“…Peaks at 228.6 and 231.7 eV were readily assigned to Mo 2+ in Mo 2 C (3d 5/2 and 3d 3/2 , respectively). − Peaks at 232.1 and 235.1 were assigned to a Mo 5+ species (3d 5/2 and 3d 3/2 , respectively), while the peaks at 232.7 and 235.7 eV are typical for Mo 6+ in MoO 3 (3d 5/2 and 3d 3/2 , respectively). ,− On the basis of the area ratios of the Mo 3d 5/2 for the Mo 5+ and Mo 6+ species in Figure F, the fraction of Mo 5+ species in MoO x shell on the Mo 2 C@MoO x nanoclusters was calculated to be ∼60%. The O 1s XPS spectra for C/Mo 2 C@MoO x (Figure G) were deconvoluted into 4 peaks: O–Mo 6+ (530.6 eV) and O–Mo 5+ (531.3 eV) in MoO x , adsorbed hydroxyl O–H or C=O (532.1 eV), and adsorbed water or carbonate (533.4 eV). , The C 1s spectra for C/Mo 2 C@MoO x were well-fitted by five peaks at 283.8, 284.7, 285.6, 286.5, and 288.4 eV, which could readily be assigned to C–Mo (as Mo 2 C), C–C, C–N, C–O, and O–C=O species (Figure H), respectively. ,− Except for the C–Mo peak, all of the other peaks are associated with the N-doped carbon support or adventitious hydrocarbons. The XPS results strongly support the formation of carbon-supported Mo 2 C@MoO x nanoclusters (consistent with the HRTEM results), with Mo 5+ the dominant Mo species in the oxide shell of the core–shell structured nanoclusters.…”