Inorganic Chemistry Frontiers最新文献

{"title":"Simultaneous synthesis of oxygen doped carbon electrode at anode and cathode via potential cycling for promoted H2O2 electrosynthesis","authors":"Suhua Mao, Xin Li, Bingshuang Li, Jin Li, Xiaoxi Huang","doi":"10.1039/d4qi02539c","DOIUrl":"https://doi.org/10.1039/d4qi02539c","url":null,"abstract":"Oxygenated groups functionalized carbon materials are promising catalysts for the electrochemical production of hydrogen peroxide (H2O2) via two-electron oxygen reduction reaction (ORR). Electrochemical activation of carbon materials to introduce oxygenated groups has exhibited attractive features compared with chemical oxidation method. However, the knowledge is limited as to how electrochemical treatment influences the resulting ORR performance. Herein, we describe the synthesis of carbon electrodes modified with oxygenated groups at both anodic and cathodic sides by using potential cycling in neutral Na2SO4 solution. Composition analysis based on XPS and electrochemical FTIR indicates the successful modification of oxygenated groups. The production rate of H2O2 is significantly enhanced after potential cycling. The oxidized carbon electrode can catalyze ORR at an industrial-current-density to produce H2O2 with selectivity close to 100% in a flow cell. Density functional theory (DFT) calculations demonstrate that the binding energy of *OOH is promoted after modification of oxygenated groups. These findings highlight the advantages of the electrochemical method on carbon surface functionalization and provide some guidelines for catalyst design.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"259 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142848898","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":"Theoretical Design and Experimental Realization of Fe3+-Doped Dual-Band Near-Infrared Garnet Phosphors","authors":"Yutong Wang, Anfei Chen, Sha Jiang, Zhong Lei, Li Li, Xianju Zhou, Chang-Kui Duan, Qiaoling Chen","doi":"10.1039/d4qi02523g","DOIUrl":"https://doi.org/10.1039/d4qi02523g","url":null,"abstract":"Cr<small>³⁺</small>-free near-infrared (NIR) phosphors based on Fe<small>³⁺</small> have garnered extensive attention due to their environmentally friendly and tunable optical properties. However, the reported luminescence predominantly originates from the Fe<small>³⁺</small> ion in tetrahedral coordination, with wavelengths in the range of 670-830 nm. Phosphors with luminescence from octahedrally coordinated Fe<small>³⁺</small>, which are expected to shift to longer wavelengths over 900 nm, are limited due to the challenges such as quenching mechanisms. Garnets with the formula A<small>₃</small>B<small>₂</small>C<small>₃</small>O<small>₁₂</small> are excellent hosts for phosphors due to their rigid structures and tunable luminescent properties. Theoretical analysis, supported by first-principles calculations, indicates that Fe<small>³⁺</small> can occupy both tetrahedral (Fe(T)) and octahedral (Fe(O)) sites, potentially producing dual-band emission in garnet crystals with large octahedral host ions, such as Sr<small>₃</small>(Sc/Lu/Y)<small>₂</small>Ge<small>₃</small>O<small>₁₂</small> crystals. This has guided us in the experimental realization of dual-band NIR luminescence, peaking at 720–730 nm (Fe(T)) and 980–990 nm (Fe(O)), in these materials. Consistent with our optical transition analysis, the luminescence intensities of Fe(T) and Fe(O) show different temperature dependencies. Fe(T) exhibits weaker temperature dependence, while Fe(O) experiences severe temperature quenching via the <small>²</small>T<small>₂</small> intermediate energy level. The dual-band NIR phosphors Sr<small>₃</small>(Sc/Lu/Y)<small>₂</small>Ge<small>₃</small>O<small>₁₂</small>:Fe<small>³⁺</small> show potential applications in the luminescent intensity ratio-based and luminescent decay time-based thermometers, with a significant maximum relative sensitivity of 1.24%K<small>⁻¹</small> at 155 K. The materials designed here provide a foundation for related application explorations, and the strategy developed can be applied to the exploration and development of Fe<small>³⁺</small>-activated advanced optical materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"48 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841698","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":"Enhanced ROS generation in AIE-active iridium(III) photosensitizers by cationization engineering for advanced photodynamic therapy","authors":"Shanshan Huang, Yuancheng Li, Xiaohan Xie, Jialin Tong, Guo-Gang Shan, Chao Qin, Xiyan Xiao, Qianruo Wang, Yuanyuan Li, Hualei Wang","doi":"10.1039/d4qi02477j","DOIUrl":"https://doi.org/10.1039/d4qi02477j","url":null,"abstract":"Phosphorescent iridium(III) complexes have emerged as promising photosensitizers (PSs) for clinical photodynamic therapy (PDT) due to their notable antitumor efficacy. However, their practical application is hindered by weak emission in aggregate states and insufficient reactive oxygen species (ROS) generation. In this study, we present a straightforward cationization strategy aimed at simultaneously enhancing both the emission and ROS production of Ir(III)-based PSs. Two Ir(III) complexes PPI-C1 and PPI-C2 which feature an incremental number of hexafluorophosphate counterions were strategically designed through simple ligand engineering of the neutral precursor PPI-C0. Both experimental and theoretical analyses reveal that cationization effectively modulates the aggregate behavior and excited-state properties of these complexes, with PPI-C2 displaying significantly improved AIE characteristic and effective intersystem crossing ability. As expected, the water-soluble PPI-C2 nanoparticles demonstrated superior ROS production and good biocompatibility under light irradiation, leading to cell apoptosis and significant inhibition of tumor growth in vivo. This study will offer new insights into the design of effective AIE-active Ir(III)-based photosensitizers for PDT.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"34 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841704","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In situ Conversion Reaction of Magnesium Fluoride to Boost the Performance of Sulfide-Based Electrolyte Li6PS5Cl for All-Solid-State Lithium Metal Batteries","authors":"Yuzhe Zhang, Haolong Chang, Xiaohu Hu, Shijie Xu, Xinyu Wang, Shunjin Yang, Yujiang Sun, Xiao Sun, Dehang Ren, Xing Chen, Fangyi Cheng, Yongan Yang","doi":"10.1039/d4qi02717e","DOIUrl":"https://doi.org/10.1039/d4qi02717e","url":null,"abstract":"For solid electrolytes of all-solid-state lithium metal batteries being pursued globally, Li6PS5Cl is one of the most promising candidates due to its high ionic conductivity and easy processibility. However, Li6PS5Cl is vulnerable to the lithium anode, because lithium can not only reduce Li6PS5Cl to generate passive interfaces but also grow lithium dendrites to penetrate through the Li6PS5Cl bulk and eventually short-circuit the battery. Herein this paper reports that the electrochemical performance of Li6PS5Cl can be greatly enhanced by compositing it with MgF2, which is the most effective metal fluoride among five studied materials. Specifically, the critical current density is increased by 4.7 times; the cycling durability in Li|electrolyte|Li symmetric cells is extended by 19 times; the capacity retention in Li|electrolyte|LiNi0.7Co0.2Mn0.1O2 full cells is enhanced from 76% to 86%; and the rate capability is boosted from 0.2 C to 1 C. The combinatory studies of experimental characterizations and theoretical computations find that the performance-improving mechanism is like a sustained-release effect of capsular medicines. That is, during the charging/discharging cycles can MgF2 timely scavenge lithium dendrites to generate LixMg alloy and LiF, wherein LixMg can reversibly release/uptake Li and LiF can suppress the nucleation of lithium dendrites.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832047","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In situ characterization techniques: main tools for revealing OER/ORR catalytic mechanism and reaction dynamics","authors":"Siqi Wu, Zexin Liang, Tianshi Wang, Xiaobin Liu, Shaobo Huang","doi":"10.1039/d4qi02179g","DOIUrl":"https://doi.org/10.1039/d4qi02179g","url":null,"abstract":"The oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are some of the most important reactions in electrochemical energy technologies such as fuel cells and metal–air cells. However, the lack of in-depth understanding of reaction mechanisms and clear identification of catalytic active sites hinders the development of high-performance and durable electrocatalysts for the OER and ORR. <em>In situ</em> characterization techniques enable on-site monitoring of the surface oxidation state and local atomic structural transitions, facilitating the identification of active sites and enhancing our fundamental understanding of reaction mechanisms in these systems. This article reviews the main progress in the OER/ORR process using various <em>in situ</em> techniques. By utilizing <em>in situ</em> characterization techniques, the factors affecting catalyst catalytic performance are revealed from a direct or indirect perspective. Finally, the main challenges and prospects of <em>in situ</em> characterization techniques in ORR/OER research are discussed.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"3 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832046","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":"Impact of H/D Isotopic Effects on the Physical Properties of Materials","authors":"Cheng-Dong Liu, Zi-Shuo Yao, Jun Tao","doi":"10.1039/d4qi02709d","DOIUrl":"https://doi.org/10.1039/d4qi02709d","url":null,"abstract":"H/D isotope substitution deepens our understanding of molecular interactions, hydrogen bond characteristics, and quantum effects, while also advancing the design of advanced materials, biological research, and energy applications, thereby having a profound impact in interdisciplinary fields. In materials science, deuteration can influence the structure and physical properties of hydrogen-containing solids. A notable example is the discovery in 1942 that deuteration on the strong hydrogen-bonded ferroelectric potassium dihydrogen phosphate (KDP) increases the Curie temperature (Tc) by approximately 107 K, attributed to the geometric isotope effects (GIE) induced by deuteration on hydrogen bonds. Additionally, deuteration can introduce chemical pressure within the lattice, influencing the magnetic and conductive properties of solid materials. Moreover, due to their lower vibrational modes, D atoms can reduce non-radiative transitions, thereby enhancing the optical physical properties of materials. This highlights deuteration as a viable chemical strategy for modulating the physical properties of materials. This review aims to provide a concise overview of the effects of H/D isotope substitution on material structures and physical properties, offering new insights into the regulation of material properties through recent advancements in deuteration.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"30 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832065","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":"Modulating Magnetic Exchange, Spin Dynamics and Intermacrocyclic Interactions via Oxo-bridge in Dihemes Through Stepwise Oxidations","authors":"Sayantani Banerjee, Rupesh Kumar Tiwari, Paulami Chakraborty, Gopalan Rajaraman, Sankar Prasad Rath","doi":"10.1039/d4qi02972k","DOIUrl":"https://doi.org/10.1039/d4qi02972k","url":null,"abstract":"A bis-Fe(III)-µ-oxo-porphyrin dimer, where a rigid ethene-linker covalently connects the two porphyrin units, has been exploited to investigate the effect of intermacrocyclic interaction and spin coupling upon stepwise oxidations. The complex possesses a bent FeOFe unit bringing two porphyrin macrocycles in close vicinity for strong intermacrocyclic interactions between them. Here, the two high-spin iron(III) centres undergo strong anti-ferromagnetic coupling via oxo-bridge (JFe-Fe), resulting in a large upfield shift of the protons in the diamagnetic region in its 1H NMR spectrum. 1eˉ-oxidation produces porphyrin π-cation radical which displays a well-resolved 1H NMR spectra with large isotropic shift of the downfield-shifted methylene protons, indicative of much weaker anti-ferromagnetic coupling via oxo. As observed in the X-ray structure of the complex, 1eˉ-oxidation brings two porphyrin macrocycles much closer to each other. This results in a remarkably bent FeOFe unit while the Fe-Npor and Fe-O distances are also significantly decreased and increased, respectively, in the 1eˉ-oxidized complex causing a significant decrease in the JFe-Fe value. The dication diradical complex that results from 2eˉ-oxidation, on the other hand, exhibits a weakly paramagnetic nature with significant upfield shifts of the methylene proton signals as well as smaller isotropic shifts than its 1eˉ-oxidized complex. Most interestingly, 1H NMR chemical shift of the methylene protons of the 1eˉ- and 2eˉ-oxidized complexes behave completely differently upon varying the temperature and follow Curie and anti-Curie behavior, respectively, which have been rationalized considering the thermal population of the ground and excited states at the recorded temperatures. Variable temperature magnetic investigation in the solid state indicated antiferromagnetic coupling between the iron centres through the oxo-bridge which follows the order (JFe-Fe): oxo-bridged dimer (-130.4 cm-1 ) &gt; 2eˉ-oxidized complex (-116.1 cm-1 ) &gt;&gt; 1eˉ-oxidized complex (-37.8 cm-1 ). On the other hand, the spin couplings between unpaired iron spin with porphyrin π-cation radical (JFe-r) follows an order: 2eˉ-oxidized complex (-27.2 cm-1 ) &gt; 1eˉ-oxidized complex (-16.5 cm-1 ). The DFT calculations reproduce the experimental J values very well but provide an insight that both FeOFe angle and Fe-O distances determine the overall J while the bridging ethylene linker promoting ferromagnetic coupling.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"38 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832048","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High-efficiency photodriven coupling of CO2 and various epoxides via multi-shelled hollow ZIF/MXene derived composite with low activation energy","authors":"Yang Wang, Meili Ding, Xiaotong Fu, Jianfeng Yao","doi":"10.1039/d4qi02269f","DOIUrl":"https://doi.org/10.1039/d4qi02269f","url":null,"abstract":"Photo-induced carbon dioxide (CO2) conversion is a promising pathway to synthesize value-added chemicals in a sustainable manner, but the process is usually hampered by the high activation energy, low light harvesting capability, and the fast recombination of charge carriers. Herein, cobalt nanoparticles encapsulated in N-doped hierarchically porous carbon/TiO2/MXene (CoNHPC/TM) composites were synthesized by high temperature pyrolysis, employing a multilayer ZIF-8@ZIF-67@ZIF-8@ZIF-67 (4L-ZIF)/MXene hybrid as a precursor. During the pyrolysis process, the multilayer 4L-ZIF solid was transformed into CoNHPC with a multi-shell hollow structure, while TiO2 nanoparticles formed in situ on the MXene surface. This unique structure induces multiple reflections of internal light, thus increasing the efficiency of light energy harvesting and photothermal conversion, as well as significantly improving mass diffusion and the separation efficiency of photogenerated carriers. Consequently, a 96% yield for cyclic carbonate was achieved by the optimal CoNHPC/TM-8 (initial mass ratio of 4L-ZIF to MXene: 8:1) under irradiation of full spectrum light at 350 mW/cm2 for 6 h. Additionally, its high catalytic efficiency was maintained even under simulated flue gas conditions. Further investigations revealed a decrease in the activation energy and a synergistic photocatalytic-photothermal effect in the reaction systems with CoNHPC/TM-8. Our research provides inspiration for the rational design of MOF-based photocatalysts with desirable practical applicability for enhancing CO2 transformation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"91 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841701","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":"Strategically designed anisotropic organic-inorganic metal halides (OIMHs) with superior balance between bandgap and birefringence","authors":"Ming-Chang Wang, Huai-Yu Wu, Miao-Bin Xu, Jia-Jia Li, Kezhao Du, Jin Chen","doi":"10.1039/d4qi02883j","DOIUrl":"https://doi.org/10.1039/d4qi02883j","url":null,"abstract":"This study reports two novel organic-inorganic metal halides (OIMHs) with outstanding ultraviolet birefringences, namely Cd(C6H4NO2)I·H2O (1) and Cd(C6H5NO2)2I2 (2). Both of them feature 1D neutral chain, in which the 1D [Cd(C6H4NO2)I·H2O]∞ is built from Cd2I2N2O6 dimers and (C6H4NO2)- anions via the connection of Cd-N bonds, whereas each pair of antiparallel (C6H5NO2) groups hang at 1D [CdI2]∞ forming 1D [Cd(C6H5NO2)2I2]∞ chain. Importantly, birefringence measurements exhibit that both 1 and 2 features exceptional birefringent properties with values of 0.243 @ 550 nm and 0.388 @ 550 nm, respectively, which are not only greater than commercial materials (α-BaB2O4, 0.122 @ 546 nm), but also 8.1 and 12.8 times that of inorganic CdI2. Additionally, the UV-vis spectra show that both 1 and 2 have short adsorption edges of 280 nm and 284 nm, relating to wide bandgaps of 4.23 eV and 3.94 eV. Therefore, they, especially 2, are strong candidates for potential ultraviolet birefringent materials. This study innovatively proposes a design strategy for the NA-Cd-I system, which means construct organic-inorganic metal halide systems (OIMHs), providing new insights into the exploration of new high-performance birefringent crystals.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"76 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832067","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":"Rare Earth Pillars for Stabled Layered Birnessite Cathode Propelling Aqueous Zinc-Ion Batteries with Ultra-Long Cyclability","authors":"Jianwei Wang, Kangning Wang, Wenlin Zhang, Jinbo Zhang, Yanzhong Zhen, Feng Fu, Yaping Du","doi":"10.1039/d4qi02654c","DOIUrl":"https://doi.org/10.1039/d4qi02654c","url":null,"abstract":"The weak structural stability, low intrinsic conductivity, and strong electrostatic interaction of cathode materials are still bottlenecks in aqueous zinc-ion batteries. Herein, a novel win-win strategy was proposed to fabricate the yttrium ions pre-intercalation birnessite-MnO2 cathode material. Benefiting from the unique advantages of rare earth ions with large radius, it could serve as interlayer pillars in the crystal lattice to stabilize the structure and enhance ionic conductivity. Furthermore, the high valence state of rare earth ions could significantly weaken the electrostatic interaction between zinc ions and host structures, thereby reducing charge transfer resistance and promoting ion transport. As a result, Y0.04K0.16Mn2O4·2.3H2O exhibits an ultra-long cycle stability of 24,000 cycles at a high current density of 8 A g-1, and the average capacity decay rate is only 0.002% per cycle. This work paves the way for the application of rare earth elements in energy storage.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"3 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832066","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}