得益于较高的理论能量密度、环境友好性和丰富的海水储量,海水基锌-空气电池(S-ZABs)被认为是一种极具应用前景的储能和能源转换装置,是解决能源短缺和环境污染问题的能源装置之一。然而对于S-ZABs而言,构筑在海水中具有高耐氯离子腐蚀...得益于较高的理论能量密度、环境友好性和丰富的海水储量,海水基锌-空气电池(S-ZABs)被认为是一种极具应用前景的储能和能源转换装置,是解决能源短缺和环境污染问题的能源装置之一。然而对于S-ZABs而言,构筑在海水中具有高耐氯离子腐蚀性与高性能的阴极氧还原反应电催化剂仍然具有挑战性。因此,我们通过高温硒化策略,在氮掺杂介孔碳材料上设计了超薄碳铠甲层封装的Co_(9)Se_(8)纳米颗粒高效ORR电催化剂(命名为NMC-Co_(9)Se_(8))。外部的超薄碳铠甲层不仅可以改善催化过程中的电子转移过程,抑制纳米颗粒的团聚,而且可以作为盔甲保护内部活性位点免受Cl^(-)吸附和腐蚀。得益于这种独特的结构,NMC-Co_(9)Se_(8)在0.1 mol·L^(-1)KOH海水电解质中表现出优异的ORR性能,其起始电位为0.904V,半波电位为0.860 V。更重要的是,基于NMC-Co_(9)Se_(8)催化剂的S-ZABs可提供172.4 m W·cm^(-2)的功率密度和超过150h的优异长期放电稳定性,均高于基于Pt/C的S-ZABs性能。这项工作为开发用于海水基锌-空气电池和其他能源转换技术具有耐氯离子腐蚀且高效的ORR催化剂提供了新思路。展开更多
Employing the alkaline water electrolysis system to generate hydrogen holds great prospects but still poses significant challenges,particularly for the construction of hydrogen evolution reaction(HER)catalysts operati...Employing the alkaline water electrolysis system to generate hydrogen holds great prospects but still poses significant challenges,particularly for the construction of hydrogen evolution reaction(HER)catalysts operating at ampere-level current density.Herein,the unique Ru and RuP_(2)dual nano-islands are deliberately implanted on N-doped carbon substrate(denoted as Ru-RuP_(2)/NC),in which a built-in electric field(BEF)is spontaneously generated between Ru-RuP_(2)dual nano-islands driven by their work function difference.Experimental and theoretical results unveil that such constructed BEF could serve as the driving force for triggering fast hydrogen spillover process on bridged Ru-RuP_(2)dual nano-islands,which could invalidate the inhibitory effect of high hydrogen coverage at ampere-level current density,and synchronously speed up the water dissociation on Ru nano-islands and hydrogen adsorption/desorption on RuP_(2)nano-islands through hydrogen spillover process.As a result,the Ru-RuP_(2)/NC affords an ultra-low overpotential of 218 mV to achieve 1.0 A·cm^(−2)along with the superior stability over 1000 h,holding the great promising prospect in practical applications at ampere-level current density.More importantly,this work is the first to advance the scientific understanding of the relationship between the constructed BEF and hydrogen spillover process,which could be enlightening for the rational design of the cost-effective alkaline HER catalysts at ampere-level current density.展开更多
Oxygen reduction reaction(ORR)plays an important role in the next-generation energy storage technologies,whereas it involves the sluggish and complicated proton-coupled electron transfer(PCET)steps that greatly limit ...Oxygen reduction reaction(ORR)plays an important role in the next-generation energy storage technologies,whereas it involves the sluggish and complicated proton-coupled electron transfer(PCET)steps that greatly limit the ORR kinetics.Therefore,it is urgent to construct an efficient catalyst that could simultaneously achieve the rapid oxygen-containing intermediates conversion and fast PCET process but remain challenging.Herein,the adjacent Fe_(3)C nanoparticles coupling with single Fe sites on the bubble-wrap-like porous N-doped carbon(Fe_(3)C@FeSA-NC)were deliberately constructed.Theoretical investigations reveal that the adjacent Fe_(3)C nanoparticles speed up the water dissociation and serve as proton-feeding centers for boosting the ORR kinetics of single Fe sites.Benefiting from the synergistic effect of the Fe_(3)C and single Fe sites,the Fe_(3)C@FeSA-NC affords an excellent half-wave potential of 0.88 V,and enables the assembled Zn-air batteries with the high peak power density of 164.5 mW·cm^(-2)and long-term stability of over 200 h at high current densities at 50 mA·cm^(-2).This work clarifies the mechanism for improving ORR kinetics of single atomic sites by engineering the adjacent proton-feeding centers,shedding light on the rational design of cost-effective electrocatalysts for energy conversion and storage technologies.展开更多
Interface engineering has gradually attracted substantial research interest in constructing active bifunctional catalysts toward urea electrolysis.The fundamental understanding of the crystallinity transition of the c...Interface engineering has gradually attracted substantial research interest in constructing active bifunctional catalysts toward urea electrolysis.The fundamental understanding of the crystallinity transition of the components on both sides of the interface is extremely significant for realizing controllable construction of catalysts through interface engineering,but it still remains a challenge.Herein,the Ni/NiO heterogenous nanoparticles are successfully fabricated on the porous N-doped carbon spheres by a facile hydrothermal and subsequent pyrolysis strategy.And for the first time we show the experimental observation that the Ni/NiO interface can be fine-tuned via simply tailoring the heating rate during pyrolysis process,in which the crystalline/amorphous or crystalline/crystalline Ni/NiO heterostructure is deliberately constructed on the porous N-doped carbon spheres(named as CA-Ni/NiO@NCS or CC-Ni/NiO@NCS,respectively).By taking advantage of the unique porous architecture and the synergistic effect between crystalline Ni and amorphous NiO,the well-designed CA-Ni/NiO@NCS displays more remarkable urea oxidation reaction(UOR)and hydrogen evolution reaction(HER)activity than its crystalline/crystalline counterpart of CC-Ni/NiO@NCS.Particularly,the whole assembled two-electrode electrolytic cell using the elaborate CANi/NiO@NCS both as the anode and cathode can realize the current density of 10 mA·cm^(−2)at a super low voltage of 1.475 V(264 mV less than that of pure water electrolysis),as well as remarkable prolonged stability over 63 h.Besides,the H_(2)evolution driven by an AA battery and a commercial solar cell is also studied to enlighten practical applications for the future.展开更多
文摘得益于较高的理论能量密度、环境友好性和丰富的海水储量,海水基锌-空气电池(S-ZABs)被认为是一种极具应用前景的储能和能源转换装置,是解决能源短缺和环境污染问题的能源装置之一。然而对于S-ZABs而言,构筑在海水中具有高耐氯离子腐蚀性与高性能的阴极氧还原反应电催化剂仍然具有挑战性。因此,我们通过高温硒化策略,在氮掺杂介孔碳材料上设计了超薄碳铠甲层封装的Co_(9)Se_(8)纳米颗粒高效ORR电催化剂(命名为NMC-Co_(9)Se_(8))。外部的超薄碳铠甲层不仅可以改善催化过程中的电子转移过程,抑制纳米颗粒的团聚,而且可以作为盔甲保护内部活性位点免受Cl^(-)吸附和腐蚀。得益于这种独特的结构,NMC-Co_(9)Se_(8)在0.1 mol·L^(-1)KOH海水电解质中表现出优异的ORR性能,其起始电位为0.904V,半波电位为0.860 V。更重要的是,基于NMC-Co_(9)Se_(8)催化剂的S-ZABs可提供172.4 m W·cm^(-2)的功率密度和超过150h的优异长期放电稳定性,均高于基于Pt/C的S-ZABs性能。这项工作为开发用于海水基锌-空气电池和其他能源转换技术具有耐氯离子腐蚀且高效的ORR催化剂提供了新思路。
基金the National Natural Science Foundation of China(Nos.22279124 and 52261145700)Shandong Province Natural Science Foundation(No.ZR2022ZD30)National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(Nos.NRF-2020R1A2C3004146 and RS-2023-00235596).
文摘Employing the alkaline water electrolysis system to generate hydrogen holds great prospects but still poses significant challenges,particularly for the construction of hydrogen evolution reaction(HER)catalysts operating at ampere-level current density.Herein,the unique Ru and RuP_(2)dual nano-islands are deliberately implanted on N-doped carbon substrate(denoted as Ru-RuP_(2)/NC),in which a built-in electric field(BEF)is spontaneously generated between Ru-RuP_(2)dual nano-islands driven by their work function difference.Experimental and theoretical results unveil that such constructed BEF could serve as the driving force for triggering fast hydrogen spillover process on bridged Ru-RuP_(2)dual nano-islands,which could invalidate the inhibitory effect of high hydrogen coverage at ampere-level current density,and synchronously speed up the water dissociation on Ru nano-islands and hydrogen adsorption/desorption on RuP_(2)nano-islands through hydrogen spillover process.As a result,the Ru-RuP_(2)/NC affords an ultra-low overpotential of 218 mV to achieve 1.0 A·cm^(−2)along with the superior stability over 1000 h,holding the great promising prospect in practical applications at ampere-level current density.More importantly,this work is the first to advance the scientific understanding of the relationship between the constructed BEF and hydrogen spillover process,which could be enlightening for the rational design of the cost-effective alkaline HER catalysts at ampere-level current density.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.52261145700 and 22279124)the Natural Science Foundation of Shandong Province(No.ZR2020ZD10)the Fundamental Research Funds for the Central Universities(No.202262010).
文摘Oxygen reduction reaction(ORR)plays an important role in the next-generation energy storage technologies,whereas it involves the sluggish and complicated proton-coupled electron transfer(PCET)steps that greatly limit the ORR kinetics.Therefore,it is urgent to construct an efficient catalyst that could simultaneously achieve the rapid oxygen-containing intermediates conversion and fast PCET process but remain challenging.Herein,the adjacent Fe_(3)C nanoparticles coupling with single Fe sites on the bubble-wrap-like porous N-doped carbon(Fe_(3)C@FeSA-NC)were deliberately constructed.Theoretical investigations reveal that the adjacent Fe_(3)C nanoparticles speed up the water dissociation and serve as proton-feeding centers for boosting the ORR kinetics of single Fe sites.Benefiting from the synergistic effect of the Fe_(3)C and single Fe sites,the Fe_(3)C@FeSA-NC affords an excellent half-wave potential of 0.88 V,and enables the assembled Zn-air batteries with the high peak power density of 164.5 mW·cm^(-2)and long-term stability of over 200 h at high current densities at 50 mA·cm^(-2).This work clarifies the mechanism for improving ORR kinetics of single atomic sites by engineering the adjacent proton-feeding centers,shedding light on the rational design of cost-effective electrocatalysts for energy conversion and storage technologies.
基金the National Natural Science Foundation of China(No.21775142)the Natural Science Foundation of Shandong Province(No.ZR2020ZD10)the Deputyship for Research&Innovation,Ministry of Education in Saudi Arabia(project number 510).
文摘Interface engineering has gradually attracted substantial research interest in constructing active bifunctional catalysts toward urea electrolysis.The fundamental understanding of the crystallinity transition of the components on both sides of the interface is extremely significant for realizing controllable construction of catalysts through interface engineering,but it still remains a challenge.Herein,the Ni/NiO heterogenous nanoparticles are successfully fabricated on the porous N-doped carbon spheres by a facile hydrothermal and subsequent pyrolysis strategy.And for the first time we show the experimental observation that the Ni/NiO interface can be fine-tuned via simply tailoring the heating rate during pyrolysis process,in which the crystalline/amorphous or crystalline/crystalline Ni/NiO heterostructure is deliberately constructed on the porous N-doped carbon spheres(named as CA-Ni/NiO@NCS or CC-Ni/NiO@NCS,respectively).By taking advantage of the unique porous architecture and the synergistic effect between crystalline Ni and amorphous NiO,the well-designed CA-Ni/NiO@NCS displays more remarkable urea oxidation reaction(UOR)and hydrogen evolution reaction(HER)activity than its crystalline/crystalline counterpart of CC-Ni/NiO@NCS.Particularly,the whole assembled two-electrode electrolytic cell using the elaborate CANi/NiO@NCS both as the anode and cathode can realize the current density of 10 mA·cm^(−2)at a super low voltage of 1.475 V(264 mV less than that of pure water electrolysis),as well as remarkable prolonged stability over 63 h.Besides,the H_(2)evolution driven by an AA battery and a commercial solar cell is also studied to enlighten practical applications for the future.
基金supported by the Natural Science Foundation of Shandong Province(ZR2020ZD10)the National Natural Science Foundation of China(21775142)Shenzhen Natural Science Fund(20200925154115001 and JCYJ20210324115809026).
