Guannan Zhou, Zhenxing Fang, Lu Li, Shaowei Wu, Guangfeng Wu, Rui Wang
{"title":"Oxygen-Sensitive Nanomaterials Synthesized in an Open System: Water-Triggered Nucleation and Its Controllability in the Growth Process","authors":"Guannan Zhou, Zhenxing Fang, Lu Li, Shaowei Wu, Guangfeng Wu, Rui Wang","doi":"10.1021/acs.inorgchem.4c05392","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05392","url":null,"abstract":"A novel method has been developed for synthesizing the oxygen-sensitive nanomaterial W<sub>18</sub>O<sub>49</sub>, utilizing 1,3-propanediol as a solvent, with water-triggered nucleation and controllable crystal growth in an open system. The amount of water addition was precisely investigated for the effect of the crystal growth process. Furthermore, the incorporation of 2,5-furandicarboxylic acid into the process led to the successful preparation of a functionalized nanocomposite polyester, W<sub>18</sub>O<sub>49</sub>/poly(propylene 2,5-furandicarboxylate) (PTF), through in situ polymerization, exhibiting superior thermal insulation properties.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"215 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723798","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}
{"title":"Oxygen Atom Migration in Ni2P/TiO2 Heterostructures Dynamically Regulates the Electrocatalytic CO2 Reduction Pathway","authors":"Dailing Jia, Jingying Wei, Dongfen Hou, Huaiguo Xue, Jingqi Tian, Tengfei Jiang","doi":"10.1021/acs.inorgchem.5c00500","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00500","url":null,"abstract":"Transition metal phosphides (TMPs) are widely applied in electrocatalytic reactions, such as the hydrogen evolution reaction (HER), due to their excellent physicochemical properties. However, when utilized in CO<sub>2</sub> reduction reactions, severe hydrogen evolution limits the activation of CO<sub>2</sub> molecules. In this study, oxygen atoms were successfully migrated from TiO<sub>2</sub> into Ni<sub>2</sub>P nanoparticles through a simple impregnation and low-temperature phosphidation process, constructing an O–Ni<sub>2</sub>P/TiO<sub>2</sub> nanowire array electrode that modulates the surface electronic structure, inhibits hydrogen evolution, and promotes CO<sub>2</sub> activation. At a potential of −0.4 V (vs RHE), the CH<sub>4</sub> production rate reached 1.46 μmol·h<sup>–1</sup>·cm<sup>–2</sup>, with a Faraday efficiency of 11.8%, and maintained long-term stability during the 36-h electrocatalytic process. <i>In situ</i> infrared spectroscopy revealed that CO* and CH<sub>3</sub>* intermediates are easily formed on the surface of the material, which are key intermediates directly related to the CO<sub>2</sub> to CH<sub>4</sub>. Further density functional theory (DFT) calculations indicated that the oxygen-doped Ni<sub>2</sub>P surface has a lower barrier for the formation of CHO*, thereby facilitating the conversion of CO<sub>2</sub> to CH<sub>4</sub>.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"183 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734147","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}
Xiaoqing Li, Gui Wang, Dongyang Zhou, Ziwei Lan, Fengling Jiang, Dickon H. L. Ng, Jia Li
{"title":"Zirconium Metal–Organic Frameworks as Micromotors with Enzyme-like Activity for Glutathione Detection","authors":"Xiaoqing Li, Gui Wang, Dongyang Zhou, Ziwei Lan, Fengling Jiang, Dickon H. L. Ng, Jia Li","doi":"10.1021/acs.inorgchem.5c00494","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00494","url":null,"abstract":"Herein, we report a novel UiO-67-Co(bpy)<sub>0.35</sub> micromotor synthesized by a facile postsynthesis metalation via introducing cobalt salts ligated with 2,2′-bipyridine-5,5′dicarboxylic acid into UiO-67-bpy<sub>0.35</sub> framework. The Co<sup>2+</sup> active sites can decompose H<sub>2</sub>O<sub>2</sub> to generate bubbles to power UiO-67-Co(bpy)<sub>0.35</sub>. Meanwhile, the UiO-67-Co(bpy)<sub>0.35</sub> micromotor exhibits robust peroxidase-like activity through catalyzing H<sub>2</sub>O<sub>2</sub> to generate <sup>•</sup>OH under neutral conditions. Based on this, a sensing platform was constructed for the colorimetric detection of GSH. Due to the synergy of self-driven motion and excellent peroxide-like activity, UiO-67-Co(bpy)<sub>0.35</sub> micromotor can sensitively detect GSH with a low analytic limitation as 0.13 μM for GSH detection. This study provides a new sight of using the postsynthesis metalation method to prepare Zr(Co)-MOF micromotor for highly selective, sensitive, and facile detection of GSH.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"72 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734146","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}
Ishfaq A. Bhat, Subhalaxmi Panda, Manju Sharma, Pradeepta K. Panda
{"title":"Double-Decker Ferrocene Analogue Derived from Flexible 14π Triphyrin(2.1.1) along with an Unusual Diels–Alder Adduct: Synthesis, Characterization, and Mechanistic Studies","authors":"Ishfaq A. Bhat, Subhalaxmi Panda, Manju Sharma, Pradeepta K. Panda","doi":"10.1021/acs.inorgchem.5c00249","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00249","url":null,"abstract":"14π-Triphyrin(2.1.1) is used to synthesize a double-decker sandwich complex like ferrocene. The presence of only two meso-CF<sub>3</sub> substituents provides the macrocycle with enough flexibility to undergo bowl-shaped deformation in order to complex with Fe(II) ions, forming a low-spin diamagnetic complex. Further, the Cp ligand of the metal carrier [{Fe(CO)<sub>2</sub>(Cp)}<sub>2</sub>] forms a Diels–Alder adduct with the triphyrin macrocycle at higher temperatures, which does not undergo complexation. The plausible role of factors behind the formation of sandwich complexes in [14]triphyrin(2.1.1) was explored using first-principles molecular dynamics.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723799","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}
{"title":"Local Electronic Regulation by Oxygen Coordination with Single- Atomic Iridium on Ultrathin Cobalt Hydroxide Nanosheets for Electrocatalytic Oxygen Evolution","authors":"Youkui Zhang, Yujuan Pu, Wenhao Li, Yunxiang Lin, Haoyuan Li, Yingshuo Wu, Tao Duan","doi":"10.1021/acs.inorgchem.5c00659","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00659","url":null,"abstract":"Rationally optimizing the atomic and electronic structure of electrocatalysts is an effective strategy to improve the activity of the electrocatalytic oxygen evolution reaction (OER), yet it remains challenging. In this work, atomic heterointerface engineering is developed to accelerate OER by decorating iridium atoms on low-crystalline cobalt hydroxide nanosheets (Ir–Co(OH)<sub><i>x</i></sub>) via oxygen-coordinated bonds to modulate the local electronic structure. Leveraging detailed spectroscopic characterizations, the Ir species were proved to promote charge transfer through Ir–O–Co coordination between the Ir atom and the Co(OH)<sub><i>x</i></sub> support. As a result, the optimized Ir–Co(OH)<sub><i>x</i></sub> exhibits excellent electrocatalytic OER activity with a low overpotential of 251 mV to drive 10 mA cm<sup>–2</sup>, which is 63 mV lower than that of pristine Co(OH)<sub><i>x</i></sub>. The experimental results and density functional theory calculations reveal that the isolated Ir atoms can regulate the local coordination environment and electronic configuration of Co(OH)<sub><i>x</i></sub>, thus accelerating the catalytic OER kinetics. This work provides an atomistic strategy for the electronic modulation of metal active sites in the design of high-performance electrocatalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713620","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}
Li-Wen Chen, Hai Zhu, Hua-Wei Zhou, Hao-Zhe Zhang, Sheng-Ze Zhao, Yong-Hua Li, Shi Wang
{"title":"Halogen-Driven Spin Dynamics: Exploring Correlation of Cooperativity and Spin Crossover in Solid-State Mononuclear Fe(III) Schiff-Base Complexes","authors":"Li-Wen Chen, Hai Zhu, Hua-Wei Zhou, Hao-Zhe Zhang, Sheng-Ze Zhao, Yong-Hua Li, Shi Wang","doi":"10.1021/acs.inorgchem.5c00885","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00885","url":null,"abstract":"We report the synthesis, crystal structures, and magnetic properties of four new mononuclear iron(III) complexes, [Fe(5-X-sal<sub>2</sub>trien)]ReO<sub>4</sub> (X = F (<b>1</b>); X= Cl (<b>2</b>); X = Br (<b>3</b>); X = I (<b>4</b>)), where (5-X-sal<sub>2</sub>trien)<sup>2–</sup> is a halogen-substituted hexadentate Schiff-base (N<sub>4</sub>O<sub>2</sub>)<sup>2–</sup> ligand. Magnetic susceptibility measurements demonstrated that complex <b>1</b> maintains a high-spin (HS) state, while complexes <b>3</b> and <b>4</b> display a very gradual spin crossover (SCO) above 300 K. Complex <b>2</b> exhibits a unique two-step thermo-induced spin-state switching at <i>T</i><sub>1/2</sub> = 250 K (1) and 209 K (2) with symmetry breakings. Single-crystal X-ray structures of <b>2</b> are obtained at 300, 250, and 100 K, respectively, indicating two structural phase transitions (<i>Pccn</i>–<i>Pmmn</i>–<i>P</i>2<sub>1</sub>/<i>m</i>). The introduction of halogen substituents on (sal<sub>2</sub>trien)<sup>2–</sup> ligands has a great influence on cooperativity and finally the magnetic properties of Fe(III) SCO complexes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"183 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723837","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}
Yang Zhou, Fan Yin, Shao-Jun Hu, Li-Peng Zhou, Jian Yang, Qing-Fu Sun
{"title":"Supramolecular Eu(III)4L4 Tetrahedra-Based Films for Luminescence Sensing of Volatile Amines with Sub-ppt-Level Detection Limit","authors":"Yang Zhou, Fan Yin, Shao-Jun Hu, Li-Peng Zhou, Jian Yang, Qing-Fu Sun","doi":"10.1021/acs.inorgchem.4c05480","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05480","url":null,"abstract":"Metal–organic cages are a class of discrete supramolecular architectures endowed with a well-defined cavity and diverse functionalities, offering a broad range of applications that, however, are predominantly confined to liquid phases. In this study, we present the self-assembly of supramolecular Eu(III)<sub>4</sub>L<sub>4</sub> tetrahedra, constructed from triarylborane-cored tritopic tridentate ligands, which were fabricated into spin-coated films with bright emission, smooth surfaces, and uniform thickness. These films demonstrated ultralow detection limits for a series of volatile amines, reaching the sub-ppt level. This work serves as a compelling example of the preparation and application of metal–organic-cage-based films, paving the way for broader application scenarios.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"218 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723836","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}
Yiming Zhang, Zhipeng Li, Baihua Qu, Xing Shen, Le Tong, Jin Wang, Jingqin Cui, Xin Li, Qingshui Xie, Jingfeng Wang
{"title":"In Situ Assembly Engineering-Induced 3D MOF-Driven MXene Framework for Highly Stable Na Metal Anodes","authors":"Yiming Zhang, Zhipeng Li, Baihua Qu, Xing Shen, Le Tong, Jin Wang, Jingqin Cui, Xin Li, Qingshui Xie, Jingfeng Wang","doi":"10.1021/acs.inorgchem.4c04230","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04230","url":null,"abstract":"Sodium metal, with its high theoretical capacity, low redox potential, and cost-effectiveness, presents a promising anode candidate for next-generation high-energy-density batteries. However, the development of Na metal anodes is significantly challenged by issues such as uncontrolled dendrite growth, uncontrolled volume expansion, and associated safety concerns. Designing and developing advanced materials to enhance the conductivity of sodium metal anodes and promote uniform sodium ion deposition are of urgent importance. Herein, a MXene-based hybrid material was developed by integrating MOF-derived Zn, Co, N, and C dopants with Ti<sub>3</sub>C<sub>2</sub>T<sub><i>x</i></sub> MXene to serve as a hosting substrate for the Na metal anode. The MXene provided a conductive framework, while the MOF-derived dopants introduced sodiophilic sites, promoting uniform Na deposition and mitigating volume expansion. The optimized material demonstrated an average Coulombic efficiency of 99.99% over 3000 cycles and stable cycling for over 5000 h in symmetrical cells and maintained over 80% capacity retention at 3 C after 500 cycles in full-cell tests, highlighting its potential as a robust Na metal anode material.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"63 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723800","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}
Rebecca X. Skalla, Christine M. Montone, Maren Pink, Olivia K. Walters, Eric D. Bloch
{"title":"Role of Solvent Decomposition in the Synthesis and Composition of Porous Zirconium-Based Coordination Cages","authors":"Rebecca X. Skalla, Christine M. Montone, Maren Pink, Olivia K. Walters, Eric D. Bloch","doi":"10.1021/acs.inorgchem.4c04982","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04982","url":null,"abstract":"Porous zirconium-based coordination cages are promising materials for applications in gas adsorption, catalysis, and molecular separation due to their tunability and stability. However, their synthesis is often complicated by the formation of competing phases, including insoluble or poorly soluble byproducts that impact purity and composition. Moreover, product composition and solubility can vary widely due to factors such as humidity, seasonal fluctuations, and lab-to-lab variations, highlighting the inherent lack of robustness in these syntheses. In this work, we investigate how solvothermal synthesis conditions, particularly temperature and solvent decomposition, influence the formation and composition of these cages. We show that elevated temperatures accelerate solvent breakdown, leading to the incorporation of formate and acetate byproducts that alter the final cage structures and contribute to the formation of insoluble zirconium-based, amorphous solids. By systematically varying the reaction conditions, we optimized the composition of the isolated cage products, achieving improved phase purity. By optimizing synthetic parameters, we achieve control over cage formation and particle morphology while mitigating the effects of solvent decomposition. Our findings provide insights into the balance between ligand coordination and solvent effects, enabling the development of strategies to enhance the purity, porosity, and functionality of these molecular cages.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713617","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}
{"title":"SUF4: A Terminal Monosulfido Complex of Uranium(VI) with a Linear SUF Moiety","authors":"Qingxiu He, Xiuting Chen, Yu Gong","doi":"10.1021/acs.inorgchem.4c05157","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05157","url":null,"abstract":"Although there have been a few terminal sulfido complexes of uranium(VI) with either SUO or SUN moiety, it remains a question whether the terminal sulfido ligand can be stabilized in the absence of such multiply bound oxo or nitrido ligands. Herein, we report a terminal monosulfide complex of uranium(VI) in the form of SUF<sub>4</sub> bearing a linear SUF moiety that was prepared via the reaction of laser-ablated uranium atoms with SF<sub>4</sub> in cryogenic matrixes. On the basis of the results from infrared spectroscopy combined with density functional theory calculations at the B3LYP level, the SUF<sub>4</sub> complex possesses a trigonal bipyramid structure with singlet ground state and nonplanar <i>C</i><sub>3<i>v</i></sub> symmetry where the terminal sulfido ligand is stabilized by the monovalent fluoro ligand trans to sulfur. A triple U–S bond with a positively charged sulfur atom was identified according to the natural bond orbital analysis. Inverse trans influence is present in SUF<sub>4</sub> as revealed by the difference in bond length between U–F<sub>axial</sub> from the linear SUF moiety and U–F<sub>equatorial</sub> from the UF<sub>3</sub> equatorial plane, which is further supported by bonding analysis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"72 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713618","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}