Inorganica Chimica Acta最新文献_第4页

Novel zinc Metalloporphyrin based metal-organic framework for Quantitative & Reusable Sensing of nitrobenzene 基于锌金属卟啉的新型金属有机框架用于硝基苯的定量和可重复使用传感

IF 2.7 3区化学

Inorganica Chimica Acta Pub Date : 2025-05-23 DOI: 10.1016/j.ica.2025.122785

Zachary Magnuson , Brielle Wolfe , Jacob M. Mayers , Lukasz Wojtas , Weijie Zhang , Shengqian Ma , Randy W. Larsen

{"title":"Novel zinc Metalloporphyrin based metal-organic framework for Quantitative & Reusable Sensing of nitrobenzene","authors":"Zachary Magnuson , Brielle Wolfe , Jacob M. Mayers , Lukasz Wojtas , Weijie Zhang , Shengqian Ma , Randy W. Larsen","doi":"10.1016/j.ica.2025.122785","DOIUrl":"10.1016/j.ica.2025.122785","url":null,"abstract":"<div><div>Porphyrins and metalloporphyrins have been exploited for a wide range of applications including sensing and catalysis in both homogeneous and heterogeneous formats. An emerging class of porous materials that utilize porphyrins and metalloporphyrins for diverse applications are the metal organic frameworks (MOFs) containing porphyrins as guests within the MOF cavities or as integral components of the framework by serving as a metal node linker. Here, a novel metal metalloporphyrin framework (MMPF-X) was synthesized using a solvothermal method from a 4′,4″‘,4″“‘,4″““‘-(porphyrin-5,10,15,20-tetrayl)tetrakis(([1″“,1″“‘-biphenyl]-3,5-dicarboxylic acid)) (TDBP) ligand and zinc paddlewheel metal building blocks (MBBs), yielding C 2/m space group crystals with a cph pattern of crisscross metalloporphyrin lattices that result in complex interconnected channels. The MMPF-X functions as a heterogeneous sensor for nitroaromatics, exhibiting reversible fluorescence quenching in the presence of nitrobenzene. The level of detection (LOD) was determined and compared to ZnTDBP in solution, highlighting MMPF-x's potential for quantitative sensing of nitrobenzene and related compounds across a wide concentration range. The quenching mechanism was evaluated using a modified stern-Volmer analysis for fractional components consistent with the porosity of the MOF.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"586 ","pages":"Article 122785"},"PeriodicalIF":2.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144166242","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Binding and activation of dihydrogen and other small molecules in a dirhodium paddle wheel unit based three-dimensional porous coordination polymer: FTIR and computational studies 基于三维多孔配位聚合物的双氢和其他小分子的结合和活化：FTIR和计算研究

IF 2.7 3区化学

Inorganica Chimica Acta Pub Date : 2025-05-23 DOI: 10.1016/j.ica.2025.122778

Peter A. Georgiev , Nikola Drenchev

{"title":"Binding and activation of dihydrogen and other small molecules in a dirhodium paddle wheel unit based three-dimensional porous coordination polymer: FTIR and computational studies","authors":"Peter A. Georgiev , Nikola Drenchev","doi":"10.1016/j.ica.2025.122778","DOIUrl":"10.1016/j.ica.2025.122778","url":null,"abstract":"<div><div>We have studied the electronic structure and reactivity of coordinatively unsaturated rhodium centers, being part of the dirhodium paddle wheel type Secondary Building Unit (SBU), in a microporous Metal-Organic Framework (MOF). This dirhodium structure manifests a Rh(I)-like local electronic structure at the coordinatively unsaturated accessible adsorption sites, prone to relatively strong interactions with small molecule guests like dihydrogen, dinitrogen, nitrous oxide, iodine and iodine containing compounds, as a few examples. Thе local adsorption site Rh(I)-like chemistry is confirmed by in situ FTIR spectroscopy of CO, detecting the corresponding monocarbonyl species at about 2100 cm−1. The corresponding metal-dihydrogen complex is manifested via the stretching dihydrogen(deuterium) vibrations observed at 3808 cm−1 (2737 cm−1). Our computational work predicts optimal binding energy in this complex for hydrogen storage applications, in the order of 24 kJ/mol at ambient temperatures, owing to a substantial dihydrogen σ-bond electron donation into the frontier Rh 4 s state. Interestingly, and in contrast to all other known σ-bond dihydrogen-metal complexes, here a back-donation from rhodium d-states into the dihydrogen σ⁎ antibonding states is practically absent, and hence the resultant metal-dihydrogen complex appears a pure σ-bond complex. Furthermore, the particular electronic structure of the dirhodium unit appears very suitable for applications related to the capture and utilization of iodine (its radionuclides) containing volatile species as well as separation of isoelectronic species like nitrous oxide and carbon dioxide. Computed strong adsorption energies for nitric oxide, in excess of 80 kJ/mol, as compared to about 50 kJ/mol for water, imply possible controlled delivery and continuous release in aqueous solutions, for instance in medicinal and generally biological applications.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"586 ","pages":"Article 122778"},"PeriodicalIF":2.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144166238","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Vanadium Oxo Sulfate (VOSO4) for hydrogen generation and catalytic hydrogenation 用于制氢和催化加氢的硫酸钒（VOSO4）

IF 2.7 3区化学

Inorganica Chimica Acta Pub Date : 2025-05-22 DOI: 10.1016/j.ica.2025.122774

Hani Nasser Abdelhamid

{"title":"Vanadium Oxo Sulfate (VOSO4) for hydrogen generation and catalytic hydrogenation","authors":"Hani Nasser Abdelhamid","doi":"10.1016/j.ica.2025.122774","DOIUrl":"10.1016/j.ica.2025.122774","url":null,"abstract":"<div><div>This work investigated the catalytic characteristics of vanadium (IV) oxide sulfate hydrate (VOSO4·3H2O) for hydrogen production and the hydrogenation of organic contaminants. The crystalline structure of VOSO4·3H2O was characterized using various analytical methods. Structural study verified the existence of a monoclinic crystalline phase consisting of [VO(H2O)3]2+ octahedral units and SO42− tetrahedral anions linked through hydrogen bonding. Optical investigations demonstrated a semiconducting characteristic with a 3.1–3.3 eV band gap and an intense blue color. VOSO4·3H2O exhibited exceptional catalytic efficacy in facilitating the hydrolysis of sodium borohydride (NaBH4) and ammonia borane (NH3BH3), markedly improving hydrogen production under mild circumstances. The hydrogen generation rate (HGR) attained 2000 mL/min·g with increased NaBH₄ loading (2 wt%). Furthermore, VOSO4·3H2O facilitated the reduction of several nitroaromatic compounds and organic dyes, attaining over 90 % conversion efficiency in 60 min. The catalyst demonstrated remarkable recyclability across five consecutive cycles with no loss in activity. These results highlight the potential of VOSO4·3H2O as a recyclable and effective catalyst for hydrogen generation and environmental remediation applications, i.e., catalytic hydrogenation.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"586 ","pages":"Article 122774"},"PeriodicalIF":2.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144166237","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Synthesis, structures and optical properties of a series of zinc(II) complexes bearing salophen ligands derived from 3,5-di-tert-butyl-2-hydroxybenzaldehyde 3,5-二叔丁基-2-羟基苯甲醛系列含salophen配体锌（II）配合物的合成、结构和光学性质

IF 2.7 3区化学

Inorganica Chimica Acta Pub Date : 2025-05-22 DOI: 10.1016/j.ica.2025.122777

Van Thong Pham , Ninh Thi Minh Giang , Tran Ngoc Dung , Thanh Chung Pham , Luc Van Meervelt , Le Thi Hong Hai

{"title":"Synthesis, structures and optical properties of a series of zinc(II) complexes bearing salophen ligands derived from 3,5-di-tert-butyl-2-hydroxybenzaldehyde","authors":"Van Thong Pham , Ninh Thi Minh Giang , Tran Ngoc Dung , Thanh Chung Pham , Luc Van Meervelt , Le Thi Hong Hai","doi":"10.1016/j.ica.2025.122777","DOIUrl":"10.1016/j.ica.2025.122777","url":null,"abstract":"<div><div>The photophysical and spectral characteristics of a series of Zn(II)-salophen complexes ZnL1–ZnL6 were systematically analyzed using various analytical techniques. The SC-XRD results of ZnL1 and ZnL4-ZnL6 show that in the crystals of the four complexes, each central metal Zn(II) has a coordination number of five, bonded to the ligand through four donor atoms O^N^N^O and an ethanol molecule. In ethanol at room temperature, all complexes displayed a strong emission at 530–550 nm, characterized by a fluorescence quantum yield of 25–71 % with a significant Stokes shift of 115–129 nm. The complexes fluoresce weaker in the solid state with Φ = 0.4–1.1 % with a red shift in wavelength compared to that in ethanol. The lifetime measured using time-correlated single photon counting showed longer lifetime in solid state (0.37–0.59 ns) than in ethanol (0.14–0.33 ns). Quantum chemical calculations were performed using DFT and TD-DFT methods to obtain structural parameters and the optical properties of complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"586 ","pages":"Article 122777"},"PeriodicalIF":2.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144134328","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Three one-dimensional coordination polymers based on a mixed benzimidazole–dicarboxylate strategy: Syntheses, structures, hirshfeld surface analysis and fluorescence properties 基于苯并咪唑-二羧酸盐混合策略的三种一维配位聚合物：合成、结构、hirshfeld表面分析和荧光性质

IF 2.7 3区化学

Inorganica Chimica Acta Pub Date : 2025-05-22 DOI: 10.1016/j.ica.2025.122776

Zhaolong Liu, Yuanyue Ma, Rongrong Gao, Junjie Teng, Yanli Bi, Huilu Wu

{"title":"Three one-dimensional coordination polymers based on a mixed benzimidazole–dicarboxylate strategy: Syntheses, structures, hirshfeld surface analysis and fluorescence properties","authors":"Zhaolong Liu, Yuanyue Ma, Rongrong Gao, Junjie Teng, Yanli Bi, Huilu Wu","doi":"10.1016/j.ica.2025.122776","DOIUrl":"10.1016/j.ica.2025.122776","url":null,"abstract":"<div><div>Three new zinc(II) and cadmium(II) coordination polymers (CPs) with 2-(6-(1H-benzo[d]imidazol-2-yl)pyridin-2-yl)-1-(pyridin-4-ylmethyl)-1H-benzo[d]- imidazole (4pybbp) and 2-(6-(1H-benzo[d]imidazol-2-yl)pyridin-2-yl)-1-(pyridin-3- ylmethyl)-1H-benzo[d]-imidazole (3pybbp) as ligands, namely, [Zn(4pybbp)(terephthalate)]n (1), [Cd(4pybbp)(terephthalate)]n (2), {[Cd(3pybbp)(terephthalate)]·(DMF}n (3) (DMF = N,N-dimethylformamide), have been solvothermally synthesized and characterized. Single crystal X-ray diffraction shows that although all three coordination polymers have one-dimensional chain structure, 1 is a linear-chain zinc(II) CP, while 2 and 3 are zigzag-chain cadmium(II) CPs, which highlights the key role of the metal ion radius in structural adjustment. Moreover, hydrogen bonds and π-interactions guide the self-organization of one-dimensional chain to form two-dimensional supramolecular structures. Hirshfeld surface analysis reveals a detailed scrutiny of intermolecular interactions experienced by each coordination polymers. The solid-state fluorescence properties indicate that the fluorescence peaks of the CPs 1–3 belong to the π*-π transition of the ligand 3pybbp or 4pybbp, which occur significant blue-shift and enhancement. This is because the coordination between ligands and metal ions leads to the increase of the energy level difference of π *-π orbital and the decrease of the energy loss of thermal vibration. The fluorescence properties of the CPs 1–3 imply that they may be good candidates for optical materials.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"586 ","pages":"Article 122776"},"PeriodicalIF":2.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144115815","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

1,2-Bis(2-bromophenyl)ethynes: The influence of 5′-methoxy and 5′-difluoromethoxy groups on the electronic properties and crucial bond lengths 1,2-双（2-溴苯基）乙炔：5 ' -甲氧基和5 ' -二氟甲氧基对电子性质和关键键长的影响

IF 2.7 3区化学

Inorganica Chimica Acta Pub Date : 2025-05-20 DOI: 10.1016/j.ica.2025.122773

David H.I. Maier, Frederick J.F. Jacobs, Barend C.B. Bezuidenhoudt, Alice Brink, Charlene Marais

{"title":"1,2-Bis(2-bromophenyl)ethynes: The influence of 5′-methoxy and 5′-difluoromethoxy groups on the electronic properties and crucial bond lengths","authors":"David H.I. Maier, Frederick J.F. Jacobs, Barend C.B. Bezuidenhoudt, Alice Brink, Charlene Marais","doi":"10.1016/j.ica.2025.122773","DOIUrl":"10.1016/j.ica.2025.122773","url":null,"abstract":"<div><div>The effect of methoxy and difluoromethoxy groups para to the bromo substituent of 1,2-bis(2-bromophenyl)ethynes on the conformation of the molecule and the properties of the C<img>C and C<img>Br bonds was investigated by single crystal X-ray diffractometry and Nuclear Magnetic Resonance spectroscopy. The difluoromethoxy and methoxy groups both activated the ortho positions, as was evident from the shielding of both the proton and carbon atoms at these positions in NMR experiments. The C6-C≡C-C6 system in 1,2-bis(2-bromophenyl)ethyne, 1,2-bis(2-bromo-5-(difluoromethoxy)phenyl)ethyne, 1,2-bis(2-bromo-5-methoxyphenyl)ethyne and 1-bromo-2-((2-bromophenyl)ethynyl)-4-methoxybenzene is in effect coplanar, with the dihedral angle between the two ring planes ranging from 0° to 5.8°. Substitution has little effect on the electronic properties of the triple bond, as was evident from the similar 13C NMR spectroscopy chemical shifts and crystallographic bond distances. This is also reflected in the similar angles at the sp- centra, which deviate only slightly from linearity (177.3(2) – 179.6(1)°). The OCF2H substituent resulted in a small contraction of the C<img>Br bond and OCH3 in a slight elongation. The bromo-bearing carbon was shielded with 3.8 ppm by the OCF2H group and by more than 9 ppm relative to an H atom by the OCH3 group in 13C NMR spectroscopy experiments.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"586 ","pages":"Article 122773"},"PeriodicalIF":2.7,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144115812","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Synthesis and structure of triosmium clusters bearing an organosilicon ligand 含有机硅配体的三锇团簇的合成与结构

IF 2.7 3区化学

Inorganica Chimica Acta Pub Date : 2025-05-18 DOI: 10.1016/j.ica.2025.122765

Md. Selim Reza , Subas Rajbangshi , Vladimir N. Nesterov , German E. Pieslinger , Shariff E. Kabir , Shishir Ghosh

{"title":"Synthesis and structure of triosmium clusters bearing an organosilicon ligand","authors":"Md. Selim Reza , Subas Rajbangshi , Vladimir N. Nesterov , German E. Pieslinger , Shariff E. Kabir , Shishir Ghosh","doi":"10.1016/j.ica.2025.122765","DOIUrl":"10.1016/j.ica.2025.122765","url":null,"abstract":"<div><div>The reactions of 4-methylquinoline-capped triosmium cluster [Os3(CO)9(μ3-η1,κ1-H3CC9H5N)(μ-H)] (1) with various organosilicon ligands of the general formula R'R2SiH have been examined. Treatment of 1 with R'R2SiH in refluxing benzene leads to the stepwise formation of [Os3(CO)9(SiR2R)(μ-η1,κ1-H3CC9H5N)(μ-H)2] (2) and [Os3(CO)8(SiR2R)(μ3-η1,κ1-H3CC9H5N)(μ-H)2] (3), respectively, as confirmed by control experiments. In these reactions, oxidative-addition of the Si<img>H bond to 1 affords 2 whose decarbonylation leads to the formation of 3. X-ray crystallography has been used to determine the molecular structure of the products, while the bonding in them has been investigated by electronic structure calculations. Both 2 and 3 exist as a pair of isomers in solution.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"586 ","pages":"Article 122765"},"PeriodicalIF":2.7,"publicationDate":"2025-05-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144115814","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Crystal structure, DFT and Hirshfeld surface studies of a novel zinc(II) ion pair complex based on coumarin Mannich base: In vitro antiproliferative activity 基于香豆素曼尼希碱的新型锌离子对配合物的晶体结构、DFT和Hirshfeld表面研究：体外抗增殖活性

IF 2.7 3区化学

Inorganica Chimica Acta Pub Date : 2025-05-16 DOI: 10.1016/j.ica.2025.122770

Erik Ortiz-Blanco , Gabriela Alejandra Sosa-Ortiz , Ricardo Tovar-Miranda , Eva Luz Montoya-Hernández , Enrique Juárez-Aguilar , Tomás Guerrero

{"title":"Crystal structure, DFT and Hirshfeld surface studies of a novel zinc(II) ion pair complex based on coumarin Mannich base: In vitro antiproliferative activity","authors":"Erik Ortiz-Blanco , Gabriela Alejandra Sosa-Ortiz , Ricardo Tovar-Miranda , Eva Luz Montoya-Hernández , Enrique Juárez-Aguilar , Tomás Guerrero","doi":"10.1016/j.ica.2025.122770","DOIUrl":"10.1016/j.ica.2025.122770","url":null,"abstract":"<div><div>Due to their critical biochemical role and low toxicity, zinc(II) complexes have emerged as promising alternatives to platinum-based anticancer agents, and great efforts have been made to describe many complexes with antiproliferative activity. Still, mononuclear anionic zinc(II) complexes remain largely underexplored, particularly those incorporating privileged medicinal scaffolds, such as coumarins. Herein, we report the synthesis, structural characterization, and antiproliferative evaluation of a novel anionic zinc(II) complex [HL]+[ZnLCl₂]− derived from 7-Hydroxy-4-methyl-8-(1-pyrrolidinylmethyl)-2H-1-benzopyran-2-one, a ligand that has aroused interest as a potential chemotherapeutic and was previously described by our research group. Single-crystal X-ray diffraction revealed an unusual ionic structure, where the protonated ligand acts as a counterion to a tetrahedral Zn(II) center, which is coordinated to one negatively charged ligand and two chlorides. Hirshfeld surface analysis and Density Functional Theory (DFT) further clarified the anionic complex's non-covalent interactions and electronic properties. The complex showed antiproliferative effects (as assessed by MTT-based viability assay) on HeLa (cervical cancer) and PC3 (prostate cancer) cell lines. These results highlight the critical role of zinc coordination in enhancing bioactivity, and our findings underscore the potential of anionic Zn(II) complexes as tunable platforms for anticancer drug design, expanding the limited repertoire of characterized anionic zinc species and paving the way for further exploration of their therapeutic applications.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"585 ","pages":"Article 122770"},"PeriodicalIF":2.7,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

In situ growth of CoP on nickel foam for peroxymonosulfate activation via non-radical pathways in rhodamine B degradation 在罗丹明B降解过程中，通过非自由基途径在泡沫镍上原位生长CoP以活化过氧单硫酸盐

IF 2.7 3区化学

Inorganica Chimica Acta Pub Date : 2025-05-16 DOI: 10.1016/j.ica.2025.122771

Xiaoyu Qiu, Zhimei Li, Jianmei Cen, Hong Tang

{"title":"In situ growth of CoP on nickel foam for peroxymonosulfate activation via non-radical pathways in rhodamine B degradation","authors":"Xiaoyu Qiu, Zhimei Li, Jianmei Cen, Hong Tang","doi":"10.1016/j.ica.2025.122771","DOIUrl":"10.1016/j.ica.2025.122771","url":null,"abstract":"<div><div>Transition metal-based materials have emerged as a promising catalyst for peroxymonosulfate (PMS) activation in pollutant removal. However, challenges such as nano-material agglomeration, high metal ion leaching, and low reactive oxygen species (ROS) yield still hinder their practical application. In this work, the CoP/NF successfully was synthesized to tune PMS activation from a radical pathway to a non-radical dominated pathway for efficient degradation of organic pollutants. The incorporation of phosphorus element modulated the cobalt-based catalyst surface charge state and induced local charge density, facilitating the catalytic activity. Consequently, at optimal conditions (catalyst = 1.5 cm2, PMS = 0.3 g/L), CoP/NF achieved nearly complete removal of 40 mg/L rhodamine B (RhB) within 2 min over a wide pH (3.0–9.0), and maintained a strong anti-interference capacity for NO3−, PO42−, Cl−. Furthermore, the degradation efficiency of RhB in the CoP/NF + PMS system remained 98 % even after 5 cycles. Impressively, ROS trapping and electron spin resonance (EPR) analyses revealed that the degradation process was dominantly driven by superoxide radicals (O2•–) and singlet oxygen (1O2), which served as the key mechanism for the CoP/NF + PMS system. This work provided further insights into tuning PMS activation pathway via the integration of metal phosphides growth on nickel foam for sustainable water treatment.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"585 ","pages":"Article 122771"},"PeriodicalIF":2.7,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Reactivity of B12N12 nanocage toward nitrosyl halides: Adsorption of NOF, NOCl, and NOBr using DFT framework B12N12纳米笼对亚硝基卤化物的反应性：利用DFT框架吸附NOF、NOCl和NOBr

IF 2.7 3区化学

Inorganica Chimica Acta Pub Date : 2025-05-16 DOI: 10.1016/j.ica.2025.122772

Poonam Parkar , Mohsen Doust Mohammadi , Danial Velayati , Ajay Chaudhari

{"title":"Reactivity of B12N12 nanocage toward nitrosyl halides: Adsorption of NOF, NOCl, and NOBr using DFT framework","authors":"Poonam Parkar , Mohsen Doust Mohammadi , Danial Velayati , Ajay Chaudhari","doi":"10.1016/j.ica.2025.122772","DOIUrl":"10.1016/j.ica.2025.122772","url":null,"abstract":"<div><div>The adsorption mechanisms of nitrosyl halides (NOF, NOCl, and NOBr) on a B12N12 nanocage were investigated. All three gases exhibited physisorption, with adsorption energies of 0.59, 0.32 and 0.27 eV for NOF, NOCl and NOBr respectively. NOF showed the strongest adsorption due to its high electronegativity and strong dipole-dipole interactions between fluorine and the nanocage. The adsorption of NOF was thermodynamically feasible at room temperature, with significant charge transfer of 0.057 e− from the gas molecule to the nanocage, enhancing its sensitivity. Notably, NOF-adsorbed structures displayed the highest dipole moment (8.09 Debye). Adsorption of gas molecule improved the reactivity of nanocage by reducing its chemical hardness and increasing electronegativity and electrophilicity, indicating enhanced interaction potential. The recovery times for NOF, NOCl, and NOBr are 1402, 4.17 × 10−2, and 6.57 × 10−3 μs, respectively, highlighting the suitability of nanocage for real time applications. These findings suggest that the B12N12 nanocage is an effective substrate for detecting, adsorbing, and removing nitrosyl halide pollutants. Its properties make it a promising candidate for advanced electronic devices aimed at environmental remediation and pollutant sensing.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"586 ","pages":"Article 122772"},"PeriodicalIF":2.7,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144166374","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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