The uniform pore size distribution and inherent particle inseparability of iron-based metal-organic frameworks(Fe-MOFs)have been shown to significantly hinder their light-harvesting capabilities and charge carrier sep...The uniform pore size distribution and inherent particle inseparability of iron-based metal-organic frameworks(Fe-MOFs)have been shown to significantly hinder their light-harvesting capabilities and charge carrier separation efficiency.These intrinsic limitations compromise catalyst recyclability and reaction kinetics in practical scenarios,thereby impeding their applicability in the degradation of antibiotic pollutants such as levofloxacin(LEV)in aquatic environments.Here,we report an S-type heterojunction photocatalyst,MnFe2O4@MIL-101(Fe),prepared via hydrothermal coupling of magnetic MnFe2O4 nanoparticles with MIL-101(Fe).The synergistic effect of Fe3+/Fe2+and Mn3+/Mn2+redox pairs,combined with the heterojunction interface and built-in electric field,significantly enhances visible-light-driven photo-Fenton activity.The catalyst degraded over 95%of LEV with a rate constant of 0.05056 min-1 and retained 87%activity after five cycles.LC-MS analysis revealed defluorination and demethylation pathways,while toxicity assessments confirmed lower LC50,mutagenicity,and developmental toxicity of intermediates,validating the environmental viability of the photo-Fenton process.展开更多
Bi/Bi2Fe4O9nanocomposites consisting of Bi2Fe4O9nanosheets decorated with Bi nanodots were synthesized by a hydrothermal method.The formation of Bi nanodots on the Bi2Fe4O9nanosheet surfaces...Bi/Bi2Fe4O9nanocomposites consisting of Bi2Fe4O9nanosheets decorated with Bi nanodots were synthesized by a hydrothermal method.The formation of Bi nanodots on the Bi2Fe4O9nanosheet surfaces was attributed to the reducibility of 2-methoxyethanol in the precursor solution.Comparative photocatalytic evaluation reveals that the Bi/Bi2Fe4O9nanocomposites significantly enhance the degradation efficiency(99.0%)of bisphenol A compared with Bi2Fe4O9nanosheets(64.2%)under 120 min simulated solar irradiation.This remarkable enhancement can be attributed to the established Bi/Bi2Fe4O9heterojunction structure,which effectively facilitates the separation of photogenerated electron-hole pairs and accelerates interfacial charge transfer between the metallic Bi nanodots and semiconductor Bi2Fe4O9nanosheets.The synergistic effects arising from this unique architecture ultimately lead to superior photocatalytic performance.展开更多
【Purposes】In photocatalytic CO2reduction reaction,since the electron transfer efficiencies of CH4 and CO are close and their thermodynamic properties are similar,achieving high electron selectivity for CH4 sti...【Purposes】In photocatalytic CO2reduction reaction,since the electron transfer efficiencies of CH4 and CO are close and their thermodynamic properties are similar,achieving high electron selectivity for CH4 still faces significant challenges.【Methods】In this study,a single-atom Nidoped C3N4catalyst(CN-Ni)was first synthesized and then hydroxyl-modified to obtain hCN-Ni through the hydrothermal method.【Results】Experimental results show that the hydroxyl-modified hCN-Ni catalyst exhibits excellent CO2reduction performance,with CO and CH4 generation rates of 22 and 3.3µmol·g-1·h−1,respectively,and the CH4 electron selectivity reaches 37.5%.The remarkable performance enhancement stems from the synergistic effect of hydroxyl modification and Ni monoatoms.On one hand,the introduction of hydroxyl groups enhances the hydrophilicity of the catalyst surface,and promotes the adsorption of water molecules as well as the formation of a local waterrich microenvironment,while its asymmetric steric hindrance effectively inhibits the recombination of photogenerated carriers;On the other hand,the dispersed Ni monoatoms on the surface of hCN-Ni serve as active centers for CO2adsorption and activation,and protons enriched on the hydroxyl-modified surface can be rapidly transferred to these Ni active sites,thus significantly facilitating the hydrogenation of CO2to CH4.展开更多
水系锌离子电池中,VOPO4·2H2O正极材料在充放电循环过程中易受电解液中自由水的侵蚀而发生溶解,导致严重的电压衰减和容量损失。高浓度双三氟甲磺酰亚胺锂(LiTFSI)虽可通过其丰富的磺酰基氧原子作为氢键受体有效降低自由水含...水系锌离子电池中,VOPO4·2H2O正极材料在充放电循环过程中易受电解液中自由水的侵蚀而发生溶解,导致严重的电压衰减和容量损失。高浓度双三氟甲磺酰亚胺锂(LiTFSI)虽可通过其丰富的磺酰基氧原子作为氢键受体有效降低自由水含量,从而抑制正极材料溶解,但其成本高昂且黏度过大,限制了实际应用。针对该问题,本研究提出一种三氟甲磺酸锌(Zn(OTf)2)电解液协同替代策略,采用低成本果糖(Fru)部分替代高浓度LiTFSI,在保持氢键受体总数相近的前提下,显著降低电解液黏度和成本,同时优化Zn2+传输动力学,成功构建了4.5 m Zn(OTf)2+11 m Fru+8.5 m LiTFSI(m表示mol/kg水)优化电解液体系,并将其与4 m Zn(OTf)2及1 m Zn(OTf)2+18 m LiTFSI电解液进行系统对比。XRD、SEM-EDS、TEM表征结果表明,VOPO4·2H2O粉末结晶性良好,呈明显片层堆积结构。浸泡实验显示,VOPO4·2H2O粉末在4 m Zn(OTf)2电解液中仅10 min即发生明显溶解,而在含LiTFSI的两种电解液中浸泡10 d后仍未发生显著溶解。电化学测试结果表明,优化电解液显著提升了VOPO4·2H2O正极的循环稳定性和倍率性能,在1 C倍率下循环150次后容量保持率达95%,优于对比体系。动力学分析进一步揭示,优化电解液有效降低了电荷转移电阻,并显著提升了Zn2+扩散系数。拉曼光谱分析证实,优化电解液中,果糖分子凭借其五个羟基的灵活构型,与LiTFSI上丰富的氢键位点协同作用,与水分子形成致密氢键网络,显著降低自由水含量,从而抑制了VOPO4·2H2O的溶解及不可逆相变。本研究通过低成本、环境友好的电解液设计策略,解决了高浓度LiTFSI电解液体系的高黏度与高成本难题,为水系锌离子电池中VOPO4·2H2O正极材料的结构稳定化提供了有效途径,展现出良好的应用潜力。展开更多
Zn-based thermal charging devices,utilizing the synergistic effect of ion thermoextraction and thermodiffusion,are able to efficiently convert thermal energy into electrical energy and storage in the devices,making th...Zn-based thermal charging devices,utilizing the synergistic effect of ion thermoextraction and thermodiffusion,are able to efficiently convert thermal energy into electrical energy and storage in the devices,making them a highly promising technology for low-grade heat recovery and utilization.However,the low output power density and energy conversion efficiency resulted by the slow diffusion kinetics of Zn2+hinder their development.Herein,we present a highperformance thermal charging cell design using Zn2+/NH4+hybrid ion electrolyte,which not only maintains the high output voltage of the Zn-based thermoelectric system,but also significantly enhances the output power density due to the fast diffusion kinetics of NH4+.Based on this strategy,the thermal charging cell displays a high thermopower of 12.5 mV K-1and an excellent normalized power density of 19.6 mW m-2K-2at a temperature difference of 35 K.The Carnot-relative efficiency is as high as 12.74%.Moreover,it can operate continuously for over 72 h when the temperature difference persists,achieving a balance between thermoelectric conversion and output.This work provides a simple and effective strategy for the design of high-performance thermal charging cells for low-grade heat conversion and utilization.展开更多
基金supported by the National Natural Science Foundation of China(No.22178325)the Research Fund of Key Laboratory of the Ministry of Education for Advanced Catalysis Materials,Zhejiang Key Laboratory of Advanced Catalysis and Adsorption Materials。
摘要The uniform pore size distribution and inherent particle inseparability of iron-based metal-organic frameworks(Fe-MOFs)have been shown to significantly hinder their light-harvesting capabilities and charge carrier separation efficiency.These intrinsic limitations compromise catalyst recyclability and reaction kinetics in practical scenarios,thereby impeding their applicability in the degradation of antibiotic pollutants such as levofloxacin(LEV)in aquatic environments.Here,we report an S-type heterojunction photocatalyst,MnFe2O4@MIL-101(Fe),prepared via hydrothermal coupling of magnetic MnFe2O4 nanoparticles with MIL-101(Fe).The synergistic effect of Fe3+/Fe2+and Mn3+/Mn2+redox pairs,combined with the heterojunction interface and built-in electric field,significantly enhances visible-light-driven photo-Fenton activity.The catalyst degraded over 95%of LEV with a rate constant of 0.05056 min-1 and retained 87%activity after five cycles.LC-MS analysis revealed defluorination and demethylation pathways,while toxicity assessments confirmed lower LC50,mutagenicity,and developmental toxicity of intermediates,validating the environmental viability of the photo-Fenton process.
基金Funded by the National Natural Science Foundation of China(No.50902108)。
摘要Bi/Bi2Fe4O9nanocomposites consisting of Bi2Fe4O9nanosheets decorated with Bi nanodots were synthesized by a hydrothermal method.The formation of Bi nanodots on the Bi2Fe4O9nanosheet surfaces was attributed to the reducibility of 2-methoxyethanol in the precursor solution.Comparative photocatalytic evaluation reveals that the Bi/Bi2Fe4O9nanocomposites significantly enhance the degradation efficiency(99.0%)of bisphenol A compared with Bi2Fe4O9nanosheets(64.2%)under 120 min simulated solar irradiation.This remarkable enhancement can be attributed to the established Bi/Bi2Fe4O9heterojunction structure,which effectively facilitates the separation of photogenerated electron-hole pairs and accelerates interfacial charge transfer between the metallic Bi nanodots and semiconductor Bi2Fe4O9nanosheets.The synergistic effects arising from this unique architecture ultimately lead to superior photocatalytic performance.
基金National Natural Science Foundation of China(52472300)。
摘要【Purposes】In photocatalytic CO2reduction reaction,since the electron transfer efficiencies of CH4 and CO are close and their thermodynamic properties are similar,achieving high electron selectivity for CH4 still faces significant challenges.【Methods】In this study,a single-atom Nidoped C3N4catalyst(CN-Ni)was first synthesized and then hydroxyl-modified to obtain hCN-Ni through the hydrothermal method.【Results】Experimental results show that the hydroxyl-modified hCN-Ni catalyst exhibits excellent CO2reduction performance,with CO and CH4 generation rates of 22 and 3.3µmol·g-1·h−1,respectively,and the CH4 electron selectivity reaches 37.5%.The remarkable performance enhancement stems from the synergistic effect of hydroxyl modification and Ni monoatoms.On one hand,the introduction of hydroxyl groups enhances the hydrophilicity of the catalyst surface,and promotes the adsorption of water molecules as well as the formation of a local waterrich microenvironment,while its asymmetric steric hindrance effectively inhibits the recombination of photogenerated carriers;On the other hand,the dispersed Ni monoatoms on the surface of hCN-Ni serve as active centers for CO2adsorption and activation,and protons enriched on the hydroxyl-modified surface can be rapidly transferred to these Ni active sites,thus significantly facilitating the hydrogenation of CO2to CH4.
摘要水系锌离子电池中,VOPO4·2H2O正极材料在充放电循环过程中易受电解液中自由水的侵蚀而发生溶解,导致严重的电压衰减和容量损失。高浓度双三氟甲磺酰亚胺锂(LiTFSI)虽可通过其丰富的磺酰基氧原子作为氢键受体有效降低自由水含量,从而抑制正极材料溶解,但其成本高昂且黏度过大,限制了实际应用。针对该问题,本研究提出一种三氟甲磺酸锌(Zn(OTf)2)电解液协同替代策略,采用低成本果糖(Fru)部分替代高浓度LiTFSI,在保持氢键受体总数相近的前提下,显著降低电解液黏度和成本,同时优化Zn2+传输动力学,成功构建了4.5 m Zn(OTf)2+11 m Fru+8.5 m LiTFSI(m表示mol/kg水)优化电解液体系,并将其与4 m Zn(OTf)2及1 m Zn(OTf)2+18 m LiTFSI电解液进行系统对比。XRD、SEM-EDS、TEM表征结果表明,VOPO4·2H2O粉末结晶性良好,呈明显片层堆积结构。浸泡实验显示,VOPO4·2H2O粉末在4 m Zn(OTf)2电解液中仅10 min即发生明显溶解,而在含LiTFSI的两种电解液中浸泡10 d后仍未发生显著溶解。电化学测试结果表明,优化电解液显著提升了VOPO4·2H2O正极的循环稳定性和倍率性能,在1 C倍率下循环150次后容量保持率达95%,优于对比体系。动力学分析进一步揭示,优化电解液有效降低了电荷转移电阻,并显著提升了Zn2+扩散系数。拉曼光谱分析证实,优化电解液中,果糖分子凭借其五个羟基的灵活构型,与LiTFSI上丰富的氢键位点协同作用,与水分子形成致密氢键网络,显著降低自由水含量,从而抑制了VOPO4·2H2O的溶解及不可逆相变。本研究通过低成本、环境友好的电解液设计策略,解决了高浓度LiTFSI电解液体系的高黏度与高成本难题,为水系锌离子电池中VOPO4·2H2O正极材料的结构稳定化提供了有效途径,展现出良好的应用潜力。
基金supported by the Leading Edge Technology of Jiangsu Province(BK20222009-X.Z.,BK20202008-X.Z.)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)National Undergraduate Innovation Training Program of NUAA(202410287179Y).
摘要Zn-based thermal charging devices,utilizing the synergistic effect of ion thermoextraction and thermodiffusion,are able to efficiently convert thermal energy into electrical energy and storage in the devices,making them a highly promising technology for low-grade heat recovery and utilization.However,the low output power density and energy conversion efficiency resulted by the slow diffusion kinetics of Zn2+hinder their development.Herein,we present a highperformance thermal charging cell design using Zn2+/NH4+hybrid ion electrolyte,which not only maintains the high output voltage of the Zn-based thermoelectric system,but also significantly enhances the output power density due to the fast diffusion kinetics of NH4+.Based on this strategy,the thermal charging cell displays a high thermopower of 12.5 mV K-1and an excellent normalized power density of 19.6 mW m-2K-2at a temperature difference of 35 K.The Carnot-relative efficiency is as high as 12.74%.Moreover,it can operate continuously for over 72 h when the temperature difference persists,achieving a balance between thermoelectric conversion and output.This work provides a simple and effective strategy for the design of high-performance thermal charging cells for low-grade heat conversion and utilization.