Inorganic Chemistry最新文献

{"title":"Tailoring of Unsaturated Metal Sites in Metal–Organic Frameworks to Promote the Conversion of CO2 into High-Value-Added Products","authors":"Chunlong Yu, Xinglei He, Chenxu Gong, Jingheng Li, Ke-Yin Ye","doi":"10.1021/acs.inorgchem.5c00235","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00235","url":null,"abstract":"Well-defined metal–organic frameworks (MOFs) provide an attractive platform for catalysis. Understanding the intrinsic structure–activity relationship of MOFs helps guide the design of novel catalysts. In this work, a new three-dimensional (3D) Mn^II(salen)-based MOF (<b>1</b>) with strong adsorption capacity and high selectivity for CO₂ was synthesized. Through sequential demetallization and remetallization, the flexible tailoring of the metal centers was realized to obtain a series of remetallized MOFs (<b>r1</b>^<b>M</b>; M = Mn, Co, Cu, Ni, V). Among them, <b>r1</b>^<b>Co</b> was proved to be the most active catalyst for the cycloaddition of CO₂ and epoxides. Mechanistic studies reveal that <b>r1</b>^<b>Co</b> displays a high CO₂ affinity and Lewis acidity. In addition, kinetic studies suggest that <b>r1</b>^<b>Co</b> has a lower activation energy than the original MOF (<b>1</b>) and demetallized MOF (<b>d1</b>). Remarkably, <b>r1</b>^<b>Co</b> could be reused five times without affecting its catalytic activity.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"35 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734138","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":"Modulation of S and N Active Sites for Coordination Polymers to Achieve Enhanced Hg2+ Sensing Performances","authors":"Jinfang Zhang, Yinlong Yue, Xingyu Tao, Dejing Yin, Chi Zhang","doi":"10.1021/acs.inorgchem.5c00308","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00308","url":null,"abstract":"It is challenging and vital to develop coordination polymers (CPs) with an outstanding sensing performance. In this work, CP-based sensors with active S and N sites are first exploited. Three new Cu-CPs [Cu(<b>L</b>)(SCN)₂·2DMF]_n (<b>1</b>), [Cu(<b>L</b>)(SCN)·2DMF]_n (<b>2</b>), and [Cu(<b>L</b>)(CN)·2DMF]_n (<b>3</b>) were successfully synthesized by 9,10-bis(di(pyrimidin-5-yl)methylene)-9,10-dihydroanthracene (<b>L</b>) and SCN^–/CN^– ligands. <b>1</b> demonstrates a 1D wavelike chain, fabricated by <b>L</b> bridges linking with Cu(SCN)₂ units. <b>2</b> exhibits a 2D (3,3)-connected network fabricated by SCN^–, 3-connected <b>L</b>, and Cu units. <b>3</b> exhibits a 3D framework, built by 4-connected Cu centers, CN^–, and <b>L</b> bridges. <b>1</b>–<b>3</b> have good water, pH, and thermal stabilities. <b>1</b> and <b>2</b> have uncoordinated S and N active sites and can detect Hg²⁺ through the fluorescence enhancing (“turn-on”) effect. Meanwhile, <b>3</b> only has uncoordinated N active sites and shows a negative Hg²⁺ sensing ability. <b>1</b> and <b>2</b> have ultrahigh Hg²⁺ sensing sensitivity and selectivity. The K_SV and LOD of <b>1</b> toward Hg²⁺ are about 3 and 5 times superior to those of <b>2</b>, separately. <b>1</b> and <b>2</b> represent the first S- and N-rich CP-based sensors and exhibit an excellent “turn-on” Hg²⁺ sensing capacity. Their “turn-on” Hg²⁺ sensing mechanism and difference sensing performances are discussed in detail.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"30 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734143","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":"Impact of Molecular Distortions on Bistability in Spin Crossover Complexes","authors":"Shuang Yuan, Nadeem Natt, Benjamin J. Powell","doi":"10.1021/acs.inorgchem.5c00746","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00746","url":null,"abstract":"We present a simple model of molecular distortions in spin crossover complexes, based on crystal field theory and transition state theory. This allows us to model the effects of molecular distortions on <i>T</i>_1/2, the characteristic temperature of thermal crossover, and <i>T</i>_LIESST, the maximum temperature at which trapped excited high spin (HS) complexes are stable. <i>T</i>_1/2 is a purely thermodynamic quantity, determined by the relative free energies of the HS and low spin (LS) states (Δ<i>G</i> = <i>G</i>_HS – <i>G</i>_LS). The average distortion across HS and LS species <i></i><math display=\"inline\"><mo stretchy=\"false\">[</mo><mover><mi mathvariant=\"normal\">Σ</mi><mo accent=\"true\" stretchy=\"false\">¯</mo></mover><mo>=</mo><mrow><mo stretchy=\"false\">(</mo><msub><mi mathvariant=\"normal\">Σ</mi><mrow><mi mathvariant=\"normal\">H</mi><mi mathvariant=\"normal\">S</mi></mrow></msub><mo>+</mo><msub><mi mathvariant=\"normal\">Σ</mi><mrow><mi mathvariant=\"normal\">L</mi><mi mathvariant=\"normal\">S</mi></mrow></msub><mo stretchy=\"false\">)</mo></mrow><mo>/</mo><mn>2</mn><mo stretchy=\"false\">]</mo></math> and the change in distortion between spin states (ΔΣ = Σ_HS – Σ_LS) have a significant impact on Δ<i>G</i>. However, the inner coordination sphere stiffness (<i>k</i>) has little impact on Δ<i>G</i>. Therefore, <i></i><math display=\"inline\"><mover><mi mathvariant=\"normal\">Σ</mi><mo accent=\"true\" stretchy=\"false\">¯</mo></mover></math> and ΔΣ have large effects on <i>T</i>_1/2 whereas <i>k</i> does not. <i>T</i>_LIESST is largely determined by the height of the barrier (<i>E</i>_b) between the metastable HS state and the LS state. <i>E</i>_b is strongly affected by ΔΣ, <i></i><math display=\"inline\"><mover><mi mathvariant=\"normal\">Σ</mi><mo accent=\"true\" stretchy=\"false\">¯</mo></mover></math>, and <i>k</i>; thus <i>T</i>_LIESST is strongly dependent on all of these quantities. Thus, increasing both the relative and absolute distortion of SCO complexes increases <i>T</i>_LIESST and decreases <i>T</i>_1/2, providing a route to high temperature spin-state switching via molecular distortions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"19 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734145","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":"Synergistic Effect of Topological Semimetal TiSi and Plasmonic Cu for Enhanced Photoelectrocatalytic Water Splitting of TiO2 Nanorod Array","authors":"Zhengwang Cheng, Shengjia Li, Yuan Cao, Gang Yuan, Jiyan Liu, Hui Lv, Zhuo Peng, Changcun Han, Mei Wang, Fhulufhelo Nemangwele, Xinguo Ma, Minghu Pan","doi":"10.1021/acs.inorgchem.5c00103","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00103","url":null,"abstract":"Developing high-efficiency and low-cost catalysts for PEC water splitting is vital for solving the issues of energy consumption, environmental pollution, and global warming. In this study, we designed and prepared a composite photoanode TiO₂/TiSi/Cu by depositing a topological semimetal TiSi film and plasmonic Cu nanoparticles onto a TiO₂ nanorod array. Due to the synergistic effect of the topological bands of TiSi and the SPR effect of Cu, TiO₂/TiSi/Cu exhibits significantly enhanced optical absorption in the visible-light region. Under wavelength (λ) &gt; 420 nm light irradiation, the photocurrent density of TiO₂/TiSi/Cu reaches 4.46 mA cm^–2 at 1.9 V vs RHE, about 17.84 times that of pure TiO₂. The carrier lifetime is prolonged from 25.04 ns for pure TiO₂ to 31.13 ns for TiO₂/TiSi/Cu. Furthermore, the TiO₂/TiSi/Cu photoanode demonstrates good long-term cyclic stability, with an average hydrogen production rate of 8.12 μmol cm^–2 h^–1. Our results indicate that the synergistic effect of topological semimetal TiSi and plasmonic Cu is an effective strategy to enhance the PEC performance of TiO₂. This approach could be applied to other topological catalysts, providing new opportunities for developing novel and efficient catalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"59 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734139","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":"MOF Etching-Induced NiCo-Embedded Hollow N-Doped Carbon Nanocube for Enhanced Ratiometric Molecularly Imprinted Electrochemical Sensing of Carbendazim","authors":"Linbo Deng, Shuya Xue, Li Li, Rongrong Huang, Pingying Xie, Jiawei Liu, Linyu Wang, Xiaoqiang Wang, Xuemin Duan, Limin Lu","doi":"10.1021/acs.inorgchem.5c00325","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00325","url":null,"abstract":"Metal–organic framework (MOF)-derived carbon materials are commonly used as sensing materials, but their limited accessibility to active sites and specific surface area restrict their applications. In this study, we proposed a simple method involving facile tannic acid etching and calcination to create NiCo-embedded hollow N-doped carbon nanocubes (NiCo@HNC) using MOFs as sacrificial templates. The resulting NiCo@HNC material has a large specific surface area, improved mass transport channels, and enhanced exposure of electroactive sites due to its unique hollow structure and high porosity, leading to enhanced electrocatalytic activity. Moreover, with the utilization of NiCo@HNC as a substrate material and dopamine as a functional monomer, a ratiometric molecularly imprinted electrochemical sensor was developed for the selective and sensitive detection of carbendazim (CBZ). This sensor demonstrated a wide linear range of 0.0003–10 μM and a low detection limit of 0.1 nM. In addition, the sensor was utilized for the accurate quantification of CBZ in actual carrot/strawberry samples with a recovery range of 96.0–103.0%, indicating its potential for practical application.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734144","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-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 W₁₈O₄₉, 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, W₁₈O₄₉/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 CO₂ reduction reactions, severe hydrogen evolution limits the activation of CO₂ molecules. In this study, oxygen atoms were successfully migrated from TiO₂ into Ni₂P nanoparticles through a simple impregnation and low-temperature phosphidation process, constructing an O–Ni₂P/TiO₂ nanowire array electrode that modulates the surface electronic structure, inhibits hydrogen evolution, and promotes CO₂ activation. At a potential of −0.4 V (vs RHE), the CH₄ production rate reached 1.46 μmol·h^–1·cm^–2, 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 CH₃* intermediates are easily formed on the surface of the material, which are key intermediates directly related to the CO₂ to CH₄. Further density functional theory (DFT) calculations indicated that the oxygen-doped Ni₂P surface has a lower barrier for the formation of CHO*, thereby facilitating the conversion of CO₂ to CH₄.","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}

{"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-CF₃ 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)₂(Cp)}₂] 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":"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)_0.35 micromotor synthesized by a facile postsynthesis metalation via introducing cobalt salts ligated with 2,2′-bipyridine-5,5′dicarboxylic acid into UiO-67-bpy_0.35 framework. The Co²⁺ active sites can decompose H₂O₂ to generate bubbles to power UiO-67-Co(bpy)_0.35. Meanwhile, the UiO-67-Co(bpy)_0.35 micromotor exhibits robust peroxidase-like activity through catalyzing H₂O₂ to generate ^•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)_0.35 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}

{"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)_<i>x</i>) 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)_<i>x</i> support. As a result, the optimized Ir–Co(OH)_<i>x</i> exhibits excellent electrocatalytic OER activity with a low overpotential of 251 mV to drive 10 mA cm^–2, which is 63 mV lower than that of pristine Co(OH)_<i>x</i>. 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)_<i>x</i>, 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}