An OER catalyst showing both high activity and stability in promoting oxygen evolution is important for its practical application in electrochemical water-splitting. Here, we report the screening of such a catalyst by optimizing the Ni(II)-doping in Co(III)-based layered double hydroxides (LDHs). Such LDH samples tailored with Ni(II)-doping are prepared by an oxidative intercalation reaction where brucite-like Ni(II)xCo(II)1−x(OH)2 (0 ≤ x ≤ 0.50) is reacted with Br2 in acetonitrile. These samples exhibit a volcano-like trend in OER activity related to the fraction of the dopant. At the optimized doping level (x = 0.20), the activity of the catalyst exceeds that of Ni(II)–Fe(III) LDHs at overpotentials higher than 375 mV. In situ Raman spectroscopy and Fourier-transformed alternating current voltammetry reveal that Ni cations can promote the formation of Co(IV)-oxo intermediates, thereby accelerating the kinetics of the OER. The volcano-like activity trend manifests the underlying synergistic communication between Ni and Co cations.
{"title":"Optimized Ni(II)-doping in Co(III)-based layered double hydroxides towards electrochemical oxygen evolution catalysis","authors":"Huiling Si, Yanhong Ma, Hang Zu, Jianbo Liang","doi":"10.1039/d4dt02912g","DOIUrl":"https://doi.org/10.1039/d4dt02912g","url":null,"abstract":"An OER catalyst showing both high activity and stability in promoting oxygen evolution is important for its practical application in electrochemical water-splitting. Here, we report the screening of such a catalyst by optimizing the Ni(<small>II</small>)-doping in Co(<small>III</small>)-based layered double hydroxides (LDHs). Such LDH samples tailored with Ni(<small>II</small>)-doping are prepared by an oxidative intercalation reaction where brucite-like Ni(<small>II</small>)<small><sub><em>x</em></sub></small>Co(<small>II</small>)<small><sub>1−<em>x</em></sub></small>(OH)<small><sub>2</sub></small> (0 ≤ <em>x</em> ≤ 0.50) is reacted with Br<small><sub>2</sub></small> in acetonitrile. These samples exhibit a volcano-like trend in OER activity related to the fraction of the dopant. At the optimized doping level (<em>x</em> = 0.20), the activity of the catalyst exceeds that of Ni(<small>II</small>)–Fe(<small>III</small>) LDHs at overpotentials higher than 375 mV. <em>In situ</em> Raman spectroscopy and Fourier-transformed alternating current voltammetry reveal that Ni cations can promote the formation of Co(<small>IV</small>)-oxo intermediates, thereby accelerating the kinetics of the OER. The volcano-like activity trend manifests the underlying synergistic communication between Ni and Co cations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"84 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056852","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}
Cage compounds are potential kinetic rocks and thermodynamic powerhouses. Their strain energy plays a crucial role. Hence, cubane, homocubanes, and bishomocubane skeletons have become prominent recently. However, research on the design and development of azahomocubane-based energetic materials has yet to be explored. The aim of the present work is to illustrate the potential of azahomocubanes as next-generation propellants, explosives and oxidizers. The energetic potential of any new materials was determined using B3LYP/6-31+G**, G2, and MP2/6-311++G** levels at the Gaussian 03 suite of programs. The new azahomocubanes possess a density range of 1.33 g/cm3 to 2.14 g/cm3. Most of the azahomocubanes have significantly elevated high-positive heats of formation (Hf° (s) = 289.82 kJ/mol to 728.41 kJ/mol). Compounds AHC-12-19 have superior potentials as solid propellants in rocket propulsion. Additionally, this study reveals that compounds AHC-20 and AHC-21 could be highly effective primary explosives (AHC-20, P = 44.46 GPa, D = 9706 ms-1; AHC-21, P = 45.64 GPa, D = 9708 ms-1) exceeding the performance of RDX, HMX and comparable to that of ONC and CL-20. Our finding suggests that azahomocubanes have great potential in the field of energetic materials.
{"title":"Unveiling the Energetic Potential of Azahomocubane (AHC): A New Class of Potential Propellants, Explosives and Oxidizers","authors":"Sohan Lal, Haixiang Gao, Jean'ne M. Shreeve","doi":"10.1039/d4dt03457k","DOIUrl":"https://doi.org/10.1039/d4dt03457k","url":null,"abstract":"Cage compounds are potential kinetic rocks and thermodynamic powerhouses. Their strain energy plays a crucial role. Hence, cubane, homocubanes, and bishomocubane skeletons have become prominent recently. However, research on the design and development of azahomocubane-based energetic materials has yet to be explored. The aim of the present work is to illustrate the potential of azahomocubanes as next-generation propellants, explosives and oxidizers. The energetic potential of any new materials was determined using B3LYP/6-31+G**, G2, and MP2/6-311++G** levels at the Gaussian 03 suite of programs. The new azahomocubanes possess a density range of 1.33 g/cm3 to 2.14 g/cm3. Most of the azahomocubanes have significantly elevated high-positive heats of formation (Hf° (s) = 289.82 kJ/mol to 728.41 kJ/mol). Compounds AHC-12-19 have superior potentials as solid propellants in rocket propulsion. Additionally, this study reveals that compounds AHC-20 and AHC-21 could be highly effective primary explosives (AHC-20, P = 44.46 GPa, D = 9706 ms-1; AHC-21, P = 45.64 GPa, D = 9708 ms-1) exceeding the performance of RDX, HMX and comparable to that of ONC and CL-20. Our finding suggests that azahomocubanes have great potential in the field of energetic materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"37 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143071677","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}
Katharina Bleher, Patrick Arthur Cieslik, Peter Comba
Bispidines are extremely rigid ligands, easy to prepare in a large variety, with denticities of four to ten, various donor sets and charges, for mono- and oligonuclear transition metal, main group and rare earth complexes. In the last approx. 20 years significantly more than 50 new bispidine based ligands were prepared and their coordination chemistry studied. Biological probes and medicinal applications is one main area in bispidine coordination chemistry, where fast complex formation, high stability, metal ion selectivity and inertness are of utmost importance. Oxygen activation and oxidation catalysis is another main focus in bispidine coordination chemistry, with catalyst efficiency and stability as well as product selectivity as important requirements. Particularly successful applications in these areas are presented and discussed in detail, in addition to fundamental principles that show the importance of ligand rigidity, cavity size and shape as overarching fundamental properties.
{"title":"Bispidine Coordination Chemistry","authors":"Katharina Bleher, Patrick Arthur Cieslik, Peter Comba","doi":"10.1039/d5dt00050e","DOIUrl":"https://doi.org/10.1039/d5dt00050e","url":null,"abstract":"Bispidines are extremely rigid ligands, easy to prepare in a large variety, with denticities of four to ten, various donor sets and charges, for mono- and oligonuclear transition metal, main group and rare earth complexes. In the last approx. 20 years significantly more than 50 new bispidine based ligands were prepared and their coordination chemistry studied. Biological probes and medicinal applications is one main area in bispidine coordination chemistry, where fast complex formation, high stability, metal ion selectivity and inertness are of utmost importance. Oxygen activation and oxidation catalysis is another main focus in bispidine coordination chemistry, with catalyst efficiency and stability as well as product selectivity as important requirements. Particularly successful applications in these areas are presented and discussed in detail, in addition to fundamental principles that show the importance of ligand rigidity, cavity size and shape as overarching fundamental properties.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"53 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056853","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}
Gauri S Malankar, Divyesh S. Shelar, R. J. Butcher, Sudesh T Manjare
Mercury(II) is highly toxic thus the selective and sensitive detection of Hg(II) is important. This research article deals with the synthesis and characterization of the fluorogenic system based on diselenide containing rhodamine by single crystal XRD. The probe has been used for selective detection of Hg(II) in aqueous media with detection limit of 62.3 nM. The reaction of the Hg(II) with the probe induces opening of the spirolactam ring triggering fluorescence turn-on response. This reaction causes color change of the probe solution from colorless to pink. In addition, the probe showed the reversible binding behavior with Hg(II) and S2-. The effectiveness of the probe was evaluated using prostate cancer cell line through live cell imaging.
{"title":"Development of diselenide-based fluorogenic system for the selective and sensitive detection of the Hg(II) in aqueous media","authors":"Gauri S Malankar, Divyesh S. Shelar, R. J. Butcher, Sudesh T Manjare","doi":"10.1039/d4dt02967d","DOIUrl":"https://doi.org/10.1039/d4dt02967d","url":null,"abstract":"Mercury(II) is highly toxic thus the selective and sensitive detection of Hg(II) is important. This research article deals with the synthesis and characterization of the fluorogenic system based on diselenide containing rhodamine by single crystal XRD. The probe has been used for selective detection of Hg(II) in aqueous media with detection limit of 62.3 nM. The reaction of the Hg(II) with the probe induces opening of the spirolactam ring triggering fluorescence turn-on response. This reaction causes color change of the probe solution from colorless to pink. In addition, the probe showed the reversible binding behavior with Hg(II) and S2-. The effectiveness of the probe was evaluated using prostate cancer cell line through live cell imaging.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"11 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056854","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) are promising candidates for thermochromic materials. In this study, a hydrogen-bonded 3D porous metal-organic framework, Co-BTC(Co3(BTC)2·12H2O, BTC = 1,3,5-benzenetricarboxylic acid), exhibited a pink color at room temperature, attributed to the d-d transition of Co2+ ions within the framework, and displayed reversible thermochromic behavior due to alterations in the coordination environment of Co2+ ions. Additionally, Co-BTC/PVB thermochromic film was successfully designed and fabricated as smart window with a monolayer structure. The window exhibited reversible thermochromic behavior comparable to Co-BTC, with visible transmittance modulation of 10.73%, near-infrared transmittance modulation of 25.87%, and solar transmittance modulation of 12.63%. Compared to a pure PVB window, the smart window reduced indoor temperature by 5.7 °C in field tests, indicating a significant energy-saving effect. This research presents a potential application for the rational design of MOFs in the development of advanced smart windows.
{"title":"Application of reversible thermochromic Co-MOF in smart windows","authors":"Xuan Yang, Ping-Chun Guo, Zesen Yu, Hedong Jiang, Huanhuan Guo, Jian Sun, Jiake Li, Yanxiang Wang, Hua Zhu","doi":"10.1039/d4dt03423f","DOIUrl":"https://doi.org/10.1039/d4dt03423f","url":null,"abstract":"Metal-organic frameworks (MOFs) are promising candidates for thermochromic materials. In this study, a hydrogen-bonded 3D porous metal-organic framework, Co-BTC(Co3(BTC)2·12H2O, BTC = 1,3,5-benzenetricarboxylic acid), exhibited a pink color at room temperature, attributed to the d-d transition of Co2+ ions within the framework, and displayed reversible thermochromic behavior due to alterations in the coordination environment of Co2+ ions. Additionally, Co-BTC/PVB thermochromic film was successfully designed and fabricated as smart window with a monolayer structure. The window exhibited reversible thermochromic behavior comparable to Co-BTC, with visible transmittance modulation of 10.73%, near-infrared transmittance modulation of 25.87%, and solar transmittance modulation of 12.63%. Compared to a pure PVB window, the smart window reduced indoor temperature by 5.7 °C in field tests, indicating a significant energy-saving effect. This research presents a potential application for the rational design of MOFs in the development of advanced smart windows.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055607","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}
Gunasekaran Arunkumar, Govindan Deviga, Mariappan Mariappan, Mehboobali Pannippara, Abdullah G. Al-Sehemi, Savarimuthu Philip Anthony
Cobalt/iron terephthalic acid (CoFeTPA) metal organic frameworks with nano/microcrystalline structures were synthesized and investigated their bifunctional electrocatalytic OER, HER and overall water splitting in alkaline medium. Co-TPA produced microcrystalline particles whereas FeTPA produced nano/microrods. Bimetallic CoFeTPA exhibited broken microrods/particles with varying the ratio of Co and Fe. FeTPA showed relatively stronger OER activity (220 mV overpotential for 10 mA/cm2) compared to CoTPA and bimetallic CoFeTPA. In contrast, bimetallic CoFeTPA displayed better HER activity (202 mV overvoltage for 10 mA/cm2) compared to CoTPA and FeTPA. The strong bifunctional activity of CoFeTPA was utilized for overall water splitting. Bimetallic CoFeTPA catalyst required 1.68 V and cell voltage to achieve 10 mA/cm2 current density. The bimetallic MOF was further utilized for sea water splitting. The current-time studies indicated good stability of the catalyst for over 12 hr. After catalysis analysis indicated that bimetallic CoFeTPA MOF produced catalytic active cobalt oxyhydroxide and iron oxyhydroxide during the catalysis. Thus, the present work suggests the opportunity to fabricate cost effective bifunctional electrocatalyst by integrating multiple metal ions in the MOFs.
{"title":"Fabricating bimetallic cobalt-iron MOF nano/microcrystalline particles: strong bifunctional electrocatalytic activity and overall water splitting","authors":"Gunasekaran Arunkumar, Govindan Deviga, Mariappan Mariappan, Mehboobali Pannippara, Abdullah G. Al-Sehemi, Savarimuthu Philip Anthony","doi":"10.1039/d4dt03102d","DOIUrl":"https://doi.org/10.1039/d4dt03102d","url":null,"abstract":"Cobalt/iron terephthalic acid (CoFeTPA) metal organic frameworks with nano/microcrystalline structures were synthesized and investigated their bifunctional electrocatalytic OER, HER and overall water splitting in alkaline medium. Co-TPA produced microcrystalline particles whereas FeTPA produced nano/microrods. Bimetallic CoFeTPA exhibited broken microrods/particles with varying the ratio of Co and Fe. FeTPA showed relatively stronger OER activity (220 mV overpotential for 10 mA/cm2) compared to CoTPA and bimetallic CoFeTPA. In contrast, bimetallic CoFeTPA displayed better HER activity (202 mV overvoltage for 10 mA/cm2) compared to CoTPA and FeTPA. The strong bifunctional activity of CoFeTPA was utilized for overall water splitting. Bimetallic CoFeTPA catalyst required 1.68 V and cell voltage to achieve 10 mA/cm2 current density. The bimetallic MOF was further utilized for sea water splitting. The current-time studies indicated good stability of the catalyst for over 12 hr. After catalysis analysis indicated that bimetallic CoFeTPA MOF produced catalytic active cobalt oxyhydroxide and iron oxyhydroxide during the catalysis. Thus, the present work suggests the opportunity to fabricate cost effective bifunctional electrocatalyst by integrating multiple metal ions in the MOFs.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"23 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055622","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}
Indium(III) complexes of S-thiobenzoylthioglycolate (Stbtg) with nitrogen-donor ligands, such as 2,2'-bipyridyl and 1,10-phenanthroline, have been synthesized. The complexes [In(1,10-phen)(Stbtg)₃] (1), [In(2,2'-bipy)(Stbtg)₃] (2), and a thioglycolate salt, Na[In((2,2'-bipy)(SCH₂COO)₂].H₂O (3), obtained by decomposition of thiobenzoylthioglycolate complex, were fully characterized using NMR, IR spectroscopy, and single-crystal X-ray diffraction. The catalytic activities of these complexes were evaluated for two significant types of reactions. Complex 1 demonstrated exceptional catalytic efficiency in the Knoevenagel condensation and Knoevenagel-initiated multicomponent reactions (MCRs) for the synthesis of 2-amino-4H-chromene derivatives, including cyclohexane-1,3-dione, 5,5-dimethylcyclohexane-1,3-dione, 4-hydroxycoumarin, barbituric acid, and 2-aminobenzimidazole. Additionally, the complexes were found to be highly effective in CO₂ fixation reactions, with complex 1 exhibiting the highest activity, followed by 2 and 3. These results highlight the potential of In(III) complexes as catalysts in a variety of applications, such as organic synthesis and environmentally significant CO₂ fixation, demonstrating the broad applicability of non-transition metal complexes in sustainable chemical processes.
{"title":"Synthesis and characterization of In(III) S-thiobezoylethioglycolate complexes and their catalytic applications in CO2 fixation and multicomponent synthetic reactions","authors":"Mrituanjay D. Pandey, Subrato Bhattacharya, Rajesh Pratap, Raj Kumar Sahani, Tarkeshwar Maddeshiya, Himanshu Shekhar Tripathi","doi":"10.1039/d4dt03382e","DOIUrl":"https://doi.org/10.1039/d4dt03382e","url":null,"abstract":"Indium(III) complexes of S-thiobenzoylthioglycolate (Stbtg) with nitrogen-donor ligands, such as 2,2'-bipyridyl and 1,10-phenanthroline, have been synthesized. The complexes [In(1,10-phen)(Stbtg)₃] (1), [In(2,2'-bipy)(Stbtg)₃] (2), and a thioglycolate salt, Na[In((2,2'-bipy)(SCH₂COO)₂].H₂O (3), obtained by decomposition of thiobenzoylthioglycolate complex, were fully characterized using NMR, IR spectroscopy, and single-crystal X-ray diffraction. The catalytic activities of these complexes were evaluated for two significant types of reactions. Complex 1 demonstrated exceptional catalytic efficiency in the Knoevenagel condensation and Knoevenagel-initiated multicomponent reactions (MCRs) for the synthesis of 2-amino-4H-chromene derivatives, including cyclohexane-1,3-dione, 5,5-dimethylcyclohexane-1,3-dione, 4-hydroxycoumarin, barbituric acid, and 2-aminobenzimidazole. Additionally, the complexes were found to be highly effective in CO₂ fixation reactions, with complex 1 exhibiting the highest activity, followed by 2 and 3. These results highlight the potential of In(III) complexes as catalysts in a variety of applications, such as organic synthesis and environmentally significant CO₂ fixation, demonstrating the broad applicability of non-transition metal complexes in sustainable chemical processes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"120 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055608","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}
Layered materials, such as tungsten dichalcogenides (TMDs), are being studied for a wide range of applications, due to their unique and varied properties. Specifically, their use as either a support for low dimensional catalysts or as an ultrathin diffusion barrier in semiconductor devices interconnect structures are particularly relevant. In order to fully realise these possible applications for TMDs, understanding the interaction between metals and the monolayer they are deposited on is of utmost importance. The morphology that arises due to given metal–substrate combinations determines their possible applications and thus is a central characteristic. Previous theoretical studies typically focus on the effects which single metal adatoms, or dopants, have on a TMDs’ electronic and optical properties, thereby leaving a knowledge gap in terms of thin film nucleation on TMD monolayers. To address this, we present a density functional theory (DFT) study of the adsorption of small Cu clusters on a range of TMD monolayers, namely WS2, WSe2, and WTe2. We explore how metal–substrate and metal–metal interactions contribute to both the stability of these Cu clusters and their morphology, and investigate the role of the chalcogen in these interactions. We find that single Cu atoms adsorb most strongly to the adsorption site above the W atom, however as nanocluster size increases, Cu tends to be adsorbed atop the chalcogen atoms in the monolayer to facilitate Cu–Cu bond formation. We show that Cu–Cu interactions drive the stability of the adsorbed Cu nanoclusters, with a clear preference for 3D structures on all 3 monolayers studied. Furthermore, significant Cu migration occurs during 0 K relaxation. This, combined with the small activation barriers found for Cu migration suggest facile and dynamic cluster behaviour at finite temperature on all three monolayers. Finally, we find that Cu clusters are generally most stable on WTe2 and least stable on WSe2. This difference however is typically only in the range of 0.1 eV.
{"title":"Structure and stability of copper nanoclusters on monolayer tungsten dichalcogenides","authors":"Michael Sweetman, Cara-Lena Nies, Michael Nolan","doi":"10.1039/d4dt02985b","DOIUrl":"https://doi.org/10.1039/d4dt02985b","url":null,"abstract":"Layered materials, such as tungsten dichalcogenides (TMDs), are being studied for a wide range of applications, due to their unique and varied properties. Specifically, their use as either a support for low dimensional catalysts or as an ultrathin diffusion barrier in semiconductor devices interconnect structures are particularly relevant. In order to fully realise these possible applications for TMDs, understanding the interaction between metals and the monolayer they are deposited on is of utmost importance. The morphology that arises due to given metal–substrate combinations determines their possible applications and thus is a central characteristic. Previous theoretical studies typically focus on the effects which single metal adatoms, or dopants, have on a TMDs’ electronic and optical properties, thereby leaving a knowledge gap in terms of thin film nucleation on TMD monolayers. To address this, we present a density functional theory (DFT) study of the adsorption of small Cu clusters on a range of TMD monolayers, namely WS<small><sub>2</sub></small>, WSe<small><sub>2</sub></small>, and WTe<small><sub>2</sub></small>. We explore how metal–substrate and metal–metal interactions contribute to both the stability of these Cu clusters and their morphology, and investigate the role of the chalcogen in these interactions. We find that single Cu atoms adsorb most strongly to the adsorption site above the W atom, however as nanocluster size increases, Cu tends to be adsorbed atop the chalcogen atoms in the monolayer to facilitate Cu–Cu bond formation. We show that Cu–Cu interactions drive the stability of the adsorbed Cu nanoclusters, with a clear preference for 3D structures on all 3 monolayers studied. Furthermore, significant Cu migration occurs during 0 K relaxation. This, combined with the small activation barriers found for Cu migration suggest facile and dynamic cluster behaviour at finite temperature on all three monolayers. Finally, we find that Cu clusters are generally most stable on WTe<small><sub>2</sub></small> and least stable on WSe<small><sub>2</sub></small>. This difference however is typically only in the range of 0.1 eV.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"53 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055624","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 this paper, we describe the synthesis of two six-coordinate, pseudo(octahedral) bis(formazanate) Fe(II) complexes based on new redox-active benzothiazole substituted formazanate ligands. Complexes [FeII(L1)2], 1 and [FeII(L2)2], 2 were synthesized by reacting 1-(benzothiazol-2-yl)-5-phenyl-3-(pyren-1-yl)formazan (L1H) and 1-(benzothiazol-2-yl)-5-(2-benzoyl-4-chlorophenyl)-3-phenylformazan (L2H) respectively with the appropriate Fe(II) precursors at room temperature. The molecular structure of both the bis(formazanate) iron complexes has been established using Single-Crystal XRD, and other characterization methods were utilized to characterize these complexes further, as well as the newly synthesized ligands. Furthermore, the cyclic voltammetry of these compounds is documented, revealing that both complexes may undergo electrochemical reductions to create anionic and dianionic species. These complexes were further employed as the cathode of one-compartment membrane-less H2O2 fuel cells, operating in 0.5 M H2O2 with nickel foam serving as the anode. The maximum power densities achieved by the designed H2O2 fuel cell for complexes 1 and 2 were 1.88 mW cm-2 and 3.08 mW cm-2, respectively. This study demonstrates the significant potential for investigating formazanate-based compounds in the development of cathode materials for H2O2 fuel cells.
{"title":"Bis(formazanate) Iron(II) Complexes as Cathode Material for One-Compartment H2O2 Fuel Cell","authors":"Sunita Birara, Moumita Majumder, Ramesh K. Metre","doi":"10.1039/d4dt03253e","DOIUrl":"https://doi.org/10.1039/d4dt03253e","url":null,"abstract":"In this paper, we describe the synthesis of two six-coordinate, pseudo(octahedral) bis(formazanate) Fe(II) complexes based on new redox-active benzothiazole substituted formazanate ligands. Complexes [Fe<small><sup>II</sup></small>(L1)<small><sub>2</sub></small>], <strong>1</strong> and [Fe<small><sup>II</sup></small>(L2)<small><sub>2</sub></small>], <strong>2</strong> were synthesized by reacting <em>1-(benzothiazol-2-yl)-5-phenyl-3-(pyren-1-yl)formazan</em> (L1H) and <em>1-(benzothiazol-2-yl)-5-(2-benzoyl-4-chlorophenyl)-3-phenylformazan</em> (L2H) respectively with the appropriate Fe(II) precursors at room temperature. The molecular structure of both the bis(formazanate) iron complexes has been established using Single-Crystal XRD, and other characterization methods were utilized to characterize these complexes further, as well as the newly synthesized ligands. Furthermore, the cyclic voltammetry of these compounds is documented, revealing that both complexes may undergo electrochemical reductions to create anionic and dianionic species. These complexes were further employed as the cathode of one-compartment membrane-less H<small><sub>2</sub></small>O<small><sub>2</sub></small> fuel cells, operating in 0.5 M H<small><sub>2</sub></small>O<small><sub>2</sub></small> with nickel foam serving as the anode. The maximum power densities achieved by the designed H<small><sub>2</sub></small>O<small><sub>2</sub></small> fuel cell for complexes <strong>1</strong> and <strong>2</strong> were 1.88 mW cm<small><sup>-2</sup></small> and 3.08 mW cm<small><sup>-2</sup></small>, respectively. This study demonstrates the significant potential for investigating formazanate-based compounds in the development of cathode materials for H<small><sub>2</sub></small>O<small><sub>2</sub></small> fuel cells.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"84 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050592","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}
An effective way to improve the cycling performance of metal sulfide materials is to blend them with conductive materials. In this paper, three-dimensional (3D) hollow MXene/ZnS heterostructures (ZnSMX) were prepared via a two-step process involving hydrothermal and template methodology. The formation of Ti-O-Zn bonds enables the firm bonding between ZnS nanoparticles and the MXene substrate at heterogeneous interfaces, which can act as "electron bridges" to facilitate electron and charge transfer. Most importantly, 3D hollow ZnSMX not only enhances the conductivity of ZnS, enabling rapid charge transfer, but also effectively restacking of MXene nanosheets to maintain structural stability during the charge/discharge process. More importantly, the 3D macroporous structure provides ultrafast interfacial ion transport pathways and extra surficial and interfacial storage sites, and thus, boosts the excellent storage performances in lithium-ion batteries applications. The 3D ZnSMX exhibited a high capacity of 782.1 mAh g-1 at 1 A g-1 current, excellent cycling stability (providing a high capacity of 1027.8 mA h g-1 after 350 cycles at 2 A g-1), and excellent rate performance. This indicates that 3D ZnS/MXene heterostructure has the potential to be a highly promising anode material for high-multiplication lithium-ion batteries.
{"title":"Three-Dimensional Hollow ZnS/MXene Heterostructure with Stable Ti-O-Zn Bonding for Enhanced Lithium-Ion Storage","authors":"Rujia Zou, Wei Yang, Wenqing Wang, Shidi Huang, Mengluan Gao, Fuming Weng","doi":"10.1039/d4dt03381g","DOIUrl":"https://doi.org/10.1039/d4dt03381g","url":null,"abstract":"An effective way to improve the cycling performance of metal sulfide materials is to blend them with conductive materials. In this paper, three-dimensional (3D) hollow MXene/ZnS heterostructures (ZnSMX) were prepared via a two-step process involving hydrothermal and template methodology. The formation of Ti-O-Zn bonds enables the firm bonding between ZnS nanoparticles and the MXene substrate at heterogeneous interfaces, which can act as \"electron bridges\" to facilitate electron and charge transfer. Most importantly, 3D hollow ZnSMX not only enhances the conductivity of ZnS, enabling rapid charge transfer, but also effectively restacking of MXene nanosheets to maintain structural stability during the charge/discharge process. More importantly, the 3D macroporous structure provides ultrafast interfacial ion transport pathways and extra surficial and interfacial storage sites, and thus, boosts the excellent storage performances in lithium-ion batteries applications. The 3D ZnSMX exhibited a high capacity of 782.1 mAh g-1 at 1 A g-1 current, excellent cycling stability (providing a high capacity of 1027.8 mA h g-1 after 350 cycles at 2 A g-1), and excellent rate performance. This indicates that 3D ZnS/MXene heterostructure has the potential to be a highly promising anode material for high-multiplication lithium-ion batteries.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"59 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050589","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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