The adsorptive denitrification performance of MIL-101(Cr)-0.5 toward pyridine,aniline or quinoline in simulated fuels with basic nitrogen content of 1732μg/g was evaluated separately.Furthermore,the effects of adsorp...The adsorptive denitrification performance of MIL-101(Cr)-0.5 toward pyridine,aniline or quinoline in simulated fuels with basic nitrogen content of 1732μg/g was evaluated separately.Furthermore,the effects of adsorption temperature,adsorption time and adsorbent dosage on their adsorptive denitrification performance were systematically investigated.The experimental results demonstrated that under a fixed adsorbent dosage of 0.05 g and a simulated fuel volume of 10 mL,the optimal removal efficiency for aniline was achieved at 30℃ within 30 min,whereas higher temperatures and longer times(40℃and 40 min)were required for effective removal of pyridine and quinoline.Density Functional Theory(DFT)calculations were conducted via Materials Studio(MS)software to study the adsorptive denitrification mechanism of MIL-101(Cr)toward these three basic nitrogen-containing compounds.The simulation calculation results revealed that the interaction between pyridine and MIL-101(Cr)primarily involved coordination adsorption.In contrast,the interaction between aniline or quinoline and MIL-101(Cr)proceeded mainly through coordination,with additional contributions fromπ-complexation and hydrogen bonding.The overall adsorption strength order is pyridine>aniline>quinoline.During the adsorption process,pyridine and quinoline transfer electrons to the MIL-101(Cr)surface through the H→C→N→Cr^(3+)pathway,while aniline transfers electrons to the MIL-101(Cr)surface through various pathways,including N→Cr^(3+),N→C→Cr^(3+)and N→H→O.Furthermore,adsorption kinetics studies indicated that the adsorption processes for all three basic nitrogen-containing compounds followed the quasi second order kinetic models.The experimental results on the effect of benzene on the adsorptive denitrification performance of MIL-101(Cr)-0.5 demonstrated that benzene exerted a more significant impact on the adsorption of aniline and quinoline.Finally,the adsorbent was regenerated using ethanol washing.It was found that MIL-101(Cr)-0.5 retained stable denitrification performance after two regeneration cycles.展开更多
The practical deployment of aqueous zinc metal batteries(AZMBs)is critically challenged by uncontrolled dendrite formation and parasitic side reactions,both arising from unstable interfacial chemistry.Herein,we propos...The practical deployment of aqueous zinc metal batteries(AZMBs)is critically challenged by uncontrolled dendrite formation and parasitic side reactions,both arising from unstable interfacial chemistry.Herein,we propose a dual-region interfacial engineering strategy that concurrently regulates both the outer and inner Helmholtz planes(OHP/IHP)by introducing the N,N-dimethylethanolamine(DMEA)into the ZnSO_(4) electrolyte.In the OHP,DMEA coordinates with Zn^(2+)to reshape the solvation structure and attenuate Zn^(2+)-H_(2)O interactions,thereby lowering water activity and suppressing hydrogen evolution.Meanwhile,DMEA molecules chemisorb onto the Zn surface within the IHP,forming a robust organic interphase that homogenizes the electric field and promotes uniform Zn nucleation.This dual functionality guides crystallographic evolution toward the thermodynamically favorable(101)facet,which supports lateral Zn growth and effectively mitigates dendrite propagation.Benefiting from the interfacial-crystallographic synergy,Zn‖Zn symmetric cells exhibit ultralong cycling stability over5000 h at 1 mA cm^(-2) and maintain dendrite-free operation for over 1000 h at 5 mA cm^(-2).Furthermore,Zn‖NH_(4)V_(4)O_(10) full cells deliver high specific capacities with 80.06%capacity retention after1000 cycles at 5 A g^(-1).This work offers a mechanistically guided and scalable electrolyte design that bridges solvation chemistry with crystallographic control,providing a promising route toward dendrite-free,high-efficiency AZMBs.展开更多
基金Supported by Basic Scientific Research Project of the Liaoning Provincial Department of Education Has Been Unveiled to Facilitate Local Project Funding (JYTMS20230835)Enhanced Scientific Research Project Funded by the Departmentof Higher Education in Liaoning Province (General program)(JYTMS20230852)。
文摘The adsorptive denitrification performance of MIL-101(Cr)-0.5 toward pyridine,aniline or quinoline in simulated fuels with basic nitrogen content of 1732μg/g was evaluated separately.Furthermore,the effects of adsorption temperature,adsorption time and adsorbent dosage on their adsorptive denitrification performance were systematically investigated.The experimental results demonstrated that under a fixed adsorbent dosage of 0.05 g and a simulated fuel volume of 10 mL,the optimal removal efficiency for aniline was achieved at 30℃ within 30 min,whereas higher temperatures and longer times(40℃and 40 min)were required for effective removal of pyridine and quinoline.Density Functional Theory(DFT)calculations were conducted via Materials Studio(MS)software to study the adsorptive denitrification mechanism of MIL-101(Cr)toward these three basic nitrogen-containing compounds.The simulation calculation results revealed that the interaction between pyridine and MIL-101(Cr)primarily involved coordination adsorption.In contrast,the interaction between aniline or quinoline and MIL-101(Cr)proceeded mainly through coordination,with additional contributions fromπ-complexation and hydrogen bonding.The overall adsorption strength order is pyridine>aniline>quinoline.During the adsorption process,pyridine and quinoline transfer electrons to the MIL-101(Cr)surface through the H→C→N→Cr^(3+)pathway,while aniline transfers electrons to the MIL-101(Cr)surface through various pathways,including N→Cr^(3+),N→C→Cr^(3+)and N→H→O.Furthermore,adsorption kinetics studies indicated that the adsorption processes for all three basic nitrogen-containing compounds followed the quasi second order kinetic models.The experimental results on the effect of benzene on the adsorptive denitrification performance of MIL-101(Cr)-0.5 demonstrated that benzene exerted a more significant impact on the adsorption of aniline and quinoline.Finally,the adsorbent was regenerated using ethanol washing.It was found that MIL-101(Cr)-0.5 retained stable denitrification performance after two regeneration cycles.
基金the financial support from the Scientific Research Fund of Liaoning Provincial Education Department of China(No.JYTQN2023289)the Liaoning Provincial Science and Technology Joint Plan(Fund)Project(No.2023BSBA-259)+4 种基金the opening project of State Key Laboratory of Metastable Materials Science and Technology,Yanshan University(No.202404)the support from the National Natural Science Foundation of China(Grant No.52402279)the China Postdoctoral Science Foundation Special Funding(Grant No.T2025T180002)the China Postdoctoral Science Foundation General Program(Grant No.2024M751753)the opening project of State Key Laboratory of Metastable Materials Science and Technology(Yanshan University)(No.202401)。
文摘The practical deployment of aqueous zinc metal batteries(AZMBs)is critically challenged by uncontrolled dendrite formation and parasitic side reactions,both arising from unstable interfacial chemistry.Herein,we propose a dual-region interfacial engineering strategy that concurrently regulates both the outer and inner Helmholtz planes(OHP/IHP)by introducing the N,N-dimethylethanolamine(DMEA)into the ZnSO_(4) electrolyte.In the OHP,DMEA coordinates with Zn^(2+)to reshape the solvation structure and attenuate Zn^(2+)-H_(2)O interactions,thereby lowering water activity and suppressing hydrogen evolution.Meanwhile,DMEA molecules chemisorb onto the Zn surface within the IHP,forming a robust organic interphase that homogenizes the electric field and promotes uniform Zn nucleation.This dual functionality guides crystallographic evolution toward the thermodynamically favorable(101)facet,which supports lateral Zn growth and effectively mitigates dendrite propagation.Benefiting from the interfacial-crystallographic synergy,Zn‖Zn symmetric cells exhibit ultralong cycling stability over5000 h at 1 mA cm^(-2) and maintain dendrite-free operation for over 1000 h at 5 mA cm^(-2).Furthermore,Zn‖NH_(4)V_(4)O_(10) full cells deliver high specific capacities with 80.06%capacity retention after1000 cycles at 5 A g^(-1).This work offers a mechanistically guided and scalable electrolyte design that bridges solvation chemistry with crystallographic control,providing a promising route toward dendrite-free,high-efficiency AZMBs.
