Jiashuo Wang, Linkai Guo, Chang Liu, Kun Li, Yurong Ren, Huilong Dong, Zhidong Chen, Changhai Liu
P2-Na₀.₆₇Ni₀.₃₃Mn₀.₆₇O₂ has emerged as a promising cathode material for sodiumion batteries due to its high theoretical specific capacity and excellent air stability. However, this material suffers from two critical bottlenecks: first, it is prone to undergo an irreversible oxygen evolution reaction at a voltage of 4.2 V; second, it experiences significant specific capacity fade under high current density conditions. This work addresses these issues by using a solid-state reaction method to fabricate the Na 0.66 Sr 0.01 Ni 0.32 Li 0.01 Mn 0.67 O 2 material via codoping modification with trace amounts of Li and Sr. The research results demonstrate that the Li and Sr co-doped material exhibits significantly enhanced spatial structural stability at high voltages and effectively suppresses the P2-O2 phase transition. The modified material shows superior rate capability (delivering a reversible specific capacity of 62 mA h g⁻¹ at 20 C) and cycling stability (achieving a capacity retention of 87% after 1000 cycles at 10 C). In summary, this Li/Sr synergistic doping strategy provides an effective and straightforward approach for designing layered oxide cathode materials that combine high rate capability with long cycling stability.
P2-Na₀。₆₇倪₀。₃₃Mn₀。₆₇O₂因其较高的理论比容量和优异的空气稳定性，成为一种很有前途的钠电池正极材料。然而，这种材料有两个关键的瓶颈：首先，它容易在4.2 V的电压下发生不可逆的析氧反应；其次，在高电流密度条件下，它会经历显著的比容量衰减。本文采用固相反应方法，通过微量Li和Sr共掺杂改性制备了Na 0.66 Sr 0.01 Ni 0.32 Li 0.01 Mn 0.67 o2材料。研究结果表明，Li和Sr共掺杂材料在高电压下具有显著增强的空间结构稳定性，并有效抑制了P2-O2相变。改性后的材料显示出优越的速率能力（在20℃下提供62毫安时的可逆比容量）和循环稳定性（在10℃下循环1000次后容量保持87%）。总之，这种Li/Sr协同掺杂策略为设计高倍率性能和长循环稳定性相结合的层状氧化物正极材料提供了一种有效而直接的方法。
{"title":"Unveiling Li-/Sr-induced reinforced transition metal-oxygen in P2-type layered oxide cathode for highly stable sodium-ion batteries","authors":"Jiashuo Wang, Linkai Guo, Chang Liu, Kun Li, Yurong Ren, Huilong Dong, Zhidong Chen, Changhai Liu","doi":"10.1039/d5qi02610e","DOIUrl":"https://doi.org/10.1039/d5qi02610e","url":null,"abstract":"P2-Na₀.₆₇Ni₀.₃₃Mn₀.₆₇O₂ has emerged as a promising cathode material for sodiumion batteries due to its high theoretical specific capacity and excellent air stability. However, this material suffers from two critical bottlenecks: first, it is prone to undergo an irreversible oxygen evolution reaction at a voltage of 4.2 V; second, it experiences significant specific capacity fade under high current density conditions. This work addresses these issues by using a solid-state reaction method to fabricate the Na 0.66 Sr 0.01 Ni 0.32 Li 0.01 Mn 0.67 O 2 material via codoping modification with trace amounts of Li and Sr. The research results demonstrate that the Li and Sr co-doped material exhibits significantly enhanced spatial structural stability at high voltages and effectively suppresses the P2-O2 phase transition. The modified material shows superior rate capability (delivering a reversible specific capacity of 62 mA h g⁻¹ at 20 C) and cycling stability (achieving a capacity retention of 87% after 1000 cycles at 10 C). In summary, this Li/Sr synergistic doping strategy provides an effective and straightforward approach for designing layered oxide cathode materials that combine high rate capability with long cycling stability.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"7 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147393515","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}
Marcin Kaźmierczak, Vladyslav Maliuzhenko, Aleksandra Tołoczko, Marek Weselski, Miłosz Siczek, Juliusz Wolny, Volker Schünemann, Robert Bronisz
6-(1,2,3-triazol-1-ylmethyl)coumarin (L1), able to combine in Fe(II) complex a molecule photoreactivity and a spin crossover activity, was prepared in the reaction of 6-(bromomethyl)coumarin with sodium salt of 1,2,3-triazole. L1 forms mononuclear systems [Fe(L1)6](ClO4)2·nCH3CN (n = 0, 2). Solvated form (1) exhibits complete, one step spin crossover at T1/2 = 155 K. In 1 there is a competition between two coumarin fragments from two ligands molecules for an access to a third one located between them. Distances between double bonds of lactone rings are equal to 3.70 and 3.92 Å and irradiation with a light of wavelength 365 nm results in [2+2] cycloaddition. Due to the competition photoconversion occurrs in two directions and results in two dimensional polymeric layer of frustrated topology. The resulted complex (1c) also exhibits spin crossover, shifted to slightly lower temperatures (T1/2 = 141 K). The non-solvated complex (2) exhibits two-step spin crossover (T11/2 = 83 K, T21/2 = 62 K). In contrast to 1, there exists only one type of ligands pair for which topochemical requirements are fulfilled. In effect a regular (2,2) polymeric layer is formed as a result of [2+2] photocycloaddition (λ = 365 nm). It results in an unprecedented shift of spin crossover to higher temperatures up to 197 K. The product of the photoconversion (2c) is characterized by a presence of strong strains involving dimerized ligand molecules, particularly cyclobutane rings. The DFT modelling based on the structure of the dimerized ligand reveals a significant difference in this strain, the energetic effect of it (stress) being more than 240 kJmol-1 higher for the ligands corresponding to the complex in the HS state in line with the observed 114 K shift of transition temperature on going from the initial mononuclear complex to the 2D structure of the photoconverted one.
{"title":"[2+2] photocycloaddition induces 114 K high-temperature shift of spin crossover transition - the role of the cycloaddition induced strain","authors":"Marcin Kaźmierczak, Vladyslav Maliuzhenko, Aleksandra Tołoczko, Marek Weselski, Miłosz Siczek, Juliusz Wolny, Volker Schünemann, Robert Bronisz","doi":"10.1039/d5qi02305j","DOIUrl":"https://doi.org/10.1039/d5qi02305j","url":null,"abstract":"6-(1,2,3-triazol-1-ylmethyl)coumarin (L1), able to combine in Fe(II) complex a molecule photoreactivity and a spin crossover activity, was prepared in the reaction of 6-(bromomethyl)coumarin with sodium salt of 1,2,3-triazole. L1 forms mononuclear systems [Fe(L1)<small><sub>6</sub></small>](ClO<small><sub>4</sub></small>)<small><sub>2</sub></small>·nCH<small><sub>3</sub></small>CN (n = 0, 2). Solvated form (1) exhibits complete, one step spin crossover at T<small><sub>1/2</sub></small> = 155 K. In 1 there is a competition between two coumarin fragments from two ligands molecules for an access to a third one located between them. Distances between double bonds of lactone rings are equal to 3.70 and 3.92 Å and irradiation with a light of wavelength 365 nm results in [2+2] cycloaddition. Due to the competition photoconversion occurrs in two directions and results in two dimensional polymeric layer of frustrated topology. The resulted complex (1c) also exhibits spin crossover, shifted to slightly lower temperatures (T<small><sub>1/2</sub></small> = 141 K). The non-solvated complex (2) exhibits two-step spin crossover (T<small><sup>1</sup></small><small><sub>1/2</sub></small> = 83 K, T<small><sup>2</sup></small><small><sub>1/2</sub></small> = 62 K). In contrast to 1, there exists only one type of ligands pair for which topochemical requirements are fulfilled. In effect a regular (2,2) polymeric layer is formed as a result of [2+2] photocycloaddition (λ = 365 nm). It results in an unprecedented shift of spin crossover to higher temperatures up to 197 K. The product of the photoconversion (2c) is characterized by a presence of strong strains involving dimerized ligand molecules, particularly cyclobutane rings. The DFT modelling based on the structure of the dimerized ligand reveals a significant difference in this strain, the energetic effect of it (stress) being more than 240 kJmol<small><sup>-1</sup></small> higher for the ligands corresponding to the complex in the HS state in line with the observed 114 K shift of transition temperature on going from the initial mononuclear complex to the 2D structure of the photoconverted one.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"71 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383884","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}
Driven by the growing global demand for public safety and environmental protection, there is an urgent need to develop efficient and accurate methods for detecting trace explosives such as 2,4,6-trinitrophenol (TNP). This study presents a fluorescence-enhanced sensing platform leveraging the intrinsic slow-light effect in covalent organic framework photonic crystals (COF PhCs). This strategy overcomes the low porosity limitations of polymer-based PhCs and significantly improves the detection sensitivity of fluorescent poly(tannic acid) nanoparticles (FPTA NPs), enabling selective and environmentally benign monitoring of TNP. Specifically, three-dimensional COF PhCs were fabricated via evaporation-induced self-assembly, with their diffraction wavelengths meticulously aligned with the emission profiles of fluorescent FPTA NPs. Experimental results reveal that the PL signal exhibit a remarkable enhancement by a factor of up to 10.34 when the blue edge of the photonic band gap was aligned with the emission peak of the FPTA NPs. Furthermore, the imine-based conformationally locked polymers facilitate efficient accumulation of TNP molecules through strong intermolecular interactions, thereby significantly enhancing the sensitivity for trace TNP detection and achieving a detection limit as low as 20.7 nM. This research underscores the considerable potential of PhCs for enhancing luminescence signals to enable sensitive detection of trace environmental pollutants.
{"title":"A Fluorescence Sensor Utilizing 3D COF Photonic Crystals for Enhanced Detection of TNP","authors":"Ledi Zhang, Yuji Zhou, Wenxiang Zheng, Zihui Meng, Yongjie Zhao, Lili Qiu","doi":"10.1039/d6qi00127k","DOIUrl":"https://doi.org/10.1039/d6qi00127k","url":null,"abstract":"Driven by the growing global demand for public safety and environmental protection, there is an urgent need to develop efficient and accurate methods for detecting trace explosives such as 2,4,6-trinitrophenol (TNP). This study presents a fluorescence-enhanced sensing platform leveraging the intrinsic slow-light effect in covalent organic framework photonic crystals (COF PhCs). This strategy overcomes the low porosity limitations of polymer-based PhCs and significantly improves the detection sensitivity of fluorescent poly(tannic acid) nanoparticles (FPTA NPs), enabling selective and environmentally benign monitoring of TNP. Specifically, three-dimensional COF PhCs were fabricated via evaporation-induced self-assembly, with their diffraction wavelengths meticulously aligned with the emission profiles of fluorescent FPTA NPs. Experimental results reveal that the PL signal exhibit a remarkable enhancement by a factor of up to 10.34 when the blue edge of the photonic band gap was aligned with the emission peak of the FPTA NPs. Furthermore, the imine-based conformationally locked polymers facilitate efficient accumulation of TNP molecules through strong intermolecular interactions, thereby significantly enhancing the sensitivity for trace TNP detection and achieving a detection limit as low as 20.7 nM. This research underscores the considerable potential of PhCs for enhancing luminescence signals to enable sensitive detection of trace environmental pollutants.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"25 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147384170","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 study, a novel nitrogen-doped carbon-based copper nanozyme (Cu–N/C) was constructed via an in situ derivatization of designed copper complexes, which shows excellent laccase-like catalytic activity. In it, a copper complex was synthesized using copper chloride dihydrate and 1,10-phenanthroline as the precursors, and then a controlled pyrolysis strategy was conducted to obtain the nitrogen-doped carbon-based composites with atomically dispersed copper active sites. These isolated copper sites are anchored within the nitrogen-doped carbon framework, providing an effective catalytic center that mimics natural laccase. In the catalytic process, the Cu–N/C nanozyme exhibits better substrate affinity and faster catalytic rates in comparison with other laccase mimics. The catalytic mechanism studies demonstrate that the Cu–N/C nanozyme directly drives the substrate oxidation by using activating oxygen molecules, and the reaction path is similar to that of natural laccase. These Cu–N/C nanozymes maintain satisfactory catalytic activity at high temperatures and across a wide pH range, and can also be used in high-salt environments, thereby overcoming the operation limitations of biological laccase. Based on that, we have developed a smartphone-assisted portable colorimetric sensing platform to achieve a rapid visual detection of phenolic contaminants in the water. More interestingly, these Cu–N/C nanozymes can also efficiently degrade dye contaminants, with a decolorization rate of more than 75% within 40 min. The work highlights a ‘coordination–pyrolysis’ strategy as an effective way to design a biomimetic nanozyme with tunable active sites, and its stable catalytic performance provides a feasible solution to environmental detection and pollutant degradation.
{"title":"Multifunctional copper–nitrogen/carbon laccase-mimicking nanozyme for colorimetric sensing of phenolic compounds and degradation of organic pollutants","authors":"Xu Liu, Hongtian Yang, Yide Han, Yufeng Liu, Ying Zhang, Wenhao Li, Xia Zhang","doi":"10.1039/d5qi02310f","DOIUrl":"https://doi.org/10.1039/d5qi02310f","url":null,"abstract":"In this study, a novel nitrogen-doped carbon-based copper nanozyme (Cu–N/C) was constructed <em>via</em> an <em>in situ</em> derivatization of designed copper complexes, which shows excellent laccase-like catalytic activity. In it, a copper complex was synthesized using copper chloride dihydrate and 1,10-phenanthroline as the precursors, and then a controlled pyrolysis strategy was conducted to obtain the nitrogen-doped carbon-based composites with atomically dispersed copper active sites. These isolated copper sites are anchored within the nitrogen-doped carbon framework, providing an effective catalytic center that mimics natural laccase. In the catalytic process, the Cu–N/C nanozyme exhibits better substrate affinity and faster catalytic rates in comparison with other laccase mimics. The catalytic mechanism studies demonstrate that the Cu–N/C nanozyme directly drives the substrate oxidation by using activating oxygen molecules, and the reaction path is similar to that of natural laccase. These Cu–N/C nanozymes maintain satisfactory catalytic activity at high temperatures and across a wide pH range, and can also be used in high-salt environments, thereby overcoming the operation limitations of biological laccase. Based on that, we have developed a smartphone-assisted portable colorimetric sensing platform to achieve a rapid visual detection of phenolic contaminants in the water. More interestingly, these Cu–N/C nanozymes can also efficiently degrade dye contaminants, with a decolorization rate of more than 75% within 40 min. The work highlights a ‘coordination–pyrolysis’ strategy as an effective way to design a biomimetic nanozyme with tunable active sites, and its stable catalytic performance provides a feasible solution to environmental detection and pollutant degradation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"72 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147361127","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}
Transition metal oxides are promising materials for electrochemical energy storage, but they still have the problem of volume change during electrochemical processes. Through the reasonable design of the microstructure of materials, the stress caused by electrode materials during the electron transmission process can be alleviated. This study successfully synthesized MnMoO4 with a yolk–shell structure using a novel self-templating method. A systematic investigation of the precursor metal ratio (Mn : Mo) and annealing temperature revealed their critical influence on the formation of the yolk–shell structure and the resulting electrochemical performance. When used as a supercapacitor electrode material, MMA-500 delivers a high specific capacitance of 361 F g−1 at a current density of 0.5 A g−1. Additionally, the assembled MMA-500//AC asymmetric supercapacitor showed outstanding cycling stability, maintaining 81.14% capacitance retention after 9000 cycles. This performance surpasses that of most reported MnMoO4-based cathode materials. Our findings provide robust experimental evidence and valuable insights into optimizing the electrochemical performance of yolk–shell structured binary transition metal oxides for energy storage applications.
过渡金属氧化物是一种很有前途的电化学储能材料，但在电化学过程中仍存在体积变化的问题。通过对材料微观结构的合理设计，可以缓解电子传输过程中电极材料产生的应力。本研究利用一种新颖的自模板方法成功合成了具有蛋黄壳结构的MnMoO4。对前驱体金属比例（Mn: Mo）和退火温度的系统研究揭示了它们对蛋黄壳结构的形成和由此产生的电化学性能的关键影响。当用作超级电容器电极材料时，MMA-500在0.5 a g−1的电流密度下提供361 F g−1的高比电容。此外，组装的MMA-500//AC非对称超级电容器具有出色的循环稳定性，在9000次循环后保持81.14%的电容保持率。这一性能超过了大多数报道的基于mnmoo4的正极材料。我们的研究结果为优化用于储能应用的蛋黄壳结构二元过渡金属氧化物的电化学性能提供了强有力的实验证据和有价值的见解。
{"title":"Rational construction of 3D hierarchical yolk–shell MnMoO4 micro/nanospheres for electrochemical energy storage","authors":"Yaxun Hu, Songtao Zhang, Xingyu Huang, Jinfeng Wang, Chenlu Zhao, Weifeng Peng, Xiaotian Guo, Guangxun Zhang, Yecan Pi, Tian Tian, Yi Xu, Huan Pang","doi":"10.1039/d5qi02325d","DOIUrl":"https://doi.org/10.1039/d5qi02325d","url":null,"abstract":"Transition metal oxides are promising materials for electrochemical energy storage, but they still have the problem of volume change during electrochemical processes. Through the reasonable design of the microstructure of materials, the stress caused by electrode materials during the electron transmission process can be alleviated. This study successfully synthesized MnMoO<small><sub>4</sub></small> with a yolk–shell structure using a novel self-templating method. A systematic investigation of the precursor metal ratio (Mn : Mo) and annealing temperature revealed their critical influence on the formation of the yolk–shell structure and the resulting electrochemical performance. When used as a supercapacitor electrode material, MMA-500 delivers a high specific capacitance of 361 F g<small><sup>−1</sup></small> at a current density of 0.5 A g<small><sup>−1</sup></small>. Additionally, the assembled MMA-500//AC asymmetric supercapacitor showed outstanding cycling stability, maintaining 81.14% capacitance retention after 9000 cycles. This performance surpasses that of most reported MnMoO<small><sub>4</sub></small>-based cathode materials. Our findings provide robust experimental evidence and valuable insights into optimizing the electrochemical performance of yolk–shell structured binary transition metal oxides for energy storage applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358905","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}
PVDF-based polymer electrolyte has been widely studied because of its good mechanical strength, easy processing, excellent thermal/chemical stability. However, pure PVDF has the problems of low ionic conductivity and insufficient interface stability with the electrodes. Herein, this research presents a facile strategy for fabricating Ce-MOF-derived rodlike nanocrystalline CeO2 to incorporate composite polymer electrolytes for Li-metal batteries. The CeO2-PVDF-HFP composite polymer electrolytes (CPEs) could achieve enhanced ionic conductivity and interfacial stability.Notably, the ultrasmall nanocrystalline CeO2-PVDF-HFP CPEs demonstrates superior Li⁺ transport kinetics (5.04×10⁻⁴ S cm⁻¹), lithium dendrite suppression and an extended electrochemical stability window up to 4.6 V. When applied in Li| LiMn0.6Fe0.4PO4 full batteries, the quasi-solid polymer electrolyte system could maintain a discharge capacity of 94 mAh g⁻¹ after 100 cycles at 0.5 C, deliver good cycling stability and rate capability retaining 99% capacity after prolonged 500 circles at 1 C. These advancements highlight special functional nanocrystalline fillers improve the performance of PVDF-based polymer electrolyte, offering a promising pathway for developing reliable solid-state lithium metal batteries.
{"title":"Ultrasmall nanocrystalline CeO2 Fillers Improving the Performance of PVDF-based Polymer Electrolytes for Lithium Metal Batteries","authors":"Zikang Ruan, Xianhe Meng, Tingting Jiang, Nengjun Yu, Yufei Gong, Xiaoyu Hu, Anchun Tang, Qiaoling Kang, Lijing Yan, Chubin Wan","doi":"10.1039/d6qi00187d","DOIUrl":"https://doi.org/10.1039/d6qi00187d","url":null,"abstract":"PVDF-based polymer electrolyte has been widely studied because of its good mechanical strength, easy processing, excellent thermal/chemical stability. However, pure PVDF has the problems of low ionic conductivity and insufficient interface stability with the electrodes. Herein, this research presents a facile strategy for fabricating Ce-MOF-derived rodlike nanocrystalline CeO2 to incorporate composite polymer electrolytes for Li-metal batteries. The CeO2-PVDF-HFP composite polymer electrolytes (CPEs) could achieve enhanced ionic conductivity and interfacial stability.Notably, the ultrasmall nanocrystalline CeO2-PVDF-HFP CPEs demonstrates superior Li⁺ transport kinetics (5.04×10⁻⁴ S cm⁻¹), lithium dendrite suppression and an extended electrochemical stability window up to 4.6 V. When applied in Li| LiMn0.6Fe0.4PO4 full batteries, the quasi-solid polymer electrolyte system could maintain a discharge capacity of 94 mAh g⁻¹ after 100 cycles at 0.5 C, deliver good cycling stability and rate capability retaining 99% capacity after prolonged 500 circles at 1 C. These advancements highlight special functional nanocrystalline fillers improve the performance of PVDF-based polymer electrolyte, offering a promising pathway for developing reliable solid-state lithium metal batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147361129","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}
Dongbo Xu, Song Zhang, Cai Ning, Xiaoying Gao, Weidong Shi
The poor oxygen evolution kinetics on the surface of BiVO4 have severely limited the industrialization of BiVO4 photoelectrodes. In this work, we report a bimetallic trace Ni-doped vanadium borate (Ni-VB) modification of the BiVO4 photoelectrode surface (Ni-VB/BiVO4) using the photo-electrodeposition method for photoelectrochemical (PEC) water splitting. The Ni-VB/BiVO4 photoelectrode exhibited an excellent photocurrent density that reached 4.8 mA cm−2 at 1.23 V (vs. reversible hydrogen electrode, RHE) under AM 1.5 G illumination, which is four times higher than that of the pristine BiVO4 photoelectrode, and the charge injection efficiency of Ni-VB/BiVO4 reached 94.5%. Meanwhile, the Ni-VB/BiVO4 photoelectrode remained stable at a bias voltage of 0.8 V (vs. RHE) for ten hours. Density functional theory (DFT) calculations for the oxygen evolution reaction (OER) in this work demonstrate that the Ni-VB on the surface of the BiVO4 photoelectrode promotes interfacial charge transfer and accelerates the oxygen evolution kinetics, resulting in excellent PEC performance for water splitting.
BiVO4表面较差的析氧动力学严重限制了BiVO4光电极的产业化。在这项工作中，我们报道了一种双金属痕量ni掺杂硼酸钒（Ni-VB）修饰BiVO4光电极表面（Ni-VB/BiVO4）的光电沉积方法用于光电化学（PEC）水分解。在AM 1.5 G光照下，Ni-VB/BiVO4光电极在1.23 V（相对于可逆氢电极，RHE）下表现出良好的光电流密度，达到4.8 mA cm−2，是原始BiVO4光电极的4倍，电荷注入效率达到94.5%。同时，Ni-VB/BiVO4光电极在0.8 V （vs. RHE）的偏置电压下保持稳定10小时。本研究的密度泛函理论（DFT）计算表明，BiVO4光电极表面的Ni-VB促进了界面电荷转移并加速了析氧动力学，从而获得了优异的析氧性能。
{"title":"Modification of the BiVO4 photoelectrode surface with Ni-doped vanadium borate for improved charge transfer and photoelectrochemical water splitting","authors":"Dongbo Xu, Song Zhang, Cai Ning, Xiaoying Gao, Weidong Shi","doi":"10.1039/d6qi00144k","DOIUrl":"https://doi.org/10.1039/d6qi00144k","url":null,"abstract":"The poor oxygen evolution kinetics on the surface of BiVO<small><sub>4</sub></small> have severely limited the industrialization of BiVO<small><sub>4</sub></small> photoelectrodes. In this work, we report a bimetallic trace Ni-doped vanadium borate (Ni-VB) modification of the BiVO<small><sub>4</sub></small> photoelectrode surface (Ni-VB/BiVO<small><sub>4</sub></small>) using the photo-electrodeposition method for photoelectrochemical (PEC) water splitting. The Ni-VB/BiVO<small><sub>4</sub></small> photoelectrode exhibited an excellent photocurrent density that reached 4.8 mA cm<small><sup>−2</sup></small> at 1.23 V (<em>vs.</em> reversible hydrogen electrode, RHE) under AM 1.5 G illumination, which is four times higher than that of the pristine BiVO<small><sub>4</sub></small> photoelectrode, and the charge injection efficiency of Ni-VB/BiVO<small><sub>4</sub></small> reached 94.5%. Meanwhile, the Ni-VB/BiVO<small><sub>4</sub></small> photoelectrode remained stable at a bias voltage of 0.8 V (<em>vs.</em> RHE) for ten hours. Density functional theory (DFT) calculations for the oxygen evolution reaction (OER) in this work demonstrate that the Ni-VB on the surface of the BiVO<small><sub>4</sub></small> photoelectrode promotes interfacial charge transfer and accelerates the oxygen evolution kinetics, resulting in excellent PEC performance for water splitting.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147361128","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}
Tianyu Huang, Yangyang Sun, Houqiang Ji, Jiahui Huang, Wanchang Feng, Zheng Liu, Wenlin Xu, Huan Pang
In this work, a ternary heterojunction photocatalyst with oxygen vacancies, TiO2@MIL-125(Ti)/MXene (MM-350), was successfully designed and synthesized. TiO2 nanoparticles were generated in situ via the co-oxidation of MIL-125(Ti) and MXene, uniformly coated around the MIL-125(Ti)/MXene (MM) composite to form a stable ternary heterojunction structure. MM-350, along with enhanced structural stability, achieved a remarkable photocatalytic nitrogen fixation rate of 76.92 μmol g−1 h−1, which was nearly double that of MM (44.78 μmol g−1 h−1). Mechanistic studies revealed that the superior performance of MM-350 originates from the synergistic effects of an S-scheme heterojunction between TiO2 and MIL-125(Ti) and a Schottky junction between MIL-125(Ti) and MXene. The intrinsic built-in electric field at the TiO2/MIL-125(Ti) interface drives directional charge migration from TiO2 to MIL-125(Ti), and MXene serves as an efficient electron reservoir, promoting electron accumulation and N2 activation at Ti active sites. The presence of dual charge transfer routes significantly promotes photogenerated carrier separation and utilization, thereby enabling effective N2 reduction under visible light. This work provides a rational design strategy for constructing multi-interface heterostructures with synergistic charge transfer for efficient photocatalytic nitrogen fixation.
{"title":"Construction of a TiO2/Ti-MOF/MXene ternary heterojunction for enhanced photocatalytic nitrogen fixation","authors":"Tianyu Huang, Yangyang Sun, Houqiang Ji, Jiahui Huang, Wanchang Feng, Zheng Liu, Wenlin Xu, Huan Pang","doi":"10.1039/d5qi02570b","DOIUrl":"https://doi.org/10.1039/d5qi02570b","url":null,"abstract":"In this work, a ternary heterojunction photocatalyst with oxygen vacancies, TiO<small><sub>2</sub></small>@MIL-125(Ti)/MXene (MM-350), was successfully designed and synthesized. TiO<small><sub>2</sub></small> nanoparticles were generated <em>in situ via</em> the co-oxidation of MIL-125(Ti) and MXene, uniformly coated around the MIL-125(Ti)/MXene (MM) composite to form a stable ternary heterojunction structure. MM-350, along with enhanced structural stability, achieved a remarkable photocatalytic nitrogen fixation rate of 76.92 μmol g<small><sup>−1</sup></small> h<small><sup>−1</sup></small>, which was nearly double that of MM (44.78 μmol g<small><sup>−1</sup></small> h<small><sup>−1</sup></small>). Mechanistic studies revealed that the superior performance of MM-350 originates from the synergistic effects of an S-scheme heterojunction between TiO<small><sub>2</sub></small> and MIL-125(Ti) and a Schottky junction between MIL-125(Ti) and MXene. The intrinsic built-in electric field at the TiO<small><sub>2</sub></small>/MIL-125(Ti) interface drives directional charge migration from TiO<small><sub>2</sub></small> to MIL-125(Ti), and MXene serves as an efficient electron reservoir, promoting electron accumulation and N<small><sub>2</sub></small> activation at Ti active sites. The presence of dual charge transfer routes significantly promotes photogenerated carrier separation and utilization, thereby enabling effective N<small><sub>2</sub></small> reduction under visible light. This work provides a rational design strategy for constructing multi-interface heterostructures with synergistic charge transfer for efficient photocatalytic nitrogen fixation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"55 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358909","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}
Long-wavelength broadband near-infrared (NIR) phosphors serve as a cornerstone for versatile NIR spectroscopy applications. However, achieving simultaneous enhancement in both bandwidth and luminescence intensity at long wavelengths remains a significant challenge. Here, we report two novel NIR phosphors, Ba3ZrTa4O15:Cr3+ and Ba3Al0.5Ta4.5O15:Cr3+, both exhibiting dual luminescent centers (Cr1 and Cr2). Ba3ZrTa4O15:0.04Cr3+ emits at 905 nm with a bandwidth of 239 nm under 470 nm excitation. Upon substituting Zr4+–Zr4+ with Al3+–Ta5+, the bandwidth increases to 290 nm (room temperature), and the luminescence intensity rises 4 fold. The enhanced luminescence intensity is attributed to lattice contraction, which not only suppresses the non-radiative transitions of Cr1 but also reduces the energy transfer distance between Cr1 and Cr2. This finding offers a new avenue for improving the performance of ultra-broadband NIR phosphors.
{"title":"Simultaneous broadening and enhancement of Cr3+ photoluminescence in Ba3ZrTa4O15 by chemical unit co-substitution","authors":"Lipeng Jiang, Yuxi Qiao, Jing Wang, Hongbo Yu, Weiwei Jiang, Zhongxiang Shi, Liangliang Zhang, Yanjing Su","doi":"10.1039/d5qi02501j","DOIUrl":"https://doi.org/10.1039/d5qi02501j","url":null,"abstract":"Long-wavelength broadband near-infrared (NIR) phosphors serve as a cornerstone for versatile NIR spectroscopy applications. However, achieving simultaneous enhancement in both bandwidth and luminescence intensity at long wavelengths remains a significant challenge. Here, we report two novel NIR phosphors, Ba<small><sub>3</sub></small>ZrTa<small><sub>4</sub></small>O<small><sub>15</sub></small>:Cr<small><sup>3+</sup></small> and Ba<small><sub>3</sub></small>Al<small><sub>0.5</sub></small>Ta<small><sub>4.5</sub></small>O<small><sub>15</sub></small>:Cr<small><sup>3+</sup></small>, both exhibiting dual luminescent centers (Cr1 and Cr2). Ba<small><sub>3</sub></small>ZrTa<small><sub>4</sub></small>O<small><sub>15</sub></small>:0.04Cr<small><sup>3+</sup></small> emits at 905 nm with a bandwidth of 239 nm under 470 nm excitation. Upon substituting Zr<small><sup>4+</sup></small>–Zr<small><sup>4+</sup></small> with Al<small><sup>3+</sup></small>–Ta<small><sup>5+</sup></small>, the bandwidth increases to 290 nm (room temperature), and the luminescence intensity rises 4 fold. The enhanced luminescence intensity is attributed to lattice contraction, which not only suppresses the non-radiative transitions of Cr1 but also reduces the energy transfer distance between Cr1 and Cr2. This finding offers a new avenue for improving the performance of ultra-broadband NIR phosphors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"84 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358910","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}
Kai-Ping Xie, Xiao-Yin Weng, Kai-Ye Lin, Jing-Yin Liu, Ming Lu, Ziyi Du, Yi-Fei Deng, Zhongli Peng, Si-Guo Wu, Guo-Cong Liu
Spin-crossover (SCO) materials hold promising application prospects in fields such as information storage and molecular switches; however, achieving multi-step transitions and controllable regulation of hidden spin states remains challenging. In this study, a host-guest coordination polymer based on a Hofmann-type framework was synthesized, and its magnetic behavior, photo-response, and structural evolution were systematically investigated. The compound exhibits notable thermal stability and asymmetric multi-step SCO behavior, with its transition process accompanied by a significant kinetic trapping effect. Upon photoexcitation, the material demonstrates reversible light-induced excited spin-state trapping and reverse trapping effects, enabling stable cyclic switching between the high-spin state and the hidden low-spin state. Variable-temperature single-crystal structural analysis reveals that the spin transition occurs synergistically with conformational changes of the guest molecules. Through host-guest lattice strain transmission, a structural basis for the multi-step spin transition is established. This work achieves multi-state spin regulation via a dynamic host-guest coupling strategy, offering a new pathway for the development of novel stimulus-responsive SCO materials.
{"title":"Host-Guest Synergistic Regulation of Multi-Step Spin-Crossover Behavior in a Hofmann-Type Complex","authors":"Kai-Ping Xie, Xiao-Yin Weng, Kai-Ye Lin, Jing-Yin Liu, Ming Lu, Ziyi Du, Yi-Fei Deng, Zhongli Peng, Si-Guo Wu, Guo-Cong Liu","doi":"10.1039/d6qi00300a","DOIUrl":"https://doi.org/10.1039/d6qi00300a","url":null,"abstract":"Spin-crossover (SCO) materials hold promising application prospects in fields such as information storage and molecular switches; however, achieving multi-step transitions and controllable regulation of hidden spin states remains challenging. In this study, a host-guest coordination polymer based on a Hofmann-type framework was synthesized, and its magnetic behavior, photo-response, and structural evolution were systematically investigated. The compound exhibits notable thermal stability and asymmetric multi-step SCO behavior, with its transition process accompanied by a significant kinetic trapping effect. Upon photoexcitation, the material demonstrates reversible light-induced excited spin-state trapping and reverse trapping effects, enabling stable cyclic switching between the high-spin state and the hidden low-spin state. Variable-temperature single-crystal structural analysis reveals that the spin transition occurs synergistically with conformational changes of the guest molecules. Through host-guest lattice strain transmission, a structural basis for the multi-step spin transition is established. This work achieves multi-state spin regulation via a dynamic host-guest coupling strategy, offering a new pathway for the development of novel stimulus-responsive SCO materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358913","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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