Zhaochi Feng

Photocatalytic Overall Water Splitting Promoted by an α–β phase Junction on Ga2O3

When Alpha met Beta: a tuneable α-β surface phase junction on Ga(2)O(3) can significantly improve photocatalytic overall water splitting into H(2) and O(2) over individual α-Ga(2)O(3) or β-Ga(2)O(3) surface phases. This enhanced photocatalytic performance is mainly attributed to the efficient charge separation and transfer across the α-β phase junction.

UV RESONANCE RAMAN SPECTROSCOPIC IDENTIFICATION OF TITANIUM ATOMS IN THE FRAMEWORK OF TS-1 ZEOLITE

Framework titanium atoms in titanium-substituted silicalite (TS-1) can be identified by UV resonance Raman spectroscopy since the associated Raman bands at 1125, 530, and 490 cm(-1) (see figure) are observed only when the charge transfer transition associated with the framework Ti atoms is excited by a UV laser. Thus, framework Ti atoms can be distinguished from nonframework Ti atoms and other defect sites. This method can be applicable to identifying transition metal atoms in the frameworks of other molecular sieves.

Trap states and carrier dynamics of TiO2 studied by photoluminescence spectroscopy under weak excitation condition

Anatase and rutile TiO(2) were investigated with photoluminescence techniques under the weak excitation condition, where trap states play a vital role in carrier dynamics. The visible emission of anatase and near-infrared (NIR) emission of rutile both exhibit extremely long lifetimes up to milliseconds. The decay processes can be well described by the power-law decay which corresponds to the trapping-detrapping effect. These results indicate that the luminescence processes in both anatase and rutile TiO(2) have a close relationship with trap states. The visible emission band was assigned to the donor-acceptor recombination. Oxygen vacancies and hydroxyl groups mainly serve as the donor and acceptor sites, respectively. The NIR luminescence is originated from the recombination of trapped electrons with free holes, while the trapped electrons were formed through two paths, direct trapping or trap-to-trap hopping. The trap states in anatase and rutile TiO(2) may largely influence the photocatalysis process of TiO(2) and determine the photocatalytic activity under stationary illumination.

UV Raman Spectroscopic Studies on Active Sites and Synthesis Mechanisms of Transition Metal-Containing Microporous and Mesoporous Materials

Microporous and mesoporous materials are widely used as catalysts and catalyst supports. Although the incorporation of transition metal ions into the framework of these materials (by isomorphous substitution of Al and Si) is an effective means of creating novel catalytic activity, the characterization of the transition metal species within these materials is difficult. Both the low concentration of the highly dispersed transition metal and the coexistence of extraframework transition metal species present clear challenges. Moreover, the synthetic mechanisms that operate under the highly inhomogeneous conditions of hydrothermal synthesis are far from well understood. A useful technique for addressing these challenges is UV Raman spectroscopy, which is a powerful technique for catalyst characterization and particularly for transition metal-containing microporous and mesoporous materials. Conventional Raman spectroscopy, using visible and IR wavelengths, often fails to provide the information needed for proper characterization as a result of fluorescence interference. But shifting the excitation source to the UV range addresses this difficulty: interference from fluorescence (which typically occurs at 300-700 nm or greater) is greatly diminished. Moreover, signal intensity is enhanced because Raman intensity is proportional to the fourth power of the scattered light frequency. In this Account, we review recent advances in UV Raman spectroscopic characterization of (i) highly dispersed transition metal oxides on supports, (ii) transition metal ions in the framework of microporous and mesoporous materials, and (iii) the synthetic mechanisms involved in making microporous materials. By taking advantage of the strong UV resonance Raman effect, researchers have made tremendous progress in the identification of isolated transition metal ions incorporated in the framework of microporous and mesoporous materials such as TS-1, Ti-MCM-41, Fe-ZSM-5, and Fe-SBA-15. The synthetic mechanisms involved in creating microporous materials (such as Fe-ZSM-5 and zeolite X) have been investigated with resonance and in situ UV Raman spectroscopy. The precursors and intermediates evolved in the synthesis solution and gels can be sensitively detected and followed during the course of zeolite synthesis. This work has resulted in a greater understanding of the structure of transition metal-containing microporous and mesoporous materials, providing a basis for the rational design and synthesis of microporous and mesoporous catalysts.

Visible emission characteristics from different defects of ZnS nanocrystals

Various sized ZnS nanocrystals were prepared by treatment under H(2)S atmosphere. Resonance Raman spectra indicate that the electron-phonon coupling increases with increasing the size of ZnS. Surface and interfacial defects are formed during the treatment processes. Blue, green and orange emissions are observed for these ZnS. The blue emission (430 nm) from ZnS without treatment is attributed to surface states. ZnS sintered at 873 K displays orange luminescence (620 nm) while ZnS treated at 1173 K shows green emission (515 nm). The green luminescence is assigned to the electron transfer from sulfur vacancies to interstitial sulfur states, and the orange emission is caused by the recombination between interstitial zinc states and zinc vacancies. The lifetimes of the orange emission are much slower than that of the green luminescence and sensitively dependent on the treatment temperature. Controlling defect formation makes ZnS a potential material for photoelectrical applications.

Sustainable Synthesis of Zeolites without Addition of Both Organotemplates and Solvents

The development of sustainable and environmentally friendly techniques for synthesizing zeolites has attracted much attention, as the use of organic templates and solvents in the hydrothermal synthesis of zeolites is a major obstacle for realizing green and sustainable synthesis ways. Recently, the introduction of the organotemplate-free synthesis method allowed avoiding the use of organic templates, but water as solvent was still required; solvent-free routes on the other hand beared the potential to significantly reduce the amount of polluted wastewater, but organic templates were still present. In this work, we have demonstrated a combined strategy of both organotemplate- and solvent-free conditions to synthesize aluminosilicate zeolites Beta and ZSM-5 (S-Beta and S-ZSM-5), two of the most important zeolites relevant for industry. The samples are thoroughly characterized by XRD patterns, SEM images, N2 sorption isotherms, UV-Raman spectra, and (29)Si and (27)Al MAS NMR spectra. The results demonstrate that S-Beta and S-ZSM-5 zeolites exhibit almost the same textural parameters (e.g., BET surface area and pore volume) and catalytic performance in cumene cracking and m-xylene isomerization as those of conventional Beta and ZSM-5 zeolites synthesized under hydrothermal conditions (C-Beta and C-ZSM-5). The organotemplate- and solvent-free syntheses of S-Beta and S-ZSM-5 take place at a low-pressure regime and are free of harmful gases as well as give high product yields together with highly efficient consumption of the starting raw materials. These advantages plus the very simple procedures opened the pathway to a highly sustainable zeolite synthesis protocol compared to conventional methods currently employed for C-Beta and C-ZSM-5. Very interestingly, this simple synthesis is a good model for understanding zeolite crystallization. The detail characterizations indicate that the S-Beta crystals are formed from the assembly of zeolite building units, mainly 4MRs, while the 5MRs in the framework are just formed in the crystallization of S-ZSM-5, rather than existence in the starting solid mixture. During the crystallization processes, small traces of water play an important role for the hydrolysis and condensation of silica and/or aluminosilicate species.

Direct Imaging of Highly Anisotropic Photogenerated Charge Separations on Different Facets of a Single BiVO4 Photocatalyst

Spatially resolved surface photovoltage spectroscopy (SRSPS) was employed to obtain direct evidence for highly anisotropic photogenerated charge separation on different facets of a single BiVO4 photocatalyst. Through the controlled synthesis of a single crystal with preferentially exposed {010} facets, highly anisotropic photogenerated hole transfer to the {011} facet of single BiVO4 crystals was observed. The surface photovoltage signal intensity on the {011} facet was 70 times stronger than that on the {010} facets. The influence of the built-in electric field in the space charge region of different facets on the anisotropic photoinduced charge transfer in a single semiconductor crystal is revealed.

Highly Active and Recyclable Sn-MWW Zeolite Catalyst for Sugar Conversion to Methyl Lactate and Lactic Acid

Highly active and recyclable sn-mww zeolite catalyst for sugar conversion to methyl lactate and lactic acid

UV Raman spectroscopic study on the synthesis mechanism of zeolite X

The synthesis of zeolite X is characterized by UV Raman spectroscopy, NMR spectroscopy, and X-ray diffraction. UV Raman spectra of the liquid phase of the synthesis system indicate that AI(OH); species are incorporated into silicate species, and the polymeric silicate species are depolymerized into monomeric silicate species during the early stage of zeolite formation. An. intermediate species possessing Raman bands at 307, 503, 858 and 1020 cm(-1) is detected during the crystallization ill the solid phase transformation. The intermediate species is attributed to the beta cage, the secondary building unit of zeolite X. A model for the formation of zeolite X is proposed, which involves four-membered rings connecting to each other via six-membered ring to form beta cages, then the beta cages interconnect via double six-membered rings to form the framework of zeolite X

From Molecular Fragments to Crystals: A UV Raman Spectroscopic Study on the Mechanism of Fe-ZSM-5 Synthesis

The nucleation process of iron-exchanged zeolite Fe-ZSM-5, from the assembly of distorted tetrahedrally coordinated iron species and silicate rings in the precursor to the final Fe-ZSM-5 crystals, as well as variations in the coordination environment of iron, were studied by UV resonance Raman spectroscopy and complementary techniques.The entire sequence of crystallization events of Fe-ZSM-5 was monitored by UV Raman spectroscopy in combination with HRTEM, UV/Vis spectroscopy, X-ray diffraction patterns, and periodic DFT calculations. Fe-ZSM-5 was synthesized by an organic-free method to avoid signal interference from the organic template in Raman spectra. Framework iron atoms with resonance Raman bands at 516, 1115, and 1165 cm(-1), and a Raman band at 1016 cm(-1) are detected for Fe-ZSM-5. In the early stage of Fe-ZSM-5 synthesis, the precursor contains iron atoms in distorted tetrahedral coordination and five- and six-membered silicate rings. Nucleation by aggregation of the precursor species was monitored by UV Raman spectroscopy based on the resonance Raman effect, and confirmed by periodic DFT calculations. Evolution of iron species on the surface and in the bulk phase was monitored by UV Raman spectroscopy with excitation at 244 and 325 nm, as well as HRTEM. Nucleation takes place first in the core of the amorphous particles, and crystalline nuclei with Fe-ZSM-5 structure are formed in the core by consuming the amorphous shell. Finally the amorphous particles are completely transformed into Fe-ZSM-5 crystals.