NiSO4溶液的DFT和EXAFS研究

由密度泛函理论(DFT)和扩展X-射线吸收精细结构(EXAFS)光谱研究硫酸镍溶液的微观水合结构。对硫酸镍水合团簇[NiSO4(H2O)n]0 (n=1-12) 的结构优化和能量计算采用DFT计算中的B3LYP方法进行。对于每一个团簇尺寸尽可能考虑所有初始构型,并以此确定能量最低结构。 DFT计算结果表明,在[NiSO4(H2O)n]0团簇中六配位结构的Ni2+为稳定构型. 水合能计算结果表明,当水合团簇尺寸较小时(n≤5),六配位直接接触离子对(CIP)为稳定构型;而当6≤n≤10时, 溶剂共享离子对 (SSIP)为稳定结构。随着团簇尺寸的增加,当n≥11时,x个水分子分割离子对 (xSIP, x是Ni2+和SO42-之间的水分子数目,且x≥2)为稳定构型。对 NiSO4溶液和NiSO4?6H2O进行EXAFS实验,结果证实Ni2+第一水合层是由六个水分子形成的稳定八面体结构,且当 NiSO4溶液浓度从0.70 mol/L到2.22 mol/L(近似饱和溶液)并未发现CIP构型。Ni-O距离和配位数(CN)分别是 2.040±0.020 ? 和6.0±1.0,这些结论与[NiSO4(H2O)n]0水合团簇的DFT计算结果一致。     

NH4Cl水溶液的结构和物性研究

通过密度泛函理论(DFT)计算、拉曼光谱和同步辐射X射线散射法,研究了质量分数为1.0%～28.0%的NH₄Cl水溶液的微观结构。在室温下测量了粘度、接触角和电导率。由DFT计算和拉曼光谱结果可知,当溶质浓度升高至10.0%时,在2 900 cm^-1和3 100 cm^-1附近出现了明显的N-H作用峰,且随着质量分数的升高,NH₄Cl水溶液中的DDAA型氢键转变为DA和DAA型氢键。X射线散射结果表明,当NH₄Cl水溶液质量分数升高至10.0%时,差值对分布函数G(r)在0.298 nm附近出现明显双峰,表明在该浓度下溶液中NH₄⁺-Cl^-接触离子对开始成为主要微观作用形式。NH₄Cl水溶液的粘度、接触角和电导率均随着NH₄Cl水溶液质量分数的增加而增大。NH₄Cl水溶液中氢键类型的转变、O-H...N键占比增多以及逐渐增加的NH₄     

NH4Cl水溶液的微观结构和宏观物性研究

通过拉曼光谱、同步辐射X射线散射和密度泛函理论(DFT)模拟,研究了质量分数为1.0 %-28.0 %的NH₄Cl水溶液的微观结构变化。同时在室温下测量了粘度、接触角和电导率。由拉曼光谱和密度泛函理论模拟结果可知,当溶质浓度升高至10.0 %时,在2900 cm_-1^和3100 cm_-1^{附近出现了明显的}N-H作用峰,且随着质量分数的升高,NH₄Cl水溶液中的氢键类型发生了转变。X射线散射结果表明,当NH₄Cl水溶液质量分数升高至10.0 %时,差值对分布函数G(r)在2.98 ?附近出现明显双峰,表明在该浓度下溶液中NH₄₊^-Cl_-^{接触离子对开始成为主要微观作用形式。对}NH₄Cl水溶液的宏观物性研究表明,粘度、接触角和电导率均随着NH₄Cl水溶液质量分数的增加而增大。作者推断,NH₄Cl水溶液中氢键类型的转变、O-H...N键占比增多以及逐渐增加的NH₄₊^-Cl_-^{接触离子对},是粘度和接触角随溶质浓度增加而增加的微观本质因素;电导率的增加与溶液中有效导电离子数量增加有关。     

Li2SO4溶液中离子间的缔合相互作用:基于密度泛函理论和分子动力学模拟的研究

基于密度泛函理论,使用B3LYP/aVDZ方法对[Li_2SO_4(H_2O)_n]~0(n=0~10、18)水合团簇的结构和性质进行了系统地研究,并结合Car-Parrinello分子动力学(CPMD)模拟了不同浓度的Li_2SO_4溶液结构,目的在于理解在Li_2SO_4溶液中离子间缔合相互作用及可能存在的物种。研究发现,对于[Li_2SO_4(H_2O)_n]~0(n=0~10、18)水合团簇,双配位单齿螯合接触离子对结构比双配位双齿螯合接触离子对结构更稳定,溶剂共享离子对结构最不稳定。同时,CPMD模拟结果表明,在3.09和3.17 mol/kg的Li_2SO_4溶液中,双配位单齿螯合接触离子对结构仍然是主要物种。以上结果表明在饱和的Li_2SO_4溶液(3.16 mol/kg)中,Li~+和SO_4~(2-)离子间的相互缔合作用主要以双配位单齿螯合接触离子对结构的物种存在,而具有双配位双齿螯合离子对结构的物种占少数,溶剂共享离子对结构几乎不存在。     

Mg(BO2)2在MgSO4和MgCl2-MgSO4水溶液中分解的相平衡与物种化学平衡

硫酸镁亚型盐湖老卤是MgCl₂、MgSO₄的饱和溶液体系,富集了Mg、B、Li等元素。本文针对含硼水盐体系热力学难以表达的问题,开展了硼在水盐体系存在形态及其平衡关系的研究。利用易于水解的Mg(BO₂)₂作为硼源,借助拉曼光谱和X射线衍射(XRD)为检测手段,定量研究Mg(BO₂)₂在MgSO₄-H₂O、MgSO₄-MgCl₂-H₂O体系中水解硼物种转化规律。结果表明:(1)Mg(BO₂)₂在MgSO₄溶液中的水解固相为MgB₂O(OH)6、MgB₄O₇·9H₂O和Mg(OH)₂;在MgSO₄-MgCl₂-H₂O溶液中水解固相为Mg₂B₆O₁₁·15H₂O、MgB₄O₇·9H₂O、Mg₂Cl(OH)₃·4H₂O。(2)Mg(BO₂)₂在MgSO₄溶液中水解,液相硼物种主要有B₃O₃(OH)-₄、B₃O₃(OH)₅2-、B(OH)-₄、B₄O₅(OH)₄2-、H₃BO₃,其分布受MgSO₄浓度影响很大,MgSO₄浓度从0增加至饱和,B₃O₃(OH)-₄始终占总硼量的50.07%以上,B₃O₃(OH)₅2-占液相总硼从4.77%上升至37.16%为第2化学物种。(3)在MgSO₄-MgCl₂-H₂O溶液中,硼物种的主要形态有B₃O₃(OH)-₄、B₃O₃(OH)₅2-、B(OH)-₄,其分布 随[Cl₂2-]/([Cl₂2-]+[SO₄2-])变化很大,在MgCl₂和MgSO₄的共饱溶液中,分别占液相总硼量的58.91%,14.62%和12.81%。(4)液相硼物种之间平衡关系的活度商lnQ,不仅与溶液pH、水活度有关,还与MgSO₄、MgCl₂摩尔浓度呈二元线性关系,这样就可将硼在H₃BO₃-NaOH体系物种分布关系的lnQ扩展到 (MgSO₄,MgCl₂,MgSO₄-MgCl₂)水溶液的多元体系。由此获得硼物种的量化关系,可为推算硼在水盐体系的物种分布,进而计算含硼电解质溶液热力学性质提供依据。     

A review on the ambit and prospects of C3 and C4 plants in Nigeria

Despite the enormous applications of photosynthesis in global carbon budget and food security, photosynthesis research has not been adequately explored as a research focus in Nigeria. Previous works on C₃ and C₄ plants in Nigeria were mainly on the use of anatomical characteristics to delimit plant species into their respective pathways, with no attention being paid to its applications. In this review, past and present knowledge gaps in this area of study are elucidated. Information used in this review were sourced from referred research articles and books in reputable journals. The results revealed that C₃ and C₄ plants are distributed among 21 genera and 11 families in Nigeria. In addition there is dearth of informatio such that only three genera have been classified based on diverse photosynthetic pathways with no information found on the physiological and biochemical characterization of these genera. Moreover, further research is also suggested for tackling new challenges in the area of food productivity and climate change.     

Fe3O4/Mg(OH)2复合材料的制备及形貌控制

通过种子沉积法制备出Fe_3O_4/Mg(OH)_2复合材料并进行XRD、SEM测试分析。探究了氨水的浓度与加入速度、搅拌速度及等因素对磁性复合材料形貌的影响。氨水浓度与注入速度的降低,对氢氧化镁基体形貌的影响是相同的,但要使合成磁性复合材料形貌和四氧化三铁粒子在氢氧化镁中分散性均匀,应控制氨水浓度(ω=2.5%)或加入速度在一个合理的较低值。     

南极大气CO_2、CH_4和N_2O本底趋势特征分析

对南极大气温室气体CO_2(含δ~(13)C-CO_2和δ~(18)O-CO_2)、CH_4和N_2O长期测值进行比较分析。结果表明,南极是全球大气温室气体浓度(CO_2稳定同位素丰度值)随纬度分布变化中的最低(高)区域。南极大气温室气体浓度值变化趋势、年增长率与全球整体上一致,但在具体数值上存在差异。南极CO_2平均年增长率(1958—2014年)为(1.43±0.59)mg·L~(–1)·a~(–1),低于同期赤道(1.51±0.72)mg·L~(–1)·a~(–1),但1980—2014年和2000—2014年年增长率均高于南半球中纬度地区。δ~(13)C-CO_2和δ~(18)O-CO_2丰度趋势揭示了化石燃料排放和全球尺度过程对CO_2的影响,但南极是受影响最小的区域。1983—2014年南极CH_4平均增长率为(6.2±4.9)μg·L~(–1)·a~(–1),低于北半球中纬度(6.5±5.6)μg·L~(–1)·a~(–1)而高于赤道(5.6±5.3)μg·L~(–1)·a~(–1)和南半球中纬度(6.1±4.9)μg·L~(–1)·a~(–1),这与CH_4人为排放增强主要在北半球中纬度地区而显著被OH氧化在赤道和中纬度地区的事实是吻合的。南极N_2O平均年增长率为(0.87±0.15)μg·L~(–1)·a~(–1)(2005—2013年),与南半球中纬度地区接近但低于北半球而高于赤道地区。     

Mg2B2O5晶须增强AZ91D镁基复合材料在Cl-溶液中腐蚀行为*

用电化学方法测量了Mg_2B_2O_5晶须增强AZ91D镁基复合材料在3.5%NaCl溶液中的开路电位、动电位极化曲线和交流阻抗,研究了晶须体积分数对镁合金基体耐腐蚀性能的影响,并利用SEM和XRD表征了腐蚀后复合材料表面的微观形貌和相组成。结果表明,随着Mg_2B_2O_5晶须体积分数的增加,AZ91D镁基复合材料的耐腐蚀性逐渐提高。当硼酸镁晶须的体积分数为35%时,材料的自腐蚀电位提高0.2V以上,自腐蚀流密度降低了1个数量级;SEM测试表明,复合材料表面生成了一层晶须增韧的腐蚀钝化膜,对基体起到保护作用。     

不同浓度Li2S04水溶液结构的X射线衍射研究

用θ—2θ型粉末衍射仪反射法精确测量了不同浓度的Li2SO4水溶液的衍射数据，通过数据处理给出了溶液的结构函数和径向分布函数，由几何结构模型的最小二乘法精修，得到了溶液中阳离子和阴离子第一、二水合层的结构参数。     

NH4Cl-CaCl2-H3BO3-H2O体系中H3BO3介稳区性质的研究

为探究南翼山油田水中NH_4Cl对H_3BO_3低温介稳区性质的影响,采用浊度法测量了253.15 K～303.15 K温度范围不同浓度的NH_4Cl对CaCl_2溶液中硼酸的溶解度影响和介稳区宽度;依次根据Nyvlt自洽方程理论求得成核级数m、经典三维成核理论求得固—液界面能γ,实验结果表明,CaCl_2溶液中的NH_4Cl对H_3BO_3溶解度影响很小;CaCl_2溶液中H_3BO_3的介稳区宽度随着NH_4Cl浓度的增加先变小后变大,氯化铵质量分数在0.12%～1.13%之间存在着一个临界值,此时硼酸的介稳区宽度最小。     

Microstructure of NH4Cl-NH3-H2O System Studied by ATR-FTIR, Raman and MD Simulation

The solubility of ammonium chloride in aqueous ammonia decreases then increases with increasing ammonia concentrations. The molecular mechanism behind this trend is unclear. In this study,ATR-FTIR and Raman spectroscopic techniques were used to determine the effect of ammonium chloride on hydrogen bonding in aqueous ammonia and ultimately explain the observed solubility trend. Spectral analyses were conducted in the wavelength range of 2500-4000 cm~(-1). The results showed that the addition of ammonium chloride endorses the formation of N-H…N hydrogen bonds between ammonium ions and ammonia molecules when the concentration of ammonia is greater than 10% ammonia. However,for concentrations lower than 10%,ammonium ions mainly bond to water molecules,leading to hydrogen bonds of the N-H…O type that are generally less stable than N-H…N bonds. The spectral analyses are confirmed by MD simulations. The results presented herein are useful in the development of novel techniques for the separation of ammonium potassium chloride.     

Fluxes of CO2 and CH4 in high latitude wetlands: measuring, modelling and predicting response to climate change

This review covers selected aspects of recent international efforts to measure and model greenhouse gas emission from northern wetlands, to identify the environmental factors that control gas emission, and to investigate wetlands'responses (particularly with respect to gas emission) to global change. Both bottom-up and top-to-bottom approaches, based respectively on local observations plus inventory of gas fluxes and inverse modelling of global circulation, agree on the size of the high latitude (>60_°N) contribution to global methane, which should be about 13% or 70 Tg/year. It has been shown that winter and spring fluxes are an essential part in the annual budget of CH₄ and especially CO₂ exchange (varying from 5 to 50%). Soil micro-organisms were shown to be able to respire during winter even at-16_°C. In comparison to aerobically respiring organisms, anaerobic methanogenic bacteria were less active in frozen soil, although they are subjected to significant stimulation by soil freeze-thaw cycles. The absence of immediate coupling of methanogenesis with plant photosynthesis implies that substrates for methane formation are derived from peat decomposition rather than from root exudation.     

崇明东滩湿地CO2 、CH4和N2O 排放的时空差异

通过静态暗箱—气相色谱法研究了长江口崇明东滩四类典型湿地(围垦湿地、高潮滩、中潮滩和低潮滩)CO₂、CH₄和N₂O排放特征及影响因素。结果表明,在生长季尺度下,CO₂、CH₄和N₂O均以排放为主;在昼夜尺度下,CO₂和CH₄在夜间排放量大于白昼排放量,而N₂O的排放高峰出现在下午;在潮水退去、潮滩暴露初期,CH₄和N₂O有大量排放,CO₂正好相反。崇明东滩温室气体排放通量自岸向海有明显的梯度变化,总体趋势是越近岸通量值越大。观测与实验表明,温度、潮汐、土壤理化性质、植物和土地利用变化都对温室气体排放通量有明显的影响,其中滨海潮滩湿地特有环境因子潮汐以"淹没—暴露"光滩沉积物的方式控制温室气体的排放。     

浓氯化钙水溶液中高配位Ca-Cl离子团簇:分子动力学模拟研究

采用分子动力学(MD)模拟研究了5.55 mol·kg~(-1)氯化钙溶液的微观结构特征,尤其是溶液中高配位Ca-Cl离子团簇的结构与性质,探究了温度对于高配位Ca-Cl离子团簇的影响。结果显示,5.55 mol·kg~(-1)氯化钙溶液中,除形成[CaCl]~+、[CaCl_2]~0离子对外,还存在一些高配位[CaCl_x]~(2-)~x(x=3～6)离子团簇。高配位[CaCl_x]~(2-)~x(x=3～6)离子团簇在5.55 mol·kg~(-1)氯化钙溶液中介稳存在,易解离或进一步缔合形成更大Ca-Cl离子团簇,这可能与溶液中大量未完全水合Ca~(2+)对高配位[CaCl_x]~(2-)~x(x=3～6)离子团簇水壳层的扰动破坏有关。温度升高,氯化钙溶液中Ca-Cl离子缔合增强,但高配位Ca-Cl离子团簇的平均存在时间(t_(av))减小,这表示高温下溶液中Ca-Cl离子团簇频繁地解离与缔合,离子团聚趋势更为显著。本工作观测到的高配位[CaCl_x]~(2-)~x(x=3～6)离子团簇可能是浓氯化钙溶液Ca-Cl离子缔合过程中一种热力学不稳定结构,但这些高配位Ca-Cl离子团簇的形成可能对溶液结晶及相关化学过程产生不利影响。     

Fe3O4/Mg(OH)2复合材料的制备及对铅离子的移除应用

通过种子沉积法制备出Fe_3O_4/Mg(OH)_2复合材料并进行了XRD、SEM、TEM、SAED测试分析。将该复合材料对水溶液中Pb~(2+)进行移除应用实验,接触时间为240 min时达到平衡。平衡时,水溶液中的Pb~(2+)超过90%被移除,移除量为950.8 mg/g。通过动力学研究发现,移除过程符合准二级动力学模型,这意味着移除过程中可能为化学吸附及沉淀过程。     

Magnetic properties of hydrothermally synthesized greigite (Fe3 S4 )—II. High- and low-temperature characteristics

The magnetic behaviour of hydrothermally synthesized greigite was analysed in the temperature range from 4 K to 700 °C. Below room temperature, hysteresis parameters were determined as a function of temperature, with emphasis on the temperature range below 50 K. Saturation magnetization and initial susceptibility were studied above room temperature, along with X-ray diffraction analysis of material heated to various temperatures. The magnetic behaviour of synthetic greigite on heating is determined by chemical alteration rather than by magnetic unblocking. Heating in air yields more discriminative behaviour than heating in argon. When heated in air, the amount of oxygen available for reaction with greigite determines the products and magnetic behaviour. In systems open to contact with air, haematite is the final reaction product. When the contact with air is restricted, magnetite is the final reaction product. When air is excluded, pyrrhotite and magnetite are the final reaction products; the amount of magnetite formed is determined by the purity of the starting greigite and the degree of its surficial oxidation. The saturation magnetization of synthetic greigite is virtually independent of temperature from room temperature down to 4 K. The saturation remanent magnetization increases slowly by 20–30 per cent on cooling from room temperature to 4 K. A broad maximum is observed at ~10 K which may be diagnostic of greigite. The coercive and remanent coercive force both increase smoothly with decreasing temperature to 4 K. The coercive force increases from ~50 mT at room temperature to approximately 100–120 mT at 4 K, and the remanent coercive force increases from approximately 50–80 mT at room temperature to approximately 110–180 mT at 4 K.