Identifying the isolated transition metal ions/oxides in molecular sieves and on oxide supports by UV resonance Raman spectroscopy

Isolated transition metal ions/oxides in molecular sieves and on surfaces are a class of active sites for selective oxidation of hydrocarbons. Identifying the active sites and their coordination structure is vital to understanding their essential role played in catalysis and designing and synthesizing more active and selective catalysts. The isolated transition metal ions in the framework of molecular sieves (e.g., TS-1, Fe-ZSM-5, and V-MCM-41) or on the surface of oxides (e.g., MoO3/Al2O3 and TiO2/SiO2) were successfully identified by UV resonance Raman spectroscopy. The charge transfer transitions between the transition metal ions and the oxygen anions are excited by a UV laser and consequently the UV resonance Raman effect greatly enhances the Raman signals of the isolated transition metal ions. The local coordination of these ions in the rigid framework of molecular sieves or in the relatively flexible structure on the surface can also be differentiated by the shifts of the resonance Raman bands. The relative concentration of the isolated transition metal ion/oxides could be estimated by the intensity ratio of Raman bands. This study demonstrates that the UV resonance Raman spectroscopy is a general technique that can be widely applied to the in-situ characterization of catalyst synthesis and catalytic reactions. (C) 2003 Elsevier Science (USA). All rights reserved.

A 2-kW COIL with a square pipe-array JSOG and nitrogen buffer gas

A 2-kW-class chemical oxygen-iodine laser (COIL) using nitrogen buffer gas has been developed and tested since industrial applications of COIL devices will require the use of nitrogen as the buffer gas. The laser, with a gain length of 11.7 cm, is energized by a square pipe-array jet-type singlet oxygen generator (SPJSOG) and employs a nozzle bank with a designed Mach number of 2.5. The SPJSOG has advantages over the traditional plate-type JSOG in that it has less requirements on basic hydrogen peroxide (BHP) pump, and more important, it has much better operational stability. The SPJSOG without a cold trap and a gas-liquid separator could provide reliable operations for a total gas flow rate up to 450 mmol/s and with a low liquid driving pressure of around 0.7 atm or even lower. The nozzle bank was specially designed for a COIL using nitrogen as the buffer gas. The cavity was designed for a Mach number of 2.5, in order to provide a gas speed and static temperature in the cavity similar to that for a traditional COIL with helium buffer gas and a Mach 2 nozzle. An output power of 2.6 kW was obtained for a chlorine flow rate of 140 mmol/s, corresponding to a chemical efficiency of 20.4%. When the chlorine flow rate was reduced to 115 mmol/s, a higher chemical efficiency of 22.7% was attained. Measurements showed that the SPJSOG during normal operation could provide a singlet oxygen yield Y greater than or equal to 55%, a chlorine utilization U greater than or equal to 85%, and a relative water vapor concentration w = [H2O]/([O-2] + [Cl-2]) less than or equal to 0.1.

Gas permeability of a novel cellulose membrane

A novel cellulose membrane was prepared by using amine oxides as the solvent and its mechanical performance was measured. Steady-state permeation rates of carbon dioxide, hydrogen, methane, nitrogen, oxygen, argon and helium in the homogeneous dense cellulose membrane were measured in the temperature range of 298-353 K and under gas pressures up to 1 MPa. The effect of swelling on hydrophilic membrane permeability was studied in some detail on the cellulose membrane. The difference in gas permeability between the "dry" cellulose membrane and the "water-swollen" cellulose membrane was investigated, and the gas permeability between the cellulose membrane and the Cellophane was compared. In this paper, the separation performance Of CO2 over H-2 in a "water-swollen" cellulose membrane is reported for the first time and the separation factor Of CO2/H-2 can be up to 15. (C) 2002 Elsevier Science B.V. All rights reserved.

Specific Adsorption of Trace Amounts of Calcium and Strontium by Hydrous Oxides of Iron and Aluminum1

Freshly prepared Fe and Al hydrous oxide gels and the amorphous product of heating gibbsite selectively adsorbed traces of Ca and Sr from solutions containing a large excess (∼1M) of NaNO3. The fraction of the added Ca (Sr) adsorbed depended principally on the suspension pH, the amount of solid present, and to a lesser extent on the NaNO3 concentration. Significant Ca and Sr adsorption occurred on the Fe and Al gels, and heated gibbsite, at pH values below the points of zero charge (8.1, 9.4, and 8.3±0.1, respectively), indicating specific adsorption. The pH (± 0.10) at which 50% of the Ca was adsorbed (pH50) occurred at pH 7.15 for the Fe gel (0.093M Fe), 8.35 for the Al gel (0.093M Al), and 6.70 for the heated gibbsite (0.181M Al); for Sr, the pH50 values were 7.10, 9.00, and 6.45, respectively. For the Fe gel and heated gibbsite, an empirical model based on the law of mass action described the pH dependence of adsorption reasonably well and suggested that for each Ca or Sr fraction adsorbed, approximately one proton was released. Failure of the Al gel to fit this model may have resulted from its rapid aging.

Nitrogen-15 signals of leaf-litter-soil continuum as a possible indicator of ecosystem nitrogen saturation by forest succession and N loads

National Key Research and Development Program [2010CB833502]; National Natural Science Foundation of China [30600071, 40601097, 30590381]; Chinese Academy of Sciences [KZCX2-YW-432, O7V70080SZ, LENOM07LS-01]; GUCAS [O85101PM03]

Short-term effect of increasing nitrogen deposition on CO2, CH4 and N2O fluxes in an alpine meadow on the Qinghai-Tibetan Plateau, China

National Key Research and Development Program [2010CB833500]; Natural Science Foundation of China [30590381]; Knowledge Innovation Project of Chinese Academy of Sciences [KZCX2-YW-432]

Effects of temperature, glucose and inorganic nitrogen inputs on carbon mineralization in a Tibetan alpine meadow soil

High levels of available nitrogen (N) and carbon (C) have the potential to increase soil N and C mineralization We hypothesized that with an external labile C or N supply alpine meadow soil will have a significantly higher C mineralization potential and that temperature sensitivity of C mineralization will increase To test the hypotheses an incubation experiment was conducted with two doses of N or C supply at temperature of 5 15 and 25 C Results showed external N supply had no significant effect on CO2 emission However external C supply increased CO2 emission Temperature coefficient (Q(10)) ranged from 113 to 1 29 Significantly higher values were measured with C than with N addition and control treatment Temperature dependence of C mineralization was well-represented by exponential functions Under the control CO2 efflux rate was 425 g CO2-Cm-2 year(-1) comparable to the in situ measurement of 422 g CO2-Cm-2 year(-1) We demonstrated if N is disregarded microbial decomposition is primarily limited by lack of labile C It is predicted that labile C supply would further increase CO2 efflux from the alpine meadow soil (C) 2010 Elsevier Masson SAS All rights reserved

Effects of nitrogen fertilization on soil respiration in temperate grassland in Inner Mongolia, China

Nitrogen addition to soil can play a vital role in influencing the losses of soil carbon by respiration in N-deficient terrestrial ecosystems. The aim of this study was to clarify the effects of different levels of nitrogen fertilization (HN, 200 kg N ha(-1) year(-1); MN, 100 kg N ha(-1) year(-1); LN, 50 kg N ha(-1) year(-1)) on soil respiration compared with non-fertilization (CK, 0 kg N ha(-1) year(-1)), from July 2007 to September 2008, in temperate grassland in Inner Mongolia, China. Results showed that N fertilization did not change the seasonal patterns of soil respiration, which were mainly controlled by soil heat-water conditions. However, N fertilization could change the relationships between soil respiration and soil temperature, and water regimes. Soil respiration dependence on soil moisture was increased by N fertilization, and the soil temperature sensitivity was similar in the treatments of HN, LN, and CK treatments (Q (10) varied within 1.70-1.74) but was slightly reduced in MN treatment (Q (10) = 1.63). N fertilization increased soil CO2 emission in the order MN > HN > LN compared with the CK treatment. The positive effects reached a significant level for HN and MN (P < 0.05) and reached a marginally significant level for LN (P = 0.059 < 0.1) based on the cumulative soil respiration during the 2007 growing season after fertilization (July-September 2007). Furthermore, the differences between the three fertilization treatments and CK reached the very significant level of 0.01 on the basis of the data during the first entire year after fertilization (July 2007-June 2008). The annual total soil respiration was 53, 57, and 24% higher than in the CK plots (465 g m(-2) year(-1)). However, the positive effects did not reach the significant level for any treatment in the 2008 growing season after the second year fertilization (July-September 2008, P > 0.05). The pairwise differences between the three N-level treatments were not significant in either year (P > 0.05).

Drivers of soil net nitrogen mineralization in the temperate grasslands in Inner Mongolia, China

Soil net nitrogen mineralization (NNM) of four grasslands across the elevation and precipitation gradients was studied in situ in the upper 0-10 cm soil layer using the resin-core technique in Xilin River basin, Inner Mongolia, China during the growing season of 2006. The primary objectives were to examine variations of NNM among grassland types and the main influencing factors. These grasslands included Stipa baicalensis (SB), Aneulolepidum Chinense (AC), Stipa grandis (SG), and Stipa krylovii (SK) grassland. The results showed that the seasonal variation patterns of NNM were similar among the four grasslands, the rates of NNM and nitrification were highest from June to August, and lowest in September and October during the growing season. The rates of NNM and nitrification were affected significantly by the incubation time, and they were positively correlated with soil organic carbon content, total soil nitrogen (TN) content, soil temperature, and soil water content, but the rates of NNM and nitrification were negatively correlated with available N, and weakly correlated with soil pH and C:N ratio. The sequences of the daily mean rates of NNM and nitrification in the four grasslands during the growing season were AC > SG > SB > SK, and TN content maybe the main affecting factors which can be attributed to the land use type.

Radiation-use efficiency and the harvest index of winter wheat at different nitrogen levels and their relationships to canopy spectral reflectance

Radiation-use efficiency (RUE, g/MJ) and the harvest index (HI, unitless) are two helpful characteristics in interpreting crop response to environmental and climatic changes. They are also increasingly important for accurate crop yield simulation, but they are affected by various environmental factors. In this study, the RUE and HI of winter wheat and their relationships to canopy spectral reflectance were investigated based on the massive field measurements of five nitrogen (N) treatments. Crop production can be separated into light interception and RUE. The results indicated that during a long period of slow growth from emergence to regreening, the effect of N on crop production mainly showed up in an increased light interception by the canopy. During the period of rapid growth from regreening to maturity, it was present in both light interception and RUE. The temporal variations of RUEAPAR (aboveground biomass produced per unit of photosynthetically active radiation absorbed by the canopy) during the period from regreening to maturity had different patterns corresponding to the N deficiency, N adequacy and N-excess conditions. Moreover, significant relationships were found between the RUEAPAR and the accumulative normalised difference vegetation index (NDVI) in the integrated season (R-2 = 0.68), between the HI and the accumulative NDVI after anthesis (R-2 = 0.89), and between the RUEgrain (ratio of grain yield to the total amount of photosynthetically active radiation absorbed by the canopy) and the accumulative NDVI of the whole season (R-2 = 0.89) and that after anthesis (R-2 = 0.94). It suggested that canopy spectral reflectance has the potential to reveal the spatial information of the RUEAPAR, HI and RUEgrain. It is hoped that this information will be useful in improving the accuracy of crop yield simulation in large areas.

PIFA-Mediated Oxidative Cyclization of 1-Carbamoyl-1-oximylcycloalkanes: Synthesis of Spiro-Fused Pyrazolin-5-one N-Oxides

convenient and efficient synthesis of spiro-fused pyrazolin-5-one N-oxides starting from readily available 1-carbamoyl-1-oximylcycloalkanes is developed. This general protocol features a novel and facile way for access to the five-membered azaheterocycles by formation of a new N-N single bond. The key cyclization step utilizes the formation of an N-oxonitrenium intermediate, mediated by the hypervalent iodine reagent PIFA, and its subsequent intramolecular trapping by the amide moiety under rather mild experimental conditions.

Formation of Fullerooxazoles from C61HPh3-: The Regioselectivity of Heteroatom Additions

The formation of fullerooxazoles from C61HPh3- has been examined in benzonitrile (PhCN), m-methoxybenzonitrile (m-OCH3PhCN), m-tolunitrile (m-CH3PhCN), and o-tolunitrile (o-CH3PhCN), where cis-1 bisadducts wit h Ph-, m-OCH3Ph-, m-CH3Ph-, and o-CH3Ph-substituted cyclic imidate next to the phenylmethano are formed its evidenced by various characterizations. Interestingly, only regioisomers 2a-d with the oxygen atom bonded to C4/C5 and the nitrogen atom bonded to C3/C6 are generated its demonstrated by heteronuclear multiple bond coherence (HMBC) NMR, while the alternative regioisomers 3a-d, which have the oxygen and nitrogen atoms at C3/C6 and C4/C5, respectively, are not formed from the reactions, even though the DFT (density functional theory) calculations have predicted that the energy differences between the two types of regioisomers are very small, with regioisomers 3a-d actually having lower energies than 2a-d The results are rationalized by the charge distributions Of C61HPh3-, where computational calculations have shown that the negative charges on C4 and C5 are greater than those on C3 and C6, indicating that the exhibited site selectivity of heteroatoms is a result of the charge-directed addition process