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
Oxygen vacancy engineering in heterogeneous catalysts has attracted considerable interest for peroxymonosulfate(PMS)activation.In this study,nano-Co3O4-encapsulated montmorillonite catalysts with tunable oxygen ...Oxygen vacancy engineering in heterogeneous catalysts has attracted considerable interest for peroxymonosulfate(PMS)activation.In this study,nano-Co3O4-encapsulated montmorillonite catalysts with tunable oxygen vacancy(OV)concentrations(denoted as Co3O4−Mt-xOV,x=2,4,6)were synthesized for enhanced PMS activation.These OV defects not only modulate the electronic structure of Co3O4but also strengthen PMS and contaminant adsorption.The optimized Co3O4−Mt-xOV/PMS system exhibited exceptional ofloxacin(OFL)degradation efficiency,achieving 2.74–3.43-fold enhancement over OV-free Co3O4−Mt.Density functional theory calculations and experimental studies revealed that the performance improvement stemmed from OV formation,which synergistically enhanced redox pair cycling,strengthened PMS adsorption,and promoted active species generation during electron transfer.Further studies demonstrated that OV sites selectively drive PMS decomposition to generate high-valent cobalt-oxo species(Co(Ⅳ)=O)and singlet oxygen(1O2)as the dominant reactive species for OFL oxidation.The in-depth investigation into the catalytic mechanism revealed that the Co(Ⅳ)=O species facilitated O2•−generation in surpassing the reaction energy barrier,which subsequently converted to1O2.This non-radical pathway endowed the system with robust anti-interference capability against complex water matrices.The critical role of OV in PMS activation was mechanistically confirmed through experimental and theoretical analyses.Furthermore,Co3O4−Mt-4OV demonstrated outstanding chemical stability and recyclability,highlighting its practical potential.This work provides fundamental insights into vacancy defect engineering for advanced PMS activation and offers strategic guidance for designing high-performance catalysts.展开更多
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.
基金supported by National Natural Science Foundation of China(Nos.22476116,52074176,52400090)Natural Science Foundation of Shandong Province(Nos.ZR2024ME156,ZR2024QB138)Qingdao Natural Science Foundation(No.24-4-4-zrjj-70-jch).
摘要Oxygen vacancy engineering in heterogeneous catalysts has attracted considerable interest for peroxymonosulfate(PMS)activation.In this study,nano-Co3O4-encapsulated montmorillonite catalysts with tunable oxygen vacancy(OV)concentrations(denoted as Co3O4−Mt-xOV,x=2,4,6)were synthesized for enhanced PMS activation.These OV defects not only modulate the electronic structure of Co3O4but also strengthen PMS and contaminant adsorption.The optimized Co3O4−Mt-xOV/PMS system exhibited exceptional ofloxacin(OFL)degradation efficiency,achieving 2.74–3.43-fold enhancement over OV-free Co3O4−Mt.Density functional theory calculations and experimental studies revealed that the performance improvement stemmed from OV formation,which synergistically enhanced redox pair cycling,strengthened PMS adsorption,and promoted active species generation during electron transfer.Further studies demonstrated that OV sites selectively drive PMS decomposition to generate high-valent cobalt-oxo species(Co(Ⅳ)=O)and singlet oxygen(1O2)as the dominant reactive species for OFL oxidation.The in-depth investigation into the catalytic mechanism revealed that the Co(Ⅳ)=O species facilitated O2•−generation in surpassing the reaction energy barrier,which subsequently converted to1O2.This non-radical pathway endowed the system with robust anti-interference capability against complex water matrices.The critical role of OV in PMS activation was mechanistically confirmed through experimental and theoretical analyses.Furthermore,Co3O4−Mt-4OV demonstrated outstanding chemical stability and recyclability,highlighting its practical potential.This work provides fundamental insights into vacancy defect engineering for advanced PMS activation and offers strategic guidance for designing high-performance catalysts.