Understanding Synergistic Catalysis on Cu-Se Dual Atom Sites via Operando X-ray Absorption Spectroscopy in Oxygen Reduction Reaction.

The construction and understanding of synergy in well-defined dual-atom active sites is an available avenue to promote multistep tandem catalytic reactions. Herein, we construct a dual-hetero-atom catalyst that comprises adjacent Cu-N4 and Se-C3 active sites for efficient oxygen reduction reaction (ORR) activity. Operando X-ray absorption spectroscopy coupled with theoretical calculations provide in-depth insights into this dual-atom synergy mechanism for ORR under realistic device operation conditions. The heteroatom Se modulator can efficiently polarize the charge distribution around symmetrical Cu-N4 moieties, and serve as synergistic site to facilitate the second oxygen reduction step simultaneously, in which the key OOH*-(Cu1 -N4 ) transforms to O*-(Se1 -C2 ) intermediate on the dual-atom sites. Therefore, this designed catalyst achieves satisfied alkaline ORR activity with a half-wave potential of 0.905 V vs. RHE and a maximum power density of 206.5 mW cm-2 in Zn-air battery.

Preparation, optical and electrical properties of PTCDA nanostructures.

Film, nanorods (NRs), nanowires (NWs), and nanoparticles (NPs) of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) were prepared by organic molecular beam deposition (OMBD) on porous anodic alumina oxide (AAO) at different substrate temperatures (Ts). Scanning electron microscopy (SEM) study showed that the morphologies of the nanostructures (NS) formed on AAO strongly depend on the Ts. The absorption spectra of different PTCDA NS present strong absorbance in the wavelength range of 400-600 nm, and the photoluminescence (PL) spectra show a blue shift as Ts increases. The current versus voltage (I-V) characteristic illustrates that the electrical conductivity of the single-crystal NW is about 3 ± 0.1 S m(-1), which is much higher than the conductivity of PTCDA film reported previously.

Electronic structures of bare and terephthalic acid adsorbed TiO2(110)-(1 × 2) reconstructed surfaces: origin and reactivity of the band gap states.

Combined core level spectroscopy, valence spectroscopy and density functional theory studies have probed the terephthalic acid (TPA) adsorption behavior and the electronic structure of the rutile TiO2(110)-(1 × 2) reconstructed surface at room temperature. The TiO2(110)-(1 × 2) reconstructed surface exhibits an electron rich nature owing to the unsaturated coordination of the surface terminated Ti2O3 rows. Deprotonation of TPA molecules upon adsorption produces both surface bridging hydroxyl (ObH) and bidentate terephthalate species with a saturation coverage of nearly 0.5 monolayers (ML). In contrast to the TiO2(110)-(1 × 1) surface, the band gap states (BGSs) on the bare (1 × 2) surface exhibit an asymmetric spectral feature, which is originated from integrated contributions of the Ti2O3 termination and the defects in the near-surface region. The Ti2O3 originated BGSs are found to be highly sensitive to the TPA adsorption, a phenomenon well reproduced by the density functional theory (DFT) calculations. Theoretical simulations of the adsorption process also suggest that the redistribution of the electronic density on the (1 × 2) reconstructed surface accompanying the hydroxyl formation promotes the disappearance of the Ti2O3-row derived BGS.

A direct Fe-O coordination at the FePc/MoO(x) interface investigated by XPS and NEXAFS spectroscopies.

Molecule-substrate interaction plays a vital role in determining the electronic structures and charge transfer properties in organic-transition metal oxides (TMOs) hybridized devices. In this work, the interactions at the FePc/MoO3 interface has been investigated in detail by using synchrotron radiation photoemission spectroscopy (SRPES) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Compared with the annealing of the bare MoO3 film, the FePc adsorption is found to promote the thermal reduction of the underlying MoO3 film. XPS and NEXAFS experimental results unanimously demonstrate a strong electronic coupling between FePc molecules and the MoOx (x < 3) substrate. A direct Fe-O coordination at the interface as well as an electron transfer from the molecules toward the substrate is proposed. This strong coupling is compatible with a facile electron transfer from FePc molecules toward electrode through a MoOx interlayer. The understanding of the molecule-substrate interaction at the atomic level is of significance in engineering functionalized surfaces with potential applications in nanoscience, molecular electronics and photonics.

Charge transfer dynamics of 3,4,9,10-perylene-tetracarboxylic-dianhydride molecules on Au(111) probed by resonant photoemission spectroscopy.

Charge transfer dynamics across the lying-down 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) organic semiconductor molecules on Au(111) interface has been investigated using the core-hole clock implementation of resonant photoemission spectroscopy. It is found that the charge transfer time scale at the PTCDA∕Au(111) interface is much larger than the C 1s core-hole lifetime of 6 fs, indicating weak electronic coupling between PTCDA and the gold substrate due to the absence of chemical reaction and∕or bonding.

Electronic structure of Eu-C(70) fullerides.

The electronic structure of Eu-intercalated C(70) has been studied by a synchrotron radiation photoemission spectroscopy technique. At low intercalation levels (below the stoichiometry of Eu(3)C(70)), the photoemission data clearly exhibit charge transfer from Eu 6s states to the lowest-unoccupied-molecular-orbital (LUMO) and the LUMO + 1 of C(70). The amount of charge transfer reaches its maximum far before intercalation saturation. Detailed analysis reveals that most of the 5d6s electrons of Eu occupy the so-called interstitial states in the saturation phase (Eu(9)C(70)). The interstitial states are induced by a Eu sub-lattice formed at heavy intercalation levels, and comprise substantial 6s-π hybridized states. The π states participating in the hybridization are mainly the HOMO - n (n = 6-10) orbitals. The PES data also reveal the semiconducting property for both Eu(3)C(70) and Eu(9)C(70). The 6s-(HOMO - n) hybridization and the semiconducting property should play important roles in understanding the ferromagnetic mechanism for Eu(9)C(70).