2019 Vol. 32, No. 5

2019, 32(5): i-i.
Chinese abstract
Chinese Abstracts
2019, 32(5): ii-iii.
We present an enhancement of the fluorescence of shallow (<10 nm) nitrogen-vacancy (NV-) centers by using atomic layer deposition to deposit titanium oxide layers on the diamond surface. In this way, the shallow NV- center charge states were stabilized, leading to the increasing fluorescence intensity of about 2 times. This surface coating technique could produce a protective layer of controllable thickness without any damages to the solid-state quantum system surface, which might be an approach to the further passivation or packaging techniques for the solid-state quantum devices.
Photocatalysis of CH3OH on the ZnO(0001) surface has been investigated by using temperature-programmed desorption (TPD) method with a 266 nm laser light. TPD results show that part of the CH3OH adsorbed on ZnO(0001) surface are in molecular form, while others are dissociated. The thermal reaction products of H2, CH3·, H2O, CO, CH2O, CO2 and CH3OH have been detected. Experiments with the UV laser light indicate that the irradiation can promote the dissociation of CH3OH/CH3O· to form CH2O, which can be future converted to HCOO- during heating or illumination. The reaction between CH3OHZnand OHad can form the H2O molecule at the Zn site. Both temperature and illumination promote the desorption of CH3· from CH3O·. The research provides a new insight into the photocatalytic reaction mechanism of CH3OH on ZnO(0001).
The [1+1] two-photon dissociation dynamics of mass-selected 79Br2+ has been studied in acold ion beam using a cryogenic cylindrical ion trap velocity map imaging spectrometer. The quartet 14Σ-u,3/2 state of 79Br2+ is employed as an intermediate state to initiate resonance enhanced two-photon excitation to high-lying dissociative states in the 4.0-5.0 eV energy region above the ground rovibronic state. Total kinetic energy release (TKER) and the twodimensional recoiling velocity distributions of fragmented 79Br+ ions are measured using the technique of DC-slice velocity map imaging. Branching ratios for individual state-resolved product channels are determined from the TKER spectra. The measured photofragment angular distributions indicate that the dissociation of 79Br2+ occurs in dissociative Ω=3/2 state via ΔΩ=0 parallel transition from the 14Σ-u,3/2 intermediate state. Due to the considerable spin-orbit coupling effects in the excited states of 79Br2+, higher-lying dissociative quartet states are likely responsible for the observed photodissociation processes.
High-resolution absorption spectra of atomic krypton in the range of 11870-12700 cm?1 were recorded by employing concentration modulation absorption spectroscopy technique with a tunable single-mode cw Ti:Sapphire laser. The krypton atoms were excited to the absorbing energy states by discharge-burning in a mixture of helium and krypton. A total of 120 lines of neutral krypton were observed, among them 33 lines had already been classified in previous studies, 45 lines were newly classi ed with the known energy levels, and 42 lines cannot be classi ed. These unclassified lines indicate that up to now unknown energy levels of Kr must exist. Further, an analysis of the unclassi ed lines to get possible new energy levels with a classi cation program is reported.
Due to outstanding mechanical properties, heat resistance, and relatively facile production, nanoclay reinforced epoxy composites (NCRE composites) have been suggested as candidate materials for use on external surfaces of spacecraft residing in the low Earth orbit (LEO) environment. The resistance of the NCRE composites to bombardment by atomic oxygen (AO), a dominant component of the LEO environment, has been investigated. Four types of samples were used in this study. They were pure epoxy (0 wt% nanoclay content), and NCRE composites with different loadings of nanoclay—1 wt%, 2 wt%, and 4 wt%. Etch depths decreased with increasing nanoclay content, and for the 4 wt% samples it ranged from 28% to 37% compared to that of pure epoxy. X-ray photoelectron spectroscopy (XPS) indicates that after AO bombardment, relative area of C-C/C-H peak decreased, while the area of the C-O, ketones peaks increased, and the oxidation degree of surfaces increased. New carbon-related component carbonates were detected on nanoclay containing composite surfaces. Scanning electron microscopy indicates that aggregates formed on nanoclay-containing surfaces after AO bombardment. The sizes and densities of aggregates increased with nanoclay content. The combined erosion depths, XPS and SEM results indicate that although all the studied surfaces got eroded and oxidized after AO bombardment, the nanoclay containing composites showed better AO resistance compared to pure epoxy, because the produced aggregates on surface potentially act as a physical “shield”, e ectively retarding parts of the surface from further AO etching.
Raman spectra of 1,2,4-triazole-3-carboxylate (TC- anion) and its ring-deprotonated derivative (dpTC2- dianion) in aqueous solutions were measured respectively. The density functional theory calculations were performed using MN15 functional and PCM solvent model to investigate their structures, as well as the vibrational frequencies and Raman intensities. With the aid of the calculated spectra, all the observed Raman bands of dpTC2- were clearly assigned, with taking into account the deuteration shifts. Moreover, various protonic tautomers of TC- anion were compared in the present theoretical calculations, and 2H-tautomer was found more stable. The experimental Raman spectrum of TC- solution was roughly consistent with the calculated spectrum of the monomeric 2H-tautomer of TC-, but some splits existed for a few bands when compared to the calculated spectra, which might be contributed by the hydrogen-bonding dimers of TC-.
Transition metal phthalocyanines (TMPc) and relevant derivatives can act as pervasive molecules for their electronic, magnetic, and optical applications. Numerous researches based on TMPc are carried out, attempting to synthesize novel two-dimensional (2D) metal-organic frameworks. Recently, some 2D poly-TMPc frameworks including FePc [J. Am. Chem. Soc. 133, 1203 (2011)], CoPc [Chem. Commun. 51, 2836 (2015)], and Ni-NiPc [J. Mater. Chem. A 6, 1188 (2018)] frameworks have been successfully synthesized experimentally. Meanwhile, potential applications in catalysis, gas storage, and spintronics were predicted by theoretical studies. Here, we propose a new kind of 2D poly-TMPc frameworks with kagome lattice (denoted as kag-TMPc) and systematically investigate their electronic and magnetic properties by employing first-principles calculations. We have demonstrated that the 2D kag-MnPc framework displays quite stable ferromagnetic ordering with Curie temperature about 125 K as indicated by Monte Carlo simulations based on Heisenberg model and prefers out-of-plane easy-magnetization axis. The 2D kag-CrPc framework is an ideal candidate for S=2 kagome antiferromagnet with RT3 magnetic order. Particularly, the investigations on optical absorption suggest that when the TMPc molecules are self-assembled into 2D kag-TMPc frameworks, their absorption wave bands are broadened, especially in visible region.
Searching alternatives to Pt-based catalyst for producing hydrogen via water splitting has gathered enormous attention to develop renewable energy. Phosphorene has been investigated widely for its large surface area, low cost, and high carrier mobility, however, the poor activity in hydrogen evolution reaction (HER) and low conductivity limit its practical application. Herein, on the basis of first-principles calculations, we demonstrate that the catalytic HER in phosphorene can be enhanced significantly with cobalt intercalations. The Co-intercalated phosphorene is metallic with charge transfer from Co atoms to phosphorene, which could enhance the catalytic activity of phosphorene. In addition, the calculated Gibbs free energy of hydrogen adsorption on Co-intercalated phosphorene bilayer is comparable to that on Pt(111) surface, independent of the degree of hydrogen coverage. Our study implies that the Co intercalation provides an effective approach to enhance the catalytic HER inphosphorene.
Due to the magnetic bistability, single-molecule spin-crossover (SCO) complexes have been considered to be the most promising building blocks for molecular spintronic devices. Here, we explore the SCO behavior and coherent spin transport properties of a six-coordinate FeN6 complex with the low-spin (LS) and high-spin (HS) states by performing extensive first-principles calculations combined with non-equilibrium Green’s function technique. Theoretical results show that the LS?HS spin transition via changing the metal-ligand bond lengths can be realized by external stimuli, such as under light radiation in experiments. According to the calculated zero-bias transmission coefficients and density of states as well as the I-V curves under small bias voltages of FeN6 SCO complex with the LS and HS states sandwiched between two Au electrodes, we find that the examined molecular junction can act as a molecular switch, tuning from the OFF (LS) state to the ON (HS) state. Moreover, the spin-down electrons govern the current of the HS molecular junction, and this observed perfect spin-filtering effect is not sensitive to the detailed anchoring structure. These theoretical findings highlight this examined six-coordinate FeN6 SCO complex for potential applications in molecular spintronics.
Using the highly accurate G4 method, we computed the thermodynamic data of 1287 possible reaction products under a wide range of reaction conditions in the Fischer-Tropcsh synthesis (FTS) process. These accurate thermodynamic data provide basic thermodynamic quantities for the actual chemical engineering process and are useful in analyzing product distribution because FTS demonstrates many features of an equilibrium-controlled system. Our results show that the number of thermodynamically allowed products to increase when lowering temperature, raising pressure, and raising H2/CO ratio. At low temperature, high pressure and high H2/CO ratio, many products are thermodynamically allowed and the selectivity of product has to be controlled by kinetic factors. On the other hand, high selectivity of lighter products can be realized in thermodynamics by raising temperature and lowering pressure. We found that the equilibrium product yield will reach a maximum and remain unchanged when lowering temperature, raising pressure, and raising H2/CO ratio to some limits, implying that optimizing reaction conditions has no effect on equilibrium product yields beyond these limits. The thermodynamic analysis is also useful in designing and evaluating FTS reaction mechanisms. We found that reaction pathways through formaldehyde should be discarded because of its extremely low equilibrium yield. Recently, in the FTS process using metal-oxide-zeolite catalysts for the highly selective production of C2-C4 olefins and aromatic hydrocarbons, there are several guesses on the possible reaction intermediates entering the zeolite channel. Our results show that ketene, methanol, and dimethyl ether are three possible reaction intermediates.
Divergences of the single reference perturbation theories due to the addition of diffusion basis functions have been investigated for both closed-shell and open-shell molecular systems. It is found that the oscillatory range of perturbation energies of open-shell systems increases as the spin multiplicity of systems changes from 2 to 4. Feenberg transformation is exploited to treat the divergence problems. It is found numerically that within the interval of Feenberg parameter there exists a minimum perturbation order at which the perturbation series become convergent. It is also found for the open-shell systems that the magnitude of the corresponding Feenberg parameter becomes larger as the spin multiplicity of the system of interest changes from 2 to 4.
Proteins and peptides perform a vital role in living systems, however it remains a challenge for accurate description of proteins at the molecular level. Despite that surface-enhanced Raman spectroscopy (SERS) can provide the intrinsic fingerprint information of samples with ultrahigh sensitivity, it suffers from the poor reproducibility and reliability. Herein, we demonstrate that the silver nanorod array fabricated by an oblique angle deposition method is a powerful substrate for SERS to probe the protein secondary structures without exogenous labels. With this method, the SERS signals of two typical proteins (lysozyme and cytochrome c) are successfully obtained. Additionally, by analyzing the spectral signals of the amide III of protein backbone, the influence of concentration on the folding status of proteins has been elucidated. With the concentration increasing, the components of α-helix and β-sheet structures of lysozyme increase while the secondary structures of cytochrome c almost keep constant. The SERS method in this work offers an effective optical marker to characterize the structures of proteins.
This study investigated the positive effect of surface modification with ozone on the photocatalytic performance of anatase TiO2 with dominated (001) facets for toluene degradation. The performance of photocatalyst was tested on a home-made volatile organic compounds degradation system. The ozone modi cation, toluene adsorption and degradation mechanism were established by a combination of various characterization methods, in situ diffuse reflectance infrared fourier transform spectroscopy, and density functional theory calculation. The surface modi cation with ozone can significantly enhance the photocatalytic degradation performance for toluene. The abundant unsaturated coordinated 5c-Ti sites on (001) facets act as the adsorption sites for ozone. The formed Ti-O bonds reacted with H2O to generate a large amount of isolated Ti5c-OH which act as the adsorption sites for toluene, and thus significantly increase the adsorption capacity for toluene. The outstanding photocatalytic performance of ozone-modified TiO2 is due to its high adsorption ability for toluene and the abundant surface hydroxyl groups, which produce very reactive OH radicals under irradiation. Furthermore, the O2 generated via ozone dissociation could combine with the photogenerated electrons to form superoxide radicals which are also conductive to the toluene degradation.
On-surface synthesis of semiconducting graphdiyne nanowires usually suffer severe side reactions owing to the high reactivity of the butadiynylene units at noble metal surfaces, limiting the production of isolated nanowires. In this work, we report the high-yield synthesis of branchless graphdiyne nanowires [-C≡C-Ph2-C≡C-]n via on-surface Ullmann coupling of 1,4-bis(4-bromophenyl)-1,3-butadiyne molecules with chemical vapor deposition method. Non-contact atomic force microscopy with single-bond resolution reveals that single gold adatoms act as effective protecting groups for butadiynylene units by forming Au-π ligand bonds, preventing unwanted branched coupling reactions and enabling the synthesis of ultralong isolated graphdiyne nanowires. This study will stimulate further investigation on the role of various surface adatoms in protecting on-surface reactions.
The development of low-cost, earth-abundant and highly-efficient cocatalysts is still important to promote the photocatalytic H2 evolution reaction over semiconductors. Herein, a series of Ni nanoclusters (NCs) modified brookite TiO2 quasi nanocubes (BTN) (marked as Ni/BTN) are fabricated via a chemical reduction process. It is found that the loading content and oxidation state of Ni NCs can significantly influence the optical absorption, photocat-alytic activity, and stability of Ni/BTN composites. Among the resultant Ni NCs-loaded products, 0.1%Ni/BTN composite delivers the best H2 evolution activity (156 μmol/h), which is 4.3 times higher than that of the BTN alone (36 μmol/h). Furthermore, the Ni NCs with ultra ne size (∽2 nm) and high dispersity enable shorter charge transfer distance by quickly capturing the photoexcited electrons of BTN, and thus result in the improved activity even though the oxidization of some Ni NCs on BTN is harmful to the activity for H2 evolution due to the much lower electron capturing capability of NiO than metallic Ni. This study not only clari es that brookite TiO2 would be a promising high-efficient photo-catalyst for H2 evolution, but also reveals vital clues for further improving its photocatalytic performance using low-cost Ni-based cocatalyst.
In this work, a simple method was carried out to successfully fabricate superoleophilic and superhydrophobic N-dodecyltrimethoxysilane@tungsten trioxide coated copper mesh. The as-fabricated copper mesh displayed prominent superoleophilicity and superhydrophobicity with a huge water contact angle about 154.39° and oil contact angle near 0°. Moreover, the coated copper mesh showed high separation efficiency approximately 99.3%, and huge water flux about 9962.3 L·h-1·m-2, which could be used to separate various organic solvents/water mixtures. Furthermore, the coated copper mesh showed favorable stability that the separation efficiency remained above 90% after 10 separation cycles. Benefiting from the excellent photocatalytic degradation ability of tungsten trioxide, the coated copper mesh possessed the self-cleaning capacity. Therefore, the mesh contaminated with lubricating oil could regain superhydrophobic property, and this property of self-cleaning permitted that the fabricated copper mesh could be repeatedly used for oil and water separation.