The photocatalytic conversion of CO2into high-value fuels represents a promising strategy for achieving carbon neutrality by utilizing solar energy.Overcoming kinetic barriers in multi-electron transfer and C–C co...The photocatalytic conversion of CO2into high-value fuels represents a promising strategy for achieving carbon neutrality by utilizing solar energy.Overcoming kinetic barriers in multi-electron transfer and C–C coupling is critical for photocatalytic CO2-to-C2H4conversion.Herein,Zn-doped CuInS2(Zn-CIS)with spontaneously generated sulfur vacancies(Sv)was designed and constructed for highly selective photocatalytic CO2reduction.Experimental and density functional theory studies reveal that Zn2+preferentially substitutes In3+sites,inducing Svformation via charge compensation.Svacts as an electron reservoir,elevating the Fermi level(Ef)by 0.375 eV and prolonging lifetime of photogenerated charge carriers.Moreover,Zn2+substitution creates adjacent Cu–Zn dual sites with a 2.60Åspacing,enabling an asymmetric coordination where CO2bonds via Cu–C and Zn–O interactions.Furthermore,Sv-mediated charge redistribution activates the Zn 3d orbitals,driving their coupling with the CO2bonding orbitals(4σ/1π),which synergizes with Cu 3d-CO22π*antibonding hybridization and promotes the adsorption and activation of CO2molecules.This dual-site synergy reduces the energy barrier of the rate-determining step by 0.41 eV and drives efficient*CO→*CHO→*COCHO dimerization,resulting in a 15.9μmol g–1h–1C2H4yield,5.9-fold enhancement with 77.5%electron selectivity.This work highlights the effectiveness of defect-mediated dual-site engineering,coupled with orbital-level insights,facilitating efficient C2 product formation and provides a new paradigm for solar-driven carbon resource conversion.展开更多
Aqueous zinc‐ion batteries(AZIBs)have attracted increasing attention in energy storage owing to their high energy density,low redox potential,and cost‐effectiveness.Nevertheless,uncontrolled dendrite accumulation,ga...Aqueous zinc‐ion batteries(AZIBs)have attracted increasing attention in energy storage owing to their high energy density,low redox potential,and cost‐effectiveness.Nevertheless,uncontrolled dendrite accumulation,gas generation,and severe side‐reaction problems hinder the cycling lifespan,which prevents their commercial applications.Herein,array‐like porous channels decorated by Na2SiO3sites were in situ created on the diatomite layers by etching with NaOH(DH).DFT calculation results demonstrate that in situ formed Na2SiO3possesses improved Zn2+affinity.The negative 3D porous channels combined with zincophilic Na2SiO3sites provide a fast Zn2+transport pathway and facilitate the ion‐pair dissociation of ZnSO4,ensuring favorable Zn2+transfer kinetics and inhibited side reactions.Moreover,the ordered array‐like structure not only can exert a spatial confinement effect to suppress the 2D diffusion of Zn2+but also drive Zn metal preferential deposit toward the rigid microaligned channels and curb the formation of large‐scale zinc dendrites.Additionally,the hydrophobic diatomite protective layer can accelerate desolvation kinetics of Zn(H2O)62+and suppress the hydrogen evolution reactions.As a result,the DH‐modified Zn anode(DH@Zn)achieves a long cycle lifespan of 2500 h at 1 mA cm−2,much more than that of bare Zn(~100 h lifespan)in symmetrical cells.Besides,the DH@Zn//NH4V4O10(NVO)full cells demonstrate a high‐capacity retention of 93.3%after 1800 cycles at 5 A g−1.This work provides a promising strategy and new insights into the design of electrolyte‐anode interfacial protection.展开更多
Heterometallic doping can modulate the electron distribution of a catalyst,thereby influencing its intrinsic activity.In this study,we pioneer zinc doping within copper hydroxy oxides(CuOxHy)to alter the electro...Heterometallic doping can modulate the electron distribution of a catalyst,thereby influencing its intrinsic activity.In this study,we pioneer zinc doping within copper hydroxy oxides(CuOxHy)to alter the electronic structure and geometry,unlocking a distinct proton-coupled dynamic catalysis mechanism and significantly improving electrochemical CO2 reduction reaction(CO2RR)pathway selectivity toward formate.The Cu0.4Zn0.6OxHy catalyst,synthesized via a template co-precipitation method,exhibits a 4.1-fold enhancement of Faraday efficiency of formate over pristine CuOxHy at-1.1 V vs.RHE.In-situ Raman and X-ray photoelectron spectroscopy results confirm that the Cu0.4Zn0.6OxHy catalyst undergoes surface electron reconfiguration while maintaining bulk structural integrity with sustained Cu redox cycling,preserving the key active sites that sustain performance during CO2RR.Density functional theory calculations show that Zn doping effectively modulates the d-band center of Cu,enhances interfacial charge transfer with the*HCOO adsorbate,and lowers the energy barrier of the limiting step(CO2→*HCOO),thereby boosting CO2RR performance.This work establishes a design principle for modulating the electronic structure of Cu-based hydroxides by zinc doping,highlighting dopant-induced electronic redistribution as a critical factor for achieving high formate selectivity.展开更多
目的构筑一种兼具抗冻性、弱冰黏附性与耐磨性的多功能复合型防冰涂层,并揭示ZnCl2、甘油与PVDF协同调控水凝胶界面的行为机理。方法以AAm/DMAPS/AA构建水凝胶骨架,通过Zn2+-羧基/羟基配位与多重氢键构筑动态网络,辅以甘油调控结...目的构筑一种兼具抗冻性、弱冰黏附性与耐磨性的多功能复合型防冰涂层,并揭示ZnCl2、甘油与PVDF协同调控水凝胶界面的行为机理。方法以AAm/DMAPS/AA构建水凝胶骨架,通过Zn2+-羧基/羟基配位与多重氢键构筑动态网络,辅以甘油调控结合水结构以提升低温润滑性,并采用云滴法将NMP溶解的PVDF均匀嵌入凝胶中形成疏水微相。系统开展SEM、FTIR、拉曼、AFM、DSC等结构表征,并通过冻结延迟测试、冰黏附力测试、拉伸测试、自修复实验和耐磨循环评估材料的功能性能。结果所制备复合涂层在-20℃实现10~15 min的液滴冻结延迟,表现出显著抗结霜能力;在-20至-45℃区间保持极低的冰黏附力,且经历150次磨损循环后仍能保持稳定脱冰性能;涂层具有约450%的断裂伸长率和超过750 k Pa的拉伸强度,同时具备良好的自修复能力与结构耐久性。结论Zn2+-氢键动态网络、甘油诱导的弱润滑层与PVDF疏水微相的协同作用共同促进不可冻结水的富集与准液体润滑层(QLL)的形成,使所得复合水凝胶兼具抗冻、防冰和耐磨特性。本文提出的多尺度协同构筑策略为开发高性能、耐久型防冰涂层提供了新的材料体系与设计思路,并具有广泛的低温工程应用潜力。展开更多
以三苯胺衍生物为原料,通过引入不同苯胺衍生物,构建了4种席夫碱荧光探针(FY1—FY4)用于Zn2+的检测,其结构均用1 H NMR进行了表征.实验结果表明,探针FY1—FY4对Zn2+都显示出特异性响应及良好的抗干扰能力.当Zn2+浓度在一定范...以三苯胺衍生物为原料,通过引入不同苯胺衍生物,构建了4种席夫碱荧光探针(FY1—FY4)用于Zn2+的检测,其结构均用1 H NMR进行了表征.实验结果表明,探针FY1—FY4对Zn2+都显示出特异性响应及良好的抗干扰能力.当Zn2+浓度在一定范围内时,探针FY1—FY4的荧光强度与Zn2+浓度均呈良好的线性关系.其中,探针FY2的检测阈值最低,为1.15μmol/L.Job's Plot实验表明,探针FY1—FY4与Zn2+配位的化学计量比约为2∶1.展开更多
基金supported by the National Natural Science Foundation of China(52473327,51572295,21273285)the National Key R&D Program of China(2021YFA1501300,2019YFC1907602).
摘要The photocatalytic conversion of CO2into high-value fuels represents a promising strategy for achieving carbon neutrality by utilizing solar energy.Overcoming kinetic barriers in multi-electron transfer and C–C coupling is critical for photocatalytic CO2-to-C2H4conversion.Herein,Zn-doped CuInS2(Zn-CIS)with spontaneously generated sulfur vacancies(Sv)was designed and constructed for highly selective photocatalytic CO2reduction.Experimental and density functional theory studies reveal that Zn2+preferentially substitutes In3+sites,inducing Svformation via charge compensation.Svacts as an electron reservoir,elevating the Fermi level(Ef)by 0.375 eV and prolonging lifetime of photogenerated charge carriers.Moreover,Zn2+substitution creates adjacent Cu–Zn dual sites with a 2.60Åspacing,enabling an asymmetric coordination where CO2bonds via Cu–C and Zn–O interactions.Furthermore,Sv-mediated charge redistribution activates the Zn 3d orbitals,driving their coupling with the CO2bonding orbitals(4σ/1π),which synergizes with Cu 3d-CO22π*antibonding hybridization and promotes the adsorption and activation of CO2molecules.This dual-site synergy reduces the energy barrier of the rate-determining step by 0.41 eV and drives efficient*CO→*CHO→*COCHO dimerization,resulting in a 15.9μmol g–1h–1C2H4yield,5.9-fold enhancement with 77.5%electron selectivity.This work highlights the effectiveness of defect-mediated dual-site engineering,coupled with orbital-level insights,facilitating efficient C2 product formation and provides a new paradigm for solar-driven carbon resource conversion.
基金financially supported by the National Natural Science Foundation of China(Grant No.52276184)the Science and Technology Talent Lifting Project of Hunan Province(Grant No.2023TJ‐N04)+1 种基金the Natural Science Foundation of Hunan Province in China(Grant No.2023JJ40305)the Natural Science Foundation of Fujian Province(Grant No.2025J01572).
摘要Aqueous zinc‐ion batteries(AZIBs)have attracted increasing attention in energy storage owing to their high energy density,low redox potential,and cost‐effectiveness.Nevertheless,uncontrolled dendrite accumulation,gas generation,and severe side‐reaction problems hinder the cycling lifespan,which prevents their commercial applications.Herein,array‐like porous channels decorated by Na2SiO3sites were in situ created on the diatomite layers by etching with NaOH(DH).DFT calculation results demonstrate that in situ formed Na2SiO3possesses improved Zn2+affinity.The negative 3D porous channels combined with zincophilic Na2SiO3sites provide a fast Zn2+transport pathway and facilitate the ion‐pair dissociation of ZnSO4,ensuring favorable Zn2+transfer kinetics and inhibited side reactions.Moreover,the ordered array‐like structure not only can exert a spatial confinement effect to suppress the 2D diffusion of Zn2+but also drive Zn metal preferential deposit toward the rigid microaligned channels and curb the formation of large‐scale zinc dendrites.Additionally,the hydrophobic diatomite protective layer can accelerate desolvation kinetics of Zn(H2O)62+and suppress the hydrogen evolution reactions.As a result,the DH‐modified Zn anode(DH@Zn)achieves a long cycle lifespan of 2500 h at 1 mA cm−2,much more than that of bare Zn(~100 h lifespan)in symmetrical cells.Besides,the DH@Zn//NH4V4O10(NVO)full cells demonstrate a high‐capacity retention of 93.3%after 1800 cycles at 5 A g−1.This work provides a promising strategy and new insights into the design of electrolyte‐anode interfacial protection.
摘要Heterometallic doping can modulate the electron distribution of a catalyst,thereby influencing its intrinsic activity.In this study,we pioneer zinc doping within copper hydroxy oxides(CuOxHy)to alter the electronic structure and geometry,unlocking a distinct proton-coupled dynamic catalysis mechanism and significantly improving electrochemical CO2 reduction reaction(CO2RR)pathway selectivity toward formate.The Cu0.4Zn0.6OxHy catalyst,synthesized via a template co-precipitation method,exhibits a 4.1-fold enhancement of Faraday efficiency of formate over pristine CuOxHy at-1.1 V vs.RHE.In-situ Raman and X-ray photoelectron spectroscopy results confirm that the Cu0.4Zn0.6OxHy catalyst undergoes surface electron reconfiguration while maintaining bulk structural integrity with sustained Cu redox cycling,preserving the key active sites that sustain performance during CO2RR.Density functional theory calculations show that Zn doping effectively modulates the d-band center of Cu,enhances interfacial charge transfer with the*HCOO adsorbate,and lowers the energy barrier of the limiting step(CO2→*HCOO),thereby boosting CO2RR performance.This work establishes a design principle for modulating the electronic structure of Cu-based hydroxides by zinc doping,highlighting dopant-induced electronic redistribution as a critical factor for achieving high formate selectivity.
摘要目的构筑一种兼具抗冻性、弱冰黏附性与耐磨性的多功能复合型防冰涂层,并揭示ZnCl2、甘油与PVDF协同调控水凝胶界面的行为机理。方法以AAm/DMAPS/AA构建水凝胶骨架,通过Zn2+-羧基/羟基配位与多重氢键构筑动态网络,辅以甘油调控结合水结构以提升低温润滑性,并采用云滴法将NMP溶解的PVDF均匀嵌入凝胶中形成疏水微相。系统开展SEM、FTIR、拉曼、AFM、DSC等结构表征,并通过冻结延迟测试、冰黏附力测试、拉伸测试、自修复实验和耐磨循环评估材料的功能性能。结果所制备复合涂层在-20℃实现10~15 min的液滴冻结延迟,表现出显著抗结霜能力;在-20至-45℃区间保持极低的冰黏附力,且经历150次磨损循环后仍能保持稳定脱冰性能;涂层具有约450%的断裂伸长率和超过750 k Pa的拉伸强度,同时具备良好的自修复能力与结构耐久性。结论Zn2+-氢键动态网络、甘油诱导的弱润滑层与PVDF疏水微相的协同作用共同促进不可冻结水的富集与准液体润滑层(QLL)的形成,使所得复合水凝胶兼具抗冻、防冰和耐磨特性。本文提出的多尺度协同构筑策略为开发高性能、耐久型防冰涂层提供了新的材料体系与设计思路,并具有广泛的低温工程应用潜力。
摘要以三苯胺衍生物为原料,通过引入不同苯胺衍生物,构建了4种席夫碱荧光探针(FY1—FY4)用于Zn2+的检测,其结构均用1 H NMR进行了表征.实验结果表明,探针FY1—FY4对Zn2+都显示出特异性响应及良好的抗干扰能力.当Zn2+浓度在一定范围内时,探针FY1—FY4的荧光强度与Zn2+浓度均呈良好的线性关系.其中,探针FY2的检测阈值最低,为1.15μmol/L.Job's Plot实验表明,探针FY1—FY4与Zn2+配位的化学计量比约为2∶1.