NH_(3),derived from electrocatalytic nitrogen reduction reaction(NRR),is promising to satisfy the need of food production and serve as a carbon-free liquid energy carrier in the near future.Yet major challenges remain...NH_(3),derived from electrocatalytic nitrogen reduction reaction(NRR),is promising to satisfy the need of food production and serve as a carbon-free liquid energy carrier in the near future.Yet major challenges remain in enhancing NH_(3) yield rate and conversion efficiency of available electrocatalysts.This work achieved an ultrahigh electrocatalytic NH_(3)yield rate on the_(0.50)Fe-Bi_(2)W0_(6) catalyst by a facile Fe-doped strategy.Up to 289μg·h^(-1)·mg_(cat)^(-1) of NH_(3) formation rate was obtained at-0.75 V vs.RHE,which was reliably quantized by indophenol blue and ^(1)H NMR methods.The impressive result is an order of magnitude higher than that of the reported Fe-and Bi-based catalysts,even more superior than the result of single atom Ru catalyst.The key of the outstanding NRR behaviors on the_(0.50)Fe-Bi_(2)W0_(6) catalyst is the significant hydrogen evolution reaction(HER)suppression and the synergy between Bi and Fe,which can effectively modulate the electron distribution and accelerate the electron transport.This work endows a new insight to further explore the high-performance electrocatalysts toward NRR.展开更多
To achieve a flexible single-crystal multifunctional membrane,the freestanding process of a rigid epitaxial transition metal oxide thin film via a buffered water-dissolution sacrificial layer has attracted reasonable ...To achieve a flexible single-crystal multifunctional membrane,the freestanding process of a rigid epitaxial transition metal oxide thin film via a buffered water-dissolution sacrificial layer has attracted reasonable attentions.Owing to the difference in chemical potential,specific element affinity,and lattice constant between the target membrane and the sacrificial layer,the freestanding process may cause an indelible change of physics property once the target thin film is sensitive to the above factors.Here,the heterostructures composed of the generally adopted sacrificial layer Sr_(3)Al_(2)O_(6)(SAO)and LaMnO_(3)(LMO)have been systematically investigated.The electrical and magnetic properties of LMO show extreme sensitivity to the thickness of SAO(tSAO).Then we have also found that LMO/SAO heterostructures can exhibit the coexistence of two ferromagnetic phases,the significantly enhanced Curie temperature~342 K,and the large magnetoresistance-23.3%at 300 K,which is similar to the optimal-doped manganite such as La_(2/3)Sr_(1/3)MnO_(3).X-ray diffraction results show that continuously tunable strain from out-of-plane tension to relaxation and then to compression can be generated by adjusting tSAO.This strain can stabilize the migrated oxygen from LMO to SAO,which is induced by the large oxygen affinity difference between Bsite Mn and Al.It is believed that these unexpected electrical/magnetic phenomena are originated from the combined effects of interfacial element diffusion and strain.Our study provides a strategy for designing new magnetic phases,and a reference for the fundamental understanding of strongly correlated transition metal oxide systems in the freestanding process.展开更多
A new highly selective salicylate electrode based on N,N’-bis(3-nitrosalicylidene)-2,6-Pyridinediamine manganese(Ⅱ) complex[Mn(Ⅱ)-BNSPD]as neutral carrier is studied first,which displays an excellent electric poten...A new highly selective salicylate electrode based on N,N’-bis(3-nitrosalicylidene)-2,6-Pyridinediamine manganese(Ⅱ) complex[Mn(Ⅱ)-BNSPD]as neutral carrier is studied first,which displays an excellent electric potential response and an anti-Hofmeister selectivity sequence which is:Sal->SCN-> ClO4-> I-> Br-> NO3-> Cl-> NO2-> SO32-> SO42-.The electrode exhibits Nernstian potential linear range to salicylate from 1.0×10-1 to 6.0×10-6 mol·dm-3 with a detection limit 2.0×10-6 mol·dm-3 and a slope of 58.5 mV/dec in pH 5.0 of phosphorate buffer solution at 28℃.The electrode response mechanism is studied with the UV spectroscopy technology.The electrode is designed to be applied in medicine analysis with a satisfactory result worked out.展开更多
Zinc ion hybrid supercapacitors(ZHS)have received much attention due to the enhanced potential window range and high specific capacity.However,the appropriate positive materials with high electrochemical performance a...Zinc ion hybrid supercapacitors(ZHS)have received much attention due to the enhanced potential window range and high specific capacity.However,the appropriate positive materials with high electrochemical performance are still a challenge.Herein,NH_(4)^(+)and glycerate anions pre-inserted Mo glycerate(N-MoG)spheres are synthesized and serve as the template to form NH_(4)^(+)intercalated Ni_(3)S_(2)/Ni_(3)O_(2)(OH)_(4)@MoS_(2)core–shell nanoflower(N-NiMo-OS)in-situ grown on nickel foam(NF)(N-NiMo-OS/NF)by sulfurization treatment.Compared with the product using traditional MoG as a template,N-NiMo-OS/NF inheriting a larger core structure from N-MoG delivers enhanced space for ions transport and volume expansion during the energy storage process,together with the synergistic effects of multi-components and the heterostructure,the as-prepared N-NiMo-OS/NF nanoflower exhibits excellent performance for the battery-type hybrid supercapacitors(BHS)and ZHS devices.Notably,the ZHS device delivers superior electrochemical performance to the BHS device,such as a higher specific capacity of 327.5 mAh·g^(−1)at 1 A·g^(−1),a preeminent energy density of 610.6 Wh·kg^(−1)at 1710 W·kg^(−1),long cycle life.The in-situ Raman,ex-situ X-ray photoelectron spectroscopy(XPS),theoretical calculation demonstrate the extra Zn^(2+)insertion/extraction storage mechanism provides enhanced electrochemical performance for ZHS device.Therefore,the dual-ion pre-inserted strategy can be extended for other advanced electrode materials in energy storage fields.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21675151,21705145 and 21721003)the Ministry of Science and Technology of China(No.2016YFA0203203).
文摘NH_(3),derived from electrocatalytic nitrogen reduction reaction(NRR),is promising to satisfy the need of food production and serve as a carbon-free liquid energy carrier in the near future.Yet major challenges remain in enhancing NH_(3) yield rate and conversion efficiency of available electrocatalysts.This work achieved an ultrahigh electrocatalytic NH_(3)yield rate on the_(0.50)Fe-Bi_(2)W0_(6) catalyst by a facile Fe-doped strategy.Up to 289μg·h^(-1)·mg_(cat)^(-1) of NH_(3) formation rate was obtained at-0.75 V vs.RHE,which was reliably quantized by indophenol blue and ^(1)H NMR methods.The impressive result is an order of magnitude higher than that of the reported Fe-and Bi-based catalysts,even more superior than the result of single atom Ru catalyst.The key of the outstanding NRR behaviors on the_(0.50)Fe-Bi_(2)W0_(6) catalyst is the significant hydrogen evolution reaction(HER)suppression and the synergy between Bi and Fe,which can effectively modulate the electron distribution and accelerate the electron transport.This work endows a new insight to further explore the high-performance electrocatalysts toward NRR.
基金financial support from the National Natural Science Foundation of China(No.12074149)support from the Natural Science Foundation of Shandong Province(No.ZR2020QA057)+4 种基金support from the National Natural Science Foundation of China(No.51871112)the Major Basic Research Projects of Shandong Province(No.ZR2020ZD28)the 111 Project(No.B13029)support from the Taishan Scholar Project of Shandong Province(No.ts20190939)the Independent Cultivation Program of Innovation Team of Ji’nan City(No.2021GXRC043)。
文摘To achieve a flexible single-crystal multifunctional membrane,the freestanding process of a rigid epitaxial transition metal oxide thin film via a buffered water-dissolution sacrificial layer has attracted reasonable attentions.Owing to the difference in chemical potential,specific element affinity,and lattice constant between the target membrane and the sacrificial layer,the freestanding process may cause an indelible change of physics property once the target thin film is sensitive to the above factors.Here,the heterostructures composed of the generally adopted sacrificial layer Sr_(3)Al_(2)O_(6)(SAO)and LaMnO_(3)(LMO)have been systematically investigated.The electrical and magnetic properties of LMO show extreme sensitivity to the thickness of SAO(tSAO).Then we have also found that LMO/SAO heterostructures can exhibit the coexistence of two ferromagnetic phases,the significantly enhanced Curie temperature~342 K,and the large magnetoresistance-23.3%at 300 K,which is similar to the optimal-doped manganite such as La_(2/3)Sr_(1/3)MnO_(3).X-ray diffraction results show that continuously tunable strain from out-of-plane tension to relaxation and then to compression can be generated by adjusting tSAO.This strain can stabilize the migrated oxygen from LMO to SAO,which is induced by the large oxygen affinity difference between Bsite Mn and Al.It is believed that these unexpected electrical/magnetic phenomena are originated from the combined effects of interfacial element diffusion and strain.Our study provides a strategy for designing new magnetic phases,and a reference for the fundamental understanding of strongly correlated transition metal oxide systems in the freestanding process.
文摘A new highly selective salicylate electrode based on N,N’-bis(3-nitrosalicylidene)-2,6-Pyridinediamine manganese(Ⅱ) complex[Mn(Ⅱ)-BNSPD]as neutral carrier is studied first,which displays an excellent electric potential response and an anti-Hofmeister selectivity sequence which is:Sal->SCN-> ClO4-> I-> Br-> NO3-> Cl-> NO2-> SO32-> SO42-.The electrode exhibits Nernstian potential linear range to salicylate from 1.0×10-1 to 6.0×10-6 mol·dm-3 with a detection limit 2.0×10-6 mol·dm-3 and a slope of 58.5 mV/dec in pH 5.0 of phosphorate buffer solution at 28℃.The electrode response mechanism is studied with the UV spectroscopy technology.The electrode is designed to be applied in medicine analysis with a satisfactory result worked out.
基金the National Natural Science Foundation of China(Nos.21702116,51772162,and 52072197)the 111 Project of China(No.D20017)+5 种基金Shandong Provincial Key Research and Development Program,China(No.2019GSF107087)Qingdao Postdoctoral Sustentation Fund,Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(No.2019KJC004)Outstanding Youth Foundation of Shandong Province,China(No.ZR2019JQ14)Taishan Scholar Young Talent Program(No.tsqn201909114)Major Scientific and Technological Innovation Project(No.2019JZZY020405)Major Basic Research Program of Natural Science Foundation of Shandong Province(No.ZR2020ZD09).
文摘Zinc ion hybrid supercapacitors(ZHS)have received much attention due to the enhanced potential window range and high specific capacity.However,the appropriate positive materials with high electrochemical performance are still a challenge.Herein,NH_(4)^(+)and glycerate anions pre-inserted Mo glycerate(N-MoG)spheres are synthesized and serve as the template to form NH_(4)^(+)intercalated Ni_(3)S_(2)/Ni_(3)O_(2)(OH)_(4)@MoS_(2)core–shell nanoflower(N-NiMo-OS)in-situ grown on nickel foam(NF)(N-NiMo-OS/NF)by sulfurization treatment.Compared with the product using traditional MoG as a template,N-NiMo-OS/NF inheriting a larger core structure from N-MoG delivers enhanced space for ions transport and volume expansion during the energy storage process,together with the synergistic effects of multi-components and the heterostructure,the as-prepared N-NiMo-OS/NF nanoflower exhibits excellent performance for the battery-type hybrid supercapacitors(BHS)and ZHS devices.Notably,the ZHS device delivers superior electrochemical performance to the BHS device,such as a higher specific capacity of 327.5 mAh·g^(−1)at 1 A·g^(−1),a preeminent energy density of 610.6 Wh·kg^(−1)at 1710 W·kg^(−1),long cycle life.The in-situ Raman,ex-situ X-ray photoelectron spectroscopy(XPS),theoretical calculation demonstrate the extra Zn^(2+)insertion/extraction storage mechanism provides enhanced electrochemical performance for ZHS device.Therefore,the dual-ion pre-inserted strategy can be extended for other advanced electrode materials in energy storage fields.
