High efficiency synthesis of HKUST-1 under mild conditions with high BET surface area and CO2 uptake capacity

This study focuses on the development of a hydrothermal method for the rapid synthesis of good quality copper benzene-1,3,5-tricarboxylate(referred to as HKUST-1)with high yield under mild preparation conditions to address the issues associated with reported methods.Different synthesis conditions and activation methods were studied to understand their influence on the properties of HKUST-1.It was found that mixing the precursors at50°C for 3 h followed by activation via methanol refluxing led to the formation of a product with the highest BET specific surface area of 1615 m~2/g and a high yield of 84.1%.The XRD and SEM data illustrated that the product was highly crystalline.The sample was also tested on its capacity in CO_2 adsorption.The results showed strong correlation between surface area of the sample and its CO_2 uptake at 1 bar and 27°C.The HKUST-1 prepared in this study demonstrated a high CO_2 uptake capacity of 4.2 mmol/g.It is therefore concluded that this novel and efficient method can be used in the rapid preparation of HKUST-1 with high surface area and CO_2 uptake capacity.     

Preparation of composite adsorbent with high performance of heat and mass transfer

To develop a new composite adsorbent with high performance,fir sawdust and CaCl2are selected as raw materials.The mass transfer is enhanced by carbonizing and activating the sawdust and heat transfer is enhanced by adding expanded graphite into the adsorbent.The effect of the preparation temperature and the expanded graphite content on the adsorption performance is investigated.The results show that the new adsorbent exhibits a high adsorption performance due to its high porosity,uniform distribution and high content of CaCl2and high thermal conductivity.Also,the experimental results indicate that the rate of ammonia adsorption on the adsorbent depends on the expanded graphite content and the carbonization and activation temperature.The adsorbent prepared at 500°C and with the expanded graphite content of 30%has the best performance in terms of the adsorption refrigeration,which adsorbs ammonia as high as 0.37 g g 1at 10 min.     

含金属元素的常温CO2固体吸附剂研究进展

当今世界环境保护已经成为大家关注的重点问题。随着大量化石燃料的燃烧,过量的CO₂被排放到大气中,在工业生产中如何降低CO₂的排放量成为了众多研究者所探索的对象。利用固体吸附剂对CO₂进行吸附,在众多的减排方式中被认为是一种无腐蚀、无污染、易于操作且吸附性能更高的方式。对含金属元素固体吸附剂的分类、改性方式、吸附原理、吸附效率等不同方面进行了综述,重点介绍了在常温下对CO₂有较高吸附性能的几种改性材料,同时对含金属元素固体吸附剂吸附CO₂的研究方向和前景作出展望。     

Fluxes of CO2, N2O and CH4 from a typical temperate grassland in Inner Mongolia and its daily variation

Using a dark enclosed chamber technique, the fluxes of CO₂, N₂O and CH₄ from nature and disturbed grassland were measured on the spot in Inner Mongolian Temperate Grassland along the annual rainfall gradient section ranging from 450 to 200 mm. The results showed that the measured mean fluxes of CO₂, N₂O and CH₄ were (1 180.4 ± 308.7), (0.010 ± 0.004) and (−0.039 ± 0.016) mg · m⁻²/h, respectively. The decrease of the fluxes of CO₂, N₂O and CH₄ follows with that of annual rainfall gradient in the measurement area. Human activities, such as grazing and reclamation are also critical factors to affect the fluxes of these gases from grassland. Daily continuous measurement of CO₂, N₂O and CH₄ fluxes showed a strong diurnal variation with higher emission in the daytime. A good relationship between the fluxes of CO₂, N₂O, CH₄ and temperature was exposed in this study.     

New crystal structure of molecular complex 1-piperidine carboxylate-piperidinium-H<Subscript>2</Subscript>O studied by X-ray single crystal diffraction

Piperidine absorbs CO2 and H2O in air to form a molecular complex： piperidium-l-piperidinecarboxylate-H2O. The structure of the complex was characterized by X-ray single crystal diffraction. The crystal structure was determined to be triclinic, space group P1^-with a=0.648 6（8） nm, b=0.809 200） nm, c= 1.357 1（16） nm, a=96.96706）°, β =102.506（15）°,γ=104.202 05）°, Z=2. The complex is stabilized via five hydrogen bonds between the three components, N-O electrostatic interaction and O-O interaction （electron transfer） betweenl-piperidinecarboxylate and H2O. Due to electron transference of carbamate ion, the oxygen atom in water molecule is strongly negatively charged and the O-H bond is considerably shorter than that of the free molecule of water. The formation of the molecular complex is a reversible process and will decompose upon heating. The mechanism of formation and stabilization is further investigated herein.     

Modification of free-energy density functional theory approach for prediction of high-pressure mixture adsorption

A modified non-local free energy density functional theory （NDFT） model, with the consideration of the nonadditivity term of solid-fluid and fluid-fluid interactions and finite pore wall thickness （≈2 layers）, was developed to model the confined fluid mixtures in slit pore. This improved NDFT approach, combining with the pore size distribution （PSD） analysis of adsorbent material can be applied to predicting the adsorption equilibria of high-pressure gas mixtures on activated carbon. Compared with the conventional NDFT method, this new approach partly improves the correlation performance of adsorption equilibrium for pure species and increases the reliability of the PSD analysis. For the mixtures, CH4/N2 and CO2/N2, a relatively improved performance has been observed for the adsorption equilibrium prediction of the mixtures under high-pressure conditions, especially for the weakly adsorbed species.     

Trend, seasonal and diurnal variations of atmospheric CO2 in Beijing

The concentration of atmospheric CO₂ in Beijing increased rapidly at a mean growth rate of 3.7% · a⁻¹ from 1993 to 1995. After displaying a peak of (409.7±25.9) μmol · mol⁻¹ in 1995, it decreased slowly. Both the almost stable anthropogenic CO₂ source and increasing biotic CO₂ sink contribute to the drop of CO₂ concentration from 1995 to 2000. The seasonal variation of CO₂ concentration exhibits a clear cycle with a maximum in winter, averaging (426.8±20.6) μmol · mol⁻¹, and a minimum in summer, averaging (369.1±6.1) μmol·mol⁻¹. The seasonal variation of CO₂ concentration is mainly controlled by phenology. The mean diurnal variation of atmospheric CO₂ concentration for a year in Beijing is highly clear: daily maximum CO₂ concentration usually occurs at night, but daily minimum CO₂ concentration does in the daytime, with a mean diurnal difference more than 34.7 μmol·mol⁻¹. It has been revealed that the interannual variations of atmospheric CO₂ concentration in winter and autumn regulated the interannual trend of atmospheric CO₂, whereas the interannual variation of CO₂ concentration in summer affected the general tendency of atmospheric CO₂ in a less degree.     

The comparison of Cu（ll） adsorption capability of baker＇s yeast,nano-titania and their composite adsorbent

The anatase nano-TiO2 powder, with crystal size between 40 and 80 nm, was prepared by the liquid phase hydrolysis of TiCI4. At the same time, the nano-TiO2 was utilized with the baker＇s yeast biomass as a composite adsorbent to adsorb the Cu ions in the artificial aqueous solution. The investigation showed that the composite adsorbent had a fine adsorption efficiency. The TiO2 in the composite adsorbent could cooperate well with baker＇s yeast to improve the adsorbing capability of Cu^2＋ under the following experimental conditions as well： a quantity of composite adsorbent of 5 g·L^-1, pH≥4.0, an adsorption time of 40 min and an initial concentration of Cu ions of 10 mg·L^-1. In addition, the results of measurements, obtained with a scanning electron microscope, an infrared spectrophotometer and a Zeta potential analyzer, revealed that the baker＇s yeast and nano-TiO2 produced the composite adsorbent through coordination and hydrogen bonds in particular, etc. The stability of the composite adsorbent and the amount of titania loaded were largely dependent on the concentration of hydrogen ion in the solution.     

Coordination behavior between zinc salts and L-α-methionine

The solubility properties of ZnCl\-2/ZnAc\-2/ZnSO\-4_Met_H\-2O systems at 25℃ in the whole cocentration range have been investigated by phase equilibrium method. The results indicate that ZnAc\-2 and ZnSO\-4 systems are both simple systems, which do not exist any compound; there are 2 complexes formed in ZnCl\-2 system: Zn(Met)Cl\-2 and Zn(Met)\-2Cl\-2·2H\-2O. Under the direction of phase equilibrium result, 2 solid complexes have been prepared in water and characterized by chemical analysis, IR, X_ray diffraction. Their combustion energies have also been determined by means of a RBC_type_1 rotating_bomb calorimeter, and their standard enthalpies of formation, Δ f, coor(s)H O-, have been calculated which are (-828.32±3.00) kJ·mol -1 and (-1 117.08±6.15) kJ·mol -1, respectively.     

Water solubility in orthopyroxene: Dependence on temperature and Al content

The water solubility in Al-Fe-Mg orthopyroxene [(Mg,Fe,Al)(Si,Al)O₃: X _Fe = 0.1] was investigated as a function of temperature and Al contents. Experiments were performed at 10 kbar with temperatures ranging from 800 to 1200°C under water-saturated conditions. Water contents in the (Mg,Fe)SiO₃-H₂O-Al₂O₃ system were determined using unpolarized Fourier transform infrared spectroscopy. The present results show that water solubility in Al-bearing orthopyroxene decreases systematically with temperature from approximately 1 weight % at 800°C to 568 ± 58 ppm at 1200°C and increase significantly with increasing Al₂O₃ contents under the same annealing temperature and pressure. Combined with published results on the dependence of hydroxyl solubility on water fugacity and pressure, the present results can be described by the relation $C_{OH} = A(T)f_{H_2 O}^{n = 0.5} \exp \left( { - \frac{{\Delta H^{1bar} + \Delta V^{solid} P}} {{RT}}} \right)$ where A = 0.0024 ± 0.0015 ppm/bar^0.5, ΔH ^1bar = ?103.348 ± 9.768 kJ/mol, and solid ΔV ^solid = 9.2 ± 1.1 cm³/mol. This equation implies that the incorporation mechanism of water in aluminous orthopyroxene involves the isolated OH groups. Based on the experimentally established solubility model used in this study, it is suggested that water solubility decreases with increasing temperature under typical upper mantle pressure. The predicted temperature dependence of water solubility is in good agreement with the previous experimental observations in Al-bearing orthopyroxene, but the opposite dependence is observed in Al-free systems. Moreover, our estimation of the water solubility in upper-mantle minerals as a function of depth for a typical oceanic geotherm might be of potential importance in interpreting the geophysical observations.     

Li3O+超碱团簇的结构及储氢性能的理论研究

采用杂化密度泛函理论(DFT)的B3LYP方法,在6-311++G (d, p)基组水平上对Li₃O ^{0, +}超碱团簇的几何结构和稳定性进行理论计算,并研究了Li₃O⁺团簇的储氢性能。结果表明,Li₃O⁺团簇结构相比中性Li₃O团簇结构的动力学稳定性要高。氢分子在Li₃O⁺团簇表面能以介于物理吸附与化学吸附之间的形式吸附,每个Li原子最多可以有效吸附三个H₂,储氢质量分数可达33.01 wt%。H₂分子在Li₃O⁺团簇表面的平均吸附能范围为1.959~3.591 kCal/mol,该吸附能满足在近室温条件下可逆吸放氢反应的热力学要求。     

Effect of CO<Subscript>2</Subscript> and H<Subscript>2</Subscript>O on gasification dissolution and deep reaction of coke

To more comprehensively analyze the effect of CO₂ and H₂O on the gasification dissolution reaction and deep reaction of coke, the reactions of coke with CO₂ and H₂O using high temperature gas-solid reaction apparatus over the range of 950-1250℃ were studied, and the thermodynamic and kinetic analyses were also performed. The results show that the average reaction rate of coke with H₂O is about 1.3-6.5 times that with CO₂ in the experimental temperature range. At the same temperature, the endothermic effect of coke with H₂O is less than that with CO₂. As the pressure increases, the gasification dissolution reaction of coke shifts to the high-temperature zone. The use of hydrogen-rich fuels is conducive to decreasing the energy consumed inside the blast furnace, and a corresponding high-pressure operation will help to suppress the gasification dissolution reaction of coke and reduce its deterioration. The interfacial chemical reaction is the main rate-limiting step over the experimental temperature range. The activation energies of the reaction of coke with CO₂ and H₂O are 169.23 kJ·mol-1 and 87.13 kJ·mol-1, respectively. Additionally, water vapor is more likely to diffuse into the coke interior at a lower temperature and thus aggravates the deterioration of coke in the middle upper part of blast furnace.     

Preparation and catalytic effect of porous Co3O4 on the hydrogen storage properties of a Li-B-N-H system

A porous Co_3O_4 with a particle size of 1–3 μm was successfully prepared by heating Co-based metal organic frameworks MOF-74(Co) up to 500 °C in air atmospheric conditions. The as-prepared porous Co_3O_4 significantly reduced the dehydrogenation temperatures of the LiBH_4-2LiNH_2 system and improved the purity of the released hydrogen. The LiBH_4-2LiNH_2-0.05/3Co_3O_4 sample started to release hydrogen at 140 °C and released hydrogen levels of approximately 9.7 wt% at 225 °C. The end temperature for hydrogen release was lowered by 125 °C relative to that of the pristine sample. Structural analyses revealed that the as-prepared porous Co_3O_4 is in-situ reduced to metallic Co, which functions as an active catalyst, reducing the kinetic barriers and lowering the dehydrogenation temperatures of the LiBH_4-2LiNH_2 system. More importantly, the porous Co_3O_4-containing sample exhibited partially improved reversibility for hydrogen storage in the LiBH_4-2LiNH_2 system.     

The v-v energy transfer of highly vibrationally excited states (I)

The relaxation of the highly vibrationally excited CO (v = 1–8) by CO₂ is studied by timeresolved Fourier transform infrared emission spectroscopy (TR FTIR). 193 nm laser photolysis of the mixture of CHBr₃ with O₂ generates the highly vibrationally excited CO(v) molecules. TR FTIR records the intense infrared emission of CO(v→v-1). The vibrational populations of each level of CO(v) have been determined by the method of spectral simulation. Based on the evolution of the time resolved populations and the differential method, 8 energy transfer rate constants of CO(v = 1–8) to CO₂ molecules areobtained: (5.7±0.1), (5.9±0.1), (5.2±0.2), (3.4±0.2), (2.4±0.3), (2.2±0.4), (2.0±0.4) and (1.8±0.6) (10¹⁴ cm³ · molecule⁻¹ · s⁻¹), respectively. A two-channel energy transfer model can explain the feature of the quenching of CO(v) by CO². For the lower vibrational states of CO, the vibrational energy transfers preferentially to the u³ mode of CO² For the higher levels, the major quenching channel changes to the vibrational energy exchange between CO(v→v-1) and the u¹ mode of CO².     

Preparation of metal oxide doped ACNFs and their adsorption performance for low concentration SO2

Metal oxide （TiO2 or Co304） doped activated carbon nanofibers （ACNFs） were prepared by electrospinning. These nanofibers were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and Brunner- Emmett-Teller method （BET）. The results show that the average diameters of ACNFs were within the range of 200-500 nm, and the lengths were several tens of micrometers. The specific surface areas were 1146.7 m2/g for TiO2-doped ACNFs and 1238.5 m2/g for Co304-doped ACNFs, respectively. The electrospun nanofibers were used for adsorption of low concentration sulfur dioxide （SO2）. The results showed that the adsorption rates of these ACNFs increased with an increase in SO2concentration. When the SO2 concentration was 1.0 μg/mL, the adsorption rates of TiO2-doped ACNFs and Co3Oa-doped ACNFs were 66.2% and 67.1%, respectively. The adsorption rate also increased as the adsorption time increased. When the adsorption time was 40 min, the adsorption rates were 67.6% and 69.0% for TiO2-doped ACNFs and Co304-doped ACNFs, respectively. The adsorption rate decreased as the adsorption temperature increased below 60℃, while it increased as the adsorption temperature increased to more than 60℃.     

尿素辅助模板法合成介孔氮掺杂CeO2及其CO2捕获应用研究

以硝酸铈为前驱物,以尿素为助剂,采用一种简单的模板法合成了介孔氮掺杂CeO₂材料.利用X射线衍射仪(XRD)、吸附-脱附仪(BET)、透射电子显微镜(TEM)和傅里叶变换红外光谱(FT-IR)等设备对合成材料进行表征.多种测试结果证明:试验得到的纳米材料具有均一的介孔结构和较高的比表面积(124.8 m²·g^-1)并掺杂了氮元素.同时,测定了介孔CeO₂材料对于CO₂的吸附性能,并研究了氮掺杂对CeO₂材料的CO₂吸附性能的影响.结果表明:相比未掺杂氮的介孔CeO₂,氮掺杂的介孔CeO₂具有更好的CO₂吸附性能和循环吸附脱附性能.     

Selective catalytic oxidation of ammonia to nitrogen over orderly mesoporous CuFe2O4 with high specific surface area

Orderly mesoporous CuFe2O4 spinel-type mixed oxide with high specific surface area was prepared successfully by a hard-template method in which KIT-6 mesoporous silica was selected as the hard template. The KIT-6 hard template and CuFe2O4 samples were charac- terized by X-ray diffraction, X-ray photoelectron spec- troscopy, X-ray fluorescence, transmission electron microscopy, scanning electron microscopy, nitrogen physisorption, and hydrogen-temperature programmed reduction. The KIT-6 hard template had perfect crystalli- zation and ordered mesoporous structure with a probable pore distribution of about 9.1 nm, large enough to be filled by the spinel precursor. The mesoporous CuFe2O4 spinel oxide synthesized inside the KIT-6 mesopores had a rela- tively small pore size （4.3 nm）, orderly arrangement, and high specific area （194 m2/g）. The catalytic activity of the mesoporous CuFe2O4 was tested for the selective oxidation of ammonia to nitrogen. The conversion of ammonia reached nearly 100 % at 300 ℃with a nitrogen selectivity as high as 96 %. The nitrogen selectivity remained high with increasing temperature and even maintained a value of 80 % at 600 ℃.     

Adsorption of rhodamine B from aqueous solution onto heat-activated sepiolite

The heat-activated sepiolite, which was prepared using sepiolite by thermal treatment at different temperatures, was used as an absorbent for the removal of rhodamine B (RhB) from aqueous solutions. The structure and morphology of the as-prepared samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques, respectively. The adsorption capacity of RhB onto the heat-activated sepiolite has been examined with pH, adsorbent dosage, contact time, initial dye concentration, and temperature. Kinetic studies showed that the equilibrium was attained within 40 min, and the kinetic data were well described by the pseudo-second-order kinetic model. Besides, the experimental data (R ²>0.999) fitted the Freundlich model better than the Langmuir model. The as-prepared sample showed higher adsorption capacity (8.33 mg/g) for the removal of RhB than that of sepiolite, which could be attributed to more adsorption sites caused by appropriate heat treatment. The adsorbent can be well regenerated by calcination at 400 °C for 2 h and regenerated sepiolite did not exhibited significant loss of adsorption activity after five recycles.     

Diurnal and monthly variations of carbon dioxide flux in an alpine shrub on the Qinghai-Tibet Plateau

Long-term flux observation is an efficient approachto collect CO2 emission or assimilation data in an ecosys-tem. In cooperation with a series of international coopera-tion programs including those sponsored by IGBP (Inter-national Geosphere-Biosphere Program), WCRP (WorldClimate Research Program), IHDP (International HumanDimension of Global Environment Change), GCTE(Global Change and Terrestrial Ecosystem) and LUCC(Land Use and Land Cover Change), a lot of researchwork conce…     

Characterization and adsorption behavior of a novel triolein-embedded activated carbon composite adsorbent

A novel triolein-embedded activated carbon composite adsorbent was developed. Experiments were carried out in areas such as the preparation method, the characterization of physicochemicai properties, and the adsorption behavior of the composite adsorbent in removing dieldrin from aqueous solution. Results suggested that the novel composite adsorbent was composed of the supporting activated carbon and the surrounding triolein-embedded cellulose acetate membrane. The adsorbent was stable in water, for no triolein leakage was detected after soaking the adsorbent for five weeks. The adsorbent had good adsorption capability to dieldrin, which was indicated by a residual dieldrin concentration of 0.204μg·L^-1. The removal efficiency of the composite adsorbent was higher than the traditional activated carbon adsorbent.