采用Co_(3)O_(4)吸附脱除模拟柴油中的喹啉、吡啶或苯胺,考察了最佳吸附温度、吸附时间等条件,同时进行了吸附热力学和动力学研究;基于第一性原理对Co_(3)O_(4)晶胞进行相分析,对3种氮化物进行最高占据分子轨道(HOMO)-最低未占据分子轨...采用Co_(3)O_(4)吸附脱除模拟柴油中的喹啉、吡啶或苯胺,考察了最佳吸附温度、吸附时间等条件,同时进行了吸附热力学和动力学研究;基于第一性原理对Co_(3)O_(4)晶胞进行相分析,对3种氮化物进行最高占据分子轨道(HOMO)-最低未占据分子轨道(LUMO)分析,计算了吸附构型的吸附能和最稳定吸附构型的Mulliken电荷转移与电子密度。结果表明:在15 mL模拟柴油中加入0.6 g Co_(3)O_(4),苯胺、吡啶、喹啉的最佳吸附温度分别为20、20和30℃,最佳吸附时间分别为30、30、40 min,吸附容量由大到小顺序均为苯胺>吡啶>喹啉。热力学与动力学分析表明,喹啉、吡啶、苯胺的吸附均更符合多分子层吸附的Freundlich模型和准二级动力学方程。HOMO-LUMO分析结果表明,Co_(3)O_(4)为电子接受体,3种氮化物为电子给予体,Co_(3)O_(4)对喹啉、吡啶的配位吸附结构最稳定,对苯胺的π络合吸附最稳定。电荷转移计算表明,苯胺、吡啶、喹啉向Co_(3)O_(4)团簇转移的电荷数分别为0.423、0.394、0.368,说明Co_(3)O_(4)吸附3种氮化物的吸附能力大小为苯胺>吡啶>喹啉;电子密度图结果表明,最稳定吸附结构中Co_(3)O_(4)与3种氮化物均形成了化学键。展开更多
NH_(4)V_(4)O_(10)(NVO)is considered a promising cathode material for aqueous zinc-ion batteries due to its high theoretical capacity.However,its practical application is limited by irreversible deamination,structural ...NH_(4)V_(4)O_(10)(NVO)is considered a promising cathode material for aqueous zinc-ion batteries due to its high theoretical capacity.However,its practical application is limited by irreversible deamination,structural collapse,and sluggish reaction kinetics during cycling.Herein,K+and C_(3)N_(4)co-intercalated NVO(KNVO-C_(3)N_(4))nanosheets with expanded interlayer spacing are synthesized for the first time to achieve high-rate,stable,and wide-temperature cathodes.Molecular dynamics and experimental results confirm that there is an optimal C_(3)N_(4)content to achieve higher reaction kinetics.The synergistic effect of K^(+)and C_(3)N_(4)co-intercalation significantly reduces the electrostatic interaction between Zn^(2+)and the[VOn]layer,improves the specific capacity and cycling stability.Consequently,the KNVO-C_(3)N_(4)electrode displays outstanding electrochemical performance at room temperature and under extreme environments.It exhibits excellent rate performance(228.4 m Ah g^(-1)at 20 A g^(-1)),long-term cycling stability(174.2 m Ah g^(-1) after 10,000 cycles at 20 A g^(-1)),and power/energy density(210.0 Wh kg^(-1)at 14,200 W kg^(-1))at room temperature.Notably,it shows remarkable storage performance at-20℃(111.3 m Ah g^(-1)at 20 A g^(-1))and 60℃(208.6 m Ah g^(-1)at 20 A g^(-1)).This strategy offers a novel approach to developing high-performance cathodes capable of operating under extreme temperatures.展开更多
文摘采用Co_(3)O_(4)吸附脱除模拟柴油中的喹啉、吡啶或苯胺,考察了最佳吸附温度、吸附时间等条件,同时进行了吸附热力学和动力学研究;基于第一性原理对Co_(3)O_(4)晶胞进行相分析,对3种氮化物进行最高占据分子轨道(HOMO)-最低未占据分子轨道(LUMO)分析,计算了吸附构型的吸附能和最稳定吸附构型的Mulliken电荷转移与电子密度。结果表明:在15 mL模拟柴油中加入0.6 g Co_(3)O_(4),苯胺、吡啶、喹啉的最佳吸附温度分别为20、20和30℃,最佳吸附时间分别为30、30、40 min,吸附容量由大到小顺序均为苯胺>吡啶>喹啉。热力学与动力学分析表明,喹啉、吡啶、苯胺的吸附均更符合多分子层吸附的Freundlich模型和准二级动力学方程。HOMO-LUMO分析结果表明,Co_(3)O_(4)为电子接受体,3种氮化物为电子给予体,Co_(3)O_(4)对喹啉、吡啶的配位吸附结构最稳定,对苯胺的π络合吸附最稳定。电荷转移计算表明,苯胺、吡啶、喹啉向Co_(3)O_(4)团簇转移的电荷数分别为0.423、0.394、0.368,说明Co_(3)O_(4)吸附3种氮化物的吸附能力大小为苯胺>吡啶>喹啉;电子密度图结果表明,最稳定吸附结构中Co_(3)O_(4)与3种氮化物均形成了化学键。
基金the financial support provided by the PolyU Postdoc Matching Fund 1-W34P,ITF project ITP/023/22TP,PolyU RCRE fund 1-BBCB,IWEAR fund 1-CD8E,MTR Research Funding Scheme(PTU24019)the Hong Kong Polytechnic University(P0043508 and P0044761)。
文摘NH_(4)V_(4)O_(10)(NVO)is considered a promising cathode material for aqueous zinc-ion batteries due to its high theoretical capacity.However,its practical application is limited by irreversible deamination,structural collapse,and sluggish reaction kinetics during cycling.Herein,K+and C_(3)N_(4)co-intercalated NVO(KNVO-C_(3)N_(4))nanosheets with expanded interlayer spacing are synthesized for the first time to achieve high-rate,stable,and wide-temperature cathodes.Molecular dynamics and experimental results confirm that there is an optimal C_(3)N_(4)content to achieve higher reaction kinetics.The synergistic effect of K^(+)and C_(3)N_(4)co-intercalation significantly reduces the electrostatic interaction between Zn^(2+)and the[VOn]layer,improves the specific capacity and cycling stability.Consequently,the KNVO-C_(3)N_(4)electrode displays outstanding electrochemical performance at room temperature and under extreme environments.It exhibits excellent rate performance(228.4 m Ah g^(-1)at 20 A g^(-1)),long-term cycling stability(174.2 m Ah g^(-1) after 10,000 cycles at 20 A g^(-1)),and power/energy density(210.0 Wh kg^(-1)at 14,200 W kg^(-1))at room temperature.Notably,it shows remarkable storage performance at-20℃(111.3 m Ah g^(-1)at 20 A g^(-1))and 60℃(208.6 m Ah g^(-1)at 20 A g^(-1)).This strategy offers a novel approach to developing high-performance cathodes capable of operating under extreme temperatures.
