Improving Copper Active Site Speciation on Cu-Ce/SSZ-13 for Ammonia Oxidation via Si/Al Ratio Modulation.

Catalytic oxidation is a promising purification technique for ammonia (NH3) emission. However, high ignition temperatures and NOx peroxide generation limit its effectiveness due to a lack of active sites. Herein, the effects of Si/Al ratio (SAR) modulation on the speciation of copper active sites and the reaction mechanism at different acidic sites were investigated by loading CuO-CeO2 onto SSZ-13 with different SARs (Cu-Ce/SAR15, 20, and 30). Among them, Cu-Ce/SAR20 exhibits the lowest induction temperature (T20 = 180 °C) and the highest nitrogen selectivity (above 95%), attributing to a higher number of Cu2+ exchange sites. In situ IR spectroscopy and isotopic (18O2) transient response experiments indicate that more active Cu2+ in Cu-Ce/SAR20 provides sufficient Lewis acidic sites for NH3 adsorption and favors the stability of Si-OH-Al structures (Brønsted acid sites). NH3 adsorbed at Lewis acidic sites tends to form peroxide byproducts (NOx), while the NH4+ adsorbed at Brønsted acidic sites generates the key intermediate NH4NO2, which decomposes to N2 at high temperatures, thus enhancing nitrogen selectivity. The whole process mainly follows the Mars-van Krevelen (M-K) mechanism, with the Langmuir-Hinshelwood (L-H) mechanism playing a supporting role. Z2Cu2+ coordinates with adjacent Al atoms within the six-membered ring (6MR) and undergoes a slight deformation at high temperatures, facilitating the migration of the lattice oxygen. SAR plays a crucial role in local environmental speciation of reactive Cu2+, where the sufficient isolated Al provided in SAR20 pulls Cu2+ into the eight-membered ring (8MR), allowing it to come into contact with NH3 more readily.

Synthesis of Cu2O micro/nanocrystals for catalytic combustion of high-concentration CO: The crucial role of glucose.

Cubic Cu2O micro/nanocrystals were successfully synthesized by liquid-phase reduction using copper salt of CuSO4 or CuCl2·2H2O, and glucose or ascorbic acid as reducing agent, respectively. The activity of the catalysts was evaluated by light-off curves of CO self-sustained catalytic combustion via temperature-programmed oxidation of CO (CO-TPO), with the results showing the activity of catalysts following the order of Cu2O-Cl-GLU > Cu2O-S-GLU > Cu2O-S-AA > Cu2O-Cl-AA, (Cl denotes CuCl2·2H2O, GLU denotes glucose, S denotes CuSO4 and AA denotes ascorbic acid, respectively), corresponding to the ignition temperature of 109 °C, 122 °C, 137 °C and 186 °C, respectively. The crystal structure, elemental valence, morphology and redox property of the prepared catalysts were analyzed by using various characterization techniques. Combined with in situ infrared spectrum, the CO self-sustained catalytic combustion over Cu2O catalysts mainly follows the Mars-van-Krevelen (M-v-K) mechanism: the adsorbed and activated CO reacts with lattice oxygen to yield CO2 and oxygen vacancy, and then the oxygen vacancy can be replenished by gaseous oxygen. Combined with catalytic performance of high-concentration CO, it is found that the catalysts prepared using glucose as reducing agent are more angular compared with ascorbic acid. The Cu2O-Cl-GLU synthesized with glucose and CuCl2·2H2O exhibits the best catalytic activity among all the catalysts tested, attributing to its more obvious edge and rough crystal surface. The unique structure of Cu2O-Cl-GLU leads to the high exposure rate and coordination unsaturation of atoms on the cubic Cu2O micro/nanocrystals that can improve the ability of activating gaseous O2 and low temperature reducibility, and consequently facilitating the catalytic activity.

Efficient Synthesis of Sugar Alcohols under Mild Conditions Using a Novel Sugar-Selective Hydrogenation Catalyst Based on Ruthenium Valence Regulation.

Sugar alcohols are the prominent alternatives of sugars in food, medical, and health industries. The ruthenium supported on multiwalled carbon nanotubes (Ru/MWCNTs) catalysts were prepared based on the Ru valence regulation strategy and applied for selective sugar hydrogenation to prepare various sugar alcohols including xylitol, arabinitol, sorbitol, mannitol, and galactitol for the first time, with high selectivity (>99.0%) and yield (>98.0%) under mild conditions (≤110 °C, 3.0 MPa H2 pressure). The hydrogenation reaction of xylose was further optimized and under mild conditions (100 °C, 3.0 MPa H2 pressure, and 500 rpm), which were lower than ever reported for high efficient synthesis of xylitol, 99.8% xylose conversion and 99.0% xylitol yield were achieved after 120 min of reaction.

A lipopeptide biosurfactant from Bacillus sp. Lv13 and their combined effects on biodesulfurization of dibenzothiophene.

The process of using biodesulfurization (BDS) to remove sulfur compounds in petroleum has limitations such as low efficiency and low mass transfer. Therefore, it is important to study the combined effects of biosurfactant and the strain on BDS. A thermophilic desulfurization strain, Bacillus sp. Lv13, was isolated from the oilfield and used to produce biosurfactant (BS). The strain was identified as Bacillus licheniformis, a moderate thermophilic bacterium. Its BS was identified as lipopeptide using thin-layer chromatography (TLC), gas chromatography-mass spectrometry (GC-MS) and Fourier transform infrared spectroscopy (FT-IR). The emulsification efficiency after 24 h (E 24) and critical micelle concentration (CMC) were determined to be 46.93% and 30 mg L-1, respectively. The combined effects of biosurfactant and the strain on BDS was confirmed using the Gibbs assay, GC-MS and BaCl2 test. Results showed that the yield of 2-hydroxybiphenyl (2-HBP) from dibenzothiophene significantly increased after the addition of lipopeptide into the reaction system. This could be illustrated by the stabilization of emulsion, lower CMC value, higher mass transfer rate with the addition of lipopeptide, and the enhancement in the capacity of BDS as well as the catalytic ability of the microbial cell.

Adsorption of benzene, cyclohexane and hexane on ordered mesoporous carbon.

Ordered mesoporous carbon (OMC) with high specific surface area and large pore volume was synthesized and tested for use as an adsorbent for volatile organic compound (VOC) disposal. Benzene, cyclohexane and hexane were selected as typical adsorbates due to their different molecular sizes and extensive utilization in industrial processes. In spite of their structural differences, high adsorption amounts were achieved for all three adsorbates, as the pore size of OMC is large enough for the access of these VOCs. In addition, the unusual bimodal-like pore size distribution gives the adsorbates a higher diffusion rate compared with conventional adsorbents such as activated carbon and carbon molecular sieve. Kinetic analysis suggests that the adsorption barriers mainly originated from the difficulty of VOC vapor molecules entering the pore channels of adsorbents. Therefore, its superior adsorption ability toward VOCs, together with a high diffusion rate, makes the ordered mesoporous carbon a promising potential adsorbent for VOC disposal.

Porous graphitized carbon for adsorptive removal of benzene and the electrothermal regeneration.

Graphitized carbons with mesoporous and macroporous structures were synthesized by a facile template-catalysis procedure using resorcinol and formaldehyde as carbon precursors and particulate hydrated metal oxides as both template and catalyst precursors. The materials were used as novel adsorbents for low-concentration benzene vapor. Furthermore, on the basis of the good electrical conductivities associated with the graphitized structures, an electrothermal desorption technique, which involved passing electric currents through the adsorbents to generate Joule heat, was employed to regenerate the saturated adsorbents and produce enriched benzene vapors. In comparison to microporous activated carbon, the porous graphitized carbons could afford a much quicker and more efficient regeneration by electrothermal desorption technique due to their enhanced conductivity and larger pore sizes. In addition, the concentration of the desorbed organics could be controlled by adjusting the applied voltages, which might be interesting for practical secondary treatment. It is promising that the joint utilization of porous graphitized carbon adsorbents and electrothermal desorption technique might develop effective and energy-saving processes for VOCs removal.

Adsorption and desorption performance of benzene over hierarchically structured carbon-silica aerogel composites.

Hierarchically structured carbon-silica aerogel (CSA) composites were synthesized from cheap water glass precursors and granulated activated carbon via a post-synthesis surface modification with trimethylchlorosilane (TMCS) and a low-cost ambient pressure drying procedure. The resultant CSA composites possess micro/mesoporous structure and hydrophobic surface. The adsorption and desorption performance of benzene on carbon-silica aerogel composite (CSA-2) under static and dynamic conditions were investigated, comparing with pure silica aerogel (CSA-0) and microporous activated carbon (AC). It was found that CSA-2 has high affinity towards aromatic molecules and fast adsorption kinetics. Excellent performance of dynamic adsorption and desorption observed on CSA-2 is related to its higher adsorption capacity than CSA-0 and less mass transfer resistance than AC, arising from the well-developed microporosity and open foam mesostructure in the CSA composites.

Investigation of formaldehyde oxidation over Co3O4-Ce2 and Au/Co3O4-CeO2 catalysts at room temperature: effective removal and determination of reaction mechanism.

Formaldehyde is regarded as the major indoor pollutant emitted from widely used building and decorative materials in airtight buildings, which should be eliminated under indoor environmental conditions. We report here catalytic oxidation process of formaldehyde over mesoporous Co(3)O(4), Co(3)O(4)-CeO(2), Au/Co(3)O(4), and Au/Co(3)O(4)-CeO(2) catalysts and their excellent catalytic performances at room temperature. These catalysts were prepared by a "nanocasting" method with the mesostructure generated from SBA-15 silica with 2D structure. The adsorbed surface species in the formaldehyde oxidation process are analyzed, and some key steps in the oxidation pathway, active sites, and intermediate species are proposed. Among the detected species, some kinds of formate species formed on the catalysts were indentified as intermediates, which further transformed into bicarbonate or carbonate and which decomposed to carbon dioxide. The role of the mesoporous Co(3)O(4) and the gold nanoparticles in the mechanism are also revealed.

Adsorption performance of VOCs in ordered mesoporous silicas with different pore structures and surface chemistry.

Ordered mesoporous silicas with different pore structures, including SBA-15, MCM-41, MCM-48 and KIT-6, were functionalized with phenyltriethoxysilane by a post-synthesis grafting approach. It was found that phenyl groups were covalently anchored onto the surface of mesoporous silicas, and the long-range ordering of the mesoporous channels was well retained after the surface functionalization. The static adsorption of benzene and the dynamic adsorption of single component (benzene) and bicomponent (benzene and cyclohexane) on the original and functionalized materials were investigated. As indicated by the adsorption study, the functionalized silicas exhibit improvement in the surface hydrophobicity and affinity for aromatic compounds as compared with the original silicas. Furthermore, the pore structure and the surface chemistry of materials can significantly influence adsorption performance. A larger pore diameter and cubic pore structure are favorable to surface functionalization and adsorption performance. In particular, the best adsorption performance observed with phenyl-grafted KIT-6 is probably related to the highest degree of surface functionalization, arising from the relatively large mesopores and bi-continuous cubic pore structure which allow great accessibility for the functional groups. In contrast, functionalized MCM-41 exhibits the lowest adsorption efficiency, probably owing to the small size of mesopores and 1D mesoporous channels.