Electrochemical reduction reaction of nitrogen(NRR)offers a promising pathway to produce ammonia(NH_(3))from renewable energy.However,the development of such process has been hindered by the chemical inertness of N_(2...Electrochemical reduction reaction of nitrogen(NRR)offers a promising pathway to produce ammonia(NH_(3))from renewable energy.However,the development of such process has been hindered by the chemical inertness of N_(2).It is recently proposed that hydrogen species formed on the surface of electrocatalysts can greatly enhance NRR.However,there is still a lack of atomiclevel connection between the hydrogenation behavior of electrocatalysts and their NRR performance.Here,we report an atomistic understanding of the hydrogenation behavior of a highly twinned ZnSe(T-ZnSe)nanorod with a large density of surface atomic steps and the activation of N_(2)molecules adsorbed on its surface.Our theoretical calculations and in situ infrared spectroscopic characterizations suggest that the atomic steps are essential for the hydrogenation of T-ZnSe,which greatly reduces its work function and efficiently activates adsorbed N_(2)molecules.Moreover,the liquid-like and free water over T-ZnSe promotes its hydrogenation.As a result,T-ZnSe nanorods exhibit significantly enhanced Faradaic efficiency and NH3 production rate compared with the pristine ZnSe nanorod.This work paves a promising way for engineering electrocatalysts for green and sustainable NH3 production.展开更多
We demonstrated the controlled growth of two-dimensional （2D） hexagonal tin disulfide （SnS2） nanoflakes with stacked monolayer atomic steps. The morphology was similar to flat-topped and step-sided mesa plateaus o...We demonstrated the controlled growth of two-dimensional （2D） hexagonal tin disulfide （SnS2） nanoflakes with stacked monolayer atomic steps. The morphology was similar to flat-topped and step-sided mesa plateaus or step pyramids. The SnS2 nanoflakes were grown on mica substrates via an atmospheric-pressure chemical vapor deposition process using tin monosulfide and sulfur powder as precursors. Atomic force microscopy （AFM）, electron microscopy, and Raman characterizations were performed to investigate the structural features, and a sequential layer-wise epitaxial growth mechanism was revealed. In addition, systematic Raman characterizations were performed on individual SnS2 nanoflakes with a wide range of thicknesses （1-100 nm）, indicating that the A1g peak intensity and Raman shifts were closely related to the thickness of the SnS2 nanoflakes. Moreover, photoconductive AFM was performed on the monolayer-stepped SnS2 nanoflakes, revealing that the flat surface and the edges of the SnS2 atomic steps had different electrical conductive properties and photoconductive behaviors. This is ascribed to the dangling bonds and defects at the atomic step edges, which caused a height difference of the Schottky barriers formed at the interfaces between the PtIr-coated AFM tip and the step edges or the flat surface of the SnS2 nanoflakes. The 2D SnS2 crystals with regular monolayer atomic steps and fast photoresponsivity are promising for novel applications in photodetectors and integrated optoelectronic circuits.展开更多
The fabrication of electrocatalysts with high activity and acid stability for acidic oxygen evolution reaction(OER)is an urgent need,yet extremely challenging.Here,we report the design and successful fabrication of a ...The fabrication of electrocatalysts with high activity and acid stability for acidic oxygen evolution reaction(OER)is an urgent need,yet extremely challenging.Here,we report the design and successful fabrication of a high performance self-supported cogwheel arrays-like nanoporous Ir_(x)Ru_(1−x)O_(2) catalyst with abundant atomic steps for acidic OER using a facile alloy-spinningelectrochemical activation method that allows large-scale fabrication.The obtained Ir_(x)Ru_(1−x)O_(2) catalysts merely need overpotentials of 211 and 295 mV to deliver catalytic current densities of 10 and 300 mA·cm^(−2) in 0.5 M H_(2)SO_(4),respectively,and can sustain constant OER electrolysis for at least 140 h at a high current density of 300 mA·cm^(−2).Further density functional theory(DFT)calculations uncover that such high intrinsic activities mainly originate from the largely exposed high-index atomic step planes,which markedly lower the limiting potential of the rate-determining step(RDS)of OER.These findings provide an insight into the exploration of high performance electrocatalysts,and open up an avenue for further developing the state-of-theart Ir and/or Ru-based catalysts for large-scale practical applications.展开更多
Multimetallic Pt-based alloys with excavated structures have attracted great interest owing to their compositional and morphological tunability, high specific surface areas, and impressive electro-catalytic activities...Multimetallic Pt-based alloys with excavated structures have attracted great interest owing to their compositional and morphological tunability, high specific surface areas, and impressive electro-catalytic activities. Herein, we report the first facile one-pot synthesis of trimetallic Pt-Ni-Cu highly excavated rhombic dodecahedrons （ERDs） with a yield approaching 100%. More importantly, these highly uniform nanocrystals have three-dimensionally accessible excavated surfaces, where abundant stepped atoms are observed. Benefiting from the highly excavated rhombic dodecahedral structures, electronic and synergistic effects within the trimetallic allo3~ and abundant stepped atoms, the as-prepared trimetallic Pt-Ni-Cu ERDs exhibit an enhanced electro-catalytic performance for the electro-oxidation of methanol compared to commercial Pt/C and bimetallic Pt-Cu ERDs and Pt-Ni-Cu solid rhombic dodecahedrons solid rhombic dodecahedrons （SRDs）.展开更多
We have introduced a 5-parameter Morse function to simulate the pairwise poten-tial and studied the adsorption and diffusion of hydrogen atoms on the Ni low indexsurfaces by pairwise method and satistying results were...We have introduced a 5-parameter Morse function to simulate the pairwise poten-tial and studied the adsorption and diffusion of hydrogen atoms on the Ni low indexsurfaces by pairwise method and satistying results were obtained. In this letter,we further investigate the properties of the adsorption and diffusion of hydrogen at-oms on the Ni (115) stepped surface by the same method and the optimumparameters.展开更多
基金the National Natural Science Foundation of China(Nos.52071231 and 51722103)the Natural Science Foundation of Tianjin city(No.19JCJQJC61900).
文摘Electrochemical reduction reaction of nitrogen(NRR)offers a promising pathway to produce ammonia(NH_(3))from renewable energy.However,the development of such process has been hindered by the chemical inertness of N_(2).It is recently proposed that hydrogen species formed on the surface of electrocatalysts can greatly enhance NRR.However,there is still a lack of atomiclevel connection between the hydrogenation behavior of electrocatalysts and their NRR performance.Here,we report an atomistic understanding of the hydrogenation behavior of a highly twinned ZnSe(T-ZnSe)nanorod with a large density of surface atomic steps and the activation of N_(2)molecules adsorbed on its surface.Our theoretical calculations and in situ infrared spectroscopic characterizations suggest that the atomic steps are essential for the hydrogenation of T-ZnSe,which greatly reduces its work function and efficiently activates adsorbed N_(2)molecules.Moreover,the liquid-like and free water over T-ZnSe promotes its hydrogenation.As a result,T-ZnSe nanorods exhibit significantly enhanced Faradaic efficiency and NH3 production rate compared with the pristine ZnSe nanorod.This work paves a promising way for engineering electrocatalysts for green and sustainable NH3 production.
基金Acknowledgements We thank Prof. Qian Yu at Zhejiang University for the help in the aspect of high-resolution TEM charac- terizations. This work is supported by National Basic Research Program of China （No. 2015CB659300）, National Materials Genome Project （No. 2016YFB0700600）, National Natural Science Foundation of China （Nos. 21403105 and 21573108）, China Postdoctoral Science Foundation （Nos. 2015M580408, 2015M581775, 2015M580413 and 2015M581769）, Natural Science Foundation of Jiangsu Province （Nos. BK20150571 and BK20160647）, Fundamental Research Funds for the Central Universities and a project funded by the Priority Academic Program Development （PAPD） of Jiangsu Higher Education Institutions.
文摘We demonstrated the controlled growth of two-dimensional （2D） hexagonal tin disulfide （SnS2） nanoflakes with stacked monolayer atomic steps. The morphology was similar to flat-topped and step-sided mesa plateaus or step pyramids. The SnS2 nanoflakes were grown on mica substrates via an atmospheric-pressure chemical vapor deposition process using tin monosulfide and sulfur powder as precursors. Atomic force microscopy （AFM）, electron microscopy, and Raman characterizations were performed to investigate the structural features, and a sequential layer-wise epitaxial growth mechanism was revealed. In addition, systematic Raman characterizations were performed on individual SnS2 nanoflakes with a wide range of thicknesses （1-100 nm）, indicating that the A1g peak intensity and Raman shifts were closely related to the thickness of the SnS2 nanoflakes. Moreover, photoconductive AFM was performed on the monolayer-stepped SnS2 nanoflakes, revealing that the flat surface and the edges of the SnS2 atomic steps had different electrical conductive properties and photoconductive behaviors. This is ascribed to the dangling bonds and defects at the atomic step edges, which caused a height difference of the Schottky barriers formed at the interfaces between the PtIr-coated AFM tip and the step edges or the flat surface of the SnS2 nanoflakes. The 2D SnS2 crystals with regular monolayer atomic steps and fast photoresponsivity are promising for novel applications in photodetectors and integrated optoelectronic circuits.
基金supported by the S&T Partnership and International S&T Cooperation Program of Shanghai Cooperation Organization(No.2020E01040)the High-level Talent Project of Xinjiang Uygur Autonomous Region(No.2020000039)+3 种基金the National Key R&D Program of China(Nos.2018YFB0104400 and 2016YFB0100100)the National Natural Science Foundation of China(Nos.62104073,21825202,92045302,21972055,and 21733012)Newton Advanced Fellowships(No.NAF/R2/180603)B.L.acknowledges the support by the National Natural Science Foundation of China(No.21573255).
文摘The fabrication of electrocatalysts with high activity and acid stability for acidic oxygen evolution reaction(OER)is an urgent need,yet extremely challenging.Here,we report the design and successful fabrication of a high performance self-supported cogwheel arrays-like nanoporous Ir_(x)Ru_(1−x)O_(2) catalyst with abundant atomic steps for acidic OER using a facile alloy-spinningelectrochemical activation method that allows large-scale fabrication.The obtained Ir_(x)Ru_(1−x)O_(2) catalysts merely need overpotentials of 211 and 295 mV to deliver catalytic current densities of 10 and 300 mA·cm^(−2) in 0.5 M H_(2)SO_(4),respectively,and can sustain constant OER electrolysis for at least 140 h at a high current density of 300 mA·cm^(−2).Further density functional theory(DFT)calculations uncover that such high intrinsic activities mainly originate from the largely exposed high-index atomic step planes,which markedly lower the limiting potential of the rate-determining step(RDS)of OER.These findings provide an insight into the exploration of high performance electrocatalysts,and open up an avenue for further developing the state-of-theart Ir and/or Ru-based catalysts for large-scale practical applications.
文摘Multimetallic Pt-based alloys with excavated structures have attracted great interest owing to their compositional and morphological tunability, high specific surface areas, and impressive electro-catalytic activities. Herein, we report the first facile one-pot synthesis of trimetallic Pt-Ni-Cu highly excavated rhombic dodecahedrons （ERDs） with a yield approaching 100%. More importantly, these highly uniform nanocrystals have three-dimensionally accessible excavated surfaces, where abundant stepped atoms are observed. Benefiting from the highly excavated rhombic dodecahedral structures, electronic and synergistic effects within the trimetallic allo3~ and abundant stepped atoms, the as-prepared trimetallic Pt-Ni-Cu ERDs exhibit an enhanced electro-catalytic performance for the electro-oxidation of methanol compared to commercial Pt/C and bimetallic Pt-Cu ERDs and Pt-Ni-Cu solid rhombic dodecahedrons solid rhombic dodecahedrons （SRDs）.
文摘We have introduced a 5-parameter Morse function to simulate the pairwise poten-tial and studied the adsorption and diffusion of hydrogen atoms on the Ni low indexsurfaces by pairwise method and satistying results were obtained. In this letter,we further investigate the properties of the adsorption and diffusion of hydrogen at-oms on the Ni (115) stepped surface by the same method and the optimumparameters.
