Alkaline earth lithoaluminates with the UCr4C4-type structure have demonstrated considerable potential in achieving narrow-band emissions from Eu 2+ . However, obtaining single-phase powder samples with green-emitting remains challenging. In this study, we address this issue by co-doping Ba 2+ into the novel UCr4C4-type system Sr5/6-xBaxLi17/6Al7/6O4:Eu 2+ , which significantly enhances phase purity and structural homogeneity. This approach not only reduces the emission bandwidth from 66 nm (2241 cm -1 ) to 51 nm (1830 cm -1 ) but also induces a blue shift to 529 nm, fine-tuning the emission into the desired deep green region. Through detailed mechanistic studies-including low-temperature spectroscopy and luminescence decay analysis-we identify the presence of multiple Eu 2+ emission centers associated with distinct Sr 2+ sites. Ba 2+ doping is shown to promote dominant Eu 2+ emission in the green spectral region, thereby facilitating spectral narrowing.The optimized phosphor achieves a high absorption efficiency of 64.6% and an external quantum yield of 22.2%. When integrated into a white LED prototype, it enables a color gamut covering 97.6% of the NTSC (National Television System Committee) standard, outperforming a commercial β-SiAlON:Eu 2+ -based device. This study provides an effective cationic codoping strategy for designing high-performance narrow-band oxide phosphors and highlights a promising candidate for nextgeneration display technologies.
具有ucr4c4型结构的碱土岩铝酸盐在实现Eu 2+窄带发射方面显示出相当大的潜力。然而，获得具有绿色发光的单相粉末样品仍然具有挑战性。在本研究中，我们通过将Ba 2+共掺杂到新型ucr4c4型体系Sr5/6-xBaxLi17/6Al7/6O4:Eu 2+中来解决这一问题，该体系显著提高了相纯度和结构均匀性。这种方法不仅将发射带宽从66 nm （2241 cm -1）减少到51 nm (1830 cm -1)，而且还诱导蓝移到529 nm，将发射微调到所需的深绿色区域。通过详细的机制研究，包括低温光谱和发光衰变分析，我们确定了与不同Sr 2+位点相关的多个Eu 2+发射中心的存在。Ba 2+的掺杂促进了Eu 2+在绿色光谱区域的主导发射，从而促进了光谱的收窄。优化后的荧光粉具有64.6%的吸收效率和22.2%的外量子产率。当集成到白光LED原型中时，它的色域覆盖了NTSC（国家电视系统委员会）标准的97.6%，优于基于β-SiAlON:Eu 2+的商用设备。该研究为设计高性能窄带氧化物荧光粉提供了一种有效的阳离子共掺杂策略，并突出了下一代显示技术的前景。
{"title":"Ba 2+ Co-doping Enhances Phase Purity and Enables Narrow-Band Green Emission in Sr 5/6 Li 17/6 Al 7/6 O 4 :Eu 2+ Phosphor for Backlight Display Applications","authors":"Chenyang Zhan, Zihao Wang, Sisi Liang, Zhi-Ying Zhao, Hanru Chen, Jiahe Yu, Haomiao Zhu","doi":"10.1039/d6qi00092d","DOIUrl":"https://doi.org/10.1039/d6qi00092d","url":null,"abstract":"Alkaline earth lithoaluminates with the UCr4C4-type structure have demonstrated considerable potential in achieving narrow-band emissions from Eu 2+ . However, obtaining single-phase powder samples with green-emitting remains challenging. In this study, we address this issue by co-doping Ba 2+ into the novel UCr4C4-type system Sr5/6-xBaxLi17/6Al7/6O4:Eu 2+ , which significantly enhances phase purity and structural homogeneity. This approach not only reduces the emission bandwidth from 66 nm (2241 cm -1 ) to 51 nm (1830 cm -1 ) but also induces a blue shift to 529 nm, fine-tuning the emission into the desired deep green region. Through detailed mechanistic studies-including low-temperature spectroscopy and luminescence decay analysis-we identify the presence of multiple Eu 2+ emission centers associated with distinct Sr 2+ sites. Ba 2+ doping is shown to promote dominant Eu 2+ emission in the green spectral region, thereby facilitating spectral narrowing.The optimized phosphor achieves a high absorption efficiency of 64.6% and an external quantum yield of 22.2%. When integrated into a white LED prototype, it enables a color gamut covering 97.6% of the NTSC (National Television System Committee) standard, outperforming a commercial β-SiAlON:Eu 2+ -based device. This study provides an effective cationic codoping strategy for designing high-performance narrow-band oxide phosphors and highlights a promising candidate for nextgeneration display technologies.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"4 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506931","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}
Wenjie Lei, Yang Shao, Fangya Ren, Mengdi Guo, Qing You, Xianjun Fang, Jie Kong, Meng Zhou, Baoqi Yin, Zhixun Luo
Superatomic metal nanoclusters (NCs) often exhibit typically enhanced stability, granted by electron-shell closure and ligand protection, but also result in a considerable challenge for achieving reversible structural interconversion between homologous systems. Here we report two classes of superatomic NCs, [M1Ag14(DPPP)6Cl4]2+ and [M1Ag18(DPPP)6Cl8]2+ (M = Pd, Pt; DPPP = 1,3-bis(diphenylphosphine)propane), which undergo reversible stimuli-responsive transformation triggered simply by UV light and polar solvents, accompanied by a 48-fold increase or decrease in the luminescence intensity. These superatoms feature the same icosahedral M@Ag12 core and a closed shell of eight electrons pertaining to superatomic electronic configuration of 1S21P6. The rigid structure of [M1Ag14(DPPP)6Cl4]2+, with its uniform μ₄-Ag coordination, suppresses non-radiative decay to "turn on" emission. In contrast, the flexible structure of [M1Ag18(DPPP)6Cl8]2+ facilitates vibrational energy dissipation and consequently quenches the luminescence. Femtosecond transient absorption spectroscopy revealed a shell-mediated emission mechanism, in which the surface rigidification switches the electronic configuration from the singlet state (M1Ag18) to the triplet state (M1Ag14). Furthermore, dopant-dependent HOMO-LUMO gaps and core-shell charge distribution dictate their stability and transformation kinetics. This work underscores the potential of surface engineering and heteroatom doping to regulate photophysical behaviors of superatoms, thereby paving the way for the rational design of stimuli-responsive luminescent nanomaterials.
{"title":"Superatomic interconversion causes reversible on-off luminescence of doped silver nanoclusters","authors":"Wenjie Lei, Yang Shao, Fangya Ren, Mengdi Guo, Qing You, Xianjun Fang, Jie Kong, Meng Zhou, Baoqi Yin, Zhixun Luo","doi":"10.1039/d6qi00312e","DOIUrl":"https://doi.org/10.1039/d6qi00312e","url":null,"abstract":"Superatomic metal nanoclusters (NCs) often exhibit typically enhanced stability, granted by electron-shell closure and ligand protection, but also result in a considerable challenge for achieving reversible structural interconversion between homologous systems. Here we report two classes of superatomic NCs, [M1Ag14(DPPP)6Cl4]2+ and [M1Ag18(DPPP)6Cl8]2+ (M = Pd, Pt; DPPP = 1,3-bis(diphenylphosphine)propane), which undergo reversible stimuli-responsive transformation triggered simply by UV light and polar solvents, accompanied by a 48-fold increase or decrease in the luminescence intensity. These superatoms feature the same icosahedral M@Ag12 core and a closed shell of eight electrons pertaining to superatomic electronic configuration of 1S21P6. The rigid structure of [M1Ag14(DPPP)6Cl4]2+, with its uniform μ₄-Ag coordination, suppresses non-radiative decay to \"turn on\" emission. In contrast, the flexible structure of [M1Ag18(DPPP)6Cl8]2+ facilitates vibrational energy dissipation and consequently quenches the luminescence. Femtosecond transient absorption spectroscopy revealed a shell-mediated emission mechanism, in which the surface rigidification switches the electronic configuration from the singlet state (M1Ag18) to the triplet state (M1Ag14). Furthermore, dopant-dependent HOMO-LUMO gaps and core-shell charge distribution dictate their stability and transformation kinetics. This work underscores the potential of surface engineering and heteroatom doping to regulate photophysical behaviors of superatoms, thereby paving the way for the rational design of stimuli-responsive luminescent nanomaterials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"86 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506932","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}
jinyu wang, Jiafeng Zhu, Jiacheng Zhang, Hong Li, Qingyuan Bi, Jinchen Fan, Zichao Lian, Guisheng Li
The inefficient separation and migration of photogenerated charges remain a primary obstacle for photocatalytic hydrogen evolution. Herein, a novel oxygen-defect-mediated S-scheme heterojunction of Mo-ZnIn2S4/BiOCl (Mo-ZIS/BOC) was constructed for efficient production of hydrogen using visible light. The introduction of Mo species not only optimizes the electron structure of ZnIn2S4 but, more importantly, effectively modulates the interfacial electric field (IEF) at the heterojunction interface. The optimum Mo-ZIS/BOC catalyst exhibits an impressive hydrogen evolution rate of 18.16 mmol g⁻¹ h⁻¹, which is 11.9 times higher than that of pure ZnIn2S4 and also surpasses the undoped ZIS/BOC heterojunction. The high activity and excellent stability of Mo-ZIS/BOC were attributed to the enhanced IEF and oxygen-defect-mediated S-scheme pathway, significantly promoting directional charge transfer and separation. Combined with photoelectrochemical characterizations and theoretical calculations, the mechanism of Mo in modulating the IEF and the charge transfer pathway was elucidated. This work offers profound insights into how elemental doping can intensify the IEF of S-scheme heterojunctions for advanced solar energy conversion.
{"title":"Modulating interfacial electric field in oxygen-defect-mediated S-scheme Mo-ZnIn2S4/BiOCl heterostructures for efficient photocatalytic hydrogen evolution","authors":"jinyu wang, Jiafeng Zhu, Jiacheng Zhang, Hong Li, Qingyuan Bi, Jinchen Fan, Zichao Lian, Guisheng Li","doi":"10.1039/d6qi00261g","DOIUrl":"https://doi.org/10.1039/d6qi00261g","url":null,"abstract":"The inefficient separation and migration of photogenerated charges remain a primary obstacle for photocatalytic hydrogen evolution. Herein, a novel oxygen-defect-mediated S-scheme heterojunction of Mo-ZnIn2S4/BiOCl (Mo-ZIS/BOC) was constructed for efficient production of hydrogen using visible light. The introduction of Mo species not only optimizes the electron structure of ZnIn2S4 but, more importantly, effectively modulates the interfacial electric field (IEF) at the heterojunction interface. The optimum Mo-ZIS/BOC catalyst exhibits an impressive hydrogen evolution rate of 18.16 mmol g⁻¹ h⁻¹, which is 11.9 times higher than that of pure ZnIn2S4 and also surpasses the undoped ZIS/BOC heterojunction. The high activity and excellent stability of Mo-ZIS/BOC were attributed to the enhanced IEF and oxygen-defect-mediated S-scheme pathway, significantly promoting directional charge transfer and separation. Combined with photoelectrochemical characterizations and theoretical calculations, the mechanism of Mo in modulating the IEF and the charge transfer pathway was elucidated. This work offers profound insights into how elemental doping can intensify the IEF of S-scheme heterojunctions for advanced solar energy conversion.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"14 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496504","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}
Tingyang Li, Qian Liu, Zheng Xiong, Peng Ji, Ruiyang Zhao, Jishu Han, Lei Wang
Hydrogen, a source of clean energy, has great potential for applications in the field of renewable energy. Developing low-cost, high-efficiency composite photocatalysts with high performance and good stability characteristics has broad application prospects. In this study, the Ni0.7Co0.3P/MnCo2S4 composite photocatalysts were prepared by the in situ deposition of Ni0.7Co0.3P nanoparticles on the surface of the MnCo2S4 yolk–shell nanoflowers derived from MnCo-layered double hydroxide. The hydrogen production performance of the photocatalysts was modified by regulating the Co-dopant amount in Ni1−xCoxP and the loading amount of Ni0.7Co0.3P. The measurements illustrated that the hydrogen generation rate of Ni0.7Co0.3P/MnCo2S4 under visible light irradiation was markedly increased and the composite photocatalyst maintained good stability. The modification of Ni0.7Co0.3P helped to enhance its light absorption capacity, thus providing more active sites. Meanwhile, the Z-scheme heterojunction formed between MnCo2S4 and Ni0.7Co0.3P could expedite the shift of photogenerated carriers, limit the recombination of photogenerated electrons and holes and contribute to H2 production. This work affords a novel approach for the development of high-performance composite photocatalysts.
{"title":"Ni0.7Co0.3P nanoparticle-loaded MnCo2S4 yolk–shell nanoflowers with a Z-scheme heterojunction for efficient photocatalytic hydrogen evolution","authors":"Tingyang Li, Qian Liu, Zheng Xiong, Peng Ji, Ruiyang Zhao, Jishu Han, Lei Wang","doi":"10.1039/d6qi00361c","DOIUrl":"https://doi.org/10.1039/d6qi00361c","url":null,"abstract":"Hydrogen, a source of clean energy, has great potential for applications in the field of renewable energy. Developing low-cost, high-efficiency composite photocatalysts with high performance and good stability characteristics has broad application prospects. In this study, the Ni<small><sub>0.7</sub></small>Co<small><sub>0.3</sub></small>P/MnCo<small><sub>2</sub></small>S<small><sub>4</sub></small> composite photocatalysts were prepared by the <em>in situ</em> deposition of Ni<small><sub>0.7</sub></small>Co<small><sub>0.3</sub></small>P nanoparticles on the surface of the MnCo<small><sub>2</sub></small>S<small><sub>4</sub></small> yolk–shell nanoflowers derived from MnCo-layered double hydroxide. The hydrogen production performance of the photocatalysts was modified by regulating the Co-dopant amount in Ni<small><sub>1−<em>x</em></sub></small>Co<small><sub><em>x</em></sub></small>P and the loading amount of Ni<small><sub>0.7</sub></small>Co<small><sub>0.3</sub></small>P. The measurements illustrated that the hydrogen generation rate of Ni<small><sub>0.7</sub></small>Co<small><sub>0.3</sub></small>P/MnCo<small><sub>2</sub></small>S<small><sub>4</sub></small> under visible light irradiation was markedly increased and the composite photocatalyst maintained good stability. The modification of Ni<small><sub>0.7</sub></small>Co<small><sub>0.3</sub></small>P helped to enhance its light absorption capacity, thus providing more active sites. Meanwhile, the Z-scheme heterojunction formed between MnCo<small><sub>2</sub></small>S<small><sub>4</sub></small> and Ni<small><sub>0.7</sub></small>Co<small><sub>0.3</sub></small>P could expedite the shift of photogenerated carriers, limit the recombination of photogenerated electrons and holes and contribute to H<small><sub>2</sub></small> production. This work affords a novel approach for the development of high-performance composite photocatalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506933","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}
In this work, by systematic modulation of the concentration of the cetyltrimethylammonium bromide (CTAB) surfactant in growth solution, the competitive deposition of Pt on Au nanorods (AuNRs) and Br- ions induced oxidative etching of AuNR were achieved under high-temperature conditions. As a result, two representative AuNR-Pt heterostructures were successfully obtained, named G- and E-Au-Pt structures featured by the growth of dense Pt spikes on the surface of AuNRs and the thin Pt shell on etched AuNRs, respectively. The E-Au-Pt shows an ultra-low overpotential of 9.8 mV at 10 mA cm−2 for alkaline hydrogen evolution reaction (HER), superior to the G-Au-Pt structure and commercial Pt/C. The water activation capability arising from the abundant active sites of E-Au-Pt endow it with enhanced alkaline catalytic activity. The occurrence of the oxidative etching of AuNR assisted by Br- played a crucial role in forming the highly active sites in the E-Au-Pt structure. This unique step provides new insights and important reference for the rational design and synthetic control of advanced electrocatalysts and thus is helpful to expand their practical applications in various fields.
本文通过系统调节生长溶液中十六烷基三甲基溴化铵（CTAB）表面活性剂的浓度，在高温条件下实现了Pt在Au纳米棒（AuNR）上的竞争性沉积和Br离子诱导的氧化刻蚀。结果，成功获得了两种具有代表性的AuNR-Pt异质结构，分别命名为G-和E-Au-Pt结构，其特征是在aunr表面生长致密的Pt尖刺，在蚀刻的aunr表面生长薄的Pt壳。E-Au-Pt在10 mA cm−2条件下具有9.8 mV的超低过电位，优于G-Au-Pt结构和商用Pt/C。E-Au-Pt丰富的活性位点所产生的水活化能力使其具有增强的碱性催化活性。在Br-的辅助下，unr氧化蚀刻的发生对E-Au-Pt结构中高活性位点的形成起着至关重要的作用。这一独特的步骤为先进电催化剂的合理设计和合成控制提供了新的见解和重要参考，有助于扩大其在各个领域的实际应用。
{"title":"Tuning the Growth Mode of Pt on AuNRs via Modulating the Competition of Pt Deposition and Oxidative Etching of Au Nanorods","authors":"Yu Xia, Xingchen Ye, Sijia Zhao, Lingyu Zhang, Yujie Ma, Xing Wang, Yong Liu, Yawen Wang, Xianying Wang, Shaoyan Wang, Yuhua Feng","doi":"10.1039/d6qi00111d","DOIUrl":"https://doi.org/10.1039/d6qi00111d","url":null,"abstract":"In this work, by systematic modulation of the concentration of the cetyltrimethylammonium bromide (CTAB) surfactant in growth solution, the competitive deposition of Pt on Au nanorods (AuNRs) and Br- ions induced oxidative etching of AuNR were achieved under high-temperature conditions. As a result, two representative AuNR-Pt heterostructures were successfully obtained, named G- and E-Au-Pt structures featured by the growth of dense Pt spikes on the surface of AuNRs and the thin Pt shell on etched AuNRs, respectively. The E-Au-Pt shows an ultra-low overpotential of 9.8 mV at 10 mA cm−2 for alkaline hydrogen evolution reaction (HER), superior to the G-Au-Pt structure and commercial Pt/C. The water activation capability arising from the abundant active sites of E-Au-Pt endow it with enhanced alkaline catalytic activity. The occurrence of the oxidative etching of AuNR assisted by Br- played a crucial role in forming the highly active sites in the E-Au-Pt structure. This unique step provides new insights and important reference for the rational design and synthetic control of advanced electrocatalysts and thus is helpful to expand their practical applications in various fields.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"33 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492592","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}
Frustrated Lewis pairs (FLPs) have been realized for a wide range of element combinations, yet systems constructed from two phosphorus centers in distinct oxidation states remain unexplored. Here, we report an intramolecular dative R3P→PR4+ bond that functions as a masked FLP. The architecture enables the heterolytic activation of C-H and X-H bonds (X = O, N), affording phosphonium/phosphorane products. The cooperative reactivity is further exploited in the hydroarylation of alkenes, demonstrating how P-P frameworks featuring mixed phosphorus oxidation states can be harnessed for main-group catalysis.
{"title":"Masked P(III)/P(V) Frustrated Lewis Pair for C-H and X-H Bond Cleavage and Catalytic Hydroarylation of Alkenes","authors":"Lijun You, Lutz Greb","doi":"10.1039/d6qi00241b","DOIUrl":"https://doi.org/10.1039/d6qi00241b","url":null,"abstract":"Frustrated Lewis pairs (FLPs) have been realized for a wide range of element combinations, yet systems constructed from two phosphorus centers in distinct oxidation states remain unexplored. Here, we report an intramolecular dative R3<small><sub></sub></small>P→PR<small><sub>4</sub></small><small><sup>+</sup></small> bond that functions as a masked FLP. The architecture enables the heterolytic activation of C-H and X-H bonds (X = O, N), affording phosphonium/phosphorane products. The cooperative reactivity is further exploited in the hydroarylation of alkenes, demonstrating how P-P frameworks featuring mixed phosphorus oxidation states can be harnessed for main-group catalysis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"50 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492595","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}
Persistent phosphors capable of long-lasting emission after excitation are crucial for emerging display, lighting, and sensing technologies. In this study, manganese and gallium co-doped lithium zinc germanate (Li<small><sub>2</sub></small>ZnGeO<small><sub>4</sub></small>) phosphors were synthesized via a high-temperature solid-state route, exhibiting bright and thermally stable green persistent luminescence. Comprehensive characterization using X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS) confirmed the phase purity, morphology, and chemical states of the phosphor. The oxidation state and local coordination of Ga ions were further confirmed by synchrotron-based X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses. The incorporation of gallium ions (Ga<small><sup>3+</sup></small>) introduced defect states within the host lattice, as supported by density functional theory (DFT) calculations, revealing a defect-assisted mechanism responsible for the prolonged afterglow. Manganese ions (Mn<small><sup>2+</sup></small>) occupying tetrahedral coordination sites generated intense green emission, while Ga<small><sup>3+</sup></small> co-doping enhanced both the persistence duration and quantum efficiency without compromising colour purity or thermal stability. Thermoluminescence (TL) studies further validated the role of increased trap centers on Ga<small><sup>3+</sup></small> co-doping in enhancing the persistent luminescence. The optimized Li<small><sub>2</sub></small>ZnGeO<small><sub>4</sub></small>:10% Ga<small><sup>3+</sup></small>,0.25% Mn<small><sup>2+</sup></small> phosphor exhibited an exceptional afterglow lasting over 1800 seconds and demonstrated strong applicability in thermally stable and very bright green phosphor-converted light-emitting diodes (pc-LEDs). Overall, this work establishes a comprehensive co-doping and defect-engineering strategy, supported by synchrotron and theoretical insights, for developing next-generation, thermally stable persistent phosphors for advanced optoelectronic applications.defect states within the host lattice, as confirmed by synchrotron-based EXAFS and supported by DFT calculations, revealing a defect-assisted mechanism responsible for the long afterglow. Mn<small><sup>2+</sup></small> doping produced intense green emission, while Ga<small><sup>3+ </sup></small>co-doping enhanced both persistence duration and quantum efficiency without compromising color purity or stability. The optimized LZGGO:0.25%Mn<small><sup>2+</sup></small>phosphor displayed an exceptional afterglow exceeding 1800 seconds and demonstrated strong applicability in phosphor-converted LEDs. These findings establish a robust co-doping and defect-engineering approach for designing next-generation, thermally stable persistent phosphors for advanced opto
{"title":"Defect-Engineered Mn2+, Ga3+ Co-Doped Li2ZnGeO4 Phosphors Exhibiting Long-Lasting Green Luminescence for Advanced Optoelectronic Applications","authors":"Reshmi Thekke Parayil, Brindaban Modak, Sreevalsa Subhagan, Nitesh S. Kanojiya, Ashok Kumar Yadav, Subrata Das, Manoj Mohapatra, Santosh Kumar Gupta","doi":"10.1039/d5qi02251g","DOIUrl":"https://doi.org/10.1039/d5qi02251g","url":null,"abstract":"Persistent phosphors capable of long-lasting emission after excitation are crucial for emerging display, lighting, and sensing technologies. In this study, manganese and gallium co-doped lithium zinc germanate (Li<small><sub>2</sub></small>ZnGeO<small><sub>4</sub></small>) phosphors were synthesized via a high-temperature solid-state route, exhibiting bright and thermally stable green persistent luminescence. Comprehensive characterization using X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS) confirmed the phase purity, morphology, and chemical states of the phosphor. The oxidation state and local coordination of Ga ions were further confirmed by synchrotron-based X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses. The incorporation of gallium ions (Ga<small><sup>3+</sup></small>) introduced defect states within the host lattice, as supported by density functional theory (DFT) calculations, revealing a defect-assisted mechanism responsible for the prolonged afterglow. Manganese ions (Mn<small><sup>2+</sup></small>) occupying tetrahedral coordination sites generated intense green emission, while Ga<small><sup>3+</sup></small> co-doping enhanced both the persistence duration and quantum efficiency without compromising colour purity or thermal stability. Thermoluminescence (TL) studies further validated the role of increased trap centers on Ga<small><sup>3+</sup></small> co-doping in enhancing the persistent luminescence. The optimized Li<small><sub>2</sub></small>ZnGeO<small><sub>4</sub></small>:10% Ga<small><sup>3+</sup></small>,0.25% Mn<small><sup>2+</sup></small> phosphor exhibited an exceptional afterglow lasting over 1800 seconds and demonstrated strong applicability in thermally stable and very bright green phosphor-converted light-emitting diodes (pc-LEDs). Overall, this work establishes a comprehensive co-doping and defect-engineering strategy, supported by synchrotron and theoretical insights, for developing next-generation, thermally stable persistent phosphors for advanced optoelectronic applications.defect states within the host lattice, as confirmed by synchrotron-based EXAFS and supported by DFT calculations, revealing a defect-assisted mechanism responsible for the long afterglow. Mn<small><sup>2+</sup></small> doping produced intense green emission, while Ga<small><sup>3+ </sup></small>co-doping enhanced both persistence duration and quantum efficiency without compromising color purity or stability. The optimized LZGGO:0.25%Mn<small><sup>2+</sup></small>phosphor displayed an exceptional afterglow exceeding 1800 seconds and demonstrated strong applicability in phosphor-converted LEDs. These findings establish a robust co-doping and defect-engineering approach for designing next-generation, thermally stable persistent phosphors for advanced opto","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"81 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496505","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}
Jinlei Cui, Yuting Li, Da-Jiang Liu, Marco Mais, Jie Zhang, Long Qi, Aaron D Sadow, Takeshi Kobayashi
Zeolite-supported single-site lanthanum borohydride catalyzes C–H borylation of hydrocarbons while the related silica-supported complex is inactive under comparable conditions. The identical composition of support–La(BH4)2(THF)2 sites in the two materials implies that the support bestows underlying structural features onto La that are required for bond activation catalysis, yet the nature of those effects, which could include confinement effects and/or electronic modulation of the site itself, remain to be identified. We used solid-state nuclear magnetic resonance (SSNMR) spectroscopy and molecular dynamics simulations with machine-learning potentials (ML-MD) to analyze the electronic and steric effects imparted by the faujasite support on precatalyst structure to correlate with catalytic activity. DFT calculations show that THF dissociates from La under the influence of confinement, leading to coordinatively unsaturated sites in the zeolite pores. Then, the La complex grafts on Brønsted acid sites (LaBAS) or isolated silanols (LaSiO) or remains physisorbed in the zeolite pores. Catalytic studies comparing compounds supported on faujasite zeolites containing or lacking BAS and/or silanols show that only the former complexes lead to active sites, ruling out confinement as the sole requirement for catalysis. The DFT calculations and ML-MD simulations also reveal that the surface-lanthanum coordination number is two (bidentate) for LaBAS, with the metal center forming long, flexible bonds to two of the oxygen bridging Si and Al, but only one oxygen (monodentate) for LaSiO. The structure-activity relationship identifies confined, BAS-grafted species as active sites and provides important guidance for the design of enhanced atom-efficient catalysts.
{"title":"Solid-State NMR and Theoretical Studies Illuminate Lanthanum Borohydride C-H Borylation Catalysts Confined Within a Zeolite","authors":"Jinlei Cui, Yuting Li, Da-Jiang Liu, Marco Mais, Jie Zhang, Long Qi, Aaron D Sadow, Takeshi Kobayashi","doi":"10.1039/d5qi02586a","DOIUrl":"https://doi.org/10.1039/d5qi02586a","url":null,"abstract":"Zeolite-supported single-site lanthanum borohydride catalyzes C–H borylation of hydrocarbons while the related silica-supported complex is inactive under comparable conditions. The identical composition of support–La(BH<small><sub>4</sub></small>)<small><sub>2</sub></small>(THF)<small><sub>2</sub></small> sites in the two materials implies that the support bestows underlying structural features onto La that are required for bond activation catalysis, yet the nature of those effects, which could include confinement effects and/or electronic modulation of the site itself, remain to be identified. We used solid-state nuclear magnetic resonance (SSNMR) spectroscopy and molecular dynamics simulations with machine-learning potentials (ML-MD) to analyze the electronic and steric effects imparted by the faujasite support on precatalyst structure to correlate with catalytic activity. DFT calculations show that THF dissociates from La under the influence of confinement, leading to coordinatively unsaturated sites in the zeolite pores. Then, the La complex grafts on Brønsted acid sites (La<small><sup>BAS</sup></small>) or isolated silanols (La<small><sup>SiO</sup></small>) or remains physisorbed in the zeolite pores. Catalytic studies comparing compounds supported on faujasite zeolites containing or lacking BAS and/or silanols show that only the former complexes lead to active sites, ruling out confinement as the sole requirement for catalysis. The DFT calculations and ML-MD simulations also reveal that the surface-lanthanum coordination number is two (bidentate) for La<small><sup>BAS</sup></small>, with the metal center forming long, flexible bonds to two of the oxygen bridging Si and Al, but only one oxygen (monodentate) for La<small><sup>SiO</sup></small>. The structure-activity relationship identifies confined, BAS-grafted species as active sites and provides important guidance for the design of enhanced atom-efficient catalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"78 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492596","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}
Zengxin Lou, Kai Kang, Pingping Zhang, Qi Zhong, Yong Liu, Kaiqiang Liu, Wenzhuo Yuan, Yongchao Bao, Yongchao Bao, Juan Liu
Urea photosynthesis from CO₂ and nitrate presents a sustainable solution to mitigate carbon and nitrogen pollution. Nonetheless, simultaneously activating both substrates and directing selective C–N coupling remains challenging. In this study, we present the first construction of atomically coordinated Cu–Ti dual sites on a MXene-derived TiO₂/Ti₃C₂ heterostructure for direct urea synthesis. Asymmetric Cu–O–Ti dual sites are engineered by anchoring isolated Cu single atoms. HAADF-STEM and in-situ XPS/XAFS analyses confirm atomically dispersed Cu and light-induced, reversible Cu⁺/Cu²⁺ cycling. In-situ FTIR and DFT studies reveal that Cu sites convert CO2 to *CO, Ti sites catalyze the eight-electron nitrate reduction to *NH2, and the Cu-O-Ti bridge reduces the energy barrier for C-N coupling to urea intermediates, thereby suppressing CO and NH3 by-products. Under simulated sunlight, the optimized catalyst (0.5 wt% Cu) achieves a urea production rate of 11.57 μmol·gcat−1·h−1, which is 2.2 times higher than that of TiO2/Ti3C2, with excellent cycling stability. This MXene-enabled single-atom coordination strategy provides a general approach for renewable-energy-driven C-N coupling and pollutant valorization.
二氧化碳和硝酸盐的尿素光合作用是缓解碳和氮污染的可持续解决方案。然而，同时激活两种底物并指导选择性C-N偶联仍然具有挑战性。在这项研究中，我们首次在mxene衍生的TiO₂/Ti₃C₂异质结构上构建了原子配位的Cu-Ti双位点，用于直接合成尿素。不对称Cu - o - ti双位是通过锚定孤立的Cu单原子来设计的。HAADF-STEM和原位XPS/XAFS分析证实了原子分散的Cu和光诱导的、可逆的Cu + /Cu 2 +循环。原位FTIR和DFT研究表明，Cu位点将CO2转化为*CO， Ti位点催化8电子硝酸盐还原为*NH2， Cu- o -Ti桥降低了C-N偶联到尿素中间体的能垒，从而抑制了CO和NH3副产物。在模拟阳光下，优化后的催化剂（0.5 wt% Cu）的尿素产率为11.57 μmol·gcat−1·h−1，是TiO2/Ti3C2的2.2倍，且具有良好的循环稳定性。这种支持mxene的单原子配位策略为可再生能源驱动的碳氮耦合和污染物增值提供了一种通用方法。
{"title":"Atomically Anchored Cu on MXene-Derived TiO₂/Ti₃C₂ Enables Cu-Ti Dual Sites for Selective Urea Photosynthesis from CO₂ and Nitrate","authors":"Zengxin Lou, Kai Kang, Pingping Zhang, Qi Zhong, Yong Liu, Kaiqiang Liu, Wenzhuo Yuan, Yongchao Bao, Yongchao Bao, Juan Liu","doi":"10.1039/d6qi00180g","DOIUrl":"https://doi.org/10.1039/d6qi00180g","url":null,"abstract":"Urea photosynthesis from CO₂ and nitrate presents a sustainable solution to mitigate carbon and nitrogen pollution. Nonetheless, simultaneously activating both substrates and directing selective C–N coupling remains challenging. In this study, we present the first construction of atomically coordinated Cu–Ti dual sites on a MXene-derived TiO₂/Ti₃C₂ heterostructure for direct urea synthesis. Asymmetric Cu–O–Ti dual sites are engineered by anchoring isolated Cu single atoms. HAADF-STEM and in-situ XPS/XAFS analyses confirm atomically dispersed Cu and light-induced, reversible Cu⁺/Cu²⁺ cycling. In-situ FTIR and DFT studies reveal that Cu sites convert CO2 to *CO, Ti sites catalyze the eight-electron nitrate reduction to *NH2, and the Cu-O-Ti bridge reduces the energy barrier for C-N coupling to urea intermediates, thereby suppressing CO and NH3 by-products. Under simulated sunlight, the optimized catalyst (0.5 wt% Cu) achieves a urea production rate of 11.57 μmol·gcat−1·h−1, which is 2.2 times higher than that of TiO2/Ti3C2, with excellent cycling stability. This MXene-enabled single-atom coordination strategy provides a general approach for renewable-energy-driven C-N coupling and pollutant valorization.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"7 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489357","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 (NIR) phosphors constitute a significant class of luminescent materials for light-emitting diodes (LEDs). Recently, considerable research efforts in this active field have been devoted to the development of Cr3+-doped oxide, fluoride, and chloride phosphors for NIR luminescence emission, in which the unique d-d transition enables their tunable luminescence properties suitable for diverse LED applications such as plant growth lighting, bioimaging, night vision, non-destructive testing, and compositional analysis. This review article provides a comprehensive overview of recent advances in Cr3+-doped NIR phosphors, with emphasis on their detailed preparation methods, luminescence properties, and application potential in LED devices. Additionally, significant research challenges are outlined to guide the development of Cr3+-activated NIR phosphors, supported by a comprehensive list of representative references.
{"title":"Recent advances in Cr3+-doped near-infrared phosphors: preparation, luminescence, and LED applications","authors":"Qingmei Fan, Jing Wan, Zhengliang Wang, Zhong Lei, Chunyan Jiang, Qiang Zhou, Lei Zhou, Mingmei Wu","doi":"10.1039/d6qi00195e","DOIUrl":"https://doi.org/10.1039/d6qi00195e","url":null,"abstract":"Near-infrared (NIR) phosphors constitute a significant class of luminescent materials for light-emitting diodes (LEDs). Recently, considerable research efforts in this active field have been devoted to the development of Cr3+-doped oxide, fluoride, and chloride phosphors for NIR luminescence emission, in which the unique d-d transition enables their tunable luminescence properties suitable for diverse LED applications such as plant growth lighting, bioimaging, night vision, non-destructive testing, and compositional analysis. This review article provides a comprehensive overview of recent advances in Cr3+-doped NIR phosphors, with emphasis on their detailed preparation methods, luminescence properties, and application potential in LED devices. Additionally, significant research challenges are outlined to guide the development of Cr3+-activated NIR phosphors, supported by a comprehensive list of representative references.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"2 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478623","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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