Hierarchical nitrogen-doped carbon nanocages （hNCNC） with large specific surface areas were used as a catalyst support to immobilize Pt nanoparticles by a microwave-assisted polyol method. The Pt/hNCNC catalyst with 20 wt% loading has a homogeneous dispersion of Pt nanoparticles with the average size of 3.3 nm, which is smaller than 4.3 and 4.9 nm for the control catalysts with the same loading supported on hierarchical carbon nanocages （hCNC） and commercial Vulcan XC-72, respec- tively. Accordingly, Pt/hNCNC has a larger electrochemical surface area than Pt/hCNC and Pt/XC-72. The Pt/hNCNC catalyst exhibited excellent electrocatalytic activity and stability for methanol oxidation, which was better than the control catalysts. This was attributed to the en- hanced interaction between Pt and hNCNC due to nitrogen participation in the anchoring function. By making use of the unique advantages of the hNCNC support, a heavy Pt loading up to 60 wt% was prepared without serious agglomeration, which gave a high peak-current density per unit mass of catalyst of 95.6 mA/mg for achieving a high power density. These results showed the potential of the Pt/hNCNC catalyst for methanol oxidation and of the new hNCNC support for wide applications.
Taking advantage of the nitrogen(N)-participation and large surface area of N-doped carbon nanocages(NCNCs),the Co Ox nanocrystals are conveniently immobilized onto the NCNCs with high dispersion.The Co Ox/NCNCs hybrid exists in the mixed valence with predominant Co O over Co3O4 and demonstrates superb oxygen reduction reaction activity and stability remaining^94%current density even after operation over 100 h.These results suggest a promising strategy to develop advanced electrocatalysts with the novel NCNCs or even beyond.
The unique hierarchical nitrogen-doped carbon nanocages(h NCNC) are used as a new support to homogeneously immobilize spinel Co Fe_2O_4 nanoparticles by a facile solvothermal method. The so-constructed hierarchical Co Fe_2O_4/h NCNC catalyst exhibits a high oxygen reduction activity with an onset potential of0.966 V and half-wave potential of 0.819 V versus reversible hydrogen electrode, far superior to the corresponding 0.846 and 0.742 V for its counterpart of Co Fe_2O_4/h CNC with undoped hierarchical carbon nanocages(h CNC) as the support, which locates at the top level for spinel-based catalysts to date.Consequently, the Co Fe_2O_4/h NCNC displays the superior performance to the Co Fe_2O_4/h CNC, when used as the cathode catalysts in the home-made Al-air batteries. X-ray photoelectron spectroscopy characterizations reveal the more charge transfer from Co Fe_2O_4 to h NCNC than to h CNC, indicating the stronger interaction between Co Fe_2O_4 and h NCNC due to the nitrogen participation. The enhanced interaction and hierarchical morphology favor the high dispersion and modification of electronic states for the active species as well as the mass transport during the oxygen reduction process, which plays a significant role in boosting the electrocatalytic performances. In addition, we noticed the high sensitivity of O 1 s spectrum to the particle size and chemical environment for spinel oxides, which is used as an indicator to understand the evolution of ORR activities for all the Co Fe_2O_4-related contrast catalysts. Accordingly,the well-defined structure-performance relationship is demonstrated by the combination of experimental characterizations with theoretical calculations. This study provides a promising strategy to develop efficient, inexpensive and durable oxygen reduction electrocatalysts by tuning the interaction between spinel metal oxides and the carbon-based supports.
