Inorganic Chemistry Frontiers最新文献

{"title":"Carbon-coated W-doped NiMoN catalysts with enhanced antioxidant properties for robust water electrolysis under fluctuating electricity","authors":"Rufei Zhang, Hui Teng, Jinyuan Miao, Jianing Kang, Lili Zhou, Linting Cheng, Zhiqun Bai, Jianwen Zhang, Jia Liu, Yang Tang, Pingyu Wan","doi":"10.1039/d4qi03100h","DOIUrl":"https://doi.org/10.1039/d4qi03100h","url":null,"abstract":"For renewable energy-driven water electrolysis, developing low cost, highly active and durable electrocatalysts is essential. Here, we prepared a W-doped NiMoN microcolumn coated with a nitrogen doped carbon layer (W-NiMoN@NC) as an excellent non-precious electrocatalyst. This material displays excellent hydrogen evolution reaction (HER) activity with low overpotentials of 13 and 67 mV at 10 and 100 mA cm<small>⁻²</small>, outperforming commercial Pt/C. DFT calculations show that W doping optimizes the water dissociation and H* adsorption processes, improving HER activity. Additionally, W doping coupled with an ultrathin NC coating enhances the intrinsic anti-oxidation ability of NiMoN. After 100 cycles of harsh fluctuating electrolysis, the incremental overpotential of W-NiMoN@NC is only 8 mV at 1000 mA cm<small>⁻²</small>, significantly less than that of undoped NiMoN@NC (56 mV). The excellent anti-oxidation ability of W-NiMoN@NC resulting from its high reserves of Ni<small>⁰</small> was proved by XPS analysis after fluctuating electrolysis. This inside-out strategy endows W-NiMoN@NC with an exceptional feature of long-term durability under harsh fluctuating conditions and a promising potential for application in renewable energy-powered electrolysis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640078","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":"Machine Learning Assisted Design of Oxygen-containing Inorganic Coating Materials on Separator for Lithium Metal Anode","authors":"Chenxi Xu, Teng Zhao, Ji Qian, Ke Wang, Tianyang Yu, Wangming Tang, Li Li, Feng Wu, Renjie Chen","doi":"10.1039/d5qi00111k","DOIUrl":"https://doi.org/10.1039/d5qi00111k","url":null,"abstract":"The growth of lithium dendrites and its associated challenges pose significant obstacles to the widespread adoption of lithium metal. Although numerous inorganic materials offer the potential for stabilizing lithium metal anodes, the trial-error experiments are time-consuming and cost-intensive. In this work, firstly, a high-throughput screening workflow embedded with machine learning and calculation has been used to identify possible materials, which incorporates several key indicators encompassing electronic conductivity, phase stability, mechanical properties, chemical stability, and lithium-ion transport performance. Four materials were used for experiment, and both characterization and electrochemical test results show that HfO2@PP exhibits the best performance, which has the highest Young's modulus, and the Li||Li symmetry cell assembled at 1 mA cm-2, 1 mAh cm-2 can have a stable cycle of over 1000h, and the assembled Li||LFP cell has a capacity retention rate of more than 90% and an average coulombic efficiency of 99.7% after 200 cycles at 1C. This work provides a design method and ideas for Inorganic coating materials on a separator for lithium metal anode.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"43 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640004","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":"Fluorescence of europium from absence to emergence in cadmium-induced heterobimetallic organic frameworks for ratiometric sensing","authors":"Meiling Li, Weiting Yang, Shui-Xing Wu, Zhong-Min Su, Qinhe Pan","doi":"10.1039/d5qi00365b","DOIUrl":"https://doi.org/10.1039/d5qi00365b","url":null,"abstract":"Lanthanide-organic frameworks (Ln-MOFs) have garnered increasing research interest as photoluminescent materials. However, the characteristic fluorescence of Ln3+ ions is constrained by the energy level matching between Ln3+ ions and organic ligands, and the impact of the spatial structure of Ln-MOFs on the energy transfer process remains insufficiently explored, thereby limiting their broader optical applications. In this work, we propose a Cd2+-induced heterobimetallic Ln-MOF (HNU-72) as a fluorescence modulation strategy, marking a significant breakthrough in activating the characteristic fluorescence of Ln3+ ions, transitioning from absence to emergence. Both experimental measurements and theoretical calculations reveal that the incorporation Cd2+ ion reconfigures the energy transfer pathway, thereby enhancing the energy transfer modulation between H4TCPE (1, 1, 2, 2-tetri (4-carboxyphenyl) ethylene) and Eu3+ ion. Furthermore, leveraging the dual fluorescence emission peaks observed in HNU-72, we achieve an ultra-low detection limit of 14 ppb for the proportional fluorescence detection of dimethyl sulfide in marine environments. This study not only deepens our understanding of the energy transfer mechanisms in Ln-MOF materials but also paves the way for the development of multifunctional fluorescence sensing platforms.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"124 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640076","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":"Efficient screening rooted in a series of transition-metal atom anchored conjugated organic frameworks toward multifunctional HER/OER/ORR via modification of chalcogen ligands: a machine learning and constant potential study","authors":"Xiaomeng Cui, Yuanrui Li, Qiang Zhang, Xihang Zhang, Weiju Hao, Yuling Song, Renxian Qin, Yali Lu","doi":"10.1039/d5qi00061k","DOIUrl":"https://doi.org/10.1039/d5qi00061k","url":null,"abstract":"The pursuit of two-dimensional single-atom catalysts (SACs) holds far-reaching significance for advancing energy conversion and storage technologies by providing efficient, stable, and low-cost alternatives to precious metals for hydrogen evolution (HER), oxygen evolution (OER), and oxygen reduction reactions (ORR). The synergy between the tunable ligands, abundant transition metal active sites, and diverse substrate materials opens new avenues for realizing both stability and enhanced catalytic activity. This study presents a thorough examination of the catalytic HER/OER/ORR activities in 161 TM@C<small>₁₅</small>N<small>₆</small>XY<small>₂</small>H<small>₅</small> SACs, combing density functional theory with machine learning. Thirteen configurations were identified, comprising 11 single-function OER/ORR catalysts, a bifunctional OER/ORR catalyst Cu@C<small>₁₅</small>N<small>₆</small>O<small>₃</small>H<small>₅</small>, and notably, Au@C<small>₁₅</small>N<small>₆</small>OS<small>₂</small>H<small>₅</small> , which demonstrates trifunctional HER/OER/ORR catalytic activity. A pronounced hybridization between Cu/Au-<em>d</em> orbitals and O-<em>p</em> orbitals of oxygenated adsorbates directs lone electrons to antibonding states before transitioning to bonding orbitals, enabling efficient adsorption of oxygenated intermediates on the surface. The data obtained through ML applications indicate that the atomic radius ( <em>r</em><small>_TM</small>) and electronegativity ( <em>χ</em>) of TM are the primary descriptors for HER activity, while the d-electron count (<em>θ</em>) and atomic radius (<em>r</em><small>_TM</small>) of the atoms are the key descriptors for OER/ORR activities. Utilizing SISSO method, a clear and robust correlation between intrinsic properties and adsorption energy was derived, realizing each-step prediction. Additionally, the constant-potential model shows that electric double-layer capacitance modulates the reaction barrier, meanwhile, pH- and voltage-dependent adsorption free energies indicate that acidic and alkaline conditions (pH 5.3/9.9, Cu@C<small>₁₅</small>N<small>₆</small>O<small>₃</small>H<small>₅</small>/Au@C<small>₁₅</small>N<small>₆</small>OS<small>₂</small>H<small>₅</small> ) enhance OER efficiency, while pH 0 is optimal for ORR.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"69 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640079","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":"Distortable functionalized ligand implantation in ultra-microporous MOFs for efficient C2H2 purification","authors":"Hong-Juan Lv, Yun-Hui Zhai, Ying-Ying Xue, Jiao Lei, Wenyu Yuan, Quan-Guo Zhai","doi":"10.1039/d5qi00475f","DOIUrl":"https://doi.org/10.1039/d5qi00475f","url":null,"abstract":"Adsorption-based separation techniques are pivotal in the purification of C2H2, leveraging their eco-friendly and energy-efficient attributes. However, the reusability of adsorbents is highly restricted by the trade-off between adsorption capacity and adsorption enthalpy, which is required to be urgently addressed. Herein, we demonstrated that implantation of distortable ligands with functional groups is efficient to solve the above issue. The functional groups provided binding sites for C2H2 adsorption, while the distortable ligands optimized the pore structures to reduce adsorption enthalpy, thus balancing the trade-off between adsorption capacity and enthalpy. A series of ultra-microporous MOFs was successfully constructed via employing different pyridine ligands. The adsorption capacity was effectively enhanced, while the adsorption enthalpy nearly have not been increased due to the adjustable ligand torsion angle. Breakthrough experiments and GCMC simulations further verified the potential C2H2/CO2 separation applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"212 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640193","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":"Achieving High Performance Ultra-Broadband Near-infrared Emission through Multi-site Occupancy and Energy Transfer Strategy for NIR LED Applications","authors":"Mingkai Wei, Zixi Chen, Yongying Chen, Xinxiang Liang, Na Li, Xuejie Zhang, Wei Li, Haoran Zhang, Maxim S. Molokeev, Bingfu Lei","doi":"10.1039/d5qi00215j","DOIUrl":"https://doi.org/10.1039/d5qi00215j","url":null,"abstract":"Broadband near-infrared (NIR) phosphor-converted light-emitting diodes (pc-LEDs) are considered to be at the forefront of the development of next-generation NIR light sources. However, the performance of NIR pc-LEDs is severely limited due to the narrow band emission, low quantum efficiency, and thermal quenching of NIR-emitting materials. Herein, an efficient and thermally stable broadband NIR LaMgGa11O19:Cr3+,Yb3+ (LMG:Cr3+,Yb3+) phosphor has been successfully designed by [Cr3+-Yb3+] co-doping. The broadband emission phenomenon of LaMgGa11O19:Cr3+ was confirmed to be due to selective lattice occupancy of Cr3+ ions based on the analysis of crystal structures, crystal field calculations, and fluorescence lifetimes. The NIR emission spectra in the range of 1000-1200 nm were enriched by using the highly efficient energy transfer of Cr3+→Yb3+ ions and the detailed the energy transfer mechanism is discussed in detail. The prepared LMG:Cr3+,Yb3+ phosphors exhibit highly efficient ultra-broadband NIR emission from 650 to 1200 nm under 440 nm excitation with high internal and external quantum efficiencies of 94.2%/40.5% and excellent luminescence thermal stability of 89.3%@373 K. A NIR pc-LED prototype was fabricated by combining the optimized phosphor with a commercial 440 nm blue LED chip, providing 84.5 mW NIR output power at 350 mA driven current. Finally, the potential applications of the phosphor in night vision lighting and non-destructive testing were demonstrated. The results show that this work is expected to provide a new strategy for efficient ultra-broadband NIR phosphor design.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640077","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":"Facilitated gallium incorporation in blue-emitting In1-xGaxP alloy quantum dots via monomeric gallium precursors","authors":"Taewan Kim, Se-Yup Kim, Sooho Lee, Ji-Sang Park, Hyeonjun Lee, Doh C. Lee","doi":"10.1039/d5qi00302d","DOIUrl":"https://doi.org/10.1039/d5qi00302d","url":null,"abstract":"Demand for environmentally friendly quantum dots (QDs) in wide color-gamut displays has led to successful development of red- and green-emitting InP QDs with outstanding optical properties. While progress in developing blue-emitting variants remains challenging, In1-xGaxP alloy QDs have recently garnered attention as blue emitters. However, Ga incorporation in these In1-xGaxP QDs is hindered by the limited reactivity of conventional gallium halide-derived precursors having a dimeric molecular structure. Here, we adopt trimethylgallium which yields monomeric gallium carboxylates as a Ga precursor in the colloidal synthesis of In1-xGaxP QDs. This approach promotes efficient Ga incorporation into In1-xGaxP QDs with narrow size distributions. The use of zinc chloride and oleylamine for ZnS shell growth on the In1-xGaxP cores further adjusts the photoluminescence (PL) wavelength to the blue range and enhances PL quantum yield. The resulting In1-xGaxP/ZnS core/shell QDs exhibit a peak emission at 470 nm, 67% of photoluminescence quantum yield, and 40 nm of emission linewidth. Successful employment of these QDs into light-emitting diodes demonstrates their potential as a blue electroluminescent emitter for future QD displays.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"69 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640003","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":"Crystallization-controlled microstructure of titanium species in TS-1 zeolite for tailored catalytic performance","authors":"Siqi Chen, Jingxuan Wang, Tianjun Zhang, Risheng Bai","doi":"10.1039/d5qi00403a","DOIUrl":"https://doi.org/10.1039/d5qi00403a","url":null,"abstract":"TS-1 zeolite, celebrated for its superior catalytic performance in selective oxidation reactions, presents a significant challenge in optimizing the microstructure of its titanium active sites to maximize efficiency for specific applications. In this study, we successfully manipulated the microstructure of titanium species within TS-1 by kinetically controlling the crystallization process, thereby achieving the formation of poly-hexacoordinated Ti species in the initial amorphous titanosilicate phase and the construction of framework TiO₄ species in fully crystallized TS-1 zeolite. Notably, the amorphous titanosilicate catalyst exhibited high efficiency in the oxidative desulfurization of dibenzothiophene, while showing negligible activity in 1-hexene epoxidation. Conversely, the crystalline TS-1 catalyst demonstrated outstanding performance in alkene epoxidation but limited efficacy in oxidative desulfurization. This study outlines a controlled crystallization process that allows precise tuning of zeolite active sites, thereby enhancing their catalytic effectiveness for targeted applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"33 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635306","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":"Conducting oxide surface engineering enables growth of low-defect carbon nitride film for unbiased photoelectrochemical water splitting","authors":"Suqin Wu, Wenjie Deng, Chen Lai, Fengmei Zhi, Shuai Xiong, Shubin Xiong, Mao He, Menny Shalom, Guiming Peng","doi":"10.1039/d5qi00428d","DOIUrl":"https://doi.org/10.1039/d5qi00428d","url":null,"abstract":"The favorable crystal surface exposure of substrate benefits the growth of semiconductor film with strong adhesion and fast charge transfer at the interface. Herein, exposure of (211) of SnO2:F (FTO) by surface etching led to uniform synthesis of crystalline carbon nitride (CN) film. The as-synthesized CN film shows preferable electron transfer from CN to FTO, low structural defects, and excellent charge separation and transport. It produces the state-of-art photovoltage of 0.64 V. Photoelectrochemical (PEC) water splitting investigation demonstrated excellent performance with low water oxidation onset potential of 0.22 V vs RHE, as well as impressive unbiased photocurrent of 12.4 μA cm-2. Cocatalyst of NiCo-LDH led to high photocurrent of 440 μA cm-2 in triethanolamine containing electrolyte, with H2 yield of 40.9 mmol m-2 h-1 and IPCE (400 nm) of 26.7%. This work demonstrates a good example for growth of high-quality CN film with high PEC performance enabled by substrate surface engineering, which would also expand CN film’s other applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"24 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635135","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":"Regulation of solid-electrolyte interphases formation via Li3PO4 artificial layer for ultra-stable germanium anodes","authors":"Haifeng Yan, Kun Chao, Zhonghua Zhang, Zhenfang Zhou, Yuanming Li, Xuguang Liu, Jing Liu, Xiaosong Guo, Changming Mao, Guicun Li","doi":"10.1039/d4qi03038a","DOIUrl":"https://doi.org/10.1039/d4qi03038a","url":null,"abstract":"Germanium (Ge) emerges as a promising candidate anode for building high energy density and fast-charging lithium-ion batteries. However, detrimental Ge particle pulverization caused by volume changes needs to be resolved. In this work, an artificial Li3PO4/C layer has been successfully developed on Ge anode to protect it from pulverization. Through a simple impregnation and subsequent annealing method, the lithiated phytate (PL) simultaneously converts to Li3PO4 and carbon composite coating layer. Theoretical calculations reveal that Li3PO4 can specifically adsorb fluoroethylene carbonate (FEC), which subsequently induces the formation of LiF-rich SEIs as demonstrated by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) analyses. In-situ X-ray diffraction (XRD) results also demonstrate a highly reversible alloying and de-alloying process for Li3PO4/C modified Ge anode. As a result, the as-designed Ge anode shows a high specific reversible capacity (1256 mAh g−1), excellent capacity retention (more than 96% of the reversible capacity is retained from the 2nd to the 600th cycle), and ultra-high-rate performance (more than 1200 mAh g−1 at 5.0 A g−1), which outperforms previous results. This work provides a guide to the interfacial design for alloy-type anodes for next-generation battery applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"33 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635136","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}