3.2.3. Hydroformylation 2467 3.2.4. Dimerization 2468 3.2.5. Oxidative Cleavage and Ozonolysis 2469 3.2.6. Metathesis 2470 4. Terpenes 2472 4.1. Pinene 2472 4.1.1. Isomerization: R-Pinene 2472 4.1.2. Epoxidation of R-Pinene 2475 4.1.3. Isomerization of R-Pinene Oxide 2477 4.1.4. Hydration of R-Pinene: R-Terpineol 2478 4.1.5. Dehydroisomerization 2479 4.2. Limonene 2480 4.2.1. Isomerization 2480 4.2.2. Epoxidation: Limonene Oxide 2480 4.2.3. Isomerization of Limonene Oxide 2481 4.2.4. Dehydroisomerization of Limonene and Terpenes To Produce Cymene 2481

Chemical Routes for the Transformation of Biomass into Chemicals

Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels.

Spinels can serve as alternative low-cost bifunctional electrocatalysts for oxygen reduction/evolution reactions (ORR/OER), which are the key barriers in various electrochemical devices such as metal-air batteries, fuel cells and electrolysers. However, conventional ceramic synthesis of crystalline spinels requires an elevated temperature, complicated procedures and prolonged heating time, and the resulting product exhibits limited electrocatalytic performance. It has been challenging to develop energy-saving, facile and rapid synthetic methodologies for highly active spinels. In this Article, we report the synthesis of nanocrystalline M(x)Mn(3-x)O(4) (M = divalent metals) spinels under ambient conditions and their electrocatalytic application. We show rapid and selective formation of tetragonal or cubic M(x)Mn(3-x)O(4) from the reduction of amorphous MnO(2) in aqueous M(2+) solution. The prepared Co(x)Mn(3-x)O(4) nanoparticles manifest considerable catalytic activity towards the ORR/OER as a result of their high surface areas and abundant defects. The newly discovered phase-dependent electrocatalytic ORR/OER characteristics of Co-Mn-O spinels are also interpreted by experiment and first-principle theoretical studies.

Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts

Spinels with the formula of AB2O4 (where A and B are metal ions) and the properties of magnetism, optics, electricity, and catalysis have taken significant roles in applications of data storage, biotechnology, electronics, laser, sensor, conversion reaction, and energy storage/conversion, which largely depend on their precise structures and compositions. In this review, various spinels with controlled preparations and their applications in oxygen reduction/evolution reaction (ORR/OER) and beyond are summarized. First, the composition and structure of spinels are introduced. Then, recent advances in the preparation of spinels with solid-, solution-, and vapor-phase methods are summarized, and new methods are particularly highlighted. The physicochemical characteristics of spinels such as their compositions, structures, morphologies, defects, and substrates have been rationally regulated through various approaches. This regulation can yield spinels with improved ORR/OER catalytic activities, which can furth...

Spinels: Controlled Preparation, Oxygen Reduction/Evolution Reaction Application, and Beyond

In this paper we report on the activity of Cu- and Ni-containing cerium oxide catalysts for low-temperature water-gas shift (WGS). Bulk catalysts were prepared in nanocrystalline form by the urea co-precipitation–gelation method. Lanthanum dopant (10 at.%) was used as a structural stabilizer of ceria, while the content of Cu or Ni was in the range of 5–15 at.% (2–8 wt.%). At low metal loadings, Cu or Ni were present in the form of highly dispersed oxide clusters, while at high loadings, clusters as well as particles of CuO or NiO (>10 nm in size) were present on ceria. Both Cu and Ni increased the reducibility of ceria, as evidenced by H2-TPR experiments. The WGS reaction activity of Ce(La)Ox was increased significantly by addition of a small amount (2 wt.%) of Cu or Ni. The catalysts were not activated prior to testing. Steady-state WGS kinetics were measured over the temperature range of 175–300 and 250–300°C, respectively, for Cu- and Ni–Ce(La)Ox. The activation energy of the reaction over Ce(La)Ox was 58.5 kJ/mol, while it was 38.2 and 30.4 kJ/mol, respectively, over the 5 at.% Ni–Ce(La)Ox and 5 at.% Cu–Ce(La)Ox catalysts in CO-rich conditions. A co-operative redox reaction mechanism, involving oxidation of CO adsorbed on the metal cluster by oxygen supplied to the metal interface by ceria, followed by H2O capping the oxygen vacancy on ceria, was used to fit the kinetics. Parametric studies were mainly performed with the 5 at.% Cu–(La)Ox catalyst. Notably, this material requires no activation and retains high WGS activity and stability at temperatures up to 600°C.

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Low-temperature water-gas shift reaction over Cu- and Ni-loaded cerium oxide catalysts

Elderly patients are more prone than younger patients to develop cerebral desaturation because of the reduced physiologic reserve that accompanies aging. To evaluate whether monitoring cerebral oxygen saturation (rSO(2)) minimizes intraoperative cerebral desaturation, we prospectively monitored rSO(2) in 122 elderly patients undergoing major abdominal surgery with general anesthesia. Patients were randomly allocated to an intervention group (the monitor was visible and rSO(2) was maintained at > or =75% of preinduction values; n = 56) or a control group (the monitor was blinded and anesthesia was managed routinely; n = 66). Cerebral desaturation (rSO(2) reduction <75% of baseline) was observed in 11 patients of the treatment group (20%) and 15 patients of the control group (23%) (P = 0.82). Mean (95% confidence intervals) values of mean rSO(2) were higher (66% [64%-68%]) and the area under the curve below 75% of baseline (AUCrSO2(2)< 75% of baseline) was lower (0.4 min% [0.1-0.8 min%]) in patients of the treatment group than in patients of the control group (61% [59%-63%] and 80 min% [2-144 min%], respectively; P = 0.002 and P = 0.017). When considering only patients developing intraoperative cerebral desaturation, a lower Mini Mental State Elimination (MMSE) score was observed at the seventh postoperative day in the control group (26 [25-30]) than in the treatment group (28 [26-30]) (P = 0.02), with a significant correlation between the AUCrSO(2) < 75% of baseline and postoperative decrease in MMSE score from preoperative values (r(2)= 0.25, P = 0.01). Patients of the control group with intraoperative cerebral desaturation also experienced a longer time to postanesthesia care unit (PACU) discharge (47 min [13-56 min]) and longer hospital stay (24 days [7-53] days) compared with patients of the treatment group (25 min [15-35 min] and 10 days [7-23 days], respectively; P = 0.01 and P = 0.007). Using rSO(2) monitoring to manage anesthesia in elderly patients undergoing major abdominal surgery reduces the potential exposure of the brain to hypoxia; this might be associated with decreased effects on cognitive function and shorter PACU and hospital stay.

Continuous monitoring of cerebral oxygen saturation in elderly patients undergoing major abdominal surgery minimizes brain exposure to potential hypoxia.

Temperature-programmed reduction (TPR) has been used in this work to study the reduction of copper in CuOZnO catalysts with different Cu Zn atomic ratios using H2 as reducing agent In all catalysts, CuO was completely reduced to metal The influence exerted by ZnO on the reduction of copper was evaluated for a wide range of composition and a scale of reducibility was established ZnO affects the hydrogen reduction of copper, CuOZnO samples showing a different behaviour with respect to the pure copper oxide The reduction is always promoted and, in particular, catalysts with lower copper loading (Cu:Zn

Study of the reducibility of copper in CuOZnO catalysts by temperature-programmed reduction

In this work the results of a TPR and XPS investigation of CoxOy–CuO mixed oxides in the range of composition Co : Cu=100:0–8:92 are reported and compared. The final catalysts were obtained by thermal decomposition in air and N2 at 723 K for 24 h of single‐phase cobalt–copper hydroxycarbonates prepared by coprecipitation at constant pH. The Co : Cu=100 : 0 specimen calcined in air formed the Co2+[Co3]2O4 (Co3O4) spinel phase. The copper‐containing catalysts (Co : Cu=85 : 15–8 : 92) showed mainly two phases: (i) spinels, like Co2+[Co3+]2O4, Co 1-x 2+ Cu x 2+ [Co3+]2O4 and (ii) pure CuO, the relative amount of each phase depending on the Co : Cu atomic ratio. The results of the XPS study are consistent with the bulk findings and revealed the presence of Co2+, Co3+ and Cu2+ species at the catalyst surface. Moreover, the surface quantitative analysis evidenced a cobalt enrichment, in particular for the most diluted cobalt samples. The TPR study showed that the catalyst reduction is affected by a strong mutual influence between cobalt and copper. The reducibility of the mixed oxide catalysts was always promoted with respect to that of the pure Co3O4 and CuO phases and the reduction of cobalt was markedly enhanced by the presence of copper. Cobalt and copper were both reduced to metals regardless of the catalyst composition. On the other hand, the Co : Cu=100 : 0 specimen calcined in N2 formed, as expected, CoO. The initial addition of copper resulted in the formation of the Cu+Co3+O2 compound, besides CoO, up to a Co/Cu=1 atomic ratio at which the CuCoO2 phase was the main component. A further addition of copper led to the formation of CuCoO2 and CuO phases. The XPS results were in good agreement with these findings and the surface quantitative analysis revealed a less enrichment of cobalt with respect to the catalysts calcined in air. The TPR analysis confirmed that the reduction of the N2‐calcined catalysts was also remarkably promoted by the presence of copper. Also in this case cobalt and copper metal were the final products of reduction.

TPR and XPS study of cobalt–copper mixed oxide catalysts: evidence of a strong Co–Cu interaction

Presentation des resultats spectrometriques XPS pour le systeme catalytique CuO-ZnO prepare a partir de Cu 2 CO 3 (OH) 2 ou de (Cu, Zn) 5 (CO 3 ) 2 (OH) 6 . Etude de la chimie de surface

G. Fierro

Papers

Continuous monitoring of cerebral oxygen saturation in elderly patients undergoing major abdominal surgery minimizes brain exposure to potential hypoxia.

Study of the reducibility of copper in CuOZnO catalysts by temperature-programmed reduction

TPR and XPS study of cobalt–copper mixed oxide catalysts: evidence of a strong Co–Cu interaction

Characterization of CuO–ZnO catalysts by X‐ray photoelectron spectroscopy: Precursors, calcined and reduced samples

A Study of Anomalous Temperature-Programmed Reduction Profiles of Cu2O, CuO, and CuO-ZnO Catalysts