Guo-Liang Chai

Active sites engineering leads to exceptional ORR and OER bifunctionality in P,N Co-doped graphene frameworks

Bifunctional catalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are highly desirable for rechargeable metal–air batteries and regenerative fuel cells. However, the commercial oxygen electrocatalysts (mainly noble metal based) can only exhibit either ORR or OER activity and also suffer from inherent cost and stability issues. It remains challenging to achieve efficient ORR and OER bifunctionality on a single catalyst. Metal-free structures offer relatively large scope for this bifunctionality to be engineered within one catalyst, together with improved cost-effectiveness and durability. Herein, by closely coupled computational design and experimental development, highly effective bifunctionality was achieved in a phosphorus and nitrogen co-doped graphene framework (PNGF) – with both ORR and OER activities reaching the theoretical limits of metal-free catalysts, superior to their noble metal counterparts in both (bi)functionality and durability. In particular, with the identification of active P–N sites for OER and N-doped sites for ORR, we successfully intensified these sites by one-pot synthesis to tailor the PNGF. The resulting catalyst achieved an ORR potential of 0.845 V vs. RHE at 3 mA cm−2 and an OER potential of 1.55 V vs. RHE at 10 mA cm−2. Its combined ORR and OER overpotential of 705 mV is much lower than those previously reported for metal-free bifunctional catalysts.

Planar tetra-coordinate carbon resulting in enhanced third-order nonlinear optical response of metal-terminated graphene nanoribbons

Metal-terminated graphene nanoribbons (M-GNRs) with planar tetra-coordinate carbons (PtC) are investigated theoretically for a third-order nonlinear optical (NLO) response by using the sum-over-states (SOS) method. The third order NLO polarizability, two-photon absorption (TPA) and nonlinear reflectivity are investigated within the third-harmonic generation (THG) or degenerate four-wave mixing (DFWM) processes. The origins of third order NLO polarizability and TPA are analyzed in terms of the charge transfer process, which indicates that tetra-coordinate carbons in M-GNRs have an important role in the third-order NLO response. The dynamic nonlinear reflectivity of the M-GNR presents a resonant characteristic due to the large third order NLO polarizability. Moreover, the third order NLO polarizability and TPA cross section values increase as the ribbon size increases in the low frequency region of incident light, which indicates that their NLO properties can be tailored by controlling the ribbon size. This paper aims to shed light on the design of NLO properties and understanding of the NLO response mechanisms of graphene related materials.

First-principles study of CN carbon nitride nanotubes

The structural, electronic and optical properties of carbon nitride (CN) nanotubes (CNNTs) built from triazine units were investigated by using density-functional theory (DFT) within the generalized gradient approximation. The total energies per CN unit (relative values) of armchair CNNTs are smaller than those of zigzag CNNTs for the same tube index. This leads to unsmooth tubular surfaces for nitrogen-nitrogen lone pair repulsions and porous structures. The armchair CNNTs appear as polygons while zigzag CNNTs are circles. Both the armchair and zigzag CNNTs are direct band gap semiconductors and their band gaps are dependent on tube size and chirality. The calculated dielectric functions of CNNTs are dependent on tube size and the directions of polarization. Moreover, they may be used as photocatalysts to split water to produce hydrogen.

First-principles study of ZnO cluster-decorated carbon nanotubes

We have investigated the structural, electronic and carbon monoxide (CO) detection properties of the ZnO cluster-decorated single-walled carbon nanotubes (SWCNTs) by using density functional theory (DFT). The stable structures of hybrid ZnO/SWCNT materials are that the ZnO cluster plane is perpendicular to the surface of SWCNTs with the Zn atoms towards the SWCNTs (Zn atom above axial C-C bond or above the C atom). For the ZnO cluster-decorated semiconducting SWCNTs, the SWCNTs present p-type characteristics which may lead to the decrease of conductance upon illumination with ultraviolet (UV) light. The CO can be adsorbed on the hybrid ZnO/SWCNT materials due to the charge transfer between them. Compared with isolated ZnO clusters or bare SWCNTs, the ZnO/SWCNT network would have excellent CO detection ability due to their suitable adsorption energy and conductivity.

Structure dependent electronic and magnetic properties of graphitic GaN–ZnO nanoribbons

We investigate the electronic and magnetic properties of GaN–ZnO nanoribbons with density functional theory methods. The obtained large binding energies suggest that these graphitic nanostructures are stable and can hence be effectively synthesized. Their calculated properties strongly depend on the edge atomic configuration: armchair nanoribbons are non-magnetic semiconductors and zigzag ones are half-metals with net magnetism depending on the ribbon width.

Graphitic GaN-ZnO and corresponding nanotubes

Graphitic GaN–ZnO is predicted theoretically. It is much softer than graphene and easier to wrap up into a nanotube. The g-GaN–ZnO and corresponding nanotubes have relatively uniform band gap independent of structures. Moreover, they are potential photocatalysts for water splitting and light-emitting in the UV light region.

THEORETICAL STUDY OF ONE- AND TWO-PHOTON ABSORPTION PROPERTIES FOR THREE SERIES OF DIPHENYLAMINE AND DIFLUORENYLAMINE SUBSTITUTED CONJUGATED COMPOUNDS

The one-photon (OPA) and two-photon (TPA) absorption properties of three series of symmetrically substituted quadrupolar compounds with structure of donor-π bridge-donor (D–π–D) were investigated by time-dependent density functional theory (TDDFT) based on the Hartree–Fock (HF)-optimized geometrical structures. These compounds were constructed with either phenyl or fluorenyl groups connected by vinylene unit as the central π-conjugated bridges and either diphenylamine or difluorenylamine groups as terminal electron donors. The calculated OPA spectra are dominated by two strong transitions which are attributed to the charge transfers from the donor groups to central conjugated chains. The OPA and TPA transition strength all increase with the extension of conjugated chain length in each series and the corresponding wavelength shifts red in general. The transition strength in either OPA or TPA process also increases from series one to series two or three by replacing the phenyl groups with fluorenyl groups. The intramolecular charge transfers make significant contributions to the TPA activity. According to the three-state model, the enhanced TPA activity comes from the enhancement of transition moment between states–states as conjugated chain increases.

Nitrogen-Mediated Graphene Oxide Enables Highly Efficient Proton Transfer

Two-dimensional (2D) graphene and graphene oxide (GO) offer great potential as a new type of cost-efficient proton-exchange membranes (PEM) for electrochemical devices. However, fundamental issues of proton transfer mechanism via 2D membranes are unclear and the transfer barrier for perfect graphene are too high for practical application. Using ab initio molecular dynamic simulations, we screened the proton transfer barrier for different un-doped and nitrogen doped GO membranes, and clarified the corresponding transfer mechanisms. More significantly, we further identify that N-mediated GO can be built into a highly efficient PEM with a proton transfer rate of seven orders of magnitude higher than an un-doped case via. a proton relay mechanism between a ketone-like oxygen and a pyridine-like nitrogen across the vacancy site. The N-doped 2D GO is also impermeable to small molecules, and hence a highly efficient PEM for practical applications.

A THEORETICAL STUDY ON SECOND HARMONIC GENERATION HYPERPOLARIZABILITIES OF PHENYLALANINE POLYPEPTIDES

The second harmonic generation (SHG) hyperpolarizabilities of phenylalanine and homopolypeptides are investigated by configuration interaction among singly excited configurations (CIS) technique combined with the sum-over-states (SOS) method. The geometries of peptides containing phenylalanine (Phe)n(n = 1–8) are optimized by B3LYP/6-31g(d) method, and they form the special structures like β-sheet (a common protein secondary structure). It is found that the energy gaps of various peptides are reduced and the hyperpolarizabilities are increased with the peptide chains lengthened. We discuss the origin of the second-order nonlinear optical response in phenylalanine homopolypeptides and confirm that the π → π* transitions in the aromatic residue of phenylalanine make the most important contributions to the second-order polarizability. Our results strongly suggest that the hyperpolarizabilities are dominated from the propagation direction of peptide chains.

ELECTRONIC STRUCTURES, EXCITED SPECTRA, AND NONLINEAR OPTICAL PROPERTIES OF N-METHYL-FULLEROPYRROLIDINE-OLIGOANILINE DYADS NMPC60-AN(n)(n = 1-5): QUANTUM CHEMISTRY STUDY

The geometrical and electronic structures of a series of dyads NMPC60–ANn (n = 1–5) were investigated at B3LYP/6-31G* level. Then, the excited states were calculated at TDB3LYP/3-21G* level to investigate the photophysical properties. The third-order polarizabilities of degenerate four-wave mixing (DFWM), electric-field-induced second-harmonic generation (EFISHG), and third-harmonic generation (THG) were calculated in combination with the sum-over-states (SOS) method. The obtained absorption spectra show a remarkable red shift. The average value of third-order polarizabilities 〈γ〉 away from the resonant region increases with n for NMPC60–ANn. The charge transfers from the oligoanilines to C60 cage make the main contribution to the large third-order polarizabilities of this series of compounds. It is found that 〈γ〉 can be expressed as a function of the chain length of linked oligoaniline and 11.74 × 10-34esu is the upper limit after n = 7 for NMPC60–ANn in the static state.