Inorganic Chemistry最新文献_第9页

Stable Polyoxometalate-Based Metal–Organic Framework: Synthesis, Modification, and Catalytic Activity

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.4c04616

Sa-Sa Wang, Su-Yuan Feng, Zhong-Yi Rong, Xiao-Yuan Wu, Weiming Wu, Can-Zhong Lu

{"title":"Stable Polyoxometalate-Based Metal–Organic Framework: Synthesis, Modification, and Catalytic Activity","authors":"Sa-Sa Wang, Su-Yuan Feng, Zhong-Yi Rong, Xiao-Yuan Wu, Weiming Wu, Can-Zhong Lu","doi":"10.1021/acs.inorgchem.4c04616","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04616","url":null,"abstract":"Metal–organic frameworks (MOFs) with polyoxometalates (POMs) as the nodes usually feature a high stability. Those with available space and modifiable groups are expected to serve as a catalytic platform. In this work, a polyoxometalate-based metal–organic framework (POMOF)-bearing channel with a transversal surface of ca. 1.1 × 1.8 nm, [Ni(en)2]4H{[Ni6(tris)(en)3(SIP)1.5][B-α-PW9O34]}2·32H2O (1), was resulted by the collaboration of multiple ligands. The channel was lined with abundant amino groups that bonded with water molecules in it via hydrogen bonds. Compound 1 exhibited excellent thermal and chemical stabilities, which was confirmed by immersion experiments, in situ variable temperature powder X-ray diffraction, and reversible dehydration–hydration behavior. Pristine 1 showed remarkable activity in the hydrogen evolution reaction. According to the presence of amino groups in the channel, 1 was modified by Pd species. Resultantly, Pd was loaded into the channel successfully. The yielding material 1-Pd smoothly catalyzed the Suzuki–Miyaura coupling reactions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"41 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401919","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

Photocatalytic Recovery of Noble Metals by Covalent Silyl Polyoxophosphotungstate–Porphyrin Copolymers

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.4c04890

Zhaohui Huo, Brahim Akhsassi, Jiamin Yu, Mingxiu Zheng, Tongying Lan, Qianting He, Corinne Boudon, Guojun Xu, Anna Proust, Guillaume Izzet, Laurent Ruhlmann

{"title":"Photocatalytic Recovery of Noble Metals by Covalent Silyl Polyoxophosphotungstate–Porphyrin Copolymers","authors":"Zhaohui Huo, Brahim Akhsassi, Jiamin Yu, Mingxiu Zheng, Tongying Lan, Qianting He, Corinne Boudon, Guojun Xu, Anna Proust, Guillaume Izzet, Laurent Ruhlmann","doi":"10.1021/acs.inorgchem.4c04890","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04890","url":null,"abstract":"The photocatalytic recovery of noble metals on photosensitive semiconductors such as TiO2 is well-established for forming M/TiO2 but has notable drawbacks. TiO2 suffers from low conversion efficiency due to significant recombination of photogenerated electron–hole pairs. Its wide energy band gap (3.2 eV) also restricts excitation to high-energy UV light, limiting its use with solar energy. This study proposes an efficient alternative using hybrid polyoxometalate (POM)–porphyrin copolymers for the photocatalytic recovery of Ag and Pt under visible light. Copolymeric films composed of hybrid polyoxometalates and porphyrins have been obtained by the electrooxidation of 5,15-(di-p-tolyl)porphyrin (H2T2P) or 2,3,7,8,12,13,17,18-octaethylporphine zinc(II) (ZnOEP) together with Keggin or Wells–Dawson-type organosilyl polyoxophosphotungstate ([PW11Si2O40C26H16N2]TBA3 or [P2W17Si2O62C26H16N2]TBA6). In these films, porphyrin subunits can be excited under visible illumination, acting as photosensitizers that transfer electrons to the polyoxometalate catalysts. Notably, POM–porphyrin films demonstrated high efficiency in Pt(IV) photoreduction over repeated cycles without catalyst degradation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"60 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401920","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

Thermally Stable Broadband Cr3+-Doped RbAl3P6O20 Phosphor for Near-Infrared Spectroscopy Applications

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.4c05081

Xiaozhong Wu, Decai Huang, Qiuming Lin, Lei Han, Weixiong You, Jing Zhu, Xinyu Ye

{"title":"Thermally Stable Broadband Cr3+-Doped RbAl3P6O20 Phosphor for Near-Infrared Spectroscopy Applications","authors":"Xiaozhong Wu, Decai Huang, Qiuming Lin, Lei Han, Weixiong You, Jing Zhu, Xinyu Ye","doi":"10.1021/acs.inorgchem.4c05081","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05081","url":null,"abstract":"The research on near-infrared (NIR) phosphors has become a trending topic, as their optical properties directly impact the performance of the NIR phosphor-converted light-emitting diode (pc-LED). NIR pc-LED has emerged as a multifunctional light source across various fields due to its unique advantages of high penetration and invisibility. Herein, a peculiar broadband NIR-emitting phosphor is presented, RbAl3P6O20: Cr3+ (RAPO: Cr3+), with an NIR emission range from 650 to 1000 nm and peaking at ∼785 nm with a full-width at half-maximum (fwhm) of ∼1900 cm–1. Gaussian fitting analysis reveals that broadband emission originates from Cr3+, occupying two different octahedral sites in the host. The optimized phosphor RAPO: 0.08Cr3+ exhibits an internal quantum efficiency of 60% and excellent thermal stability (90% at 423 K). The application of pc-LED devices was evaluated by assembling a RAPO: 0.08Cr3+ phosphor with an InGaN-based LED (450 nm), achieving a remarkable NIR output power of 27.9 mW at 120 mA. The results demonstrate that RAPO: Cr3+ is an optimistic phosphor for NIR photoelectron (pc-LED) light sources.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401921","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

Structural Stability and Photoluminescence Property of Cs2UCl6 Single Crystal Derived from Spent Nuclear Fuel

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.4c04076

Yibo Wang, Kun Yang, Feida Chen, Xianlin Qu, Yanmei He, Daniu Han, Xiaobin Tang

{"title":"Structural Stability and Photoluminescence Property of Cs2UCl6 Single Crystal Derived from Spent Nuclear Fuel","authors":"Yibo Wang, Kun Yang, Feida Chen, Xianlin Qu, Yanmei He, Daniu Han, Xiaobin Tang","doi":"10.1021/acs.inorgchem.4c04076","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04076","url":null,"abstract":"The recycling and reuse of trace uranium from spent nuclear fuel is of great significance for the safety management of the nuclear fuel cycle. However, stabilization of low-valent uranium has always been a challenge due to the ultraoxidizable nature of uranium ions, which remains relatively uncharted territory in spent fuel treatment. In the current study, U4+ was immobilized in Cs2UCl6 single crystal with a perovskite structure from uranyl under a strong acidic environment. A comprehensive and detailed understanding of Cs2UCl6 at the atomic scale has been achieved by combining density functional theory (DFT) with high-resolution integrated differential phase contrast scanning transmission electron microscopy (iDPC-STEM) imaging, which was captured by utilizing Cs-corrected TEM for the first time. Furthermore, the results obtained from X-ray excitation and the photoexcitation effects produced by PL at 280, 330, and 360 nm provide compelling evidence for the ability of U4+ to form excitable bands around the Fermi level. The as-synthesized Cs2UCl6 demonstrates excellent thermal stability above 275 °C, as evidenced by in situ Raman spectroscopy and thermogravimetric analysis, while a degradation pathway initiated by CsCl upon exposure to water vapor was revealed by synchrotron X-ray diffraction. Thermal and chemical stability can be further elevated by consolidating it into a metal–organic framework (MOF) via hot pressing. The current study provides a promising strategy to reuse and functionalize the spent nuclear fuel.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"47 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393610","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

Solid-State Synthesis Enables Enhanced Crystallinity and Tunable Optical Properties in Lanthanum Oxytelluride

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.4c04594

Melissa S. Orr, Hoa H. Nguyen, Thomas S. Ie, Muhammad N. Huda, Mercouri G. Kanatzidis, Michael Bozlar, Robin T. Macaluso

{"title":"Solid-State Synthesis Enables Enhanced Crystallinity and Tunable Optical Properties in Lanthanum Oxytelluride","authors":"Melissa S. Orr, Hoa H. Nguyen, Thomas S. Ie, Muhammad N. Huda, Mercouri G. Kanatzidis, Michael Bozlar, Robin T. Macaluso","doi":"10.1021/acs.inorgchem.4c04594","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04594","url":null,"abstract":"Elucidating synthetic parameters to produce crystalline solid-state materials with specific properties remains an outstanding obstacle. Oxychalcogenide materials present their own challenges; gaseous reagents are difficult to control and quantify, and reactions cannot be monitored in situ at elevated temperatures. In this paper, we aim to address the lack of fundamental understanding of oxychalcogenides through the synthesis of La2O2Te, by two different routes: traditional solid-state and hydrogen gas-assisted methods. We elucidate the two synthetic pathways by X-ray diffraction (XRD) and scanning electron microscopy to demonstrate distinct characteristics between the crystalline and bulk structures, as well as the growth mechanisms of the oxytelluride products. The differences in optical properties at the macroscopic scale correlate with shifts and broadening of the XRD peaks that distinguish two oxytelluride products. The combination of DFT calculations and photoemission yield spectroscopy suggests that oxygen vacancies may explain differences in the optical properties. Finally, this work provides critical synthetic parameters that will enhance the exploratory synthesis of oxychalcogenide materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393611","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

One-Dimensional Perovskite RbGeI3 with Large Optical Anisotropy

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.5c00212

Huige Chen, Deshuai Xiao, Pifu Gong, Xinyuan Zhang, Zheshuai Lin, Lei Kang

引用次数: 0

Synthesis and Reactivity of Germyl-Substituted Gallapnictenes

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.4c05097

Yuanyuan Wang, Harsha S. Karnamkkott, Jicheng Wang, Yanling Zhu, Manbo Zhang, Manoj Kumari, Kartik Chandra Mondal, Bin Li

{"title":"Synthesis and Reactivity of Germyl-Substituted Gallapnictenes","authors":"Yuanyuan Wang, Harsha S. Karnamkkott, Jicheng Wang, Yanling Zhu, Manbo Zhang, Manoj Kumari, Kartik Chandra Mondal, Bin Li","doi":"10.1021/acs.inorgchem.4c05097","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05097","url":null,"abstract":"Decarbonylation of the phospha- and arsaketenyl germylenes (L)GeECO (E = P, As; L = CH[C(Me)NAr]2, Ar = 2,6-iPr2C6H3) in the presence of the Ga(I) precursor (L)Ga afforded the corresponding germyl-substituted gallaphosphene 1 and gallaarsene 3, respectively. Both 1 and 3 are examples of unsaturated chains with heavier group 13/15/14 elements. The germylene center and the polarized Pn = Ga (Pn = P or As) double bond provide multiple sites for small-molecule activation. For example, gallaarsene 3 reacted with adamantyl azide in a formal [3 + 2]-cyclization to give 4 containing a GaAsN3 heterocycle, clearly underlining the analogy between the As = Ga and C–C multiple bonds. By contrast, the reaction of 3 with Me–I afforded the 1,3-addition product 5, which indicates frustrated Lewis pair character in 3. DFT calculations indicate that the Ga–P/As bonds are highly polarized toward the pnictogen center. EDA-NOCV calculations further support this description and additionally shed light on ambiguous bonding scenarios in 4 and 5. These calculations prove that orbital interactions are outweighed by electrostatic interactions, resulting in polar bonds with significant ionic character.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"60 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401923","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

Correction to “Dense Hydrated Magnesium Carbonate MgCO3·3H2O Phases”

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.5c00431

Benedito Donizeti Botan-Neto, David Santamaria-Perez, Lkhamsuren Bayarjargal, Elena Bykova, Javier Gonzalez-Platas, Alberto Otero-dela-Roza

引用次数: 0

Solvent Extraction and Coordination Properties of 1,10-Phenanthroline-2,9-dicarboxylic Acid Diamides with Alkyl-Aryl Substituents toward Lanthanides(III) and Americium(III)

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.4c04770

Mariia V. Evsiunina, Petr I. Matveev, Paulina Kalle, Enni K. Khult, Pavel S. Lemport, Nane A. Avagyan, Vladimir G. Petrov, Yury A. Ustynyuk, Valentine G. Nenajdenko

{"title":"Solvent Extraction and Coordination Properties of 1,10-Phenanthroline-2,9-dicarboxylic Acid Diamides with Alkyl-Aryl Substituents toward Lanthanides(III) and Americium(III)","authors":"Mariia V. Evsiunina, Petr I. Matveev, Paulina Kalle, Enni K. Khult, Pavel S. Lemport, Nane A. Avagyan, Vladimir G. Petrov, Yury A. Ustynyuk, Valentine G. Nenajdenko","doi":"10.1021/acs.inorgchem.4c04770","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04770","url":null,"abstract":"For a wide range of 1,10-phenanthroline-2,9-dicarboxylic acid diamides (DAPhen), differing in the structure of the amide substituent and the presence of chlorine atoms in the 4,7-positions of the phenanthroline core, the extraction properties for lanthanides(III) and americium(III) were studied. Protonation and binding constants to Eu(III) were determined by using UV–vis titration. The values of binding constants and protonation constants are higher for nonsubstituted diamides than for 4,7-chlorinated diamides, which is in good agreement with the solvent extraction data. The structures of more than 20 complexes with lanthanide nitrates in the solid state have been determined using X-ray diffraction analysis. Unusual DAPhen ligand complexes with lanthanum and neodymium nitrates were obtained. For the first time, the possibility of entering a water molecule into the internal coordination sphere of neodymium in a complex with the DAPhen ligand was shown, resulting in the coordination number of neodymium increasing to 11. An unusual complex with a bridge structure was obtained for lanthanum nitrate in which the lanthanum ions have different coordination numbers of 10 and 12.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401917","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

Modulating Defect Concentration of Boron Nitride Flowers for CO2 Photoreduction

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-11 DOI: 10.1021/acs.inorgchem.4c05019

Zhehao Liu, Baker Rhimi, Zheyang Liu, Liang Mao, Min Zhou, Zhaochen Jiang, Zhifeng Jiang

{"title":"Modulating Defect Concentration of Boron Nitride Flowers for CO2 Photoreduction","authors":"Zhehao Liu, Baker Rhimi, Zheyang Liu, Liang Mao, Min Zhou, Zhaochen Jiang, Zhifeng Jiang","doi":"10.1021/acs.inorgchem.4c05019","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05019","url":null,"abstract":"The efficient conversion of carbon dioxide into high-value chemicals presents a promising strategy for achieving carbon neutrality. Defects play a critical role in numerous catalytic reactions. However, an excessive number of defects can lead to electron trapping, deactivating the catalyst surface. Optimizing the defect concentration is crucial for significantly enhancing catalytic performance. In this work, two types of flower-like BN-based photocatalysts composed of nanofibers were synthesized by in situ self-assembly and high-temperature calcination. The BN-based photocatalyst with fewer defects (Vpoor-BNF) achieved a CO2 reduction rate 2 times higher than that of the BN-based photocatalyst with more defects (Vrich-BNF), with a CO yield of 32 μmol g–1 h–1 with 86.9% selectivity. Importantly, the mechanism of enhanced CO2 reduction activity over BN-like photocatalysts was investigated in combination with various advanced characterization. The results show that excessive C doping causes carbon deposition, creating more defects that trap photogenerated electrons and affect the photocatalytic activity. In contrast, the Vpoor-BNF has longer photogenerated carrier lifetime and better photoelectric properties, which are beneficial for the CO2 photoreduction reaction. In addition, the good stability of the catalyst was confirmed by the cyclic experiment. This study presents an effective approach for synthesizing defect-controlled catalysts, which is beneficial for the development of advanced photocatalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393715","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