Inorganic Chemistry最新文献_第2页

Designing Suitable Pore Size and Anionic Framework of MOFs for Improving Proton Conductivity and Separation of Organic Dyes 设计合适孔径和阴离子结构的MOFs以提高质子导电性和有机染料的分离

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-03 DOI: 10.1021/acs.inorgchem.5c01569

Ronghua Liu, Xin Li, Liyang Chen, Shuping Song, Xueke Han, Hongjie Zhu, Xiangjin Kong, Huawei Zhou, Xia Li, Suna Wang, Yunwu Li, Mingyu Dou, Dichang Zhong, Hongguo Hao

{"title":"Designing Suitable Pore Size and Anionic Framework of MOFs for Improving Proton Conductivity and Separation of Organic Dyes","authors":"Ronghua Liu, Xin Li, Liyang Chen, Shuping Song, Xueke Han, Hongjie Zhu, Xiangjin Kong, Huawei Zhou, Xia Li, Suna Wang, Yunwu Li, Mingyu Dou, Dichang Zhong, Hongguo Hao","doi":"10.1021/acs.inorgchem.5c01569","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01569","url":null,"abstract":"Reasonable design of metal–organic frameworks (MOFs) with multifunction pore environment and anionic structure for proton conduction and dye adsorption has important application value. Herein, we report two novel and stable isomorphic three-dimensional (3D) lanthanide metal–organic frameworks (LCUH-121 and LCUH-122). Both MOFs have unique pore sizes, which are respectively made up of smaller proton-conducting channels (LCUH-121: 6.8 × 11.4 Å2, LCUH-122: 6.1 × 11.4 Å2) and larger dye adsorption cavities (LCUH-121: 10.2 × 11.4 Å2, LCUH-122: 10.1 × 11.4 Å2). Remarkably, the high-density dimethylamine cations ([(CH3)2NH2]+) in the one-dimensional channel also endow them with dual functions, exhibiting both efficient proton conduction pathways and excellent cationic dye adsorption performance. The abundance of dimethylamine cations and the special environment of small pores give LCUH-121 and LCUH-122 proton conductivity (σ) values as high as 1.62 × 10–2 and 1.46 × 10–2 S·cm–1 (80 °C, 100% RH), which is the highest reported anionic MOFs to date. Meanwhile, the synergistic effect of the optimal large pore size and anion framework resulted in adsorption capacities of 1.23 and 1.20 g·g–1 for methylene blue (MB) by LCUH-121 and LCUH-122, respectively, and exhibited record-breaking adsorption rate constants (0.0698 and 0.0662 g·mg–1·min–1). More importantly, the Grand Canonical Monte Carlo (GCMC) elucidated that the proton conduction mechanism and dye adsorption mechanism mainly rely on a unique size dual pathway mechanism, in which protons are conducted through the small-pore framework and dye molecules are accommodated in a large pore framework.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202309","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}

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La3Ga5HfO14: Rare-Earth Polyhedron Coupled with Structural Protected Octahedron for Designing Nonlinear Optical Material with Wide Bandgap and Well-Balanced Properties La3Ga5HfO14：稀土多面体与结构保护八面体耦合用于设计具有宽禁带和良好平衡性能的非线性光学材料

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-03 DOI: 10.1021/acs.inorgchem.5c00959

Jingxuan Hou, Dingxuan Zhao, Zifan Xu, Shihui Ma, Jiajia Wang, Hongwei Yu, Guang Peng, Ning Ye, Zhanggui Hu

{"title":"La3Ga5HfO14: Rare-Earth Polyhedron Coupled with Structural Protected Octahedron for Designing Nonlinear Optical Material with Wide Bandgap and Well-Balanced Properties","authors":"Jingxuan Hou, Dingxuan Zhao, Zifan Xu, Shihui Ma, Jiajia Wang, Hongwei Yu, Guang Peng, Ning Ye, Zhanggui Hu","doi":"10.1021/acs.inorgchem.5c00959","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00959","url":null,"abstract":"Laser damage threshold (LDT) is one of the key parameters of nonlinear optical (NLO) crystals, which can seriously affect the energy output of frequency conversion laser. The traditional design of NLO crystals introduces strongly distorted structural units, which hope to obtain an enhanced second harmonic generation (SHG) coefficient. However, this approach presents a fundamental conflict with the bandgap; it inevitably induces bandgap compression, which in turn significantly degrades the LDT. Herein, we propose a highly symmetric octahedron [HfO6] to enhance the bandgap of La3Ga5SiO14 (LGS) while keeping sufficient SHG response. Incorporating Hf into the LGS framework allows us to leverage the symmetry protection of the octahedra, effectively mitigating the bandgap reduction typically associated with cation energy level splitting in the distorted octahedra. We successfully synthesized a novel NLO crystal La3Ga5HfO14 (LGHf), which possesses a wide bandgap of 5.06 eV, which leads to a significantly enhanced LDT of 1.59 GW/cm2 (@ 1064 nm), while its SHG intensity reaches 3.5 × KH2PO4 (@1064 nm) and 0.35 × AgGaS2 (@ 2090 nm). This design strategy successfully achieves the synergistic optimization between wide bandgap characteristics and balanced NLO response, offering a new material solution for high-power mid-infrared laser systems.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"17 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202425","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}

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Tailoring a Glass Network Structure through Addition of Transition Metal Oxides to Enhance Ionic Conductivity in Phosphate Glasses 通过添加过渡金属氧化物以增强磷酸盐玻璃中的离子电导率来剪裁玻璃网络结构

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-03 DOI: 10.1021/acs.inorgchem.5c00313

Sanja Renka, Grégory Tricot, Tomáš Hostinský, Petr Mošner, Ladislav Koudelka, Ahmed Ibrahim, Shiro Kubuki, Zdravko Siketić, Ana Šantić

{"title":"Tailoring a Glass Network Structure through Addition of Transition Metal Oxides to Enhance Ionic Conductivity in Phosphate Glasses","authors":"Sanja Renka, Grégory Tricot, Tomáš Hostinský, Petr Mošner, Ladislav Koudelka, Ahmed Ibrahim, Shiro Kubuki, Zdravko Siketić, Ana Šantić","doi":"10.1021/acs.inorgchem.5c00313","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00313","url":null,"abstract":"In the development of oxide glass-based electrolytes and electrodes for solid-state batteries, high ionic conductivity represents an ultimate challenge. One way of increasing the ionic conductivity in these materials is to increase the mobility of ions through the addition of transition metal oxides. In this study, we report a significant enhancement of lithium-ion conductivity due to structural changes induced by addition of WO3 and MoO3. Despite the potential of WO3 and MoO3 to induce polaronic (electronic) conductivity, these glasses are purely ionic conductors. The increase in lithium-ion conductivity is approximately 5 and 4 orders of magnitude with addition of up to ≈40 mol % WO3 and MoO3, respectively. A detailed structural analysis shows that the increase in the mobility of Li+ ions is related to a strong facilitating effect of tungstate and molybdate units in the glass network. Moreover, this study also discusses similarities and differences in the dynamics of lithium and sodium ions in phosphate glasses containing WO3 and MoO3, and shows that the addition of WO3 can enhance the cathode performance of these glasses in both lithium-ion and sodium-ion batteries.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"81 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202420","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

Aerobic Oxidation Desulfurization of Dibenzothiophene Derivatives in Diesel Oil: Role of Electron-Rich Sites in Bimetallic Catalysts 柴油中二苯并噻吩衍生物的好氧氧化脱硫：富电子位在双金属催化剂中的作用

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-03 DOI: 10.1021/acs.inorgchem.5c00845

Chenchao Hu, Chen Qian, Suhang Xun, Haiyan Ji, Zhenjiang Qiu, Minqiang He, Xifeng Zhang, Huaming Li, Wenshuai Zhu

{"title":"Aerobic Oxidation Desulfurization of Dibenzothiophene Derivatives in Diesel Oil: Role of Electron-Rich Sites in Bimetallic Catalysts","authors":"Chenchao Hu, Chen Qian, Suhang Xun, Haiyan Ji, Zhenjiang Qiu, Minqiang He, Xifeng Zhang, Huaming Li, Wenshuai Zhu","doi":"10.1021/acs.inorgchem.5c00845","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00845","url":null,"abstract":"The difficulty in removing dibenzothiophene derivatives from diesel, especially 4,6-dimethyldibenzothiophene (4,6-DMDBT), remains a huge obstacle to achieving efficient and clean desulfurization of oil products. However, the construction of a catalyst with efficient activation and utilization of O2 for the oxidation of sulfur-containing substrates remains a major challenge for the industrial application of aerobic oxidative desulfurization (AODS). In this article, we manipulate the electronic structure and surface acid–base environment of the MoOx catalyst by introducing Ta atoms with low electronegativity and constructing bimetallic catalysts to promote the generation of more electron-rich active sites. The optimal MoTa-2 catalyst realizes a 100% sulfur removal rate within 5 h for 4,6-DMDBT and displays amazing cycling stability across 26 cycles, surpassing the performance of known heterogeneous catalysts. This study extends a novel understanding of drawing support from electronic structure control strategies to enhance AODS ability.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"42 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202422","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}

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Structure-Nanomechanical Property Correlation in Photosalient Isostructural Metal–Organic Crystals 光凸等结构金属-有机晶体结构-纳米力学性能的相关性研究

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-03 DOI: 10.1021/acs.inorgchem.5c00943

Basudeb Dutta, Amit Mondal, Raghavender Medishetty, Aditya Choudhury, Sourav Roy, C. Malla Reddy, Mohammad Hedayetullah Mir

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Enabling Excitation-Wavelength and Temperature-Responsive Chromatic Indicators via the Integration of Dual Luminescent Centers 通过双发光中心的集成实现激发波长和温度响应色指示器

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-03 DOI: 10.1021/acs.inorgchem.5c01684

Yi Wang, Yukun Li, Yi Hu, Tengyue Wang, Jiaren Du, Hengwei Lin

{"title":"Enabling Excitation-Wavelength and Temperature-Responsive Chromatic Indicators via the Integration of Dual Luminescent Centers","authors":"Yi Wang, Yukun Li, Yi Hu, Tengyue Wang, Jiaren Du, Hengwei Lin","doi":"10.1021/acs.inorgchem.5c01684","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01684","url":null,"abstract":"Owing to their vibrant chromatic representation and distinctive optical characteristics, stimuli-responsive multicolor luminescent materials have attracted heightened interest within the domains of information security and intelligent systems. Nonetheless, developing phosphors that exhibit stimuli responsiveness, especially those with luminescence influenced by both temperature variations and excitation wavelengths, continues to pose considerable difficulties. In this study, we present a multicolor luminescent compound derived from tridymite-structured CaGa2O4 codoped with Bi3+ and Eu3+. Significantly, this Bi3+/Eu3+ coactivated phosphor demonstrates responsiveness to thermal variations and excitation wavelengths, along with exceptional chromatic tunability ranging from yellow to orange red. The observed tunability of the color is attributed to the distinct thermal quenching behaviors associated with Bi3+ and Eu3+ emitters. Thermoluminescence profiles, in conjunction with persistent luminescence decay analysis and photostimulated luminescence, elucidate the distribution and photoactive nature of these traps. Finally, we illustrate potential applications in visual thermometry and information display using CaGa2O4:Bi3+, Eu3+-based luminescent ink. This study not only provides strategic insights for the development of inorganic phosphors with adjustable emission spectra and stimuli-responsive properties but also underscores significant potential in fields such as information security, thermal distribution visualization, anticounterfeiting, and smart platforms.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"52 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202310","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

Unravelling the Strain: Accurate Ring Strain Energies in Chalcogeniranes and Predictive Models for Most p-Block Three-Membered Rings 应变的揭示：硫原烷中精确的环应变能和大多数p块三元环的预测模型

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-03 DOI: 10.1021/acs.inorgchem.5c01736

Arturo Espinosa Ferao

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Plate-like Multiprincipal Cation Ceramic Powders with Aurivillius and Perovskite Structures Fabricated by Molten Salt Synthesis 熔融盐合成具有钙钛矿和aurillius结构的片状多主阳离子陶瓷粉末

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-03 DOI: 10.1021/acs.inorgchem.5c01197

Ziyao Wei, Zhuozhao Wu, Yan Fang, Zhihao Lou, Haoqi Xu, Jie Xu, Feng Gao

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O–O Bond Homolysis Inhibition Strategy on B-g-C3N4 Boosts Selectivity for the Photosynthesis of H2O2 抑制B-g-C3N4的O-O键均解策略提高H2O2光合作用的选择性

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-03 DOI: 10.1021/acs.inorgchem.5c01159

Yinhao Li, Yongli Shen, Fan Yang, Shuang Yao, Wen Zhang, Davronbek Bekchanov, Changhua An

{"title":"O–O Bond Homolysis Inhibition Strategy on B-g-C3N4 Boosts Selectivity for the Photosynthesis of H2O2","authors":"Yinhao Li, Yongli Shen, Fan Yang, Shuang Yao, Wen Zhang, Davronbek Bekchanov, Changhua An","doi":"10.1021/acs.inorgchem.5c01159","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01159","url":null,"abstract":"Photocatalytic oxygen reduction offers a green and sustainable route for hydrogen peroxide production. Among various photocatalysts, graphitic carbon nitride (g-C3N4) stands out owing to its low cost and tunable electronic structure. However, the competing four-electron O2 reduction reaction (ORR) to H2O significantly compromises the selectivity, posing a major challenge for practical applications. In this study, we propose a boron atom decoration strategy on carbon nitride tubes (BCN) to enhance H2O2 production. Combined experimental and theoretical analyses reveal that the incorporation of B atoms facilitates O2 adsorption and inhibits O–O bond homolysis, improving the selectivity of the two-electron ORR pathway to H2O2. Moreover, B atoms, acting as Lewis acid sites, stabilize the •O2– intermediate through acid–base interactions. As a result, the optimized BCN catalyst (BCN400) achieves a remarkable H2O2 yield of 30 μmol·h–1, representing a 4-fold increase in H2O2 production. This study provides a novel strategy for the design of photocatalysts with optimized active sites, offering significant potential for a wide range of applications in sustainable chemical production.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202306","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 Pd(II) → Pd(0) → Pd(II) Catalytic Cycle Enables the Generation of Bis(o-carborane)s: Confirmed by Reproduced Yields and Ratios, Regioselectivities, Additive and Substituent Effects A Pd（II）→Pd(0)→Pd（II）催化循环生成双（o-碳硼烷）s：通过再现产率和比率、区域选择性、加性和取代基效应证实

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-03 DOI: 10.1021/acs.inorgchem.5c00652

Wei-Hua Mu, Lin Zhu, Jia-Wei Yu, Xue Zhao, Liangfei Duan, Ke Cao, Guo Liu

{"title":"A Pd(II) → Pd(0) → Pd(II) Catalytic Cycle Enables the Generation of Bis(o-carborane)s: Confirmed by Reproduced Yields and Ratios, Regioselectivities, Additive and Substituent Effects","authors":"Wei-Hua Mu, Lin Zhu, Jia-Wei Yu, Xue Zhao, Liangfei Duan, Ke Cao, Guo Liu","doi":"10.1021/acs.inorgchem.5c00652","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00652","url":null,"abstract":"The palladium-catalyzed generation of bis(o-carborane)s via regioselective B–B coupling was explored by using density functional theory (DFT). It is found that the reaction proceeds through sequential regioselective B4–H activation, B4′–H/B5′–H activation, and reductive elimination, yielding bis(o-carborane)s ultimately. The palladium catalyst tends to experience a Pd(II) → Pd(0) → Pd(II) rather than Pd(II) → Pd(IV) → Pd(II) catalytic cycle, in which the second B–H (B4′–H/B5′–H) activation serves as the rate-determining step (RDS). Computed RDS step’s activation barriers (27.0/29.0 kcal·mol–1, TS2a_I/TS2a′_I) consist well with experimental yields and selectivities (P1a:P2a = 57%:23%). The regioselectivity is primarily controlled by the second B–H (B4′–H/B5′–H) activation process, with the electronic effect playing a key role and steric hindrance influencing somewhat, as confirmed by the natural bond orbital (NBO) and noncovalent interaction (NCI) analyses. Computed rate-determining free-energy barriers (27.0/29.6/31.1 kcal·mol–1) for the AgOAc/AgF/NiCl2-co-assisted (Path a_I), AgOAc/AgF-co-assisted (Path a_II), and AgOAc-assisted (Path a_III) cases agree perfectly with corresponding experimental trends (obtained 57%/43%/12% of P1a, respectively). Theoretical predictions of substituent effects also demonstrate consistency with experimental observations. This perfect agreement between experiments and computations validates the Pd(II) → Pd(0) → Pd(II) cycle, providing crucial insights into the B–B coupling of o-carboranes and thus aiding the controllable synthesis of functional carborane materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202421","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