Currently,dual atomic catalysts(DACs)with neighboring active sites for oxygen reduction reaction(ORR)still meet lots of challenges in the synthesis,especially the construction of atomic pairs of elements from differen...Currently,dual atomic catalysts(DACs)with neighboring active sites for oxygen reduction reaction(ORR)still meet lots of challenges in the synthesis,especially the construction of atomic pairs of elements from different blocks of the periodic table.Herein,a“rare earth(Ce)-metalloid(Se)”non-bonding heteronuclear diatomic electrocatalyst has been constructed for ORR by rational coordination and carbon support defect engineering.Encouraging,the optimized Ce-Se diatomic catalysts(Ce-Se DAs/NC)displayed a half-wave potential of 0.886 V vs.reversible hydrogen electrode(RHE)and excellent stability,which surpass those of separate Ce or Se single atoms and most single/dual atomic catalysts ever reported.In addition,a primary zinc-air battery constructed using Ce-Se DAs/NC delivers a higher peak power density(209.2 mW·cm^(−2))and specific capacity(786.4 mAh·gZn^(−1))than state-of-the-art noble metal catalysts Pt/C.Theoretical calculations reveal that the Ce-Se DAs/NC has improved the electroactivity of the Ce-N_(4)region due to the electron transfer towards the nearby Se specific activity(SA)sites.Meanwhile,the more electron-rich Se sites promote the adsorptions of key intermediates,which results in the optimal performances of ORR on Ce-Se DAs/NC.This work provides new perspectives on electronic structure modulations via non-bonded long-range coordination micro-environment engineering in DACs for efficient electrocatalysis.展开更多
The interactions between the embedded atom X (X=Li,Na,K,Rb,Cs; F,Cl,Br,I) and C60cage in the endohedral-form complexes (X@C60) are calculated and discussed according to molecular mechanics from the point of view of th...The interactions between the embedded atom X (X=Li,Na,K,Rb,Cs; F,Cl,Br,I) and C60cage in the endohedral-form complexes (X@C60) are calculated and discussed according to molecular mechanics from the point of view of the bonding and non-bonding.It is found from the computational results that for atoms with radii larger than Li’s,their locations with the minimum interaction in (X@C60) are at the cage center,while atom Li has an off-center location with the minimum interaction deviation of-0.05 nm,and the cage-environment in C60 can be regarded as sphero-symmetry in the region with radius r of ~0.2 nm.It is shown that the interaction between X and C60 cage is of non-bonding characteristic,and this non-bonding interaction is not purely electrostatic.The repulsion and dispersion in non-bonding interactions should not be neglected,which make important contribution to the location with minimum interaction of X,at center or off center.Some rules about the variations of interactions with atomic radii have been展开更多
At present, research interest in C<sub>60</sub> is mainly focused on its complexes and its chemical modification and doping. Putting an atom (or a radical) or a molecule into another molecule to form a s...At present, research interest in C<sub>60</sub> is mainly focused on its complexes and its chemical modification and doping. Putting an atom (or a radical) or a molecule into another molecule to form a stable compound is a completely new novel field in chemistry. The quite large cavity in football-like C<sub>60</sub> cage has put forward the possibility of trapping inside it an atom or a radical to form the endohedral complexes (X@C<sub>60</sub>). The alkali-containing complex (Alkali@C<sub>60</sub>) formed from C<sub>60</sub> cage and alkali atoms is one kind of this endohedral complex. On these entirely new endohedral complexes, much valuable展开更多
基金the support from the National Key R&D Program of China(No.2021YFA1501101)the National Natural Science Foundation of China(No.21971117)+12 种基金the National Natural Science Foundation of China/Research Grant Council of Hong Kong Joint Research Scheme(No.N_PolyU502/21)the National Natural Science Foundation of China/Research Grants Council(RGC)of Hong Kong Collaborative Research Scheme(No.CRS_PolyU504/22)the Functional Research Funds for the Central Nankai University(No.63186005)the Tianjin Key Lab for Rare Earth Materials and Applications(No.ZB19500202)the Open Funds(No.RERU2019001)the State Key Laboratory of Rare Earth Resource Utilization,the 111 Project(No.B18030)from Chinathe Beijing-Tianjin-Hebei Collaborative Innovation Project(No.19YFSLQY00030)the Outstanding Youth Project of Tianjin 21 Natural Science Foundation(No.20JCJQJC00130)the Key Project of Tianjin Natural Science Foundation(No.20JCZDJC00650)the funding for Projects of Strategic Importance of The Hong Kong Polytechnic University(Project Code:1-ZE2V)the Shenzhen Fundamental Research Scheme-General Program(No.JCYJ20220531090807017)the Natural Science Foundation of Guangdong Province(No.2023A1515012219)the Departmental General Research Fund(Project Code:ZVUL)from The Hong Kong Polytechnic University.
文摘Currently,dual atomic catalysts(DACs)with neighboring active sites for oxygen reduction reaction(ORR)still meet lots of challenges in the synthesis,especially the construction of atomic pairs of elements from different blocks of the periodic table.Herein,a“rare earth(Ce)-metalloid(Se)”non-bonding heteronuclear diatomic electrocatalyst has been constructed for ORR by rational coordination and carbon support defect engineering.Encouraging,the optimized Ce-Se diatomic catalysts(Ce-Se DAs/NC)displayed a half-wave potential of 0.886 V vs.reversible hydrogen electrode(RHE)and excellent stability,which surpass those of separate Ce or Se single atoms and most single/dual atomic catalysts ever reported.In addition,a primary zinc-air battery constructed using Ce-Se DAs/NC delivers a higher peak power density(209.2 mW·cm^(−2))and specific capacity(786.4 mAh·gZn^(−1))than state-of-the-art noble metal catalysts Pt/C.Theoretical calculations reveal that the Ce-Se DAs/NC has improved the electroactivity of the Ce-N_(4)region due to the electron transfer towards the nearby Se specific activity(SA)sites.Meanwhile,the more electron-rich Se sites promote the adsorptions of key intermediates,which results in the optimal performances of ORR on Ce-Se DAs/NC.This work provides new perspectives on electronic structure modulations via non-bonded long-range coordination micro-environment engineering in DACs for efficient electrocatalysis.
基金Project Supported by the National Natural Science Foundation of China
文摘The interactions between the embedded atom X (X=Li,Na,K,Rb,Cs; F,Cl,Br,I) and C60cage in the endohedral-form complexes (X@C60) are calculated and discussed according to molecular mechanics from the point of view of the bonding and non-bonding.It is found from the computational results that for atoms with radii larger than Li’s,their locations with the minimum interaction in (X@C60) are at the cage center,while atom Li has an off-center location with the minimum interaction deviation of-0.05 nm,and the cage-environment in C60 can be regarded as sphero-symmetry in the region with radius r of ~0.2 nm.It is shown that the interaction between X and C60 cage is of non-bonding characteristic,and this non-bonding interaction is not purely electrostatic.The repulsion and dispersion in non-bonding interactions should not be neglected,which make important contribution to the location with minimum interaction of X,at center or off center.Some rules about the variations of interactions with atomic radii have been
基金the National Natural Science Foundation of China.
文摘At present, research interest in C<sub>60</sub> is mainly focused on its complexes and its chemical modification and doping. Putting an atom (or a radical) or a molecule into another molecule to form a stable compound is a completely new novel field in chemistry. The quite large cavity in football-like C<sub>60</sub> cage has put forward the possibility of trapping inside it an atom or a radical to form the endohedral complexes (X@C<sub>60</sub>). The alkali-containing complex (Alkali@C<sub>60</sub>) formed from C<sub>60</sub> cage and alkali atoms is one kind of this endohedral complex. On these entirely new endohedral complexes, much valuable