A highly active interface can enhance the catalytic efficiency of catalysts toward the oxygen evolution reaction(OER).However,accurately tuning their atomic interface configurations of defects with sufficient activity...A highly active interface can enhance the catalytic efficiency of catalysts toward the oxygen evolution reaction(OER).However,accurately tuning their atomic interface configurations of defects with sufficient activity and stability remains a grand challenge.Herein,we report on breaking the activity and stability limits of CoO_(x) nanosheets in the OER process by constructing copious high-energy atomic steps and cavities,in which S or Ce atoms simultaneously replace O or Co atoms from CoO_(x),thus achieving high-energy atomic interface Ce,O-Co_(3)S_(4) nanosheets.By combining in situ characterization and density functional theory calculations,it is shown that the unique orbital coupling between Ce-4f,O(S)-2p,and Co-3d causes it to be closer to the Fermi level,leading to faster charge transfer capability.More importantly,the novel structure breaks the stability limit of cobalt sulfide with planar defects,which gives high catalytic activity and stability in 0.1 M KOH solutions,better than commercial RuO_(2) and IrO_(2) noble metal catalysts.As expected,Ce,O-Co_(3)S_(4) possesses much better turnover frequency activity(0.064 s^(-1))at an overpotential of 300 mV,which is ~7 times larger than that of Ce-CoO_(x)(0.009 s^(-1)).Our work presents a new perspective of designing catalysts with atomically dispersed orbital electronic coupling defects toward efficient OER electrocatalysis.展开更多
基金supported by the National Natural Science Foundation of China(NSFC)(grant no.22075223)the Natural Science Foundation of Jiangsu(grant no.BK20201120)+2 种基金the Innovation Project of Jiangsu Province,Excellent Scientific and Technological Innovation Team of Colleges and Universities of Jiangsu Province(grant no.SUJIAOKE 2021 No.1)the Key Subject of Ecology of Jiangsu Province(grant no.SUJIAOYANHAN 2022 No.2)Scientific and Technological Innovation Team of Nanjing(grant no.NINGJIAOGAOSHI 2021 No.16).
文摘A highly active interface can enhance the catalytic efficiency of catalysts toward the oxygen evolution reaction(OER).However,accurately tuning their atomic interface configurations of defects with sufficient activity and stability remains a grand challenge.Herein,we report on breaking the activity and stability limits of CoO_(x) nanosheets in the OER process by constructing copious high-energy atomic steps and cavities,in which S or Ce atoms simultaneously replace O or Co atoms from CoO_(x),thus achieving high-energy atomic interface Ce,O-Co_(3)S_(4) nanosheets.By combining in situ characterization and density functional theory calculations,it is shown that the unique orbital coupling between Ce-4f,O(S)-2p,and Co-3d causes it to be closer to the Fermi level,leading to faster charge transfer capability.More importantly,the novel structure breaks the stability limit of cobalt sulfide with planar defects,which gives high catalytic activity and stability in 0.1 M KOH solutions,better than commercial RuO_(2) and IrO_(2) noble metal catalysts.As expected,Ce,O-Co_(3)S_(4) possesses much better turnover frequency activity(0.064 s^(-1))at an overpotential of 300 mV,which is ~7 times larger than that of Ce-CoO_(x)(0.009 s^(-1)).Our work presents a new perspective of designing catalysts with atomically dispersed orbital electronic coupling defects toward efficient OER electrocatalysis.
