Pd 4d Orbital Overlapping Modulation on Au@Pd Nanowires for Efficient H2O2 Production.

Isolating Pd atoms has been shown to be crucial for the design of a Pd-based electrocatalyst toward 2e- oxygen reduction reaction (ORR). However, there are limited studies focusing on the systematic compositional design that leads to an optimal balance between activity and selectivity. Herein, we design a series of Au@Pd core@shell structures to investigate the influence of the Pd 4d orbital overlapping degree on 2e- ORR performance. Density functional theory (DFT) calculations indicate that enhanced H2O2 selectivity and activity are achieved at Pdn clusters with n ≤ 3, and Pd clusters larger than Pd3 should be active for 4e- ORR. However, experimental results show that Au@Pd nanowires (NWs) with Pd4 as the primary structure exhibit the optimal H2O2 performance in an acidic electrolyte with a high mass activity (7.05 A mg-1 at 0.4 V) and H2O2 selectivity (nearly 95%). Thus, we report that Pd4, instead of Pd3, is the upper threshold of Pd cluster size for an ideal 2e- ORR. It results from the oxygen coverage on the catalyst surface during the ORR process, and such an oxygen coverage phenomenon causes electron redistribution and weakened *OOH binding strength on active sites, leading to enhanced activity of Pd4 with only 0.06 V overpotential in acidic media.

Effect of Adventitious Carbon on Pit Formation of Monolayer MoS2.

Forming pits on molybdenum disulfide (MoS2 ) monolayers is desirable for (opto)electrical, catalytic, and biological applications. Thermal oxidation is a potentially scalable method to generate pits on monolayer MoS2 , and pits are assumed to preferentially form around undercoordinated sites, such as sulfur vacancies. However, studies on thermal oxidation of MoS2 monolayers have not considered the effect of adventitious carbon (C) that is ubiquitous and interacts with oxygen at elevated temperatures. Herein, the effect of adventitious C on the pit formation on MoS2 monolayers during thermal oxidation is studied. The in situ environmental transmission electron microscopy measurements herein show that pit formation is preferentially initiated at the interface between adventitious C nanoparticles and MoS2 , rather than only sulfur vacancies. Density functional theory (DFT) calculations reveal that the C/MoS2 interface favors the sequential adsorption of oxygen atoms with facile kinetics. These results illustrate the important role of adventitious C on pit formation on monolayer MoS2 .

Promoting H2O2 production via 2-electron oxygen reduction by coordinating partially oxidized Pd with defect carbon.

Electrochemical synthesis of H2O2 through a selective two-electron (2e-) oxygen reduction reaction (ORR) is an attractive alternative to the industrial anthraquinone oxidation method, as it allows decentralized H2O2 production. Herein, we report that the synergistic interaction between partially oxidized palladium (Pdδ+) and oxygen-functionalized carbon can promote 2e- ORR in acidic electrolytes. An electrocatalyst synthesized by solution deposition of amorphous Pdδ+ clusters (Pd3δ+ and Pd4δ+) onto mildly oxidized carbon nanotubes (Pdδ+-OCNT) shows nearly 100% selectivity toward H2O2 and a positive shift of ORR onset potential by ~320 mV compared with the OCNT substrate. A high mass activity (1.946 A mg-1 at 0.45 V) of Pdδ+-OCNT is achieved. Extended X-ray absorption fine structure characterization and density functional theory calculations suggest that the interaction between Pd clusters and the nearby oxygen-containing functional groups is key for the high selectivity and activity for 2e- ORR.