Inorganic Chemistry Frontiers最新文献

{"title":"Efficient inverse CO2/C2H2 separation driven by rare thermodynamic affinities difference in a porous MOF","authors":"Hai-Yu Duan, Xiu-Yuan Li, Lei Hou, Si-Ru Liu, Xiangyu Liu, Ping Wang","doi":"10.1039/d4qi02531h","DOIUrl":"https://doi.org/10.1039/d4qi02531h","url":null,"abstract":"Separating C2H2 from CO2 is crucial in the industry of petrochemicals but extremely difficult, owing to their very close molecular sizes and similar physical characteristics. Herein, a new porous MOF with 1D rhombus channels featuring plentiful open metal sites was built. The activated framework presents a high CO2 uptake of 83.1 cm3 cm-3 at 298 K under 100 kPa and uncomon inverse selectivity for the CO2/C2H2 mixtures. What’s more, the MOF can directly yield high-purity C2H2 (≥ 99.9 %) from CO2/C2H2 mixtures (v/v = 50/50 and 10/90) under ambient conditions through single breakthrough separation process, which significantly increased the separation efficience and reduced energy consumption. The GCMC simulations revealed that highly efficient inverse CO2/C2H2 separation performance arose from the higher thermodynamic affinities for CO2 than C2H2.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756161","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":"Unravelling the formation pathway and energetic landscape of lanthanide cages based on bis-β-diketonato ligands","authors":"Maria Rando, Alice Carlotto, Silvia Carlotto, Roberta Seraglia, Marzio Rancan, Lidia Armelao","doi":"10.1039/d4qi02530j","DOIUrl":"https://doi.org/10.1039/d4qi02530j","url":null,"abstract":"A systematic investigation was conducted to unravel the formation process of lanthanide cages based on bis-β-diketonato ligands. By employing the diamagnetic La<small>³⁺</small> ion, NMR spectroscopy coupled to ESI-MS analyses revealed the consecutive and competitive formation of four different species: [La<small>₂</small>L]<small>⁴⁺</small>, [La<small>₂</small>L<small>₂</small>]<small>²⁺</small>, [La<small>₂</small>L<small>₃</small>], [La<small>₂</small>L<small>₄</small>]<small>^2-</small>. Stepwise and overall stability constants were derived. Further insights on the energetics of the equilibrium between the two most stable species the triple-stranded [La<small>₂</small>L<small>₃</small>] and the quadruple-stranded [La<small>₂</small>L<small>₄</small>]<small>^2-</small> cage have been conducted through variable temperature analyses, indicating that the interconversion is exergonic, endothermic and mainly entropy driven. DFT thermochemical calculations including also the explicit coordinated solvent allowed to better evaluate the role of the enthalpic and entropic factors on the step-by-step ligand association. This study focuses on the self-assembly mechanisms of triple- and quadruple-stranded lanthanide cages and on their solution behaviour, particularly concerning equilibrium and cage interconversion.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"195 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142742568","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 review on framework (MOF/COF/POP)-based materials for efficient conversion of CO2 to bio-active oxazolidinones","authors":"Pooja Rani, Rajesh Das, C. M. Nagaraja","doi":"10.1039/d4qi02101k","DOIUrl":"https://doi.org/10.1039/d4qi02101k","url":null,"abstract":"Excessive reliance on fossil fuels has increased atmospheric CO2 emissions, resulting in the greenhouse effect that endangers global climate stability and human well-being. Consequently, the storage and chemical conversion of CO2 into sustainable products can play a vital role in reducing anthropogenic emissions. Hence, there is an upsurge in research on selective carbon capture, sequestration and utilization (CCSU) to mitigate the rising atmospheric CO2 concentration. The carbon capture and utilization (CCU), in particular, has attracted considerable interest because it enables the utilization of CO2 as a C1 feedstock for generating commodity chemicals and fuels such as cyclic or polycarbonates, cyclic carbamates, oxazolidinones, formamides, methane, methanol and so on. Out of these, oxazolidinones are essential five-membered heterocyclic compounds found in several important pharmaceuticals. Oxazolidinones also function as versatile intermediates and chiral agents in organic synthesis. Thus, developing highly efficient heterogeneous catalysts containing dense basic and catalytic sites is potentially significant for effectively capturing and transforming CO2 into 2-oxazolidinones under ambient conditions. In this regard, porous framework-based materials viz metal-organic frameworks (MOFs), covalent organic frameworks (COFs) and porous organic polymers (POPs) are excellent candidates owing to their fascinating attributes, like ample active sites, intrinsic porosity and accessible functionalities. These framework-based materials have been exploited as recyclable catalysts in efficient cyclization of CO2 with aziridines, propargylic amines and alcohols coupled with amines/epoxides to produce oxazolidinones. The present review provides a detailed analysis of recent advancements in developing porous framework-based recyclable catalysts for environmentally friendly conversion of CO2 to oxazolidinones. Furthermore, future considerations and challenges for fabricating efficient framework-based catalysts in transforming CO2 into value-added oxazolidinones are also discussed.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"259 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142753411","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 cobalt(II)-nitronyl nitroxide single chain magnet with record blocking temperature and low coercivity.","authors":"Thomaz de Andrade de Andrade Costa, Mihai Răducă, Julio Cesar da Rocha, Miguel Alexandre Novak, Rafael A. A. Cassaro, Marius Andruh, Maria G. F. Vaz","doi":"10.1039/d4qi02703e","DOIUrl":"https://doi.org/10.1039/d4qi02703e","url":null,"abstract":"Two one-dimensional coordination polymers were synthesized: [M(hfac)2(9-PhentNIT)]n, where MII= Mn (1) or Co (2), hfac- is hexafluoroacetylacetonato and 9-PhentNIT is a new stable nitronyl nitroxide organic radical 2-(9-Phenantrenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (9-PhentNIT). These two complexes are isomorphous and crystallized with the metal ions coordinated by two aminoxyl groups, arising from two bridging 9-PhentNIT radical and two hfac- chelating ligands. The asymmetric unit has two independent metal(II) sites, resulting in two crystallographically independent chains. The investigation of the magnetic properties shows that both compounds are ferrimagnetic chains with strong antiferromagnetic coupling between S = 5/2 or 3/2 and 1/2 spin carriers. The anisotropic compound 2 shows the highest blocking temperature TB = 15.5 K reported so far for a Single Chain Magnet (SCM) and exhibits magnetic hysteresis with low coercivity up to 22 K. In addition, we found evidence of magnetic irreversibility and relaxation of a small portion of long chains up to about 50 K.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"83 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142735835","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":"Bimetallic ZnSe-SnSe2 heterostructure functionalized separator for high-rate Li-S battery","authors":"Jiayi Xue, Daotong Yang, Jianhua Lin, Quan Zhuang, Minxun Jia, Tong Wu, Lei Ji, Yingying Zhang, Zhiqiang Niu, Jinghai Liu","doi":"10.1039/d4qi02476a","DOIUrl":"https://doi.org/10.1039/d4qi02476a","url":null,"abstract":"The commercialization of lithium-sulfur (Li-S) batteries is significantly hampered by challenges such as rapid capacity degradation and short cycle life. The key to addressing these issues lies in suppressing the shuttle effect as well as inhibiting the growth of dendrites. In this work, we rationally designed a composite with heterostructured ZnSe-SnSe2 grown in situ on graphene-like oxidized carbon nitride (OCN) as a sulfur species immobilizer and a guiding agent for the uniform deposition of lithium ions in Li-S batteries. Benefitting from these, ZnSe-SnSe2, which has both thiophilic and lithophilic, enhances the ability of OCN to inhibit diffusion and catalyze the conversion of polysulfides, as thoroughly demonstrated from experimental to theoretical calculations. When ZnSe-SnSe2@OCN was coated onto the separator to be prepared as a functionalized separator, it demonstrated desirable electrochemical properties, including an initial discharge specific capacity of 1265 mAh g-1 (0.1C), a high-rate performance of 609 mAh g-1 at 5C, and a favorable cycling stability with 1C for 350 cycles with a decay rate of 0.11%. This work provides a viable solution for the design and preparation of functionalized separators for high-rate Li-S batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"20 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142735837","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":"Ionothermal Synthesis of a Stable Three-Dimensional [Cu4I4] Cluster Scintillator with Near-Unity Quantum Efficiency and Weak Thermal Quenching","authors":"Qing-Hua Zou, Wen Hao Yang, Ling-Kun Wu, Lu-Lu Jiang, Shuaihua Wang, Lang Liu, Renfu Li, Heng-Yun Ye, Jian-Rong Li","doi":"10.1039/d4qi02590c","DOIUrl":"https://doi.org/10.1039/d4qi02590c","url":null,"abstract":"A facile and environmentally friendly ionothermal synthesis was employed to prepare a highly luminescent hybrid scintillator, Cu4I4(C6H14N2)2 (1, (C6H14N2)2 = 1,4-dimethylpiperazine). 1 features a 3-D structure of (Cu4I4) cubane cluster connected by 1,4-dimethylpiperazine. The optical properties of 1 under UV light and X-ray excitation were investigated. The results revealed that its excellent electronic transport properties enable a near-100% quantum yield. Moreover, its luminescent intensity at 110°C can still maintain 90% of its room temperature value. After being placed in air for 100 days, the luminescent intensity retains 88.34% of its initial one. The compound demonstrates a strong X-ray response, achieving an effective photon yield of 48538 photons/MeV and a detection limit of 30.68 nGy/s, far below the medical diagnostic dose of 5.5 μGy/s. The successful development of this compound provides inspiration for green, non-toxic, and efficient detection applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142735833","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":"Microwave-assisted fabrication of self-supported graphene-based high-entropy alloy electrode for efficient and stable electrocatalytic nitrate reduction to ammonia","authors":"Yun Ling, Qingyun Feng, Xuan Zheng, Hui Su, Yuanyuan Zhang, Zehua Zou, Aifen Liu, Yang Huang, Jing Tang, Yi Li, Maosheng Zhang, Qingxiang Wang","doi":"10.1039/d4qi02881c","DOIUrl":"https://doi.org/10.1039/d4qi02881c","url":null,"abstract":"Direct electrochemical nitrate reduction for ammonia (NRA) synthesis is an efficient and environmentally friendly production technology. However, the development of highly selective electrocatalysts is still a challenge due to its nine-proton and eight-electron reaction. High-entropy alloys (HEAs) have a wide range of elements and adjustable properties, giving them excellent application potential in multi-step reactions. In this work, we skillfully use the local high temperature and excellent thermal conductivity generated at the reduced graphene oxide (rGO) defect in the microwave process to achieve a rapid quenching process in 10 seconds. This approach overcomes element immiscibility and results in a self-supported, single-phase, non-precious metal and uniform FeCoNiCuSn alloy electrode. The HEA reaches a remarkable NH3 yield of 883.7±11.2 μg h<small>^-1</small> cm<small>^-2</small>, the maximum Faradaic efficiency (FE) of 94.5±1.4%, and the highest NH3 selectivity of 90.4±2.7%. Experimental and theoretical calculations reveal that the presence of multiple adjacent elements in HEA triggers a synergistic catalytic effect, while the excellent mass and charge transfer properties of rGO jointly encourage the performance of electrochemical NRA. In particular, NO<small>₃</small><small>⁻</small> favors vertical adsorption at Fe-Fe sites, and the desorption of NH3 is identified as the rate-determining step (RDS) with a extremely small ΔG of 0.7eV.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"58 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142735836","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":"MOF nanozymes: Active sites and sensing applications","authors":"Ziyan Zhang, Yujie Li, Zhishuang Yuan, Lingxia Wu, Jiping Ma, Weiqiang Tan, Yingjie Sun, Guangyao Zhang, Huining Chai","doi":"10.1039/d4qi02555e","DOIUrl":"https://doi.org/10.1039/d4qi02555e","url":null,"abstract":"Metal-organic frameworks (MOFs) are porous organic-inorganic coordination materials with numerous active sites, enabling them to mimic the properties of natural enzymes and making them highly promising for sensing applications. This review provides a detailed overview of recent advancements in leveraging MOFs for the design of catalytic active sites in nanozymes. MOFs utilize metal ions and organic ligands as active centers for biomimetic catalysis, while their porous frameworks efficiently bind and stabilize multiple guest active units. Furthermore, MOFs can undergo chemical transformations to produce derivatives such as porous carbon materials and nanostructured metal compounds, enhancing their catalytic performance and broadening their applications as nanozymes. This review also explores the progress of MOF-based nanozymes across various catalytic modes in analytical sensing, highlighting their ability to significantly improve detection sensitivity, selectivity, and range. Additionally, the critical role of diverse active sites in sensing processes is emphasized, with attention to the design and synthesis strategies required to optimize the performance of MOF nanozymes. Finally, the review discusses future prospects for the development of MOF nanozymes and outlines key challenges that must be addressed to advance this field.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"25 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142718987","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":"Correction: Amorphous heterojunction and fluoride-induced effects enable a F-Ni(OH)2/Ni–B electrocatalyst for efficient and stable alkaline freshwater/seawater hydrogen evolution at a high current density","authors":"Shenyi Chen, Haoming Chu, Ziyin Xie, Lihui Dong, Bin Li, Minguang Fan, Huibing He and Zhengjun Chen","doi":"10.1039/D4QI90087A","DOIUrl":"10.1039/D4QI90087A","url":null,"abstract":"<p >Correction for ‘Amorphous heterojunction and fluoride-induced effects enable a F-Ni(OH)<small>₂</small>/Ni–B electrocatalyst for efficient and stable alkaline freshwater/seawater hydrogen evolution at a high current density’ by Shenyi Chen <em>et al.</em>, <em>Inorg. Chem. Front.</em>, 2024, <strong>11</strong>, 8212–8222, https://doi.org/10.1039/D4QI01853B.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 1","pages":" 379-379"},"PeriodicalIF":6.1,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/qi/d4qi90087a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142718975","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pivotal role of solid phase interactions for the pressure-induced bi-stability of cyanide-bridged Fe2Co2 square complexes","authors":"Buqin Xu, Yanling Li, Geoffrey Gontard, Keevin Béneut, Paraskevas Parisiades, Maxime Deutsch, Rodrigue Lescouezec","doi":"10.1039/d4qi02499k","DOIUrl":"https://doi.org/10.1039/d4qi02499k","url":null,"abstract":"Cyanide-bridged FeCo coordination clusters, recognized as exceptional candidates for molecular switches, have been the subject of extensive research efforts aimed at unraveling the key factors governing the charge transfer process. Previously, we have observed that the square complex {[Fe(Tp)(CN)3]2[Co(vbik)2]2}2+ with Tp = tris(pyrazolyl)borate and vbik = bis(1-vinyl-2-imidazolyl)ketone, abbreviated as {Fe2Co2}, undergoes thermal charge transfer in MeOH solution near room temperature allowing the obtention of a solvatomorph pair exhibiting distinct electronic configurations at 300 K: {FeIII2CoII2}·2BF4·2MeOH (1) and {FeII2CoIII2}·2BF4·10H2O·2MeOH (2). While 2 keeps charge transfer ability in solid state, 1 is trapped in the paramagnetic state by solid phase interactions down to 2 K, which make it a good candidate for investigating electron transfer under hydrostatic pressure, an external stimulus scarcely used for these systems. In the present work, we demonstrated that the synthesis method can be used to obtain new solvatomorph with remarkable pressure-induced electron transfer. The paramagnetic {{FeIII2CoII2}·2(PF6)·2MeOH (3) and the diamagnetic {[FeII2CoIII2}·2(PF6)·nH2O·mMeOH (4), isostructural to 1 and 2 respectively, were obtained. The stronger intermolecular interactions due to the PF6 anion leads to a greater distortion of the core structures of 3 and 4, affecting their magnetic properties under ambient and hydrostatic pressure. Notably, 3 exhibits a partial pressure-induced conversion from a paramagnetic to a diamagnetic state followed by a back conversion above a pressure threshold value, which is rationalized by a symmetry-breaking phase transition at ca 0.96-1.0 GPa. This unusual behavior has been analyzed using magnetometry, X-ray diffraction, and μ-Raman spectroscopy under various pressures. A deeper understanding of the electron transfer process in 3 was achieved by analyzing its structural data under various pressures and comparing them to that of 1. The distinct electron transfer behaviors observed in the two complexes are likely correlated to the differing distortions in their square core structures induced by pressure.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142719036","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}