Tiancun Xiao

Preparation of highly visible-light active N-doped TiO2 photocatalyst

A series of N-doped anatase TiO2 samples have been prepared using a solvothermal method in an organic amine/ethanol–water reaction system. The effects of different starting N : Ti atomic ratios on the catalysts structure, surface property and catalytic activity have been investigated. The photocatalytic activity and stability of the N-doped TiO2 samples were evaluated through using the decomposition of Methylene blue (MB) and Methyl orange (MO) as model reaction under visible light irradiation. Characterization results show that the nitrogen dopant has a significant effect on the crystallite size and optical absorption of TiO2. It was found that the N-doped TiO2 catalysts have enhanced absorption in the visible light region, and exhibit higher activity for photocatalytic degradation of model dyes (e.g. MB and MO). The catalyst with the highest performance was the one prepared using N : Ti molar ratio of 1.0. Electron paramagnetic resonance (EPR) measurement suggests the materials contain Ti 3+ ions, with both the degree of N doping and oxygen vacancies make contributions to the visible light absorption of TON. The presence of superoxide radicals (O u � ) and hydroxyl radicals (OH) on the surface of TON were found to be responsible for MB and MO solution decoloration under visible light. Based on the results of the present study, a visible light induced photocatalytic mechanism has been proposed for N-doped anatase TiO2.

Brief Overview of the Partial Oxidation of Methane to Synthesis Gas

A review of the main developments in the partial oxidation of methane to synthesis gas since the first paper in 1929 to the present day is given. The reaction is discussed from the view of the thermodynamics; the main catalysts studied for the reaction are summarised, and the reaction mechanism is discussed. The review is not comprehensive, but it is designed to provide a general background to the most important developments in the field.

Turning carbon dioxide into fuel.

Our present dependence on fossil fuels means that, as our demand for energy inevitably increases, so do emissions of greenhouse gases, most notably carbon dioxide (CO2). To avoid the obvious consequences on climate change, the concentration of such greenhouse gases in the atmosphere must be stabilized. But, as populations grow and economies develop, future demands now ensure that energy will be one of the defining issues of this century. This unique set of (coupled) challenges also means that science and engineering have a unique opportunity—and a burgeoning challenge—to apply their understanding to provide sustainable energy solutions. Integrated carbon capture and subsequent sequestration is generally advanced as the most promising option to tackle greenhouse gases in the short to medium term. Here, we provide a brief overview of an alternative mid- to long-term option, namely, the capture and conversion of CO2, to produce sustainable, synthetic hydrocarbon or carbonaceous fuels, most notably for transportation purposes. Basically, the approach centres on the concept of the large-scale re-use of CO2 released by human activity to produce synthetic fuels, and how this challenging approach could assume an important role in tackling the issue of global CO2 emissions. We highlight three possible strategies involving CO2 conversion by physico-chemical approaches: sustainable (or renewable) synthetic methanol, syngas production derived from flue gases from coal-, gas- or oil-fired electric power stations, and photochemical production of synthetic fuels. The use of CO2 to synthesize commodity chemicals is covered elsewhere (Arakawa et al. 2001 Chem. Rev. 101, 953–996); this review is focused on the possibilities for the conversion of CO2 to fuels. Although these three prototypical areas differ in their ultimate applications, the underpinning thermodynamic considerations centre on the conversion—and hence the utilization—of CO2. Here, we hope to illustrate that advances in the science and engineering of materials are critical for these new energy technologies, and specific examples are given for all three examples. With sufficient advances, and institutional and political support, such scientific and technological innovations could help to regulate/stabilize the CO2 levels in the atmosphere and thereby extend the use of fossil-fuel-derived feedstocks.

Methane Oxyforming for Synthesis Gas Production

This article is concerned with the reforming of methane to synthesis gas; a review of the steam reforming Rxn is presented, and the dry reforming and partial oxidation Rxns introduced. Collectively, these processes are known as “oxyforming.” A background to oxyforming, industrial practice, and some of the most important latest developments will be presented, along with a section on the uses of synthesis gas. The current understanding of the Rxn mechanisms for the three processes and the problem of deactivation by carbon deposition will be discussed in detail. Finally, the economics of synfuel production will be addressed and compared with the production of other fuels, and the future directions and outlook for oxyforming will be forwarded. This article should allow the reader to make comparisons between these three important industrial reactions.

Surface WO4 tetrahedron: the essence of the oxidative coupling of methane over M-W-Mn/SiO2 catalysts

Abstract A series of MWMn/SiO2 catalysts (M = Li, Na, K, Ba, Ca, Fe, Co, Ni, and Al) have been prepared and their catalytic performance for the oxidative coupling of methane (OCM) was evaluated in a continuous-flow microreactor. The structural properties of the catalysts have been studied using X-ray photoelectron spectroscopy (XPS), laser Raman spectroscopy (LRS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). In the trimetallic catalysts studied, there was evidence for WO4 tetrahedron on the surface in the Li, Na, and KWMn/SiO2 catalysts, which is mainly present in the subsurface of the BaWMn/SiO2 catalyst. It appears that the WO4 has a strong interaction with the α-cristobalite support and is stabilized in the Na and KWMn/SiO2 catalysts. However, the WO4 species appear to be less stable in Li or BaWMn/SiO2 catalysts, in which the support turns into quartz SiO2 or amorphous SiO2. The WO4 tetrahedron on the catalyst surface appears to play an essential role in achieving high CH4 conversion and high C2 hydrocarbon selectivity in the OCM reaction. Calculations suggest that the WO4 tetrahedron interacts with the CH4, giving suitable geometry and energy matching with CH4, and this may account for the high OCM activities.

Effect of carburising agent on the structure of molybdenum carbides

Molybdenum carbides have been prepared by the temperature programmed reaction method using mixtures of hydrogen and methane, hydrogen and ethane, and hydrogen and butane, and characterised with X-ray diffraction, transmission electron microscopy, 13C solid state NMR and EXAFS spectroscopy. The results show that the choice of hydrocarbon used to synthesise molybdenum carbide significantly affects the structure and texture of the resultant materials. Increasing the chain length of the carburising agent reduces the particle size and the temperature for complete phase transformation from molybdenum oxide to carbide is lowered. Carburising with a mixture of hydrogen and methane gives rise to hexagonal closed packed (hcp) carbide, while when using butane as the carbon source, molybdenum oxide is mainly reduced to face centred cubic (fcc) carbide. However, using ethane as the carbon source, the resultant carbide has a mixed phase composition with the hcp phase predominant. The molybdenum carbide prepared with ethane as the carbon source has the roughest surface and highest hydrogen adsorption capacity, while that prepared with butane has a very condensed surface. There is a substantial difference in the molybdenum co-ordination environments present among the carbides prepared with different carburising agents.

The Role of Photoinduced Defects in TiO2 and Its Effects on Hydrogen Evolution from Aqueous Methanol solution

The hydrogen evolution from aqueous methanol solutions was found to follow two stages of zero order kinetics during photoreactions using TiO 2 as the photocatalyst. Maximal hydrogen evolution was found at the 10% (v/v) methanol solution. X-ray photoelectron spectroscopy (XPS) shows that Ti(1566) defects are formed on the surface of TiO 2 and X-ray powder diffraction (XRD) indicates that Ti(1566) defects are also formed in the bulk after photoreaction. Formation of defects is also shown by broadening of Bragg peaks and blue shifts and peak broadening in Raman spectroscopy. The defect disorder results in the increase of hydrogen evolution. UV-vis diffuse reflection spectra confirm that new absorptions in the visible light region are related to the defect content. At high methanol concentration, XPS implies that the active sites of the surface are blocked by hydroxyl groups, which results in the decrease of hydrogen evolution. TEM images showed that the photoreaction occurred on the surface of the photocatalyst as the surface of the TiO 2 became rough after the photoreaction.

Study on the mechanism of partial oxidation of methane to synthesis gas over molybdenum carbide catalyst

The performance of molybdenum carbide catalyst for partial oxidation of methane to syngas has been evaluated in a micro-reactor under various conditions. The molybdenum carbide catalyst is stable in methane partial oxidation to syngas at high reaction temperatures, high pressures and with a low space velocity of reactants. Pre-treatment has a significant effect on the catalyst activity and selectivity. The reaction mechanism over molybdenum carbide has been studied using 13C isotope exchange and in situ laser Raman. It is seen that the carbon in the lattice of the molybdenum carbide takes an active part in the reaction. The deactivation of molybdenum carbide catalyst results from the oxidation of the catalyst surface.

Low-temperature synthesis of visible-light active fluorine/sulfur co-doped mesoporous TiO2 microspheres.

Reaching for the sun! The synthesis and photo-catalytic activity of mesoporous microspheres of anatase TiO2 doped with fluorine and sulfur is described (see graphic). The photo-degradation of methyl orange under ambient visible-light conditions only occurs in the presence of co-doping.

Study on preparation of high surface area tungsten carbides and phase transition during the carburisation

A detailed study of step-by-step carburisation of WO3 using 20%CH4/H2 and 10%C2H6/H2 under various conditions is described. The catalyst materials have been characterised using thermogravimetric analysis and differential scanning calorimetry (TGA-DTC), temperature programmed reaction (TPR), surface area measurement using the Brunauer–Emmett–Teller (BET) method, X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), and elemental X-ray micro-analysis (EDX). The structures of the product carbides were found to be functions of the conditions of synthesis. The use of C2H6/H2 gave the highest surface area materials. During the early steps in the carburisation process at lower temperatures, disorder intergrowth occurs and non-stoichiometric crystallographic shear tungsten oxide (i.e. WO3−x), and then WO2 are formed. Three steps are identified during the conversion of WO3 to WC using 10% C2H6/H2. First WO2 is formed by the reduction with hydrogen at temperatures of 670–720 K. This is carburised to WOxCy or β-W2C between 800–870 K. Finally, a second carburisation occurs at temperatures between 870–920 K to produce α-WC.