Inorganic Chemistry Frontiers最新文献

{"title":"Reconstruction and immobilization of polymolybdate induced by metal-organic coordination units for enhanced electrocatalytic hydrogen generation","authors":"Jingyi Ma, Zhihan Chang, Xue Xi, Juju Liang, Yuchun Lin, Yaling Zhu, Xiuli Wang","doi":"10.1039/d4qi02311k","DOIUrl":"https://doi.org/10.1039/d4qi02311k","url":null,"abstract":"Electrocatalytic water cracking for hydrogen evolution has drawn the concern from researchers owing to its high efficiency. Polymolybdate has excellent redox behaviors and O-rich surface, becoming attractive electrocatalytic materials. In this work, iso- and hetro-polymolybdate anions were introduced in the crystalline metal-organic coordination system as electrocatalytic electrode material for hydrogen evolution reaction. Semi-rigid bi-pyrazole bi-amide ligand was taken as the organic component, and four complexes were yielded under hydrothermal condition. The reconstruction and oriented immobilization of polymolybdate occur during the assembly of the architectures, owing to the potential template effect from the metal-organic units. This phenomenon influnce the distribution of active sites from polymolybdate. The discrete [AlMo6(OH)7O17]2- anions in complex 3 were immobilized among the directionally arranged metal-organic chains, and expose more active sites. The carbon cloth-based electrode modified by complex 3 possess obvious electrocatalytic activity by achieving a low overpotential of 17.0 mV at the current density of 10 mA cm-2 in 1 M KOH for hydrogen evolution reaction. Meanwhile, the overpotential can achieve 33.7 mV when the current density is 10 mA cm-2 in simulated seawater.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574347","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":"Lithium extraction by metal-organic frameworks","authors":"Zongsu Han, Joshua Rushlow, Yihao Yang, Jiatong Huo, Wei Shi, Hong-Cai Zhou","doi":"10.1039/d4qi02228a","DOIUrl":"https://doi.org/10.1039/d4qi02228a","url":null,"abstract":"The extraction of lithium has become increasingly critical due to the soaring demand for lithium-ion batteries, which power a wide range of products from smartphones to electric vehicles. Lithium, the lightest metal, boasts exceptional energy density, making it ideal for portable electronics and renewable energy storage solutions, addressing environmental pollution issues simultaneously. However, extracting and recycling lithium ion is highly challenging due to its low natural abundance, significant mining difficulties, and environmental concerns. Metal-organic frameworks (MOFs), with their intricate and designable structures as well as abundant and regulated pore environments, have emerged as promising candidates for lithium extraction. The tailored porous structures of MOFs could enable efficient lithium ion sieving and capture. This review aims to discuss the design principles of targeted MOFs and their lithium extraction capabilities, as well as the common analysis methods during these processes. We seek to provide a comprehensive summary of the field and promote the development of advanced materials for practical lithium extraction applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574321","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":"Strontium doping RuO2 electrocatalyst with abundant oxygen vacancies for boosting OER performance","authors":"Bei An, Xiaoqian Li, Yuan Lin, Fanfan Shang, Huijie He, Hairui Cai, Xiaoxiao Zeng, Weitong Wang, Shengchun Yang, Bin Wang","doi":"10.1039/d4qi02070g","DOIUrl":"https://doi.org/10.1039/d4qi02070g","url":null,"abstract":"Oxygen evolution reaction (OER) plays a crucial role as the anode reaction of electrolytic water in various applications. To date, it is still a great challenge to develop highly active and durable electrocatalysts for acidic electrolytic water. Herein, we highlight an effective strategy to regulate the oxidation state of Ru species and oxygen vacancies in RuO2 by introducing Sr heteroatom into its lattice based on the principle of charge equilibrium. The as-prepared Sr0.1RuOx exhibits excellent OER activity with an overpotential of 201 mV at the current density of 10 mA cm-2, which should be ascribed to the higher proportion of Ru4+ induced by Sr doping. Moreover, both experimental and theoretical calculations revealed that the introduced oxygen vacancies inhabited Ru to be overoxidized to Run>4+ during the OER process, thus enhancing the stability of Sr0.1RuOx. Therefore, the PEM electrolyzer by using Sr0.1RuOx as the anode catalyst can be operated for 240 hours at 10 mA cm-2 without obvious attenuation. This work presented an effective strategy to regulate the structure of the OER electrocatalysts with excellent performance.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562351","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":"Zero-dimensional cuprous halide scintillator with ultra-high anti-water stability for X-ray imaging","authors":"Jing-Ning Lv, Na Lin, Jia-Yi Zhang, Yu-Meng Liu, Li-Chuang Niu, Jie Shi, Xiao-Wu Lei, Zhi-Wei Chen","doi":"10.1039/d4qi02149e","DOIUrl":"https://doi.org/10.1039/d4qi02149e","url":null,"abstract":"Zero-dimensional (0D) cuprous organic–inorganic hybrid halides have emerged as a new kind of scintillator due to their high light yield and adjustable emission properties in the whole visible spectral range. However, their practical application in the radiation industry is seriously hindered by the instability of Cu<small>^I</small> ions under humid atmospheres and oxidizing environments. Herein, we designed a new Cu(<small>I</small>)-based halide of [CEOMTPP]<small>₂</small>Cu<small>₄</small>Br<small>₆</small> (CEOMTPP = ethoxycarbonylmethyl(triphenyl) phosphonium cation) containing a discrete [Cu<small>₄</small>Br<small>₆</small>]<small>²⁻</small> nanocluster, which displays strong broadband yellow light emission with near-unity photoluminescence quantum yield (PLQY) and large Stokes shift of 206 nm. Remarkably, [CEOMTPP]<small>₂</small>Cu<small>₄</small>Br<small>₆</small> shows ultra-high anti-water and anti-oxidation stability with steady emitting performance in water for over one year and in an acid–base aqueous solution for one day. Benefiting from the near-unity PLQY, large Stokes shift and negligible self-absorption, [CEOMTPP]<small>₂</small>Cu<small>₄</small>Br<small>₆</small> exhibits excellent scintillation properties with a high light yield of 69 500 phonon per meV and low detection limit of 113.0 <em>n</em>Gy s<small>⁻¹</small>. Furthermore, a high spatial resolution of 14.5 lp mm<small>⁻¹</small> is achieved in X-ray imaging based on a [CEOMTPP]<small>₂</small>Cu<small>₄</small>Br<small>₆</small>@EVA composite-assembled scintillation screen, demonstrating its potential application in medical photography. This research provides a fundamental structural engineering strategy to design highly efficient and stable low-dimensional Cu(<small>I</small>) halides for X-ray radiation application.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561973","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":"Moss-like CoB/CeO2 heterojunction as an efficient electrocatalyst for oxygen evolution reaction under alkaline conditions","authors":"Weijie Fang, Chaofan Liu, Jiang Wu, Weikai Fan, Le Chen, Zaiguo Fu, Lin Peng, Ping He, Jia Lin, Zhongwei Chen","doi":"10.1039/d4qi02325k","DOIUrl":"https://doi.org/10.1039/d4qi02325k","url":null,"abstract":"Heterostructure construction has become increasingly recognized as an effective strategy to enhance oxygen evolution reaction (OER) performance due to the exposed active surfaces and improved mass/charge transfer. Inspired by natural plant structures, this study develops a unique moss-like amorphous/crystalline (CoB/CeO2) heterojunction. This distinctive moss-like morphology facilitates the formation of staggered sheet structures in the catalyst, providing more active sites and open channels for reaction intermediates and gas release. Benefiting from the hydrophilic properties offered by the moss-like morphology, CoB/CeO2 exhibits excellent OER catalytic performance in 1M KOH, requiring only 247 mV at 100 mA cm−2. Physicochemical characterization and mechanistic studies reveal that the close nanoscale features between CoB and CeO2 create abundant binary interfaces, optimize the electronic configuration, induce changes in electronic states, and provide abundant defect sites, thereby enhancing charge transfer capabilities. This work presents a new paradigm for the design of efficient and durable OER electrocatalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561795","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":"A novel extra-broadband visible-emitting garnet phosphor for efficient single-component pc-WLEDs","authors":"Qianyi Chen, Zhenjie Lun, Dongdan Chen, Yongsheng Sun, Puxian Xiong, Siyun Li, Shanhui Xu, Zhongmin Yang","doi":"10.1039/d4qi01824a","DOIUrl":"https://doi.org/10.1039/d4qi01824a","url":null,"abstract":"The development of extra-broadband visible emission phosphors is crucial to achieve next-generation illumination with better color experience. Herein, a defect engineering strategy mediated by the structural cationic substitution is proposed and experimentally demonstrated for specific ultra-broadband emission in a garnet phosphor. The induced oxygen vacancies and interstitial cation through lattice distortion break the periodic potential field of the crystal and provide electronic levels in the band gap. As a result, excited by blue-light-emitting diodes, the novel Y<small>₃</small>Sc<small>₂</small>Al<small>₃</small>O<small>₁₂</small>:B<small>³⁺</small> shows an ultra-broad emission with a full width at half maximum (FWHM) of ∼170 nm. Compared to general defect-emitting phosphors, the unique Y<small>₃</small>Sc<small>₂</small>Al<small>₃</small>O<small>₁₂</small>:B<small>³⁺</small> exhibits excellent thermal quenching resistance and superior internal quantum efficiency of up to 95%. These findings not only show great promise of Y<small>₃</small>Sc<small>₂</small>Al<small>₃</small>O<small>₁₂</small>:B<small>³⁺</small> as an extra-broadband emitter but also provide a new design strategy to achieve a full-visible-spectrum phosphor in a single-component material for white-light applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561974","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":"Ni non-equivalent doped La-MOF toward enhanced photocatalytic CO2 reduction through oxygen vacancy regulation and electronic structure optimization","authors":"Tongzheng Zhang, Zhaohui Huang, Guanshun Xie, Le Liao, Changqiang Yu, Xiuqiang Xie, Nan Zhang","doi":"10.1039/d4qi02143f","DOIUrl":"https://doi.org/10.1039/d4qi02143f","url":null,"abstract":"Photocatalytic CO2 reduction holds promise for mitigating global warming and achieving carbon neutrality. Metal-organic frameworks (MOFs) are particularly promising as photocatalysts due to their ability to tune metal-oxo cluster electronic structures and facilitate CO2 adsorption. In this study, chemically stable La-MOF modified with Ni-doped metal-oxo clusters has been synthesized through a one-pot solvent-thermal reaction. The experimental and in-situ test results show that the introduction of Ni atoms leads to the formation of oxygen vacancies(VOs)induced by the unsaturated coordination of La/Ni-MOF, which facilitates the adsorption and activation of CO2. The electronic structure of metal oxo (La-O- ) clusters is also effectively regulated, which enhances electron-accepting ability of La-O clusters and promotes the photo-induced electron transfer from the lowest unoccupied molecular orbital (LUMO) of electron donor to the conduction band (CB) of La-MOF. In addition, the additional built-in metal atom (Ni) acts as an active site for CO2 adsorption and activation, achieving effective charge transfer and activated CO2 adsorption integrated construction. The synergy of these effects leads to the optimal La/Ni-MOF withCO selectivity of 96.8% and theyield of 669.3 μmol/g, which is 2.5-fold and more than 5-fold as high as that of the pure La-MOF and Ni-MOF, respectively. This work provides a facile but efficient approach for the construction of coordination unsaturated metal sites and VOs as well as the regulation of the electronic structure of MOFs as efficient photocatalysts towards enhanced performances.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556007","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":"Enhancing CO2 Electroreduction with Decamethylcucurbit[5]uril-Alkaline Earth Metal Modified Pd Nanoparticles","authors":"Tao Shao, Xianmeng Song, Zongnan Wei, Shuaibing Yang, Siying Zhang, Rong Cao, Minna Cao","doi":"10.1039/d4qi02135e","DOIUrl":"https://doi.org/10.1039/d4qi02135e","url":null,"abstract":"Electrochemical CO2 reduction reaction (CO2RR) offers a promising pathway to convert CO2 into value-added chemicals, with CO production being a primary target. While the conversion of CO2 to CO hinges on the delicate balance of *COOH and *CO binding energies, this study introduces a series of Pd-based hybrid catalysts, Me10CB[5]-M/Pd (M=Sr, Ca, Cd), to address this challenge. The catalysts were synthesized via thermal treatment of supramolecular precursors formed by Me10CB[5], M2+, and [PdCl4]2- ions. Notably, Me10CB[5]-Sr/Pd exhibited exceptional CO selectivity (91.3% FECO at -0.7 V vs. RHE) and long-term stability. The incorporation of Me10CB[5]-Sr into the Pd catalyst system enhanced CO2 adsorption, modulated the electronic structure of Pd, and optimized the adsorption/desorption energies of critical intermediates, ultimately leading to superior CO2RR performance. This work underscores the potential of supramolecular engineering in designing high-performance electrocatalysts for CO2 conversion.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556006","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":"A novel cerium-based metal-organic framework supported Pd catalyst for semi-hydrogenation of phenylacetylene","authors":"Xiangdi Zeng, Zi Wang, Meng He, Wanpeng Lu, Wenyuan Huang, Bing An, Jiangnan Li, Li Mufan, Ben Spencer, Sarah Day, Floriana Tuna, Eric J L McInnes, Martin Schroder, Sihai Yang","doi":"10.1039/d4qi02225d","DOIUrl":"https://doi.org/10.1039/d4qi02225d","url":null,"abstract":"Phenylacetylene is a detrimental impurity in the polymerisation of styrene, capable of poisoning catalysts even at ppm levels and significantly degrading the quality of polystyrene. The semi-hydrogenation of phenylacetylene to styrene instead of ethylbenzene is, therefore, an important industrial process. We report a novel cerium(IV)-based metal-organic framework (denoted as Ce-bptc), which is comprised of {Ce6} clusters bridged by biphenyl-3,3’,5,5’-tetracarboxylate linkers. Ce-bptc serves as an ideal support for palladium nanoparticles and the Pd@Ce-bptc catalyst demonstrates an excellent catalytic performance for semi-hydrogenation of phenylacetylene, achieving a selectivity of 93% to styrene on full conversion under ambient conditions with excellent reusability. In situ synchrotron X-ray powder diffraction and electron paramagnetic resonance spectroscopy revealed the binding domain of phenylacetylene within Ce-bptc and details of the reaction mechanism.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542215","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":"Reversible on–off switching of a single-chain magnet via single-crystal-to- single-crystal transition- and light-induced metal-to-metal electron transfer","authors":"Meng-Jia Shang, Han-Han Lu, Qiang Liu, Ren-He Zhou, Hui-Ying Sun, Zhen Shao, Liang Zhao, Yin-Shan Meng, Tao Liu","doi":"10.1039/d4qi01691b","DOIUrl":"https://doi.org/10.1039/d4qi01691b","url":null,"abstract":"The development of single-chain magnets with reversible and adjustable properties is of great significance for achieving high-density information storage and switching devices with multi-stimuli responsiveness whilst remains a challenging task. In this work, we synthesized a new cyano-bridged {Fe<small>₂</small>Co}-based coordination polymer, {[(<small>^Pz</small>Tp)Fe(CN)<small>₃</small>]<small>₂</small>Co(Ipi)<small>₂</small>}·2MeOH·0.5H<small>₂</small>O (<strong>1·solv</strong>; <small>^pz</small>Tp, tetra-kis(1-pyrazolyl)borate; Ipi, 1-(4-iodophenyl)-1H-imidazole). <strong>1·solv</strong> displayed reversible metal-to-metal electron transfer (MMET) between Fe<small>^III</small><small>_LS</small>(<em>μ</em>-CN)Co<small>^II</small><small>_HS</small>(<em>μ</em>-NC)Fe<small>^III</small><small>_LS</small> (LS, low spin; HS, high spin) and Fe<small>^III</small><small>_LS</small>(<em>μ</em>-CN)Co<small>^III</small><small>_LS</small>(<em>μ</em>-NC)Fe<small>^II</small><small>_LS</small> states under alternating irradiations with 808 and 532 nm lasers, respectively, as verified by photomagnetic and <em>in-situ</em> photo-monitored X-ray diffraction studies. The bidirectional light irradiations induced significant changes in magnetic anisotropy and intrachain exchange interactions, demonstrating the on/off switching of single-chain magnet (SCM) behavior by 808 and 532 nm light irradiations. <strong>1·solv</strong> underwent a thermally induced single-crystal to single-crystal (SCSC) phase transition to a desolvated {[(<small>^Pz</small>Tp)Fe(CN)<small>₃</small>]<small>₂</small>Co(Ipi)<small>₂</small>} (<strong>1·desolv</strong>) phase, accompanying with the MMET. Magnetic susceptibilities measurements indicated that <strong>1·desolv</strong> exhibited thermally induced incomplete MMET behavior and field-induced nanomagnet behavior. <strong>1·desolv</strong> also displayed a substantial dielectric anomaly during the electron transfer process, presenting a new case showing the synergetic switching of dielectric and magnetic properties. Interestingly, <strong>1·desolv</strong> can revert to the solvated phase <strong>1·resolv</strong> after soaking in the mother liquor, whose SCM behavior was erased by the reversible SCSC transition. This study provides a new approach for the swift and reversible control of SCM behavior via both SCSC transition and light-induced MMET.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541124","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}