201×7强碱性阴离子交换树脂吸附浓海水中溴的热力学研究

研究了201×7强碱性阴离子交换树脂吸附浓海水中溴的热力学行为,测定了不同温度下的吸附等温线,并计算出吸附过程的热力学参数ΔG、ΔH和ΔS。研究表明,该树脂对溴的吸附容量为2.489mg Br2/mL湿树脂,吸附率达到98%;吸附平衡数据符合Langmuir吸附等温方程;ΔG为负值,该吸附过程可自发进行;ΔH>0,且其绝对值小于40kJ/mol,表明该吸附过程吸热且属于物理吸附;ΔS>0,该吸附过程属于熵增过程。     

碧螺春绿茶对碱性染料灿烂绿的吸附

为了探讨碧螺春茶叶用于吸附灿烂绿的可能性,研究了碧螺春绿茶吸附灿烂绿的最佳吸附条件及解吸附条件。研究结果表明,在吸附条件为当溶液起始p H值为4.1,茶叶与灿烂绿质量比为833∶1,接触时间为45 min,室温(25±1)℃时,茶叶对灿烂绿吸附率达80%,吸附量为0.96 mg/g。对Na OH、CH_3COOH和HCl3种解吸附剂的研究表明,最佳解吸附剂是Na OH,解吸1.5 h解吸率最高达93.20%。该吸附过程符合Langmuir等温吸附方程,属于单分子层吸附。吸附过程热力学参数自由能变化ΔG0,焓变ΔH=102.32 k J/mol0,熵变ΔS=0.33 k J/(mol·K)0,说明吸附过程是自发的吸热熵增过程。     

BSA在不同形貌氧化锌材料上的吸附热力学

采用高分子模板法合成了4种不同形貌的ZnO,分别为球状颗粒(ZnO NPs)、针状(ZnO NRs)、片状(ZnO NSs)和棒状(ZnO NBs).利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和能谱仪(EDS)对产物进行了表征.通过傅里叶变换红外光谱仪(FTIR)和圆二色光谱仪(CD)研究了小牛血清白蛋白(BSA)在不同形貌ZnO上的等温吸附规律、吸附热力学和吸附作用机理.结果表明,4种不同形貌的ZnO对BSA的吸附均较好地符合Langmuir等温吸附模型;吸附量随温度的升高略有增加;从热力学参数(ΔG,ΔH,ΔS)可知,吸附反应为自发进行的吸热反应,作用机理主要为氢键和静电作用.从热力学角度,针状的ZnO更有利于BSA的吸附.     

两种大孔吸附树脂对麻黄碱和伪麻黄碱的吸附动力学和热力学研究

通过等温静态吸附实验研究大孔树脂AB-8和D101对麻黄碱及伪麻黄碱的等温吸附过程,根据Langmuir平衡吸附速率方程考察两种树脂对两种成分吸附的平衡速率常数,用Van’t Hoff公式计算各热力学参数(ΔHm,ΔGm及ΔSm)。结果表明麻黄碱、伪麻黄碱的吸附平衡数据符合Freundlich吸附等温方程和Langmuir平衡吸附速率方程,相关性良好。吸附的焓变(ΔHm)和熵变(ΔSm)均大于零,吉布斯自由能变(ΔGm)均小于零,表明麻黄碱及伪麻黄碱在树脂上的吸附属于自发的物理吸附过程。     

原位合成羟基磷灰石/壳聚糖复合吸附剂及除氟特性研究

利用原位共沉淀法合成了羟基磷灰石/壳聚糖复合吸附剂,通过扫描电镜、X射线粉末衍射、红外光谱和N2吸附-脱附曲线,研究复合前后羟基磷灰石的理化特征变化。实验结果表明与壳聚糖复合后羟基磷灰石的晶型并没有改变,只是结晶度有所降低,且复合后表面形成了不规则的凹凸结构,表面粗糙度增加。比表面积从106.75m2/g增加到127.58m2/g。复合吸附剂孔径大部分集中在10~50nm,属于介孔结构。利用Langmuir和Freundlich吸附等温方程对实验数据进行了拟合,对比相关系数R2值,Langmuir模型能更好地描述该吸附过程。复合吸附剂对氟离子的吸附符合拟二级反应动力学方程。计算了吸附热力学和动力学参数值,探讨了复合吸附剂对氟离子的吸附机理。ΔG0<0、ΔH0>0和ΔS0>0,说明复合吸附剂对氟离子的吸附是自发的、吸热的熵增过程,温度升高有利于吸附。吸附活化能(Ea)=15.03kJ·mol-1,迁移能(E)=7.639kJ·mol-1,说明该吸附过程以物理吸附为主。     

碳纳米管吸附水溶液中双酚A的热力学

以甲醇和去离子水组成的体系（体积比90∶10）为流动相,建立了以香烟过滤嘴作吸附剂,固相萃取（SPE）与高效液相色谱（HPLC）联用测定水中双酚A(Bisphenol A,BPA)的新方法。研究了水溶液中碳纳米管(CNTs)吸附双酚A的热力学特性,测定了不同温度下的吸附等温线,并探讨了其可能的吸附机理。结果表明,CNTs对BPA 的吸附主要以快速吸附为主,常温下,碳纳米管对于70 mg·L-1的双酚A水溶液的吸附量可达到 24.65 mg g-1,吸附量随初始浓度的增加而增加,随温度的降低而增大,采用Freundlich和Langmuir方程拟合,相关系数均大于0.99,热力学函数ΔG、ΔH及ΔS分别为-39.48 ~ -43.51 KJ·mol-1、-18.06 KJ·mol-1、71.73 J·mol-1·K-1,吸附为放热、熵增的自发过程,降低温度有利于吸附,并且具有物理吸附特征。     

羟基磷灰石及其复合材料对重金属的吸附研究进展

羟基磷灰石具有特殊的晶体结构,对二价的重金属离子有很强的结合力,是一种可用于环境污染治理的新型功能性材料。它可有效地吸附去除水中的Pb2+,Cd2+,Cu2+,Zn2+,Co2+,Ni2+等重金属离子,但其粉体的结构却限制了它在水环境中的实际应用。随着纳米技术、复合材料技术的发展,在羟基磷灰石的基础上开发出的具有高效吸附性能或分离特性的新型材料在重金属吸附研究中显示了潜在的优势。本文综述了羟基磷灰石及其复合材料对水中重金属去除方面的研究进展,探讨了它对重金属吸附机理,并对羟基磷灰石进一步的研究提出了展望。     

D-101大孔吸附树脂对黄花蒿黄酮的吸附热力学和动力学研究

通过静态吸附实验,研究了D-101大孔吸附树脂对黄花蒿黄酮的吸附热力学和动力学过程。结果表明,当温度在298~318K和在实验研究浓度范围内,D-101大孔吸附树脂对黄花蒿黄酮的吸附符合Freundlich等温吸附方程;ΔG0,吸附过程能自发进行;ΔH0,为放热过程;ΔS0,D-101大孔吸附树脂吸附黄花蒿黄酮的作用大于水的解吸过程,导致熵减。分别采用准一级动力学方程、准二级动力学方程和粒内扩散动力学模型探讨其吸附特性,研究结果表明,吸附过程符合准二级动力学方程,粒内扩散与膜扩散交互控制黄花蒿黄酮在D-101大孔吸附树脂上的吸附。     

硅胶的表面硫醇化改性及对水溶液中罗丹明B的固载

运用γ-巯丙基三乙氧基硅烷对硅胶表面硫醇化修饰改性,红外及拉曼光谱分析表明硅胶的表面硫醇化借助硅胶表面羟基与γ-巯丙基二乙氧基硅烷间的化学键联实现。实验条件下改性硅胶对水体罗丹明B的吸附性能明显提升,改性硅胶表面罗丹明B的吸附动力学符合准二级动力学模型,吸附等温线服从Langmuir等温线规律,由等温吸附计算得到的热力学函数变化表明吸附系自发、放热过程。吸附动力学、热力学及光谱表征均表明改性硅胶上罗丹明B的吸附主要为其在改性硅胶表面借助电价和共价键联的化学吸附。     

大孔吸附树脂对湖南黑茶茶多酚的吸附热力学和动力学研究

以湖南黑茶为原料,采用超声法提取湖南黑茶中茶多酚,后通过静态吸附和解吸实验,对5种大孔吸附树脂进行筛选,研究大孔吸附树脂对湖南黑茶茶多酚的吸附热力学和动力学。结果表明,大孔吸附树脂D-101对湖南黑茶茶多酚有较大的吸附量、较强的解吸能力。大孔吸附树脂D-101对黑茶茶多酚的吸附符合Freundlich等温吸附方程;且ΔH0、ΔG0、ΔS0,表明黑茶茶多酚在大孔吸附树脂D-101上的吸附属于可自发进行的物理吸附,吸附过程为放热、熵减过程。吸附动力学研究结果表明,准二级动力学方程的计算值与实验值吻合较好,适合描述大孔吸附树脂D-101对黑茶茶多酚的吸附过程。     

Humic acid sorption onto a quartz sand surface: A kinetic study and insight into fractionation

A kinetic study of Aldrich humic acid sorption onto a quartz sand surface has revealed an initial rapid uptake of humic acid molecules followed by a much slower sorption. The humic acid molecular weight and chemical fractionation resulting from adsorption onto the simple quartz sand surface were investigated for the two kinetic steps by coupled asymmetric flow-field flow fractionation-UV/visible absorption spectrophotometry. The molecular weight distribution of residual humic acid in solution after adsorption deviated from the original molecular weight distribution, showing preferential adsorption of certain molecular weight components. This fractionation is different after the two kinetic steps. Humic acid molecules characterised by a molecular weight below 4800 Da and with a weight-average molecular weight (M(w)) of 1450 Da were adsorbed after the fast kinetic step, whereas humic acid molecules in the molecular weight range 1400-9200 Da and of M(w) 3700 Da were adsorbed after the slower uptake. Therefore, the adsorption of low molecular weight humic components takes place initially, and is then followed by the adsorption of higher molecular weight components. Chemical adsorptive fractionation, investigated by studying the 253 nm/203 nm absorbance ratio over time, shows that aromatic components are preferentially adsorbed during the fast kinetic step. The fractionation pattern may be explained by the physicochemical characteristics of the Aldrich humic acid and the underlying sorption processes. The trend for the sorption kinetics of europium onto the quartz sand surface in the presence of humic acid is similar to that of the humic acid itself.     

冲积平原区土壤中重金属元素的存在形态分析

采用0.1mol／L氢氧化钠浸提腐殖酸的方法,将土壤中的腐殖酸及与腐殖酸结合的重金属元素分离出来;分别用分光光度法、原子荧光光谱法、等离子质谱法测定样品中腐殖酸及重金属元素的含量;初步测定结果显示：与腐殖酸结合的重金属元素是冲积平原区表层土壤中重金属元素的1种重要存在形态,而且可能是土壤中重金属污染元素主要的存在形式。     

Humic acid adsorption on fly ash and its derived unburned carbon

Fly ash is solid waste from combustion process, containing oxide minerals and unburned carbon. In this investigation, fly ash has been separated into metal oxide mineral section and unburned carbon. The fly ash with different contents of unburned carbon was employed for humic acid adsorption to investigate the influence of unburned carbon on adsorption. It is found that metal oxides and unburned carbon in fly ash exhibit significant difference in humic acid adsorption. The unburned carbon plays the major role in adsorption. Higher content of unburned carbon in fly ash results in higher surface area and thus higher humic acid adsorption. Fly ash and unburned carbon exhibit adsorption capacity of humic acid of 11 and 72 mg/g, respectively, at 30 degrees C, pH 7. Humic acid adsorption is also affected by ion strength, pH, and temperature. The thermodynamic calculations indicate that the adsorption is endothermic nature with DeltaH(0) and DeltaS(0) as 5.79 kJ/mol and 16.0 J/K mol, respectively.     

Solvation Excess of Urea over Water in Humic Acid in Three-Component Solutions Saturated with the Biopolymer

Humic acids were extracted from brown coals of the Kara-Keche deposit (Kyrgyzstan) and characterized. The solubility of humic acid in aqueous urea solutions was studied. The solvation excess of urea over water on humic acid in solution was calculated. The possibility of simultaneous binding of urea molecules on three independent centers of humic acids was shown. An estimation of humic acid molecular dimensions in aqueous urea solutions is given.     

有机改性凹凸棒土对腐殖酸的吸附性能研究

合成了十六烷基三甲基氯化铵(CTAC)改性的凹凸棒土吸附剂,并研究了其对水中腐殖酸的吸附行为。通过FTIR、TG对改性前后凹凸棒土进行表征。结果表明,十六烷基三甲基氯化铵成功结合到凹凸棒土表面,结合到凹凸棒土表面的量为9.78%。在25℃时,腐殖酸在吸附剂上吸附行为符合Freundlich方程,吸附动力学符合拟二级动力学方程,初始浓度为54.60~200.20mg/L时,ATP-CTAC对腐殖酸的最大吸附量为253mg/g;温度对吸附行为影响不大;改性后的凹凸棒土对腐殖酸的吸附随pH的增大而降低;改性后的凹凸棒土显著地提高了对腐殖酸的吸附量。     

Environmental photochemistry: Electron transfer from excited humic acid to TiO2 colloids and semiconductor mediated reduction of oxazine dyes by humic acid

The ability of naturally occurring Suwanee River Humic acid to sensitize a large bandgap semiconductor such as colloidal TiO₂ has been investigated by fluorescence emission. The charge injected from the humic acid sensitizer into the semiconductor was used to reduce a series of oxazine dyes viz:, N,N,N’,N’-tetraethyloxonine and Nile Blue A. The mechanism of such a sensitized reduction process was elucidated by laser flash photolysis methods. The quantum yield for such a reduction calculated from these transient absorption techniques was 0.005.     

Ultrafiltration of protein and humic substances: effect of solution chemistry on fouling and flux decline

The rate and extent of adsorption of a protein and a humic acid onto membranes was measured at varying conditions of pH and ionic strength. The resistance-in-series approach was used to calculate reversible and irreversible fouling resistances, which were then compared for static (no flow) and dynamic runs in order to determine the effect of convective flow and electrostatic interactions on fouling behavior. Although convective forces tended to increase the amount of material accumulated near the membrane surface, electrostatic interactions played a stronger role, as evident in the irreversible adsorption results for the static and dynamic cases. Electrostatic interactions affected reversible and irreversible resistances. Both resistances were higher at the isoelectric point (iep) of the protein and decreased at higher pH values. Humic acid adsorption decreased as pH was increased from 4.7 to 10. Humic acid filtration resulted in a higher resistance per unit mass than protein filtration.     

Quantification of refractory organic substances in freshwaters: further insight into the response of the voltammetric method

A recently published method for quantifying refractory organic matter (often referred to as humic substances) in freshwaters was applied to a wide range of International Humic Substance Society (IHSS) humic compounds in order to (i) gain a better understanding of the mechanism of the voltammetric response which is the basis of the analytical method and (ii) provide guidance on choosing the optimal standard to be used. At the same time, the sensitivity of the technique has been increased by switching from the pulse mode initially proposed to the square-wave mode. The results obtained show that (i) differences in adsorption onto the electrode rather than differences in complexation strength are responsible for the differences in the intensity of the signal obtained for the different humic compounds, (ii) carboxylate, N- and S-containing groups do not play a role in the voltammetric signal.     

腐植酸类物质应用研究进展

腐植酸作为一种资源广泛存在于自然界中,它是影响环境生态平衡的重要因素,也是潜在的、可大力开发和综合利用的有机资源.腐植酸类物质具有多种活性官能团,具有酸性、亲水性、界面活性、阳离子交换能力、络合作用及吸附分散能力.本文对腐植酸进行了分类,综述了其应用领域以及腐植酸类物质应用中存在的问题和应用前景.     

Adsorption and rheological characteristics of humic acid salts at liquid-gas interfaces

Du Noöy ring and oscillating droplet methods are used to study the adsorption and dilatation rheological characteristics (viscoelastic modulus and phase angle) of aqueous solutions of humic acid salts at liquid-gas interfaces. It is established that the equilibrium surface tension and limiting surface elasticity of humic acid salt solutions are in good agreement with the model of a real two-dimensional solution that was previously proposed for biopolymers. Based on the results of analyzing dynamic surface tension and adsorption kinetics, it is shown that humic acid salts are characterized by a nondiffusion (barrier) adsorption mechanism.