Ziyi Shui, Huiying Tian, Hang Mu, Liuyun Xu, Xiaoming Gao, Xi Chen
{"title":"Mn doping regulating electronic structure of Co3O4 to construct dual active sites for Oxygen electrocatalysis","authors":"Ziyi Shui, Huiying Tian, Hang Mu, Liuyun Xu, Xiaoming Gao, Xi Chen","doi":"10.1039/d4qi03005b","DOIUrl":"https://doi.org/10.1039/d4qi03005b","url":null,"abstract":"Efficient bifunctional catalysts for oxygen reduction reactions (ORR) and oxygen evolution reactions (OER) are crucial for rechargeable Zn-air batteries (ZABs). However, these catalysts often suffer from poor O<small><sub>2</sub></small> conversion efficiency and a lack of dual active sites for oxygen reactions. Regulating electronic structure through element doping is an efficient solution to construct dual active sites of catalysts. Nevertheless, the mechanisms of O<small><sub>2</sub></small> adsorption/activation, the nature of the reaction active sites, and the associated energy barriers remain poorly understood. Herein, we report on a Mn-doped Co<small><sub>3</sub></small>O<small><sub>4</sub></small> (MnCo<small><sub>2</sub></small>O<small><sub>4</sub></small>) bimetallic oxide. The impact of Mn doping on the ORR/OER performance of Co<small><sub>3</sub></small>O<small><sub>4</sub></small> is investigated by both density functional theory (DFT) calculations and experimental methods. The DFT findings indicate that Mn doping modifies the electronic structure, activates Co sites in Co<small><sub>3</sub></small>O<small><sub>4</sub></small>, and introduces new Mn active sites, resulting in dual active sites for OER/ORR. As predicted, MnCo<small><sub>2</sub></small>O<small><sub>4</sub></small> exhibits remarkable ORR/OER performance, with a potential difference (ΔE) as low as 0.87 V, which is 0.11 V smaller than that of Co<small><sub>3</sub></small>O<small><sub>4</sub></small>. Furthermore, Rechargeable ZAB delivers a narrow discharge-charge voltage gap (0.76 V), high cycle stability over long periods (90 h), and outputs a peak power density of up to 97 mW·cm<small><sup>-2</sup></small> in a liquid system. Such excellent results demonstrate that Mn-Co bimetallic synergistic catalysis is an effective strategy for improving ORR/OER selectivity.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"40 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258369","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}
Songlin Yan, Weihong Liu, Jianjun Long, Kun Wang, Qilu Yao, Gang Feng, Zhang-Hui Lu
{"title":"Photothermal conversion enhances selective hydrogenation over MOF-derived Cu-MoO2 interfaces at ambient condition","authors":"Songlin Yan, Weihong Liu, Jianjun Long, Kun Wang, Qilu Yao, Gang Feng, Zhang-Hui Lu","doi":"10.1039/d4qi03188a","DOIUrl":"https://doi.org/10.1039/d4qi03188a","url":null,"abstract":"The selective hydrogenation of nitroaromatic compounds to produce phenylamines plays a crucial role in various industrial processes. Here we introduce a Cu-MoO2@C catalyst which is synthesized by pyrolyzing a polyoxometalate-based metal-organic framework (POMOF), exhibiting remarkable catalytic efficiency in the selective hydrogenation of nitroaromatics. Specifically, nearly 100% conversion and 97% selectivity in hydrogenation of 4-nitrostyrene (4-NS) to 4-aminostyrene (4-AS) was achieved over Cu-MoO2@C catalyst under light irradiation. This promoted yield of 4-AS is ascribed to the plasmonic photothermal effect of Cu nanoparticles (NPs) which facilitate efficient photothermal conversion, as well as the strong electronic interactions at Cu/MoO2 interfaces which facilitate the selective reduction of the N=O bond and minimizing reduction of the C=C bond. Furthermore, the Cu-MoO2@C catalyst demonstrates outstanding stability, maintaining high catalytic activity across eight cycles with minimal performance degradation. Its versatility was evidenced by the effective hydrogenation of a variety of nitroaromatic substrates containing different reducible functional groups. This study underscores the potential of Cu-MoO2@C as an efficient, stable, and adaptable catalyst for the selective hydrogenation of nitroaromatic compounds, presenting a promising solution for industrial applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"44 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258364","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":"Reconfiguring the helmholtz plane with a trace polar additive for highly reversible Zinc anodes","authors":"Yu Lu, Yanxin Wang, Chenyang Guo, Mingyue Chen, Kunyu Hao, Pengcheng Qi, Yiwen Tang","doi":"10.1039/d5qi00035a","DOIUrl":"https://doi.org/10.1039/d5qi00035a","url":null,"abstract":"The performance stability of aqueous zinc-ion batteries (AZIBs) is closely linked to the properties of the inner Helmholtz plane (IHP) at the zinc anode/electrolyte interface. Excessive reactive H2O in the IHP significantly contributes to side reactions, including hydrogen evolution, passivation, and zinc dendrites formation. Here, a trace additive with abundant polar functional groups, thioacetamide (TAA), is introduced to modify the internal structure of the IHP and enhance the stability of zinc anodes. Both theoretical calculations and experiments demonstrate that TAA preferentially adsorbs onto the IHP at the zinc surface, reducing the decomposition of active H2O and suppressing side reactions. TAA also facilitates the uniform deposition of Zn2+ ions on the (002) crystal plane, effectively preventing dendrite formation. Consequently, the addition of 10 mM TAA to the ZnSO4 electrolyte significantly boosts the reversibility of zinc, achieving an improvement of nearly 13 times compared to the pure ZnSO4 electrolyte. Furthermore, the Zn||V6O13 full cell with the optimized electrolyte maintains excellent stability after 2000 cycles 3 A g-1, surpassing the performance of the pure ZnSO4 electrolyte.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258366","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":"Design, analysis, and application of metal–organic framework derived carbons","authors":"Joshua Andrew Powell, Yihao Yang, Hong-Cai Zhou","doi":"10.1039/d4qi03205e","DOIUrl":"https://doi.org/10.1039/d4qi03205e","url":null,"abstract":"Metal-organic framework-derived carbons (MOFdCs) have emerged as a rapidly growing class of porous materials over the past 15 years. Inspired by the principles of templated synthesis used in organic chemistry and nanomaterials, MOFdCs combine the highly tunable features of metal-organic frameworks with the versatility and stability of traditional porous carbon materials. Although many advances in MOFdC applications have been driven by an exploratory approach, there is a growing body of systematic, hypothesis-driven studies of the underlying chemistry and materials science of MOFdC structure, design, and structure-property relationships. This review summarizes developments in the systematic design and characterization of MOFdCs and strategies developed to control the structure of these materials. The role of variables such as pyrolysis temperature, gas environment, and the atomic- and nanoscale structure of the template MOF are described, with particular emphasis on their relationship to MOFdC structure and applications. By focusing on the fundamental principles underpinning MOFdC design, this work will lead to more rationally designed MOFdC materials and greater efficiencies in the development of MOFdCs for a host of applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"79 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258368","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":"Multicolor Mechanoluminescence for Integrated Dual-mode Stress and Temperature Sensing","authors":"Pengfei Zhang, Ziyi Guo, Zhiting Wei, Wenbo Chen, Qinping Qiang, Bitao Liu, Tianchun Lang, Lingling Peng, Wenjie Wang, Lei Zhao","doi":"10.1039/d4qi03338h","DOIUrl":"https://doi.org/10.1039/d4qi03338h","url":null,"abstract":"The advancements of the new industrial era demand higher standards for integrated intelligent sensors. These multi-parameter coupling sensors require sensing materials that can swiftly respond to various physical stimuli, including stress, temperature, and humidity et al. Mechanoluminescence (ML), with its unique mechanical-optical response, serves as an effective medium for stress sensing. In ML materials, constructing multiple luminescent centers not only enables multicolor ML but also allows for temperature sensing through the differential thermal quenching properties of various luminescent centers. In this study, we present an energy transfer strategy that leverages high-energy blue-emitting ML from the host material, combined with Tb3+ and Mn2+, to achieve multicolor ML. The mechanical response is correlated with the integrated intensity of ML, while the temperature response is governed by the dynamic ML intensity ratio of ITb/IMn. This approach simplifies the design of multifunctional sensors and facilitates remote, dual-mode sensing. Moreover, we develop a highly secure encryption system based on the integration of multicolor PL and ML, with an ML-triggering mechanism that is both convenient and reliable. This work presents an effective strategy for developing multicolor ML materials and advancing multimodal sensing.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"27 2 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192617","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}
Wei Yang, Yaofeng Wang, Alexey A. Popov, Fupin Liu
{"title":"Pyramidal Nd2ScN inside an icosahedral C80 cage","authors":"Wei Yang, Yaofeng Wang, Alexey A. Popov, Fupin Liu","doi":"10.1039/d4qi03135k","DOIUrl":"https://doi.org/10.1039/d4qi03135k","url":null,"abstract":"Engineering the structure of the M<small><sub>3</sub></small>N cluster within a fullerene cage by the combination of versatile metal ions is one of the most powerful strategies to build metallofullerenes with fine-tuned structures and properties. However, alongside their compositional versatility, mixed-metal clusters pose a challenge for structural elucidation because of the overlapping positions of different metal atoms. Here, we expand the size of metal ions in M<small><sub>2</sub></small>ScN@C<small><sub>80</sub></small> to M = Nd<small><sup>3+</sup></small> (<em>R</em><small><sup>3+</sup></small> = 0.983 Å), whose large ionic radius results in the pyramidalization of encapsulated Nd<small><sub>2</sub></small>ScN, which is the first example of a pyramidal M<small><sub>2</sub></small>ScN cluster inside C<small><sub>80</sub></small>. The combination of the pyramidalization, strong alteration of Nd–N and Sc–N bond lengths, and an overlap of two cluster orientations results in four nitrogen sites, which were unambiguously located by single crystal X-ray diffraction (SC-XRD). We demonstrate that judicious modelling of non-metal and overlapping metal positions is paramount for precise SC-XRD determination of structural parameters in metallofullerenes, which will otherwise suffer from erroneous structural interpretations. These results deepen our understanding of the fascinating M<small><sub>3</sub></small>N@C<small><sub>80</sub></small> and pave the way for better control over the fine-tuning of their structures and properties.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"21 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192598","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":"Structural Disproportionation of Ag20Cu10 Highlights the Impact of Cluster Structure on Electrocatalytic Properties for CO2 reduction","authors":"Yujiao Wang, Lin Xiong, Qian Cheng, Daqiao Hu, Shan Jin, Manzhou Zhu","doi":"10.1039/d4qi03264k","DOIUrl":"https://doi.org/10.1039/d4qi03264k","url":null,"abstract":"Understanding the relationship between cluster structure and catalytic performance is fundamental for developing advanced cluster-based catalysts. The interactions between SbF6⁻ ions and metal nanoclusters prove particularly significant in modulating cluster structures and properties. Herein, we report the synthesis of a novel Ag20Cu10(Dppm)2(SAdm)14Cl8 (Ag20Cu10 for short) nanocluster featuring an Ag17 barrel-like core surrounded by an Ag3Cu10(Dppm)2(SR)14Cl8 shell. Upon introduction of NaSbF6, Ag20Cu10 undergoes structural disproportionation transformation to form superatomic alloy clusters [Ag8Cu12(Dppm)4(SAdm)8Cl8]2+ (2e and Ag8Cu12 for short) and [Ag17Cu15(SAdm)13(Dppm)3Cl9]2+ (8e and Ag17Cu15 for short). These three structures share similar staples and Ag-bridging atoms, indicating core recombination while maintaining peripheral motifs during transformation. Electronic structure analysis through density functional theory (DFT) calculations reveals distinct characteristics of these Ag-Cu nanoclusters. Evaluation of their CO2 reduction reaction (CO2RR) capabilities demonstrates superior catalytic performance of Ag20Cu10 compared to Ag8Cu12 and Ag17Cu15. This enhanced performance highlights the unique structural and electronic properties of Ag₂₀Cu₁₀, which enable more effective catalytic activity during the CO₂RR process. These findings emphasize the pivotal role of SbF6⁻ in modulating Ag-Cu nanocluster structures and highlight the impact of structural features on electrocatalytic performance.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"39 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124556","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}
Anna Krot, Nataliya E. Borisova, Daniil Novichkov, Alexander Trigub, Aleksander Fedoseev, Alina A. Sivolap, Mikhail S. Grigoriev, Paulina Kalle, Vladimir G. Petrov, Stepan Kalmykov, Petr I. Matveev
{"title":"Redox transformations and cation-cation interactions of neptunium in organic solutions","authors":"Anna Krot, Nataliya E. Borisova, Daniil Novichkov, Alexander Trigub, Aleksander Fedoseev, Alina A. Sivolap, Mikhail S. Grigoriev, Paulina Kalle, Vladimir G. Petrov, Stepan Kalmykov, Petr I. Matveev","doi":"10.1039/d4qi03170a","DOIUrl":"https://doi.org/10.1039/d4qi03170a","url":null,"abstract":"Neptunium is a minor actinide with diverse redox chemistry and high tendency to form unique non-covalent interactions. As a result, the fate of neptunium during nuclear fuel reprocessing remains underexplored. In this work we aim to understand neptunium chemistry in organic solutions with tetradentate N,O-donor ligand that is pre-organized to stabilize 5f-elements in contact with concentrated nitric acid solutions. Crystal structures of neptunium(V) and (VI) complexes with ligand revealed the formation of three types of species: [LNpVIO2NO3][NpVIO2(NO3)3], [LNpVIO2NO3]2[NpVIO2(NO3)4] ion pairs, and [LNpVO2NO3]2⋅NpVIO2(NO3)2. The latter one is a mixed-valence NpV-NpVI complex with ligand-coordinated neptunium(V), which stabilizes poorly extractable neptunium(V) in organic solution. Neptunium speciation in organic solutions after extraction from neptunium(V) and (VI) aqueous solutions was investigated using a combination of XAS and 1H-NMR spectroscopies, and computational studies. The results demonstrate that neptunium(V) is extracted as a complex with ligand and then oxidized to form [LNpVIO2NO3]NO3. Extraction of neptunium(VI) leads to the formation of ion pairs. The formation of mixed-valence NpV-NpVI complexes was not observed in solvent extraction systems, but proved to be stable in acetonitrile solution. This study provides valuable insights into the chemical processes behind the extraction of neptunium(V) and (VI) under conditions relevant to spent nuclear fuel reprocessing.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"134 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124552","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":"Stepwise Carbon Coated Submicron Silicon Dioxide Anode for Long Life Lithium Ion Batteries","authors":"Mengqi Man, Yong Guo, Tianran Hu, Ying Sun, Aikai Yang, Xiqing Chen, Xingchao Wang","doi":"10.1039/d4qi03127j","DOIUrl":"https://doi.org/10.1039/d4qi03127j","url":null,"abstract":"The preparation of SiOx materials that exhibit enduring stable cycling performance and high initial coulombic efficiency (ICE) through cost-effective methods remains a substantial hurdle. Herein, hybrid carbon-coated SiO-20/G@TMA composite was synthesized using an integrated strategy that combines high-energy ball milling and high-temperature carbonization, employing graphene (G) and trimeric acid (TMA) as carbon sources. The three-dimensional crosslinked conductive network, formed by the mechanically flexible graphene and the carbon-rigid TMA, induces the generation of a LiF-rich SEI film. This film reduces interfacial side reactions and improves the ICE to 74.2%. Furthermore, the SiO-20/G@TMA electrode, characterized by a rigid-flexible hybrid structure, demonstrates excellent capacity retention and impressive rate performance over extended cycling periods. The discharge capacity of the SiO-20/G@TMA anode reaches 848.3 mAh g-1 at a current density of 0.5 A g-1, with a reversible capacity of 77% (about 649.1 mAh g-1) maintained after 600 cycles. When paired with LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode, the SiO-20/G@TMA anode achieve a reversible capacity of 140.0 mAh g-1 at the current density of 0.2 A g-1. After 100 cycles, the capacity retention rate is 85% and the energy density is 474.7 Wh kg-1.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"85 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124555","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":"Design strategies and applications of electrochemiluminescence from metal nanoclusters","authors":"Tingting Li, Jiyu Sui, Weinan Dong, Yu Zhang, Ying Zhang, Yanan Li, Zhennan Wu, Xue Bai","doi":"10.1039/d4qi02461c","DOIUrl":"https://doi.org/10.1039/d4qi02461c","url":null,"abstract":"Metal nanoclusters have recently gained significant attention in the field of electrochemiluminescence (ECL) due to their unique redox properties as well as optical properties, holding great potential for applications in biosensors, devices, and diagnostics. Constrained by complex pumping kinetics, elusive oxidant–reductant interactions, and the unclear non-radiative transition mechanism, the ECL efficiency is often unsatisfactory thus significantly affecting their sensitivity, stability, and functionality. This review aims to summarize the efforts made to raise the ECL efficiency, providing new ideas and insights for a deeper exploration of metal nanocluster ECL.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"30 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124554","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}