A stepwise synthesis method was used to immobilize tetrachloro tetramethyl porphyrins in the supercages of NaCoX molecular sieve. The immobilized porphyrin was characterized by means of UV Vis, IR, DTA, SEM and E...A stepwise synthesis method was used to immobilize tetrachloro tetramethyl porphyrins in the supercages of NaCoX molecular sieve. The immobilized porphyrin was characterized by means of UV Vis, IR, DTA, SEM and EPR. A comparision was made for the activities among tetrachloro tetramethyl porphyrins, its cobalt(Ⅱ) complex, NaCoX molecular sieve and the immobilized porphyrin as catalysts in the oxidation reaction of styrene and p cresol. The stability and catalytic capability of the metalloporphyrin is increased after the combination of porphyrin with molecular sieve. In addition, this new type of catalyst tetrachloro tetramethyl porphyrin immobilized in the supercages of NaCoX molecular sieve not only possesses the advantages of both porphyrin and molecular sieve, but also makes up for their respective deficiencies. The experimental results confirmed that both the stability and catalytic capability of metalloporphyrin immobilized in the supercages of molecular sieve are increased.展开更多
Although promising strategies have been developed to resolve the critical drawbacks of lithium-sulfur(Li-S)batteries,the intractable issues including undesirable shuttling of polysulfides and sluggish redox reaction k...Although promising strategies have been developed to resolve the critical drawbacks of lithium-sulfur(Li-S)batteries,the intractable issues including undesirable shuttling of polysulfides and sluggish redox reaction kinetics have still been unresolved thoroughly.Herein,a cobalt single-atom(CoSA)catalyst comprising of atomic Co distributed homogeneously within nitrogen(N)-doped porous carbon(Co-NPC)nanosphere is constructed and utilized as a separator coating in Li-S batteries.The Co-NPC exposes abundant active sites participating in sulfur redox reactions,and remarkable catalytic activity boosting the rapid polysulfide conversions.As a result,Li-S batteries with Co-NPC coating layer realize significantly enhanced specific capacity(1295 mAh·g^(-1)at 0.2 C),rate capability(753 mAh·g^(-1)at 3.0 C),and long-life cyclic stability(601 mAh·g^(-1)after 500 cycles at 1.0 C).Increasing the areal sulfur loading to 6.2 mg·cm^(-2),an extremely high areal capacity of 7.92 mAh·cm^(-2)is achieved.Further in situ X-ray diffraction,density functional theory calculations,and secondary ion mass spectrometry confirm the high catalytic capability of CoSA towards reversible polysulfide conversion.This study supplies new insights for adopting single-atom catalyst to upgrade the electrochemical performance of Li-S batteries.展开更多
文摘A stepwise synthesis method was used to immobilize tetrachloro tetramethyl porphyrins in the supercages of NaCoX molecular sieve. The immobilized porphyrin was characterized by means of UV Vis, IR, DTA, SEM and EPR. A comparision was made for the activities among tetrachloro tetramethyl porphyrins, its cobalt(Ⅱ) complex, NaCoX molecular sieve and the immobilized porphyrin as catalysts in the oxidation reaction of styrene and p cresol. The stability and catalytic capability of the metalloporphyrin is increased after the combination of porphyrin with molecular sieve. In addition, this new type of catalyst tetrachloro tetramethyl porphyrin immobilized in the supercages of NaCoX molecular sieve not only possesses the advantages of both porphyrin and molecular sieve, but also makes up for their respective deficiencies. The experimental results confirmed that both the stability and catalytic capability of metalloporphyrin immobilized in the supercages of molecular sieve are increased.
基金financially supported by the National Natural Science Foundation of China(No.22005003)the Natural Science Research Project of Anhui Province Education Department(Nos.2022AH030046 and 2022AH050334)+2 种基金the Yong Scientific Foundation of Anhui University of Technology for Top Talent(No.DT2100000947)the Scientific Research Foundation of Anhui University of Technology for Talent Introduction(No.DT19100069)The theoretical simulations were carried out at Shanxi Supercomputing Center of China,and performed on TianHe-2.
文摘Although promising strategies have been developed to resolve the critical drawbacks of lithium-sulfur(Li-S)batteries,the intractable issues including undesirable shuttling of polysulfides and sluggish redox reaction kinetics have still been unresolved thoroughly.Herein,a cobalt single-atom(CoSA)catalyst comprising of atomic Co distributed homogeneously within nitrogen(N)-doped porous carbon(Co-NPC)nanosphere is constructed and utilized as a separator coating in Li-S batteries.The Co-NPC exposes abundant active sites participating in sulfur redox reactions,and remarkable catalytic activity boosting the rapid polysulfide conversions.As a result,Li-S batteries with Co-NPC coating layer realize significantly enhanced specific capacity(1295 mAh·g^(-1)at 0.2 C),rate capability(753 mAh·g^(-1)at 3.0 C),and long-life cyclic stability(601 mAh·g^(-1)after 500 cycles at 1.0 C).Increasing the areal sulfur loading to 6.2 mg·cm^(-2),an extremely high areal capacity of 7.92 mAh·cm^(-2)is achieved.Further in situ X-ray diffraction,density functional theory calculations,and secondary ion mass spectrometry confirm the high catalytic capability of CoSA towards reversible polysulfide conversion.This study supplies new insights for adopting single-atom catalyst to upgrade the electrochemical performance of Li-S batteries.
