The identification of active N species in N-doped carbon carriers that improve the activity of Fe electrocatalysts towards the oxygen evolution reaction.

Nitrogen-doped carbon nanomaterials have become some of the most effective carriers for transition metal-based electrocatalysts towards the oxygen evolution reaction. However, the specific active nitrogen species in nitrogen-doped carriers remains unclear up to now. To identify the active nitrogen species, herein, we prepare nitrogen-doped carbon nanospheres containing different types of nitrogen species and a small amount of Fe atoms. Electrochemical tests demonstrate that the Fe/nitrogen-doped carbon nanospheres with more graphitic nitrogen exhibit much higher activity for the oxygen evolution reaction than those with more pyridinic nitrogens and pyrrolic nitrogens in alkaline media, revealing that the graphitic nitrogen is the active species that greatly improves the activity of Fe catalysts. Density functional theory calculations further reveal that the graphitic nitrogen enhances the activity and stability of Fe-based catalysts mainly through increasing the adsorption energy, charge and spin densities of the Fe atoms loaded around it. These findings provide a brand-new perspective for rationally designing more effective transition metal-based electrocatalysts for the oxygen evolution reaction through controlling the active graphitic nitrogen distribution in carbon carriers.

Tuning the Geometrical Structures and Optical Properties of Blue-Emitting Iridium(III) Complexes through Dimethylamine Substitutions: A Theoretical Study.

The geometrical structures and photophysical properties of Ir(4,6-dFppy)2(pic) (FIrpic) and its derivative (o-FIr, m-FIr, p-FIr) with dimethylamine substituted at the picolinic acid (N∧O) ligand were fully investigated by density functional theory and time-dependent density functional theory. The simulated electronic structure, as well as absorption and emission spectra of FIrpic are in good agreement with the experimental observations. The introduction of dimethylamine at the N∧O ligand at different positions is beneficial to extend the π-electron delocalization, increase HOMO energy levels, and hence improve the hole injection and transfer ability compared with those of FIrpic. Furthermore, o-FIr, m-FIr, and p-FIr have large absorption intensity and participation of metal-to-ligand charge transfer (MLCT) contribution in the main absorption spectra, which would be useful to improve the intersystem crossing (ISC) from the singlet to triplet excited state. More importantly, the high quantum yield of o-FIr (which is explained based on the detailed analysis of triplet energy, ET1), participation of ³MLCT contribution in the phosphorescent spectra, and energy difference between ³MLCT and triplet metal centered (³MC) d-d excited state compared with m-FIr and p-FIr indicate that o-FIr is expected to be an excellent blue phosphorescence emitter with high efficiency.

Charge Transfer Enhancement in the D-π-A Type Porphyrin Dyes: A Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) Study.

The electronic geometries and optical properties of two D-π-A type zinc porphyrin dyes (NCH3-YD2 and TPhe-YD) were systematically investigated by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) to reveal the origin of significantly altered charge transfer enhancement by changing the electron donor of the famous porphyrin-based sensitizer YD2-o-C8. The molecular geometries and photophysical properties of dyes before and after binding to the TiO2 cluster were fully investigated. From the analyses of natural bond orbital (NBO), extended charge decomposition analysis (ECDA), and electron density variations (Δρ) between the excited state and ground state, it was found that the introduction of N(CH3)2 and 1,1,2-triphenylethene groups enhanced the intramolecular charge-transfer (ICT) character compared to YD2-o-C8. The absorption wavelength and transition possess character were significantly influenced by N(CH3)2 and 1,1,2-triphenylethene groups. NCH3-YD2 with N(CH3)2 groups in the donor part is an effective way to improve the interactions between the dyes and TiO2 surface, light having efficiency (LHE), and free energy change (ΔGinject), which is expected to be an efficient dye for use in dye-sensitized solar cells (DSSCs).

Triphenylamine-based indoline derivatives for dye-sensitized solar cells: a density functional theory investigation.

A new series of triphenylamine-based indoline dye sensitizers were molecularly designed and investigated for their potential use in dye-sensitized solar cells (DSSCs). Theoretical calculations revealed that modifying donor part of D149 by triphenylamine significantly altered the electronic structures, MO energies, and intramolecular charge transfer (ICT) absorption band. Key parameters associated with the light-harvesting efficiency at a given wavelength LHE(λ), the driving force ΔG inject, and the open-circuit photovoltage V oc were characterized. More importantly, these designed (dimeric) dye sensitizers were found to have similar broad absorption spectra to their corresponding monomers, indicating that modifying the donor part with triphenylamine may stop unfavorable dye aggregation. Further analyses of the dye-(TiO2)9 cluster interaction confirmed that there was strong electronic coupling at the interface. These results are expected to provide useful guidance in the molecular design of new highly efficient metal-free organic dyes.

Theoretical studies of the interactions of ethylene and formaldehyde with gold clusters.

We studied the adsorption of C(2)H(4) and CH(2)O on the gold clusters Au(n) (n = 1-5) in various adsorption modes using density functional theory PW91 functional. We found that the binding energies of pi-C(2)H(4) and pi and O-sigma modes of CH(2)O increase first and then decrease with the cluster size. Natural bonding orbital (NBO) analyses reveal that the donor-acceptor interaction plays an important role in these adsorption complexes and there is a nice linear relationship between the calculated binding energy and the stabilization energy estimated with second-order perturbation theory in the framework of NBO analysis. It is demonstrated that the bonding interaction between adsorbates and clusters follows the di-sigma > pi > O-sigma mode. However, due to adsorption induced structural deformation of adsorbates and clusters, the binding energies of different adsorption modes are comparable. It is shown that C(2)H(4) interacts more strongly with the clusters than CH(2)O does and that the previously assigned adsorption mode of C(2)H(4) on Au/MgO may not be the pi modes, but the C-sigma configuration.

A theoretical study of the effects of the charge state and size of gold clusters on the adsorption and dissociation of H2.

The adsorption and dissociation of H(2) on the neutral and charged gold clusters Au(n) (m)(m=0,+/-1; n=1-6) is investigated using the density functional theory PW91 functional. H(2) interacts very weakly with Au(n) (-1), whereas the interaction with Au(n) (+1) is relatively strong. The binding energies on neutral clusters are between those on the cationic and anionic systems. The binding energy decreases monotonically with the size increase of the cationic clusters while it goes up first and then goes down on the neutral systems with the maximum value of 0.78 eV at Au(3). Au cations show no propensity for the dissociation barrier reduction and are thermodynamically unfavorable for the dissociation. For the first time we find that H(2) dissociation involves valley-ridge inflection points on some clusters. Our results indicate that H(2) dissociates facilely at low temperatures on both neutral and cationic Au(4) and Au(5). The phenomenon that H(2) dissociation was not observed experimentally is not due to the higher dissociation barrier and weak binding of H(2). We also show that the coordination number of the Au atom may not play a determining role in H(2) dissociation.