039/d5qi01021g","DOIUrl":"https://doi.org/10.1039/d5qi01021g","url":null,"abstract":"Li2FeSiO4 is a promising cathode material for lithium-ion batteries, due to its high capacity, low cost, and superior stability. However, its low conductivity and slow Li⁺ diffusion hinder further development. In this work, polyhedron structures constructed from ultrafine Li2FeSiO4/C nanoparticles (2-10 nm) were successfully synthesized via an in situ confined chelation strategy. Citric acid served as both a carbon source, forming a conductive carbon layer on Li2FeSiO4, and a chelating agent, confining Fe3⁺ within the tetraethyl orthosilicate network. This approach enabled the formation of ultrafine Li2FeSiO4 with enhanced Li⁺ and electron transport pathways. Additionally, the polyhedron structure also exposed more active facets for Li+ diffusion, leveraging reversible Fe0/Fe2+, Fe2+/Fe3+ and Fe3+/Fe4+ redox reactions. The optimized sample showed high capacity (178.7 mAh g-1 at 0.03 A g-1 and 660.9 mAh g-1 at 0.4 A g-1) and superior cycling stability (126.9 mAh g1 at 0.1 A g-1 and 678.1 mAh g-1 at 0.5 A g-1 after 200 cycles). The Li2FeSiO4//Li2FeSiO4 symmetric full battery achieved a reversible capacity of 141.1 mAh g-1 at 0.03 A g-1 with an excellent cycling stability. Electrode kinetics and phase transitions were further analyzed using In-situ EIS. This work presents a simple and efficient method for synthesizing ultrafine nanocrystals and opens new possibilities for symmetric lithium-ion batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144237626","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":"Hydroxyl Deficiency-Induced Mixed Linkages in Covalent Pyrimidine Frameworks towards Enhancing Stability During H2O2 Photosynthesis","authors":"Yongxia Li, Jingyang Zhang, Xingyu Zhang, Wenbo Li, Aiguo Kong","doi":"10.1039/d5qi00919g","DOIUrl":"https://doi.org/10.1039/d5qi00919g","url":null,"abstract":"Covalent organic frameworks (COFs) showed great potential as visible-light-responsive photocatalysts for artificial photosynthesis of hydrogen peroxide (H2O2), but susceptible to self-degradation caused by photoinduced holes. Herein a novel mixed-linkage strategy was developed to improve the stability of COFs during photocatalysis. To incorporate a single hydroxyl deficiency in building unit resulted in a mixed imine and β-ketene amine linkage (50 % each) within pyrimidine-based COFs (COF-BD). This modification endowed it with enhanced robustness and improved efficiency in H2O2 photosynthesis. Specifically, the photocatalytic production rate of H2O2 reached 5,312 µmol gcat.-1 h-1 in pure water within one hour, accompanied by the enhancing stability. In comparison, pure β-keteneamine-linked COFs (COF-TP) initially showed a high H2O2 production rate of 14,480 µmol gcat.-1 h-1 within the first 10 minutes, but rapidly decreased to 6,104 µmol gcat.-1 h-1 after one hour. The enhanced durability of COF-BD is attributed to its optimized electron distribution, which lowers the valence band maximum (VBM) from 1.88 V vs. reversible hydrogen electrode (RHE) in COF-TP to 1.62 V vs. RHE in COF-BD. This shift changes the dominant H2O2 photosynthetic pathway from 2e⁻ oxygen reduction reaction (ORR)/2e⁻ water oxidation reaction (WOR) on COF-TP to 2e⁻ ORR/4e⁻ WOR on COF-BD. Theoretical calculations suggest that the mixed linkages promote the rapid consumption of photoinduced holes, thereby enhancing the performance of COF-BD in H2O2 photosynthesis. These results not only highlight an effective mixed-linkage strategy for boosting the robustness of organic photocatalysts, but also underscore the importance of fine-tuning hydroxyl deficiencies to modulate the electronic properties of materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"20 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144228959","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":"Sodium-Ion Battery Cathode Materials: Towards an improved energy-based descriptor for investigating material stability against moisture","authors":"Rahul Kumar, Abhijit Chatterjee","doi":"10.1039/d5qi00892a","DOIUrl":"https://doi.org/10.1039/d5qi00892a","url":null,"abstract":"The poor stability of transition metal (TM) layered oxide cathode materials upon exposure to moisture poses a significant challenge, hindering their widespread practical use in sodium-ion batteries. To facilitate the selection of suitable dopants for enhancing air-stability, we propose energy-based descriptors to assess the material stability and the water-material interactions. These descriptors are assessed through density functional theory (DFT) calculations, focusing on the onset of water insertion in NaTmxNi1-xO2 (Tm= Ti, Mn) cathode materials. The importance of energy-based descriptors is highlighted by examples discussed where despite having large sodium layer disruption and expansion of the surface layers due to water insertion, the formation of hydrogen bond and charge transfer between water and the oxide layers greatly stabilizes the NaTmxNi1-xO2 structure, thus promoting water insertion. The energy descriptors are used in a materials screening protocol to predict the water stability trends in sodium-ion battery materials and to understand the effect of dopants in mitigating the air-stability issue.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"52 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219354","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":"Controlling Intramolecular Electronic Communication through the Conformation Changes via Stepwise Oxidations in Dicopper(II) and Dinickel(II) Porphyrin Dimers","authors":"Syed Jehanger Shah, Rupesh Kumar Tiwari, Niva Ghosh, Eugenio Garribba, Masatoshi Ishida, Gopalan Rajaraman, Hiroyuki Furuta, Sankar Prasad Rath","doi":"10.1039/d5qi01135c","DOIUrl":"https://doi.org/10.1039/d5qi01135c","url":null,"abstract":"Herein, we report a shape-dependent intramolecular electronic communication in neutral and oxidized complexes of dinickel(II) and dicopper(II) porphyrin dimers. Upon careful manipulation of the reaction conditions, nano-size molecules having different shapes, namely ‘linear’, ‘cofacially sloping’, and ‘clamshell bucket’, were synthesized by varying the concentration of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Detailed structural, spectroscopic viz. UV-vis-NIR, NMR, EPR, ESI-MS, VT magnetic study, and extensive computational investigation have been exploited to investigate long-range electronic communication. The varying shapes and extent of conjugation of the porphyrin dimers are responsible for several prominent attributes, including colours, polarity, π-conjugation, intensity of NIR absorption bands and narrow HOMO−LUMO gaps, etc. Notably, the addition of carbonyl moieties at the methine bridge in ‘clamshell bucket’ facilitates stronger electronic communication through it followed by the ‘linear’ and ‘cofacially sloping’ complexes. Upon stepwise oxidations, highly stable mono-cation radical and di-cation di-radicals were isolated that exhibited long-range charge/radical delocalization via the bridge to produce strong NIR bands. The spin-density plots for the neutral, 1e–, and 2e– oxidised complexes demonstrate the crucial role of metal ions, the bridge, and their shapes in long-range electronic communication. -Conjugation between two macrocycles in the 2e–-oxidized complexes is better in the linear ‘butterfly-like’ molecule, followed by curved ‘cofacially sloping’ and carbonyl-inserted 'clamshell bucket’, while nickel(II) dominates over copper(II) motifs. Notably, the distinct signatures of the triplet state in the EPR spectra were observed due to the magnetic interaction between the two Cu(II) centres in the 2e–-oxidized complexes. The carbonyl group acts as a good π-mediator in the oxidized complex for through-space intramolecular communication between the two rings.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"42 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144228960","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":"Application of Isomorphic Anion Incorporation to Enhance Electrochemical Performance in Vanadium-Based NASICON Cathode Materials","authors":"Kang Tang, Xiang Yao, Yanjun Cai, Hualing Tian, Yanhui Zhang, Yingbo Wang, He Ren, Mofan Zhu, Juan Ding, Zhi Su","doi":"10.1039/d5qi00906e","DOIUrl":"https://doi.org/10.1039/d5qi00906e","url":null,"abstract":"Polyanionic fluorophosphate NaVPO4F is an ideal cathode material for high power sodium-ion batteries due to its high theoretical specific capacity and operating voltage. However, its practical application has been hindered by low electronic conductivity and limited ionic mobility. To address this issue, this study successfully prepared SiO44- incorporating NaV(PO4)1-x(SiO4)xF cathode material. Research findings indicate that the incorporation of SiO44- not only markedly reduces the material's diffusion activation energy but also enhances the kinetics of sodium-ion transport. Consequently, the modified NaV(PO4)0.9(SiO4)0.1F (NVPF-SiO10) cathode material exhibits a several orders of magnitude improvement in sodium-ion diffusion rate, leading to superior rate performance (achieving a specific capacity of 89.3 mAh g-1 at 30 C) and exceptional cycling stability (retaining 75.3% capacity after 2000 cycles at 10 C). Furthermore, when integrated into full battery with hard carbon, the battery exhibits exceptional reliability and stability for high-performance applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219352","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":"M@C2(10612)-C72 (M = Ce, Gd): Synthesis and Characterization of Open-Shell Paramagnetic Mono-metallofullerenes","authors":"Rongrong Luo, Yunpeng Xia, Yang-Rong Yao, Ning Chen","doi":"10.1039/d5qi00923e","DOIUrl":"https://doi.org/10.1039/d5qi00923e","url":null,"abstract":"Paramagnetic metallofullerenes are critical as exceptionally promising spin materials, yet their characteristic open-shell electronic configurations made them challenging to stabilize and isolate. Herein, we report the successful synthesis and isolation of two paramagnetic mono-metallofullerenes, M@C2(10612)-C72 (M = Gd, Ce), which possess open-shell electronic configuration but are stably isolable in their pristine form. The crystallographic analysis reveals that Ce@C2(10612)-C72 is isolable in its pristine form without exohedral stabilizing functionalization and bears a non-IPR carbon cage featuring a pair of adjacent pentagons. The spectroscopic characterizations on M@C2(10612)-C72 support a three-electron transfer from the encapsulated metal, endowing the fullerene compounds with a paramagnetic property. This work updates our understanding of the open-shell paramagnetic mono-metallofullerenes, demonstrating that paramagnetic small-caged mono-EMFs can also exist stably without external stabilizing groups and providing a new paradigm for the development of metallofullerene-based spin materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"17 1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219355","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":"Peptide-mediated Al(III) (oxy)(hydr)oxide formation: The specific stages of phase separation for additive interactions matter","authors":"Miodrag J. Lukić, Nele Marquardt, Tim Schmalz, Denis Gebauer","doi":"10.1039/d5qi00870k","DOIUrl":"https://doi.org/10.1039/d5qi00870k","url":null,"abstract":"We demonstrate how Al(III) interactions with a ‘biomimetic’ model homo-peptide, polyaspartic (pAsp), with a narrow size distribution (around 20 amino acids monomer units), can lead to substantially different outcomes by governing Al(III) hydrolysis/phase separation. The addition of unhydrolysed Al(III) in aqueous peptide solutions results in dominant pAsp20 destabilisation and precipitation from the solution, failing to induce effective Al(III)(oxy)(hydr)oxide formation. Allowing the peptide-free, highly energetic Al(III) system to reach specific hydrolysis/phase separation stages, i.e., just before and slightly after liquid-liquid phase separation, partly dissipating its chemical energy, followed by controlled peptide addition, leads to the formation of respective Al(III)(oxy)(hydr)oxide-peptide hybrids with smaller particles, higher Al(III) content, and well-preserved chemical properties of the peptide. This constitutes a hydrolysis “spin-off” strategy that exploits Al(III)-peptide interactions in distinct hydrolytic precursors, an approach transferable to multiple metals and polymeric systems. The reaction energetics determined by revisited isothermal titration calorimetry assays reflect an Al(III) hydrolysis “footprint” and its role in metal-peptide interactions. These insights are important for various applications of aluminium species, from vaccine adjuvants and related toxicity to enhancements of corrosion resistance.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144211162","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":"Hexafluoroantimonate intercalated NiFe layered double hydroxide enables stable alkaline seawater oxidation at ampere-level current densities","authors":"Qiuying Dai, Zhengwei Cai, Chaoxin Yang, Zixiao Li, Shengjun Sun, Yue Meng, Xiaolan Tang, Xun He, Yujie Yuan, hong tang, Yongchao Yao, Dongdong Zheng, Yongsong Luo, Mohamed S. Hamdy, Fatma A. Ibrahim, Tingshuai Li, Xuping Sun, Bo Tang","doi":"10.1039/d4qi02892a","DOIUrl":"https://doi.org/10.1039/d4qi02892a","url":null,"abstract":"Renewable electricity-driven seawater electrolysis for hydrogen production offers substantial potential for sustainable energy solutions. However, the high concentration of chloride ions (Cl−) in seawater triggers competitive chemical reactions and severe corrosion, posing a challenge to the durability of the anode. In this study, we present a hexafluoroantimonate-intercalated NiFe layered double hydroxide nanosheet array on Ni foam (SbF6−-NiFe LDH/NF), which serves as a highly active and stable electrocatalyst for alkaline seawater oxidation (ASO). SbF6−-NiFe LDH/NF requires only an overpotential of 379 mV to achieve a current density of 1000 mA cm−2, significantly outperforming NiFe LDH/NF (396 mV). Furthermore, it exhibited excellent long-term stability over 600 hours at 1000 mA cm−2, with only trace amounts of active chlorine detected during the ASO process. In situ Raman spectroscopy confirms that the insertion of SbF6− into the LDH layers promotes the formation of active sites. More importantly, SbF6− efficiently repels Cl−, thus providing robust protection to the anode. This development represents a significant advancement in the design of noble-metal-free, durable anode electrodes for ASO.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144211161","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":"Iridium complex-based ferroptosis inducer for cancer sonodynamic therapy","authors":"Guihong Ren, Qingxuan Meng, Panpan Li, Chenyi Wang, Chenglong Wu, Senqiang Zhu, Yuhao Li, Rui Liu, Chenjie Zhu, Hongjun Zhu","doi":"10.1039/d5qi00746a","DOIUrl":"https://doi.org/10.1039/d5qi00746a","url":null,"abstract":"Sonodynamic therapy (SDT) offers distinct advantages for deep tumor ablation due to its excellent tissue penetration ability and demonstrates significant preclinical and clinical potential. However, its therapeutic effectiveness is frequently limited by the sonosensitizer's restricted ability to produce reactive oxygen species (ROS). In this study, we designed an iridium(III) complex to evaluate its potential as an SDT anticancer agent. Ir-1 has a relatively long triplet excited state lifetime of 2.57 μs. This sonosensitizer demonstrated efficient ROS generation under ultrasound (US) irradiation, with a rate constant for DPBF oxidation of 0.04081 min-1, which is higher than that of Ru(bpy)3Cl2. It exhibits high sonocytotoxicity and effectively inhibits tumor growth in 4T1 cells. Additionally, it demonstrated favorable biocompatibility. This work provides valuable insights into the design of first-row transition metal complexes for SDT applications and enhances our understanding of the regulatory mechanisms of iridium complexes as sonosensitizers.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144201688","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}