Inorganic Chemistry Frontiers最新文献

{"title":"Complexes (TBA+){(TMI-NPS)2.Ln(III)I4)(-) (Ln = Dy, Tb) with two axial photochromic spiropyran ligands: photoswitching and zero-field SIM behaviour with a high magnetization blocking barrier for the Dy complex","authors":"Nikita Osipov, Maxim A. Faraonov, Alexey A. Dmitriev, Nina P. Gritsan, Alexey V. Kuzmin, Salavat S. Khasanov, N. N. Denisov, Akihiro Otsuka, Hiroshi Kitagawa, Dmitri V. Konarev","doi":"10.1039/d4qi03198a","DOIUrl":"https://doi.org/10.1039/d4qi03198a","url":null,"abstract":"Two photochromic spiropyran molecules (1,3,3-trimethylindolino-β-naphthopyrylospiran, TMI-NPS) react in the open form with LnIII iodides (Ln = Dy, Tb) to form in the presence of TBAI crystalline (TBA+){(TMI-NPS)2.Ln(III)I4)(-).0.5C6H4Cl2 (1 and 2, respectively). Two TMI-NPS ligands are coordinated to lanthanides (Ln) by oxygen atoms at the axial position, and four iodide anions located at the equatorial position are weakly coordinated to Ln. Three types of anion complexes {(TMI-NPS)2.Ln(III)I4}(-) with slightly different geometries were found. The Ln-O bond lengths are in the range 2.18-2.25 Å, while the Ln-I bond lengths are 3.06-3.09 Å. The geometry of the lanthanide complexes is favorable for the manifestation of single-ion magnetism (SIM). Compound 1 with Dy exhibits in zero magnetic field a slow magnetic relaxation with a high magnetization reversal barrier Ueff of 470 cm-1. Magnetic hysteresis loops for 1 were recorded at 0.5-8 K, the divergence between zero-field and in-field cooling curves was also observed below 8 K, indicating a magnetization blocking temperature of 8 K. Ab initio calculations showed that the electronic structure of three types of Dy complexes is close and Ueff value of at least 760 cm-1 is predected for all of them, while the experimental value lies between the first (E2 = 300 cm-1) and second (E3 = 600 cm-1) Kramers doublets. The Tb compound 2 exhibits a SIM behavior only in an external magnetic field of 2000 Oe, magnetic hysteresis is not observed for it at 2 K. Ab initio calculations predicted significantly different energies of the lowest excited non-Kramers doublets and very small tunneling splitting of the ground doublet for the three types of Tb complexes, the latter is much smaller than their splitting in a 2000 Oe magnetic field. Photodissociation of the Dy complex was detected in solution under green light excitation (548 nm). The complex was recovered very slowly, but the irradiation with UV light at 365 nm significantly accelerates the complexation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"102 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990683","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pt Single Atom and Atomic Cluster-Enhanced TiO2 Janus Micromotors for Efficient Bubble Propulsion and Photocatalytic Environmental Remediation","authors":"Chang Lv, Tao Wang, Yeting Fang, YULONG YING, Lvlv Ji, Lei Liu, Sheng Wang","doi":"10.1039/d4qi02963a","DOIUrl":"https://doi.org/10.1039/d4qi02963a","url":null,"abstract":"Bubble-propelled catalytic micro-/nanomotors, known for their strong thrust, rapid speeds, and long lifespan independent of ionic strength, have attracted significant attention. Despite significant advances in single-atom catalysis for its remarkable catalytic efficiency, single-atom catalysts alone generally lack sufficient activity to decompose hydrogen peroxide (H<small>₂</small>O<small>₂</small>) efficiently, limiting their applicability in bubble-propelled micro-/nanomotors for environmental use. Herein, we report a novel approach for fabricating Pt-decorated titanium dioxide micro-bowls (Pt<small>_SA&amp;C</small>-TiO<small>₂</small>) featuring dual active sites with atomically dispersed Pt single atoms (SAs) and atomic clusters (Cs). This design significantly enhances the propulsion capabilities of Janus micromotors, allowing the Pt<small>_SA&amp;C</small>-TiO<small>₂</small> Janus micromotors to reach a speed of 113 ± 47 μm/s by decomposing H<small>₂</small>O<small>₂</small> in aqueous solution, benefiting from the metallic characteristics of atomic clusters. Additionally, Pt<small>_SA&amp;C</small>-TiO<small>₂</small> Janus micromotors exhibit superior photocatalytic performance in pollutant degradation, demonstrating promising potential for environmental remediation. Finally, we investigated the effects of temperature and solute transport on the self-assembly of Janus TiO<small>₂</small> micro-bowls, demonstrating the morphology’s controllability, which supports scalable production of these micromotors. This study not only highlights the potential of Pt<small>_SA&amp;C</small>-TiO<small>₂</small> Janus micromotors for environmental applications but also offers new insights into the design and application of single-atom-based micromotors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989760","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Utilizing decavanadate as an artificial solid electrolyte interface to effectively suppress dendrite formation on lithium metal anode","authors":"Jian Song, Yuanyuan Jiang, Yizhong Lu, Chang-Hao Zhao, Yun-Dong Cao, Lin-Lin Fan, Hong Liu, Guanggang Gao","doi":"10.1039/d4qi03139c","DOIUrl":"https://doi.org/10.1039/d4qi03139c","url":null,"abstract":"For lithium metal batteries (LMBs), the intrinsic issues of lithium dendrites and unstable interface between lithium metal anode and electrolyte pose severe safety risks. In this study, a novel strategy is proposed for modifying the lithium surface using the decavanadate Na6V10O28⋅18H2O (V10) as a protective layer. The constructing V10 artificial solid electrolyte interface (ASEI) protective layer on lithium metal is a simplified and effective strategy for conquering lithium dendrites. During lithium plating/stripping process, V10 reversibly transforms into Lix[V10O28] (x = 6-9), serving as an “ion sponge” to absorb a large amount of lithium ions to compensate for the shortage of lithium ions on anode surface. Therefore, the electric field strength on lithium anode surface is adjusted to suppress dendrites growth. Additionally, V10 accelerates the desolvation of lithium ion from solvent clusters, which contributes to the homogeneous migration of lithium ions. Consequently, Li//Li symmetric cells using V10 modified foils exhibit stable cycling for 1200 h under the conditions of a current density of 5 mA cm-2 and an areal capacity of 1 mAh cm-2, with an overpotential of only 110 mV. The assembled Li-S cells demonstrate excellent rate performance, achieving the reversible capacity of 470 mAh g-1 under 5 C.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"24 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990682","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Thermal conductivity and balanced performance in infrared nonlinear optical multicomponent chalcogenides LixAg1-xGayIn1-ySe2","authors":"Ludmila Isaenko, Bohui Xu, K.E. Korzhneva, Pifu Gong, D.A. Samoshkin, Aleksey Kurus, Zheshuai Lin","doi":"10.1039/d4qi02886d","DOIUrl":"https://doi.org/10.1039/d4qi02886d","url":null,"abstract":"The performance of infrared (IR) nonlinear optical (NLO) materials is significantly affected by the thermal conductivity kL, but the studies on the structure and property relationship of kL in these materials are very rare. In this work we evaluate the kL in IR NLO multicomponent chalcogenides LixAg1-xGayIn1-ySe2 with a smooth change in the composition x and y by using machine learning approach and laser flash measurements, combined with available experimental results. The found patterns of kL dependence on atomic mass, bond length and electronegativity provide an effective understanding for navigation in the process of searching for new chalcogenide crystals with an optimal set of parameters that allow them to be effectively used as a frequency converter of laser radiation in the IR range. Moreover, the compositions Li0.5Ag0.5GaSe2, Li0.81Ag0.19InSe2 and AgGa0.5In0.5Se2 are demonstrated to exhibit a balanced combination of the parameters kL, NLO effects, energy band gaps, and birefringence for IR NLO applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989334","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pyrazolate-based MOFs with open Zn2+ sites for highly effective and rapid adsorption of iodine in water","authors":"Xin-Dan Zhang, Yong-zheng Zhang, Tingting Li, Yu-Xiang Zuo, Xiao-Nan Li, Da-Shuai Zhang, Longlong Geng, Bin Wang, Hongliang Huang, Xiuling Zhang","doi":"10.1039/d4qi03110e","DOIUrl":"https://doi.org/10.1039/d4qi03110e","url":null,"abstract":"Capturing radioactive iodine from water is a critical challenge in nuclear waste management and environmental conservation, necessitating the development of superior adsorbents. In this work, we introduce pyrazolate-based metal-organic frameworks (MOFs) as highly efficient adsorbents for iodine capture from aqueous solutions. We synthesized two novel Zn-triazolate MOFs, [Zn3(HTPPA)2(CH3COO)2] (DZU-109) and [Zn7(OH)2(TPPA)4(H2O)] (DZU-110), utilizing the tris(4-(1H-pyrazol-4-yl)phenyl)amine (H3TPPA) ligand and Zn2+ ions, employing a modulator-induced synthesis approach. SCXRD analysis revealed structural diversities in the two MOFs, attributed to the conformational flexibility of the triazolate ligand and the distinct coordination modes of Zn-building units. In a static I3− (I2/KI in water) adsorption setup, DZU-110 outperformed DZU-109, achieving an adsorption capacity of 2.31 g g−1 and a rate of 3.08×10−2 g mg−1 min−1, establishing a new benchmark among pristine MOFs in iodine capture from water. DZU-110 also displayed remarkable removal efficiency and adsorption capacity in dynamic flow-through conditions. Mechanistic investigations indicate that the synergistic action of pyrazolate rings and open Zn2+ sites in DZU-110 is pivotal for I3− adsorption, enabling various interactions such as I···Zn, I···π, I···H and I···N between the framework and iodine species. This study not only offers a valuable strategy for the synthesis and structural modulation of pyrazolate-based MOFs but also underscores the potential of these materials as promising candidates for iodine adsorption in water purification processes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"30 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selenoborates: A Latent Structure Resource for Infrared Functional Crystal Materials","authors":"Yihan Yun, Abudukadi Tudi, Zhihua Yang, Guangmao Li, Shilie Pan","doi":"10.1039/d4qi02770a","DOIUrl":"https://doi.org/10.1039/d4qi02770a","url":null,"abstract":"Optoelectronic functional crystal materials are crucial components in laser systems and could be applied as polarized light converters, modulators, photorefractive devices, and window materials etc. Borates and chalcogenides are well-established source of ultraviolet (UV) and infrared (IR) optoelectronic functional crystal materials. The selenoborate system, which merges the structural diversity of borates and extensive optical transmission range of metal selenides, holds promise as IR functional materials. While, research on selenoborates remains limited. This review aims to stimulate further research into IR optoelectronic functional crystal materials within the selenoborate system. Firstly, this work offers a comprehensive review of all selenoborates (21) reported to date, categorized according to their structural motifs from zero to three dimensions. Secondly, the unique synthesis methods of selenoborates were summarized. Additionally, first-principles calculations are utilized to analyze the bandgaps of these materials. As a result, it is concluded that selenoborates possess considerable potential for further investigation as IR functional materials, especially in terms of the structure and properties regulated by excellent microstructural groups.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"27 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Phosphorus ring expansion at cobalt: targeted synthesis of P4, P5, and P7 ligands","authors":"Karolina Trabitsch, Sebastian Hauer, Kai Schwedtmann, Philipp Royla, Jan J Weigand, Robert Wolf","doi":"10.1039/d4qi02683g","DOIUrl":"https://doi.org/10.1039/d4qi02683g","url":null,"abstract":"We report the synthesis of extended polyphosphorus ligands through the condensation of CoP&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt; and CoP&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt; frameworks with P&lt;small&gt;&lt;sub&gt;1&lt;/sub&gt;&lt;/small&gt; and P&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt; units. Tetraphosphido complexes [(L)Co(CN)(η&lt;small&gt;&lt;sup&gt;3&lt;/sup&gt;&lt;/small&gt;-P&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;R&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;)] (&lt;strong&gt;1a-R&lt;/strong&gt;: L = PHDI; R = Cy, Ph; &lt;strong&gt;1b-R&lt;/strong&gt;: L = Ar*BIAN; R = Cy, N(&lt;em&gt;i&lt;/em&gt;Pr)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;) were obtained by treatment of the anionic &lt;em&gt;cyclo&lt;/em&gt;-P&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt; complexes [&lt;em&gt;n&lt;/em&gt;Bu&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;N][(PHDI)Co(CN)(η&lt;small&gt;&lt;sup&gt;3&lt;/sup&gt;&lt;/small&gt;-P&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;)] (&lt;strong&gt;H&lt;/strong&gt;, PHDI = bis(2,6-diisopropylphenyl)phenanthrene-9,10-diimine) and [K(18c 6)][(Ar*BIAN)Co(CN)(η&lt;small&gt;&lt;sup&gt;3&lt;/sup&gt;&lt;/small&gt;-P&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;)] (&lt;strong&gt;I&lt;/strong&gt;, BIAN = 1,2-bis(arylimino)acenaphthene diimine with aryl being 2,6-dibenzhydryl-4-isopropylphenyl) with diorganochlorophosphanes (R&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;PCl, R = Cy, Ph, or &lt;em&gt;i&lt;/em&gt;Pr&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;N). Similar reactions of the &lt;em&gt;cyclo&lt;/em&gt;-P&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt; complex [K(18c-6)][(Ar*BIAN)Co(η&lt;small&gt;&lt;sup&gt;4&lt;/sup&gt;&lt;/small&gt;-P&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;)] (&lt;strong&gt;K&lt;/strong&gt;) yielded pentaphosphido complexes [K(18c-6)][(Ar*BIAN)Co(η&lt;small&gt;&lt;sup&gt;4&lt;/sup&gt;&lt;/small&gt;-P&lt;small&gt;&lt;sub&gt;5&lt;/sub&gt;&lt;/small&gt;R&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;)] (&lt;strong&gt;2b-R&lt;/strong&gt;; R = &lt;em&gt;t&lt;/em&gt;Bu, N(&lt;em&gt;i&lt;/em&gt;Pr)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;). Importantly, we show that the previously reported cationic tetraphosphane [(L&lt;small&gt;&lt;sub&gt;C&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;P&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;][OTf]&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt; (&lt;strong&gt;G&lt;/strong&gt;[OTf]&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;, L&lt;small&gt;&lt;sub&gt;C&lt;/sub&gt;&lt;/small&gt; = 4,5-dimethyl-1,3-diisopropylimidazol-2-yl) can be used to introduce [L&lt;small&gt;&lt;sub&gt;C&lt;/sub&gt;&lt;/small&gt;‒P]&lt;small&gt;&lt;sup&gt;+&lt;/sup&gt;&lt;/small&gt; and [L&lt;small&gt;&lt;sub&gt;C&lt;/sub&gt;&lt;/small&gt;‒P]&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;&lt;small&gt;&lt;sup&gt;2+&lt;/sup&gt;&lt;/small&gt; units. Depending on the stoichiometry and reaction conditions, the reaction of &lt;strong&gt;G&lt;/strong&gt;[OTf]&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt; with complex &lt;strong&gt;H&lt;/strong&gt; furnishes complexes [(PHDI)Co(CN)(η&lt;small&gt;&lt;sup&gt;3&lt;/sup&gt;&lt;/small&gt;-P&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;L&lt;small&gt;&lt;sub&gt;C&lt;/sub&gt;&lt;/small&gt;)] (&lt;strong&gt;3a&lt;/strong&gt;) and [(PHDI)Co(CN)(η&lt;small&gt;&lt;sup&gt;3&lt;/sup&gt;&lt;/small&gt;-P&lt;small&gt;&lt;sub&gt;5&lt;/sub&gt;&lt;/small&gt;(L&lt;small&gt;&lt;sub&gt;C&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;)][OTf] (&lt;strong&gt;4a&lt;/strong&gt;OTf) with η&lt;small&gt;&lt;sup&gt;3&lt;/sup&gt;&lt;/small&gt; coordinated tetra- and pentaphosphido ligands. Expanding this strategy, the &lt;em&gt;cyclo&lt;/em&gt;-P&lt;small&gt;&lt;sub&gt;7&lt;/sub&gt;&lt;/small&gt; and &lt;em&gt;cyclo&lt;/em&gt;-P&lt;small&gt;&lt;sub&gt;5&lt;/sub&gt;&lt;/small&gt; complexes [(PHDI)Co(μ&lt;small&gt;&lt;sup&gt;3&lt;/sup&gt;&lt;/small&gt;:η&lt;small&gt;&lt;sup&gt;2&lt;/sup&gt;&lt;/small&gt;:η&lt;small&gt;&lt;sup&gt;2&lt;/sup&gt;&lt;/small&gt;,η&lt;small&gt;&lt;sup&gt;1&lt;/sup&gt;&lt;/small&gt;,η&lt;small&gt;&lt;sup&gt;1&lt;/sup&gt;&lt;/small&gt;-P&lt;small&gt;&lt;sub&gt;7&lt;/sub&gt;&lt;/small&gt;L&lt;small&gt;&lt;sub&gt;C&lt;/sub&gt;&lt;/small&gt;){W(CO)&lt;small&gt;&lt;sub&gt;5&lt;/sub&gt;&lt;/small&gt;}&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;] (&lt;strong&gt;5a","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"37 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987892","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Magnetic Field Enhances Interfacial Electron Redistribution to Promote Magnetoelectrocatalytic Hydrogen Evolution","authors":"Chong Liu, Lianqing Yu, Nannan Chen, Gege Tian, Haifeng Zhu","doi":"10.1039/d4qi02993c","DOIUrl":"https://doi.org/10.1039/d4qi02993c","url":null,"abstract":"The rational design of efficient and cost-effective electrocatalysts for the hydrogen evolution reaction (HER) presents significant challenges. Enhancing the overall performance of electrocatalytic reactions mainly focuses on optimizing catalytic materials and structures. Furthermore, the implementation of external magnetic fields may also effectively stimulate electron transportation. In this context, a novel method was introduced to enhance the HER efficiency of layered ferro-catalysts (Mo2C/Fe3C) by integrating intrinsic driving forces and non-contact field stimulation through both interface engineering and external magnetic fields. Experiments combined with theoretical calculations indicated that the built-in electric field (BEF) induced by the work function (WF) is beneficial to the redistribution of interfacial charge, thereby optimizing the Gibbs free energy of H*, which enhances HER activity. Moreover, the integration of an external magnetic field into the electrochemical system has been shown to enhance the catalytic performance further. A significant reduction in overpotential of approximately 25% was observed at a current density of 10 mA·cm-2 when subjected to a micromagnetic field of 50 mT, resulting in a decrease to 91 mV. The results show that the conductivity and interfacial charge transfer of ferromagnetic catalysts assisted by magnetic field are enhanced due to the negative magnetoresistive (MR) effect. Additionally, the Lorentz force facilitates the escape of hydrogen bubbles from the electrode surface, thereby contributing to the enhancement of reaction efficiency. This work presents a promising strategy for enhancing the catalytic activity of HER through the integration of electrical and magnetic stimuli.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"77 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of anion M-doped NiCoP (M = S, Se and N) as bifunctional catalysts for alkaline seawater and urea splitting","authors":"Han Zhao, Min Liu, Xiaoqiang Du, Xiaoshuang Zhang","doi":"10.1039/d4qi02766c","DOIUrl":"https://doi.org/10.1039/d4qi02766c","url":null,"abstract":"The current method of hydrogen generation by electrochemistry water splitting is widely accepted, but the oxygen evolution reaction (OER) at the anode involves 4 e- transfers making the kinetics slow and reducing the reaction efficiency. Two promising solutions are known, one is the exploration of robust and relatively low toxicity water splitting catalysts, and the other is the use of small molecules that can be easily oxidized to replace the OER, which results in a lower theoretical voltage at the anode and lower energy consumption. In this paper, anion M-doped NiCoP (M = S, Se and N) catalyst nanosheet arrays were in situ generated on nickel foam by hydrothermal and calcination methods, which showed not only superior hydrogen evolution reaction (HER) activity but also excellent urea oxidation reaction (UOR) performance in 1 M KOH solution containing urea. Specifically, to drive a current density of 100 mA cm-2, an overpotential of only 170 mV is required for HER, while only potential of 1.451 V is required for UOR; NiCoP-S also exhibits excellent HER performance in a 1 M KOH+ Seawater alkaline medium, with an overpotential of only 139 mV required to obtain a current density of 100 mA cm-2. Based on the excellent bifunctionality of NiCoP-S in urea, a urea electrolyser with NiCoP-S as anode and cathode requires only potential of 1.456 V to drive 10 mA cm-2. Density functional theory calculations confirmed that the doping of elements S, Se and N all altered the electron cloud distribution of NiCoP, enhanced the hydrogen adsorption ability and electrical conductivity of the electrode, and result in an promotion in the performance of the catalyst, with NiCoP-S having the best ΔGH* and metallicity. The work proposes a useful strategy for the preparation of novel bifunctional catalysts with superior performance.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988090","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multifunctions of carbon dots in CeO2/Cu2O complex catalyst for the regulation of carbon dioxide reduction","authors":"Xiong Yan, Jiacheng Li, Honglin Si, Haojie Xu, Hui Huang, Yang Liu, Zhenhui Kang","doi":"10.1039/d4qi02744b","DOIUrl":"https://doi.org/10.1039/d4qi02744b","url":null,"abstract":"For electrocatalytic reactions, the charge transfer is a very complex process and also closely related to the chemical reaction process. Herein, taking the CO2 reduction reaction (CO2RR) as an example, we report the regulation of the CeO2/Cu2O-carbon dots (Ce-Cu-CDs) on CO2RR, and show the roles of the multifunctions of CDs in this complex catalyst system. The CeO2/Cu2O (Ce-Cu) catalyst exhibits the faraday efficiency (FE) for methane exceeding 50 % across a wide potential range (-1.2 V - -1.7 V vs. RHE) in the CO2RR. The acquired Ce-Cu-CDs catalyst reveals the transformation route of CDs with the ability to store electrons and regulate the CO2RR process. The electrocatalytic performance test with Ce-Cu-CDs shows that the FE of methane is potential dependent after the addition of CDs. The combination of transient photovoltage, transient potential scanning, density functional theory calculations and in-situ infrared spectroscopy has elucidated the multifunctions of CDs in the regulation of route in CO2RR, including the enhanced charge storage, the weakening of CO2 activation, the reduction of CO2 adsorption, the increase of the energy barrier of the rate-determining step of CO2 conversion to methane, the reduction of slow electron transfer and the reduction of slow electron transfer, thus altering the path of CO2RR process. This work unveils the ability of CDs to regulate the pathway of complex electrocatalytic process and provides a new example for the application of CDs in electrochemical reactions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"83 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}