C-O Bond Activation in Mononuclear Lanthanide Oxocarbonyl Complexes OLn(η2-CO) (Ln = La, Ce, Pr, and Nd).

Fundamental investigation of metal-CO interactions is of great importance for the development of high-performance catalysts to CO activation. Herein, a series of side-on bonded mononuclear lanthanide (Ln) oxocarbonyl complexes OLn(η2-CO) (Ln = La, Ce, Pr, and Nd) have been prepared and identified in solid argon matrices. The complexes exhibit uncommonly low C-O stretching bands near 1630 cm-1, indicating remarkable C-O bond activation in these Ln analogues. The η2-CO ligand in OLn(η2-CO) can be claimed as an anion on the basis of the experimental observations and quantum chemistry investigations, although the CO anion is commonly considered to be unstable with electron auto-detachment. The CO activation in OLn(η2-CO) is attributed to the photoinduced intramolecular charge transfer from LnO to CO rather than the generally accepted metal → CO π back-donation, which conforms to the traditional Dewar-Chatt-Duncanson motif. Energy decomposition analysis combined with natural orbitals for chemical valence calculations demonstrates that the bonding between LnO and η2-CO arises from the combination of dominant ionic forces (>76%) and normal Lewis "acid-base" interactions. The fundamental findings provide guidelines for the catalyst design of CO activation.

CO Oxidation to CO2 on Uranium Dioxide Molecules through Intermediate O2U(η1-CO).

Investigations on the reactions of uranium oxide molecules with CO offer new inspiration for the design of promising high-efficiency catalysts for CO activation using actinide materials. Herein, we contribute a combined matrix-isolation infrared spectroscopic and theoretical study of CO oxidation to CO2 on uranium dioxide (UO2) molecules in solid argon. The reaction intermediate O2U(η1-CO) is generated spontaneously at the bands of 1893.0, 870.6, and 801.3 cm-1 during codeposition and annealing. Upon the following irradiation, CO2 is substantially produced by the consumption of O2U(η1-CO), indicating the catalytic conversion of CO to CO2 through the intermediate O2U(η1-CO). In C18O isotopic substitution experiments, the yields of 16OC18O convincingly confirm that one of the oxygen atoms in CO2 derives from UO2. The reaction pathways are discussed based on the theoretical and experimental results.

[Low temperature plasma technology for biomass refinery].

Biorefinery that utilizes renewable biomass for production of fuels, chemicals and bio-materials has become more and more important in chemical industry. Recently, steam explosion technology, acid and alkali treatment are the main biorefinery treatment technologies. Meanwhile, low temperature plasma technology has attracted extensive attention in biomass refining process due to its unique chemical activity and high energy. We systemically summarize the research progress of low temperature plasma technology for pretreatment, sugar platflow, selective modification, liquefaction and gasification in biomass refinery. Moreover, the mechanism of low temperature plasma in biorefinery and its further development were also discussed.

Pretreatment based on two-step steam explosion combined with an intermediate separation of fiber cells--optimization of fermentation of corn straw hydrolysates.

Pretreatment is necessary for lignocellulose to achieve a highly efficient enzymatic hydrolysis and fermentation. However, coincident with pretreatment, compounds inhibiting microorganism growth are formed. Some tissues or cells, such as thin-walled cells that easily hydrolyze, will be excessively degraded because of the structural heterogeneity of lignocellulose, and some inhibitors will be generated under the same pretreatment conditions. Results showed, compared with one-step steam explosion (1.2 MPa/8 min), two-step steam explosion with an intermediate separation of fiber cells (ISFC) (1.1 Mpa/4 min-ISFC-1.2 MPa/4 min) can increase enzymatic hydrolyzation by 12.82%, reduce inhibitor conversion by 33%, and increase fermentation product (2,3-butanediol) conversion by 209%. Thus, the two-step steam explosion with ISFC process is proposed to optimize the hydrolysis process of lignocellulose by modifying the raw material from the origin. This novel process reduces the inhibitor content, promotes the biotransformation of lignocellulose, and simplifies the process of excluding the detoxification unit operation.

[Production of ethanol and isoflavones from steam-pretreated Radix Puerariae by solid state fermentation].

The gelatinization process of the starch is replaced by unpolluted steam-pretreatment on the base of the Radix Puerariae rich in fiber and isoflavones. The production of ethanol and isoflavones by simultaneous saccharification and solid state fermentation (SSF) of steam-pretreatment Radix Puerariae is presented. The optimal technological conditions were obtained: Radix Puerariae being steam-pretreated at a saturated vapor pressure of 0.8 MPa for 3.5 min, glucoamylase(65 u/g), cellulase(1.5 u/g), 0.1%(NH4)2SO4, 0.1%KH2PO4 and activated yeasts being added in, and fermentation at 35-37 degrees C for 60 h. Under these conditions, the yield of ethanol and isoflavones from 100 g Radix Pureriae (dry basis) were 27.47 g and 4.43 g, respectively, the starch utilization rate was 95%. In comparison with the traditional fermentation technology, the simultaneous saccharification and SSF of steam-pretreatment Radix Puerariae is clean and energy-saving. It provides new way of the production of ethanol from the non-food starch material, and worthwhile to be explored and implemented in industry.