In this article, we report a facile precursor pyrolysis method to prepare porous spinel-type cobalt manganese oxides (CoxMng-xO4) with controllable morphologies and crystalline structures. The capping agent in the r...In this article, we report a facile precursor pyrolysis method to prepare porous spinel-type cobalt manganese oxides (CoxMng-xO4) with controllable morphologies and crystalline structures. The capping agent in the reaction was found to be crucial on the formation of the porous spinel cobalt manganese oxides from cubic Co2MnO4 nanorods to tetragonal CoMn2O4 microspheres and tetragonal CoMn204 cubes, respectively. All of the prepared spinel materials exhibit brilliant oxygen reduction reaction (ORR) electrocatalysis along with high stability. In particular, the cubic Co2MnO4 nanorods show the best performance with an onset potential of 0.9 V and a half-wave potential of 0.72 V which are very close to the commercial Pt/C. Meanwhile, the cubic Co2MnO4 nanorods present superior stability with negligible degradation of their electrocatalytic activity after a continuous operation time of 10,000 seconds, which is much better than the commercial Pt/C electrocatalvst.展开更多
Gas generation induced by parasitic reactions in lithium-metal batteries(LMB)has been regarded as one of the fundamental barriers to the reversibility of this battery chemistry,which occurs via the complex interplays ...Gas generation induced by parasitic reactions in lithium-metal batteries(LMB)has been regarded as one of the fundamental barriers to the reversibility of this battery chemistry,which occurs via the complex interplays among electrolytes,cathode,anode,and the decomposition species that travel across the cell.In this work,a novel in situ differential electrochemical mass spectrometry is constructed to differentiate the speciation and source of each gas product generated either during cycling or during storage in the presence of cathode chemistries of varying structure and nickel contents.It unambiguously excludes the trace moisture in electrolyte as the major source of hydrogen and convincingly identifies the layer-structured NCM cathode material as the source of instability that releases active oxygen from the lattice at high voltages when NCM experiences H2→H3 phase transition,which in turn reacts with carbonate solvents,producing both CO_(2)and proton at the cathode side.Such proton in solvated state travels across the cell and becomes the main source for hydrogen generated at the anode side.Mechanisms are proposed to account for these irreversible reactions,and two electrolyte additives based on phosphate structure are adopted to mitigate the gas generation based on the understanding of the above decomposition chemistries.展开更多
An attempt has been made to prepare terephthalic acid(TPA) by solvent-free oxidation of p-xylene(PX) with air over tetra(pchlorophenylporphinato) manganese chloride(T(p-Cl)PPMnCl) and cobalt acetate.The co-c...An attempt has been made to prepare terephthalic acid(TPA) by solvent-free oxidation of p-xylene(PX) with air over tetra(pchlorophenylporphinato) manganese chloride(T(p-Cl)PPMnCl) and cobalt acetate.The co-catalysis between T(p-Cl)PPMnCl and Co(OAc)_2 has been discovered under solvent-free conditions.TPA yield could be increased significantly when T(p-Cl)PPMnCl and Co(OAc)_2 were used together.The addition of T(p-Cl)PPMnCl into the reaction mixture over Co(OAc)_2 significantly accelerated the rate-determining step of the oxidation process of PX to TPA.The effect of temperature on reaction was also investigated.展开更多
基金We acknowledge the funding by the National Natural Science Foundation of China (Nos. 21303249, 81401464, 21425103, and 21501192), and the Natural Science Foundation of Jiangsu Province (No. SBK201341397).
文摘In this article, we report a facile precursor pyrolysis method to prepare porous spinel-type cobalt manganese oxides (CoxMng-xO4) with controllable morphologies and crystalline structures. The capping agent in the reaction was found to be crucial on the formation of the porous spinel cobalt manganese oxides from cubic Co2MnO4 nanorods to tetragonal CoMn2O4 microspheres and tetragonal CoMn204 cubes, respectively. All of the prepared spinel materials exhibit brilliant oxygen reduction reaction (ORR) electrocatalysis along with high stability. In particular, the cubic Co2MnO4 nanorods show the best performance with an onset potential of 0.9 V and a half-wave potential of 0.72 V which are very close to the commercial Pt/C. Meanwhile, the cubic Co2MnO4 nanorods present superior stability with negligible degradation of their electrocatalytic activity after a continuous operation time of 10,000 seconds, which is much better than the commercial Pt/C electrocatalvst.
基金the financial supports from the Key-Area Research and Development Program of Guangdong Province(2020B090919001)Shenzhen Key Laboratory of Solid-State Batteries(ZDSYS20180208184346531)+1 种基金Guangdong Provincial Key Laboratory of Energy Materials for Electric Power(2018B030322001)Guangdong-Hong Kong-Macao Joint Laboratory for Photonic-Thermal-Electrical Energy Materials and Devices(2019B121205001)。
文摘Gas generation induced by parasitic reactions in lithium-metal batteries(LMB)has been regarded as one of the fundamental barriers to the reversibility of this battery chemistry,which occurs via the complex interplays among electrolytes,cathode,anode,and the decomposition species that travel across the cell.In this work,a novel in situ differential electrochemical mass spectrometry is constructed to differentiate the speciation and source of each gas product generated either during cycling or during storage in the presence of cathode chemistries of varying structure and nickel contents.It unambiguously excludes the trace moisture in electrolyte as the major source of hydrogen and convincingly identifies the layer-structured NCM cathode material as the source of instability that releases active oxygen from the lattice at high voltages when NCM experiences H2→H3 phase transition,which in turn reacts with carbonate solvents,producing both CO_(2)and proton at the cathode side.Such proton in solvated state travels across the cell and becomes the main source for hydrogen generated at the anode side.Mechanisms are proposed to account for these irreversible reactions,and two electrolyte additives based on phosphate structure are adopted to mitigate the gas generation based on the understanding of the above decomposition chemistries.
文摘An attempt has been made to prepare terephthalic acid(TPA) by solvent-free oxidation of p-xylene(PX) with air over tetra(pchlorophenylporphinato) manganese chloride(T(p-Cl)PPMnCl) and cobalt acetate.The co-catalysis between T(p-Cl)PPMnCl and Co(OAc)_2 has been discovered under solvent-free conditions.TPA yield could be increased significantly when T(p-Cl)PPMnCl and Co(OAc)_2 were used together.The addition of T(p-Cl)PPMnCl into the reaction mixture over Co(OAc)_2 significantly accelerated the rate-determining step of the oxidation process of PX to TPA.The effect of temperature on reaction was also investigated.