钴/锰印迹半胱氨酸-壳聚糖对低浓度Mn~(2+)和Co~(2+)的选择性吸附

同时以硝酸锰和硝酸钴为印迹分子,采用溶胶凝胶法和反相悬浮法结合制备了交联壳聚糖微球(Co/Mn-CCTS),并通过与半胱氨酸的氨基官能团接枝合成了钴/锰双印迹半胱氨酸-壳聚糖树脂(CysCo/Mn-CCTS)。采用傅里叶红外光谱、扫描电镜对其结构进行了表征,并进行了干扰离子存在下低浓度Co2+和Mn2+静态、动态以及竞争吸附实验。静态实验结果表明,双印迹半胱氨酸-壳聚糖树脂较非印迹树脂的吸附性能有较大提高;干扰离子存在下,树脂对Co2+、Mn2+二元混合溶液中Co2+的吸附性能优于Mn2+,且对Co2+的吸附容量超过Mn2+的16倍。溶液的pH值、温度、吸附时间、干扰离子以及金属离子初始浓度均对树脂的吸附性能有较大影响,树脂对Co2+、Mn2+的吸附过程符合Lagergren准二级动力学和Langmuir模型。动态吸附实验表明,树脂对Co2+、Mn2+的吸附符合Thomas模型,对二者的穿透体积分别为308BV与506BV。     

离子印迹壳聚糖/碳纳米管复合膜对U(Ⅵ)的选择性吸附研究

铀矿开采及铀分离纯化过程中产生的含铀废水可能严重污染环境和生态系统。利用吸附法分离含铀废水中的U(Ⅵ)既可有效回收铀资源,又能减轻环境污染。为达到高效分离含铀废水中U(Ⅵ)的目的,本文结合离子印迹及化学交联法制备了离子印迹壳聚糖(CS)/碳纳米管(CNT)(ICC)复合膜,采用静态吸附法考察了ICC对水溶液中U(Ⅵ)的吸附性能,并采用SEM、XRD、FTIR及XPS对吸附前后的ICC进行表征。表征结果表明,ICC具有多孔结构以及较丰富的功能基团(氨基、羧基),且CNT在壳聚糖基质中均匀分散。吸附实验结果表明：利用不同原料配比所制备的ICC中,以CS与CNT质量比为1∶0.3的ICC-2对U(Ⅵ)吸附性能最佳,是由于其具有丰富的孔结构以及经离子印迹产生的大量与铀酰离子匹配的空腔;ICC吸附U(Ⅵ)的吸附等温线符合Langmuir模型,在pH=5.0、298 K时,最大吸附容量达215.83 mg/g;吸附动力学符合准二级动力学模型,表明以化学吸附为控速步骤;ICC-2能选择性去除水溶液中的U(Ⅵ),且吸附过程为自发吸热过程。吸附U(Ⅵ)的ICC-2利用0.2 mol/L HNO_...     

锰印迹半胱氨酸-壳聚糖树脂的制备及其对低浓度Mn~(2+)的选择性吸附

以航空煤油为有机分散介质,环氧氯丙烷为交联剂,硝酸锰为印迹分子,采用反相悬浮和溶胶凝胶法结合制备交联壳聚糖微球(Mn-CCTS),并通过与半胱氨酸的羧基官能团接枝合成锰印迹吸附树脂(Cys-Mn-CCTS)。通过SEM扫描、傅里叶红外光谱对Cys-Mn-CCTS的结构进行了表征,并进行了低浓度Mn2+的静态吸附实验。研究表明,Cys-Mn-CCTS较Mn-CCTS吸附性能有显著提高,303K温度下,Cys-Mn-CCTS对5、10 mg/L的Mn2+的去除率由未接枝前的22.56%、16.26%分别提高至82.87%、82.56%;pH值在4~9范围内,Cys-Mn-CCTS对Mn2+的吸附性能基本不受影响,在pH值为5时吸附性能最佳,吸附容量和去除率分别为7.02mg/g和96.29%;树脂对Mn2+的去除率在2h后达到91.9%,吸附过程符合Lagergren准二级动力学方程;在干扰离子Ca2+和Mg2+总浓度达到200mg/L时,Cys-Mn-CCTS对Mn2+的吸附容量和去除率分别为2.16mg/g和29.6%,表现出一定的抗干扰能力。     

交联壳聚糖-亚铁氰化镍钾球形复合吸附剂制备及其对Cs~+吸附性能研究

通过反相悬浮-溶胶凝胶法制备了壳聚糖-亚铁氰化镍钾(CTS-KNiFC)球形复合吸附剂,分析测试了其对铯离子的选择性吸附性能,并利用傅里叶红外光谱和扫描电镜进行了样品表征。吸附动力学模型分析结果表明,CTS-KNiFC对Cs~+的吸附过程以化学吸附为主。静态吸附实验结果表明,吸附过程在5h左右能达到平衡。当溶液Cs~+初始浓度大于100mg/L时,CTS-KNiFC对铯离子的饱和吸附容量约为70mg/g。溶液的pH值以及溶液中Na~+和Mg~(2+)的共存对吸附效果影响不大,NH_4~+及K~+的存在则会对吸附过程有明显的抑制作用。利用Boyd液膜扩散模型和Weber-Morris颗粒内扩散模型对实验数据进行拟合,结果表明,颗粒内扩散和液膜扩散对吸附速率均有影响。CTS-KNiFC对Cs~+的吸附更符合Langmuir模型,表明吸附过程为单分子层吸附。     

水合二氧化锰对Co2+的吸附行为研究

以KMnO₄为原料合成了水合二氧化锰（HMO）,采用XRD、BET、TG-DTA和FT-IR对HMO进行了表征。在此基础上,研究了各实验条件对HMO吸附Co²⁺的影响,并将其用于含⁶⁰Co废水的实际处理研究。结果表明：HMO对溶液中的Co²⁺具有良好吸附能力,在pH=7、T=298 K条件下,其最大吸附量达132.98 mg/g;溶液pH值能显著影响Co²⁺在HMO上的吸附,在实验pH值范围内,吸附量随pH值增大而增加;在钴初始浓度相同的条件下,吸附量随温度升高而增加;Na⁺、K⁺、Mg²⁺、Ca²⁺、Zn²⁺、Fe³⁺等离子的存在对HMO吸附Co²⁺具有一定影响。HMO对Co²⁺的吸附过程符合准二级动力学模型（R²＞0.99）,推测吸附过程中可能存在一定的化学吸附;吸附热力学行为可用Langmuir等温吸附方程进行描述（R²＞0.99）,表明Co²⁺在HMO上为单分子层吸附;由吸附热力学数据ΔH=46.96 kJ/mol、ΔG=-26.09 kJ/mol可知,此吸附行为是自发进行的吸热反应。另外,在实际处理含⁶⁰Co废水的动态柱实验中,HMO对初始放射性浓度为2.78×10⁵ Bq/L的⁶⁰Co废液的去除率可达56.90%。     

Fe3O4/改性壳聚糖磁性微球对Hg2+和UO22+的吸附

利用反相悬浮分散法和聚乙二胺改性制备成Fe3O4/壳聚糖磁性微球(PEMCS)以提高其氨基含量.采用X射线衍射(XRD)、红外(IR)、热重分析(TGA)等对其进行了表征,考察PEMCS对Hg2 和UO22 的吸附性能.结果表明,其吸附剂粒径小(15-30 μm),吸附速率快;当氨基含量6.47 mmol/g、pH＜3时可选择性分离Hg2 和UO22 ,因Hg2 能与Cl-形成络阴离子(HgCl3-),以离子交换机理吸附,而UO2 2则不能.对Hg2 与UO22 的饱和吸附容量qm(mmol/g)分别为2.19与1.38.动力学数据采用Lagergrent拟合,对Hg2 与UO22 的吸附速率常数Kad(min-1)分别为0.087和0.055.UO2 2和Hg2 可用1 mol/L H2SO4脱附,UO2 2还可用2 mol/L HCl脱附,脱附率＞90%.     

壳聚糖-生物炭复合材料对U(Ⅵ)的吸附性能试验研究

以壳聚糖（CTS）和生物炭（AC）为原料,采用原位沉淀法制备了壳聚糖-生物炭（CTS-AC）复合材料,研究了吸附时间、铀初始浓度、初始pH值、温度和干扰离子等因素对CTS-AC吸附U(Ⅵ)的影响,探讨了CTS-AC对U(Ⅵ)的吸附动力学、等温线,采用傅里叶红外光谱（FT-IR）、X射线衍射（XRD）、扫描电镜（SEM-EDS）及比表面积分析（BET）等手段进行了相关机理分析。实验结果表明,CTS-AC吸附U(Ⅵ)的最佳条件为：pH=4、CTS-AC投加量0.8～1 g/L、吸附时间240 min,在此条件下,最大吸附率可达94.85%。CTS-AC对U(Ⅵ)的吸附等温线模型符合Langmuir模型,U(Ⅵ)的吸附动力学符合准二级模型;高浓度Cu²⁺对CTS-AC吸附U(Ⅵ)的抑制作用明显;FT-IR、XRD和EDS结果表明,CTS的负载未改变AC的原结构,仅增大了其孔径、增加了结合位点。CTS-AC对U(Ⅵ)的吸附机制为配位作用以及离子交换。     

磁性氧化石墨烯/壳聚糖纳米复合材料的制备及其对UO_2~(2+)的吸附性能

以氧化石墨烯和壳聚糖为原料,1-乙基-(3-二甲基氨基丙基)3-乙基碳二亚胺盐酸盐(EDC)和N-羟基琥珀酰亚胺(NHS)为活化剂,超声法制备了磁性氧化石墨烯/壳聚糖纳米复合材料(MCGO),并研究了其对水溶液中UO_2~(2+)的吸附性能。SEM、FT-IR和XRD分析结果表明,成功制得了MCGO,且负载的Fe_3O_4尺寸为nm级。在温度为288K、pH=5.5、UO_2~(2+)初始浓度为160 mg/L、吸附时间为1.5h时,MCGO吸附容量为266.67mg/g。对实验数据进行热力学和动力学模型拟合,结果表明,MCGO吸附行为符合Langmuir模型和准二级动力学模型,且吸附为吸热自发过程。MCGO第1次重复利用率高达98.47%,经过6次吸附-脱附后,重复利用率仍有74.43%,具有较好的重复利用性。     

Removal of Co2+ from radioactive wastewater by polyvinyl alcohol (PVA)/chitosan magnetic composite

Cobalt is one of the toxic radioactive elements and the removal of Co²⁺ from radioactive wastewater has received increasing attention in recent years. In this paper, polyvinyl alcohol (PVA)/chitosan magnetic composite was prepared and used for Co²⁺ removal. The effect of initial pH, contact time and initial Co²⁺ concentration on Co²⁺ adsorption was investigated. The kinetics, thermodynamic and isotherms of Co²⁺ sorption onto the composite were determined. The results showed that pseudo second-order equation could be used to describe the Co²⁺ removal process. The maximum sorption capacity was calculated to be 14.39 mg/g at pH 6.0 and 30 °C using the Langmuir model. The analysis of FTIR and SEM-EDAX were performed before and after Co²⁺ sorption onto the PVA/chitosan magnetic beads, revealing that the functional groups –NH₂ and –OH played main role in Co²⁺ sorption process. PVA/chitosan magnetic composite is promising adsorbent for removing Co²⁺ radioactive wastewater.     

电动势法研究HAN与Fe3+氧化还原反应动力学

采用电动势法研究了硝酸体系中硝酸羟胺(HAN)还原Fe3+离子的反应动力学,得到了动力学表观速率方程-dc(Fe3+)/dt=kc0.62(HAN)c-2.80(H+)c(Fe3+)c-0.85(Fe2+);当温度为50℃、离子强度I=1.0mol/L时,表观速率常数k=(2.9±0.1)×10-6(mol/L)3.02/s,反应表观活化能Ea=(125±3)kJ/mol。硝酸根的存在对反应起到抑制作用,离子强度的增大对反应有促进作用。     

Combined Rietveld refinement of Zn2SiO4:Mn2+ using X-ray and neutron powder diffraction data

The behavior of Mn²⁺ ions doped into the crystal lattice of Zn₂SiO₄ is closely related to the luminescent properties of Zn₂SiO₄:Mn²⁺ as a color-emitting phosphor. The combined Rietveld refinement using X-ray and neutron powder diffraction was used to determine the site preference and the amount of Mn²⁺ ions in Zn₂SiO₄:Mn²⁺. Of possible cation-disorder models, the best Rietveld refinement was obtained from the model that Mn²⁺ ions partially substituted for Zn²⁺ ions in two crystallographically non-equivalent Zn sites. The final converged weighted R-factor, R_wp, and the goodness-of-fit indicator, S (=R_wp/R_e) were 8.12% and 2.28, respectively. The occupancy of Mn²⁺ ions for the two non-equivalent Zn sites was 0.034(4) and 0.003(2), respectively. The refined model described the crystal structure in space group R?3 (No. 148) with Z = 18, a (=b) = 13.9612(1) Å, c = 9.3294(1) Å and γ = 120°.     

Plasma-assisted Co/Zr-metal organic framework catalysis of CO_2 hydrogenation:influence of Co precursors

In this study, Co/Zr-metal organic framework(MOF) precursors were obtained by a roomtemperature liquid-phase precipitation method and the equivalent-volume impregnation method,respectively, using a Zr-MOF as the support, and Co/Zr-MOF-M and Co/Zr-MOF-N catalysts were prepared after calcination in a hydrogen–argon mixture gases(V_(Ar):V_(H_2)= 9: 1) at 350 °C for 2 h. The catalytic activities of the prepared samples for CO_2 methanation under atmosphericpressure cold plasma were studied. The results showed that Co/Zr-MOF-M had a good synergistic effect with cold plasma. At a discharge power of 13.0 W, V_(H_2):V_(CO_2)= 4: 1 and a gas flow rate of 30 ml·min~(-1), the CO_2 conversion was 58.9% and the CH_4 selectivity reached 94.7%,which was higher than for Co/Zr-MOF-N under plasma(CO_2 conversion 24.8%, CH_4 selectivity 9.8%). X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N_2 adsorption and desorption(Brunauer–Emmett–Teller) and x-ray photoelectron spectroscopy analysis results showed that Co/Zr-MOF-M and Co/Zr-MOF-N retained a good Zr-MOF framework structure, and the Co oxide was uniformly dispersed on the surface of the Zr-MOF. Compared with Co/Zr-MOF-N, the Co/Zr-MOF-M catalyst has a larger specific surface area and higher Co~(2+)/Cototaland Co/Zr ratios. Additionally, the Co oxide in Co/ZrMOF-M is distributed on the surface of the Zr-MOF in the form of porous particles, which may be the main reason why the catalytic activity of Co/Zr-MOF-M is higher than that of Co/ZrMOF-N.     

乙二胺改性壳聚糖磁性微球吸附Hg

采用化学交联-种子溶胀法制得乙二胺改性壳聚糖磁性微球(EMCS),考察了其对水溶液中Hg2 和UO22 的吸附性能。结果表明,EMCS粒径为50-80μm,氧化铁质量分数(w)为16%,该吸附剂在pH<2.5时可选择性吸附Hg2 和UO22 ,吸附容量随pH升高而增加;其吸附等温线用Langmuir方程拟合为:ceq/Qeq=0.440 5ceq/Qm 0.584 0(Hg2 ,r=0.996 0),ceq/Qeq=0.525 6ceq/Qm 1.343 4(UO22 ,r=0.990 6);饱和吸附容量Qm分别为2.27,1.90 mmol/g,高于磁性壳聚糖微球MCS和壳聚糖微球CS;其吸附动力学可用Lagerg-ren方程拟合为:lg(Qeq-Q)=0.361 2-0.015 5t(Hg2 ,r=0.982 1),lg(Qeq-Q)=0.302 7-0.011 2t(UO22 ,r=0.992 5);对Hg2 ,UO22 的吸附速率常数(kad)分别为0.036,0.026 min-1;EMCS可用1 mol/LH2SO4再生,脱附率大于90%,有良好的重复使用性。