The availability of polymorphs of metallic complexes provides an opportunity to reveal the relationship between crystal packing and catalytic activity.Herein,we immobilize two stable concomitant polymorphs(green NiL_(...The availability of polymorphs of metallic complexes provides an opportunity to reveal the relationship between crystal packing and catalytic activity.Herein,we immobilize two stable concomitant polymorphs(green NiL_(2)-G and red NiL_(2)-R)of mononuclear nickel NiL_(2) on electrodes as heterogeneous oxygen evolution reaction catalysts.Density functional theory calculations reveal that the formation of L_(2)Ni^(Ⅳ)=O from L_(2)Ni^(Ⅲ)-OH is the rate-determining step,whereas R-L_(2)Ni^(Ⅲ)-OH is more stable than G-L_(2)Ni^(Ⅲ)-OH,and forming L_(2)Ni^(Ⅳ)=O from the former has a much lower barrier than from the latter.Consistently,NiL_(2)-R exhibits a lower overpotential(339 mV)than NiL_(2)-G(466 mV)at 10 mA cm^(-2).展开更多
基金the financial support from the NSFC(No.21571165)National Science Foundation for Distinguished Young Scholars of China(No.21525101)the NSF of China and Guangxi Province(No.91122032,2014GXNSFFA118003).
文摘The availability of polymorphs of metallic complexes provides an opportunity to reveal the relationship between crystal packing and catalytic activity.Herein,we immobilize two stable concomitant polymorphs(green NiL_(2)-G and red NiL_(2)-R)of mononuclear nickel NiL_(2) on electrodes as heterogeneous oxygen evolution reaction catalysts.Density functional theory calculations reveal that the formation of L_(2)Ni^(Ⅳ)=O from L_(2)Ni^(Ⅲ)-OH is the rate-determining step,whereas R-L_(2)Ni^(Ⅲ)-OH is more stable than G-L_(2)Ni^(Ⅲ)-OH,and forming L_(2)Ni^(Ⅳ)=O from the former has a much lower barrier than from the latter.Consistently,NiL_(2)-R exhibits a lower overpotential(339 mV)than NiL_(2)-G(466 mV)at 10 mA cm^(-2).
