Metal-based secondary building unit and the shape of organic ligands are the two crucial factors for determining the final topology of metal-organic materials.A careful choice of organic and inorganic structural build...Metal-based secondary building unit and the shape of organic ligands are the two crucial factors for determining the final topology of metal-organic materials.A careful choice of organic and inorganic structural building units occasionally produces unexpected structures,facilitating deeper fundamental understanding of coordination-driven self-assembly behind metal-organic materials.Here,we have synthesized a triangular metal-organic polygon(MOT-1),assembled from bulky tetramethyl terephthalate and Zr-based secondary building unit.Surprisingly,the Zr-based secondary building unit serves as an unusual ditopic Zr-connector,toform metal-organic polygon MOT-1,proven to be a good candidate for water adsorption with recyclability.This study highlights the interplay of the geometrically frustrated ligand and secondary building unit in controlling the connectivity of metal-organic polygon.Such a strategy can be further used to unveil a new class of metal-organic materials.展开更多
Development of efficient non-precious catalysts for seawater electrolysis is of great significance but challenging due to the sluggish kinetics of oxygen evolution reaction(OER)and the impairment of chlorine electroch...Development of efficient non-precious catalysts for seawater electrolysis is of great significance but challenging due to the sluggish kinetics of oxygen evolution reaction(OER)and the impairment of chlorine electrochemistry at anode.Herein,we report a heterostructure of Ni_(3)S_(2)nanoarray with secondary Fe-Ni(OH)_(2)lamellar edges that exposes abundant active sites towards seawater oxidation.The resultant Fe-Ni(OH)_(2)/Ni_(3)S_(2)nanoarray works directly as a free-standing anodic electrode in alkaline artificial seawater.It only requires an overpotential of 269 mV to afford a current density of 10 mA·cm^(-2)and the Tafel slope is as low as 46 m V·dec^(-1).The 27-hour chronopotentiometry operated at high current density of 100 mA·cm^(-2)shows negligible deterioration,suggesting good stability of the Fe-Ni(OH)_(2)/Ni_(3)S_(2)@NF electrode.Faraday efficiency for oxygen evolution is up to〜95%,revealing decent selectivity of the catalyst in saline water.Such desirable catalytic performance could be benefitted from the introduction of Fe activator and the heterostructure that offers massive active and selective sites.The density functional theory(DFT)calculations indicate that the OER has lower theoretical overpotential than Cl_(2) evolution reaction in Fe sites,which is contrary to that of Ni sites.The experimental and theoretical study provides a strong support for the rational design of high-performance Fe-based electrodes for industrial seawater electrolysis.展开更多
By introduction of a new Fe(L^(1))_(2)spin-crossover(SCO)unit into the polynuclear system,a nano-scale Fe4(L^(2))_(4)molecular square architecture is designed through coordination-directed self-assembly strategy.Both ...By introduction of a new Fe(L^(1))_(2)spin-crossover(SCO)unit into the polynuclear system,a nano-scale Fe4(L^(2))_(4)molecular square architecture is designed through coordination-directed self-assembly strategy.Both the mononuclear Fe(L^(1))_(2)and tetranuclear Fe4(L^(2))_(4)complexes have bee门structurally confirmed by 1H nuclear magnetic resonance(NMR),electrospray ionization time-of-flight mass spectrometry(ESI-TOF-MS),and temperature-dependent single crystal X-ray diffraction studies.Variable-temperature magnetic susceptibility measurements reveal the presence of an abrupt SCO behavior with a thermal hysteresis width of 4K for Fe(L^(1))_(2).By clear contrast,Fe4(L^(2))_(4)undergoes a gradual spin transition behavior with enlarged thermal hysteresis width and higher spin transition temperature.展开更多
基金Korea Environment Industry&Technology Institute(KEITI)through Public Technology Program based on Environmental Policy Program,funded by Korea M inistry of Environment(MOE)(No.2018000210002)National Research Foundation(NRF)of Korea(Nos.NRF-2016R1A5A1009405,NRF-2017M3C1B4051161)D.-W.L.and H.K.acknowledge the support from the ACCEL program Japan Science and Technology Agency(JST),JPMJAC1501.J.K.acknowledges the support from NRF Grant funded by the Korean Government(No.NRF-2018H1A2A1061391-Global Ph.D.Fellowship Program).We acknowledge the Pohang Accelerator Laboratory(PAL)for 2D beamline use(2019-1st-2D-038).We would like to thank Hyeonsoo Chofor providing 3D models for possible structures shown in Fig.8.
文摘Metal-based secondary building unit and the shape of organic ligands are the two crucial factors for determining the final topology of metal-organic materials.A careful choice of organic and inorganic structural building units occasionally produces unexpected structures,facilitating deeper fundamental understanding of coordination-driven self-assembly behind metal-organic materials.Here,we have synthesized a triangular metal-organic polygon(MOT-1),assembled from bulky tetramethyl terephthalate and Zr-based secondary building unit.Surprisingly,the Zr-based secondary building unit serves as an unusual ditopic Zr-connector,toform metal-organic polygon MOT-1,proven to be a good candidate for water adsorption with recyclability.This study highlights the interplay of the geometrically frustrated ligand and secondary building unit in controlling the connectivity of metal-organic polygon.Such a strategy can be further used to unveil a new class of metal-organic materials.
基金the National Natural Science Foundation of China(No.91963113).
文摘Development of efficient non-precious catalysts for seawater electrolysis is of great significance but challenging due to the sluggish kinetics of oxygen evolution reaction(OER)and the impairment of chlorine electrochemistry at anode.Herein,we report a heterostructure of Ni_(3)S_(2)nanoarray with secondary Fe-Ni(OH)_(2)lamellar edges that exposes abundant active sites towards seawater oxidation.The resultant Fe-Ni(OH)_(2)/Ni_(3)S_(2)nanoarray works directly as a free-standing anodic electrode in alkaline artificial seawater.It only requires an overpotential of 269 mV to afford a current density of 10 mA·cm^(-2)and the Tafel slope is as low as 46 m V·dec^(-1).The 27-hour chronopotentiometry operated at high current density of 100 mA·cm^(-2)shows negligible deterioration,suggesting good stability of the Fe-Ni(OH)_(2)/Ni_(3)S_(2)@NF electrode.Faraday efficiency for oxygen evolution is up to〜95%,revealing decent selectivity of the catalyst in saline water.Such desirable catalytic performance could be benefitted from the introduction of Fe activator and the heterostructure that offers massive active and selective sites.The density functional theory(DFT)calculations indicate that the OER has lower theoretical overpotential than Cl_(2) evolution reaction in Fe sites,which is contrary to that of Ni sites.The experimental and theoretical study provides a strong support for the rational design of high-performance Fe-based electrodes for industrial seawater electrolysis.
基金the National Natural Science Foundation of China(Nos.21825107,21971237,21801241)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000).
文摘By introduction of a new Fe(L^(1))_(2)spin-crossover(SCO)unit into the polynuclear system,a nano-scale Fe4(L^(2))_(4)molecular square architecture is designed through coordination-directed self-assembly strategy.Both the mononuclear Fe(L^(1))_(2)and tetranuclear Fe4(L^(2))_(4)complexes have bee门structurally confirmed by 1H nuclear magnetic resonance(NMR),electrospray ionization time-of-flight mass spectrometry(ESI-TOF-MS),and temperature-dependent single crystal X-ray diffraction studies.Variable-temperature magnetic susceptibility measurements reveal the presence of an abrupt SCO behavior with a thermal hysteresis width of 4K for Fe(L^(1))_(2).By clear contrast,Fe4(L^(2))_(4)undergoes a gradual spin transition behavior with enlarged thermal hysteresis width and higher spin transition temperature.
