Inorganic Chemistry Frontiers最新文献_第2页

Effective electrocatalysts for hydrogen production from acetic acid by screening of monodentate ligands in cationic diiron hetero-carbyne complexes

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-23 DOI: 10.1039/d4qi02479f

Lorenzo Biancalana, Isacco Gualandi, Stefano Zacchini, Giulia Martelli, Erika Scavetta, Valerio Zanotti, Rita Mazzoni, Fabio Marchetti

{"title":"Effective electrocatalysts for hydrogen production from acetic acid by screening of monodentate ligands in cationic diiron hetero-carbyne complexes","authors":"Lorenzo Biancalana, Isacco Gualandi, Stefano Zacchini, Giulia Martelli, Erika Scavetta, Valerio Zanotti, Rita Mazzoni, Fabio Marchetti","doi":"10.1039/d4qi02479f","DOIUrl":"https://doi.org/10.1039/d4qi02479f","url":null,"abstract":"The development of efficient electrocatalysts for proton reduction (H2 production) based on earth-abundant metals is a scientific challenge with implications for energy storage and generation. Inspired by [FeFe]-hydrogenase enzymes, several compounds based on the {Fe2Cp2(CO)2} framework have been investigated in this respect but, to date, only two charge-neutral derivatives, with a terminal cyanide and a bridging dimethylamino- (CNMe2+) or methylthio- (CSMe+) carbyne ligand, were found to be effective electrocatalysts. Herein, we extended the investigation to related cationic derivatives with the cyanide ligand being replaced with various monodentate, hydrophilic N- P- or S-donor ligands. Aminocarbyne complexes [Fe2Cp2(CO)(L)(µ-CO)(µ-CNMe2)]+ (L = NH3, [2a]+; imidazole, [2b]+; pyrazole, [2c]+; thiourea, [2d]+; 1,3,5-triaza-7-phosphadamantane, PTA, [2e]+) and thiocarbyne complexes [Fe2Cp2(CO)(L)(µ-CO)(µ-CSMe)]+ (L = imidazole, [4b]+; PTA, [4e]+; 4-dimethylaminopyridine, DMAP, [4f]+; MeCN [4g]+), five of which are unprecedented, were prepared, isolated as triflate salts and characterized by IR and NMR spectroscopy and X-Ray diffraction in two cases. These nine diiron compounds were screened by cyclic voltammetry for their redox chemistry in acetonitrile and the electrocatalytic activity in the H2 evolution reaction from acetic acid. Two thiocarbyne complexes, featuring imidazole ([4b]+) and DMAP ([4f]+) as monodentate ligands emerged for their remarkable electrocatalytic activity, outperforming the previously-investigated cyanide derivatives. A mechanism for the electrocatalytic cycle is proposed based on combined electrochemical, NMR and literature data.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"64 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874669","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}

引用次数: 0

Ultrahigh Energy Storage Density in a Lead-Free Bi0.5Na0.5TiO3-Based Relaxor Ferroelectric Ceramics under Moderate Electric Fields by Manipulating Phase Fraction

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-20 DOI: 10.1039/d4qi02642j

Jiangtao fan, Lingxiang Wang, Jiaxin Wang, Zheng Chen, Langxiang Zhong, Tiantian Yang, Zhanggui Hu

引用次数: 0

Increasing Excited State Lifetimes of Cu(I) Coordination Complexes via Strategic Surface Binding

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-19 DOI: 10.1039/d4qi02410a

Jiaqi Chen, Henry C. London, Dhruba Pattadar, Charlotte Worster, Sahan R. Salpage, Elena Jakubikova, S. Scott Saavedra, Kenneth Hanson

{"title":"Increasing Excited State Lifetimes of Cu(I) Coordination Complexes via Strategic Surface Binding","authors":"Jiaqi Chen, Henry C. London, Dhruba Pattadar, Charlotte Worster, Sahan R. Salpage, Elena Jakubikova, S. Scott Saavedra, Kenneth Hanson","doi":"10.1039/d4qi02410a","DOIUrl":"https://doi.org/10.1039/d4qi02410a","url":null,"abstract":"Molecules undergo a structural change to minimize the energy of excited states generated via external stimuli such as light. This is particularly problematic for Cu(I) coordination complexes which are an intriguing alternative to the rare and expensive transition metal containing complexes (e.g., Pt, Ir, Ru, etc.) but suffer from short excited state lifetimes due to D2d to D2 distortion and solvent coordination. Here we investigate strategic surface binding as an approach to hinder this distortion and increase the excited state lifetime of Cu(I) polypyridyl complexes. Using transient absorption spectroscopy, we observe a more than 20-fold increase in excited state lifetime, relative to solution, for a Cu(I) complex that can coordinate to the ZrO2 via both carbox-ylated ligands. In contrast, the Cu(I) complex that coordinates via only one ligand has a less pronounced enhancement upon surface binding and exhibits greater sensitivity to coordinating solvents. A combination of ATR-IR and polarized visible ATR measurements as well as theoretical calculations suggest that the increased lifetime is due to surface binding which decreases the degrees of freedom for molecular distortion (e.g., D2d to D2), with the doubly bound complex exhibiting the most pronounced enhancement.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"54 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142848896","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}

引用次数: 0

Highly sensitive terbium-based metal–organic framework scintillators applied in flexible X-ray imaging

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-19 DOI: 10.1039/d4qi02736a

Peng-Kun Wang, Wen-Fei Wang, Bao-Yi Li, Rui-Xuan Qian, Zhao-Xing Gao, Shuai-Hua Wang, Fa-Kun Zheng, Guo-Cong Guo

{"title":"Highly sensitive terbium-based metal–organic framework scintillators applied in flexible X-ray imaging","authors":"Peng-Kun Wang, Wen-Fei Wang, Bao-Yi Li, Rui-Xuan Qian, Zhao-Xing Gao, Shuai-Hua Wang, Fa-Kun Zheng, Guo-Cong Guo","doi":"10.1039/d4qi02736a","DOIUrl":"https://doi.org/10.1039/d4qi02736a","url":null,"abstract":"Scintillators have played an indispensable role in public security and medical diagnosis fields due to their ability to convert X-ray photons into visible light. Metal–organic frameworks (MOFs) have the advantages of designable structures, easy preparation of flexible films and high stability, and hence show great potential in the field of scintillation. However, research on flexible X-ray imaging based on MOF scintillators has been rather limited. The exploration and development of MOF-based flexible scintillation screens would be very promising and exciting. Here, a novel terbium-based MOF (Tb-MOF-1) scintillator was synthesized and employed for X-ray detection and imaging. Benefiting from the sensitizing effect of the ligand, Tb-MOF-1 shows excellent photoluminescence and radioluminescence signals, and its scintillation sensitivity is much higher than that of the commercial scintillator Bi4Ge3O12 (BGO). Tb-MOF-1 shows a low X-ray detection limit of 1.71 μGy s−1, which is lower than the demand for medical diagnosis of 5.5 μGy s−1. The scintillation mechanism of Tb-MOF-1 is substantiated using spectroscopy and theoretical calculations. Furthermore, the robust structure of Tb-MOF-1 brings its strong tolerance against water and X-ray dosages, which facilitates its long-term operation. A flexible scintillation screen (Tb-MOF-screen) derived from Tb-MOF-1 was fabricated, achieving a high spatial resolution of 7.7 lp mm−1@MTF 0.2. Ultimately, flexible X-ray imaging tests were successfully carried out by tightly fitting the Tb-MOF-screen to different curvature radii wires, which firstly verifies the X-ray imaging potential of Ln-MOF-based scintillation screens for non-planar objects.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"51 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142848899","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}

引用次数: 0

Tin Chalcohalide Sn11(PS4)4I10 Obtained by Structural-template-oriented Synthesis: Exhibiting Balanced Infrared Nonlinear Optical Performance

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-19 DOI: 10.1039/d4qi02753a

Cuier Deng, Xi Xu, Yu-Yan Hu, Jing-Yu Guo, Li-Ming Wu, Ling Chen

引用次数: 0

Ingenious double-modified strategy to prepare “hexagonal warrior” separator for lithium metal batteries

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-18 DOI: 10.1039/d4qi02357a

Shitong Sun, Bo Jin, Hui Liu, Qing Jiang

{"title":"Ingenious double-modified strategy to prepare “hexagonal warrior” separator for lithium metal batteries","authors":"Shitong Sun, Bo Jin, Hui Liu, Qing Jiang","doi":"10.1039/d4qi02357a","DOIUrl":"https://doi.org/10.1039/d4qi02357a","url":null,"abstract":"Lithium metal batteries (LMBs) represent the favorable option for the new-generation high-energy-density batteries. Nevertheless, LMBs utilizing the merchant separators consistently encounter some issues including the irregular development of lithium dendrites, bulk fluctuation of lithium anode, and excessive electrolyte consumption. In this study, we innovatively coat the double-side of commercial polypropylene (PP) separator with an electrostatically assembled composite of CoMo-layered double hydroxide (CoMo-LDH) hollow polyhedra and high crystallinity graphitic carbon nitride to enhance the electrochemical properties of separator. The CoMo-LDH has a certain effect on accommodating the bulk variation throughout Li deposition/stripping procedure. Additionally, the triazine-based structure of graphitic carbon nitride synthesized by the molten salt assisted approach introduces Cl– to regulate the ion selectivity in separator and promotes the uniform plating of Li+. Satisfactorily, it is demonstrated that the double-modified PP (DMP) separator exhibits a significantly improved ionic conductivity (1.11 mS cm–1) and Li+ transference number (0.75) compared to conventional PP separator. In-situ puncture experiment of lithium dendrites reveals that the DMP separator withstands a lithium deposition capacity of 17 mAh cm–2. Furthermore, the DMP-equipped Li//LFP full-cell delivers a primary discharge capacity of 149 mAh g–1 and maintains 96.6% for the capacity retaining rate after 100 cycles at 0.2 C. Fortunately, after 500 cycles at 1 C, a retention rate of 94.1% is still achieved. Meantime, Li//NCM523 full-cell assembled with DMP separator exhibits a good electrochemical performance at 0.2 C. This work exhibits the universality and practicality of DMP separator as well as offers a dependable solution for restraining the development of lithium dendrites for LMBs. Furthermore, this solution would also be used to other alkali metal anodes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"27 1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142848902","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}

引用次数: 0

The Shastry-Sutherland lattice in two-dimensional magnetic lanthanide metal-organic frameworks†

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-18 DOI: 10.1039/d4qi02396j

Jing Li, Xiao Sun, Peiqiong Chen, Ruiqin Huang, Suyuan Zeng, Hou-Ting Liu, Yibo Han, Yi-Quan Zhang, Haiquan Tian

{"title":"The Shastry-Sutherland lattice in two-dimensional magnetic lanthanide metal-organic frameworks†","authors":"Jing Li, Xiao Sun, Peiqiong Chen, Ruiqin Huang, Suyuan Zeng, Hou-Ting Liu, Yibo Han, Yi-Quan Zhang, Haiquan Tian","doi":"10.1039/d4qi02396j","DOIUrl":"https://doi.org/10.1039/d4qi02396j","url":null,"abstract":"Two-dimensional magnetic lanthanide materials are highly sought after in the advancement of spintronic devices featuring atomic-thin structures. While the Shastry-Sutherland (SS) lattice presents a promising platform for such materials, its application in metal-organic systems has been constrained by synthetic complexities. Here, we developed a highly effective method to achieve the required metal-organic compound of the SS lattice through post-synthetic modification of dimer compounds, following the distinctive conjugated dihydrazide-bridged orthogonal-dimer structure. The resulting compound, DyCl2 (ppch)0.5∙2DMF, (H2ppch = N'-(pyrazine-2-carbonyl)pyrazine-2-carbohydrazide, PH-Dy), exhibited a distorted SS lattice. Notably, the easy axis of the Dy(III) ion was nearly perpendicular to the two-dimensional plane, fostering the coexistence of ferromagnetic and antiferromagnetic interactions within the structure. Furthermore, the compound demonstrates complex slow relaxation of magnetization. Theoretical computations revealed that the magnetic interactions arising from the polymerization of dimers significantly affect the relaxation dynamics of PH-Dy. This work provides a novel approach for synthesizing two-dimensional magnetic compounds, thereby paving the way for advanced materials in the field.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"25 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841700","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}

引用次数: 0

A tandem nanoreactor constructed by coating Cu2O on the surface of single-atom catalyst Ni-NC3 for electroreduction of CO2 to C2 products

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-18 DOI: 10.1039/d4qi02713b

Cheng-Peng Liang, Jia-Run Huang, Pei-Qin Liao, Xiao-Ming Chen

引用次数: 0

Stimuli-responsive gold–polyoxometalate multielectron transformers

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-18 DOI: 10.1039/d4qi02988g

Kirill Monakhov

引用次数: 0

Simultaneous synthesis of oxygen doped carbon electrode at anode and cathode via potential cycling for promoted H2O2 electrosynthesis

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-18 DOI: 10.1039/d4qi02539c

Suhua Mao, Xin Li, Bingshuang Li, Jin Li, Xiaoxi Huang

{"title":"Simultaneous synthesis of oxygen doped carbon electrode at anode and cathode via potential cycling for promoted H2O2 electrosynthesis","authors":"Suhua Mao, Xin Li, Bingshuang Li, Jin Li, Xiaoxi Huang","doi":"10.1039/d4qi02539c","DOIUrl":"https://doi.org/10.1039/d4qi02539c","url":null,"abstract":"Oxygenated groups functionalized carbon materials are promising catalysts for the electrochemical production of hydrogen peroxide (H2O2) via two-electron oxygen reduction reaction (ORR). Electrochemical activation of carbon materials to introduce oxygenated groups has exhibited attractive features compared with chemical oxidation method. However, the knowledge is limited as to how electrochemical treatment influences the resulting ORR performance. Herein, we describe the synthesis of carbon electrodes modified with oxygenated groups at both anodic and cathodic sides by using potential cycling in neutral Na2SO4 solution. Composition analysis based on XPS and electrochemical FTIR indicates the successful modification of oxygenated groups. The production rate of H2O2 is significantly enhanced after potential cycling. The oxidized carbon electrode can catalyze ORR at an industrial-current-density to produce H2O2 with selectivity close to 100% in a flow cell. Density functional theory (DFT) calculations demonstrate that the binding energy of *OOH is promoted after modification of oxygenated groups. These findings highlight the advantages of the electrochemical method on carbon surface functionalization and provide some guidelines for catalyst design.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"259 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142848898","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}

引用次数: 0