Inorganic Chemistry Frontiers最新文献

{"title":"Calcium Chloride as an Ionic Response Modulator in Metal Organic Framework-filled Nanopores (MOF@SSNs): Enhancing Ionic Current Saturation and Selectivity","authors":"Angel Luciano Huamani, Gregorio Laucirica, Juan A Allegretto, Maria Eugenia Toimil-Molares, Aline Ribeiro Passos, Agustin Silvio Picco, Marcelo Ceolín, Omar Azzaroni, Waldemar Alejandro Marmisollé, Matias Rafti","doi":"10.1039/d4qi01575d","DOIUrl":"https://doi.org/10.1039/d4qi01575d","url":null,"abstract":"We studied ionic transport properties of UiO-66 metal-organic framework-modified solid-state nanochannels (MOF@SSNs) embedded in polyethylene terephthalate (PET) membranes, focusing on the effect of calcium ions from chloride salt (CaCl2) acting as ionic response modulator. We observed a behavior known as ionic current saturation (ICS) regime in a broad pH range, which can be attributed to specific binding of divalent calcium ions to free-carboxylate moieties present in the MOF-filled nanochannels. Such binding provokes a surface charge increase and causes the ICS regime to dominate the response even in alkaline aqueous environments, which were previously shown to feature simple ohmic regimes. The primary ionic transport mechanism operating involves the presence of (mesoscopic) constructional porosity arising from defects and gaps generated during MOF formation within PET nanochannels, rather than intrinsic MOF microporosity also present. The hereby discussed example illustrates how, through straightforward chemical modification, ionic transport properties of the nanochannels can be modulated to feature specific responses necessary for high-impact applications such as ion selective transport, biosensing, or energy generation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324888","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":"High-Entropy FeCoMnCuNi diselenide Self-Standing Electrode with Outstanding Water-Electrolysis Performance in Alkaline Medium","authors":"Xinxin Guo, Mengmeng Zhou, Ziwu Liu, Shiheng Mu, Kaijia Wang, Huanqiang Shi, Fang Wang, Shijian Lu, Zhong-Hai Ni, Guiqing Liu","doi":"10.1039/d4qi01835d","DOIUrl":"https://doi.org/10.1039/d4qi01835d","url":null,"abstract":"Developing non-noble metal efficient electrocatalysts with high activity and stability is extremely essential for the hydrogen generation by water electrolysis with low cost. Herein, we report a novel binder-free high-entropy self-standing electrode with unique three-dimensional structure and petunia-, needle- and fork-like morphology prepared by the hydrothermal and selenizing methods. Due to high-entropy, lattice distortion and high-curvature tip-enhancement effects, electrochemical tests demonstrated that the prepared FeCoMnCuNiSe2 with an ultralow overpotential of 71.6 mV at 100 mA cm-2 exhibited superior activity for the hydrogen evolution reaction (HER) in 1.0 M KOH solution, far outperforming almost all reported advanced non-noble metal HER catalysts. More impressively, the assembled FeCoMnCuNiSe2||FeCoMnCuNiSe2 overall-water splitting device with more than 45 h continuous operation stability at 10, 20 and 50 mA cm-2 in 1.0 M KOH required a remarkably low cell voltage of 1.30 V at 10 mA cm-2 as well, demonstrating a promising practical application prospect in future water electrolysis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324887","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":"Elucidating the local structure of Li1+xAlxTi2–x(PO4)3 and Li3AlxTi2–x(PO4)3 (x = 0, 0.3) via total scattering","authors":"Matthew Simon Chambers, Jue Liu, Olaf Borkiewicz, Kevin Llopart, Robert Lee Sacci, Gabriel M. Veith","doi":"10.1039/d4qi01545b","DOIUrl":"https://doi.org/10.1039/d4qi01545b","url":null,"abstract":"Li<small><sub>1+x</sub></small>Al<em><small><sub>x</sub></small></em>Ti<small><sub>2–<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> (LATP) and Li<small><sub>3</sub></small>Al<em><small><sub>x</sub></small></em>Ti<small><sub>2–<em>x</em></sub></small>(PO4)3 (<em>x</em> = 0, 0.3) are promising candidates in all-solid-state batteries due to their high room temperature conductivity of 10<small><sup>–3</sup></small> S cm<small><sup>–1</sup></small> and air- and moisture-stability. They also exhibit unusual thermal expansion properties, with Li<small><sub>1+<em>x</em></sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2–<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> showing near-zero thermal expansion along the <em>a</em> axis while Li<small><sub>3</sub></small>Al<em><small><sub>x</sub></small></em>Ti<small><sub>2–<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> exhibits polynomial positive thermal expansion along the <em>a</em> axis and polynomial negative thermal expansion along the <em>c</em> axis. A crucial component to understanding these properties is understanding the local structure. Total scattering is a powerful analytical technique as it provides information on the long-range, average structure as well as the local structure. Here, we report the first X-ray and neutron total scattering experiments performed on Li<small><sub>1+<em>x</em></sub></small>Al<em><small><sub>x</sub></small></em>Ti<small><sub>2–<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> and Li<small><sub>3</sub></small>Al<em><small><sub>x</sub></small></em>Ti<small><sub>2–<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> (<em>x</em> = 0, 0.3). We show that the PO<small><sub>4</sub></small> and TiO<small><sub>6</sub></small> polyhedra experience very little expansion of the P/Ti–O bonds up to 800 °C, nor is there much expansion when the Li content increases significantly. The minor thermal expansion of the nearest-neighbor bonds of the polyhedra is revealed to be the reason behind the unusual thermal expansion properties, causing the near-zero thermal expansion along <em>a</em> in Li<small><sub>1<em>+x</em></sub></small>Al<em><small><sub>x</sub></small></em>Ti<small><sub>2–<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> and moving as whole units in Li<small><sub>3</sub></small>Al<em><small><sub>x</sub></small></em>Ti<small><sub>2–<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small>. The structural robustness of the framework is also the reason for the increased conductivity as Li content increases, as the framework remains undistorted as Li content increases, permitting Li-ion mobility as the number of charge carriers increases. This suggests that phosphate-based framework materials beyond LATP would also be a good material space t","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324908","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":"Rationally reconstructing the surface microstructure of chemical bath deposited electron transport layer for efficient and stable perovskite solar cells","authors":"Xianxuan Yang, Lexin Wang, Meihan Liu, Jiahui Jin, Lili Yang, Lin Fan, Maobin Wei, Huilian Liu, Haoran Chen, Jinghai Yang, Yulei Chang, Fengyou Wang","doi":"10.1039/d4qi01808g","DOIUrl":"https://doi.org/10.1039/d4qi01808g","url":null,"abstract":"In perovskite solar cells (PSCs), chemical bath deposition (CBD) is promising to be the core technique for preparing commercial electron transport layer (ETL) because the film prepared by CBD exhibits excellent uniform and conformal coverage of the substrate. However, metal oxide (MOx) films prepared through CBD often have defects on the surface like oxygen vacancies and hydroxyl that limit the PSCs efficiency and degrade the long-term stability. To address this obstacle to the scaled PSCs application, we here reconstructed the surface microstructure of CBD tin dioxide (SnO2) ETL by post-treatment with dilute H2SO4 solution to terminate the oxygen vacancies from the MOx surface while effectively removing the hydroxyl groups. Concurrently, the potent oxidizing property of H2SO4 facilitates the transformation from Sn (II) to Sn (IV), thereby enhancing the alignment of energy level between SnO2 and perovskite (PVK) layer within the ETL architecture. Moreover, the interaction between SO42- and perovskite precursor mitigates the difference in crystallization velocity between the perovskite upper and buried surfaces, enabling films with homogeneous phase distribution and good crystallization. Ultimately, with the assistance of this facile surface microstructure reconstruction, the power conversion efficiency (PCE) is improved from 22.48% to 24.29%.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324890","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":"Synergistic Fe,Ce doping of Ni3S2 for enhancing oxygen evolution reaction performance","authors":"Yu He, Kefan Shi, Xueqin Wang, Xingzi Zheng, Lanke Luo, Liu Lin, Zemin Sun, Genban Sun","doi":"10.1039/d4qi02187h","DOIUrl":"https://doi.org/10.1039/d4qi02187h","url":null,"abstract":"The development of low-cost, efficient, and stable electrocatalysts is critical for the anodic oxygen evolution reaction (OER). Ni<small>₃</small>S<small>₂</small> not only has the advantages of low cost, easy preparation, and environmental friendliness, but also attracts attention for its structure throughout the Ni–Ni bond, which provides metal-like electrical conductivity. In this work, the Fe and Ce double-doped Ni<small>₃</small>S<small>₂</small> nanoneedle array catalyst (Fe,Ce-Ni<small>₃</small>S<small>₂</small>@NF) was prepared by a one-step hydrothermal method. The synergistic doping of Fe and Ce optimized the microscopic morphology and the electronic structure of Ni<small>₃</small>S<small>₂</small>, which increased the exposure of catalytically active sites, enhanced the electron transfer rate in the OER process, and improved the intrinsic activity of the catalyst. The catalyst has an overpotential of 254 mV at 10 mA cm<small>⁻²</small> and a Tafel slope of 55.56 mV dec<small>⁻¹</small>, and exhibits good electrocatalytic performance under alkaline conditions (1 M KOH). Compared with the original Ni<small>₃</small>S<small>₂</small> (363 mV at 10 mA cm<small>⁻²</small>), the overpotential of Fe,Ce-Ni<small>₃</small>S<small>₂</small>@NF is reduced by 109 mV. This provides a new feasible direction for the preparation of transition metal and lanthanide metal double-doped catalysts and their application in electrocatalysis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142325324","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":"In situ growth of δ-MnO2/C fibers as binder-free and free-standing cathode for advanced aqueous Zn-ions batteries","authors":"Yan Li, Fei Zhang, Miaomiao Wu, Yong Guo, Yuanyuan Liang, Reyihanguli Ababaikeri, Luyang Wang, Qiao Liu, Xingchao Wang","doi":"10.1039/d4qi01661k","DOIUrl":"https://doi.org/10.1039/d4qi01661k","url":null,"abstract":"Manganese dioxide (MnO2) has been extensively studied in aqueous zinc ion batteries (AZIBs) due to its high redox potential, high theoretical capacity and low cost. However, its low capacity and poor structural stability result in poor performance. In this study, we propose a novel approach where δ-MnO2 is grown in situ on carbon fibers derived from coal (δ-MnO2@CCFs). The unform anchoring of δ-MnO2 on the carbon fibers allow for good flexibility and keep structural stability during cycling. The doping of heteroatoms (N) directly forms chemical bonds with δ-MnO2 and reduces electrostatic repulsion within the δ-MnO2@CCFs material, while facilitating the insertion and extraction of Zn2+ and H+ ions. Moreover, the flexible AZIBs exhibit excellent electrochemical reversibility even under bending and folding conditions. The δ-MnO2@CCFs electrode material exhibits a capacity of 352 mAh g-1 at a current density of 0.5 A g-1 after 100 cycles. Furthermore, the assembled flexible Zn//δ-MnO2@CCFs AZIBs maintain a capacity of 293.7 mAh g-1 after 50 cycles at a current density of 0.1 A g-1.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321758","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":"Copper-doped Bi2MoO6 with concurrent oxygen vacancies for enhanced CO2 photoreduction","authors":"Jiawei Liu, Xin Liu, Chunhui Dai, Chao Zeng, Sajjad Ali, Mohamed Bououdina, Yushuai Jia","doi":"10.1039/d4qi02005g","DOIUrl":"https://doi.org/10.1039/d4qi02005g","url":null,"abstract":"Photocatalytic CO2 reduction into highly-valued chemical fuels holds great promises for resolving the energy shortage and mitigating the greenhouse gas. But the current CO2 conversion efficiency is hampered by the undesirable charge transfer and deficient reactive sites of photocatalysts. Herein, we synthesize Bi2MoO6 doped by monovalence Cu with accompanying O vacancies (Ov) to accelerate the bulk and surface charge separation and transfer. Moreover, the Cu dopants serving as the reactive sites improve the adsorption and activation of CO2 molecules on catalyst’s surface. As a result, the Cu-doped Bi2MoO6 catalysts exhibit remarkedly boosted CO2 reduction activity to the pristine Bi2MoO6, and the peak activity reaches at Bi2MoO6-10% Cu with a CO evolution rate of 11.40 μmol g-1 h-1 under 300 W Xenon lamp irradiation, without any cocatalyst or sacrificial agent. This photoactivity surpasses most of the previously reported catalysts, and it is about 6-fold higher than that of Bi2MoO6 (1.94 μmol g-1 h-1). Moreover, even under natural sunlight illumination, the Bi2MoO6-10% Cu also exhibits considerable activity for CO2 photocatalytic conversion to CO. This study may inspire an efficient strategy for designing and developing high performance photocatalysts toward CO2 conversion.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321845","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":"Ferrocene- and ruthenium arene-containing glycomimetics as selective inhibitors of human galectin-1 and -3","authors":"Vojtěch Hamala, Martin Kurfiřt, Lucie Červenková Šťastná, Hedvika Hujerová, Jana Bernášková, Kamil Parkan, Jakub Kaminský, Nina Habanová, Jaroslav Kozák, Alžběta Magdolenová, Martin Zavřel, Tatiana Staroňová, Veronika Ostatná, Lucie Žaloudková, Aleš Daňhel, Jitka Holčáková, Petr Voňka, Roman Hrstka, Jindřich Karban","doi":"10.1039/d4qi01555j","DOIUrl":"https://doi.org/10.1039/d4qi01555j","url":null,"abstract":"Galectins are a family of β-galactoside-binding proteins with an evolutionarily conserved carbohydrate recognition domain. Their dysregulation has been implicated in physiological and pathological processes, including fibrotic disorders, inflammation, and cancer. For example, elevated levels of galectin-1 contribute to tumor cell migration and immune evasion, whereas overexpression of galectin-3 is associated with increased invasiveness and the formation of metastasis. Pharmacological inhibition of these galectins is a promising therapeutic strategy to counteract their oncogenic effects. In this study, we synthesized a novel series of galectin inhibitors with ferrocene and ruthenium arene motifs attached to lactose, <em>N</em>-acetyllactosamine, or thiodigalactoside scaffolds. We determined their binding affinity toward human galectin-1 (<em>h</em>gal-1) and the CRD domain of human galectin-3 (<em>h</em>gal-3-CRD) using fluorescence polarization, intrinsic fluorescence of galectin tryptophan residues, and isothermal titration calorimetry. The ferrocene analogs exhibited superior affinity for both <em>h</em>gal-1 and <em>h</em>gal-3-CRD compared with ruthenium arenes. In particular, a symmetrical diferrocene thiodigalactoside complex exhibited low nanomolar affinity for <em>h</em>gal-1 and selectivity over <em>h</em>gal-3-CRD. Asymmetrical monoferrocene thiodigalactoside complexes exhibited nanomolar affinity and good selectivity for <em>h</em>gal-3-CRD. Chronopotentiometric stripping analysis demonstrated that the inhibitors stabilized <em>h</em>gal-1 against destabilization by electric field effects. <small>¹⁹</small>F{<small>¹</small>H} NMR experiments and molecular dynamics simulations suggested that the incorporation of the ferrocene motif limited the accessible binding modes to <em>h</em>gal-3-CRD whereas binding to <em>h</em>gal-1 remained unrestricted, resulting in attenuated binding affinities to <em>h</em>gal-3-CRD and selectivity for <em>h</em>gal-1. These results open new possibilities for the design and optimization of therapeutic organometallic galectin inhibitors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324906","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":"Design of DyIII single-molecule magnets with molecularly installed luminescent thermometers based on bridging [PtII(CN)2(C^N)]– complexes","authors":"Pawel J. Bonarek, Mikolaj Zychowicz, Jan Rzepiela, Michal Liberka, Sebastian Baś, Jakub J. Zakrzewski, Szymon Chorazy","doi":"10.1039/d4qi02373k","DOIUrl":"https://doi.org/10.1039/d4qi02373k","url":null,"abstract":"Luminescent Single-Molecule Magnets (SMMs) gained broad scientific attention due to potential applications in dual sensing of temperature and magnetic field or optical thermometry for the self-monitoring of temperature in SMM-based devices. We present a route toward thermoresponsive emissive SMMs based on linking two molecular components separately providing luminescent thermometry and SMM features. We combined Dy(III) centers of a rationally constrained coordination sphere giving tunable magnetic anisotropy with an emissive dicyanido(2-phenylpyridinato)platinate(II) anion, [Pt<small>^II</small>(CN)<small>₂</small>(ppy)]<small>^–</small> exhibiting ratiometric optical thermometry. These molecular precursors undergo the self-assembly into {[Dy<small>^III</small>(MeOH)<small>₂</small>(NO<small>₃</small>)]<small>₂</small>[Pt<small>^II</small>(CN)<small>₂</small>(ppy)]<small>₄</small>}∙<em>n</em>(solvent) (<strong>1</strong>) coordination chains of a weak field-induced SMM behavior. However, upon exchange of MeOH molecules, axially aligned within eight-coordinated Dy(III) complexes, by O-donor organic ligands, including 4(1H)-pyridone (<strong>2</strong>), pyridazin-4(1H)-one (<strong>3</strong>), and N-methyl-pyridin-4(1H)-one (<strong>4</strong>), an improvement of SMM character was achieved. This is accompanied by the tuning of optical thermometry related to temperature-variable excitation and emission spectra of Pt(II) complexes which leads to the best-performance multifunctionality in a 4(1H)-pyridone-containing compound. Our work proves that a heterometallic synthetic approach provides a unique class of SMM-based luminescent thermometers where lanthanide-centered magnetism will not be affected by the light employed to monitor the temperature through an optical process occurring in attached cyanido transition metal complexes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321760","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":"Realizing Efficient Broadband Near-Infrared Emission under Blue Light Excitation in Sb3+-Doped Zero-Dimensional Organic Tin(IV)-Based Metal Halides via Coordination Structure Modulation","authors":"Bao Ke, Hui Peng, Yongqi Yang, Chengzhi Yang, Shangfei Yao, Arfan Bukhtiar, Qilin Wei, Jialong Zhao, Bingsuo Zou","doi":"10.1039/d4qi01904k","DOIUrl":"https://doi.org/10.1039/d4qi01904k","url":null,"abstract":"Realizing Sb3+-activated efficient broadband near-infrared (NIR) emission under blue light excitation remains a significant challenge in lead-free metal halides. To overcome the above difficulties, a coordination structure modulation strategy was adopted, and the broadband NIR emission under blue light excitation was achieved in Sb3+-doped zero-dimensional (0D) organic tin(IV) bromide. Compared to the weak visible light emission with a photoluminescence quantum yield (PLQY) of 2.4% for pure (TBP)2SbBr5 (TBP = Tetrabutylphosphonium), Sb3+-doped (TBP)2SnBr6 exhibits efficient broadband NIR emission band at 705 nm with PLQY of 33.2% upon 452 nm excitation, which stems from self-trapped exciton emission. Combined with experiments and theoretical calculations, we find that the large excited-state lattice distortion degree compared to the ground state and the narrow bandgap are dominant reasons for Sb3+-doped (TBP)2SnBr6 shows efficient NIR emission under blue light excitation. More particularly, Sb3+-doped (TBP)2SnBr6 also has excellent anti-water stability, existing stably in water for more than 4 hours while maintaining high luminous efficiency. Based on the excellent stability and unique optical properties of Sb3+-doped (TBP)2SnBr6, a high-performance NIR light-emitting diode (LED) was fabricated by combining a commercial blue LED chip, and its application in night vision was demonstrated.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321844","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}