Enhanced bifunctional oxygen electrochemical catalytic performance using La-doped CoFe_(2)O_(4)spinel supported by 3D-G for Zn-air batteries

The preparation of bifunctional catalysts for oxygen reduction(ORR)and oxygen evolution(OER)is crucial for Zn-air batteries.Here,we report a La doped CoFe_(2)O_(4) spinel catalyst supported on threedimensional graphene(3D-G),where La can facilitate electron transfer from Co to Fe,leading to increased electron cloud density in Fe and improved catalytic performance.The redshift of the G peak in the Raman spectra indicates the interaction between theπbond of 3D-G and d orbitals in La_(0.2)CoFe_(1.8)O_(4).La_(0.2)CoFe_(1.8)/3D-G exhibits superior ORR performance(E_(1/2)=0.86 V vs.RHE)and OER performance(E_(j=10)=1.55 V vs.RHE)to CoFe_(2)O_(4)/3D-G(E_(1/2)=0.831 V vs.RHE,E_(j=10)=1.603 V vs.RHE).Furthermore,it demonstrates excellent bifunctional oxygen catalytic performance while maintaining high power density and stability in liquid zinc-air batteries(ZABs)and flexible ZABs(F-ZABs).This work presents a viable strategy for utilizing rare earth element doped spinels to enhance oxygen catalyst and ZABs performance.

Evaluation of multi-cycle performance of chemical looping dry reforming using CO_2 as an oxidant with Fe–Ni bimetallic oxides

Chemical looping dry reforming（CLDR） is an innovative technology for CO2 utilization using the chemical looping principle.The CLDR process consists of three stages,i.e.CH4 reduction,CO2 reforming,and air oxidation.Spinel nickel ferrite（NiFe2O4） was prepared and its multi-cycle performance as an oxygen carrier for CLDR was experimentally investigated.X-ray diffraction（XRD） and Laser Raman spectroscopy showed that a pure spinel crystalline phase（NiFe2O4） was obtained by a parallel flow co-precipitating method.NiFe2O4was reduced into Fe-Ni alloy and wustite（FexO） during the CH4 reduction process.Subsequent oxidation of the reduced oxygen carrier was performed with CO2 as an oxidant to form an intermediate state：a mixture of spinel Ni（1-x）Fe（2＋x）O4,Fe（2＋y）O4 and metallic Ni.And CO was generated in parallel during this stage.Approximate 185 mL of CO was generated for 1 g spinel NiFe2O4 in a single cycle.The intermediate oxygen carrier was fully oxidized in the air oxidation stage to form a mixture of Ni（1＋x）Fe（2-x）O4 and Fe2O3.Although the original state of oxygen carrier（NiFe2O4） was not fully regenerated and agglomeration was observed,a good recyclability was shown in 10 successive redox cycles.

Organic-acid-assisted synthesis of a 3D lasagna-like Fe-N-doped CNTs-G framework： An efficient and stable electrocatalyst for oxygen reduction reactions

The scalable preparation of multi-functional three-dimensional （3D） carbon nanotubes and graphene （CNTs-G） hybrids via a well-controlled route is urgently required and challenging. Herein, an easily operated, oxalic acid-assisted method was developed for the in situ fabrication of a 3D lasagna-like Fe-N-doped CNTs-G framework （LMFC） from a precursor designed at the molecular level. The well-organized architecture of LMFC was constructed by multi-dimensionally interconnected graphene and CNTs which derived from porous graphene sheets, to form a fundamentally robust and hierarchical porous structure, as well as favorable conductive networks. The impressive oxygen reduction reaction （ORR） performances in both alkaline and acidic conditions helped confirm the significance of this technically favorable morphological structure. This product was also the subject of research for the exploration of decisive effects on the performance of ORR catalysts with reasonable control variables. The present work further advances the construction of novel 3D carbon architectures via practical and economic routes.

Ultrastable bimetallic Fe_(2)Mo for efficient oxygen reduction reaction in pH-universal applications

Iron-based nanostructures represent an emerging class of catalysts with high electroactivity for oxygen reduction reaction(ORR)in energy storage and conversion technologies.However,current practical applications have been limited by insufficient durability in both alkaline and acidic environments.In particular,limited attention has been paid to stabilizing iron-based catalysts by introducing additional metal by the alloying effect.Herein,we report bimetallic Fe_(2)Mo nanoparticles on N-doped carbon(Fe_(2)Mo/NC)as an efficient and ultra-stable ORR electrocatalyst for the first time.The Fe_(2)Mo/NC catalyst shows high selectivity for a four-electron pathway of ORR and remarkable electrocatalytic activity with high kinetics current density and half-wave potential as well as low Tafel slope in both acidic and alkaline medias.It demonstrates excellent long-term durability with no activity loss even after 10,000 potential cycles.Density functional theory(DFT)calculations have confirmed the modulated electronic structure of formed Fe_(2)Mo,which supports the electron-rich structure for the ORR process.Meanwhile,the mutual protection between Fe and Mo sites guarantees efficient electron transfer and long-term stability,especially under the alkaline environment.This work has supplied an effective strategy to solve the dilemma between high electroactivity and long-term durability for the Fe-based electrocatalysts,which opens a new direction of developing novel electrocatalyst systems for future research.