Yanjing Qin, Jianwu Wei, Jing Li, Xianli Li, Binbin Luo, Peican Chen, Liya Zhou, Jin Zhong Zhang, Qi Pang
Employing chiral (R/S)-4-chloro/bromo-α-methylbenzylamine (R/S-X-MBA, X = Cl, Br) as ligands, we prepare two zero-dimensional hybrid copper(I) iodide clusters, (R/S-Cl-MBA)4Cu4I4 (R/S-Cl) and (R/S-Br-MBA)4Cu4I4 (R/S-Br), via a simple room-temperature solvent-diffusion method. Both R/S-Cl and R/S-Br are in the C2 chiral space group with a monoclinic crystal system. Under 310 nm excitation, R/S-Cl and R/S-Br exhibit efficient orange and yellow broadband luminescence, featuring large Stokes shifts, microsecond lifetimes, and symmetric chiral CD signals. Interestingly, compared to R/S-Cl with a photoluminescence (PL) quantum yield (QY) of ∼46%, a near-unity PLQY is observed for R/S-Br, along with a longer PL lifetime (∼13.5 μs). The high PLQY is attributed to intermolecular halogen–halogen interactions, which greatly enhance lattice rigidity and suppress nonradiative recombination of triplet excitons. Furthermore, R/S-Br has been demonstrated for X-ray scintillator application. This work offers an effective strategy for designing multifunctional and efficient chiral phosphors.
{"title":"Near-unity room-temperature phosphorescence quantum yield induced by halogen–halogen interaction in chiral hybrid copper(I) iodide clusters","authors":"Yanjing Qin, Jianwu Wei, Jing Li, Xianli Li, Binbin Luo, Peican Chen, Liya Zhou, Jin Zhong Zhang, Qi Pang","doi":"10.1039/d5qi00348b","DOIUrl":"https://doi.org/10.1039/d5qi00348b","url":null,"abstract":"Employing chiral (<em>R</em>/<em>S</em>)-4-chloro/bromo-α-methylbenzylamine (<em>R</em>/<em>S</em>-X-MBA, X = Cl, Br) as ligands, we prepare two zero-dimensional hybrid copper(<small>I</small>) iodide clusters, (<em>R</em>/<em>S</em>-Cl-MBA)<small><sub>4</sub></small>Cu<small><sub>4</sub></small>I<small><sub>4</sub></small> (<em>R</em>/<em>S</em>-Cl) and (<em>R</em>/<em>S</em>-Br-MBA)<small><sub>4</sub></small>Cu<small><sub>4</sub></small>I<small><sub>4</sub></small> (<em>R</em>/<em>S</em>-Br), <em>via</em> a simple room-temperature solvent-diffusion method. Both <em>R</em>/<em>S</em>-Cl and <em>R</em>/<em>S</em>-Br are in the <em>C</em>2 chiral space group with a monoclinic crystal system. Under 310 nm excitation, <em>R</em>/<em>S</em>-Cl and <em>R</em>/<em>S</em>-Br exhibit efficient orange and yellow broadband luminescence, featuring large Stokes shifts, microsecond lifetimes, and symmetric chiral CD signals. Interestingly, compared to <em>R</em>/<em>S</em>-Cl with a photoluminescence (PL) quantum yield (QY) of ∼46%, a near-unity PLQY is observed for <em>R</em>/<em>S</em>-Br, along with a longer PL lifetime (∼13.5 μs). The high PLQY is attributed to intermolecular halogen–halogen interactions, which greatly enhance lattice rigidity and suppress nonradiative recombination of triplet excitons. Furthermore, <em>R</em>/<em>S</em>-Br has been demonstrated for X-ray scintillator application. This work offers an effective strategy for designing multifunctional and efficient chiral phosphors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677735","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}
Hard carbon (HC) is regarded as the most promising commercial anode material for sodium-ion batteries (SIBs) due to its low cost, abundant sources, large reversible capacity, and suitability. Nevertheless, HC suffers from low initial coulombic efficiency (ICE), poor rate performance, and long-term cycling performance, significantly restricting its practical application. Herein, we proceed with defined regulation of the microcrystalline structure of coal-derived HC, which obtains the reduced surface defects and the increased interlayer spacing, further enhancing the sodium storage capacity of coal-derived HC as an anode material for SIBs by coating porous HC with soft carbon (SC). Meanwhile, we successfully synthesize high-performance SC@HC composite materials through chemical crosslinking reactions by innovatively adopting the sol-gel method and SC coating for the complex composition of coal. The SC@HC composite material as an anode in SIBs can deliver a reversible capacity of 320 mAh/g at 0.01 A/g, a high ICE of 89%, and good cycling stability (capacity retention of 80% after 400 cycles at 1 A/g). This work can rationally guide the design of low-defect and much more closed pores coal-derived HC materials and provide a feasible route for the development of high-performance HC-based anode materials for SIBs applications.
{"title":"Pore Structure Modulation and Defect Engineering of Soft Carbon@Coal-Derived Hard Carbon for Enhanced Sodium Storage Application in SIBs","authors":"xinhui jin, Haoyu Ma, Guoping Liu, Xikun Zhang, Dong Wang, Dejie Mo, Jiangyan Xie, Li-rong Feng, Maochun Wu, Bao-Lian Su, Xiaohui Guo","doi":"10.1039/d4qi03237c","DOIUrl":"https://doi.org/10.1039/d4qi03237c","url":null,"abstract":"Hard carbon (HC) is regarded as the most promising commercial anode material for sodium-ion batteries (SIBs) due to its low cost, abundant sources, large reversible capacity, and suitability. Nevertheless, HC suffers from low initial coulombic efficiency (ICE), poor rate performance, and long-term cycling performance, significantly restricting its practical application. Herein, we proceed with defined regulation of the microcrystalline structure of coal-derived HC, which obtains the reduced surface defects and the increased interlayer spacing, further enhancing the sodium storage capacity of coal-derived HC as an anode material for SIBs by coating porous HC with soft carbon (SC). Meanwhile, we successfully synthesize high-performance SC@HC composite materials through chemical crosslinking reactions by innovatively adopting the sol-gel method and SC coating for the complex composition of coal. The SC@HC composite material as an anode in SIBs can deliver a reversible capacity of 320 mAh/g at 0.01 A/g, a high ICE of 89%, and good cycling stability (capacity retention of 80% after 400 cycles at 1 A/g). This work can rationally guide the design of low-defect and much more closed pores coal-derived HC materials and provide a feasible route for the development of high-performance HC-based anode materials for SIBs applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"44 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677737","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}
A graphical abstract is available for this content
{"title":"Inorganic Chemistry Frontiers Outstanding Paper Awards 2014–2023","authors":"","doi":"10.1039/d5qi90012c","DOIUrl":"https://doi.org/10.1039/d5qi90012c","url":null,"abstract":"A graphical abstract is available for this content","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"7 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677732","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}
Luca Rocchigiani, Scott Collins, J. Scott McIndoe, Mikko Linnolahti
PGSE NMR and ESI-MS studies of different grades of hydrolytic MAO demonstrate that the average dimensions and anion distribution of MAO are correlated with one another, as revealed through studies of aging and gelation of a commercial formulation of MAO. Formulations featuring an anion distribution skewed to higher m/z ratios have significantly higher activator contents as measured by 1H NMR spectroscopy in otherwise very similar formulations. PSGE NMR studies in toluene vs. chlorobenzene media demonstrate that the average hydrodynamic dimensions of MAO are largely unaffected by solvent polarity, though aggregation behavior is somewhat sensitive to solvent polarity. As for catalyst activation and ion-pair speciation, the situation in polar solvents is complicated by the formation of solvated cations (and anions) in chlorobenzene which dramatically lower dimensions. DFT studies of model aluminoxane structures in the size range for MAO featuring a variety of architectures, molar mass and Me3Al content reveal that a linear correlation between Dt, as measured by PGSE NMR, can be related to molar mass using simple relationships and estimates of molecular volume if suitable high molecular weight standards are available. There is a reasonable agreement in molar mass with available ESI-MS data, recognizing that MAO is not monodisperse.
{"title":"Comparison of PGSE NMR and ESI-MS Measurements on Methylaluminoxane","authors":"Luca Rocchigiani, Scott Collins, J. Scott McIndoe, Mikko Linnolahti","doi":"10.1039/d4qi02982h","DOIUrl":"https://doi.org/10.1039/d4qi02982h","url":null,"abstract":"PGSE NMR and ESI-MS studies of different grades of hydrolytic MAO demonstrate that the average dimensions and anion distribution of MAO are correlated with one another, as revealed through studies of aging and gelation of a commercial formulation of MAO. Formulations featuring an anion distribution skewed to higher m/z ratios have significantly higher activator contents as measured by 1H NMR spectroscopy in otherwise very similar formulations. PSGE NMR studies in toluene vs. chlorobenzene media demonstrate that the average hydrodynamic dimensions of MAO are largely unaffected by solvent polarity, though aggregation behavior is somewhat sensitive to solvent polarity. As for catalyst activation and ion-pair speciation, the situation in polar solvents is complicated by the formation of solvated cations (and anions) in chlorobenzene which dramatically lower dimensions. DFT studies of model aluminoxane structures in the size range for MAO featuring a variety of architectures, molar mass and Me3Al content reveal that a linear correlation between Dt, as measured by PGSE NMR, can be related to molar mass using simple relationships and estimates of molecular volume if suitable high molecular weight standards are available. There is a reasonable agreement in molar mass with available ESI-MS data, recognizing that MAO is not monodisperse.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672570","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}
Heme-containing oxygenases have been known to catalyze oxidation of unactivated C-H bonds. In most cases, hydroxylated compounds (alcohols) are the predominant products through oxygen rebound pathway. Alternatively, non-hydroxylated products can be obtained under certain conditions when the oxygen rebound pathway is inhibited. However, biomimetic oxidative functionalization reactions catalyzed by synthetic iron porphyrin complexes have yet to be explored, due to the fast oxygen rebound step. In this study, metal bromide LiBr was introduced to the iron-porphyrin catalyzed oxidation of hydrocarbons, such as cycloalkane, straight-chain alkanes and benzyl compounds. In all cases, brominated products were the sole products, indicating that the oxygen rebound pathway was completely inhibited in the presence of LiBr. Mechanistic studies combined with theoretical calculations revealed that the active intermediate iron(IV)-oxo porphyrin π-cation radical species interacted with lithium ion, which significantly inhibited the oxygen rebound pathway. As a result, a carbocation intermediate was formed which was responsible for the formation of brominated products. This carbocation mechanism is reminiscent of the P450 OleTJE and CYP19A1 enzymatic systems, in which the oxygen rebound is inhibited and desaturated products are obtained. These results demonstrate that the redox-inactive metal ion acting as Lewis-acid is capable to tune the reactivity of high-valent metal-oxo species from oxygen rebound to non-oxygen rebound, providing potential application to produce versatile organic compounds stem from simple hydrocarbons.
{"title":"Iron Porphyrin Catalyzed Bromination of Unactivated C-H Bonds: Inhibition of Oxygen Rebound by Redox-Inactive Metal Ions","authors":"Yiran Xu, Peng Wu, Duanfeng Xie, Yue Cui, Yuheng Zhang, Binju Wang, Mian Guo","doi":"10.1039/d5qi00508f","DOIUrl":"https://doi.org/10.1039/d5qi00508f","url":null,"abstract":"Heme-containing oxygenases have been known to catalyze oxidation of unactivated C-H bonds. In most cases, hydroxylated compounds (alcohols) are the predominant products through oxygen rebound pathway. Alternatively, non-hydroxylated products can be obtained under certain conditions when the oxygen rebound pathway is inhibited. However, biomimetic oxidative functionalization reactions catalyzed by synthetic iron porphyrin complexes have yet to be explored, due to the fast oxygen rebound step. In this study, metal bromide LiBr was introduced to the iron-porphyrin catalyzed oxidation of hydrocarbons, such as cycloalkane, straight-chain alkanes and benzyl compounds. In all cases, brominated products were the sole products, indicating that the oxygen rebound pathway was completely inhibited in the presence of LiBr. Mechanistic studies combined with theoretical calculations revealed that the active intermediate iron(IV)-oxo porphyrin π-cation radical species interacted with lithium ion, which significantly inhibited the oxygen rebound pathway. As a result, a carbocation intermediate was formed which was responsible for the formation of brominated products. This carbocation mechanism is reminiscent of the P450 OleT<small><sub>JE</sub></small> and CYP19A1 enzymatic systems, in which the oxygen rebound is inhibited and desaturated products are obtained. These results demonstrate that the redox-inactive metal ion acting as Lewis-acid is capable to tune the reactivity of high-valent metal-oxo species from oxygen rebound to non-oxygen rebound, providing potential application to produce versatile organic compounds stem from simple hydrocarbons.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"214 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672569","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}
Chao Wen, Ziyin Xie, Na Wu, Lihui Dong, Bin Li, Zhengjun Chen
Electrocatalytic CO2 reduction reaction (CO2RR) into valuable chemicals is an appealing way to ease the energy and environmental crises, but the development of efficient catalysts remains challenging. Herein, we reported a novel Ag-MnOx heterostructural catalyst and its high activity for CO2RR to CO. The obtained Ag-MnOx exhibits a CO Faraday efficiency (FECO) of up to 97.5% at −0.8 V vs reversible hydrogen electrode (RHE) and especially maintained a FECO above 90% within a broad potential window of 500 mV (−0.6 ~ −1.1 V vs. RHE). In addition, the CO₂RR performance was optimized using a flow cell, and Ag-MnOx catalyst reached a total current density of −255 mA cm-2 at −2.0 V vs. RHE. Our designed in-situ experiments and density functional theory (DFT) calculations unveil that the heterojunction interface formed between O-defective-rich MnOx and active Ag enhances CO2 adsorption and activation and simultaneously stabilizes the *COOH intermediate, thus leading to its superior catalytic performance. Furthermore, the Ag-MnOx catalyst used as cathode to assemble Zn-CO2 cell exhibits an ultimate power density of 13.63 mW cm−2 and rechargeable time over 65 h.
{"title":"Interfacial Interaction of Ag-MnOx Heterostructure for Efficient CO2 Electroreduction to CO and Aqueous Zn-CO2 Batteries","authors":"Chao Wen, Ziyin Xie, Na Wu, Lihui Dong, Bin Li, Zhengjun Chen","doi":"10.1039/d5qi00374a","DOIUrl":"https://doi.org/10.1039/d5qi00374a","url":null,"abstract":"Electrocatalytic CO2 reduction reaction (CO2RR) into valuable chemicals is an appealing way to ease the energy and environmental crises, but the development of efficient catalysts remains challenging. Herein, we reported a novel Ag-MnOx heterostructural catalyst and its high activity for CO2RR to CO. The obtained Ag-MnOx exhibits a CO Faraday efficiency (FECO) of up to 97.5% at −0.8 V vs reversible hydrogen electrode (RHE) and especially maintained a FECO above 90% within a broad potential window of 500 mV (−0.6 ~ −1.1 V vs. RHE). In addition, the CO₂RR performance was optimized using a flow cell, and Ag-MnOx catalyst reached a total current density of −255 mA cm-2 at −2.0 V vs. RHE. Our designed in-situ experiments and density functional theory (DFT) calculations unveil that the heterojunction interface formed between O-defective-rich MnOx and active Ag enhances CO2 adsorption and activation and simultaneously stabilizes the *COOH intermediate, thus leading to its superior catalytic performance. Furthermore, the Ag-MnOx catalyst used as cathode to assemble Zn-CO2 cell exhibits an ultimate power density of 13.63 mW cm−2 and rechargeable time over 65 h.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666629","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}
Bo Zhuang, Qiang-Qiang Jia, Zhi-Long Li, Jiu-Yang Liu, Ying Wang, Jia-Xun Li, Kun Ding, Zunqi Liu, Da-Wei Fu
Hybrid organic–inorganic halides have emerged as promising candidates for optoelectronic applications such as smart sensors, photodetectors and optical memory, due to their structural tunability, environmental stability, and high photoluminescence quantum yield (PLQY). Despite these merits, integrating switchable dielectric responses with strong luminescence in low-dimensional hybrid antimony materials remains exceptionally rare. Therefore, adjusting the dimensionality and enhancing the photoluminescence properties of hybrid antimony materials remains an important challenge. Herein, two different dimensional hybrid antimony bromide materials, namely (IBA)2SbBr5 and (IBA)6SbBr6·3Br (IBA = isobutylamine), were synthesized using a solvent encapsulation strategy. By taking advantage of the subtle dynamics arising from the solution composition during crystal growth, we realized two distinct structures with a switchable dielectric response. (IBA)6SbBr6·3Br features an independent octahedral structure, and its low-dimensional contributes to a high quantum yield of 10.22%. In contrast, (IBA)2SbBr5, which has a 1D structure, exhibits a higher phase transition temperature, along with a ferroelastic phase transition. Our targeted synthesis provides effective tools to illuminate the structural factors contributing to photoluminescence and enables precise formation of hybrid organic–inorganic halides switching materials.
{"title":"Dimensional tunability and photoluminescence triggered by solvent encapsulation strategies in hybrid materials","authors":"Bo Zhuang, Qiang-Qiang Jia, Zhi-Long Li, Jiu-Yang Liu, Ying Wang, Jia-Xun Li, Kun Ding, Zunqi Liu, Da-Wei Fu","doi":"10.1039/d5qi00331h","DOIUrl":"https://doi.org/10.1039/d5qi00331h","url":null,"abstract":"Hybrid organic–inorganic halides have emerged as promising candidates for optoelectronic applications such as smart sensors, photodetectors and optical memory, due to their structural tunability, environmental stability, and high photoluminescence quantum yield (PLQY). Despite these merits, integrating switchable dielectric responses with strong luminescence in low-dimensional hybrid antimony materials remains exceptionally rare. Therefore, adjusting the dimensionality and enhancing the photoluminescence properties of hybrid antimony materials remains an important challenge. Herein, two different dimensional hybrid antimony bromide materials, namely (IBA)2SbBr5 and (IBA)6SbBr6·3Br (IBA = isobutylamine), were synthesized using a solvent encapsulation strategy. By taking advantage of the subtle dynamics arising from the solution composition during crystal growth, we realized two distinct structures with a switchable dielectric response. (IBA)6SbBr6·3Br features an independent octahedral structure, and its low-dimensional contributes to a high quantum yield of 10.22%. In contrast, (IBA)2SbBr5, which has a 1D structure, exhibits a higher phase transition temperature, along with a ferroelastic phase transition. Our targeted synthesis provides effective tools to illuminate the structural factors contributing to photoluminescence and enables precise formation of hybrid organic–inorganic halides switching materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"56 7 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672571","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}
Near-infrared phosphor-converted light-emitting diodes (NIR pc-LEDs) are considered promising light sources for a variety of applications due to their cost-effectiveness, broadband emission, compact size, and high output power. The key to developing high-performance NIR pc-LEDs lies in the design of phosphors. In this study, we report a NIR Mg3Ga2SnO8:Cr3+ (MGS:Cr3+) phosphor synthesized via a traditional high-temperature solid-state method. Under 450 nm excitation, MGS:Cr3+ exhibited an intense tunable ultra-broadband NIR emission. By adjusting the concentration of Cr3+ ions, the full width at half maximum (FWHM) of the spectrum was observed to be broadened from 151 to 223 nm, while the peak wavelength shifted from 715 to 833 nm. Crystal structure analysis, low-temperature spectra, and fluorescence decay curves revealed that these fascinating tunable characteristics originated from the two-site occupation of Cr3+ ions. Additionally, the presented phosphor exhibited an impressive internal quantum efficiency (IQE = 57.8%) and superior photoluminescent thermal stability (I423 K/I303 K = 50%). Moreover, the fabricated NIR pc-LED devices based on the MGS:0.08Cr3+ and MGS:0.02Cr3+ samples proved their potential in night vision imaging, non-invasive detection, and plant growth illumination applications.
{"title":"Achieving tunable ultra-broadband NIR emission originating from the two-site occupation of Cr3+ ions in Mg3Ga2SnO8:Cr3+","authors":"Pengcheng Luo, Dashuai Sun, Zeyu Lyu, Mingxiang You, Zheng Lu, Xiaowei Zhang, Luhui Zhou, Hongpeng You","doi":"10.1039/d5qi00395d","DOIUrl":"https://doi.org/10.1039/d5qi00395d","url":null,"abstract":"Near-infrared phosphor-converted light-emitting diodes (NIR pc-LEDs) are considered promising light sources for a variety of applications due to their cost-effectiveness, broadband emission, compact size, and high output power. The key to developing high-performance NIR pc-LEDs lies in the design of phosphors. In this study, we report a NIR Mg<small><sub>3</sub></small>Ga<small><sub>2</sub></small>SnO<small><sub>8</sub></small>:Cr<small><sup>3+</sup></small> (MGS:Cr<small><sup>3+</sup></small>) phosphor synthesized <em>via</em> a traditional high-temperature solid-state method. Under 450 nm excitation, MGS:Cr<small><sup>3+</sup></small> exhibited an intense tunable ultra-broadband NIR emission. By adjusting the concentration of Cr<small><sup>3+</sup></small> ions, the full width at half maximum (FWHM) of the spectrum was observed to be broadened from 151 to 223 nm, while the peak wavelength shifted from 715 to 833 nm. Crystal structure analysis, low-temperature spectra, and fluorescence decay curves revealed that these fascinating tunable characteristics originated from the two-site occupation of Cr<small><sup>3+</sup></small> ions. Additionally, the presented phosphor exhibited an impressive internal quantum efficiency (IQE = 57.8%) and superior photoluminescent thermal stability (<em>I</em><small><sub>423 K</sub></small>/<em>I</em><small><sub>303 K</sub></small> = 50%). Moreover, the fabricated NIR pc-LED devices based on the MGS:0.08Cr<small><sup>3+</sup></small> and MGS:0.02Cr<small><sup>3+</sup></small> samples proved their potential in night vision imaging, non-invasive detection, and plant growth illumination applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"70 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666628","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}
Yuting Liu, quanjiang lv, Hang Cong, Wenfeng Zhao, Qingmei Ge, Nan Jiang, Qi-Long Zhu
Nickel-based oxygen evolution reaction (OER) electrocatalysts have garnered significant attention due to their high catalytic activity and abundant reserves. In this study, we reported a series of cucurbit[n]urils (CB[n], n = 5-8) functionalized Ni nanocomposites (CB[n]-Ni, n = 5-8) to synergistically enhance the OER catalytic activity in alkaline media. The sizes and electronic structures of CB[n]-Ni can be precisely controlled by CB[n] with varying cavity sizes. Among these CB[n]-Ni, CB[7]-Ni presented superior OER performance compared to other CB[n]-Ni (n = 5, 6, 8) and CB-free Ni nanocomposites. Operando electrochemical impedance spectroscopy (EIS) studies demonstrated that CB[7]-Ni initiated OER at a relatively low applied potential of 1.5 V vs. RHE. Additionally, spectroscopic measurements and theoretical calculations revealed that the incorporation of CB[7] regulates the electronic structure of the active Ni nanocomposite, lowered the activation energy for the formation of *OOH intermediate, thereby facilitating the OER porcess. This work not only broadens the application of supramolecular macrocycles in electrocatalysis but also provides a novel strategy for the design of electrocatalysts.
{"title":"Ultrafine cucurbit[n]uril (n = 5-8)-Ni nanocomposites as highly efficient catalysts for electrocatalytic oxygen evolution reaction","authors":"Yuting Liu, quanjiang lv, Hang Cong, Wenfeng Zhao, Qingmei Ge, Nan Jiang, Qi-Long Zhu","doi":"10.1039/d5qi00013k","DOIUrl":"https://doi.org/10.1039/d5qi00013k","url":null,"abstract":"Nickel-based oxygen evolution reaction (OER) electrocatalysts have garnered significant attention due to their high catalytic activity and abundant reserves. In this study, we reported a series of cucurbit[n]urils (CB[n], n = 5-8) functionalized Ni nanocomposites (CB[n]-Ni, n = 5-8) to synergistically enhance the OER catalytic activity in alkaline media. The sizes and electronic structures of CB[n]-Ni can be precisely controlled by CB[n] with varying cavity sizes. Among these CB[n]-Ni, CB[7]-Ni presented superior OER performance compared to other CB[n]-Ni (n = 5, 6, 8) and CB-free Ni nanocomposites. Operando electrochemical impedance spectroscopy (EIS) studies demonstrated that CB[7]-Ni initiated OER at a relatively low applied potential of 1.5 V vs. RHE. Additionally, spectroscopic measurements and theoretical calculations revealed that the incorporation of CB[7] regulates the electronic structure of the active Ni nanocomposite, lowered the activation energy for the formation of *OOH intermediate, thereby facilitating the OER porcess. This work not only broadens the application of supramolecular macrocycles in electrocatalysis but also provides a novel strategy for the design of electrocatalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666627","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}
Meichun Fu, Mei Han, Yuan Zhang, Beining Zheng, Shouhua Feng
Adjusting the concentration of free carriers is a direct strategies to attain an ideal negative permittivity. Employing chemical methods for atypical ion doping is an effective way to regulate the concentration of free carriers. Due to the A-site tunability of perovskite manganese oxides, doping with multiple valent ions becomes particularly favorable. In this study, to realize temperature-stable negative permittivity, mono-phase La1-x-yCaxKyMnO3 (named LCKMO) perovskite crystals with diverse compositions are prepared, using a ultra-high alkaline hydrothermal method. Heterovalent ion doping (La3+, Ca2+, K+) at the A-site within the perovskite crystal structure occurred with the aid of the disproportionation reaction of Mn ions at the B-site during the extreme hydrothermal conditions. By adjusting the La/Ca ratio, we are able to vary the doping content of K+. Experimental findings reveal that as the concentration of K+ increases, so does the concentration of Mn oxide states, suggesting the presence of additional free carriers resulting in a more negative permittivity and minimized dielectric loss. This work pioneers a novel synthetic pathway for the creation and design of negative permittivity materials.
{"title":"Enhanced negative permittivity by A-site heterovalent-ion doping in La1-x-yCaxKyMnO3 perovskite","authors":"Meichun Fu, Mei Han, Yuan Zhang, Beining Zheng, Shouhua Feng","doi":"10.1039/d4qi03217a","DOIUrl":"https://doi.org/10.1039/d4qi03217a","url":null,"abstract":"Adjusting the concentration of free carriers is a direct strategies to attain an ideal negative permittivity. Employing chemical methods for atypical ion doping is an effective way to regulate the concentration of free carriers. Due to the A-site tunability of perovskite manganese oxides, doping with multiple valent ions becomes particularly favorable. In this study, to realize temperature-stable negative permittivity, mono-phase La1-x-yCaxKyMnO3 (named LCKMO) perovskite crystals with diverse compositions are prepared, using a ultra-high alkaline hydrothermal method. Heterovalent ion doping (La3+, Ca2+, K+) at the A-site within the perovskite crystal structure occurred with the aid of the disproportionation reaction of Mn ions at the B-site during the extreme hydrothermal conditions. By adjusting the La/Ca ratio, we are able to vary the doping content of K+. Experimental findings reveal that as the concentration of K+ increases, so does the concentration of Mn oxide states, suggesting the presence of additional free carriers resulting in a more negative permittivity and minimized dielectric loss. This work pioneers a novel synthetic pathway for the creation and design of negative permittivity materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666630","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}
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