The development of stable and highly efficien multifunctional electrocatalysts for the hydrogen evolution reaction(HER),oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are essential for the efficient c...The development of stable and highly efficien multifunctional electrocatalysts for the hydrogen evolution reaction(HER),oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are essential for the efficient conversion and storage of renewable energy.The significant advantages of single-atom catalysts,such as strong metal slab interactions,unsaturated coordination and efficient atomic utilization,have opened new avenues for designing multifunctional catalysts.Herein,based on density functional theory,a single atom doped PdPX system was designed as a multifunctional electrocatalyst,which demonstrated the synergistic effect between defects and transition metal atoms and led to enhanced catalytic performance.The results showed that PdPS/PdPSe with P/X vacancy,PdPTe with P/Pd vacancy and Co/Rh/Ir@PdPX exhibited promising HER activity.Co@PdPS(Se),with an overpotential of 0.56(0.44)V,was predicted to be a promising OER catalyst.Moreover,Rh(Ir)@PdPS(Se)catalysts exhibited efficient catalytic properties for ORR Besides,Co@PdPS(Se),Rh(Ir)@PdPS~(V(S)),Co@PdP-Se~(V(Se))and Ir@PdPS~(V(S)-1)exihibited multifunctional catalytic performance with moderate overpotential.Next,the origin of catalytic activity was revealed by using the crystal orbital Hamilton populations theory.For a strong adsorption system,proper filling of the anti-bonding state can increase the energy of the system,weaken the adsorption strength,and facilitate the desorption of intermediates Conversely,augmenting bonding states can enhance its adsorption capacity.These findings provide theoretica guidance for the design and fabrication of novel multifunctional electrocatalysts in terms of filling of bondingstate.展开更多
Electronic tuning by para substitutions was explored to achieve a highly active manganese N-heterocyclic carbene pincer complex for the selective electrocatalytic reduction of CO_(2)to CO.[MnCNC^(OMe)]BF_(4)(L2-Mn)bea...Electronic tuning by para substitutions was explored to achieve a highly active manganese N-heterocyclic carbene pincer complex for the selective electrocatalytic reduction of CO_(2)to CO.[MnCNC^(OMe)]BF_(4)(L2-Mn)bearing an electron-donating group(-OMe)showed high activity with 63×catalytic current enhancement,average Faradaic efficiency of 104%,and a TOF_(max) value of 26,127 s^(-1),which is 127 times higher than that of unsubstituted[MnCNCH]Br(L1-Mn)reported previously.In contrast,the electron-withdrawing group(-COOMe)in[MnCNC^(CO^(OMe))]PF_(6)(L3-Mn)inhibited the electrocatalytic activity.Ambient Brønstic acid,however,suppressed the activity of L2-Mn probably due to the protonation of the-OMe group.These findings indicate a potential electronic tuning strategy to improved manganese N-heterocyclic carbene catalysts for CO_(2)reduction.展开更多
Since the discovery of ferromagnetic morphotropic phase boundary(MPB)in 2010,the connotation and extension of MPB have been becoming more and more abundant.Over the last dozen years,much experimental work has been don...Since the discovery of ferromagnetic morphotropic phase boundary(MPB)in 2010,the connotation and extension of MPB have been becoming more and more abundant.Over the last dozen years,much experimental work has been done to design magnetostrictive materials based on the MPB principle.However,due to the difficulty in direct experimental observations and the complexity of theoretical treatments,the insight into the microstructure property relationships and underlying mechanisms near the ferromagnetic MPB has not been fully revealed.Here,we have reviewed our recent computer simulation work about the super-magnetoelastic behavior near the critical region of several typical materials.Phase-field modeling and simulation are employed to explore the domain configuration and engineering in single crystals as well as the grain size effect in polycrystals.Besides,a general nano-embryonic mechanism for superelasticity is also introduced.Finally,some future perspectives and challenges are presented to stimulate a deeper consideration of the research paradigm between multiscale modeling and material development.展开更多
基金financially supported by the National Natural Science Foundation of China(No.12204215)Shandong Provincial Natural Science Foundation,China(Nos.ZR2022ME030 and ZR2021QA026)。
文摘The development of stable and highly efficien multifunctional electrocatalysts for the hydrogen evolution reaction(HER),oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are essential for the efficient conversion and storage of renewable energy.The significant advantages of single-atom catalysts,such as strong metal slab interactions,unsaturated coordination and efficient atomic utilization,have opened new avenues for designing multifunctional catalysts.Herein,based on density functional theory,a single atom doped PdPX system was designed as a multifunctional electrocatalyst,which demonstrated the synergistic effect between defects and transition metal atoms and led to enhanced catalytic performance.The results showed that PdPS/PdPSe with P/X vacancy,PdPTe with P/Pd vacancy and Co/Rh/Ir@PdPX exhibited promising HER activity.Co@PdPS(Se),with an overpotential of 0.56(0.44)V,was predicted to be a promising OER catalyst.Moreover,Rh(Ir)@PdPS(Se)catalysts exhibited efficient catalytic properties for ORR Besides,Co@PdPS(Se),Rh(Ir)@PdPS~(V(S)),Co@PdP-Se~(V(Se))and Ir@PdPS~(V(S)-1)exihibited multifunctional catalytic performance with moderate overpotential.Next,the origin of catalytic activity was revealed by using the crystal orbital Hamilton populations theory.For a strong adsorption system,proper filling of the anti-bonding state can increase the energy of the system,weaken the adsorption strength,and facilitate the desorption of intermediates Conversely,augmenting bonding states can enhance its adsorption capacity.These findings provide theoretica guidance for the design and fabrication of novel multifunctional electrocatalysts in terms of filling of bondingstate.
基金supported by the National Natural Science Foundation of China(No.21973113)the Guangdong Natural Science Funds for Distinguished Young Scholar(No.2015A030306027)the Fundamental Research Funds for the Central Universities。
文摘Electronic tuning by para substitutions was explored to achieve a highly active manganese N-heterocyclic carbene pincer complex for the selective electrocatalytic reduction of CO_(2)to CO.[MnCNC^(OMe)]BF_(4)(L2-Mn)bearing an electron-donating group(-OMe)showed high activity with 63×catalytic current enhancement,average Faradaic efficiency of 104%,and a TOF_(max) value of 26,127 s^(-1),which is 127 times higher than that of unsubstituted[MnCNCH]Br(L1-Mn)reported previously.In contrast,the electron-withdrawing group(-COOMe)in[MnCNC^(CO^(OMe))]PF_(6)(L3-Mn)inhibited the electrocatalytic activity.Ambient Brønstic acid,however,suppressed the activity of L2-Mn probably due to the protonation of the-OMe group.These findings indicate a potential electronic tuning strategy to improved manganese N-heterocyclic carbene catalysts for CO_(2)reduction.
基金supported by the Natural Science Foundation of China(Nos.51701091,12174210 and 52174346)Shandong Provincial Natural Science Foundation,China(Nos.ZR2020QE028 and ZR2022ME030)+2 种基金the Innovation Team of Higher Educational Science and Technology Program in Shandong Province(No.2019KJA025)the Research Foundation of Liaocheng University(No.318012119)the Science and Technology Innovation Foundation of Liaocheng University(No.CXCY2021139)。
文摘Since the discovery of ferromagnetic morphotropic phase boundary(MPB)in 2010,the connotation and extension of MPB have been becoming more and more abundant.Over the last dozen years,much experimental work has been done to design magnetostrictive materials based on the MPB principle.However,due to the difficulty in direct experimental observations and the complexity of theoretical treatments,the insight into the microstructure property relationships and underlying mechanisms near the ferromagnetic MPB has not been fully revealed.Here,we have reviewed our recent computer simulation work about the super-magnetoelastic behavior near the critical region of several typical materials.Phase-field modeling and simulation are employed to explore the domain configuration and engineering in single crystals as well as the grain size effect in polycrystals.Besides,a general nano-embryonic mechanism for superelasticity is also introduced.Finally,some future perspectives and challenges are presented to stimulate a deeper consideration of the research paradigm between multiscale modeling and material development.
