Electrocatalytic reduction of carbon dioxide(CO_(2))to multicarbon(C2+)products involves intricate multiple protons and electron transfer of C-C coupling,which is dictated by not only the intrinsic reactivity but also...Electrocatalytic reduction of carbon dioxide(CO_(2))to multicarbon(C2+)products involves intricate multiple protons and electron transfer of C-C coupling,which is dictated by not only the intrinsic reactivity but also the spin states of electrons in the catalyst.Here,we observe spin-enhanced CO_(2)reduction(CO_(2)RR)electrocatalytic activity on an oxidederived copper(OD-Cu)catalyst due to the existence of a specific Cu*site that carried the magnetic moments.Due to the correlation of magnetic and catalytic properties in OD-Cu,the current density through the OD-Cu electrode increases by nearly 10%at 350 mT.The field strength and angle dependence of such magnetic field effect(MFE),together with the time-resolved measurements proved that it originated from the alignment of magnetic moments on Cu*sites.The MFE on the electrocatalytic process enabled an enhancement(up to 15%)of the CO_(2)RR Faradaic efficiency using the OD-Cu catalyst.Importantly,the enhancement was attributed to the spinantiparallel alignment of electrons to promote C-C coupling on asymmetric Cu*-Cu sites;consequently,the optimal bias was reduced by∼0.2 V under the magnetic field for C2 products with Faradaic efficiency>30%and selectivity>75%.Our work uncovers a new paradigmfor spin-enhanced catalysis applicable to a broad range of chemical reactions involving spin singlet products.展开更多
We propose that the asymmetry-induced tunneling electroresistance(TER)effect in a ferroelectric tunnel junction(FTJ)could be improved by integrating a polarization-controlled resonant band.Using first-principles calcu...We propose that the asymmetry-induced tunneling electroresistance(TER)effect in a ferroelectric tunnel junction(FTJ)could be improved by integrating a polarization-controlled resonant band.Using first-principles calculations and a quantum-mechanical tunneling model,we studied an asymmetric FTJ SrRuO_(3)/BaTiO_(3)/SrTiO_(3)/SrRuO_(3).The resonant band is integrated into this FTJ by two atomic layers of BaSnO_(3)embedded in the barrier.In the elaborated FTJ SrRuO_(3)/BaTiO_(3)/BaSnO_(3)/SrTiO_(3)/SrRuO_(3),both resonant band and asymmetry work together.For one polarization direction,the BaSnO_(3)and SrTiO_(3)dielectric layers work together as barriers to provide considerable efficient barrier height for direct tunneling and lead to large tunneling resistance.For the opposite polarization,the BaSnO_(3)layer serves as a quantum well to induce resonant tunneling across the barrier and considerably reduces the tunneling resistance of the ON state.The integration of resonant band with asymmetry may provide a more efficient and applicable way to further improve the functionalities of FTJs.展开更多
基金supported by the National Natural Science Foundation of China(grant no.21873105)the National Key Research and Development Program of China(grant no.2020YFA0710303)the CAS Project for Young Scientists in Basic Research(grant no.YSBR-004).
文摘Electrocatalytic reduction of carbon dioxide(CO_(2))to multicarbon(C2+)products involves intricate multiple protons and electron transfer of C-C coupling,which is dictated by not only the intrinsic reactivity but also the spin states of electrons in the catalyst.Here,we observe spin-enhanced CO_(2)reduction(CO_(2)RR)electrocatalytic activity on an oxidederived copper(OD-Cu)catalyst due to the existence of a specific Cu*site that carried the magnetic moments.Due to the correlation of magnetic and catalytic properties in OD-Cu,the current density through the OD-Cu electrode increases by nearly 10%at 350 mT.The field strength and angle dependence of such magnetic field effect(MFE),together with the time-resolved measurements proved that it originated from the alignment of magnetic moments on Cu*sites.The MFE on the electrocatalytic process enabled an enhancement(up to 15%)of the CO_(2)RR Faradaic efficiency using the OD-Cu catalyst.Importantly,the enhancement was attributed to the spinantiparallel alignment of electrons to promote C-C coupling on asymmetric Cu*-Cu sites;consequently,the optimal bias was reduced by∼0.2 V under the magnetic field for C2 products with Faradaic efficiency>30%and selectivity>75%.Our work uncovers a new paradigmfor spin-enhanced catalysis applicable to a broad range of chemical reactions involving spin singlet products.
基金This work was supported by the National Natural Science Foundation of the People’s Republic of China(Grants 11974211 and 11974212)。
文摘We propose that the asymmetry-induced tunneling electroresistance(TER)effect in a ferroelectric tunnel junction(FTJ)could be improved by integrating a polarization-controlled resonant band.Using first-principles calculations and a quantum-mechanical tunneling model,we studied an asymmetric FTJ SrRuO_(3)/BaTiO_(3)/SrTiO_(3)/SrRuO_(3).The resonant band is integrated into this FTJ by two atomic layers of BaSnO_(3)embedded in the barrier.In the elaborated FTJ SrRuO_(3)/BaTiO_(3)/BaSnO_(3)/SrTiO_(3)/SrRuO_(3),both resonant band and asymmetry work together.For one polarization direction,the BaSnO_(3)and SrTiO_(3)dielectric layers work together as barriers to provide considerable efficient barrier height for direct tunneling and lead to large tunneling resistance.For the opposite polarization,the BaSnO_(3)layer serves as a quantum well to induce resonant tunneling across the barrier and considerably reduces the tunneling resistance of the ON state.The integration of resonant band with asymmetry may provide a more efficient and applicable way to further improve the functionalities of FTJs.