No abstract

Tantalum-oxide-based oxygen-reduction-reaction (ORR) catalysts have the ORR activity only when they are synthesized from tantalum carbonitrides. Namely pure Ta 2 O 5 does not show ORR activity, and carbon or nitrogen in precursors is inevitable to form ORR active sites and to promote ORR. To clarify this reason, we investigated structural and surface electronic properties of tantalum-oxide-based catalysts, which were synthesized by gradually oxidizing tantalum carbonitride under low partial pressure of oxygen at 1000 °C, by using X-ray absorption spectroscopy, transmission electron microscopy, and Raman spectroscopy. The results indicate that oxidized tantalum carbonitrides with high ORR activity had oxygen vacancies near the surface, indicating that the vacancies could work as an active site for ORR. We also found that carbon was deposited on the oxide's surface during oxidation of tantalum carbonitrides. The deposited carbon seems to play two important roles in formation of oxygen vacancies (ORR active sites) providing reductive atmosphere, and in producing electron conduction paths on rather insulating oxides' surface.

We analyzed the local structure of the surface Ta-oxide phase of TaCN/Ta2O5 core-shell particles that have a high oxygen reduction activity by using surface-sensitive conversion-electron-yield x-ray absorption spectroscopy, suppressing the contribution from the TaCN cores. The radial structure analysis revealed that the catalytically-active Ta2O5 phase in the TaCN/Ta2O5 particle surface contains oxygen-vacancy defects with shorter Ta–O bonds leading to the slight expansion of the first Ta–O shell. Such oxygen defects are likely responsible for the oxygen reduction capability by creating electronically favorable oxygen adsorption sites and electron conduction pathways.

A partially oxidized TaC0.58N0.42 has been investigated as a new cathode for polymer electrolyte fuel cells. The catalytic activity for oxygen reduction reaction (ORR) significantly depended on an oxidation state of the TaC0.58N0.42. TaC0.58N0.42 and Ta2O5 had a poor catalytic activity for the ORR. The onset potential on the partially oxidized TaC0.58N0.42 for the ORR had a maximum value of 0.9 V versus reversible hydrogen electrode in 0.1 mol dm−3H2SO4 at 30°C, which indicated that the partially oxidized TaC0.58N0.42 had definite catalytic activity for the ORR. Hard X-ray photoelectron spectroscopy and X-ray diffraction analyses revealed that the surfaces of the partially oxidized TaC0.58N0.42 were oxidized, although the inner parts of the partially oxidized TaC0.58N0.42 remained tantalum carbonitride. These results suggested that an appropriate oxidation of the TaC0.58N0.42 was essential to enhance the catalytic activity for the ORR.

A partially oxidized TaC0.58N0.42 has been investigated as a new cathode for polymer electrolyte fuel cells. The catalytic activity for oxygen reduction reaction (ORR) significantly depended on an oxidation state of the TaC0.58N0.42. TaC0.58N0.42 and Ta2O5 had a poor catalytic activity for the ORR. The onset potential on the partially oxidized TaC0.58N0.42 for the ORR had a maximum value of 0.9 V vs. RHE in 0.1 mol dm-3 H2SO4 at 30oC. Hard X-ray PhotoElectron Spectroscopy and XRD analyses indicated that the surfaces of the partially oxidized TaC0.58N0.42 were oxidized, although the inner parts of the partially oxidized TaC0.58N0.42 remained tantalum carbonitride. This result indicated that an appropriate oxidation of the TaC0.58N0.42 was essential to enhance the catalytic activity for the ORR.