Layered coordination polymers have attracted significant attention as a class of crystsalline materials characterized by the layer-by-layer stacking of rigid two-dimensional (2D) coordination networks. One of their remarkable features is the flexibility of their crystal structures, which allows for interlayer displacement, swelling, and exfoliation. Incorporating stimuli-responsive moieties into their structures is a promising strategy for the rational design of layered coordination polymers with targeted flexible properties and functions. Despite the challenges associated with crystal design, a variety of stimuli-responsive layered coordination polymers have been developed over the past two decades. This article provides an overview of representative examples of layered coordination polymers whose properties and functions can be modulated by photo- and thermal stimuli.
{"title":"Design of crystalline layered coordination polymers that respond to light and heat stimuli","authors":"Kenichiro Omoto, Gwenael Rapenne","doi":"10.1039/d5dt00156k","DOIUrl":"https://doi.org/10.1039/d5dt00156k","url":null,"abstract":"Layered coordination polymers have attracted significant attention as a class of crystsalline materials characterized by the layer-by-layer stacking of rigid two-dimensional (2D) coordination networks. One of their remarkable features is the flexibility of their crystal structures, which allows for interlayer displacement, swelling, and exfoliation. Incorporating stimuli-responsive moieties into their structures is a promising strategy for the rational design of layered coordination polymers with targeted flexible properties and functions. Despite the challenges associated with crystal design, a variety of stimuli-responsive layered coordination polymers have been developed over the past two decades. This article provides an overview of representative examples of layered coordination polymers whose properties and functions can be modulated by photo- and thermal stimuli.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"27 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827528","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}
The complexation behaviour of quercetin and luteolin with first-row transition metals (Cr(III), Mn(II), Co(II), Ni(II), and Zn(II)) in aqueous solution was systematically investigated using potentiometric titrations, UV-Vis and FT-IR spectroscopy, and density functional theory (DFT) calculations. The study aimed to elucidate the stability, stoichiometry, and preferred binding sites of these flavonoid-metal complexes entirely in aqueous solution at 37 °C, as a function of pH under controlled ionic strength. Speciation analysis revealed the formation of 1:1, 1:2, and 1:3 metal-to-ligand complexes, with coordination occurring primarily at the 4,5- or 3,4-binding sites, depending on the metal ion and ligand structure. UV-Vis and IR spectral changes confirmed complex formation, while computational modeling provided insights into binding site selectivity and free energy changes associated with coordination. The results highlight the influence of ligand structure on metal affinity and stability, with quercetin forming more stable complexes than luteolin due to the presence of an additional hydroxyl group at the 3-position. These findings contribute to a deeper understanding of flavonoid-metal interactions, with potential implications for antioxidant activity, metal chelation therapy, and environmental applications.
{"title":"Quercetin and luteolin complexation with first-row transition metals in purely aqueous solutions: stoichiometry and binding site selectivity","authors":"Giuseppina Anna Corrente, Luana Malacaria, Amerigo Beneduci, Tiziana Marino, Emilia Furia","doi":"10.1039/d5dt00478k","DOIUrl":"https://doi.org/10.1039/d5dt00478k","url":null,"abstract":"The complexation behaviour of quercetin and luteolin with first-row transition metals (Cr(III), Mn(II), Co(II), Ni(II), and Zn(II)) in aqueous solution was systematically investigated using potentiometric titrations, UV-Vis and FT-IR spectroscopy, and density functional theory (DFT) calculations. The study aimed to elucidate the stability, stoichiometry, and preferred binding sites of these flavonoid-metal complexes entirely in aqueous solution at 37 °C, as a function of pH under controlled ionic strength. Speciation analysis revealed the formation of 1:1, 1:2, and 1:3 metal-to-ligand complexes, with coordination occurring primarily at the 4,5- or 3,4-binding sites, depending on the metal ion and ligand structure. UV-Vis and IR spectral changes confirmed complex formation, while computational modeling provided insights into binding site selectivity and free energy changes associated with coordination. The results highlight the influence of ligand structure on metal affinity and stability, with quercetin forming more stable complexes than luteolin due to the presence of an additional hydroxyl group at the 3-position. These findings contribute to a deeper understanding of flavonoid-metal interactions, with potential implications for antioxidant activity, metal chelation therapy, and environmental applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"74 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819038","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}
A series of high-performing C-C bonded nitropyrazole and thiadiazole-based energetic materials (compounds 3-7) were synthesized and thoroughly characterized. SC-XRD studies supported the structure of compounds 3, 4, 6, and 7. The synthesized compounds exhibited high densities (≥ 1.77 g cm⁻³), compounds 3 and 5 demonstrating admirable detonation properties (VOD = 8300 and 7265 m s⁻¹; DP = 30.31 and 21.25 GPa, respectively), surpassing the present benchmark explosives HNS and TNT and setting new standards for sulfur-based energetic materials. Notably, compound 3 showed an ignition delay of 13 ms in a hot needle test, indicating its potential as an igniter.
{"title":"Exploring New Frontiers: Alliance of Pyrazole and Thiadiazole in Energetic Materials","authors":"Parasar Kumar, Vikas Ghule, Srinivas Dharavath","doi":"10.1039/d5dt00730e","DOIUrl":"https://doi.org/10.1039/d5dt00730e","url":null,"abstract":"A series of high-performing C-C bonded nitropyrazole and thiadiazole-based energetic materials (compounds 3-7) were synthesized and thoroughly characterized. SC-XRD studies supported the structure of compounds 3, 4, 6, and 7. The synthesized compounds exhibited high densities (≥ 1.77 g cm⁻³), compounds 3 and 5 demonstrating admirable detonation properties (VOD = 8300 and 7265 m s⁻¹; DP = 30.31 and 21.25 GPa, respectively), surpassing the present benchmark explosives HNS and TNT and setting new standards for sulfur-based energetic materials. Notably, compound 3 showed an ignition delay of 13 ms in a hot needle test, indicating its potential as an igniter.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"14 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819042","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}
Metal-organic frameworks (MOFs) with ZIF-67 have been widely studied. Incorporating multi-bimetals into ZIF-67 offers a strategic approach to leverage unique properties and address the limitations of traditional single-metal in ZIF-67. An environmentally friendly solid-state thermal (SST) method to simultaneously incorporate heterometals (Cu, Fe, Ru, Pd, Mn, and Ni) into the ZIF structure, referred to as M@ZIF-67, is developed. The synthesis occurs in a single step, utilizing thermally-treated mixed solid precursors of multi-bimetals and imidazole ligands without additional agents or solvents, which is the innovative green route to approach multi-bimetals ZIFs. Multiple techniques confirm that heterometals are homogeneous, uniform, and precised metal content in the iso-structure of ZIF-67. Interestingly, synthesizing M@ZIF-67 through the SST method achieves a scalable and high yield. Furthermore, the M@ZIF-67 exhibits a precise heterometal content, which plays a crucial role in enhancing the catalytic performance of CO2 cycloaddition, surpassing results obtained through traditional ZIF-67.
{"title":"Green and high yield synthesis bimetallic zeolitic imidazole framework-67 for efficient catalytic CO2 cycloaddition","authors":"Chaonan Wang, Kaixuan Guo, Zhonghan Cheng, Chongli Wang, Duozhen Chai, Dongfeng Cao, Ye Yuan, Somboon Chaemchuen","doi":"10.1039/d5dt00459d","DOIUrl":"https://doi.org/10.1039/d5dt00459d","url":null,"abstract":"Metal-organic frameworks (MOFs) with ZIF-67 have been widely studied. Incorporating multi-bimetals into ZIF-67 offers a strategic approach to leverage unique properties and address the limitations of traditional single-metal in ZIF-67. An environmentally friendly solid-state thermal (SST) method to simultaneously incorporate heterometals (Cu, Fe, Ru, Pd, Mn, and Ni) into the ZIF structure, referred to as M@ZIF-67, is developed. The synthesis occurs in a single step, utilizing thermally-treated mixed solid precursors of multi-bimetals and imidazole ligands without additional agents or solvents, which is the innovative green route to approach multi-bimetals ZIFs. Multiple techniques confirm that heterometals are homogeneous, uniform, and precised metal content in the iso-structure of ZIF-67. Interestingly, synthesizing M@ZIF-67 through the SST method achieves a scalable and high yield. Furthermore, the M@ZIF-67 exhibits a precise heterometal content, which plays a crucial role in enhancing the catalytic performance of CO2 cycloaddition, surpassing results obtained through traditional ZIF-67.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"12 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819037","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}
Xiaoxue Liu, Xi Chu, Chenghao Li, Hongyi Liu, Yihao Zheng, Hongyan Li
Based on the neutral ligands of 2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline (pip) and 2-(4-(trifluoromethylphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline) (tfpip), iridium(III) complexes [(F4ppy)2Ir(pip)](PF6) (1, F4ppy = 2-(4-fluorophenyl)pyridine), [(F4piq)2Ir(pip)](PF6) (2, F4piq = 3-(4-fluorophenyl)isoquinoline), [(F4ppy)2Ir(tfpip)] (PF6) (3), [(F4piq)2Ir(tfpip)](PF6) (4), [(F3,5ppy)2Ir(pip)](PF6) (5, F3,5ppy = 2-(3,5-difluorophenyl)pyridine), [(F3,5piq)2Ir(pip)](PF6) (6, F3,5piq = 3-(3,5-difluorophenyl)isoquinoline), [(F3,5ppy)2Ir(tfpip)](PF6) (7) and [(F3,5piq)2Ir(tfpip)](PF6) (8) were synthesized and characterized. Complexes 1−8 exhibited yellow-green and red luminescence (λ = 528−588 nm) in acetonitrile solution. The photoluminescence quantum yields (PLQYs) of complexes 1–8 were ranged from 0.44–0.80, and the complex 7 with yellow-green emission had the best PLQYs of 0.80. Electrochemical study and density functional theory (DFT) calculations showed that the luminescence characteristics of complexes are mainly controlled through the modification of cyclometalated ligands. Upon addition of CH3COO– to the solution of complexes 1 and 5, the luminescence intensity of 1 and 5 was quenched by 80% and 91%. After bubbling CO2 gas into the solution of iridium complex containing CH3COO–, complexes 1 and 5 both showed turn-on phosphorescence response with high sensitivity, excellent selectivity, good reversibility and a low detection limit down to 22.8 μM.
{"title":"Selective and sensitive detection of CO2 using phosphorescent iridium(III) complexes containing 1,10-phenanthroline derivatives as neutral ligands","authors":"Xiaoxue Liu, Xi Chu, Chenghao Li, Hongyi Liu, Yihao Zheng, Hongyan Li","doi":"10.1039/d5dt00181a","DOIUrl":"https://doi.org/10.1039/d5dt00181a","url":null,"abstract":"Based on the neutral ligands of 2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline (pip) and 2-(4-(trifluoromethylphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline) (tfpip), iridium(III) complexes [(F4ppy)2Ir(pip)](PF6) (1, F4ppy = 2-(4-fluorophenyl)pyridine), [(F4piq)2Ir(pip)](PF6) (2, F4piq = 3-(4-fluorophenyl)isoquinoline), [(F4ppy)2Ir(tfpip)] (PF6) (3), [(F4piq)2Ir(tfpip)](PF6) (4), [(F3,5ppy)2Ir(pip)](PF6) (5, F3,5ppy = 2-(3,5-difluorophenyl)pyridine), [(F3,5piq)2Ir(pip)](PF6) (6, F3,5piq = 3-(3,5-difluorophenyl)isoquinoline), [(F3,5ppy)2Ir(tfpip)](PF6) (7) and [(F3,5piq)2Ir(tfpip)](PF6) (8) were synthesized and characterized. Complexes 1−8 exhibited yellow-green and red luminescence (λ = 528−588 nm) in acetonitrile solution. The photoluminescence quantum yields (PLQYs) of complexes 1–8 were ranged from 0.44–0.80, and the complex 7 with yellow-green emission had the best PLQYs of 0.80. Electrochemical study and density functional theory (DFT) calculations showed that the luminescence characteristics of complexes are mainly controlled through the modification of cyclometalated ligands. Upon addition of CH3COO– to the solution of complexes 1 and 5, the luminescence intensity of 1 and 5 was quenched by 80% and 91%. After bubbling CO2 gas into the solution of iridium complex containing CH3COO–, complexes 1 and 5 both showed turn-on phosphorescence response with high sensitivity, excellent selectivity, good reversibility and a low detection limit down to 22.8 μM.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"246 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819041","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}
Employing H(L1) [2-((pyridine-2-ylmethyl)imino)methylphenol] or H(L2) [2-((pyridine-2-ylethyl)imino)methylphenol] and phen (1,10-phenanthroline), two novel monocopper(II) complexes, [Cu(L1/L2)(phen)](ClO4) (1 or 2), have been produced and studied. The single-crystal structure of the complex ion in 2, as determined by X-ray structure analysis, shows a trigonal bipyramidal geometry with distortion (τ, 0.65). DFT calculations were used to investigate the molecular geometry of copper(II) complexes in solution as well as their electronic characteristics. The electronic and EPR spectra in the solid-state of 1 and 2 reveal a trigonal bipyramidal geometry, whereas the geometry in solution is square pyramidal. The positive and reversible nature of the redox pair (CuII/CuI) makes redox states easily interconvertible. The catalysts in methanol and/or the buffer induced three separate chemical changes: (i) ascorbic acid → dehydroascorbic acid, (ii) benzylamine → benzaldehyde, and (iii) 3,5-di-tert-butylcatechol → 3,5-di-tert-butylquinone. Their kcat results show higher activities of amine oxidase (105 h−1). Ascorbate oxidase (107 h−1) and catechol oxidase (106 h−1) activity in the buffer yields kcat values that are closer to those of the natural enzyme. This is due to the presence of ligand flexibility, structural distortion, an appropriate chelate ring size, a labile donor, a positive redox potential, and a persistent catalyst–substrate interaction. Therefore, the two monocopper(II) complexes serve as the most efficient promiscuous catalysts, acting as complementary agents to the activity of copper oxidase enzymes and superior models for oxidation processes.
{"title":"Functional biomimetics for copper oxidases: interesting catalytic promiscuity of novel monocopper(II) complexes","authors":"Vigneswara Chellam Ravisankar, Balasubramaniam Selvakumaran, Tamilarasan Ajaykamal, Mariappan Murali","doi":"10.1039/d5dt00077g","DOIUrl":"https://doi.org/10.1039/d5dt00077g","url":null,"abstract":"Employing H(L<small><sup>1</sup></small>) [2-((pyridine-2-ylmethyl)imino)methylphenol] or H(L<small><sup>2</sup></small>) [2-((pyridine-2-ylethyl)imino)methylphenol] and phen (1,10-phenanthroline), two novel monocopper(<small>II</small>) complexes, [Cu(L<small><sup>1</sup></small>/L<small><sup>2</sup></small>)(phen)](ClO<small><sub>4</sub></small>) (<strong>1</strong> or <strong>2</strong>), have been produced and studied. The single-crystal structure of the complex ion in <strong>2</strong>, as determined by X-ray structure analysis, shows a trigonal bipyramidal geometry with distortion (<em>τ</em>, 0.65). DFT calculations were used to investigate the molecular geometry of copper(<small>II</small>) complexes in solution as well as their electronic characteristics. The electronic and EPR spectra in the solid-state of <strong>1</strong> and <strong>2</strong> reveal a trigonal bipyramidal geometry, whereas the geometry in solution is square pyramidal. The positive and reversible nature of the redox pair (Cu<small><sup>II</sup></small>/Cu<small><sup>I</sup></small>) makes redox states easily interconvertible. The catalysts in methanol and/or the buffer induced three separate chemical changes: (i) ascorbic acid → dehydroascorbic acid, (ii) benzylamine → benzaldehyde, and (iii) 3,5-di-<em>tert</em>-butylcatechol → 3,5-di-<em>tert</em>-butylquinone. Their <em>k</em><small><sub>cat</sub></small> results show higher activities of amine oxidase (10<small><sup>5</sup></small> h<small><sup>−1</sup></small>). Ascorbate oxidase (10<small><sup>7</sup></small> h<small><sup>−1</sup></small>) and catechol oxidase (10<small><sup>6</sup></small> h<small><sup>−1</sup></small>) activity in the buffer yields <em>k</em><small><sub>cat</sub></small> values that are closer to those of the natural enzyme. This is due to the presence of ligand flexibility, structural distortion, an appropriate chelate ring size, a labile donor, a positive redox potential, and a persistent catalyst–substrate interaction. Therefore, the two monocopper(<small>II</small>) complexes serve as the most efficient promiscuous catalysts, acting as complementary agents to the activity of copper oxidase enzymes and superior models for oxidation processes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"38 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813730","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}
Chong Ma, Yihao Xia, Xue Ding, Lei Qin, Zhiping Zheng
Ruthenium(II) complexes with tridentate pincer ligands were tested for catalytic hydrogen production from methanol reforming. The most sterically hindered complex (C4) achieved a turnover number of 14,050. Mechanistic studies revealed that ligand dissociation and substitution play crucial roles in activating the catalyst and transforming substrates.
{"title":"Hydrogen production via aqueous-phase reforming of methanol catalyzed by ruthenium(II) complexes with Schiff-base pincer ligands","authors":"Chong Ma, Yihao Xia, Xue Ding, Lei Qin, Zhiping Zheng","doi":"10.1039/d5dt00387c","DOIUrl":"https://doi.org/10.1039/d5dt00387c","url":null,"abstract":"Ruthenium(II) complexes with tridentate pincer ligands were tested for catalytic hydrogen production from methanol reforming. The most sterically hindered complex (<strong>C4</strong>) achieved a turnover number of 14,050. Mechanistic studies revealed that ligand dissociation and substitution play crucial roles in activating the catalyst and transforming substrates.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"30 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813461","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}
Feilong Yang, Ke Zhang, Qi Wang, Jinxi Chen, Yongbing Lou
Perovskite electrocatalysts have garnered significant attention due to their catalytic activity, environmental friendliness, tunable structure and high performance. However, their activities in the oxygen evolution reaction (OER) still require further enhancement. In this study, to address this challenge, an anion doping strategy was employed to modify La0.5Sr0.5FeO3-δ (LSFO) perovskite oxides, and a series of chloride ion doped catalysts were successfully prepared. The Cl- doping induced the selective leaching of Sr ions, leading to the formation of Sr vacancies on the perovskite surface and a significant increase in the proportion of oxidative oxygen species (O22-/O-). Additionally, a significant increase in the oxidation state of iron (Fe) in the perovskite was observed after the reaction. This synergistic effect effectively optimized the electronic conductivity of the perovskites, accelerated the intrinsic reaction kinetics, and substantially enhanced OER performance. Electrochemical testing results demonstrated that the optimal Cl-doped LSFO electrocatalyst exhibited an overpotential of only 232 mV at a current density of 10 mA cm-2, with a Tafel slope of 31 mV dec-2. Additionally, the optimal Cl-doped LSFO showed a low charge transfer resistance and excellent long-term cyclic stability. This study not only demonstrated the regulatory mechanism of Cl- doping on the catalytic activity of perovskite catalysts but also provided theoretical insights and practical strategies for the design of efficient and stable electrocatalysts.
{"title":"Facile chloride ion (Cl-) doping enhances the oxygen evolution reaction activity of La0.5Sr0.5FeO3-δ","authors":"Feilong Yang, Ke Zhang, Qi Wang, Jinxi Chen, Yongbing Lou","doi":"10.1039/d5dt00372e","DOIUrl":"https://doi.org/10.1039/d5dt00372e","url":null,"abstract":"Perovskite electrocatalysts have garnered significant attention due to their catalytic activity, environmental friendliness, tunable structure and high performance. However, their activities in the oxygen evolution reaction (OER) still require further enhancement. In this study, to address this challenge, an anion doping strategy was employed to modify La<small><sub>0.5</sub></small>Sr<small><sub>0.5</sub></small>FeO<small><sub>3-δ</sub></small> (LSFO) perovskite oxides, and a series of chloride ion doped catalysts were successfully prepared. The Cl<small><sup>-</sup></small> doping induced the selective leaching of Sr ions, leading to the formation of Sr vacancies on the perovskite surface and a significant increase in the proportion of oxidative oxygen species (O<small><sub>2</sub></small><small><sup>2-</sup></small>/O<small><sup>-</sup></small>). Additionally, a significant increase in the oxidation state of iron (Fe) in the perovskite was observed after the reaction. This synergistic effect effectively optimized the electronic conductivity of the perovskites, accelerated the intrinsic reaction kinetics, and substantially enhanced OER performance. Electrochemical testing results demonstrated that the optimal Cl-doped LSFO electrocatalyst exhibited an overpotential of only 232 mV at a current density of 10 mA cm<small><sup>-2</sup></small>, with a Tafel slope of 31 mV dec<small><sup>-2</sup></small>. Additionally, the optimal Cl-doped LSFO showed a low charge transfer resistance and excellent long-term cyclic stability. This study not only demonstrated the regulatory mechanism of Cl<small><sup>-</sup></small> doping on the catalytic activity of perovskite catalysts but also provided theoretical insights and practical strategies for the design of efficient and stable electrocatalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"75 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806354","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}
Metal-organic framework (MOF) membranes exhibit promising potential for high-precision molecule and ion sieving due to their uniform and tunable pore structures. Nevertheless, it remains a challenge to address interfacial compatibility to obtain high-performance MOF membrane. This is because there is a weak interfacial interaction between the MOF and the substrate, which leads to non-selective areas. This work presents an interface-coating method to facilitate dense nucleation and rapid growth of MOF crystals on the substrate towards reinforcing interaction and eliminating the defects. Polydopamine (PDA) and β-cyclodextrin (β-CD) were co-assembled on polyvinylidene fluoride (PVDF) substrates to modify the surface chemistry and enhance interfacial compatibility, thereby facilitating the dense growth of ZIF-8. The ZIF-8/PVDF membranes demonstrated an excellent K+ permeance of 0.33 mol m-2 h-1 and a K+/Mg2+ selectivity of 30.16. The simulation results indicate that the channel of Mg2+ through ZIF-8 must overcome a greater transport energy barrier than that of K+, resulting in a higher selectivity of K+/Mg2+.
{"title":"Improving the ion sieving performance of MOF polycrystalline membranes based on interface modification","authors":"Jianfei Zhao, Haoran Fan, Gaofeng Zhong, Chenfeng Wang, Zhan Li, Jintong Bi, Jingle Xie, Tongdan Chen, Juanli Deng, Jiang Li, Bojun Tan","doi":"10.1039/d5dt00724k","DOIUrl":"https://doi.org/10.1039/d5dt00724k","url":null,"abstract":"Metal-organic framework (MOF) membranes exhibit promising potential for high-precision molecule and ion sieving due to their uniform and tunable pore structures. Nevertheless, it remains a challenge to address interfacial compatibility to obtain high-performance MOF membrane. This is because there is a weak interfacial interaction between the MOF and the substrate, which leads to non-selective areas. This work presents an interface-coating method to facilitate dense nucleation and rapid growth of MOF crystals on the substrate towards reinforcing interaction and eliminating the defects. Polydopamine (PDA) and β-cyclodextrin (β-CD) were co-assembled on polyvinylidene fluoride (PVDF) substrates to modify the surface chemistry and enhance interfacial compatibility, thereby facilitating the dense growth of ZIF-8. The ZIF-8/PVDF membranes demonstrated an excellent K+ permeance of 0.33 mol m-2 h-1 and a K+/Mg2+ selectivity of 30.16. The simulation results indicate that the channel of Mg2+ through ZIF-8 must overcome a greater transport energy barrier than that of K+, resulting in a higher selectivity of K+/Mg2+.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"59 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806352","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}
Zeynep Kahraman, Ahmet Gungor, Merve Buldu-Aktürk, Metin Tan, Emre Alp, Emre Erdem, Aziz Genç
Transition metal oxides hold great promise across a wide range of applications due to favorable properties such as high abundance, low toxicity, and excellent stability. Nanoengineering approaches are essential for controlling the structural, optical, and electronic properties of these materials, enabling the achievement of desired characteristics in a cost-effective and environmentally friendly manner. In this study, we synthesize stoichiometric (WO3) and sub-stoichiometric (WO3-x) tungsten oxide nanowires by controlling their phases and morphologies through the hydrothermal method. This approach allows us to systematically investigate the effects of different phases and oxygen vacancies on the optical properties, as well as on photocatalytic and supercapacitance applications. We use the photodegradation of RhB as a benchmark for photocatalytic activity under various experimental conditions, revealing that oxygen vacancies significantly influence photocatalytic behavior. For example, WO3-x nanowires adsorb/degrade a substantial amount of RhB within short durations under ambient conditions, where WO3 nanowires are mostly inactive. The addition of H2O2 enhances the photocatalytic performance of WO3 nanowires over 30 minutes, with even better results under low pH conditions with H₂O₂. This study also explores the phase-dependent electrochemical properties of WO3 and WO3-x nanowires, providing insights into their potential for improved supercapacitor performance by leveraging their complementary properties in symmetric and asymmetric configurations. WO3-x, with a higher density of oxygen vacancies and thinner structure, offers enhanced conductivity and increased active sites for charge storage, resulting in superior specific capacitance and charge retention.
{"title":"Phase-dependent optical, photocatalytic and capacitive properties of tungsten oxide nanowires","authors":"Zeynep Kahraman, Ahmet Gungor, Merve Buldu-Aktürk, Metin Tan, Emre Alp, Emre Erdem, Aziz Genç","doi":"10.1039/d5dt00212e","DOIUrl":"https://doi.org/10.1039/d5dt00212e","url":null,"abstract":"Transition metal oxides hold great promise across a wide range of applications due to favorable properties such as high abundance, low toxicity, and excellent stability. Nanoengineering approaches are essential for controlling the structural, optical, and electronic properties of these materials, enabling the achievement of desired characteristics in a cost-effective and environmentally friendly manner. In this study, we synthesize stoichiometric (WO3) and sub-stoichiometric (WO3-x) tungsten oxide nanowires by controlling their phases and morphologies through the hydrothermal method. This approach allows us to systematically investigate the effects of different phases and oxygen vacancies on the optical properties, as well as on photocatalytic and supercapacitance applications. We use the photodegradation of RhB as a benchmark for photocatalytic activity under various experimental conditions, revealing that oxygen vacancies significantly influence photocatalytic behavior. For example, WO3-x nanowires adsorb/degrade a substantial amount of RhB within short durations under ambient conditions, where WO3 nanowires are mostly inactive. The addition of H2O2 enhances the photocatalytic performance of WO3 nanowires over 30 minutes, with even better results under low pH conditions with H₂O₂. This study also explores the phase-dependent electrochemical properties of WO3 and WO3-x nanowires, providing insights into their potential for improved supercapacitor performance by leveraging their complementary properties in symmetric and asymmetric configurations. WO3-x, with a higher density of oxygen vacancies and thinner structure, offers enhanced conductivity and increased active sites for charge storage, resulting in superior specific capacitance and charge retention.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"25 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806359","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：