Pub Date : 2025-03-06DOI: 10.1016/j.jallcom.2025.179621
Liang Yin, Xiangqun Chu, Huimin Chen, Bin Liu, Pinhua Zhang, Lulu Du, Guangliang Cui, Li Lv
Nitrogen dioxide (NO2) is a major atmospheric pollutant that poses a significant threat to human health, the development of efficient and accurate NO2 gas sensors is crucial for air quality monitoring. Metal-organic frameworks (MOFs) are considered ideal materials for gas sensing due to their exceptional tunability, large surface area, high porosity, and abundant active metal sites. However, the poor conductivity of MOFs limits their applications in electrochemical sensors. This study presents a ZIF-67/rGO nanocomposite synthesized by combining reduced graphene oxide (rGO) with ZIF-67 via a one-step solution method. Experimental results demonstrate that the ZIF-67/rGO nanocomposite sensor shows significant sensitivity to NO2 gas at room temperature. At 5 ppm NO2, the response is approximately 13-fold higher than that of the pure rGO sensor. More importantly, the sensor achieves a detection limit as low as 0.5 ppm, with an ultra-fast response time of 15 s and recovery time of 40 s at room temperature. Additionally, the sensor exhibits excellent repeatability, long-term stability, and high selectivity for NO2. This study presents an effective strategy for accurate real-time detection of low concentration NO2 gas and provides valuable insights for designing MOF-based hybrid sensors at room temperature.
{"title":"Room Temperature NO2 Sensing with a ZIF-67/rGO Nanocomposite: A Highly Sensitive Approach","authors":"Liang Yin, Xiangqun Chu, Huimin Chen, Bin Liu, Pinhua Zhang, Lulu Du, Guangliang Cui, Li Lv","doi":"10.1016/j.jallcom.2025.179621","DOIUrl":"https://doi.org/10.1016/j.jallcom.2025.179621","url":null,"abstract":"Nitrogen dioxide (NO<sub>2</sub>) is a major atmospheric pollutant that poses a significant threat to human health, the development of efficient and accurate NO<sub>2</sub> gas sensors is crucial for air quality monitoring. Metal-organic frameworks (MOFs) are considered ideal materials for gas sensing due to their exceptional tunability, large surface area, high porosity, and abundant active metal sites. However, the poor conductivity of MOFs limits their applications in electrochemical sensors. This study presents a ZIF-67/rGO nanocomposite synthesized by combining reduced graphene oxide (rGO) with ZIF-67 via a one-step solution method. Experimental results demonstrate that the ZIF-67/rGO nanocomposite sensor shows significant sensitivity to NO<sub>2</sub> gas at room temperature. At 5 ppm NO<sub>2</sub>, the response is approximately 13-fold higher than that of the pure rGO sensor. More importantly, the sensor achieves a detection limit as low as 0.5 ppm, with an ultra-fast response time of 15<!-- --> <!-- -->s and recovery time of 40<!-- --> <!-- -->s at room temperature. Additionally, the sensor exhibits excellent repeatability, long-term stability, and high selectivity for NO<sub>2</sub>. This study presents an effective strategy for accurate real-time detection of low concentration NO<sub>2</sub> gas and provides valuable insights for designing MOF-based hybrid sensors at room temperature.","PeriodicalId":344,"journal":{"name":"Journal of Alloys and Compounds","volume":"7 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143560725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Natural soft organisms with sophisticated perception and deformation abilities provide inspiration for developing flexible electronics. However, the development of flexible sensing and actuating hybrid systems remains a challenge. Herein, we report a bioinspired sensor and actuator hybrid pixel array (SA-HPA) that enables moisture/temperature mapping, electrothermal display, and programmable electrothermal deformation. The SA-HPA is fabricated by femtosecond laser patterning of Cu electrodes/circuits, controllable deposition of graphene, selective encapsulation, and liquid crystal elastomer integration. The versatile SA-HPA can work as a sensor array for temperature and moisture recognition, and the interference between them can be overcome by the selective encapsulation of adjacent pixels. Additionally, SA-HPAs can also serve as electrothermal pixels for programmable infrared display and actuation. As a proof-of-concept, a soft robotic system that enables active temperature and humidity sensing was demonstrated. We deem that the SA-HPA may provide a new paradigm for developing soft electronics.
{"title":"Bioinspired Sensor and Actuator Hybrid Pixel Array for Moisture/Temperature Mapping, Electrothermal Display and Programmable Deformation","authors":"Jia-Rui Zhang, Ang Li, Xi-Lin Li, Zhiyong Chang, Dong-Dong Han, Yong-Lai Zhang","doi":"10.1021/acs.nanolett.5c00294","DOIUrl":"https://doi.org/10.1021/acs.nanolett.5c00294","url":null,"abstract":"Natural soft organisms with sophisticated perception and deformation abilities provide inspiration for developing flexible electronics. However, the development of flexible sensing and actuating hybrid systems remains a challenge. Herein, we report a bioinspired sensor and actuator hybrid pixel array (SA-HPA) that enables moisture/temperature mapping, electrothermal display, and programmable electrothermal deformation. The SA-HPA is fabricated by femtosecond laser patterning of Cu electrodes/circuits, controllable deposition of graphene, selective encapsulation, and liquid crystal elastomer integration. The versatile SA-HPA can work as a sensor array for temperature and moisture recognition, and the interference between them can be overcome by the selective encapsulation of adjacent pixels. Additionally, SA-HPAs can also serve as electrothermal pixels for programmable infrared display and actuation. As a proof-of-concept, a soft robotic system that enables active temperature and humidity sensing was demonstrated. We deem that the SA-HPA may provide a new paradigm for developing soft electronics.","PeriodicalId":53,"journal":{"name":"Nano Letters","volume":"16 1","pages":""},"PeriodicalIF":10.8,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561078","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Goutam Ghosh, Tian Carey, Stevie Furxhiu, Sven Weerdenburg, Nisha Singh, Marco van der Laan, Susan E. Branchett, Sophie Jaspers, John W. Suijkerbuijk, Fedor Lipilin, Zdeněk Sofer, Jonathan N. Coleman, Peter Schall, Laurens D. A. Siebbeles
Carrier multiplication (CM), where a single high-energy photon generates multiple electron–hole pairs, offers a promising route to enhance the efficiency of solar cells and photodetectors.Transition metal dichalcogenides, such as 2H-MoTe2 and 2H-WSe2, exhibit efficient CM. Given the similar electronic band structure of 2H-MoSe2, it is expected to show comparable CM efficiency. In this study, we establish the occurrence and efficiency of CM in a solution-processed thin film of bulk-like 2H-MoSe2. We characterize the dynamics of excitons and free charge carriers by using ultrafast transient optical absorption and terahertz spectroscopy. At higher photon energy the efficiency is comparable to literature results for 2H-MoTe2 grown by chemical vapor deposition (CVD) or in bulk crystalline form. At higher photon energies the experimental CM efficiency is reproduced by theoretical modeling. We also observe CM for photon energies below the energetic threshold of twice the band gap, which is most probably due to subgap defect states. Transient optical absorption spectra of 2H-MoSe2 exhibit features of trions from which we infer that photoexcitation leads to free charge carriers. We find no signatures of excitons at the indirect band gap. From analysis of the frequency dependence of the terahertz conductivity we infer that scattering of charge carriers in our sample is less than for CVD grown or bulk crystalline 2H-MoTe2. Our findings make solution-processed 2H-MoSe2 an interesting material for exploitation of CM in photovoltaic devices.
{"title":"Carrier Multiplication and Photoexcited Many-Body States in Solution-Processed 2H-MoSe2","authors":"Goutam Ghosh, Tian Carey, Stevie Furxhiu, Sven Weerdenburg, Nisha Singh, Marco van der Laan, Susan E. Branchett, Sophie Jaspers, John W. Suijkerbuijk, Fedor Lipilin, Zdeněk Sofer, Jonathan N. Coleman, Peter Schall, Laurens D. A. Siebbeles","doi":"10.1021/acsnano.4c18254","DOIUrl":"https://doi.org/10.1021/acsnano.4c18254","url":null,"abstract":"Carrier multiplication (CM), where a single high-energy photon generates multiple electron–hole pairs, offers a promising route to enhance the efficiency of solar cells and photodetectors.Transition metal dichalcogenides, such as 2H-MoTe<sub>2</sub> and 2H-WSe<sub>2</sub>, exhibit efficient CM. Given the similar electronic band structure of 2H-MoSe<sub>2</sub>, it is expected to show comparable CM efficiency. In this study, we establish the occurrence and efficiency of CM in a solution-processed thin film of bulk-like 2H-MoSe<sub>2</sub>. We characterize the dynamics of excitons and free charge carriers by using ultrafast transient optical absorption and terahertz spectroscopy. At higher photon energy the efficiency is comparable to literature results for 2H-MoTe<sub>2</sub> grown by chemical vapor deposition (CVD) or in bulk crystalline form. At higher photon energies the experimental CM efficiency is reproduced by theoretical modeling. We also observe CM for photon energies below the energetic threshold of twice the band gap, which is most probably due to subgap defect states. Transient optical absorption spectra of 2H-MoSe<sub>2</sub> exhibit features of trions from which we infer that photoexcitation leads to free charge carriers. We find no signatures of excitons at the indirect band gap. From analysis of the frequency dependence of the terahertz conductivity we infer that scattering of charge carriers in our sample is less than for CVD grown or bulk crystalline 2H-MoTe<sub>2</sub>. Our findings make solution-processed 2H-MoSe<sub>2</sub> an interesting material for exploitation of CM in photovoltaic devices.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"16 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Andrey D. Trofimov, Andrey Emelyanov, Anna Matsukatova, Alexander A. Nesmelov, Sergei Zav'yalov, Timofey Patsaev, Pavel Forsh, Gang Liu, Vladimir Rylkov, Vyacheslav A. Demin
Resistive switching (RS) memory devices incorporated with the capabilities of in situ data sensing, storing and processing are promising for artificial intelligence applications. In this respect, controlling resistance not only by electrical but also optical stimulations provides attractive opportunities for the development of novel neuromorphic sensing and computing systems. Here, we demonstrate the RS of Cu/parylene-PbTe/ITO memristive devices and the dependence of RS on optical excitation for efficient neuromorphic computing with a high classification accuracy. The main memristive characteristics (multilevel resistive states, RS voltages, endurance, retention, RS time and energy, etc.) are evaluated with account of temporal and spatial variations. Additionally, the devices demonstrate a range of synaptic plasticity behaviors, such as spike-timing(amplitude,width)-dependent plasticity, long-term potentiation and depression. A qualitative model that describes photosensitive RS and takes into account the influence of photo-generated charge carriers on conductive filament growth is proposed based on the experimental results. This work presents an appealing approach towards the development of photosensitive memristive devices for upcoming neuromorphic sensing and computing systems.
{"title":"Photosensitive resistive switching in parylene-PbTe nanocomposite memristors for neuromorphic computing","authors":"Andrey D. Trofimov, Andrey Emelyanov, Anna Matsukatova, Alexander A. Nesmelov, Sergei Zav'yalov, Timofey Patsaev, Pavel Forsh, Gang Liu, Vladimir Rylkov, Vyacheslav A. Demin","doi":"10.1039/d5nr00456j","DOIUrl":"https://doi.org/10.1039/d5nr00456j","url":null,"abstract":"Resistive switching (RS) memory devices incorporated with the capabilities of in situ data sensing, storing and processing are promising for artificial intelligence applications. In this respect, controlling resistance not only by electrical but also optical stimulations provides attractive opportunities for the development of novel neuromorphic sensing and computing systems. Here, we demonstrate the RS of Cu/parylene-PbTe/ITO memristive devices and the dependence of RS on optical excitation for efficient neuromorphic computing with a high classification accuracy. The main memristive characteristics (multilevel resistive states, RS voltages, endurance, retention, RS time and energy, etc.) are evaluated with account of temporal and spatial variations. Additionally, the devices demonstrate a range of synaptic plasticity behaviors, such as spike-timing(amplitude,width)-dependent plasticity, long-term potentiation and depression. A qualitative model that describes photosensitive RS and takes into account the influence of photo-generated charge carriers on conductive filament growth is proposed based on the experimental results. This work presents an appealing approach towards the development of photosensitive memristive devices for upcoming neuromorphic sensing and computing systems.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"50 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The conventional production of formic acid is energy-intensive, requiring methanol and carbon monoxide reactions followed by hydrolysis under high temperature and pressure. Methanol electrochemical refinery (e-refinery) offers a sustainable alternative but faces challenges like high overpotential and competing oxygen evolution reaction (OER). This study presents Pt-nanoparticle-decorated Ni(OH)2 as a breakthrough catalyst, achieving a significantly lower onset potential of 0.5 V vs reversible hydrogen electrode (RHE) for methanol-to-formate conversion compared to previous reports (>1.35 V vs RHE), while simultaneously generating hydrogen at the cathode. The platinum valence state is identified as an effective descriptor for formate Faradaic efficiency, validated through experimental studies and density functional theory. Pt1.05@Ni(OH)2, featuring the highest platinum valence states among the catalysts studied, exhibits an exceptional formate Faradaic efficiency of 78.8% and a high formate production rate of 1.3 mmol h−1 mgcat−1 at 0.8 V versus RHE. This approach reduces overpotential, eliminates OER, and cuts carbon dioxide emissions by over 50% compared to traditional methods. Moreover, economic analysis shows profitability from the fourth year at 50 mA cm−2, supporting easier industrial adoption and low carbon dioxide emissions. These advancements offer a sustainable, energy-efficient, and economically viable method for formate production, advancing the commercialization of methanol e-refinery technology.
{"title":"Industrially viable formate production with 50% lower CO2 emissions","authors":"Fanxu Meng, Zihan Shen, Xinlong Lin, Pengfei Song, Tianze Wu, Shibo Xi, Chao Wu, Zhenhui Ma, Daniel Mandler, Zhichuan J. Xu","doi":"10.1039/d5ee00452g","DOIUrl":"https://doi.org/10.1039/d5ee00452g","url":null,"abstract":"The conventional production of formic acid is energy-intensive, requiring methanol and carbon monoxide reactions followed by hydrolysis under high temperature and pressure. Methanol electrochemical refinery (e-refinery) offers a sustainable alternative but faces challenges like high overpotential and competing oxygen evolution reaction (OER). This study presents Pt-nanoparticle-decorated Ni(OH)<small><sub>2</sub></small> as a breakthrough catalyst, achieving a significantly lower onset potential of 0.5 V vs reversible hydrogen electrode (RHE) for methanol-to-formate conversion compared to previous reports (>1.35 V vs RHE), while simultaneously generating hydrogen at the cathode. The platinum valence state is identified as an effective descriptor for formate Faradaic efficiency, validated through experimental studies and density functional theory. Pt<small><sub>1.05</sub></small>@Ni(OH)<small><sub>2</sub></small>, featuring the highest platinum valence states among the catalysts studied, exhibits an exceptional formate Faradaic efficiency of 78.8% and a high formate production rate of 1.3 mmol h<small><sup>−1</sup></small> mg<small><sub>cat</sub></small><small><sup>−1</sup></small> at 0.8 V versus RHE. This approach reduces overpotential, eliminates OER, and cuts carbon dioxide emissions by over 50% compared to traditional methods. Moreover, economic analysis shows profitability from the fourth year at 50 mA cm<small><sup>−2</sup></small>, supporting easier industrial adoption and low carbon dioxide emissions. These advancements offer a sustainable, energy-efficient, and economically viable method for formate production, advancing the commercialization of methanol e-refinery technology.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"16 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561166","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Beiye C. Li, Hugh Cairney, Yu Jin, Jinsoo Park, Siddhartha Sohoni, Lawson T. Lloyd, Yuzi Liu, Justin E. Jureller, Young Jay Ryu, Stella Chariton, Vitali B. Prakapenka, Richard D. Schaller, Giulia Galli, Gregory S. Engel
Metal halide octahedra form the fundamental functional building blocks of metal halide perovskites, dictating their structures, optical properties, electronic structures, and dynamics. In this study, we show that the connectivity of bismuth halide octahedra in Cs3Bi2Br9 and Cs3Bi2I9 quantum dots (QDs) changes with different halide elements. We use first-principles calculations to reveal the key role of the connectivity of bismuth halide octahedra on the wave function symmetry, Huang–Rhys factor, and exciton–phonon interaction strength. Following QD synthesis via a ligand-mediated transport method, the effect of connectivity is verified with transient absorption spectroscopy, where we contrast Cs3Bi2Br9 and Cs3Bi2I9 QD exciton dynamics. In photoexcited Cs3Bi2I9 QDs, phonons related to the vibrational motions of face-sharing [BiI6]3– bioctahedra couple strongly to the electronic state and drive rapid carrier relaxation. Equivalent signals are not observed for photoexcited Cs3Bi2Br9 QDs, implying a lack of phonon involvement in band-edge absorption and subsequent exciton relaxation. Our findings suggest that structural engineering can effectively tune the exciton–phonon coupling and therefore influence exciton relaxation and recombination in perovskite nanomaterials.
{"title":"Connectivity-Dependent Exciton–Phonon Coupling in Cesium Bismuth Halide Quantum Dots","authors":"Beiye C. Li, Hugh Cairney, Yu Jin, Jinsoo Park, Siddhartha Sohoni, Lawson T. Lloyd, Yuzi Liu, Justin E. Jureller, Young Jay Ryu, Stella Chariton, Vitali B. Prakapenka, Richard D. Schaller, Giulia Galli, Gregory S. Engel","doi":"10.1021/acsnano.4c18414","DOIUrl":"https://doi.org/10.1021/acsnano.4c18414","url":null,"abstract":"Metal halide octahedra form the fundamental functional building blocks of metal halide perovskites, dictating their structures, optical properties, electronic structures, and dynamics. In this study, we show that the connectivity of bismuth halide octahedra in Cs<sub>3</sub>Bi<sub>2</sub>Br<sub>9</sub> and Cs<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub> quantum dots (QDs) changes with different halide elements. We use first-principles calculations to reveal the key role of the connectivity of bismuth halide octahedra on the wave function symmetry, Huang–Rhys factor, and exciton–phonon interaction strength. Following QD synthesis via a ligand-mediated transport method, the effect of connectivity is verified with transient absorption spectroscopy, where we contrast Cs<sub>3</sub>Bi<sub>2</sub>Br<sub>9</sub> and Cs<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub> QD exciton dynamics. In photoexcited Cs<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub> QDs, phonons related to the vibrational motions of face-sharing [BiI<sub>6</sub>]<sup>3–</sup> bioctahedra couple strongly to the electronic state and drive rapid carrier relaxation. Equivalent signals are not observed for photoexcited Cs<sub>3</sub>Bi<sub>2</sub>Br<sub>9</sub> QDs, implying a lack of phonon involvement in band-edge absorption and subsequent exciton relaxation. Our findings suggest that structural engineering can effectively tune the exciton–phonon coupling and therefore influence exciton relaxation and recombination in perovskite nanomaterials.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"8 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561203","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-06DOI: 10.1016/j.jallcom.2025.179518
Shijie Liu, Fan Liu, Yanchun Shen, Guoping Yan
Recently radical polymer has increasedly been investigated as an electroactive material in organic rechargeable batteries, electrochemical supercapacitors and photovoltaic cells. The novel isoindoline nitroxide-containing polythiophene derivatives, such as poly(3-(1’,1’,3’,3’tetramethylisoindolin-2’-yloxyl-vinylene)-thiophene) (PTTMIO) and poly(3,4-di(1’,1’,3’,3’-tetramethyl-isoindolin-2’-yloxyl-amino)-thiophene-co-thiophene) (PT2TMIO), were synthesized by the incorporation of 1,1,3,3-tetramethylisoindolin-2-yloxyl (TMIO) to polythiophene, respectively. These polymers were further characterized and their properties, such as fluorescence, electron paramagnetic resonance (EPR) and electrochemical performance, were also evaluated. It is found that PTTMIO and PT2TMIO displayed the similar fluorescence and characteristic EPR spectra of isoindoline nitroxides, with typical hyperfine splitting, nitroxide g-values and nitrogen isotropic hyperfine coupling constants. Moreover, PTTMIO and PT2TMIO possessed higher capacities, higher electrochemical redox activity and lower impedance than that of polythiophene (PTh). Furthermore, PT2TMIO show good capacitance maintenance (contained 87.2% capacity after 1000 cycles) due to a rapid charging-discharging process. Therefore, isoindoline nitroxide-containing polythiophene derivatives can be considered as the potential candidates for novel good electrode materials.
{"title":"Synthesis and property of 1,1,3,3-tetramethylisoindolin-2-yloxyl-containing polythiophene","authors":"Shijie Liu, Fan Liu, Yanchun Shen, Guoping Yan","doi":"10.1016/j.jallcom.2025.179518","DOIUrl":"https://doi.org/10.1016/j.jallcom.2025.179518","url":null,"abstract":"Recently radical polymer has increasedly been investigated as an electroactive material in organic rechargeable batteries, electrochemical supercapacitors and photovoltaic cells. The novel isoindoline nitroxide-containing polythiophene derivatives, such as poly(3-(1’,1’,3’,3’tetramethylisoindolin-2’-yloxyl-vinylene)-thiophene) (PTTMIO) and poly(3,4-di(1’,1’,3’,3’-tetramethyl-isoindolin-2’-yloxyl-amino)-thiophene-co-thiophene) (PT2TMIO), were synthesized by the incorporation of 1,1,3,3-tetramethylisoindolin-2-yloxyl (TMIO) to polythiophene, respectively. These polymers were further characterized and their properties, such as fluorescence, electron paramagnetic resonance (EPR) and electrochemical performance, were also evaluated. It is found that PTTMIO and PT2TMIO displayed the similar fluorescence and characteristic EPR spectra of isoindoline nitroxides, with typical hyperfine splitting, nitroxide g-values and nitrogen isotropic hyperfine coupling constants. Moreover, PTTMIO and PT2TMIO possessed higher capacities, higher electrochemical redox activity and lower impedance than that of polythiophene (PTh). Furthermore, PT2TMIO show good capacitance maintenance (contained 87.2% capacity after 1000 cycles) due to a rapid charging-discharging process. Therefore, isoindoline nitroxide-containing polythiophene derivatives can be considered as the potential candidates for novel good electrode materials.","PeriodicalId":344,"journal":{"name":"Journal of Alloys and Compounds","volume":"300 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143560845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
As a natrium superionic conductor, NASICON-type Na3MnTi(PO4)3 (NMTP) has garnered increasing attention for large-scale sodium-ion batteries due to its high stability and power densities. Nevertheless, it still suffers from an inferior rate capability and poor cycling longevity, arising from sluggish intrinsic kinetics and severe structural degradation. Herein, vanadium (V) is used as a dopant for equal substitution of manganese (Mn) and titanium (Ti) in NMTP to alleviate voltage hysteresis and enhance the cycling performance. V-doping regulates the local coordination chemistry of transition metals and reduces derivative antisite defect concentration upon cycling. Through density functional theory analysis, Na3Mn0.9V0.2Ti0.9(PO4)3 (NMTP-V0.2) demonstrates a lower bandgap and higher electronic conductivity. Additionally, V-doping significantly lowers the diffusion barrier of Na2, leading to Na+ diffusivity that is approximately two orders of magnitude higher than that of NMTP during the Mn2+/Mn3+ redox process. The as-prepared NMTP-V0.2 delivers an excellent rate capability of 85.3 mAh g–1 under 50 C and satisfactory cycling retention of 81% with a high capacity over 1400 cycles. Thus, the assembled NMTP-V0.2/hard carbon sodium-ion full cell achieves a high energy density of 292.3 Wh kg–1 as well as outstanding capacity retention of 92% after 500 cycles under 10 C. This result not only provides an approach for suppressing voltage hysteresis in polyanion cathodes but also offers guidance for designing high-power SIBs.
{"title":"Coordination Chemistry Regulation Suppressing Voltage Hysteresis for Na3MnTi(PO4)3 in High-Rate Sodium-Ion Batteries","authors":"Shengping Deng, Chongran Song, Shuoshuo Cheng, Shiyu Li, Zhenxiang Cheng, Ying Bai","doi":"10.1021/acsnano.4c18519","DOIUrl":"https://doi.org/10.1021/acsnano.4c18519","url":null,"abstract":"As a natrium superionic conductor, NASICON-type Na<sub>3</sub>MnTi(PO<sub>4</sub>)<sub>3</sub> (NMTP) has garnered increasing attention for large-scale sodium-ion batteries due to its high stability and power densities. Nevertheless, it still suffers from an inferior rate capability and poor cycling longevity, arising from sluggish intrinsic kinetics and severe structural degradation. Herein, vanadium (V) is used as a dopant for equal substitution of manganese (Mn) and titanium (Ti) in NMTP to alleviate voltage hysteresis and enhance the cycling performance. V-doping regulates the local coordination chemistry of transition metals and reduces derivative antisite defect concentration upon cycling. Through density functional theory analysis, Na<sub>3</sub>Mn<sub>0.9</sub>V<sub>0.2</sub>Ti<sub>0.9</sub>(PO<sub>4</sub>)<sub>3</sub> (NMTP-V0.2) demonstrates a lower bandgap and higher electronic conductivity. Additionally, V-doping significantly lowers the diffusion barrier of Na<sub>2</sub>, leading to Na<sup>+</sup> diffusivity that is approximately two orders of magnitude higher than that of NMTP during the Mn<sup>2+</sup>/Mn<sup>3+</sup> redox process. The as-prepared NMTP-V0.2 delivers an excellent rate capability of 85.3 mAh g<sup>–1</sup> under 50 C and satisfactory cycling retention of 81% with a high capacity over 1400 cycles. Thus, the assembled NMTP-V0.2/hard carbon sodium-ion full cell achieves a high energy density of 292.3 Wh kg<sup>–1</sup> as well as outstanding capacity retention of 92% after 500 cycles under 10 C. This result not only provides an approach for suppressing voltage hysteresis in polyanion cathodes but also offers guidance for designing high-power SIBs.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"67 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Self-assembly of coinage metal nanoclusters constitutes an important branch for the construction of bright luminescent materials. They also serve as a class of promising building blocks for the study of hierarchically organized assemblies due to their potential of generating high structural complexity. However, the strong intercluster interactions exert great difficulty and uncertainty on the modulation of the outcome aggregation structures. To explore a feasible methodology for constructing complex structures that combine order and disorder, accompanied by emerging desirable optical performances, herein we manipulate the supramolecular interactions of a gold nanocluster, namely, DPT-AuNCs through the incorporation of an amphiphilic cation, i.e., 1-dodecyl-3-methylimidazolium (DMI+). Diverse aggregation structures are obtained through coassembly, and a sea urchin-like aggregate with a complexity index of CI = 16.5 is formed by elevating the concentration of DMI+. Moreover, a positive correlation between structural complexity and emission intensity was observed, and strongly luminescent NCs-based aggregates were obtained. The mechanism for the emergence of structural complexity is demonstrated via kinetic studies, 1H NMR titration, theoretical computation, etc. The cation-π interaction is found to be vital for the association between DMI+ and DPT-AuNCs, which modulates the supramolecular interactions for assembly and in turn facilitates the growth of aggregates in multiple dimensions. The sea urchin-like aggregate is formed through a dynamic assembly process, mediated by the pre-equilibrium of DMI+ micelles at high concentrations. Finally, the luminescent NC aggregates can also be obtained by incorporating different types of amphiphilic cations, thus generalizing the method for constructing complex assembly structures.
{"title":"Modulating the Structural Complexity of AuNCs Aggregates for Generation of Bright Luminescence","authors":"Yongjie Zhang, Dewang Niu, Liyuan Zhang, Ensheng Zhang, Jinglin Shen","doi":"10.1021/acsnano.5c01675","DOIUrl":"https://doi.org/10.1021/acsnano.5c01675","url":null,"abstract":"Self-assembly of coinage metal nanoclusters constitutes an important branch for the construction of bright luminescent materials. They also serve as a class of promising building blocks for the study of hierarchically organized assemblies due to their potential of generating high structural complexity. However, the strong intercluster interactions exert great difficulty and uncertainty on the modulation of the outcome aggregation structures. To explore a feasible methodology for constructing complex structures that combine order and disorder, accompanied by emerging desirable optical performances, herein we manipulate the supramolecular interactions of a gold nanocluster, namely, DPT-AuNCs through the incorporation of an amphiphilic cation, i.e., 1-dodecyl-3-methylimidazolium (DMI<sup>+</sup>). Diverse aggregation structures are obtained through coassembly, and a sea urchin-like aggregate with a complexity index of CI = 16.5 is formed by elevating the concentration of DMI<sup>+</sup>. Moreover, a positive correlation between structural complexity and emission intensity was observed, and strongly luminescent NCs-based aggregates were obtained. The mechanism for the emergence of structural complexity is demonstrated via kinetic studies, <sup>1</sup>H NMR titration, theoretical computation, etc. The cation-π interaction is found to be vital for the association between DMI<sup>+</sup> and DPT-AuNCs, which modulates the supramolecular interactions for assembly and in turn facilitates the growth of aggregates in multiple dimensions. The sea urchin-like aggregate is formed through a dynamic assembly process, mediated by the pre-equilibrium of DMI<sup>+</sup> micelles at high concentrations. Finally, the luminescent NC aggregates can also be obtained by incorporating different types of amphiphilic cations, thus generalizing the method for constructing complex assembly structures.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"34 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561118","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-06DOI: 10.1038/s41560-025-01738-4
Bingbin Wu, Ran Yi, Yaobin Xu, Peiyuan Gao, Yujing Bi, Libor Novák, Zhao Liu, Enyuan Hu, Nan Wang, Job Rijssenbeek, Subramanian Venkatachalam, Jing Wu, Dianying Liu, Xia Cao, Jie Xiao
Li2O is rarely used for cathode material synthesis due to its high melting point (1,438 °C). Here we discover that Li2O can sublimate at 800–1,000 °C under ambient pressure, opening new possibilities for cathode synthesis. We propose a mechanism that enables synthesis of single crystals—such as LiNi0.8Mn0.1Co0.1O2 (NMC811) or LiNi0.9Mn0.05Co0.05O2 (NMC90)—without direct contact with Li2O salts. We show that Li2O vapour successfully converts spent polycrystalline NMC811 into segregated single crystals without milling or post-treatment. The Li2O vapour, derived from Li2O solids, diffuses rapidly and reacts with precursors, mimicking a molten-salt environment, which facilitates single-crystal growth. The chemical lithiation process continuously drives Li2O sublimation, sintering the crystals. Single crystals derived from Li2O and fresh precursors or spent polycrystals exhibit outstanding cycling after 1,000 cycles in full cells. The demonstrated Li2O sublimation and its universal role in promoting single-crystal growth provides an effective approach for single-crystal synthesis, scale-up and recycling.
{"title":"Unusual Li2O sublimation promotes single-crystal growth and sintering","authors":"Bingbin Wu, Ran Yi, Yaobin Xu, Peiyuan Gao, Yujing Bi, Libor Novák, Zhao Liu, Enyuan Hu, Nan Wang, Job Rijssenbeek, Subramanian Venkatachalam, Jing Wu, Dianying Liu, Xia Cao, Jie Xiao","doi":"10.1038/s41560-025-01738-4","DOIUrl":"https://doi.org/10.1038/s41560-025-01738-4","url":null,"abstract":"<p>Li<sub>2</sub>O is rarely used for cathode material synthesis due to its high melting point (1,438 °C). Here we discover that Li<sub>2</sub>O can sublimate at 800–1,000 °C under ambient pressure, opening new possibilities for cathode synthesis. We propose a mechanism that enables synthesis of single crystals—such as LiNi<sub>0.8</sub>Mn<sub>0.1</sub>Co<sub>0.1</sub>O<sub>2</sub> (NMC811) or LiNi<sub>0.9</sub>Mn<sub>0.05</sub>Co<sub>0.05</sub>O<sub>2</sub> (NMC90)—without direct contact with Li<sub>2</sub>O salts. We show that Li<sub>2</sub>O vapour successfully converts spent polycrystalline NMC811 into segregated single crystals without milling or post-treatment. The Li<sub>2</sub>O vapour, derived from Li<sub>2</sub>O solids, diffuses rapidly and reacts with precursors, mimicking a molten-salt environment, which facilitates single-crystal growth. The chemical lithiation process continuously drives Li<sub>2</sub>O sublimation, sintering the crystals. Single crystals derived from Li<sub>2</sub>O and fresh precursors or spent polycrystals exhibit outstanding cycling after 1,000 cycles in full cells. The demonstrated Li<sub>2</sub>O sublimation and its universal role in promoting single-crystal growth provides an effective approach for single-crystal synthesis, scale-up and recycling.</p>","PeriodicalId":19073,"journal":{"name":"Nature Energy","volume":"36 1","pages":""},"PeriodicalIF":56.7,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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