Highly selective CO2 photoreduction to CO on MOF-derived TiO2.

Metal-Organic Framework (MOF)-derived TiO2, synthesised through the calcination of MIL-125-NH2, is investigated for its potential as a CO2 photoreduction catalyst. The effect of the reaction parameters: irradiance, temperature and partial pressure of water was investigated. Using a two-level design of experiments, we were able to evaluate the influence of each parameter and their potential interactions on the reaction products, specifically the production of CO and CH4. It was found that, for the explored range, the only statistically significant parameter is temperature, with an increase in temperature being correlated to enhanced production of both CO and CH4. Over the range of experimental settings explored, the MOF-derived TiO2 displays high selectivity towards CO (98%), with only a small amount of CH4 (2%) being produced. This is notable when compared to other state-of-the-art TiO2 based CO2 photoreduction catalysts, which often showcase lower selectivity. The MOF-derived TiO2 was found to have a peak production rate of 8.9 × 10-4 µmol cm-2 h-1 (2.6 µmol g-1 h-1) and 2.6 × 10-5 µmol cm-2 h-1 (0.10 µmol g-1 h-1) for CO and CH4, respectively. A comparison is made to commercial TiO2, P25 (Degussa), which was shown to have a similar activity towards CO production, 3.4 × 10-3 µmol cm-2 h-1 (5.9 µmol g-1 h-1), but a lower selectivity preference for CO (3 : 1 CH4 : CO) than the MOF-derived TiO2 material developed here. This paper showcases the potential for MIL-125-NH2 derived TiO2 to be further developed as a highly selective CO2 photoreduction catalyst for CO production.

Synthesis of TiO2-x/W18O49 hollow double-shell and core-shell microspheres for CO2 photoreduction under visible light.

TiO2-x/W18O49 with core-shell or double-shelled hollow microspheres were synthesized through a facile multi-step solvothermal method. The formation of the hollow microspheres with a double-shell was a result of the Kirkendall effect during the solvothermal treatment with concentrated NaOH. The advanced architecture significantly enhanced the electronic properties of TiO2-x/W18O49, improving by more than 30 times the CO2 photoreduction efficiency compared to the pristine W18O49. Operando DRIFTS measurements revealed that the yellow TiO2-x was a preferable CO2 adsorption and conversion site.

Synthesis and Characterization of Ru-Loaded Anodized Aluminum Oxide for Hydrogenation Catalysis.

Anodized aluminum oxides (AAOs) are synthesized and used as catalyst support in combination with Ru as metal in hydrogenation catalysis. SEM and TEM analysis of the as-synthesized AAOs reveal uniform, ordered nanotubes with pore diameters of 18 nm, which are further characterized with Kr physisorption, XRD and FTIR spectroscopy. After impregnation of the AAOs with Ru, the presence of Ru nanoparticles inside the tubular pores is evidenced clearly for the first time via HAADF-STEM-EDX. The Ru-AAOs have been tested for catalytic activity, which showed high conversion and selectivity for the hydrogenation of toluene and butanal.

Characterization and Comparison of Fast Pyrolysis Bio-oils from Pinewood, Rapeseed Cake, and Wheat Straw Using 13C NMR and Comprehensive GC × GC.

Fast pyrolysis bio-oils are feasible energy carriers and a potential source of chemicals. Detailed characterization of bio-oils is essential to further develop its potential use. In this study, quantitative 13C nuclear magnetic resonance (13C NMR) combined with comprehensive two-dimensional gas chromatography (GC × GC) was used to characterize fast pyrolysis bio-oils originated from pinewood, wheat straw, and rapeseed cake. The combination of both techniques provided new information on the chemical composition of bio-oils for further upgrading. 13C NMR analysis indicated that pinewood-based bio-oil contained mostly methoxy/hydroxyl (≈30%) and carbohydrate (≈27%) carbons; wheat straw bio-oil showed to have high amount of alkyl (≈35%) and aromatic (≈30%) carbons, while rapeseed cake-based bio-oil had great portions of alkyl carbons (≈82%). More than 200 compounds were identified and quantified using GC × GC coupled to a flame ionization detector (FID) and a time of flight mass spectrometer (TOF-MS). Nonaromatics were the most abundant and comprised about 50% of the total mass of compounds identified and quantified via GC × GC. In addition, this analytical approach allowed the quantification of high value-added phenolic compounds, as well as of low molecular weight carboxylic acids and aldehydes, which exacerbate the unstable and corrosive character of the bio-oil.

Unravelling the Ru-Catalyzed Hydrogenolysis of Biomass-Based Polyols under Neutral and Acidic Conditions.

The aqueous Ru/C-catalyzed hydrogenolysis of biomass-based polyols such as erythritol, xylitol, sorbitol, and cellobitol is studied under neutral and acidic conditions. For the first time, the complete product spectrum of C2 C6 polyols is identified and, based on a thorough analysis of the reaction mixtures, a comprehensive reaction mechanism is proposed, which consists of (de)hydrogenation, epimerization, decarbonylation, and deoxygenation reactions. The data reveal that the Ru-catalyzed deoxygenation reaction is highly selective for the cleavage of terminal hydroxyl groups. Changing from neutral to acidic conditions suppresses decarbonylation, consequently increasing the selectivity towards deoxygenation.