Alexey Tsyganov, Maria Vikulova, Ilya Zotov, Evgenii V. Korotaev, Ilya Plugin, Victor Sysoev, Demid Kirilenko, Maxim Konstantinovich Rabchinskii, Artur Asoyan, Alexander V. Gorokhovsky, Nikolay Gorshkov
{"title":"Application of W1.33CTz MXene obtained by hydrothermal etching as an additive to enhance the electrochemical energy storage properties of binder-free Ti3C2Tx MXene films","authors":"Alexey Tsyganov, Maria Vikulova, Ilya Zotov, Evgenii V. Korotaev, Ilya Plugin, Victor Sysoev, Demid Kirilenko, Maxim Konstantinovich Rabchinskii, Artur Asoyan, Alexander V. Gorokhovsky, Nikolay Gorshkov","doi":"10.1039/d5dt00413f","DOIUrl":"https://doi.org/10.1039/d5dt00413f","url":null,"abstract":"In this study, the electrochemical energy storage properties of Ti3C2Tx MXene films have been improved by the addition of W1.33CTz MXenes with ordered vacancies in their structure. W1.33CTz i-MXene was obtained from (W2/3Y1/3)2AlC i-MAX phase by etching in HCl/LiF mixture under hydrothermal conditions with following delamination by intercalation of tetramethylammonium ions. Ti3C2Tx/W1.33CTz composite electrode films were prepared from colloidal solutions, which were mixed in the appropriate ratio to achieve the W1.33CTz concentrations of 10, 20, 30 and 40 wt.%. MXenes were characterized by XRD, SEM, TEM and XPS methods. The electrochemical energy storage properties of binder-free MXene films were studied by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) methods. It has been shown that the addition of 20 wt.% W1.33CTz can significantly improve the pseudocapacitive intercalation of electrolyte ions. The specific capacitance of Ti3C2Tx/W1.33CTz (20 wt.%) electrodes in H2SO4, LiCl and KOH electrolytes was 375, 171 and 235 F•g-1, respectively, at a scan rate of 5 mV•s-1. The composite electrode showed good cycling stability (more than 93% capacity retention after 10,000 cycles). The results obtained indicated that the synthesised composite could be considered as a promising electrode material for energy storage systems.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"26 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858170","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}
Jun-Rui Liu, Yao-Mei Fu, Wen-Tao Ju, Meng Lian, Teng Liu, Xing Meng, Hai-Ning Wang and Zhong-Min Su
{"title":"Ionic porous organic polymer as a bifunctional platform for CO2 photoreduction and proton conduction†","authors":"Jun-Rui Liu, Yao-Mei Fu, Wen-Tao Ju, Meng Lian, Teng Liu, Xing Meng, Hai-Ning Wang and Zhong-Min Su","doi":"10.1039/D4DT03493G","DOIUrl":"10.1039/D4DT03493G","url":null,"abstract":"<p >To unveil the potential of ionic porous organic polymers, the ion-exchanged sample POP–BPy–PMV was synthesized, exhibiting a CO generation rate of 22.75 μmol g<small><sup>−1</sup></small> h<small><sup>−1</sup></small>. Additionally, the original POP–BPy displayed a high proton conductivity of 1.18 × 10<small><sup>−2</sup></small> S cm<small><sup>−1</sup></small> under 100% humidity at 90 °C.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 17","pages":" 6790-6794"},"PeriodicalIF":3.5,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858202","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}
E. A. Sanzhenakova, K. S. Smirnova, I. P. Pozdnyakov, A. S. Berezin, V. I. Potkin, E. V. Lider
{"title":"Structural diversity of photoluminescent lanthanide(III) coordination compounds with an isothiazole derivative","authors":"E. A. Sanzhenakova, K. S. Smirnova, I. P. Pozdnyakov, A. S. Berezin, V. I. Potkin, E. V. Lider","doi":"10.1039/d5dt00127g","DOIUrl":"https://doi.org/10.1039/d5dt00127g","url":null,"abstract":"Two different series of europium(<small>III</small>), terbium(<small>III</small>) and gadolinium(<small>III</small>) complexes with 4,5-dichloroisothiazole-3-carboxylic acid (HL) were obtained. According to the data obtained from various analysis methods, the first type of coordination compounds with the general formula of [Ln(H<small><sub>2</sub></small>O)L<small><sub>2</sub></small>(OAc)]<small><sub><em>n</em></sub></small> was polymer chains, and the second type with the general formula of [Ln<small><sub>6</sub></small>(H<small><sub>2</sub></small>O)<small><sub>10</sub></small>L<small><sub>18</sub></small>] was hexanuclear complexes, with central atoms arranged similar to octahedrons. DFT calculations were used to determine the location of the electron density in HOMO/LUMO and the value of the triplet state energy of the ligand molecule. The highest luminescence quantum yield was observed in the case of the hexanuclear terbium(<small>III</small>) complex (24%) with a millisecond luminescence lifetime, while the hexanuclear europium(<small>III</small>) compound (96%) exhibited the highest value of color purity.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"2 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858169","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}
{"title":"A Bioinspired Model for Copper Monooxygenase: A Direct Aromatic Hydroxylation Using O2","authors":"Ramamoorthy Ramasubramanian, Karunanithi Anandababu, Mukesh Kumar, Ramasamy Mayilmurugan","doi":"10.1039/d4dt02079k","DOIUrl":"https://doi.org/10.1039/d4dt02079k","url":null,"abstract":"A novel copper(I) complex, [CuI(L)(CH3CN)]CF3SO3 (1) (L = 1,1,2-tri(pyridin-2-yl)propan-1-ol), has been synthesized, characterized, and investigated as a bioinspired model for copper monooxygenases. Under aerobic conditions in CH3CN, complex 1 undergoes conversion to a dicopper complex, [(CuIIL)(CuIIL H)(SO3CF3)2]·CF3SO3·H2O (2), whose molecular structure reveals a Cu-Cu distance of 2.96 Å. A dicopper(II) complex, [(LCuII)2(SO3CF3)2] (3), has been synthesized for comparison, which exhibits a similar Cu-Cu distance of 2.97 Å. EPR spectroscopy has ascertained the solution state geometries of complexes 2 and 3, which displayed g׀׀ > g┴ values, indicative of distorted square pyramidal geometries consistent with their solid-state structures. Complex 1 selectively hydroxylates benzene in the presence of O₂ and Et₃N, affording 7% phenol based on the substrate, without any side products. However, the use of H2O2 as the oxygen source under identical conditions significantly increases the phenol yield to 19%. The catalytically active intermediates have been generated by the reaction of complex 1 with dioxygen showed an O (π*σ) → Cu ligand-to-metal charge transfer (LMCT) transition at 360 nm and a d-d transition at 650 nm. These spectral features are more pronounced with H2O2, showed a new LMCT transition at 360 nm and a very weak d-d transition at 689 nm. It is supported by solution FT-IR spectroscopy, which showed an O-O stretching frequency at 890 cm⁻¹ (DFT spectra at 829 cm⁻¹) corresponds to Cu-OOH intermediate. The structure of the [(L)CuII-OOH]+ species was optimized by DFT calculations. Kinetic isotope effect (KIE) studies using C6H6/C6D6 (1:1) (kH/kD = 1.03) and isotopic labeling experiments using H218O2 support our proposed mechanism of benzene hydroxylation. In contrast, dinuclear complexes 2 and 3 exhibited poor benzene hydroxylation activity even with H2O2 and yielded only 4% and 6% of phenol, respectively, along with by-products such as biphenyl and quinone under identical conditions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"62 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858172","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}
{"title":"Excavating the Synthesis of Ru(II)/Ir(III)/Re(I)/Rh(III) based complexes as anticancer metallopharmaceuticals: Significance, Challenges and future perspective","authors":"U. Sreelekha, Rinku Chakrabarty, Priyankar Paira","doi":"10.1039/d5dt00610d","DOIUrl":"https://doi.org/10.1039/d5dt00610d","url":null,"abstract":"Metal complexes exhibit significant potential in the field of anticancer metallotherapeutics due to their high selectivity toward cancer cells and their effectiveness in targeted drug delivery. This frontier article summarizes recent advances in the synthesis of mono-, bi-, and mixed-metallic Ru(II)/Ir(III)/Re(I)/Rh(III) complexes for anticancer applications. Additionally, various therapeutic approaches and their mechanisms of action in Ru(II)/Ir(III)/Re(I)/Rh(III)-based complexes have been explored. Here we provide the insights on the contributions of various research groups toward the development of transition metal complexes with promising therapeutic potential. Emphasis has also been given on the different challenges faced throughout the designing and application process and the future perspective of these metallopharmaceuticals.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853820","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}
{"title":"Microwave-assisted interzeolite transformations","authors":"Stanislav Ferdov, Renato Ferreira Gonçalves","doi":"10.1039/d5dt00723b","DOIUrl":"https://doi.org/10.1039/d5dt00723b","url":null,"abstract":"Microwave heating of FAU zeolite in alkaline solutions results in transformations into EDI, MER, LTJ, CAN, and ANA-type zeolites. The use of microwaves significantly accelerates the synthesis and uncovers a previously unobserved transformation to LTJ-type zeolite.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"37 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853817","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}
Xiaolong Yang, Hongyuan Song, Ruihang Yao, Haorong Wu, Kun Dong, Liangwei Chen, Bin Liu, Zhenhua Ge, Lan Yu
{"title":"High-efficiency oxygen evolution catalysts: composite hexagonal structure SrCo1-yNiyO3-δ/Sr9Ni7O21","authors":"Xiaolong Yang, Hongyuan Song, Ruihang Yao, Haorong Wu, Kun Dong, Liangwei Chen, Bin Liu, Zhenhua Ge, Lan Yu","doi":"10.1039/d5dt00324e","DOIUrl":"https://doi.org/10.1039/d5dt00324e","url":null,"abstract":"Transition metal perovskite oxides are regarded as ideal catalysts for the oxygen evolution reaction (OER) owing to the high tunability of the B-site active elements. Among them, SrCoO3 has been widely studied due to its high theoretical catalytic performance, but incomplete oxidation of the B-site elements results in poor intrinsic activity. Herein, we prepared a series of SrCo1-xNixO3-δ (x = 0-0.5) catalysts for alkaline OER using a simple sol-gel method and optimized their catalytic performance by modulating the Co/Ni ratio and annealing temperature (950 ℃ and 1050 ℃). Among the series, SrCo0.6Ni0.4O3-δ (annealed at 950 ℃) with a composite hexagonal structure (SrCo1-yNiyO3-δ/Sr9Ni7O21, y = 0.1-0.2) exhibited the best OER activity, achieving an overpotential of 321 mV at 10 mA cm-2 (1 M KOH). The introduction of Ni ions and the presence of Sr₉Ni₇O₂₁ not only enhance the Co4+/Co3+ and Ni3+/Ni2+ ratios, but also promote the generation of more highly oxidative oxygen species (O22-/O-). Additionally, the abundant Ni3+ surface facilitates the formation of highly active NiOOH phase during OER, leading to a further reduction in the overpotential (after 1000 CV cycles, the overpotential on the nickel foam electrode decreased by 45 mV).","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"91 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853822","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}
Sapargali Pazylbek, Jonas Stadulis, Guna Doke, Andris Antuzevics, Vladimir Pankratov, Greta Merkininkaite, Arturas Katelnikovas, Aleksej Zarkov
{"title":"Tunable Broadband Visible Emission Achieved by Phase Transformation-Driven Self-Reduction of Eu3+ to Eu2+ in Calcium Phosphate Matrix","authors":"Sapargali Pazylbek, Jonas Stadulis, Guna Doke, Andris Antuzevics, Vladimir Pankratov, Greta Merkininkaite, Arturas Katelnikovas, Aleksej Zarkov","doi":"10.1039/d5dt00681c","DOIUrl":"https://doi.org/10.1039/d5dt00681c","url":null,"abstract":"In this work, we report the synthesis of Eu2+-doped alpha-tricalcium phosphate (α-TCP, α-Ca3(PO4)2) via a phase transformation of Eu3+-doped CaHPO4 ∙ 2H2O. The phase conversion accompanied by a reduction of Eu3+ to Eu2+ occurred during the annealing of the starting material in a vacuum. The optical properties of the obtained α-TCP:Eu2+ were investigated by photoluminescence (PL), thermally stimulated luminescence, and persistent luminescence decay measurements. The obtained material exhibited tunable broadband PL with FWHM values ranging from 94 to 142 nm at room temperature. The PL can be tuned in terms of emission maximum and FWHM by varying the excitation wavelength. The broadband emission was achieved due to the multi-site occurrence of Eu2+ ions in the complex α-TCP matrix. Three types of traps were determined with activation energy values of 0.80, 0.75, and 0.68 eV. After irradiation with X-rays, an afterglow characterizable by a Eu2+ broadband spectrum with a maximum at around 480 nm can be detected for at least 10 h.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"43 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853819","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}
{"title":"Oxygen vacancies promoting the electrocatalytic activity of dual-shelled Co3V2O8 hollow sphere catalyst for efficient oxygen evolution","authors":"Long Li, Xiantao Lin, Qiang Hu","doi":"10.1039/d5dt00657k","DOIUrl":"https://doi.org/10.1039/d5dt00657k","url":null,"abstract":"Developing cost-effective and highly active electrocatalysts for the oxygen evolution reaction (OER) is critical for advancing water splitting technologies. Herein, we report a dual-shell Co3V2O8 hollow sphere catalyst with abundant oxygen vacancies synthesized via a facile hydrothermal method followed by controlled reduction treatment. The unique dual-shell hollow architecture provides a large surface area and exposes abundant active sites, while the introduced oxygen vacancies optimize the electronic structure of Co3V2O8, enhancing electrical conductivity and intrinsic catalytic activity. The optimized catalyst exhibits outstanding OER performance, requiring a low overpotential of 376 mV to achieve a current density of 10 mA cm⁻2 in alkaline media, along with a small Tafel slope of 86.9 mV dec⁻1. Experimental analyses reveal that oxygen vacancies facilitate charge transfer during OER. Moreover, the catalyst demonstrates excellent durability with negligible activity decay after 12 h of continuous operation. This work highlights the synergistic effect of structural engineering and defect modulation in designing high-performance OER electrocatalysts, offering a promising strategy for energy conversion applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"35 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853824","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}
Xiankun Xiong, Chaochao Lu, Zhongliang Pi, CunYuan Pei, Cheng Du
{"title":"Controlled Synthesis of Hierarchical Hollow CoxNi3-xS4 towards Enhanced Rate Capability and Excellent Cycling Stability","authors":"Xiankun Xiong, Chaochao Lu, Zhongliang Pi, CunYuan Pei, Cheng Du","doi":"10.1039/d5dt00317b","DOIUrl":"https://doi.org/10.1039/d5dt00317b","url":null,"abstract":"The strategic design and advancement of electrode materials are crucial for the effectiveness of energy storage and conversion devices. Herein, we successfully synthesized a series of CoxNi3-xS4 hollow microspheres through a combined hydrothermal and vapor-phase sulfidation process. These microspheres are composed of interlinked nanosheets featuring uniformly distributed nanoparticles on their surfaces. This distinctive hierarchical structure integrates one-dimensional, two-dimensional and three-dimensional elements, thereby facilitating the exposure of more active sites, enhancing electrolyte-active site interactions, accelerating carrier transport, and mitigating volume expansion during cycling. Specifically, varying the molar ratios results in different nanosheet thicknesses, with higher cobalt content leading to thicker nanosheets and higher nickel content producing thinner ones. The optimized (Co1Ni2)S4 electrode material demonstrates an impressive specific capacity of 204.9 mAh g-1 (1639 F g-1) at 1 A g-1, along with remarkable rate capability (holding 80.5% when the current is increased 20 times) and exceptional cycling stability (maintaining 96% of its initial capacity after 15,000 cycles). When paired with lotus pollen-derived activated carbon (AC) to form a supercapacitor device, the (Co1Ni2)S4//AC configuration reaches an energy density of 66.5 Wh kg-1 at 800 W kg-1. Notably, even after 30,000 cycles, the device retains an outstanding 98% of its initial capacity while sustaining 100% Coulombic efficiency. This study presents an encouraging method for the precise fabrication of advanced bimetallic sulfides with enhanced electrochemical characteristics, facilitating their broader application in energy storage technologies.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"128 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853821","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}