Ahmet Bulut, Mustafa Erkartal, Mehmet Yurderi, Tuba Top, Mehmet Zahmakiran
Hydrazine borane (HB) has great potential as a safe and convenient hydrogen carrier material due to its high hydrogen capacity (15.4 % wt) and good stability under ambient conditions. However, efficient hydrogen production through the complete decomposition of hydrazine borane at low temperatures (< 373 K) constitutes a major challenge. Herein, we report the successful immobilization of monodisperse Rh nanoparticles on MgO solid support, leading to the formation of the Rh@MgO catalyst. This developed catalyst exhibits outstanding catalytic performance in the dehydrogenation of HB, achieving a remarkable turnover frequency (TOF) of 2005.34 h⁻¹ at 50 °C with 100% H₂ selectivity, despite containing only 2 wt% Rh. Comparative experiments with Rh on various metal-oxide nanoparticles, other transition metal catalysts on MgO, and Ni grown on MgO in both single-phase and bimetallic forms reveal that Rh@MgO consistently outperforms these alternatives. The exceptional catalytic activity is attributed to the synergistic interaction between Rh and MgO, which involves several key factors: the homogeneous dispersion of ultrafine, monodisperse Rh particles enhances catalytic efficiency; the proximity of the work functions of Rh and MgO results in a low-energy Schottky barrier that facilitates electron transfer; and the localization of electrons in surface defects of MgO aligns with the Fermi level of Rh, further promoting electron transfer through Fermi Level Pinning (FLP). The combination of low Rh content and cost-effective MgO support presents a promising pathway for both laboratory-scale research and practical industrial applications, highlighting the potential of the Rh@MgO catalyst as an efficient and economically viable solution for catalytic processes.
{"title":"High-Performance Rh@MgO Catalysts for Complete Dehydrogenation of Hydrazine Borane: A Comparative Study","authors":"Ahmet Bulut, Mustafa Erkartal, Mehmet Yurderi, Tuba Top, Mehmet Zahmakiran","doi":"10.1039/d4qi02575j","DOIUrl":"https://doi.org/10.1039/d4qi02575j","url":null,"abstract":"Hydrazine borane (HB) has great potential as a safe and convenient hydrogen carrier material due to its high hydrogen capacity (15.4 % wt) and good stability under ambient conditions. However, efficient hydrogen production through the complete decomposition of hydrazine borane at low temperatures (< 373 K) constitutes a major challenge. Herein, we report the successful immobilization of monodisperse Rh nanoparticles on MgO solid support, leading to the formation of the Rh@MgO catalyst. This developed catalyst exhibits outstanding catalytic performance in the dehydrogenation of HB, achieving a remarkable turnover frequency (TOF) of 2005.34 h⁻¹ at 50 °C with 100% H₂ selectivity, despite containing only 2 wt% Rh. Comparative experiments with Rh on various metal-oxide nanoparticles, other transition metal catalysts on MgO, and Ni grown on MgO in both single-phase and bimetallic forms reveal that Rh@MgO consistently outperforms these alternatives. The exceptional catalytic activity is attributed to the synergistic interaction between Rh and MgO, which involves several key factors: the homogeneous dispersion of ultrafine, monodisperse Rh particles enhances catalytic efficiency; the proximity of the work functions of Rh and MgO results in a low-energy Schottky barrier that facilitates electron transfer; and the localization of electrons in surface defects of MgO aligns with the Fermi level of Rh, further promoting electron transfer through Fermi Level Pinning (FLP). The combination of low Rh content and cost-effective MgO support presents a promising pathway for both laboratory-scale research and practical industrial applications, highlighting the potential of the Rh@MgO catalyst as an efficient and economically viable solution for catalytic processes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"57 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678738","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}
The simultaneous exploitation of dual or multiple physical and chemical properties of a material is a promising strategy for developing high-tech intelligent complex systems. In this study, a copper(I) coordination polymer (CuI-CP, 2) was synthesized and utilized as a dual-purpose material to construct a self-powered photocatalytic system capable of significantly improving the power generation capabilities of triboelectric generators (TEGs) as a triboelectric layer and efficiently catalyzing the C-H arylation reaction as a photocatalyst. Compound 2 was achieved via a solvothermal method in the presence of ammonia and ethylenediamine. In contrast, only mixed-valence cooper salts ([CuII(H2O)5][CuI3(CN)5]·H2O, 1) were obtained without ammonia and ethylenediamine. Comparative analysis revealed that TEG based on 2 (2-TEG) showcased superior output performance compared to 1-TEG owing to the exceptional electron-donating ability of 2. Furthermore, under light-emitting diodes (LEDs) irradiation powered by 2-TEG, 2 demonstrated remarkable catalytic activity and selectivity in the photoinduced C-H arylation of benzothiazole, far exceeding the performance of 1. This research highlights the potential of bifunctional material 2 with a distinctive structure, renowned for its outstanding energy harvesting and conversion capabilities as well as excellent photocatalytic performance, thereby facilitating the design objectives of multitasking in self-driven complex systems.
{"title":"A dual-purpose copper(I) coordination polymer for the construction of self-driven photoinduced C-H arylation systems","authors":"Yue Zhang, Ying-Ying Zhang, Shuo Li, Fei Wang, Yuanmeng Tao, Jiaxing Cui, Chao Huang, Liwei Mi","doi":"10.1039/d4qi02381a","DOIUrl":"https://doi.org/10.1039/d4qi02381a","url":null,"abstract":"The simultaneous exploitation of dual or multiple physical and chemical properties of a material is a promising strategy for developing high-tech intelligent complex systems. In this study, a copper(I) coordination polymer (CuI-CP, 2) was synthesized and utilized as a dual-purpose material to construct a self-powered photocatalytic system capable of significantly improving the power generation capabilities of triboelectric generators (TEGs) as a triboelectric layer and efficiently catalyzing the C-H arylation reaction as a photocatalyst. Compound 2 was achieved via a solvothermal method in the presence of ammonia and ethylenediamine. In contrast, only mixed-valence cooper salts ([CuII(H2O)5][CuI3(CN)5]·H2O, 1) were obtained without ammonia and ethylenediamine. Comparative analysis revealed that TEG based on 2 (2-TEG) showcased superior output performance compared to 1-TEG owing to the exceptional electron-donating ability of 2. Furthermore, under light-emitting diodes (LEDs) irradiation powered by 2-TEG, 2 demonstrated remarkable catalytic activity and selectivity in the photoinduced C-H arylation of benzothiazole, far exceeding the performance of 1. This research highlights the potential of bifunctional material 2 with a distinctive structure, renowned for its outstanding energy harvesting and conversion capabilities as well as excellent photocatalytic performance, thereby facilitating the design objectives of multitasking in self-driven complex systems.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"7 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678739","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}
Wen-Jing Jiang, Yin-Shan Meng, Han-Han Lu, Hai-Lang Zhu, Qiang Liu, Chunying Duan, Hiroki Oshio, Tao Liu
Bistable mixed valence compounds have thermodynamically accessible phases at certain temperatures, and the electron transfer switches the electronic configurations by applying external stimuli like heat and light. Thermally induced phase transition temperatures range widely, while the photo-induced state conversions need irradiation at very low temperatures, such as below 30 K, and the photo-induced metastable state relaxes rapidly at low temperatures. We prepared new mixed-valence compounds of [Fe(bipy)(CN)4]2[CoL2] (L = 4-[(1E)-2-phenyldiazenyl]pyridine for 1-papy and 4-(2-phenylethynyl)pyridine for 1-pepy) in which cyanide-bridged squared cores form corner-shared chains with substantial interchain π–π contacts. Mössbauser spectra revealed that 1-papy and 1-pepy are in the high-spin (HS) state [(FeIIILS)2CoIIHS] at 300 K and the low-spin (LS) state [FeIILSFeIIILSCoIIILS] at 78 K, confirming the occurrence of the electron transfer coupled spin transition (ETCST). Magnetic susceptibility measurements suggested their Tc values of 231 and 260 K, respectively. Photoirradiation (808 nm) for 1-papy and 1-pepy at 10 K induced the state conversion from the [LS] to the [HS*] state, and the metastable [HS]* state relaxed to the thermodynamically stable [LS] states at temperatures (Trelax) of 130 and 90 K, respectively. Furthermore, the [LS] states in 1-papy and 1-pepy were fully converted to the [HS*] states by light irradiation at 78 and 50 K, respectively. The X-ray structural analyses showed characteristic coordination bond lengths for the metal ions in each electronic state before and after light irradiation, but shortened intrachain πL⋯πL contact distances, from 3.726(4) to 3.688(4) Å, were observed for 1-papy upon the state conversion from the [LS] to the [HS*] state, despite the swollen cell volumes from 2479 to 2566 Å3, respectively. Photomagneto and structural studies suggest that the intermolecular interactions increase the light-induced state conversion and relaxation temperatures.
双稳态混合价化合物在一定温度下具有热力学可及相，电子转移通过热和光等外部刺激切换电子构型。热诱导的相变温度范围很广，而光诱导的状态转换则需要在很低的温度下（如 30 K 以下）进行辐照，并且光诱导的阶跃态在低温下会迅速弛豫。我们制备了[Fe(bipy)(CN)4]2[CoL2]（L = 4-[(1E)-2-苯基二氮基]吡啶表示 1-papy，4-(2-苯基乙炔基)吡啶表示 1-pepy）的新型混价化合物，其中氰化物桥接的方形核形成角共享链，链间具有大量的π-π接触。莫斯鲍瑟光谱显示，1-papy 和 1-pepy 在 300 K 时处于高自旋（HS）态[(FeIIILS)2CoIIHS]，在 78 K 时处于低自旋（LS）态[FeIILSFeIIILSCoIIILS]，证实了电子转移耦合自旋转变（ETCST）的发生。磁感应强度测量表明它们的 Tc 值分别为 231 K 和 260 K。在 10 K 温度下对 1-papy 和 1-pepy 进行光照射（808 nm）可诱导[LS]态向[HS*]态转换，[HS]*态的弛豫态分别在 130 K 和 90 K 温度（Trelax）下弛豫到热力学稳定的[LS]态。此外，1-papy 和 1-pepy 中的[LS]态分别在 78 和 50 K 的光照射下完全转化为[HS*]态。X 射线结构分析表明，在光照射前后，每个电子态中金属离子的配位键长度都各具特色，但在 1-papy 从 [LS] 态转换到 [HS*] 态时，尽管晶胞体积分别从 2479 Å3 膨胀到 2566 Å3，但其晶胞内 πL⋯πL 接触距离却从 3.726(4) Å 缩短到 3.688(4) Å。光磁效应和结构研究表明，分子间的相互作用提高了光诱导的状态转换和弛豫温度。
{"title":"Interchain interactions raised the photo-induced [LS] → [HS*] transition temperature to 78 K in a cyanide-bridged [FeIII2CoII] chain","authors":"Wen-Jing Jiang, Yin-Shan Meng, Han-Han Lu, Hai-Lang Zhu, Qiang Liu, Chunying Duan, Hiroki Oshio, Tao Liu","doi":"10.1039/d4qi02428a","DOIUrl":"https://doi.org/10.1039/d4qi02428a","url":null,"abstract":"Bistable mixed valence compounds have thermodynamically accessible phases at certain temperatures, and the electron transfer switches the electronic configurations by applying external stimuli like heat and light. Thermally induced phase transition temperatures range widely, while the photo-induced state conversions need irradiation at very low temperatures, such as below 30 K, and the photo-induced metastable state relaxes rapidly at low temperatures. We prepared new mixed-valence compounds of [Fe(bipy)(CN)<small><sub>4</sub></small>]<small><sub>2</sub></small>[CoL<small><sub>2</sub></small>] (L = 4-[(1<em>E</em>)-2-phenyldiazenyl]pyridine for <strong>1-papy</strong> and 4-(2-phenylethynyl)pyridine for <strong>1-pepy</strong>) in which cyanide-bridged squared cores form corner-shared chains with substantial interchain π–π contacts. Mössbauser spectra revealed that <strong>1-papy</strong> and <strong>1-pepy</strong> are in the high-spin (HS) state [(Fe<small><sup>III</sup></small><small><sub>LS</sub></small>)<small><sub>2</sub></small>Co<small><sup>II</sup></small><small><sub>HS</sub></small>] at 300 K and the low-spin (LS) state [Fe<small><sup>II</sup></small><small><sub>LS</sub></small>Fe<small><sup>III</sup></small><small><sub>LS</sub></small>Co<small><sup>III</sup></small><small><sub>LS</sub></small>] at 78 K, confirming the occurrence of the electron transfer coupled spin transition (ETCST). Magnetic susceptibility measurements suggested their <em>T</em><small><sub>c</sub></small> values of 231 and 260 K, respectively. Photoirradiation (808 nm) for <strong>1-papy</strong> and <strong>1-pepy</strong> at 10 K induced the state conversion from the [LS] to the [HS*] state, and the metastable [HS]* state relaxed to the thermodynamically stable [LS] states at temperatures (<em>T</em><small><sub>relax</sub></small>) of 130 and 90 K, respectively. Furthermore, the [LS] states in <strong>1-papy</strong> and <strong>1-pepy</strong> were fully converted to the [HS*] states by light irradiation at 78 and 50 K, respectively. The X-ray structural analyses showed characteristic coordination bond lengths for the metal ions in each electronic state before and after light irradiation, but shortened intrachain π<small><sub>L</sub></small>⋯π<small><sub>L</sub></small> contact distances, from 3.726(4) to 3.688(4) Å, were observed for <strong>1-papy</strong> upon the state conversion from the [LS] to the [HS*] state, despite the swollen cell volumes from 2479 to 2566 Å<small><sup>3</sup></small>, respectively. Photomagneto and structural studies suggest that the intermolecular interactions increase the light-induced state conversion and relaxation temperatures.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"128 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673643","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}
Tao-Tao Li, Yu-Rui Ji, Yi-Meng Wu, Peng-Fei Wang, Zong-Lin Liu, Jie Shu, Ting-Feng Yi
The electrocatalytic activity of catalysts can be significantly enhanced through the utilization of heterogeneous structures. Nevertheless, the optimization of both catalytic activity and durability via heterojunction engineering remains a considerable challenge. In this work, we fabricated electrocatalysts of Co/CoO heterojunctions on a highly porous hollow carbon material. The formation of heterojunctions increases the abundance of accessible active sites and optimizes the electrocatalytic reaction kinetics and reactivity. Thus, the prepared catalysts (Co/CoO@N–C-40) deliver robust and stable bifunctional oxygen electrocatalytic activity during the oxygen reduction/evolution reaction (ORR/OER) process. The performance of rechargeable zinc–air batteries (ZABs) greatly depends on bifunctional oxygen electrocatalysts, which are crucial for efficient charging and discharging processes. Consequently, the Co/CoO@N–C-40-based ZABs have superior cycling stability (750 h) and show a stable energy efficiency of 55.10% at 10 mA cm−2 (53.46% after 555 h). This work offers a high-quality oxygen electrocatalyst for ZABs and extends the application of heterogeneous interfacial catalysts in various energy storage and conversion devices.
利用异质结构可以显著提高催化剂的电催化活性。然而，通过异质结工程优化催化活性和耐久性仍然是一个相当大的挑战。在这项工作中，我们在高多孔性空心碳材料上制造了 Co/CoO 异质结的电催化剂。异质结的形成增加了可访问活性位点的丰度，优化了电催化反应动力学和反应活性。因此，所制备的催化剂（Co/CoO@N-C-40）在氧还原/进化反应（ORR/OER）过程中具有强大而稳定的双功能氧电催化活性。可充电锌-空气电池（ZABs）的性能在很大程度上取决于双功能氧电催化剂，这对高效充放电过程至关重要。因此，基于 Co/CoO@N-C-40 的锌空气电池具有卓越的循环稳定性（750 h），并在 10 mA cm-2 时显示出 55.10% 的稳定能量效率（555 h 后为 53.46%）。这项工作为 ZABs 提供了一种高质量的氧电催化剂，拓展了异质界面催化剂在各种能量存储和转换设备中的应用。
{"title":"Heterogeneous interface engineering to enhance oxygen electrocatalytic activity for rechargeable zinc–air batteries","authors":"Tao-Tao Li, Yu-Rui Ji, Yi-Meng Wu, Peng-Fei Wang, Zong-Lin Liu, Jie Shu, Ting-Feng Yi","doi":"10.1039/d4qi02213k","DOIUrl":"https://doi.org/10.1039/d4qi02213k","url":null,"abstract":"The electrocatalytic activity of catalysts can be significantly enhanced through the utilization of heterogeneous structures. Nevertheless, the optimization of both catalytic activity and durability <em>via</em> heterojunction engineering remains a considerable challenge. In this work, we fabricated electrocatalysts of Co/CoO heterojunctions on a highly porous hollow carbon material. The formation of heterojunctions increases the abundance of accessible active sites and optimizes the electrocatalytic reaction kinetics and reactivity. Thus, the prepared catalysts (Co/CoO@N–C-40) deliver robust and stable bifunctional oxygen electrocatalytic activity during the oxygen reduction/evolution reaction (ORR/OER) process. The performance of rechargeable zinc–air batteries (ZABs) greatly depends on bifunctional oxygen electrocatalysts, which are crucial for efficient charging and discharging processes. Consequently, the Co/CoO@N–C-40-based ZABs have superior cycling stability (750 h) and show a stable energy efficiency of 55.10% at 10 mA cm<small><sup>−2</sup></small> (53.46% after 555 h). This work offers a high-quality oxygen electrocatalyst for ZABs and extends the application of heterogeneous interfacial catalysts in various energy storage and conversion devices.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"57 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673668","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}
Manganese-based organic metal halides, due to their excellent optoelectronic properties and stable chemical nature, have been widely applied in optoelectronic devices and sensors. In this study, through rational modulation of halogens, three novel zero-dimensional organic manganese halides (C6H8N)2MnX4 (X=Cl, Br, I) were obtained by adjusting the halogen via the solvent evaporation method. Attributed to the d-d electronic transition of Mn2+ in the tetrahedral-coordinated [MnX4]2- polyhedron, all samples exhibit strong green emission. Notably, the (C6H8N)2MnBr4 was demonstrated with a remarkable light yield of 18224 photons MeV−1 and a low detection limit of 1.9 μGy s−1, which is below the X-ray diagnostic limit and even superior to the commercial BGO scintillator. Moreover, a 9 cm×9 cm flexible scintillator film was successfully fabricated by mixing the (C6H8N)2MnBr4 crystalline powder with polymethyl methacrylate, manifesting superior radiation stability and an X-ray imaging resolution of 12.1 lp mm−1. Notably, the X-ray images captured by the flexible film demonstrate distinguished clarity as adhering perfectly to curved metal sheets. The combination of excellent performance and facile solution processing open new opportunities for low-cost, high-performance organic metal halides based large-area flexible scintillators for X-ray detection and imaging.
锰基有机金属卤化物因其优异的光电性能和稳定的化学性质，已被广泛应用于光电器件和传感器中。本研究通过合理调节卤素，利用溶剂蒸发法调节卤素的含量，得到了三种新型零维有机卤化锰（C6H8N）2MnX4（X=Cl、Br、I）。由于四面体配位[MnX4]2-多面体中 Mn2+ 的 d-d 电子转变，所有样品都表现出强烈的绿色发射。值得注意的是，(C6H8N)2MnBr4 的光产率高达 18224 光子 MeV-1，检测限低至 1.9 μGy s-1，低于 X 射线诊断限，甚至优于商用 BGO 闪烁器。此外，通过将(C6H8N)2MnBr4晶体粉末与聚甲基丙烯酸甲酯混合，成功制备出了9 cm×9 cm的柔性闪烁体薄膜，具有优异的辐射稳定性和12.1 lp mm-1的X射线成像分辨率。值得注意的是，柔性薄膜捕捉到的 X 射线图像非常清晰，能完美地附着在弯曲的金属片上。卓越的性能和简便的溶液处理相结合，为基于有机金属卤化物的低成本、高性能大面积柔性闪烁体的 X 射线探测和成像开辟了新的机遇。
{"title":"Modulation of Halogens in Organic Manganese Halides for High-Resolution and Large-area Flexible X-ray Imaging","authors":"Ying Sun, Qian Ma, Dongheng Zhao, Pan Gao, Qi Wang, Zeyu Guo, Xiaomei Jiang","doi":"10.1039/d4qi02522a","DOIUrl":"https://doi.org/10.1039/d4qi02522a","url":null,"abstract":"Manganese-based organic metal halides, due to their excellent optoelectronic properties and stable chemical nature, have been widely applied in optoelectronic devices and sensors. In this study, through rational modulation of halogens, three novel zero-dimensional organic manganese halides (C6H8N)2MnX4 (X=Cl, Br, I) were obtained by adjusting the halogen via the solvent evaporation method. Attributed to the d-d electronic transition of Mn2+ in the tetrahedral-coordinated [MnX4]2- polyhedron, all samples exhibit strong green emission. Notably, the (C6H8N)2MnBr4 was demonstrated with a remarkable light yield of 18224 photons MeV−1 and a low detection limit of 1.9 μGy s−1, which is below the X-ray diagnostic limit and even superior to the commercial BGO scintillator. Moreover, a 9 cm×9 cm flexible scintillator film was successfully fabricated by mixing the (C6H8N)2MnBr4 crystalline powder with polymethyl methacrylate, manifesting superior radiation stability and an X-ray imaging resolution of 12.1 lp mm−1. Notably, the X-ray images captured by the flexible film demonstrate distinguished clarity as adhering perfectly to curved metal sheets. The combination of excellent performance and facile solution processing open new opportunities for low-cost, high-performance organic metal halides based large-area flexible scintillators for X-ray detection and imaging.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"112 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671069","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}
Octafluoropropane (C3F8) electronic specialty gas is widely used in the process of etching and cleaning in semiconductor manufacturing industry. Removal of hexafluoropropylene (C3F6) impurities from C3F6/C3F8 mixtures thus is highly important but a formidable challenge since C3F6 and C3F8 possess similar physicochemical properties and molecular sizes. Herein we present a cobalt metal-organic framework (MOF) (termed as JXNU-21) constructed of 3-chloroisonicotinic ligands, featuring dangling 3-chloroisonicotinic ligands in the one-dimensional channels. Due to the rotation flexibility of the aromatic rings of the dangling 3-chloroisonicotinate ligands with uncoordinated nitrogen sites, the step-wise adsorption isotherms for the large-sized C3F8 were observed for JXNU-21. The high adsorption selectivity of 15.6 for C3F6/C3F8 (10:90) mixture and high C3F6 storage density (5.8 mmol g–1) under ambient conditions endow JXNU-21 with high potential for C3F6/C3F8 separation. The results of the breakthrough experiments show high-purity (99.999%) C3F8 gas can be achieved from a C3F6/C3F8 (10:90) mixture in one step. Additionally, the benchmark C3F8 productivity of 173.8 cm3 g–1 was obtained from the breakthrough experiments under ambient conditions, outperforming all other reported porous materials.
{"title":"Purification of octafluoropropane from hexafluoropropylene /octafluoropropane mixtures with a metal-organic framework exhibiting high productivity","authors":"Yuan-Qin Feng, Hui-Fang Ma, Shuai Luo, Hui-Ping Xiao, Qing-Yan Liu, Yu-Ling Wang","doi":"10.1039/d4qi02562h","DOIUrl":"https://doi.org/10.1039/d4qi02562h","url":null,"abstract":"Octafluoropropane (C3F8) electronic specialty gas is widely used in the process of etching and cleaning in semiconductor manufacturing industry. Removal of hexafluoropropylene (C3F6) impurities from C3F6/C3F8 mixtures thus is highly important but a formidable challenge since C3F6 and C3F8 possess similar physicochemical properties and molecular sizes. Herein we present a cobalt metal-organic framework (MOF) (termed as JXNU-21) constructed of 3-chloroisonicotinic ligands, featuring dangling 3-chloroisonicotinic ligands in the one-dimensional channels. Due to the rotation flexibility of the aromatic rings of the dangling 3-chloroisonicotinate ligands with uncoordinated nitrogen sites, the step-wise adsorption isotherms for the large-sized C3F8 were observed for JXNU-21. The high adsorption selectivity of 15.6 for C3F6/C3F8 (10:90) mixture and high C3F6 storage density (5.8 mmol g–1) under ambient conditions endow JXNU-21 with high potential for C3F6/C3F8 separation. The results of the breakthrough experiments show high-purity (99.999%) C3F8 gas can be achieved from a C3F6/C3F8 (10:90) mixture in one step. Additionally, the benchmark C3F8 productivity of 173.8 cm3 g–1 was obtained from the breakthrough experiments under ambient conditions, outperforming all other reported porous materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"250 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671071","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}
Recently, the researches on ammonium-ion storage have gained widespread interest, and it is still a major problem and a popular research area to produce high-performance electrode materials for aqueous ammonium ion batteries (AAIBs). Herein, the electronic structure of tunnel-like vanadium dioxide (VO2) is tailored by molybdenum doping (denoted as VO2-Mo) to enhance ammonium-ion storage properties toward highly-efficient AAIBs. VO2-Mo with unique nanobelt structure is designed and synthesized by adjusting the content of Mo via a facile hydrothermal method. Density functional theory (DFT) simulations and experimental data both demonstrate that molybdenum atom in VO2 structure can improve mass transfer, speed up ion transport, and accelerate kinetic, showing boosted NH4+-storage properties. With 2 % Mo doping, at 0.1 A g−1, VO2-Mo exhibits a specific discharge capacity of around 370 mAh g−1, surpassing VO2 (232 mAh g−1) and the vanadium oxides-based materials that have been reported for NH4+-storage. Approximately 6000 successive charging and discharging cycles at 2 A g−1, it essentially maintains the specific capacity of 140 mAh g−1. Using VO2-Mo, polyaniline (PANI) and 1 M (NH4)2SO4 as the anode, cathode, and electrolyte, respectively, VO2-Mo//PANI full battery is further built, and at 0.2 A g−1, it reaches a specific discharge capacity of up to 232 mAh g−1, surpassing the performances of the most state-of-the-art AAIBs. At 89 W·kg−1, the VO2-Mo//PANI battery can achieve an energy density (E) up to 133 Wh·kg−1. This study provides new ideas for tailoring electrode materials with enhanced NH4+-storage for AAIBs.
近年来，铵离子存储的研究受到了广泛关注，而如何制备高性能的水性铵离子电池（AAIBs）电极材料仍是一大难题和热门研究领域。本文通过掺杂钼（表示为 VO2-Mo）来定制隧道状二氧化钒（VO2）的电子结构，以增强铵离子存储性能，从而实现高效 AAIBs。通过简单的水热法调整钼的含量，设计并合成了具有独特纳米带状结构的 VO2-Mo。密度泛函理论（DFT）模拟和实验数据都表明，VO2 结构中的钼原子可以改善传质、加快离子传输和加速动力学，从而显示出更强的 NH4+ 储存性能。钼掺杂量为 2 % 时，在 0.1 A g-1 的条件下，VO2-Mo 的比放电容量约为 370 mAh g-1，超过了 VO2（232 mAh g-1）和已报道过的基于钒氧化物的 NH4+ 存储材料。在 2 A g-1 的条件下连续充放电约 6000 次后，它的比容量基本保持在 140 mAh g-1 左右。使用 VO2-Mo、聚苯胺 (PANI) 和 1 M (NH4)2SO4 分别作为阳极、阴极和电解质，进一步构建了 VO2-Mo//PANI 全电池，在 0.2 A g-1 的条件下，比放电容量高达 232 mAh g-1，超过了最先进的 AAIB 性能。在 89 W-kg-1 的条件下，VO2-Mo//PANI 电池的能量密度 (E) 可达到 133 Wh-kg-1。这项研究为为 AAIBs 定制具有更强 NH4+ 储存能力的电极材料提供了新思路。
{"title":"Tailoring electronic structure to enhance ammonium-ion storage properties of VO2 by molybdenum doping toward highly-efficient aqueous ammonium-ion battery","authors":"Yifu Zhang, Zhenhua Zhou, Xianfang Tan, Yanyan Liu, Fangfang Zhang, Changgong Meng, Xiaoming Zhu","doi":"10.1039/d4qi01910e","DOIUrl":"https://doi.org/10.1039/d4qi01910e","url":null,"abstract":"Recently, the researches on ammonium-ion storage have gained widespread interest, and it is still a major problem and a popular research area to produce high-performance electrode materials for aqueous ammonium ion batteries (AAIBs). Herein, the electronic structure of tunnel-like vanadium dioxide (VO2) is tailored by molybdenum doping (denoted as VO2-Mo) to enhance ammonium-ion storage properties toward highly-efficient AAIBs. VO2-Mo with unique nanobelt structure is designed and synthesized by adjusting the content of Mo via a facile hydrothermal method. Density functional theory (DFT) simulations and experimental data both demonstrate that molybdenum atom in VO2 structure can improve mass transfer, speed up ion transport, and accelerate kinetic, showing boosted NH4+-storage properties. With 2 % Mo doping, at 0.1 A g−1, VO2-Mo exhibits a specific discharge capacity of around 370 mAh g−1, surpassing VO2 (232 mAh g−1) and the vanadium oxides-based materials that have been reported for NH4+-storage. Approximately 6000 successive charging and discharging cycles at 2 A g−1, it essentially maintains the specific capacity of 140 mAh g−1. Using VO2-Mo, polyaniline (PANI) and 1 M (NH4)2SO4 as the anode, cathode, and electrolyte, respectively, VO2-Mo//PANI full battery is further built, and at 0.2 A g−1, it reaches a specific discharge capacity of up to 232 mAh g−1, surpassing the performances of the most state-of-the-art AAIBs. At 89 W·kg−1, the VO2-Mo//PANI battery can achieve an energy density (E) up to 133 Wh·kg−1. This study provides new ideas for tailoring electrode materials with enhanced NH4+-storage for AAIBs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"69 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673676","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}
Aleksei S. Pronin, Yakov M. Gaifulin, Taisiya S. Sukhikh, Alexander N. Lavrov, Yuri V. Mironov
Obtaining nanosized, solution-processable molecules and ions with switchable magnetic moments is crucial for the development of storage devices. In this work, two seven-nuclear rhenium cluster complexes Cs7[{Re3S4(CN)9}{Re4S4}(CN)9]·10H2O (1) and K7[{Re3Se4(CN)9}{Re4Se4}(CN)9]·15H2O (2) were prepared and comprehensively characterized. The obtained clusters with an even number of cluster valence electrons (CVE) are found to consist of triangular and tetrahedral fragments strongly bonded together by bridging inner ligands and constitute a new structural type. Magnetochemical analysis of complexes has revealed the presence of non-magnetic singlet (MS = 0) and magnetic doublet (MS = ±1) states with a temperature-dependent population. These states, according to DFT calculations, may originate from the zero-field splitted S = 1 ground state, which is quite surprising given that clusters with an even number of CVE usually possess low-spin states (S = 0) due to the delocalized nature of the frontier molecular orbitals (MOs) and the effective removal of MO degeneracy by Jahn–Teller spatial distortion of the clusters. We have also succeeded in controlling one-electron oxidation of the clusters, which results in an odd number of CVE and drives the compound into a conventional paramagnetic S = 1/2 state.
{"title":"Multispin superatoms: seven-nuclear rhenium clusters with unusual magnetic properties","authors":"Aleksei S. Pronin, Yakov M. Gaifulin, Taisiya S. Sukhikh, Alexander N. Lavrov, Yuri V. Mironov","doi":"10.1039/d4qi02353f","DOIUrl":"https://doi.org/10.1039/d4qi02353f","url":null,"abstract":"Obtaining nanosized, solution-processable molecules and ions with switchable magnetic moments is crucial for the development of storage devices. In this work, two seven-nuclear rhenium cluster complexes Cs<small><sub>7</sub></small>[{Re<small><sub>3</sub></small>S<small><sub>4</sub></small>(CN)<small><sub>9</sub></small>}{Re<small><sub>4</sub></small>S<small><sub>4</sub></small>}(CN)<small><sub>9</sub></small>]·10H<small><sub>2</sub></small>O (<strong>1</strong>) and K<small><sub>7</sub></small>[{Re<small><sub>3</sub></small>Se<small><sub>4</sub></small>(CN)<small><sub>9</sub></small>}{Re<small><sub>4</sub></small>Se<small><sub>4</sub></small>}(CN)<small><sub>9</sub></small>]·15H<small><sub>2</sub></small>O (<strong>2</strong>) were prepared and comprehensively characterized. The obtained clusters with an even number of cluster valence electrons (CVE) are found to consist of triangular and tetrahedral fragments strongly bonded together by bridging inner ligands and constitute a new structural type. Magnetochemical analysis of complexes has revealed the presence of non-magnetic singlet (<em>M</em><small><sub><em>S</em></sub></small> = 0) and magnetic doublet (<em>M</em><small><sub><em>S</em></sub></small> = ±1) states with a temperature-dependent population. These states, according to DFT calculations, may originate from the zero-field splitted <em>S</em> = 1 ground state, which is quite surprising given that clusters with an even number of CVE usually possess low-spin states (<em>S</em> = 0) due to the delocalized nature of the frontier molecular orbitals (MOs) and the effective removal of MO degeneracy by Jahn–Teller spatial distortion of the clusters. We have also succeeded in controlling one-electron oxidation of the clusters, which results in an odd number of CVE and drives the compound into a conventional paramagnetic <em>S</em> = 1/2 state.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671068","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}
Zhentao Hu, Lei Huang, Bojing Sun, Dongfang Hou, Xiu-Qing Qiao, Meidi Wang, Huijuan Ma, Dong-Sheng Li
Photocatalytic carbon dioxide reduction to solar fuels is one of the promising strategies to solve resource depletion and global climate warming. Nevertheless, the poor product selectivity greatly limits its practical application. Herein, we present a Cu nanoparticle-modified ZnCdS2/NiMoO4 Z-scheme heterojunction photocatalyst with highly selective and stable. It is worth noting that the hydrophobicity of NiMoO4 can effectively inhibit the adsorption of water, while forming a Z-scheme heterostructure with defective ZnCdS2, and thus inhibiting hydrogen evolution and improving the separation efficiency of photogenerated carriers. Meanwhile, Cu nanoparticles with surface plasmon resonance effect generate amount high-energy hot electrons during photoexcitation, which not only greatly increases the photogenerated electron density on the surface of the catalyst, resulting in a higher probability of multiple electron reactions or reduced state products, but also effectively reduces the activation energy barrier for CO2 reduction through photothermal effect. Consequently, ZCS/NMO@Cu Z-scheme heterojunction exhibits nearly 100% selectivity of CH4 with eight-electron involved reduction reaction, and outstanding CH4 yield of 92.17 μmol g-1 h-1 without sacrificial agent and co-catalyst. Furthermore, the CO2 reduction mechanism is confirmed through in-situ Fourier transform infrared spectroscopy (FTIR) analysis. This work will provide meaningful prospects for designing a carbon dioxide reduction photocatalyst with high conversion and selection.
光催化将二氧化碳还原为太阳能燃料是解决资源枯竭和全球气候变暖问题的可行策略之一。然而，产品选择性差极大地限制了其实际应用。在此，我们提出了一种铜纳米粒子修饰的 ZnCdS2/NiMoO4 Z 型异质结光催化剂，它具有高选择性和稳定性。值得注意的是，NiMoO4 的疏水性可以有效抑制水的吸附，同时与有缺陷的 ZnCdS2 形成 Z 型异质结构，从而抑制氢的演化，提高光生载流子的分离效率。同时，具有表面等离子体共振效应的 Cu 纳米粒子在光激发过程中会产生大量高能热电子，这不仅大大增加了催化剂表面的光生电子密度，导致更高的多电子反应或还原态产物的概率，而且通过光热效应有效降低了二氧化碳还原的活化能势垒。因此，ZCS/NMO@Cu Z 型异质结在八电子参与的还原反应中对 CH4 的选择性接近 100%，在不使用牺牲剂和助催化剂的情况下，CH4 产率高达 92.17 μmol g-1 h-1。此外，原位傅立叶变换红外光谱（FTIR）分析证实了二氧化碳还原机理。这项工作将为设计一种具有高转化率和高选择性的二氧化碳还原光催化剂提供有意义的前景。
{"title":"Surface plasmon resonance and structure defects synergetic effect of ZnCdS2/NiMoO4@Cu Z-scheme heterojunction for enhanced photocatalytic CO2 reduction to CH4","authors":"Zhentao Hu, Lei Huang, Bojing Sun, Dongfang Hou, Xiu-Qing Qiao, Meidi Wang, Huijuan Ma, Dong-Sheng Li","doi":"10.1039/d4qi02332c","DOIUrl":"https://doi.org/10.1039/d4qi02332c","url":null,"abstract":"Photocatalytic carbon dioxide reduction to solar fuels is one of the promising strategies to solve resource depletion and global climate warming. Nevertheless, the poor product selectivity greatly limits its practical application. Herein, we present a Cu nanoparticle-modified ZnCdS2/NiMoO4 Z-scheme heterojunction photocatalyst with highly selective and stable. It is worth noting that the hydrophobicity of NiMoO4 can effectively inhibit the adsorption of water, while forming a Z-scheme heterostructure with defective ZnCdS2, and thus inhibiting hydrogen evolution and improving the separation efficiency of photogenerated carriers. Meanwhile, Cu nanoparticles with surface plasmon resonance effect generate amount high-energy hot electrons during photoexcitation, which not only greatly increases the photogenerated electron density on the surface of the catalyst, resulting in a higher probability of multiple electron reactions or reduced state products, but also effectively reduces the activation energy barrier for CO2 reduction through photothermal effect. Consequently, ZCS/NMO@Cu Z-scheme heterojunction exhibits nearly 100% selectivity of CH4 with eight-electron involved reduction reaction, and outstanding CH4 yield of 92.17 μmol g-1 h-1 without sacrificial agent and co-catalyst. Furthermore, the CO2 reduction mechanism is confirmed through in-situ Fourier transform infrared spectroscopy (FTIR) analysis. This work will provide meaningful prospects for designing a carbon dioxide reduction photocatalyst with high conversion and selection.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665336","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}
Seawater electrolysis for green hydrogen production is a promising approach toward achieving carbon neutrality. However, the abundance of Cl– in seawater can severely corrode catalytic sites, significantly reducing the lifespan of seawater electrolysis systems. Herein, we present metal ions-chelated tannic acid nanoparticles anchored on the CoFe layered double hydroxide nanosheet array on nickel foam (CoFe LDH@CoFe-TA/NF), synthesized via an interfacial coordination assembly method, serving as an efficient and stable electrocatalyst for alkaline seawater oxidation (ASO). The formed CoFe-TA nanoparticles promote the reconstruction and generation of CoFe oxy(hydroxide), which not only drives excellent ASO performance but also enhances resistance to chlorine-induced corrosion. In addition, the CoFe-TA ligand network effectively inhibits metal ions leaching and stabilizes active sites. As a result, CoFe LDH@CoFe-TA/NF electrode requires a low overpotential of only 379 mV to obtain a current density of 1000 mA cm–2 in 1 M KOH + seawater. Furthermore, the electrode also shows a stable operation for 450 h at an industrial-level current density, underscoring its potential for sustainable energy applications.
{"title":"Tannic acid salts-modified CoFe-layered double hydroxide boosts the stable seawater oxidation at an industrial-level current density","authors":"Zhengwei Cai, Yaxin Guo, Chaoxin Yang, Zixiao Li, Shengjun Sun, Yue Meng, Xiaoyan Wang, Min Zhang, Hefeng Wang, Yongchao Yao, Dongdong Zheng, Asmaa Farouk, Fatma A. Ibrahim, Yanqin Lv, Xuping Sun, Bo Tang","doi":"10.1039/d4qi02404d","DOIUrl":"https://doi.org/10.1039/d4qi02404d","url":null,"abstract":"Seawater electrolysis for green hydrogen production is a promising approach toward achieving carbon neutrality. However, the abundance of Cl– in seawater can severely corrode catalytic sites, significantly reducing the lifespan of seawater electrolysis systems. Herein, we present metal ions-chelated tannic acid nanoparticles anchored on the CoFe layered double hydroxide nanosheet array on nickel foam (CoFe LDH@CoFe-TA/NF), synthesized via an interfacial coordination assembly method, serving as an efficient and stable electrocatalyst for alkaline seawater oxidation (ASO). The formed CoFe-TA nanoparticles promote the reconstruction and generation of CoFe oxy(hydroxide), which not only drives excellent ASO performance but also enhances resistance to chlorine-induced corrosion. In addition, the CoFe-TA ligand network effectively inhibits metal ions leaching and stabilizes active sites. As a result, CoFe LDH@CoFe-TA/NF electrode requires a low overpotential of only 379 mV to obtain a current density of 1000 mA cm–2 in 1 M KOH + seawater. Furthermore, the electrode also shows a stable operation for 450 h at an industrial-level current density, underscoring its potential for sustainable energy applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"30 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671072","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：