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Giant Charge Separation-Driving Force Together with Ultrafluent Charge Transfer in TiO2/ZnFe-LDH Photoelectrode via Ferroelectric Interface Engineering 通过铁电界面工程实现 TiO2/ZnFe-LDH 光电极中的巨大电荷分离驱动力和超顺畅电荷转移
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-12 DOI: 10.1021/acs.inorgchem.4c03125
Yanfang He, Aihua Yuan, Iltaf Khan, Ying Yang, Dawei Cao
Hydrogen fuel production using photoelectrochemical (PEC) water-splitting technology is incredibly noteworthy as it provides a sustainable and clean method to alleviate the energy environmental crisis. A highly rapid electron shuttle at the semiconductor/WOC (water oxidation cocatalyst) interface is vital to improve the bulk charge transfer and surface reaction kinetics of the photoelectrode in the PEC water-splitting system. Yet, the inevitably inferior interface transition tends to plague the performance enhancement on account of the collision of hole–electron transport across the semi/cat interface. Herein, we address these critical challenges via inserting ferroelectric layer BTO (BaTiO3) into the semi/cat interface. The embedded polarization electric field induced by ferroelectric BTO remarkably pumped hole transfer at the semiconductor/WOC (TiO2/ZnFe-LDH) interface and selectively tailored the electronic structure of LDH surface-active sites, leading to overwhelmingly improved surface hole transfer kinetics at LDH/electrolyte interface, which minish the electron–hole recombination in bulk and on the surface of TiO2. The TiO2 nanorods encapsulated by ferroelectric-assisted ZnFe-LDH achieve 105% charge separation efficiency improvement and 53.8% charge injection efficiency enhancement compared with pure TiO2. This finding offers a strategic design for electrocatalytic-assisted photoelectrode systems by ferroelectric-pumped charge extraction and transfer at the semiconductor/WOC interface.
利用光电化学(PEC)分水技术生产氢燃料是一种可持续的清洁方法,可缓解能源环境危机,因此非常值得关注。半导体/WOC(水氧化催化剂)界面上的快速电子穿梭对于改善 PEC 水分离系统中光电极的体电荷转移和表面反应动力学至关重要。然而,由于半/猫界面上的空穴-电子传输碰撞,不可避免的劣质界面转换往往会影响性能的提高。在此,我们通过在半猫/猫界面中插入铁电层 BTO (BaTiO3),解决了这些关键难题。铁电层 BTO 诱导的嵌入式极化电场显著地泵送了半导体/WOC(TiO2/ZnFe-LDH)界面上的空穴传输,并选择性地定制了 LDH 表面活性位点的电子结构,从而极大地改善了 LDH/电解质界面上的表面空穴传输动力学,减少了 TiO2 本体和表面的电子-空穴重组。与纯 TiO2 相比,铁电辅助 ZnFe-LDH 封装的 TiO2 纳米棒的电荷分离效率提高了 105%,电荷注入效率提高了 53.8%。这一发现为在半导体/WOC 界面通过铁电泵送电荷提取和转移的电催化辅助光电极系统提供了一种战略性设计。
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引用次数: 0
Preparation and Characterization of a High-Entropy Magnet, (Mg, Mn, Co, Ni, Cu)3TeO6 高熵磁体 (镁、锰、钴、镍、铜)3TeO6 的制备与表征
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-12 DOI: 10.1021/acs.inorgchem.4c02809
Vladimir B. Nalbandyan, Konstantin V. Zakharov, Maria A. Evstigneeva, Alexander N. Vasiliev, Ivan G. Sheptun, Larisa V. Shvanskaya, Tatyana M. Vasilchikova
We report on the synthesis of Mg0.6Mn0.7Co0.7Ni0.6Cu0.4TeO6, which is isostructural with multiferroic Mn3TeO6 (space group R3¯). Study of its magnetic properties indicates establishment of the long-range antiferromagnetic order at 16.3 K, slightly lower than that of pure Mn3TeO6. The tiny hysteresis of magnetization loop along with specific heat data implies the presence of ferromagnetic magnons at low temperatures. Dielectric measurements reveal sequence of well-defined steps in the real part of permittivity and peaks in the imaginary parts of permittivity at 30, 92, and 212 K attributable to the highly diffused structural changes, which are characteristic to relaxor ferroelectrics. It is shown that usual interpretation of this structure type as corundum-related is not accurate: the hexagonal oxygen packing is not close and is not double-layered. Therefore, Mn3TeO6 represents a very special structure type.
我们报告了 Mg0.6Mn0.7Co0.7Ni0.6Cu0.4TeO6 的合成,它与多铁性 Mn3TeO6(空间群𝑅3¯R3¯R3¯)具有同构结构。对其磁性能的研究表明,它在 16.3 K 时建立了长程反铁磁阶,略低于纯 Mn3TeO6 的长程反铁磁阶。磁化环路的微小磁滞和比热数据意味着低温下铁磁磁子的存在。介电测量结果表明,在 30、92 和 212 K 时,介电常数的实部和虚部会出现一系列明确的阶跃,这归因于高度扩散的结构变化,是弛豫铁电的特征。研究表明,通常将这种结构类型解释为与刚玉有关是不准确的:六方氧堆积并不紧密,也不是双层的。因此,Mn3TeO6 代表了一种非常特殊的结构类型。
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引用次数: 0
Correction to “Synthesis of Low-Symmetric α-Cobalt(II) Hydroxide-Incorporated Cyanuric Acid Layers with High Néel Temperature and Large Coercivity: Structure and Magnetism” 更正 "具有高奈尔温度和大矫顽力的低对称性α-氢氧化钴(II)掺杂氰尿酸层的合成:结构与磁性"
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-12 DOI: 10.1021/acs.inorgchem.4c04458
Qi Wang, Jun-Rong Meng, Yi-Fan Shen, Ri-Hui Zheng, Hongdan Zhu, Quan-Wen Li, Peng-Fei Yao, Qian Peng
The order of the author names and the affiliations have been corrected. Changes are reflected in this Correction and the attached Supporting Information PDF file. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c04458. Structural details, measurement details, and DFT calculations for 1, crystallographic data in CIF format, and additional plots and data for 1 (PDF) Correctionto “Synthesis of Low-Symmetric α‑Cobalt(II)Hydroxide-Incorporated Cyanuric Acid Layers with High NéelTemperature and Large Coercivity: Structure and Magnetism” 1 views 0 shares 0 downloads Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article has not yet been cited by other publications.
作者姓名和单位的顺序已更正。这些改动反映在本更正和所附的佐证资料 PDF 文件中。辅助信息可从 https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c04458 免费获取。1 的结构细节、测量细节和 DFT 计算结果、CIF 格式的晶体学数据以及 1 的附加图表和数据 (PDF) Correctionto "Synthesis of Low-Symmetric α-Cobalt(II)Hydroxide-Incorporated Cyanuric Acid Layers with High NéelTemperature and Large Coercivity:结构与磁性" 1 次浏览 0 次分享 0 次下载 无需订阅 ACS Web Editions,即可获得大多数电子版辅助信息文件。这些文件可按文章下载,用于研究用途(如果相关文章链接了公共使用许可,则该许可可能允许其他用途)。如需其他用途,可通过 RightsLink 许可系统 http://pubs.acs.org/page/copyright/permissions.html 向 ACS 申请许可。本文尚未被其他出版物引用。
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引用次数: 0
Solvent- and Concentration-Induced Topological Transformation of a Ruthenium(II)-Based Trigonal Prism to a Triply Interlocked [2] Catenane. 溶剂和浓度诱导的钌(II)基三叉棱柱向三重互锁 [2] 卡特烷的拓扑转变。
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-11 Epub Date: 2024-10-28 DOI: 10.1021/acs.inorgchem.4c03339
Shamsad Ali, Valiyakath Abdul Rinshad, Partha Sarathi Mukherjee

Synthesis of interlocked supramolecular cages has been a growing field of interest due to their structural diversity. Herein, we report the template-free synthesis of a Ru(II) triply interlocked [2] catenane using coordination-driven self-assembly. The self-assembly of a triazine-based tripyridyl donor L (2,4,6-tris(5-(pyridin-4-yl)thiophen-3-yl)-1,3,5-triazine) with a dinuclear Ru(II) acceptor M (Ru2(dhnq)(η6-p-cymene)2)(CF3SO3)2) yielded two distinct structures depending on the solvent and concentration. In methanol, a triply interlocked metalla [2] catenane (MC2) was formed, whereas in nitromethane, a non-interlocked cage (MC1) was obtained. The non-interlocked cage MC1 was gradually converted to MC2 in nitromethane by the increase in the concentration of cage MC1 from 0.5 to 9 mM. The interlocked cage (MC2) was stable after formation and was unaffected by the change in concentration. Notably, the free cage (MC1) exhibited host-guest interactions with polycyclic aromatic aldehydes, stabilizing the non-interlocked structure even at higher concentrations. In contrast, the triply interlocked [2] catenane (MC2) remains stable due to self-penetration and does not encapsulate guest molecules. This work showcases the stimuli-induced irreversible structural transformation of a triangular prismatic cage to its triply interlocked [2] catenane by employing metal-ligand coordination chemistry.

由于结构的多样性,互锁超分子笼的合成越来越受到关注。在此,我们报告了利用配位驱动的自组装技术无模板合成三重互锁 [2] 连环的 Ru(II) 的情况。基于三嗪的三吡啶供体 L(2,4,6-三(5-(吡啶-4-基)噻吩-3-基)-1,3,5-三嗪)与双核 Ru(II) 受体 M(Ru2(dhnq)(η6-p-cymene)2)(CF3SO3)2)的自组装产生了两种不同的结构,这取决于溶剂和浓度。在甲醇中,形成了三重互锁的金属[2] 梓烷(MC2),而在硝基甲烷中,得到了非互锁笼(MC1)。在硝基甲烷中,随着笼 MC1 的浓度从 0.5 mM 增加到 9 mM,非互锁笼 MC1 逐渐转化为 MC2。互锁笼(MC2)在形成后很稳定,不受浓度变化的影响。值得注意的是,游离保持架(MC1)与多环芳香醛发生了主-客相互作用,即使在较高浓度下也能稳定非互锁结构。相比之下,三重互锁的 [2] 梓烷(MC2)由于自我渗透而保持稳定,不会包裹客体分子。这项研究通过金属配体配位化学,展示了由刺激诱导的三角棱柱笼向三重互锁 [2] 梓烷的不可逆结构转变。
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引用次数: 0
High-Pressure Behaviors of Hydrogen Bonds in Fluorine-Doped Brucite 掺氟白云石中氢键的高压行为
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-11 DOI: 10.1021/acs.inorgchem.4c02676
Xuejing He, Hiroyuki Kagi, Kazuki Komatsu, Asami Sano-Furukawa, Jun Abe, Ko Fukuyama, Toru Shinmei, Satoshi Nakano
Brucite, Mg(OH)2 (Pm1, Z = 1), is a prototype material for studying hydrogen bonds in solid hydroxides. In this study, substitutional effects of fluorine (F) on the hydrogen-bonding geometries of hydrogenated and deuterated brucite were investigated under ambient conditions and at high pressure using combined experimental methods of neutron powder diffraction, Raman spectroscopy, and infrared (IR) spectroscopy. Under ambient conditions, neutron powder diffraction results showed that F substitution decreased the donor–acceptor distance and increased the hydroxyl covalent bond lengths of both hydrogenated and deuterated brucite, strengthening the hydrogen bond. Red shifts of the hydroxyl stretching modes also indicated an elongation of d(O–H) and d(O–D). High-pressure neutron diffraction experiments were performed on Mg(OH)1.81F0.19 and Mg(OD)1.74F0.26 up to 7.04 and 10.02 GPa, respectively. For both samples, changes in the hydrogen-bonding geometries did not indicate hydrogen-bond strengthening under high pressure. Compared with Mg(OD)2, the doping of F suppressed the increase of the hydroxyl covalent bond length, the hydrogen-bond angle, and the cone angle, inhibiting pressure-induced hydrogen-bond strengthening. High-pressure Raman and IR absorption spectroscopic measurements on Mg(OD)2 and Mg(OD)1.79F0.21 up to 9.7 and 13.7 GPa confirmed that F substitution restrains pressure-induced hydroxyl elongation.
青金石(Mg(OH)2 (P3̅m1, Z = 1))是研究固体氢氧化物中氢键的原型材料。本研究采用中子粉末衍射、拉曼光谱和红外光谱等综合实验方法,研究了氟 (F) 在环境条件和高压条件下对氢化和氚化青金石氢键几何形状的取代效应。在环境条件下,中子粉末衍射结果表明,F 取代减少了氢化和氚化青金石的供体-受体距离,增加了羟基共价键长度,从而加强了氢键。羟基伸展模式的红移也表明 d(O-H)和 d(O-D)被拉长。对 Mg(OH)1.81F0.19 和 Mg(OD)1.74F0.26 分别进行了高达 7.04 和 10.02 GPa 的高压中子衍射实验。对于这两种样品,氢键几何形状的变化并不表明高压下氢键的加强。与 Mg(OD)2 相比,F 的掺杂抑制了羟基共价键长度、氢键角度和锥角的增加,从而抑制了压力引起的氢键强化。在 9.7 和 13.7 GPa 下对 Mg(OD)2 和 Mg(OD)1.79F0.21 进行的高压拉曼光谱和红外吸收光谱测量证实,F 取代抑制了压力引起的羟基伸长。
{"title":"High-Pressure Behaviors of Hydrogen Bonds in Fluorine-Doped Brucite","authors":"Xuejing He, Hiroyuki Kagi, Kazuki Komatsu, Asami Sano-Furukawa, Jun Abe, Ko Fukuyama, Toru Shinmei, Satoshi Nakano","doi":"10.1021/acs.inorgchem.4c02676","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c02676","url":null,"abstract":"Brucite, Mg(OH)<sub>2</sub> (<i>P</i>3̅<i>m</i>1, <i>Z</i> = 1), is a prototype material for studying hydrogen bonds in solid hydroxides. In this study, substitutional effects of fluorine (F) on the hydrogen-bonding geometries of hydrogenated and deuterated brucite were investigated under ambient conditions and at high pressure using combined experimental methods of neutron powder diffraction, Raman spectroscopy, and infrared (IR) spectroscopy. Under ambient conditions, neutron powder diffraction results showed that F substitution decreased the donor–acceptor distance and increased the hydroxyl covalent bond lengths of both hydrogenated and deuterated brucite, strengthening the hydrogen bond. Red shifts of the hydroxyl stretching modes also indicated an elongation of <i>d</i>(O–H) and <i>d</i>(O–D). High-pressure neutron diffraction experiments were performed on Mg(OH)<sub>1.81</sub>F<sub>0.19</sub> and Mg(OD)<sub>1.74</sub>F<sub>0.26</sub> up to 7.04 and 10.02 GPa, respectively. For both samples, changes in the hydrogen-bonding geometries did not indicate hydrogen-bond strengthening under high pressure. Compared with Mg(OD)<sub>2</sub>, the doping of F suppressed the increase of the hydroxyl covalent bond length, the hydrogen-bond angle, and the cone angle, inhibiting pressure-induced hydrogen-bond strengthening. High-pressure Raman and IR absorption spectroscopic measurements on Mg(OD)<sub>2</sub> and Mg(OD)<sub>1.79</sub>F<sub>0.21</sub> up to 9.7 and 13.7 GPa confirmed that F substitution restrains pressure-induced hydroxyl elongation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599479","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A Stable Layered Microporous MOF Assembled with Y-O Chains for Separation of MTO Products. 用 Y-O 链组装的稳定层状微孔 MOF 用于分离 MTO 产品。
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-11 Epub Date: 2024-10-28 DOI: 10.1021/acs.inorgchem.4c03735
Hengbo Li, Yunzhe Zhou, Cheng Chen, Yashuang Li, Zheng Liu, Mingyan Wu, Maochun Hong

Benefiting from highly tunable pore environments, some metal-organic frameworks (MOFs) have recently shown promising prospects in the separation of methanol-to-olefin (MTO) products (mainly C3H6 and C2H4). However, the "trade-off" between gas storage capacity and selectivity always results in inefficient separation. In addition, poor stability of MOFs also limits practical separation applications. Herein, we have successfully assembled a layered Y-MOF (FJI-W9) with bent diisophthalate ligands (H4L), Y-O chains, and 2-fluorobenzoic acids. As expected, FJI-W9 not only exhibits good chemical stability but also shows significant potential for C3H6/C2H4 separation. For FJI-W9, the C3H6 uptake at 298 K and 10 kPa is 63 cm3/g, and the IAST selectivity of FJI-W9 for C3H6/C2H4 (V/V = 50/50) is calculated to be 20.5. To the best of our knowledge, both C3H6 uptake and selectivity of FJI-W9 surpass most porous materials. GCMC simulation indicates that the special supramolecular binding sites in FJI-W9 have much stronger interactions with C3H6 than C2H4 molecules. More importantly, practical breakthrough experiments demonstrate that FJI-W9 can effectively separate C3H6/C2H4 (50/50) mixtures, thus obtaining high-purity C2H4 and C3H6, respectively.

得益于高度可调的孔隙环境,一些金属有机框架(MOFs)最近在分离甲醇制烯烃(MTO)产品(主要是 C3H6 和 C2H4)方面展现出了广阔的前景。然而,气体储存能力和选择性之间的 "权衡 "总是导致分离效率低下。此外,MOFs 较差的稳定性也限制了其实际分离应用。在此,我们成功地组装了一种具有弯曲的邻苯二甲酸二异配体(H4L)、Y-O 链和 2-氟苯甲酸的层状 Y-MOF (FJI-W9)。正如预期的那样,FJI-W9 不仅具有良好的化学稳定性,而且在 C3H6/C2H4 分离方面也显示出巨大的潜力。在 298 K 和 10 kPa 条件下,FJI-W9 对 C3H6 的吸收率为 63 cm3/g,计算得出 FJI-W9 对 C3H6/C2H4 的 IAST 选择性为 20.5(V/V = 50/50)。据我们所知,FJI-W9 对 C3H6 的吸收率和选择性都超过了大多数多孔材料。GCMC 模拟表明,FJI-W9 中特殊的超分子结合位点与 C3H6 分子的相互作用远强于 C2H4 分子。更重要的是,实际突破性实验证明,FJI-W9 能有效分离 C3H6/C2H4 (50/50)混合物,从而分别获得高纯度的 C2H4 和 C3H6。
{"title":"A Stable Layered Microporous MOF Assembled with Y-O Chains for Separation of MTO Products.","authors":"Hengbo Li, Yunzhe Zhou, Cheng Chen, Yashuang Li, Zheng Liu, Mingyan Wu, Maochun Hong","doi":"10.1021/acs.inorgchem.4c03735","DOIUrl":"10.1021/acs.inorgchem.4c03735","url":null,"abstract":"<p><p>Benefiting from highly tunable pore environments, some metal-organic frameworks (MOFs) have recently shown promising prospects in the separation of methanol-to-olefin (MTO) products (mainly C<sub>3</sub>H<sub>6</sub> and C<sub>2</sub>H<sub>4</sub>). However, the \"trade-off\" between gas storage capacity and selectivity always results in inefficient separation. In addition, poor stability of MOFs also limits practical separation applications. Herein, we have successfully assembled a layered Y-MOF (<b>FJI-W9</b>) with bent diisophthalate ligands (H<sub>4</sub>L), Y-O chains, and 2-fluorobenzoic acids. As expected, <b>FJI-W9</b> not only exhibits good chemical stability but also shows significant potential for C<sub>3</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>4</sub> separation. For <b>FJI-W9</b>, the C<sub>3</sub>H<sub>6</sub> uptake at 298 K and 10 kPa is 63 cm<sup>3</sup>/g, and the IAST selectivity of <b>FJI-W9</b> for C<sub>3</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>4</sub> (V/V = 50/50) is calculated to be 20.5. To the best of our knowledge, both C<sub>3</sub>H<sub>6</sub> uptake and selectivity of <b>FJI-W9</b> surpass most porous materials. GCMC simulation indicates that the special supramolecular binding sites in <b>FJI-W9</b> have much stronger interactions with C<sub>3</sub>H<sub>6</sub> than C<sub>2</sub>H<sub>4</sub> molecules. More importantly, practical breakthrough experiments demonstrate that <b>FJI-W9</b> can effectively separate C<sub>3</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>4</sub> (50/50) mixtures, thus obtaining high-purity C<sub>2</sub>H<sub>4</sub> and C<sub>3</sub>H<sub>6</sub>, respectively.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491108","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Vanadate Inclusion Leading to Red-Ox-Rich Zircon PrCrO4: Synthesis, Magnetic, and Catalytic Properties 钒酸盐包合导致富含红氧化物的锆石 PrCrO4:合成、磁性和催化特性
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-11 DOI: 10.1021/acs.inorgchem.4c03157
Neetu Yadav, Inderjeet Singh, Rajamani Nagarajan
Rare-earth-based ternary compounds with the formula REBO4 (B = V, Cr, P, As) exhibit rich structural chemistry and associated technologically significant properties. Among the rare-earth chromates, realizing PrCrO4 in a single polymorphic modification has been challenging. Herein, we report the successful stabilization of the zircon polymorph of PrCrO4 by introducing 10 mol % of VO43– instead of CrO43– following a solution combustion method. Compositions with progressively higher amounts of vanadate have been synthesized and characterized extensively. XPS analysis of 10 and 50 mol % VO43– substituted PrCrO4 samples ascertained the existence of Pr3+/4+, Cr4+,5+, and V5+ in them, making it a red-ox-rich system. The tetragonal symmetry of PrCr0.50V0.50O4 was confirmed from the HRTEM images and SAED patterns. FTIR and Raman spectral analyses indicated distorted tetrahedral (Cr/VO4) units with a local site symmetry below D2d. Both d-d and f-f transitions of Cr4+ and Pr3+, respectively, were observed in the absorption spectra. Field and temperature-dependent magnetic measurements of PrCr0.50V0.50O4 confirmed its predominant paramagnetic behavior. The samples possessed porous morphology with a reasonable surface area. PrCr1–xVxO4 (x = 0.00–0.50) samples catalyzed the oxidation of phenol. This study demonstrated B-site tuning in ABO4 systems to select a desired polymorph preferentially.
稀土基三元化合物 REBO4(B = V、Cr、P、As)具有丰富的结构化学性质和相关的重要技术特性。在稀土铬酸盐中,实现 PrCrO4 的单一多晶型修饰一直是一项挑战。在此,我们报告了通过溶液燃烧法引入 10 摩尔%的 VO43- 而不是 CrO43-,成功稳定了 PrCrO4 的锆石多晶体。我们合成了钒酸盐含量逐渐增加的化合物,并对其进行了广泛表征。对 10 和 50 mol % VO43- 取代的 PrCrO4 样品进行的 XPS 分析表明,其中存在 Pr3+/4+、Cr4+、5+ 和 V5+,使其成为富含红氧化物的体系。从 HRTEM 图像和 SAED 图形中证实了 PrCr0.50V0.50O4 的四方对称性。傅立叶变换红外光谱和拉曼光谱分析表明,畸变四面体(Cr/VO4)单元的局部对称性低于 D2d。在吸收光谱中分别观察到了 Cr4+ 和 Pr3+ 的 d-d 和 f-f 转变。对 PrCr0.50V0.50O4 进行的磁场和温度依赖性测量证实了其主要的顺磁性。样品具有多孔形态和合理的比表面积。PrCr1-xVxO4 (x = 0.00-0.50) 样品可催化苯酚氧化。这项研究表明,ABO4 系统中的 B 位调整可优先选择所需的多晶体。
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引用次数: 0
What Can Chemical Bonding Tell Us about Photoinduced Phase Transition Reactions in Inorganic Semiconductors? Insight from Bismuth–Antimony Selenide 化学键对无机半导体光诱导相变反应有何启示?硒化铋锑的启示
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-11 DOI: 10.1021/acs.inorgchem.4c03454
Anchal Vashishtha, Subila Kurukkal Balakrishnan, Yaniv Dror, Jitendra Kumar, Priyakumari Chakkingal Parambil, Eran Edri
Photoreactive self-healing semiconductors with suitable bandgaps for solar energy conversion offer an intriguing path to making resilient and low-cost photovoltaic devices through the introduction of a self-recovery path. However, only a few inorganic photovoltaic materials have such quality, and the underlying chemical properties that enable it are unknown, which poses a significant limit to our ability to study and discover new self-healing semiconductors. Recently, we have found that antimony trichalcogenide (Sb2Se3 and Sb2S3) and chalcohalides (e.g., SbSeI) can undergo a reversible photoinduced phase transition (PIPT) in which the structure is restored after photoinduced damage incurs to the materials. This group of materials offer a unique opportunity for studying PIPT and its limits. In particular, this group of materials facilitate the study of functional permutation to specific crystalline sites and to finding the limits of PIPT occurrence, which sheds light on the origin of the PIPT and self-recovery of this class of materials. Using Raman spectroscopy of thin films, and following signature vibrations of transition species, we have found that the PIPT magnitude decays upon gradual BiSb(1) substitution in a Sb2–xBixSe3 homologous series, until nearly one in five Sb ions is substituted with Bi. Then, the PIPT diminishes completely. The homologous series occurs along a transition from covalent to metavalent chemical bonding. By expanding our search, we find that a correlation between bonding type and photoreactivity does exist but conclude that it is an insufficient condition. Instead, we suggest, based on bond order and additional DFT calculations, that sufficient bonding states at the bottom of the conduction band are also required. This joint experimental and computational study pushes the limits of designing self-healing inorganic semiconductors for various applications and provides tools for further expansion.
光活性自愈合半导体具有适合太阳能转换的带隙,通过引入自恢复路径,为制造弹性好、成本低的光伏设备提供了一条引人入胜的道路。然而,只有少数无机光伏材料具有这样的品质,而且实现这种品质的基本化学特性尚不清楚,这极大地限制了我们研究和发现新型自修复半导体的能力。最近,我们发现三卤化锑(Sb2Se3 和 Sb2S3)和卤化物(如 SbSeI)可以发生可逆的光诱导相变(PIPT),在材料受到光诱导损伤后,其结构会得到恢复。这组材料为研究 PIPT 及其限制提供了独特的机会。特别是,这组材料有助于研究特定结晶位点的功能排列,并找到 PIPT 发生的极限,从而揭示 PIPT 的起源和这一类材料的自我恢复。利用薄膜的拉曼光谱和过渡物种的特征振动,我们发现在 Sb2-xBixSe3 同源系列中,当 BiSb(1) 逐渐被取代时,PIPT 的大小会逐渐减小,直到将近五分之一的 Sb 离子被 Bi 取代。然后,PIPT 完全减小。该同源系列是沿着从共价化学键到偏价化学键的过渡而出现的。通过扩大搜索范围,我们发现键合类型与光反应之间确实存在相关性,但得出的结论是,这是一个不充分的条件。相反,根据键序和额外的 DFT 计算,我们认为导带底部也需要足够的键合状态。这项实验和计算联合研究突破了为各种应用设计自修复无机半导体的极限,并为进一步扩展提供了工具。
{"title":"What Can Chemical Bonding Tell Us about Photoinduced Phase Transition Reactions in Inorganic Semiconductors? Insight from Bismuth–Antimony Selenide","authors":"Anchal Vashishtha, Subila Kurukkal Balakrishnan, Yaniv Dror, Jitendra Kumar, Priyakumari Chakkingal Parambil, Eran Edri","doi":"10.1021/acs.inorgchem.4c03454","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03454","url":null,"abstract":"Photoreactive self-healing semiconductors with suitable bandgaps for solar energy conversion offer an intriguing path to making resilient and low-cost photovoltaic devices through the introduction of a self-recovery path. However, only a few inorganic photovoltaic materials have such quality, and the underlying chemical properties that enable it are unknown, which poses a significant limit to our ability to study and discover new self-healing semiconductors. Recently, we have found that antimony trichalcogenide (Sb<sub>2</sub>Se<sub>3</sub> and Sb<sub>2</sub>S<sub>3</sub>) and chalcohalides (e.g., SbSeI) can undergo a reversible photoinduced phase transition (PIPT) in which the structure is restored after photoinduced damage incurs to the materials. This group of materials offer a unique opportunity for studying PIPT and its limits. In particular, this group of materials facilitate the study of functional permutation to specific crystalline sites and to finding the limits of PIPT occurrence, which sheds light on the origin of the PIPT and self-recovery of this class of materials. Using Raman spectroscopy of thin films, and following signature vibrations of transition species, we have found that the PIPT magnitude decays upon gradual Bi<sub>Sb(1)</sub> substitution in a Sb<sub>2–<i>x</i></sub>Bi<sub><i>x</i></sub>Se<sub>3</sub> homologous series, until nearly one in five Sb ions is substituted with Bi. Then, the PIPT diminishes completely. The homologous series occurs along a transition from covalent to metavalent chemical bonding. By expanding our search, we find that a correlation between bonding type and photoreactivity does exist but conclude that it is an insufficient condition. Instead, we suggest, based on bond order and additional DFT calculations, that sufficient bonding states at the bottom of the conduction band are also required. This joint experimental and computational study pushes the limits of designing self-healing inorganic semiconductors for various applications and provides tools for further expansion.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Co-Catalyzed P–H Activation and Related Cp*Co(III) Phosphine Complexes 协同催化的 P-H 活化及相关的 Cp*Co(III) 磷化物
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-11 DOI: 10.1021/acs.inorgchem.4c03207
Jin Yang, Mursaleem Ansari, Dimitrios A. Pantazis, Cameron H. M. Zheng, Robert McDonald, Michael J. Ferguson, Lisa Rosenberg
This study reports that the well-known Co(III) precursor Co(η5-Cp*)I2(CO) (1) is an effective precatalyst for dehydrocoupling reactions of phosphines. Reaction monitoring by NMR, complemented by ESI-MS and EPR, suggests that Co(III) complexes containing secondary and primary phosphine ligands play an important role in this catalysis but that redox chemistry is also facile for these complexes, resulting in paramagnetic species. Representative examples of the mono(phosphine) complexes Co(η5-Cp*)I2(PR2H) (2) and Co(η5-Cp*)I2(PRH2) (4) and bis(phosphine) complexes [Co(η5-Cp*)I(PR2H)2] I (3) have been prepared. The characterization of these complexes through structural, computational, spectroscopic, and electrochemical analysis is reported and serves as a foundation for considering their mechanistic significance in the observed catalytic dehydrocoupling chemistry.
本研究报告指出,众所周知的 Co(III) 前体 Co(η5-Cp*)I2(CO) (1) 是一种有效的膦脱氢偶联反应前催化剂。通过核磁共振以及 ESI-MS 和 EPR 对反应的监测表明,含有仲膦和伯膦配体的 Co(III) 复合物在这种催化反应中发挥了重要作用,但这些复合物也很容易发生氧化还原化学反应,从而产生顺磁性物质。我们制备了具有代表性的单(膦)配合物 Co(η5-Cp*)I2(PR2H) (2) 和 Co(η5-Cp*)I2(PRH2) (4) 以及双(膦)配合物 [Co(η5-Cp*)I(PR2H)2] I (3)。报告通过结构、计算、光谱和电化学分析对这些配合物进行了表征,并以此为基础考虑它们在所观察到的催化脱氢偶联化学中的机理意义。
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引用次数: 0
In Situ Deprotection-Free Synthesis of Silver/Graphdiyne with a High Raman Sensing Effect for Detection of Polychlorophenols and Microplastics. 用于检测多氯酚和微塑料的具有高拉曼传感效应的银/石墨二炔的原位免去保护合成。
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-11 Epub Date: 2024-10-29 DOI: 10.1021/acs.inorgchem.4c03027
Linchangqing Yang, Junfang Li, Meng Yin, Yahui Li, Wei Liu, Qinghong Kong, Guangcheng Xi

Since the first synthesis of graphdiyne (GDY), it has been widely receiving a lot of attention and has great application prospects in many fields, such as energy storage, catalysis, and sensing. However, the complex deprotection treatment and long reaction time limit its mass production and applications. Here, we present a strategy for the silver-catalyzed deprotection-free rapid synthesis of GDY. Crystalline GDY was synthesized in 8 h at room temperature and atmospheric pressure, and after the reaction, Ag nanoparticles with an ultrathin diameter of 2-3 nm were formed in situ inside and on the surface of GDY. This Ag/GDY composite exhibits a high specific surface area of 672.3 m2 g-1 and strong surface plasmon resonance behavior, showing a strong surface-enhanced Raman scattering effect. The enhancement factor and the lowest detection limit for rhodamine 6G are 3.54 × 108 and 1 × 10-14 M, respectively. The Ag/GDY achieves the simultaneous enrichment and detection of polychlorophenols and ultrafine nanoplastics.

自首次合成石墨二炔(GDY)以来,它一直受到广泛关注,并在储能、催化和传感等多个领域有着巨大的应用前景。然而,复杂的脱保护处理和较长的反应时间限制了其大规模生产和应用。在此,我们提出了一种银催化免脱保护快速合成 GDY 的策略。在室温和常压下,8 小时内就合成了结晶 GDY,反应后在 GDY 内部和表面原位形成了直径为 2-3 纳米的超细银纳米颗粒。这种 Ag/GDY 复合材料具有 672.3 m2 g-1 的高比表面积和强烈的表面等离子体共振行为,显示出强烈的表面增强拉曼散射效应。罗丹明 6G 的增强因子和最低检测限分别为 3.54 × 108 和 1 × 10-14 M。Ag/GDY 实现了对多氯酚和超细纳米塑料的同时富集和检测。
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引用次数: 0
期刊
Inorganic Chemistry
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