Inorganic Chemistry最新文献

Dependence of O2 Depletion on Transition Metal Catalyst in Radical Polymerization of Cross-Linking Alkene Resins

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-04-05 DOI: 10.1021/acs.inorgchem.5c00760

Hugo den Besten, Yanrong Zhang, Linda E. Eijsink, Andy S. Sardjan, Anouk Volker, Wesley R. Browne

{"title":"Dependence of O2 Depletion on Transition Metal Catalyst in Radical Polymerization of Cross-Linking Alkene Resins","authors":"Hugo den Besten, Yanrong Zhang, Linda E. Eijsink, Andy S. Sardjan, Anouk Volker, Wesley R. Browne","doi":"10.1021/acs.inorgchem.5c00760","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00760","url":null,"abstract":"Cobalt(II) carboxylates show broad reactivity with peroxides and O2 and are the industry standard catalyst for the activation of peroxide initiators for the radical polymerization of alkenes under ambient conditions. Curing alkene-based resins containing cross-linking units, i.e., monomers containing two or more alkene units, is important in forming hard protective coatings and materials. The activation of peroxide initiators produces the propagating chain end radicals needed for polymerization. Since polymerization progress depends on the rate of initiator activation and the concentration of propagating radicals, interception of radicals by O2 can inhibit curing. Cobalt(II) carboxylates are used due to their reactivity in the presence of oxygen, even in resin coatings. Alternative catalysts based on manganese and iron are desirable. Hence, the impact of O2 on their performance in resin curing is of interest. Here, we use NIR emission and time-resolved spectroscopy, employing the O2-sensitive probe [Ru(ph2phen)3]2+, to determine the concentration of dissolved [O2] in alkene resins during curing with three representative catalysts, Co(II)(2-ethylhexanoate)2, Fe(II)-bispidine, and Mn(II)(neodecanoate)2. The rate of depletion of O2 is highly dependent on the catalyst used, but in all cases, it is well before the onset of the autoacceleration of polymerization in cross-linking resins.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"59 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782814","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

Theoretical Studies on the Reduction of N2 to NH3/N2H4 Catalyzed by Chromium Complexes

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-04-05 DOI: 10.1021/acs.inorgchem.4c05237

Ming-Tian Hao, Beibei Zhang, Deqing Li, Baerlike Wujieti, Xiaoyu Li, Bo-Zhen Chen

{"title":"Theoretical Studies on the Reduction of N2 to NH3/N2H4 Catalyzed by Chromium Complexes","authors":"Ming-Tian Hao, Beibei Zhang, Deqing Li, Baerlike Wujieti, Xiaoyu Li, Bo-Zhen Chen","doi":"10.1021/acs.inorgchem.4c05237","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05237","url":null,"abstract":"Nitrogen fixation catalyzed by transition metal complexes provides an attractive alternative to the Haber–Bosch process and has received widespread attention. In this work, the reaction pathways of N2 to NH3/N2H4 catalyzed by dinuclear and mononuclear Cr–N2 complexes bearing cyclopentadienyl-phosphine ligands and mediated by LutH+ (as proton donors) and CrCp*2 (as electron donors) were investigated systematically using density functional theory calculations. The key step of the reactions was clarified as the first hydrogenation. The effect of different combinations of six proton sources (three pyridine acids and three anilino acids) and three electron sources (CrCp*2, CoCp*2, and CoCp2) on the reduction of N2 to NH3/N2H4 was also explored by calculating the critical step of the reactions. Based on the calculations, the dinuclear Cr–N2 complex is expected to be an effective catalyst for the reduction of N2 to NH3/N2H4 when using the combinations of CrCp*2 with each of the six proton sources and of CoCp*2 with anilino acids. Our work provides insights into understanding and optimizing Cr catalytic systems for efficient dinitrogen fixations.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"54 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782812","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

Impacts of Focused Ion Beam Processing on the Fabrication of Nanoscale Functionalized Probes

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-04-05 DOI: 10.1021/acs.inorgchem.4c05458

Xiang Wang, Sandra D. Taylor, Michel Sassi, Sichuang Xue, Zhenzhong Yang, Jia Liu, Lili Liu, Xiaoxu Li, Yingge Du, Kevin M. Rosso, Xin Zhang

{"title":"Impacts of Focused Ion Beam Processing on the Fabrication of Nanoscale Functionalized Probes","authors":"Xiang Wang, Sandra D. Taylor, Michel Sassi, Sichuang Xue, Zhenzhong Yang, Jia Liu, Lili Liu, Xiaoxu Li, Yingge Du, Kevin M. Rosso, Xin Zhang","doi":"10.1021/acs.inorgchem.4c05458","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05458","url":null,"abstract":"Herein, we examine the impact of Ga+ ion kinetic energy and the target material type on the extent of ion implantation and structural damage in atomic force microscopy probes made of Al2O3 and ZnO manufactured by focused ion beam using scanning transmission electron microscopy and energy-dispersive X-ray mapping. Penetration of Ga into the Al2O3 lattice induced structural distortions and amorphization. For the ZnO probes, Ga is uniformly dispersed across the surface, resulting in the formation of distinct clusters. Atom probe tomography further validates the Ga distributions in Al2O3 and ZnO nanoprobes. Complementary Monte Carlo simulations with the transport of ions in the matter program indicated that the introduction of Ga+ prompts the generation of cation and anion vacancies, an occurrence more pronounced in Al2O3 compared to ZnO. This study not only enriches the knowledge of ion–matter interactions but also serves as a practical guide for the fabrication of nanoscale functionalized atomic force microscopy probes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"25 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782813","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

Blue-Light-Excitable Yellow Emissive One-Dimensional Hybrid Copper(I) Iodide for White-Light-Emitting Diode and Methanol Sensing Application

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-04-04 DOI: 10.1021/acs.inorgchem.5c00698

Xinhui Li, Yanjiao Zhang, Pifu Gong, Zhigang Wang, Mingxing Chen, Shujuan Zhuang, Shengnan Zhang, Zhen Jia, Mingjun Xia

{"title":"Blue-Light-Excitable Yellow Emissive One-Dimensional Hybrid Copper(I) Iodide for White-Light-Emitting Diode and Methanol Sensing Application","authors":"Xinhui Li, Yanjiao Zhang, Pifu Gong, Zhigang Wang, Mingxing Chen, Shujuan Zhuang, Shengnan Zhang, Zhen Jia, Mingjun Xia","doi":"10.1021/acs.inorgchem.5c00698","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00698","url":null,"abstract":"Copper(I) halides are promising candidates for advanced optoelectronics, such as white-light-emitting diodes (WLEDs), scintillators, and photodetectors. Designing and synthesizing low-dimensional hybrid copper halides with blue-light excitation remains an enormous challenge. Herein, we have prepared two one-dimensional (1D) hybrid Cu(I)-based metal iodides, namely, (C6H7N)CuI and (C6H8N)CuI2 single crystals, by deliberately adjusting the ratio of the reactants 4-methylpyridine (4-MePy) and CuI. (C6H7N)CuI crystals are nonluminous, while (C6H8N)CuI2 crystals exhibit an unusual yellow emission with a broad excitation band in the range of 260–500 nm Furthermore, a prototypical WLED is fabricated by combining a commercial 430 nm blue chip and (C6H8N)CuI2 phosphor, which exhibits a correlated color temperature (CCT) of 5645 K and a CIE color coordinate of (0.329, 0.334), thus demonstrating potential application for white lighting. Remarkably, (C6H8N)CuI2 crystals emit red fluorescence upon adsorption of methanol but fail for all other alcohols. Notably, the initial yellow luminescence can be recovered upon volatilization of methanol from the crystals, thus achieving a reversible photoluminescence switching. This work not only presents an important reference of blue-light-excitable hybrid Cu(I)-based metal iodide phosphor for WLEDs but also provides an intriguing fluorescence sensor for the reversible detection of methanol.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"183 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782816","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

Electrochemical Detection of Chloramphenicol with Different Modified Electrodes Based on the Metal-Cyclotriveratrylene Framework and Mesoporous Carbon

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-04-04 DOI: 10.1021/acs.inorgchem.5c00477

Yu-Ying Li, Xia Niu, Wen-Yuan Pei, Jian-Fang Ma

{"title":"Electrochemical Detection of Chloramphenicol with Different Modified Electrodes Based on the Metal-Cyclotriveratrylene Framework and Mesoporous Carbon","authors":"Yu-Ying Li, Xia Niu, Wen-Yuan Pei, Jian-Fang Ma","doi":"10.1021/acs.inorgchem.5c00477","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00477","url":null,"abstract":"Design of high-performance electrochemical sensors for detection of antibiotics is greatly desirable for human health and ecological safety. Herein, a new metal–organic framework (MOF), namely, [Zn2L(PDC)2(H2O)2]·3H2O (1), was synthesized with isophthalic acid (H2PDC), Zn(II) cation, and cyclotriveratrylene-based ligand (L). By mechanical milling, 1 was incorporated with mesoporous carbon (MC) to produce 1@MC. Subsequently, 1@MC was decorated on different bare electrodes (glass carbon (GC), Au, Pt, or W electrode). The introduction of MC significantly improved the conductivity and the current response intensity for determination of chloramphenicol (CAP). Among these sensors, the current responses of CAP on 1@MC(1:2)/GCE and 1@MC(1:2)/Au were more intense. Markedly, they exhibited relatively wide linear ranges (0.5–400 μM on 1@MC(1:2)/GCE and 1–400 μM on 1@MC(1:2)/Au) and low limits of detection (0.15 μM on 1@MC(1:2)/GCE and 0.48 μM on 1@MC(1:2)/Au). Particularly, they can be used for the measurement of CAP in eye drop and milk sample with fine recoveries.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"183 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776058","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

Inverse Design of Molecular Qudits for Quantum Circuitry

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-04-04 DOI: 10.1021/acs.inorgchem.5c00298

Edward Latham, Alice M. Bowen, Nicholas Cox, Nicholas F. Chilton

{"title":"Inverse Design of Molecular Qudits for Quantum Circuitry","authors":"Edward Latham, Alice M. Bowen, Nicholas Cox, Nicholas F. Chilton","doi":"10.1021/acs.inorgchem.5c00298","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00298","url":null,"abstract":"The development of molecular quantum bits (qubits) for quantum information processing is a lofty goal. While many contemporary works investigate their potential for error correction, fault-tolerance, memories, etc., there is still a lack of experimental examples of molecular multiqubit sequences. Herein, we perform a theoretical investigation of spin Hamiltonian parameter space to identify molecules that could be used to implement a 4-level superdense coding algorithm that has the least stringent requirements for experimental implementation. To do so, we analyze the zero-field splitting (ZFS) Hamiltonian of an S = 3/2 spin system to determine its effectiveness as a molecular qudit capable of performing the superdense coding circuit with X-band pulsed electron paramagnetic resonance (EPR), accounting for realistic constraints imposed by EPR spectrometers. For an S = 3/2 system, the optimal ZFS parameters are |D| ≈ 0.115 cm–1 and |E| ≈ −0.0383 cm–1 (|E/D| ≈ 0.33 approaching the rhombic limit of 1/3), with a field around 160 mT. Our findings highlight the need to maximize the rhombicity of the spin Hamiltonian for four-level molecular qudits.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782815","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

Approaching Hypothetical RbTl in Experiments and Theory – X-ray Structure Determination of Cs1–xRbxTl (x = 0.18, 0.42) and a Solid Solution K1–xRbxTl (x ≤ 0.69)

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-04-03 DOI: 10.1021/acs.inorgchem.4c05305

Vanessa F. Schwinghammer, Saleem A. Khan, Susanne M. Tiefenthaler, Tomáš Kovářík, Ján Minár, Stefanie Gärtner

{"title":"Approaching Hypothetical RbTl in Experiments and Theory – X-ray Structure Determination of Cs1–xRbxTl (x = 0.18, 0.42) and a Solid Solution K1–xRbxTl (x ≤ 0.69)","authors":"Vanessa F. Schwinghammer, Saleem A. Khan, Susanne M. Tiefenthaler, Tomáš Kovářík, Ján Minár, Stefanie Gärtner","doi":"10.1021/acs.inorgchem.4c05305","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05305","url":null,"abstract":"Although the binary alkali metal thallides ATl with A = Li, Na, K, and Cs have been reported in the literature, binary RbTl at ambient pressure is still missing. Experiments with a 1:1 ratio of Rb:Tl, either according to Zintl’s procedure in low-temperature experiments in liquid ammonia or classical solid-state synthesis at high temperature, did not result in the desired product. Therefore, several ternary compositions with mixtures of K/Rb and Cs/Rb have been prepared. For K/Rb mixtures, a solid solution in the KTl structure type, up to a proportion of 69% rubidium, could be obtained. Site occupancy preferences for rubidium on the alkali metal sites in the KTl type are observed in experiments and supported by theoretical calculations. In contrast to Rb/K mixtures being realizable in the KTl structure type, Rb/Cs mixtures did not allow for the isolation of materials according to the CsTl structure type. Instead, two new monoclinic compounds could be isolated (Cs0.82Rb0.18Tl: C2/c, a = 14.4136(4) Å, b = 11.1678(3) Å, c = 40.8013(11) Å, β = 96.353(2)°, V = 6527.4(3) Å3; Cs0.58Rb0.42Tl: C2/c, a = 14.2610(3) Å, b = 11.1116(2) Å, c = 27.5589(7) Å, β = 104.056(2)°, V = 4236.30(17) Å3). Detailed DFT calculations on both binary and mixed cation systems were performed and support the experimental results.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766861","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

Study of the Microstructure, Physical and Mechanical Properties of Zirconium Disilicide Ceramics: Synthesis, Experimental Characterization and Theoretical Calculations

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-04-03 DOI: 10.1021/acs.inorgchem.5c00506

Shangzhou Liu, Yongxin Hu, Jianyi Ma, Quan Zhu, Yajie Yu

{"title":"Study of the Microstructure, Physical and Mechanical Properties of Zirconium Disilicide Ceramics: Synthesis, Experimental Characterization and Theoretical Calculations","authors":"Shangzhou Liu, Yongxin Hu, Jianyi Ma, Quan Zhu, Yajie Yu","doi":"10.1021/acs.inorgchem.5c00506","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00506","url":null,"abstract":"Zirconium disilicide (ZrSi2) is often used in high-temperature applications due to its excellent mechanical properties and thermal stability. This study aims to investigate the microstructure and physical and mechanical properties of ZrSi2 ceramics prepared under high-pressure and high-temperature (HPHT) sintering conditions. The research results show that the density, Vickers hardness, and fracture toughness of the ZrSi2 ceramic sample reach 4.7 g/cm3, 10.547 GPa, and 6.905 MPa·m1/2, respectively. It is worth noting that the ZrSi2 ceramic sample exhibits excellent oxidation resistance and its oxidation starting temperature is 1463 °C. The experimentally measured thermal diffusion coefficient of the ZrSi2 ceramic sample is 2.815 mm2/s, and the specific heat capacity is 0.48 J/g·K, from which the thermal conductivity is calculated to be 6.354 W/m·K. The first-principles calculation results show that the crystal structure of ZrSi2 has good dynamic stability, and the silicon atoms and zirconium atoms are connected by strong covalent bonds. At the same time, the ZrSi2 ceramic sample obtained in this experiment has a uniform grain size distribution, a high dislocation density, and a strong texture. The results of this study are crucial for the preparation and application of ZrSi2 ceramics.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"73 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766865","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

Work Function-Induced Electronic Modulation in NiCo Alloy for Electrochemical Nitrate Reduction

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-04-03 DOI: 10.1021/acs.inorgchem.5c00362

Yan Shen, Yingnan Dou, Liping Sun, Lihua Huo, Hui Zhao

{"title":"Work Function-Induced Electronic Modulation in NiCo Alloy for Electrochemical Nitrate Reduction","authors":"Yan Shen, Yingnan Dou, Liping Sun, Lihua Huo, Hui Zhao","doi":"10.1021/acs.inorgchem.5c00362","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00362","url":null,"abstract":"The rational design of electrocatalysts is of great significance in the production of ammonia (NH3) through a nitrate reduction reaction (NO3–RR). This article proposes a design approach to regulate electron redistribution and intermediate adsorption energy by adjusting the work function of alloy compounds. As an example, the NiCo alloy is successfully electrodeposited on carbon cloth (CC) using deep eutectic solvent (DES) as medium. The results show that the ammonia production rate of the NiCo alloy is as high as 1.55 mmol h–1 cm–2 at −0.38 V vs RHE, with the Faraday efficiency to be 84.94%, and the selectivity 94%. Experimental characterizations combined with density functional theory calculations confirm that alloying is beneficial for reducing the work function of Ni. This in turn adjusts the d-band center of the alloy to approach the Fermi level, changes the rate-determining step during the reduction reaction process, and consequently improves the performance. Eventually, an investigation is conducted on the Zn–NO3– battery fabricated with Ni1Co2/CC. This further exhibits the potential of Ni1Co2/CC within the energy conversion equipment. This study brings fresh design concepts and opportunities to the development of novel electrocatalysts for NO3–RR.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"107 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766864","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

Elucidation of the Ta(O,N)6 Octahedral Arrangement in Flux-Grown BaTaO2N Photocatalysts by Experimental and Computational Structural Modeling

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-04-03 DOI: 10.1021/acs.inorgchem.4c04551

Tetsuya Yamada, Hiroh Miyagawa, Tomohito Sudare, Hiromasa Shiiba, Hideki Tanaka, Miwako Takahashi, Michihisa Koyama, Katsuya Teshima

{"title":"Elucidation of the Ta(O,N)6 Octahedral Arrangement in Flux-Grown BaTaO2N Photocatalysts by Experimental and Computational Structural Modeling","authors":"Tetsuya Yamada, Hiroh Miyagawa, Tomohito Sudare, Hiromasa Shiiba, Hideki Tanaka, Miwako Takahashi, Michihisa Koyama, Katsuya Teshima","doi":"10.1021/acs.inorgchem.4c04551","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04551","url":null,"abstract":"BaTaO2N (BTON) is a visible-light-responsive photocatalyst used for water splitting. The flux method, which involves the use of a molten salt, is an effective synthetic strategy for achieving a high photocatalytic activity. Fluxes with alkali metal cations strongly affect the photocatalytic activity of the BTON crystals. In particular, RbCl flux-grown BTON exhibits hydrogen evolution activity over several times higher than that grown in other chloride fluxes, such as NaCl, under visible-light irradiation. One factor of this difference is presumably owing to the change in the Ta(O,N)6 octahedral arrangement in the BTON triggered by the doping of alkali metal ions into the crystal lattice. However, the precise Ta(O,N)6 octahedral arrangement remains unclear. Herein, X-ray absorption spectroscopy, structural analysis by neutron diffraction, and computational structural modeling based on comprehensive structural energy predictions were performed for two types of BTONs. The results suggested that the configuration manners of Ta(O,N)6 octahedral units strongly depend on the flux composition. Specifically, in NaCl-flux-grown BTON crystals, the number of N20 cis planes parallel to the (100), (010), and (001) crystal planes in a TaO4N2 unit is anisotropic, resulting in differences in their electron–hole conduction characteristics. The findings indicate that in addition to lattice defects, the interconnections of mixed-anion units such as Ta(O,N)6 should be taken into account to improve the photocatalytic activity of BTONs and develop other mixed-anion compounds.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"108 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776059","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