David Lledó, Guillermo Grindlay, H. Q. Nimal Gunaratne, Abel de Cózar, Ana Sirvent, José Sansano
A selective extraction system of thorium(IV), formed with a TSIL derived from ciprofloxacin and [BMIM][NTf2] as a co-solvent, is described. Under acidic conditions, this IL solution was able to complex selectively this metal versus the rest of the other metals of the periodic table. The synthesis of the TSIL was detailed using known procedures and it was isolated in good overall yield. The extraction coefficients (K) were determined by a microextractive survey at 25 °C. Spectroscopic analyses of thorium(IV) and uranium(IV) complexes were performed in order to demonstrate the strength of the metal-TSIL interaction, which was supported by DFT-based computational optimization of the formation of the experimentally observed complexes. Kinetic analysis, loading tests for the extractive protocol, as well as the optimization for recycling were also performed to justify the conditions of a laboratory prototype for this selective extraction of thorium(IV) salts.
{"title":"Ciprofloxacin derived task specific ionic liquid as highly selective extractant of thorium versus uranium","authors":"David Lledó, Guillermo Grindlay, H. Q. Nimal Gunaratne, Abel de Cózar, Ana Sirvent, José Sansano","doi":"10.1039/d4ta06496h","DOIUrl":"https://doi.org/10.1039/d4ta06496h","url":null,"abstract":"A selective extraction system of thorium(IV), formed with a TSIL derived from ciprofloxacin and [BMIM][NTf2] as a co-solvent, is described. Under acidic conditions, this IL solution was able to complex selectively this metal versus the rest of the other metals of the periodic table. The synthesis of the TSIL was detailed using known procedures and it was isolated in good overall yield. The extraction coefficients (K) were determined by a microextractive survey at 25 °C. Spectroscopic analyses of thorium(IV) and uranium(IV) complexes were performed in order to demonstrate the strength of the metal-TSIL interaction, which was supported by DFT-based computational optimization of the formation of the experimentally observed complexes. Kinetic analysis, loading tests for the extractive protocol, as well as the optimization for recycling were also performed to justify the conditions of a laboratory prototype for this selective extraction of thorium(IV) salts.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487334","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}
Hui Zhang, Xinyu Du, Xudong Han, Gong Cheng, Wenchuan Cheng, Yingqi Xia, Qi Lai, Ping Yin, Si-Ping Pang
Oxygen balance is a crucial index of energetic materials that indicates the efficiency of redox process during energy release. In this work, a straightforward synthesis including N-amination and azo-coupling oxidative cyclization gave rise to 2,9-bis(trinitromethyl)bis([1,2,4]triazolo)[1,5-d:5',1'-f][1,2,3,4]tetrazine (TNF), achieving an ideal zero oxygen balance in the tetrazine-triazole framework. With a high crystal density of 1.94 gcm-3 at 296 K (1.995 gcm-3 at 150 K), TNF features an excellent detonation performance (P, 39.7 GPa, VD, 9470 ms-1), which remarkably surpasses those of RDX (P, 34.9 GPa; VD, 8795 ms-1) and HMX (P, 39.2 GPa; VD, 9144 ms-1). Furthermore, the excellent heat of detonation (Q, 7154 kJkg-1) of TNF significantly exceeds the state-of-the-art explosive CL-20 (Q, 6534 kJkg-1). Additionally, the evaluation of specific impulse values of two new compounds, TBTD and TNF, reveals notably high values of 272 s and 269 s, respectively. It possesses the application potential as a high-energy oxidizer, which renders the advantageous option in the formulation of solid rocket propellants.
{"title":"Zero-Oxygen balanced Fused 1,2,3,4-Tetrazine (TNF) as a High-Performance Energetic Material","authors":"Hui Zhang, Xinyu Du, Xudong Han, Gong Cheng, Wenchuan Cheng, Yingqi Xia, Qi Lai, Ping Yin, Si-Ping Pang","doi":"10.1039/d4ta05719h","DOIUrl":"https://doi.org/10.1039/d4ta05719h","url":null,"abstract":"Oxygen balance is a crucial index of energetic materials that indicates the efficiency of redox process during energy release. In this work, a straightforward synthesis including N-amination and azo-coupling oxidative cyclization gave rise to 2,9-bis(trinitromethyl)bis([1,2,4]triazolo)[1,5-d:5',1'-f][1,2,3,4]tetrazine (TNF), achieving an ideal zero oxygen balance in the tetrazine-triazole framework. With a high crystal density of 1.94 gcm-3 at 296 K (1.995 gcm-3 at 150 K), TNF features an excellent detonation performance (P, 39.7 GPa, VD, 9470 ms-1), which remarkably surpasses those of RDX (P, 34.9 GPa; VD, 8795 ms-1) and HMX (P, 39.2 GPa; VD, 9144 ms-1). Furthermore, the excellent heat of detonation (Q, 7154 kJkg-1) of TNF significantly exceeds the state-of-the-art explosive CL-20 (Q, 6534 kJkg-1). Additionally, the evaluation of specific impulse values of two new compounds, TBTD and TNF, reveals notably high values of 272 s and 269 s, respectively. It possesses the application potential as a high-energy oxidizer, which renders the advantageous option in the formulation of solid rocket propellants.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486296","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}
Solar-driven interfacial evaporation is regarded as a very promising strategy to alleviate the pressing freshwater scarcity. However, owing to the trade-off between thermal localization and ion transport, simultaneously achieving remarkable evaporation performance and ultra-high salt resistance is challenging. In this work, inspired by the skin effect of currents in wires, we constructed a skin-effect-inspired three-dimensional solar evaporator (SEISE) by controlling the porosity of the evaporator structure based on the principle of division of responsibilities and collaborative matching. Specifically, the SEISE with non-uniform porosity can realize the localization of water transport through its surface layer with low porosity, precisely matched with the thermal localization resulting from the internal body with high porosity and extremely low thermal conductivity, thereby greatly enhancing the interfacial evaporation performance. The maximum evaporation rate of SEISE can remarkably reach 6.0 kg·m−2·h−1 under 1 sun. Furthermore, the diffusion and convection of ions in SEISE were significantly enhanced because of the rapid water transport within its surface layer. No salt crystals were observed on the evaporation surface after continuous operation in an ultra-high salinity brine (25 wt%) for 48 h. This work demonstrates a highly-efficient and feasible strategy for developing next-generation solar evaporators.
{"title":"Skin-Effect-Inspired 3D Solar Evaporator for Simultaneously Achieving Highly-Efficient Steam Generation and Ultra-High Salt Resistance","authors":"Renzhong Deng, Yunqi Li, Qing Li, Yu Qiu, Haixiang Feng, Yangming Liu","doi":"10.1039/d4ta06352j","DOIUrl":"https://doi.org/10.1039/d4ta06352j","url":null,"abstract":"Solar-driven interfacial evaporation is regarded as a very promising strategy to alleviate the pressing freshwater scarcity. However, owing to the trade-off between thermal localization and ion transport, simultaneously achieving remarkable evaporation performance and ultra-high salt resistance is challenging. In this work, inspired by the skin effect of currents in wires, we constructed a skin-effect-inspired three-dimensional solar evaporator (SEISE) by controlling the porosity of the evaporator structure based on the principle of division of responsibilities and collaborative matching. Specifically, the SEISE with non-uniform porosity can realize the localization of water transport through its surface layer with low porosity, precisely matched with the thermal localization resulting from the internal body with high porosity and extremely low thermal conductivity, thereby greatly enhancing the interfacial evaporation performance. The maximum evaporation rate of SEISE can remarkably reach 6.0 kg·m−2·h−1 under 1 sun. Furthermore, the diffusion and convection of ions in SEISE were significantly enhanced because of the rapid water transport within its surface layer. No salt crystals were observed on the evaporation surface after continuous operation in an ultra-high salinity brine (25 wt%) for 48 h. This work demonstrates a highly-efficient and feasible strategy for developing next-generation solar evaporators.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486297","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}
Konstantina Gkini, Spyros Orfanoudakis, Filippos Harlaftis, Panagiotis Dallas, Christos Kouzios, Polychronis Tsipas, Athanassios G. Kontos, Maria Konstantakou, Thomas Stergiopoulos
Bis(trifluoromethane)sulfonimide (TFSI) treatment results in near-unity photoluminescence quantum yields in monolayer transition-metal dichalcogenides, such as MoS2, due to passivation of native defects. Surprisingly, this simple post-treatment process has never been tested in the case of metal halide perovskites which suffer from limited radiative recombination due to charge carrier trapping. Here, we adopt this strategy and treat methylammonium lead iodide perovskite films with TFSI solutions. By employing photoluminescence spectroscopy, the appearance of brighter films proves a net passivation effect, while chemical analysis explains that this is due to strong interactions between S=O groups of TFSI with under-coordinated Pb2+. A simultaneous passivation of iodide vacancies leads also to a reduction of n-doping at the perovskite surface and thus a better hole extraction through the spiro-MeOTAD which is deposited ontop. These two effects combined (chemical passivation and de-doping) result in enhanced stabilized efficiencies for the as-fabricated n-i-p solar cells. The findings pave the way for the use of TFSI-based solutions to improve the performance of perovskite optoelectronic devices.
{"title":"Influence of TFSI post-treatment on surface doping and passivation of lead halide perovskites","authors":"Konstantina Gkini, Spyros Orfanoudakis, Filippos Harlaftis, Panagiotis Dallas, Christos Kouzios, Polychronis Tsipas, Athanassios G. Kontos, Maria Konstantakou, Thomas Stergiopoulos","doi":"10.1039/d4ta06018k","DOIUrl":"https://doi.org/10.1039/d4ta06018k","url":null,"abstract":"Bis(trifluoromethane)sulfonimide (TFSI) treatment results in near-unity photoluminescence quantum yields in monolayer transition-metal dichalcogenides, such as MoS2, due to passivation of native defects. Surprisingly, this simple post-treatment process has never been tested in the case of metal halide perovskites which suffer from limited radiative recombination due to charge carrier trapping. Here, we adopt this strategy and treat methylammonium lead iodide perovskite films with TFSI solutions. By employing photoluminescence spectroscopy, the appearance of brighter films proves a net passivation effect, while chemical analysis explains that this is due to strong interactions between S=O groups of TFSI with under-coordinated Pb2+. A simultaneous passivation of iodide vacancies leads also to a reduction of n-doping at the perovskite surface and thus a better hole extraction through the spiro-MeOTAD which is deposited ontop. These two effects combined (chemical passivation and de-doping) result in enhanced stabilized efficiencies for the as-fabricated n-i-p solar cells. The findings pave the way for the use of TFSI-based solutions to improve the performance of perovskite optoelectronic devices.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486299","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}
The application of sustainable energy-driven electrocatalytic carbon dioxide reduction (CO2RR) technology enables the synthesis of valuable chemicals and feedstocks. This offers a promising pathway to effectively reduce greenhouse gas emissions associated with fossil fuels. Cu2O-based electrocatalysts have been widely investigated due to their cost-effective, environmentally friendly, and structurally tunable nature. This article provides a comprehensive review of recent advancements in the electrocatalytic reduction of carbon dioxide using Cu2O-based catalysts, with a focus on the properties, structure, and synthesis of Cu2O. It summarizes the performance of Cu2O-based catalysts in CO2 reduction and discusses several optimization strategies to enhance their stability and redox capabilities. Furthermore, it outlines the application of Cu2O-based catalysts in CO2 reduction. Finally, the opportunities, challenges and research directions for Cu2O-based catalysts in the field of CO2 electrocatalytic reduction are identified, providing guidance for their broad application in the energy and environmental sectors.
{"title":"Cu2O-based catalysts applied for CO2 electrocatalytic reduction: A review","authors":"Cong Liu, Rui-Tang Guo, Hao-wen Zhu, Heng-fei Cui, Ming-yang Liu, Wei-Guo Pan","doi":"10.1039/d4ta06287f","DOIUrl":"https://doi.org/10.1039/d4ta06287f","url":null,"abstract":"The application of sustainable energy-driven electrocatalytic carbon dioxide reduction (CO2RR) technology enables the synthesis of valuable chemicals and feedstocks. This offers a promising pathway to effectively reduce greenhouse gas emissions associated with fossil fuels. Cu2O-based electrocatalysts have been widely investigated due to their cost-effective, environmentally friendly, and structurally tunable nature. This article provides a comprehensive review of recent advancements in the electrocatalytic reduction of carbon dioxide using Cu2O-based catalysts, with a focus on the properties, structure, and synthesis of Cu2O. It summarizes the performance of Cu2O-based catalysts in CO2 reduction and discusses several optimization strategies to enhance their stability and redox capabilities. Furthermore, it outlines the application of Cu2O-based catalysts in CO2 reduction. Finally, the opportunities, challenges and research directions for Cu2O-based catalysts in the field of CO2 electrocatalytic reduction are identified, providing guidance for their broad application in the energy and environmental sectors.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487069","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}
The ultra-high theoretical specific capacity of sulfur (1672 mAh g-1) has attracted researchers to intensely explore lithium-sulfur batteries. However, the shuttle effect of polysulfides and the slow conversion kinetics of sulfur have hindered its advancement. Herein, we synthesized CoS2-MgS heterostructure catalysts deposited on acetylene black nanoparticles, which were used as separator coatings to improve lithium-sulfur battery performance. Various experiments, such as XPS, Tafel curves, Li2S6 symmetric cells, Li2S deposition, and DFT calculations, identified the advantages of the CoS2-MgS heterostructure: rapid polar adsorption of CoS2 to polysulfides through oxidized partial Co2+ to Co3+ and fast lithium-ion migration in MgS. The coin cells delivered an initial discharge capacity of 573.4 mAh g-1 and cycled stably for 600 cycles at 5 C with a capacity decay rate of 0.08% per cycle; The battery retained a specific capacity of 545.5 mAh g-1 (4.3 mAh cm-2) after 100 cycles at 0.1 C with a sulfur loading of 7.87 mg cm-2. In addition, laminated pouch cells with a sulfur of 311.5 mg exhibited excellent cycle stability, maintaining 768.3 mAh g-1 (239 mAh) after 80 cycles. This work provides ideas to find novel composites that have both fast lithium-ion migration and strong polar adsorption for sulfur conversion while providing a reference for pouch battery research.
硫的超高理论比容量（1672 mAh g-1）吸引了研究人员对锂硫电池的深入研究。然而，多硫化物的穿梭效应和硫的缓慢转化动力学阻碍了其发展。在此，我们合成了沉积在乙炔黑纳米颗粒上的 CoS2-MgS 异质结构催化剂，并将其用作隔膜涂层，以提高锂硫电池的性能。通过 XPS、Tafel 曲线、Li2S6 对称电池、Li2S 沉积和 DFT 计算等各种实验，确定了 CoS2-MgS 异质结构的优势：通过将部分 Co2+ 氧化为 Co3+，使 CoS2 快速极性吸附到多硫化物上，并在 MgS 中快速迁移锂离子。纽扣电池的初始放电容量为 573.4 mAh g-1，在 5 C 下稳定循环 600 次，每次循环的容量衰减率为 0.08%；在 0.1 C 下循环 100 次后，电池的比容量仍为 545.5 mAh g-1（4.3 mAh cm-2），硫负荷为 7.87 mg cm-2。此外，硫含量为 311.5 毫克的层叠袋状电池具有出色的循环稳定性，在 80 个循环后仍能保持 768.3 毫安时 g-1（239 毫安时）。这项研究为寻找既能快速迁移锂离子又能强力吸附硫的新型复合材料提供了思路，同时也为袋式电池的研究提供了参考。
{"title":"Accelerating Sulfur Conversion Kinetics via CoS2-MgS Heterostructure for Lithium Sulfur Batteries","authors":"xinliang Men, teng Deng, Jiangxuan Che, Juan Wang","doi":"10.1039/d4ta06086e","DOIUrl":"https://doi.org/10.1039/d4ta06086e","url":null,"abstract":"The ultra-high theoretical specific capacity of sulfur (1672 mAh g-1) has attracted researchers to intensely explore lithium-sulfur batteries. However, the shuttle effect of polysulfides and the slow conversion kinetics of sulfur have hindered its advancement. Herein, we synthesized CoS2-MgS heterostructure catalysts deposited on acetylene black nanoparticles, which were used as separator coatings to improve lithium-sulfur battery performance. Various experiments, such as XPS, Tafel curves, Li2S6 symmetric cells, Li2S deposition, and DFT calculations, identified the advantages of the CoS2-MgS heterostructure: rapid polar adsorption of CoS2 to polysulfides through oxidized partial Co2+ to Co3+ and fast lithium-ion migration in MgS. The coin cells delivered an initial discharge capacity of 573.4 mAh g-1 and cycled stably for 600 cycles at 5 C with a capacity decay rate of 0.08% per cycle; The battery retained a specific capacity of 545.5 mAh g-1 (4.3 mAh cm-2) after 100 cycles at 0.1 C with a sulfur loading of 7.87 mg cm-2. In addition, laminated pouch cells with a sulfur of 311.5 mg exhibited excellent cycle stability, maintaining 768.3 mAh g-1 (239 mAh) after 80 cycles. This work provides ideas to find novel composites that have both fast lithium-ion migration and strong polar adsorption for sulfur conversion while providing a reference for pouch battery research.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452248","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}
Correction for ‘A simple melamine-assisted exfoliation of polymeric graphitic carbon nitrides for highly efficient hydrogen production from water under visible light’ by Longtao Ma et al., J. Mater. Chem. A, 2015, 3, 22404–22412, https://doi.org/10.1039/C5TA05850C.
{"title":"Correction: A simple melamine-assisted exfoliation of polymeric graphitic carbon nitrides for highly efficient hydrogen production from water under visible light","authors":"Longtao Ma, Huiqing Fan, Mengmeng Li, Hailin Tian, Jiawen Fang, Guangzhi Dong","doi":"10.1039/d4ta90200a","DOIUrl":"https://doi.org/10.1039/d4ta90200a","url":null,"abstract":"Correction for ‘A simple melamine-assisted exfoliation of polymeric graphitic carbon nitrides for highly efficient hydrogen production from water under visible light’ by Longtao Ma <em>et al.</em>, <em>J. Mater. Chem. A</em>, 2015, <strong>3</strong>, 22404–22412, https://doi.org/10.1039/C5TA05850C.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487054","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}
Yuying Wang, Fanjun Guo, Mengzhen Zhou, Qian Wu, Tao You, Zhengxiang Zhong, Jiankun Yang, Li Liu, Yudong Huang, Mingqiang Wang
Lithium metal batteries (LMBs) have been regarded as promising electrochemical energy storage systems for their high theoretical specific capacity of metallic lithium. However, the uncontrolled growth of lithium dendrites, stemming from uneven lithium deposition, poses a significant challenge to their practical implementation. To tackle this issue, an ultra-thin composite separator, consisting of octamethacryloyloxy sesquioxane (MA-POSS), methacryloyloxy trimethoxysilane grafted holey graphene oxide (MPS-HGO), and aramid nanofibers (ANF), was prepared through a combination of phase transition-induced co-assembly and in situ polymerization techniques. Experiments indicate that the composite separator, with a thickness of only 3.8 μm, exhibits exceptional mechanical properties, specifically a tensile strength of 104 ± 5.1 MPa and a modulus of 3.23 ± 0.2 GPa, due to extensive hydrogen bonding and π-π interactions between the HGO sheets and ANF. Furthermore, benefiting from the synergistic effect of the abundant pores in MPS-HGO and the inhibition of stacking through the copolymerization of MPS-HGO and MA-POSS, the composite separator also demonstrates good electrolyte infiltration and a high lithium-ion transport number (tLi⁺ = 0.87), which not only acts as a physical obstacle but also efficiently regulates the Li-ion transport to hinder irregular dendritic growth. The simultaneous regulation of the Li-ion transport and mitigation of dendrite growth made long cycle life for Li|Li cells without dendrite deposition after 1500 cycles at a high current density of 5 mA cm-2. Moreover, the LiFePO4 (LFP)|Li battery with the composite separator displayed a capacity of 154 mA h g-1, Coulombic efficiency of 99%, and high-capacity retention of 99.6% after 250 cycles at 0.5C (85.7% after 1000 cycles at 2C). This work provides a new promising approach to fabricating high-performance lithium battery separators.
{"title":"Ultrathin phase-inversion induced co-assembly separator for high-performance lithium-metal battery","authors":"Yuying Wang, Fanjun Guo, Mengzhen Zhou, Qian Wu, Tao You, Zhengxiang Zhong, Jiankun Yang, Li Liu, Yudong Huang, Mingqiang Wang","doi":"10.1039/d4ta05967k","DOIUrl":"https://doi.org/10.1039/d4ta05967k","url":null,"abstract":"Lithium metal batteries (LMBs) have been regarded as promising electrochemical energy storage systems for their high theoretical specific capacity of metallic lithium. However, the uncontrolled growth of lithium dendrites, stemming from uneven lithium deposition, poses a significant challenge to their practical implementation. To tackle this issue, an ultra-thin composite separator, consisting of octamethacryloyloxy sesquioxane (MA-POSS), methacryloyloxy trimethoxysilane grafted holey graphene oxide (MPS-HGO), and aramid nanofibers (ANF), was prepared through a combination of phase transition-induced co-assembly and in situ polymerization techniques. Experiments indicate that the composite separator, with a thickness of only 3.8 μm, exhibits exceptional mechanical properties, specifically a tensile strength of 104 ± 5.1 MPa and a modulus of 3.23 ± 0.2 GPa, due to extensive hydrogen bonding and π-π interactions between the HGO sheets and ANF. Furthermore, benefiting from the synergistic effect of the abundant pores in MPS-HGO and the inhibition of stacking through the copolymerization of MPS-HGO and MA-POSS, the composite separator also demonstrates good electrolyte infiltration and a high lithium-ion transport number (tLi⁺ = 0.87), which not only acts as a physical obstacle but also efficiently regulates the Li-ion transport to hinder irregular dendritic growth. The simultaneous regulation of the Li-ion transport and mitigation of dendrite growth made long cycle life for Li|Li cells without dendrite deposition after 1500 cycles at a high current density of 5 mA cm-2. Moreover, the LiFePO4 (LFP)|Li battery with the composite separator displayed a capacity of 154 mA h g-1, Coulombic efficiency of 99%, and high-capacity retention of 99.6% after 250 cycles at 0.5C (85.7% after 1000 cycles at 2C). This work provides a new promising approach to fabricating high-performance lithium battery separators.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486298","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}
Danyang Xiao, Chunxiao Wu, Bufeng Liang, Shangzuo Jiang, Jianxiong Ma, Yan Li
MXene quantum dots (MQDs), stand out with biocompatibility, biodegradability, and unparalleled optical absorption properties, offering compelling potential in producing exogenous reactive oxygen species (ROS) to treat tumor or bacterial infections. However, there is a gap in the comprehensive research of MQDs in ROS generation. In this study, three representative MQDs (Ti3C2 QDs, Ti2C QDs, and V2C QDs) were synthesized by hydrothermal method, and their ROS-generating ability and mechanism were thoroughly investigated. 3,3',5,5'-tetramethylbenzidine and ascorbic acid assays verified that the three MQDs possessed high ROS generated level under UV 365nm irradiation. Then, ESR spectroscopy and Trinder reaction identified the specific types of ROS generated, including hydroxyl radicals (•OH), singlet oxygen (1O2), superoxide radicals (O2•−), and hydrogen peroxide (H2O2). In addition, UPS, PL spectroscopy and electrochemical analyses further investigated the origin of ROS. MQDs’ excellent ROS generated capability can be attributed to their unique energy band structure, high carrier separation efficiency and excellent electron transfer ability. This work demonstrates that MQDs, with their ability to efficiently generate multiple types of ROS under UV irradiation, are promising candidates for the pro-oxidant and pave the way for various related biological applications.
{"title":"Outstanding ROS generation ability and mechanism of MXene quantum dots","authors":"Danyang Xiao, Chunxiao Wu, Bufeng Liang, Shangzuo Jiang, Jianxiong Ma, Yan Li","doi":"10.1039/d4ta05167j","DOIUrl":"https://doi.org/10.1039/d4ta05167j","url":null,"abstract":"MXene quantum dots (MQDs), stand out with biocompatibility, biodegradability, and unparalleled optical absorption properties, offering compelling potential in producing exogenous reactive oxygen species (ROS) to treat tumor or bacterial infections. However, there is a gap in the comprehensive research of MQDs in ROS generation. In this study, three representative MQDs (Ti3C2 QDs, Ti2C QDs, and V2C QDs) were synthesized by hydrothermal method, and their ROS-generating ability and mechanism were thoroughly investigated. 3,3',5,5'-tetramethylbenzidine and ascorbic acid assays verified that the three MQDs possessed high ROS generated level under UV 365nm irradiation. Then, ESR spectroscopy and Trinder reaction identified the specific types of ROS generated, including hydroxyl radicals (•OH), singlet oxygen (1O2), superoxide radicals (O2•−), and hydrogen peroxide (H2O2). In addition, UPS, PL spectroscopy and electrochemical analyses further investigated the origin of ROS. MQDs’ excellent ROS generated capability can be attributed to their unique energy band structure, high carrier separation efficiency and excellent electron transfer ability. This work demonstrates that MQDs, with their ability to efficiently generate multiple types of ROS under UV irradiation, are promising candidates for the pro-oxidant and pave the way for various related biological applications.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486300","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}
Jie Zhang, Thi Ha My Pham, Shibo Xi, Liping Zhong, David Liem, Futian You, Ben Rowley, Ramesha Ganganahalli, Federico Calle-Vallejo, Boon Siang Yeo
Cobalt phthalocyanine supported on carbon nanotubes (CoPcCNT) usually catalyzes the electroreduction of CO2 (CO2RR) to CO, although several reports have also indicated methanol formation. Herein, by analyzing the effects of CoPc loading and CO2 partial pressure on CO2RR, we show that a lower rate of CO2 mass transfer to each CoPc favors methanol formation, while a higher rate of CO2 mass transfer favors CO evolution. The ratio of the production rates of methanol and CO is related to the average CO2 mass transfer rate by a power function with a negative exponent. Hence, methanol can only be formed when the supply of CO2 feed is low. This mass transfer effect is supported by supplementary experiments and computational modelling, which show that CO binding to CoPc is weaker than that of CO2, in agreement with previous works. Consequently, *CO may only be reduced to methanol when the supply of CO2 is low and the dwelling time of CO is long. We further provide a quantitative guideline for the design of methanol-selective catalysts. At -0.86 V vs. RHE, enhanced CO mass transfer boosts CORR to methanol with a Faradaic efficiency up to 70 % at a total current density of -19 mA cm-2. The production of formaldehyde, a reaction intermediate from CO to methanol, is also boosted with a Faradaic efficiency of up to 7 %. We pinpoint CoPc containing Co(I) as the active CO2RR site.
以碳纳米管为支撑的酞菁钴（CoPcCNT）通常催化二氧化碳（CO2RR）电还原为一氧化碳，但也有一些报道表明会形成甲醇。在此，我们通过分析 CoPc 负载和二氧化碳分压对 CO2RR 的影响，发现较低的二氧化碳传质到每个 CoPc 的速率有利于甲醇的形成，而较高的二氧化碳传质速率则有利于 CO 的演化。甲醇和 CO 的产生率之比与 CO2 的平均传质率呈负指数幂函数关系。因此，只有当二氧化碳进料供应量较低时，才能形成甲醇。补充实验和计算模型也支持这种传质效应，它们表明 CO 与 CoPc 的结合力比 CO2 弱，这与之前的研究结果一致。因此，*CO 只有在 CO2 供应量少、CO 停留时间长的情况下才能还原成甲醇。我们进一步为甲醇选择性催化剂的设计提供了定量指导。在总电流密度为 -19 mA cm-2 时，当 -0.86 V 对 RHE 时，增强的 CO 传质可促进 CORR 转化为甲醇，法拉第效率高达 70%。从 CO 到甲醇的反应中间产物甲醛的生成也得到了促进，法拉第效率高达 7%。我们将含有 Co（I）的 CoPc 确定为活性 CO2RR 位点。
{"title":"Low CO2 Mass Transfer Promotes Methanol and Formaldehyde Electrosynthesis on Cobalt Phthalocyanine","authors":"Jie Zhang, Thi Ha My Pham, Shibo Xi, Liping Zhong, David Liem, Futian You, Ben Rowley, Ramesha Ganganahalli, Federico Calle-Vallejo, Boon Siang Yeo","doi":"10.1039/d4ta03531c","DOIUrl":"https://doi.org/10.1039/d4ta03531c","url":null,"abstract":"Cobalt phthalocyanine supported on carbon nanotubes (CoPcCNT) usually catalyzes the electroreduction of CO2 (CO2RR) to CO, although several reports have also indicated methanol formation. Herein, by analyzing the effects of CoPc loading and CO2 partial pressure on CO2RR, we show that a lower rate of CO2 mass transfer to each CoPc favors methanol formation, while a higher rate of CO2 mass transfer favors CO evolution. The ratio of the production rates of methanol and CO is related to the average CO2 mass transfer rate by a power function with a negative exponent. Hence, methanol can only be formed when the supply of CO2 feed is low. This mass transfer effect is supported by supplementary experiments and computational modelling, which show that CO binding to CoPc is weaker than that of CO2, in agreement with previous works. Consequently, *CO may only be reduced to methanol when the supply of CO2 is low and the dwelling time of CO is long. We further provide a quantitative guideline for the design of methanol-selective catalysts. At -0.86 V vs. RHE, enhanced CO mass transfer boosts CORR to methanol with a Faradaic efficiency up to 70 % at a total current density of -19 mA cm-2. The production of formaldehyde, a reaction intermediate from CO to methanol, is also boosted with a Faradaic efficiency of up to 7 %. We pinpoint CoPc containing Co(I) as the active CO2RR site.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451615","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}
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