This perspective looks at structurally characterized examples of metal-based calix[6]arene complexes, focusing on the coordination chemistry adopted and their applications, primarily in polymerisation catalysis. In particular, we look at our attempts to utilize the ability of the calix[6]arene system to accommodate multiple metal centres, and where appropriate, we compare the catalytic behaviour with that of other metallocalix[n]arenes formed from commercially available calix[n]arenes, i.e. the smaller but more common calix[4]arene and the larger calix[8]arene system. We also discuss how synthetic efforts are now targeting calix[6]arenes for which a change of the bridge can provide additional possibilities, i.e. heteroatom bridged tetrahomodioxacalix[6]arenes (containing -CH2OCH2- bridges) and tetrahomo diazacalix[6]arenes (containing -CH2N(R)CH2- bridges, R typically is methyl). The outlook for the future, in terms of the use of calix[6]arene-based catalysts is also discussed.
{"title":"Coordination chemistry of the calix[6]arene system: application in polymerisation catalysis and beyond","authors":"Carl Redshaw","doi":"10.1039/d5dt00473j","DOIUrl":"https://doi.org/10.1039/d5dt00473j","url":null,"abstract":"This perspective looks at structurally characterized examples of metal-based calix[6]arene complexes, focusing on the coordination chemistry adopted and their applications, primarily in polymerisation catalysis. In particular, we look at our attempts to utilize the ability of the calix[6]arene system to accommodate multiple metal centres, and where appropriate, we compare the catalytic behaviour with that of other metallocalix[n]arenes formed from commercially available calix[n]arenes, i.e. the smaller but more common calix[4]arene and the larger calix[8]arene system. We also discuss how synthetic efforts are now targeting calix[6]arenes for which a change of the bridge can provide additional possibilities, i.e. heteroatom bridged tetrahomodioxacalix[6]arenes (containing -CH2OCH2- bridges) and tetrahomo diazacalix[6]arenes (containing -CH2N(R)CH2- bridges, R typically is methyl). The outlook for the future, in terms of the use of calix[6]arene-based catalysts is also discussed.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"7 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677738","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}
Triazolylidenes derived from readily accessible triazoles are useful ligands for coordination chemistry and catalysis. This work describes the synthesis of Group 11 metal complexes of new ferrocenyl-substituted triazolylidene ligands in which the ferrocene and triazolylidene moieties are separated by a carbonyl linker. In particular, complexes of types [MCl(FcC(O){CCN(Mes)NN(Me)}-κC5)] (M = Cu or Au; Fc = ferrocenyl) and [M(FcC(O){CCN(Mes)NN(Me)}-κC5)2][BF4] (M = Cu, Ag, or Au) were prepared from FcC(O)CCH and characterised by spectroscopic methods, X-ray diffraction analysis and cyclic voltammetry. Using a similar strategy, the Pd(II) complex trans-[PdCl2(Ph2PfcC(O){CCN(Mes)NN(Me)}-κ2P,C5)] (fc = ferrocene-1,1'-diyl) was synthesised and analogously characterised. The phosphinocarbene ligand in this compound coordinates as a trans P,C-chelating ligand, unlike its analogues that lack the C=O spacer and similar compounds that combine the phosphine and carbene donor groups on the ferrocene scaffold. The influence of the carbonyl spacer was evaluated in a pair of Pd(II) bis-carbene complexes, [PdBr2({C(Fc)CN(Mes)NN(Me)}-κC5)(iPr2-bimy)] and [PdBr2(FcC(O){CCN(Mes)NN(Me)}-κC5)(iPr2-bimy)] (iPr2-bimy = 1,3-diisopropyl-1,3-dihydro-2H-benzimidazol-2-ylidene), by Huynh’s electronic parameters and the FeII/FeIII redox potential from cyclic voltammetry, which suggested an electron density decrease at the ferrocenyl group and decreased σ donor ability of the triazolylidene moiety upon introduction of the C=O linker. The Group 11 metal complexes were tested as catalysts for the metal-catalysed cyclisation of N-propargylbenzamide into 2-phenyl-5-methylene-4,5-dihydrooxazole. Among them, the chlorogold complex activated with a silver salt achieved the best results.
{"title":"Changing the properties of monodentate and P,C-chelating ferrocenyl-substituted 1,2,3-triazol-5-ylidene ligands through an inserted carbonyl moiety","authors":"Vera Varmuzova, Ivana Cisarova, Petr Štěpnička","doi":"10.1039/d5dt00545k","DOIUrl":"https://doi.org/10.1039/d5dt00545k","url":null,"abstract":"Triazolylidenes derived from readily accessible triazoles are useful ligands for coordination chemistry and catalysis. This work describes the synthesis of Group 11 metal complexes of new ferrocenyl-substituted triazolylidene ligands in which the ferrocene and triazolylidene moieties are separated by a carbonyl linker. In particular, complexes of types [MCl(FcC(O){CCN(Mes)NN(Me)}-κC5)] (M = Cu or Au; Fc = ferrocenyl) and [M(FcC(O){CCN(Mes)NN(Me)}-κC5)2][BF4] (M = Cu, Ag, or Au) were prepared from FcC(O)CCH and characterised by spectroscopic methods, X-ray diffraction analysis and cyclic voltammetry. Using a similar strategy, the Pd(II) complex trans-[PdCl2(Ph2PfcC(O){CCN(Mes)NN(Me)}-κ2P,C5)] (fc = ferrocene-1,1'-diyl) was synthesised and analogously characterised. The phosphinocarbene ligand in this compound coordinates as a trans P,C-chelating ligand, unlike its analogues that lack the C=O spacer and similar compounds that combine the phosphine and carbene donor groups on the ferrocene scaffold. The influence of the carbonyl spacer was evaluated in a pair of Pd(II) bis-carbene complexes, [PdBr2({C(Fc)CN(Mes)NN(Me)}-κC5)(iPr2-bimy)] and [PdBr2(FcC(O){CCN(Mes)NN(Me)}-κC5)(iPr2-bimy)] (iPr2-bimy = 1,3-diisopropyl-1,3-dihydro-2H-benzimidazol-2-ylidene), by Huynh’s electronic parameters and the FeII/FeIII redox potential from cyclic voltammetry, which suggested an electron density decrease at the ferrocenyl group and decreased σ donor ability of the triazolylidene moiety upon introduction of the C=O linker. The Group 11 metal complexes were tested as catalysts for the metal-catalysed cyclisation of N-propargylbenzamide into 2-phenyl-5-methylene-4,5-dihydrooxazole. Among them, the chlorogold complex activated with a silver salt achieved the best results.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"21 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677773","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}
Daniel Errandonea, Javier Gonzalez-Platas, OUAHRANI Tarik, Fabio Piccinelli, Marco Bettinelli
This study presents a single-crystal X-ray diffraction investigation of the high-pressure behavior of barium metavanadate monohydrate, BaV2O6·H2O, up to 7.1 GPa. These measurements were combined with high-pressure optical absorption measurements performed up to 10.1 GPa and with density-functional theory calculations. The X-ray diffraction analysis indicates that BaV2O6·H2O adopts an orthorhombic structure described by space group P212121 at ambient pressure. This structure maintains stability up to 8 GPa, in contrast to anhydrous BaV2O6 which undergoes a phase transition at 4 GPa. Throughout the pressure range examined, the compression of the crystal is highly anisotropic with the b-axis having a nearly zero linear compressibility. Additionally, our optical absorption measurements reveal that BaV2O6·H2O exhibits an indirect band gap that decreases from 4.62(5) eV at 0.03 GPa to 4.48(5) eV at 10.1 GPa. Density-functional theory calculations give similar results as the experiments and support that the decrease of the band-gap energy with pressure is caused by the enhancement of the hybridization between O 2p and V 3d state. We have also calculated the elastic constant. According to experiments and calculations BaV2O6·H2O is one of the most compressible vanadates with a bulk modulus of 33.0(5) GPa.
{"title":"High-pressure study of barium metavanadate monohydrate","authors":"Daniel Errandonea, Javier Gonzalez-Platas, OUAHRANI Tarik, Fabio Piccinelli, Marco Bettinelli","doi":"10.1039/d5dt00423c","DOIUrl":"https://doi.org/10.1039/d5dt00423c","url":null,"abstract":"This study presents a single-crystal X-ray diffraction investigation of the high-pressure behavior of barium metavanadate monohydrate, BaV2O6·H2O, up to 7.1 GPa. These measurements were combined with high-pressure optical absorption measurements performed up to 10.1 GPa and with density-functional theory calculations. The X-ray diffraction analysis indicates that BaV2O6·H2O adopts an orthorhombic structure described by space group P212121 at ambient pressure. This structure maintains stability up to 8 GPa, in contrast to anhydrous BaV2O6 which undergoes a phase transition at 4 GPa. Throughout the pressure range examined, the compression of the crystal is highly anisotropic with the b-axis having a nearly zero linear compressibility. Additionally, our optical absorption measurements reveal that BaV2O6·H2O exhibits an indirect band gap that decreases from 4.62(5) eV at 0.03 GPa to 4.48(5) eV at 10.1 GPa. Density-functional theory calculations give similar results as the experiments and support that the decrease of the band-gap energy with pressure is caused by the enhancement of the hybridization between O 2p and V 3d state. We have also calculated the elastic constant. According to experiments and calculations BaV2O6·H2O is one of the most compressible vanadates with a bulk modulus of 33.0(5) GPa.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"3 2 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677774","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}
: Molybdenum and tungsten being congeners of the 6th group of d-bock elements are similar in many respects in terms of their properties and in fact, both the molybdoenzymes and tungstoenzymes participate in similar type oxotransferase activity in their enzymes. Molybdenum is found as the heaviest essential trace metal in all forms of life but its next heavier congener, tungsten, as the heaviest metal is found only in some prokaryotic organisms. The tungstoenzymes are generally selected by nature for carrying out the low potential redox activities under the anaerobic conditions in the prokaryotic organisms. This nature’s molybdenum vs. tungsten selectivity for their biological functions under different working conditions (surrounding temperature and aerobic/anaerobic environment) is determined mainly by the relativistic effect which is experienced in different extents by these two congeners. Understanding the mechanistic aspects of the relativistic effect controlled enzymatic activities of the tungstoenzymes is of an immense biotechnological interest to develop the eco-friendly and cost effective methods of commercial synthesis of acetaldehyde through hydration of acetylene, and commercial production of hydrogen (H2, a green fuel) by producing the tungsten incorporated nitrogenase (W-N2-ase) in CA6 (mutant strain), and to develop a biomimetic method to replace the hazardous Birch reduction in organic synthesis, etc.
{"title":"Relativistic Effect behind the Molybdenum vs. Tungsten Selectivity in Enzymes","authors":"Udita Das, Ankita Das, Asim Kumar Das","doi":"10.1039/d5dt00001g","DOIUrl":"https://doi.org/10.1039/d5dt00001g","url":null,"abstract":": Molybdenum and tungsten being congeners of the 6th group of d-bock elements are similar in many respects in terms of their properties and in fact, both the molybdoenzymes and tungstoenzymes participate in similar type oxotransferase activity in their enzymes. Molybdenum is found as the heaviest essential trace metal in all forms of life but its next heavier congener, tungsten, as the heaviest metal is found only in some prokaryotic organisms. The tungstoenzymes are generally selected by nature for carrying out the low potential redox activities under the anaerobic conditions in the prokaryotic organisms. This nature’s molybdenum vs. tungsten selectivity for their biological functions under different working conditions (surrounding temperature and aerobic/anaerobic environment) is determined mainly by the relativistic effect which is experienced in different extents by these two congeners. Understanding the mechanistic aspects of the relativistic effect controlled enzymatic activities of the tungstoenzymes is of an immense biotechnological interest to develop the eco-friendly and cost effective methods of commercial synthesis of acetaldehyde through hydration of acetylene, and commercial production of hydrogen (H2, a green fuel) by producing the tungsten incorporated nitrogenase (W-N2-ase) in CA6 (mutant strain), and to develop a biomimetic method to replace the hazardous Birch reduction in organic synthesis, etc.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"215 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677739","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}
Rahul Kalita, Aditya Kumar, Poorvi Gupta, Bharti Rana, Bitan Sardar, Manav Chauhan, Biplab Ghosh, Yukti Monga, Kuntal Manna
Oxidative bromination of arenes is an effective and environmentally friendly method for synthesizing bromoarenes. We have developed a highly robust zirconium-metal-organic framework (MOF)-supported mono bipyridyl-iron(III) chloride catalyst (bpy-UiO-FeCl3) for oxidative bromination of arenes using H2O2 as the oxidant and KBr as the bromine source. The bpy-UiO-FeCl3 catalyst exhibits high conversion rates for various substituted arenes, yielding significant amounts of bromoarenes with excellent regioselectivity, and recyclability under mild reaction conditions. The MOF-catalyst outperforms its homogeneous counterparts in terms of both activity and regioselectivity due to the stabilization of the mononuclear bipyridyl-iron(III) species within the active sites in the MOF's pores. Furthermore, the confinement of these active sites within the robust, well-defined, and uniform porous framework enhances the regioselectivity of the bromination through shape-selective catalysis. The mechanism of bpy-UiO-FeCl3 catalyzed oxidative bromination of arenes was thoroughly investigated by a combination of control experiments, spectroscopic analyses, and computational studies. These findings underscore the importance of MOFs in the development of heterogeneous catalysts based on earth-abundant metals for the sustainable synthesis of haloarenes.
{"title":"Regioselective Oxidative Bromination of Arenes by Metal-Organic Framework Confined Mono-Bipyridyl Iron(III) Catalyst","authors":"Rahul Kalita, Aditya Kumar, Poorvi Gupta, Bharti Rana, Bitan Sardar, Manav Chauhan, Biplab Ghosh, Yukti Monga, Kuntal Manna","doi":"10.1039/d5dt00443h","DOIUrl":"https://doi.org/10.1039/d5dt00443h","url":null,"abstract":"Oxidative bromination of arenes is an effective and environmentally friendly method for synthesizing bromoarenes. We have developed a highly robust zirconium-metal-organic framework (MOF)-supported mono bipyridyl-iron(III) chloride catalyst (bpy-UiO-FeCl3<small><sub></sub></small>) for oxidative bromination of arenes using H2<small><sub></sub></small>O2<small><sub></sub></small> as the oxidant and KBr as the bromine source. The bpy-UiO-FeCl3<small><sub></sub></small> catalyst exhibits high conversion rates for various substituted arenes, yielding significant amounts of bromoarenes with excellent regioselectivity, and recyclability under mild reaction conditions. The MOF-catalyst outperforms its homogeneous counterparts in terms of both activity and regioselectivity due to the stabilization of the mononuclear bipyridyl-iron(III) species within the active sites in the MOF's pores. Furthermore, the confinement of these active sites within the robust, well-defined, and uniform porous framework enhances the regioselectivity of the bromination through shape-selective catalysis. The mechanism of bpy-UiO-FeCl3<small><sub></sub></small> catalyzed oxidative bromination of arenes was thoroughly investigated by a combination of control experiments, spectroscopic analyses, and computational studies. These findings underscore the importance of MOFs in the development of heterogeneous catalysts based on earth-abundant metals for the sustainable synthesis of haloarenes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"9 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677775","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}
Selvarajan Nagendran, Ramaswamy Murugavel, Eric Rivard
{"title":"Main group element compounds in materials and catalysis.","authors":"Selvarajan Nagendran, Ramaswamy Murugavel, Eric Rivard","doi":"10.1039/d5dt90053k","DOIUrl":"https://doi.org/10.1039/d5dt90053k","url":null,"abstract":"","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.5,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143690619","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}
All-inorganic metal halide perovskite quantum dots (PQDs) hybrids with high stability, multi-model emission and responsive luminescence are of great importance for optical applications. Herein, a dual-emitting CsPbBr3/Si-1:Eu3+ composite was successfully prepared by simultaneous encapsulation of CsPbBr3 PQDs and EuBr3 through a one-step thermal diffusion method. The partial destruction of five-membered rings in Silicalite-1 (Si-1) zeolite resulted from the PbBr2 etching effect at high temperatures enhances the bonding formation between Eu3+ and Si-OH, leading to the grafting of Eu3+ onto Si-1 zeolite framework. The strongly confined CsPbBr3 PQDs in CsPbBr3/Si-1:Eu3+ exhibit ultrastable green-emission over 30 days of soaking in water. Particularly, the CsPbBr3 PQDs and red-light Eu3+ emission center display distinct thermal quenching behaviors at elevated temperatures. So the CsPbBr3/Si-1:Eu3+ composite can serve as an effective ratiometric thermometer using the fluorescence intensity ratio (FIR) technique, showing a high sensitivity of 3.4 % ℃-1 at 54 ℃ and a temperature resolution of less than 0.2 ℃ in the range of 20-100 ℃. The water-stable CsPbBr3/Si-1:Eu3+ composite is also suitable for wet fingerprint recognition. This work introduces a straightforward method for preparing dual-emissive CsPbBr3/Si-1: Eu3+ composite for multimodal applications.
{"title":"Straightforward encapsulation of ultrastable CsPbBr3 PQDs and rare-earth emitters in zeolite for ratiometric temperature sensing and wet fingerprint recognition","authors":"Zhou Yuan, Yuchi Zhang, Le Han, Yan Xu","doi":"10.1039/d5dt00368g","DOIUrl":"https://doi.org/10.1039/d5dt00368g","url":null,"abstract":"All-inorganic metal halide perovskite quantum dots (PQDs) hybrids with high stability, multi-model emission and responsive luminescence are of great importance for optical applications. Herein, a dual-emitting CsPbBr<small><sub>3</sub></small>/Si-1:Eu<small><sup>3+</sup></small> composite was successfully prepared by simultaneous encapsulation of CsPbBr<small><sub>3</sub></small> PQDs and EuBr<small><sub>3</sub></small> through a one-step thermal diffusion method. The partial destruction of five-membered rings in Silicalite-1 (Si-1) zeolite resulted from the PbBr<small><sub>2</sub></small> etching effect at high temperatures enhances the bonding formation between Eu<small><sup>3+</sup></small> and Si-OH, leading to the grafting of Eu<small><sup>3+</sup></small> onto Si-1 zeolite framework. The strongly confined CsPbBr<small><sub>3</sub></small> PQDs in CsPbBr<small><sub>3</sub></small>/Si-1:Eu<small><sup>3+</sup></small> exhibit ultrastable green-emission over 30 days of soaking in water. Particularly, the CsPbBr<small><sub>3</sub></small> PQDs and red-light Eu<small><sup>3+</sup></small> emission center display distinct thermal quenching behaviors at elevated temperatures. So the CsPbBr<small><sub>3</sub></small>/Si-1:Eu<small><sup>3+</sup></small> composite can serve as an effective ratiometric thermometer using the fluorescence intensity ratio (FIR) technique, showing a high sensitivity of 3.4 % ℃<small><sup>-1</sup></small> at 54 ℃ and a temperature resolution of less than 0.2 ℃ in the range of 20-100 ℃. The water-stable CsPbBr<small><sub>3</sub></small>/Si-1:Eu<small><sup>3+</sup></small> composite is also suitable for wet fingerprint recognition. This work introduces a straightforward method for preparing dual-emissive CsPbBr<small><sub>3</sub></small>/Si-1: Eu<small><sup>3+</sup></small> composite for multimodal applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"59 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666634","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}
In the development of electrocatalysts that are cost-effective and highly functional, central to this endeavor is the synthesis of materials and the meticulous delineation of their morphology. This article introduces a solvent-thermal method for constructing ruthenium-based electrocatalysts (Ru/MIL-53@NF), distinguished by the in situ generation of ruthenium nanoparticles (NPs) on MIL-53 with notable dispersion. The procedure requires precise control over ruthenium integration, resulting in electrocatalysts with exceptional dispersion properties. Furthermore, the optimally engineered Ru/MIL-53@NF exhibited outstanding electrocatalytic hydrogen evolution performance, registering an overpotential of merely 17 mV at 10 mA·cm-2 and a Tafel slope of 53.7 mV·dec-1, thus outstripping the standard 20 wt% Pt/C benchmark. This research highlights the careful calibration of synthetic parameters to forge ruthenium-based electrocatalysts with both high efficacy and stability.
{"title":"Controllable distribution of surface modified MIL-53 with ruthenium nanoparticles on nickel foam and its high efficiency electrocatalytic hydrogen evolution","authors":"Yuhang Wang, Gui-Xin Yang, Chao Wang, Hongtao Liu, Xinming Wang, Haijun Pang","doi":"10.1039/d5dt00287g","DOIUrl":"https://doi.org/10.1039/d5dt00287g","url":null,"abstract":"In the development of electrocatalysts that are cost-effective and highly functional, central to this endeavor is the synthesis of materials and the meticulous delineation of their morphology. This article introduces a solvent-thermal method for constructing ruthenium-based electrocatalysts (Ru/MIL-53@NF), distinguished by the in situ generation of ruthenium nanoparticles (NPs) on MIL-53 with notable dispersion. The procedure requires precise control over ruthenium integration, resulting in electrocatalysts with exceptional dispersion properties. Furthermore, the optimally engineered Ru/MIL-53@NF exhibited outstanding electrocatalytic hydrogen evolution performance, registering an overpotential of merely 17 mV at 10 mA·cm-2 and a Tafel slope of 53.7 mV·dec-1, thus outstripping the standard 20 wt% Pt/C benchmark. This research highlights the careful calibration of synthetic parameters to forge ruthenium-based electrocatalysts with both high efficacy and stability.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"22 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666637","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}
Hydrogen storage and safe transport are the most important issues for hydrogen energy applications. Hydrogen has the necessary potential to provide clean fuel for heating and transportation because its only product of this combustion is pure water. Hydrogen is identified as one of the most renewable energy sources by supplying an efficient storage method. The electrochemical method with high energy conversion efficiency, through absorbtion/desorbtion mechanisms, is considered an appropriate strategy to achieve hydrogen storage. Hence, we propose a hydrogen energy storage system based on efficient electrode materials and electrochemical method. Due to obtaining high efficiency hydrogen storage, the Pt/SnO2/Sb2O4 nanoparticle catalyst embedded in multi-walled carbon nanotubes (MWCNTs) is synthesized via a facile polyol method, as active material. The sample structure was characterized by different techniques to determine its crystal structure, surface morphology, elements and porosity. Further, the electrochemical hydrogen storage abilities and the specific capacitance values of the as-prepared nanocomposite were assessed in alkaline media by chronopotentiometry analysis. The XRD studies exhibit that the average crystallite size of the Pt/SnO2/Sb2O4 nanoparticle catalyst is estimated to be around 7.5 nm. Also, the BET measurement shows a specific surface area, pore volume and pore diameter of 137.89 m2g-1, 0.3379 cm3g-1 and 9.8 nm for Pt/SnO2/Sb2O4/MWCNTs nanocomposite, respectively. The electrochemical consequences indicate that the incorporation of Pt/SnO2/Sb2O4 nanoparticle catalyst with MWCNTs showed excellent cycle stability and a high degree of electrochemical reversibility as an optimistic active candidate for use in electrochemical hydrogen storage. The maximum discharge capacity of Pt/ SnO2/Sb2O4 /MWCNTs nanocomposite was obtained to be 3480 mAhg-1 after 12 cycles. The higher and excellent discharge capacity of nanocomposite can partially be ascribed to its higher porosity, large specific surface area and the small size of Pt/SnO2/Sb2O4 nanoparticle catalyst.
{"title":"Pt/SnO2/Sb2O4 nanoparticle catalyst embedded in Multi-walled carbon nanotubes as active material for electrochemical hydrogen storage inquiries","authors":"Raziyeh Akbarzadeh","doi":"10.1039/d5dt00336a","DOIUrl":"https://doi.org/10.1039/d5dt00336a","url":null,"abstract":"Hydrogen storage and safe transport are the most important issues for hydrogen energy applications. Hydrogen has the necessary potential to provide clean fuel for heating and transportation because its only product of this combustion is pure water. Hydrogen is identified as one of the most renewable energy sources by supplying an efficient storage method. The electrochemical method with high energy conversion efficiency, through absorbtion/desorbtion mechanisms, is considered an appropriate strategy to achieve hydrogen storage. Hence, we propose a hydrogen energy storage system based on efficient electrode materials and electrochemical method. Due to obtaining high efficiency hydrogen storage, the Pt/SnO2/Sb2O4 nanoparticle catalyst embedded in multi-walled carbon nanotubes (MWCNTs) is synthesized via a facile polyol method, as active material. The sample structure was characterized by different techniques to determine its crystal structure, surface morphology, elements and porosity. Further, the electrochemical hydrogen storage abilities and the specific capacitance values of the as-prepared nanocomposite were assessed in alkaline media by chronopotentiometry analysis. The XRD studies exhibit that the average crystallite size of the Pt/SnO2/Sb2O4 nanoparticle catalyst is estimated to be around 7.5 nm. Also, the BET measurement shows a specific surface area, pore volume and pore diameter of 137.89 m2g-1, 0.3379 cm3g-1 and 9.8 nm for Pt/SnO2/Sb2O4/MWCNTs nanocomposite, respectively. The electrochemical consequences indicate that the incorporation of Pt/SnO2/Sb2O4 nanoparticle catalyst with MWCNTs showed excellent cycle stability and a high degree of electrochemical reversibility as an optimistic active candidate for use in electrochemical hydrogen storage. The maximum discharge capacity of Pt/ SnO2/Sb2O4 /MWCNTs nanocomposite was obtained to be 3480 mAhg-1 after 12 cycles. The higher and excellent discharge capacity of nanocomposite can partially be ascribed to its higher porosity, large specific surface area and the small size of Pt/SnO2/Sb2O4 nanoparticle catalyst.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"41 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666740","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}
Jinlian Zhang, Yu Xie, Xinli Zhang, Yuanhong Zhong, Ming Sun, Lin Yu
Two-dimensional non-layered oxide nanosheets exhibit exceptional catalytic properties, offering significant potential for environmental applications. In this study, we report the development of a novel Fe-doped γ-MnO₂ material with a hierarchical microsphere morphology, achieved through a metal ion regulation strategy. Unlike conventional sea urchin-like γ-MnO₂, Fe doping induced a transformation to a two-dimensional non-layered structure composed of nanosheets, significantly increasing the specific surface area and exposing more active sites. The Fe-doped γ-MnO₂ catalysts were evaluated for the degradation of chlorimiprazole (CBZ), a persistent pollutant, using a sulfate radical-based advanced oxidation process. Among the synthesized catalysts, NF-0.25Fe exhibited superior performance, achieving 93% CBZ removal within 16 min under near-neutral conditions. This exceptional activity was attributed to the optimized morphology, higher low-valence Mn content, and enhanced surface-active oxygen species. Systematic investigations revealed that the catalyst dosage, PMS concentration, and pH critically influenced the catalytic efficiency. This work demonstrates the potential of metal ion modulation in tailoring the structural and catalytic properties of transition metal oxides. The insights gained here provide a robust foundation for designing advanced nanomaterials for environmental remediation and other catalytic applications.
{"title":"Metal Ion-Modulated Synthesis of γ-MnO2 Nanosheet for Catalytic Oxidative Degradation of Clomiprazole","authors":"Jinlian Zhang, Yu Xie, Xinli Zhang, Yuanhong Zhong, Ming Sun, Lin Yu","doi":"10.1039/d5dt00058k","DOIUrl":"https://doi.org/10.1039/d5dt00058k","url":null,"abstract":"Two-dimensional non-layered oxide nanosheets exhibit exceptional catalytic properties, offering significant potential for environmental applications. In this study, we report the development of a novel Fe-doped γ-MnO₂ material with a hierarchical microsphere morphology, achieved through a metal ion regulation strategy. Unlike conventional sea urchin-like γ-MnO₂, Fe doping induced a transformation to a two-dimensional non-layered structure composed of nanosheets, significantly increasing the specific surface area and exposing more active sites. The Fe-doped γ-MnO₂ catalysts were evaluated for the degradation of chlorimiprazole (CBZ), a persistent pollutant, using a sulfate radical-based advanced oxidation process. Among the synthesized catalysts, NF-0.25Fe exhibited superior performance, achieving 93% CBZ removal within 16 min under near-neutral conditions. This exceptional activity was attributed to the optimized morphology, higher low-valence Mn content, and enhanced surface-active oxygen species. Systematic investigations revealed that the catalyst dosage, PMS concentration, and pH critically influenced the catalytic efficiency. This work demonstrates the potential of metal ion modulation in tailoring the structural and catalytic properties of transition metal oxides. The insights gained here provide a robust foundation for designing advanced nanomaterials for environmental remediation and other catalytic applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"61 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666741","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}
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