Combined with air annealing, rutile-structured IrO 2 nanoparticles with various sizes were prepared using colloidal method. The nanoparticles were used as the electrocatalysts for the oxygen evolution reaction （OER） in acidic media, and their grain size effect was studied. The results show that with the increase in annealing temperature, the grain size of the catalyst increases, and the voltammetric charges （the electroactive areas） and apparent activity for the OER decrease. The relationship between the intrinsic activity and the annealing temperature exhibits a volcano-type curve and the catalyst annealed at 550 ℃ achieved the best result.
The nanostructure of the catalytic electrode has a great effect on the performance of direct metha- nol fuel cells （DMFCs）, including catalyst utilization, precious metal loading, water balance, and oxygen mass transfer. In this work, ordered arrays of platinum nanorods with different diameters were directly grown onto microporous layers by electrodeposition via a sacrificial template, and were used as the catalytic cathode for passive DMFCs. The use of these ordered electrodes led to a dramatic decrease in cathode polarization behavior. The maximum power density of passive DMFCs fabricated with catalytic electrodes of 200 and 100 am Pt nanorod arrays were 17.3 and 12.0 mW/cm2, respectively. The obtained improvement in performance was ascribed to the fact that the ordered nanostructured electrode not only increased the electrochemically active surface area and the catalyst utilization, but also enhanced oxygen mass transfer and water balance in the system.
Fe and Co porphyrins and phthalocyanines are excellent catalysts for the oxygen reduction reaction （ORR） and are promising alternatives to Pt in fuel cells. However, the stability of these molecular catalysts in acidic media is poor. This study explores whether demetalation through proton ex- change causes these metal macrocyclic catalysts to be unstable in acidic media. We first present a theoretical scheme for investigating exchange reactions of metal ions in metal macrocyclic com- pounds with protons in acidic media. The equilibrium concentrations of metal ions in solution when various metalloporphyrins （MPs） and metallophthalocyanines （MPcs） are brought into contact with a strongly acidic solution （pH = 1） were then estimated using density functional theory calculations; these values were used to evaluate the stability of these metal macrocyclic compounds against demetalation in acidic media, The results show that Fe, Co, Ni, and Cu phthalocyanines and porphy- rins have considerable resistance to exchange with protons, whereas Cr, Mn, and Zn phthalocya- nines and porphyrins easily undergo demetalation through ion exchange with protons, This sug- gests that the degradation in the ORR activity of Fe and Co macrocyclic molecular catalysts and of carbon materials doped with Fe（Co） and nitrogen, which are believed to have metal-nitrogen coor- dination structures similar to those of macrocyclic molecules as ORR catalytic centers, is not the result of replacement of metal ions by protons. The calculation results show that electron-donating substituents could enhance the stability of Fe and Co phthalocyanines.
We demonstrate a new and simple method for pre-treating the carbon material and iron precursor to prepare oxygen reduction reaction(ORR) catalysts, which can produce super-high performance and stability in alkaline solution, with high performance in acid solution. This strategy using cheap materials is simply controllable. Moreover, it has achieved smaller uniform nanoparticles to exhibit high stability, and the synergetic effect of Fe and N offered much higher performance in ORR than commercial Pt/C, with high maximum power density in alkaline and acid fuel cell test. So it can make this kind of catalysts be the most promising alternatives of Pt-based catalysts with best performance/price.
The stability and oxygen reduction reaction （ORR） activity of the Pt-segregated surface in various Pt-M alloys （M： transition metals） are investigated through systematic DFT calculations on the thermodynamic （alloy formation energy and Pt surface segregation energy）, surface chemical property （oxygen binding energy） and electronic （d-band center） properties. Factors af- fecting these properties, such as the atomic radii and surface energy of M and the electronic ligand interaction between Pt and M are analyzed as a function of outmost d electron numbers of M. It is shown that the electronic ligand interaction plays de- termining role in the alloy formation energy of various Pt-M alloys; the formation of Pt-segregated surface in Pt-M alloys is faw）red when alloying metals have higher surface energy and smaller radii than Pt; the oxygen binding energy on the Pt-segregated surface in Pt-M alloys varies approximately linearly with the d-band center of surface Pt atoms; the lattice strain and electronic ligand effects are simply additive in Pt-M alloys; the stain effect in Pt-M alloys nearly linearly affects the d-band center of the Pt-segregated surface in Pt-M alloys; transition metals with less than 10 d electrons mostly exhibit electron ligand effects which result in downshift of the d-band center of the segregated surface Pt atoms, while those with ten d electrons exhibit electron ligand effect upshifting the d-band center of the segregated Pt atoms.
