Rui-Qin Zhang

Carbon Dot Loading and TiO2 Nanorod Length Dependence of Photoelectrochemical Properties in Carbon Dot/TiO2 Nanorod Array Nanocomposites

Photoelectrochemcial (PEC) properties of TiO2 nanorod arrays (TNRA) have been extensively investigated as they are photostable and cost-effective. However, due to the wide band gap, only the UV part of solar light can be employed by TiO2. To enhance the photoresponse of TNRA in the visible range, carbon dots (C dots) were applied as green sensitizer in this work by investigating the effects of C dot loading and length of TiO2 nanorod on the PEC properties of TNRA/C dot nanocomposites. As the C dot loading increases, the photocurrent density of the nanocomposites was enhanced and reached a maximum when the concentration of the C dots was 0.4 mg/mL. A further increase in the C dot concentration decreased the photocurrent, which might be caused by the surface aggregation of C dots. A compromise existed between charge transport and charge collection as the length of TiO2 nanorod increased. The incident photon to current conversion efficiency (IPCE) of the TNRA/C dot nanocomposites in the visible range was up to 1.2-3.4%. This work can serve as guidance for fabrication of highly efficient photoanode for PEC cells based on C dots.

Efficient Emission Facilitated by Multiple Energy Level Transitions in Uniform Graphitic Carbon Nitride Films Deposited by Thermal Vapor Condensation

Graphitic carbon nitride (g-CN) films are important components of optoelectronic devices, but current techniques for their production, such as drop casting and spin coating, fail to deliver uniform and pinhole-free g-CN films on solid substrates. Here, versatile, cost-effective, and large-area growth of uniform and pinhole-free g-CN films is achieved by using a thermal vapor condensation method under atmospheric pressure. A comparison of the X-ray diffraction and Fourier transform infrared data with the calculated infrared spectrum confirmed the graphitic build-up of films composed of tri-s-triazine units. These g-CN films possess multiple active energy states including π*, π, and lone-pair states, which facilitate their efficient (6% quantum yield in the solid state) photoluminescence, as confirmed by both experimental measurements and theoretical calculations.

Molecular orbital analysis of the hydrogen bonded water dimer

As an essential interaction in nature, hydrogen bonding plays a crucial role in many material formations and biological processes, requiring deeper understanding. Here, using density functional theory and post-Hartree-Fock methods, we reveal two hydrogen bonding molecular orbitals crossing the hydrogen-bond’s O and H atoms in the water dimer. Energy decomposition analysis also shows a non-negligible contribution of the induction term. Our finding sheds light on the essential understanding of hydrogen bonding in ice, liquid water, functional materials and biological systems.

Dynamic crystallography reveals early signalling events in ultraviolet photoreceptor UVR8

UVB from sunlight is an important environmental signal for plants. In Arabidopsis thaliana, the UVB signal is perceived by photoreceptor AtUVR8, which undergoes light-induced dimer dissociation. Crystallographic and mutational studies have identified two tryptophan residues at the dimer interface that are crucial for UVB responses. However, the molecular events leading up to dimer dissociation remain elusive. We applied dynamic crystallography to capture light-induced structural changes in photoactive AtUVR8 crystals. Here we report two intermediate structures at 1.67u2005Å resolution. At the epicentre of UVB signalling, concerted motions associated with Trpu2005285/Trpu2005233 lead to ejection of a water molecule, which weakens a network of hydrogen bonds and salt bridges at the dimer interface. Partial opening of the β-propeller structure, due to thermal relaxation of conformational strains originating in the epicentre, further disrupts the dimer interface and leads to dissociation. These dynamic crystallographic observations provide structural insights into the photo-perception and signalling mechanism of UVR8.

Graphitic Carbon Nitride Film: An Emerging Star for Catalytic and Optoelectronic Applications

Graphitic carbon nitride (g-CN) is a unique organic semiconductor that has been widely applied as a visible-light-driven photocatalyst. However, these applications are primarily based on g-CN powders. Applications of g-CN in devices are hindered because of difficulties associated with the synthesis of high-quality g-CN films. This work reviews the latest advances in g-CN films. The deposition methods are summarized and the structural, optical, and electronic properties of g-CN films and their applications in catalysis, solar cells, and light-emitting diodes are outlined. Moreover, the challenges remaining in this field are also discussed.

Facet-Controlling Agents Free Synthesis of Hematite Crystals with High-Index Planes: Excellent Photodegradation Performance and Mechanism Insight.

Hematite (α-Fe2O3) crystals with uniform size and structure are synthesized through very facile one-pot hydrothermal methods without any additive. The as-synthesized sub-micrometer-sized α-Fe2O3 crystals with small surface areas perform superb visible light photodegradation activities, even much better than most other α-Fe2O3 nanostructures with large surface areas. Profound mechanism analyses reveal that the microwave-assisted hydrothermal (Mic-H) synthesized α-Fe2O3 is enclosed by 12 high-index {2-15} facets. The structure and the low unoccupied molecular orbital (LUMO) of the high-index planes result in the excellent photocatalytic activity. This is the first report on the formation of {2-15} plane group of hematite, and the synthesis of the hematite particles with the {2-15} planes is very simple and no any facet-controlling agent is used. This study may pave the way to further performance enhancement and practical applications of the cheap hematite materials.

Physisorption of benzene derivatives on graphene: critical roles of steric and stereoelectronic effects of the substituent

A series of benzene derivatives with different substituents adsorbed on graphene was investigated using a density-functional tight-binding method with a dispersion correction. Compared to benzene, the derivative with either an electron-withdrawing or -donating substituent exhibits stronger physisorption. Moreover, the steric size of the substituent is important in determining the adsorption strength, while the direction and the number of H atoms in the substituent affect the electron transfer from graphene. NBO analysis reveals that the stereoelectronic effect of the conjugation between the substituent and the benzene ring strongly influences the π···π interaction region between the molecule and graphene. The findings can deepen the understanding of the interaction between an aromatic molecule and graphene as well as the corresponding adsorption mechanism.

Strong orbital deformation due to CH-π interaction in the benzene-methane complex.

The orbital distribution and composition of the benzene-methane complex have been investigated systemically using ab initio calculations for the first time. Surprisingly, we find strong deformation in the HOMO-4 and LUMO+2 induced by CH-π interaction, extending the general view that nonbonding interaction does not cause orbital change of molecules.

A new insight into π–π stacking involving remarkable orbital interactions

For more than half a century, the phenomenon of π-π stacking has attracted much attention in several research fronts including materials science, chemical synthesis, and even drug design. Despite intense theoretical and experimental exploration, no unified description of the factors contributing to π-π stacking interactions and their weak bonding process has been proposed. In this work, based on calculations of the simplest prototype of π-π stacking, namely the benzene sandwich dimer (together with benzene-phenol, toluene and benzonitrile) using the density functional theory with dispersion correction, previously rarely studied intermolecular orbital interaction is discussed in detail and shown to involve considerable hybridizations of some of the orbitals which make a large contribution to the total interaction energy. We now propose a unified model for the often nebulous π-π stacking process and its analogs: firstly when the two monomers are too far apart, the dispersion effect will play a dominant role in bringing them together, but when they are too close, Pauli repulsion will force them apart. Secondly, at the equilibrium distance, electrostatic interaction, Pauli repulsion, dispersion and intermolecular orbital interaction are all pronounced, with part of the molecular orbitals of the two monomers interacting with each other to form a weak intermolecular bond.

Excited State Relaxation and Stabilization of Hydrogen Terminated Silicon Quantum Dots

Silicon is the leading semiconductor material in microelectronic industry. Owing to the large surface to volume ratio, low-dimensional Si nanostructures, for instance, silicon quantum dots exhibit diverse electronic and optical properties. Passivating the surface of Si nanostructures by a suitable species is thereby required to stabilize and engineer the dot properties in different environment. Recent theoretical advances in the investigation of the excited state properties of silicon quantum dots (QDs) are reviewed in this article. The theoretical calculations reveal that the excited state relaxation is prevalent in hydrogenated silicon nanoparticles. Stokes shift due to structure relaxation in the excited state varies with the particle size. It is therefore desirable to minimize Stokes shift for the purpose of maximizing its quantum yield or efficiency in photoluminescence applications. Consequently, surface functionalization by a suitable species turns out to be the most effective avenue. Determination of proper passivating agent is of outmost importance to satisfy the practical necessity. All these intermingled factors are briefly addressed in this article.