Hierarchical Reduced Graphene Oxide-MnO_(2)@Polypyrrole Coaxial Nanotube Composite Hydrogel as a Potential Adsorbent for Cr(Ⅵ)Removal

A hierarchical reduced graphene oxide-MnO_(2)@polypyrrole coaxial nanotube composite hydrogel was prepared via oxidative polymerization of pyrrole in the presence of MnO_(2)nanotubes,followed by the hydrothermal treatment of graphene oxide and MnO_(2)@polypyrrole coaxial nanotubes.The stable composite hydrogel with a hierarchical network was composed of one-dimensional MnO_(2)@polypyrrole coaxial nanotube and two-dimensional graphene nanosheet and characterized by scanning electron microscope,Fourier transform infrared spectroscopy,X-ray diffraction,Brunauer-Emmett-Teller surface,and X-ray photoelectron spectroscopy measurements.The composite hydrogel can be used as an efficient adsorbent for Cr(Ⅵ)removal due to the synergistic interaction between graphene and MnO_(2)@polypyrrole and the hierarchical structure of the hydrogel.Moreover,the composite hydrogel is easily separated because of its stable monolith,and it is reusable(76.8%of removal ability remaining after five adsorption-desorption cycles).The simple fabrication and cost-effective separation process together with the excellent absorption performance endow the composite hydrogel with great potential for practical wastewater treatment.

Efficient removal of Al(Ⅲ)and P507 from high concentration MgCl_(2)solution based on in-situ reaction strategy

For a highly efficient recycling of a wastewater containing a high concentration of MgCl_(2),Al(Ⅲ)and P507 were scheduled to be removed in advance.In this study,the in-situ removal of Al(Ⅲ)and P507 from a high concentration MgCl_(2)solution at different pH values and Al/P molar ratios was investigated.The results showed that P507 formed organic complexes of Al_(x)(OH)_y^(Z+)-P507 at pH of 2.0-4.0.At pH of 4.0-5.0,Al(Ⅲ)precipitated and transferred into Al(OH)_(3)with a flocculent amorphous morphology.Active sites on the Al(OH)_(3)surface enhanced the removal efficiency of P507.At pH of 6.0-6.5,Al(Ⅲ)and Mg(Ⅱ)formed layered crystalline Al(OH)_(3)and MgAl_(2)(OH)_(8with)small pore channels and fewer active sites,resulting in a reduced removal efficiency of P507.When the Al/P molar ratio exceeded 13 and the pH was between 4.0 and 5.0,the removal rates of both Al(Ⅲ)and P507 were higher than98%,while the concentration loss of Mg(Ⅱ)was only 0.2%-0.9%.

TiO2-PES Fibrous Composite Material for Ammonia Removal Using UV-A Photocatalyst

This study focused on the development and characterization of TiO2-PES composite fibers with varying TiO2 loading amounts using a phase inversion process. The resulting composite fibers exhibited a sponge-like structure with embedded TiO2 nanoparticles within a polymer matrix. Their photocatalytic performance for ammonia removal from aqueous solutions under UV-A light exposure was thoroughly investigated. The findings revealed that PeTi8 composite fibers displayed superior adsorption capacity compared to other samples. Moreover, the study explored the impact of pH, light intensity, and catalyst dosage on the photocatalytic degradation of ammonia. Adsorption equilibrium isotherms closely followed the Langmuir model, with the results indicating a correlation between qm values of 2.49 mg/g and the porous structure of the adsorbents. The research underscored the efficacy of TiO2 composite fibers in the photocatalytic removal of aqueous under UV-A light. Notably, increasing the distance between the photocatalyst and the light source resulted in de-creased hydroxyl radical concentration, influencing photocatalytic efficiency. These findings contribute to our understanding of TiO2 composite fibers as promising photocatalysts for ammonia removal in water treatment applications.

C50混凝土的制备及其对Cs^(+)、Ni^(2+)的吸附性能研究

为研究处置库屏障材料混凝土对放射性核素的阻滞能力,制备了C50混凝土材料并研究其对放射性核素的吸附能力。发现屏障材料C50混凝土主要由含钙和铝的硅酸盐矿物组成,其在微观尺度下呈现不规则多面体与板层结构,比表面积为2.786 m^(2)·g^(-1),且具有较强的非定形特征。通过吸附试验,发现实验条件下C50混凝土对Cs^(+)、Ni^(2+)具有较好的吸附能力,达到平衡后对Cs^(+)的K_(d)值达到19.400 L·mg^(-1),吸附容量达到0.316 mg·g^(-1);吸附Ni^(2+)的K_(d)值达到465.142 L·mg^(-1),吸附容量达到96.375 mg·g^(-1)。随着Cs^(+)、Ni^(2+)初始浓度的增大,C50混凝土对Cs^(+)的K_(d)值逐渐减小后趋于稳定,对Ni^(2+)的K_(d)值逐渐减小后稳定增大,吸附容量均逐渐增大。通过环境因素影响试验,发现实验条件下pH对C50混凝土吸附Cs^(+)的影响相对较小,C50混凝土对Ni^(2+)的能力随着pH上升而增大。不同离子对Cs^(+)抑制作用由大到小的顺序依次为:K^(+)、Ca^(2+)、Mg^(2+)、SO_(4)^(2-)、Cl^(-)、NO_(3)^(-),随着温度的升高,C50混凝土对Cs^(+)的吸附能力缓慢减小;对Ni^(2+)抑制作用从大到小的顺序依次为:Mg^(2+)、Ca^(2+)、SO_(4)^(2-)、CO_(3)^(2-)。Ni^(2+)的吸附能力随着温度上升缓慢增大。研究结果可为处置库的建设提供基础数据支持。

Al/Ga离子替换提升Ni^(2+)掺杂尖晶石结构MgAl_(x)Ga_(2-x)O_(4)近红外二区发光特性

近红外荧光转换发光二极管(pc-LED)在成像和检测领域的快速发展突显了对近红外二区(NIR-Ⅱ区)发光材料的迫切需求。然而,商用紫外LED芯片激发的高效NIR-Ⅱ荧光材料匮乏,制约了近红外光谱技术的应用。本文通过高温固相法成功制备了MgAl_(x)Ga_(2-x)O_(4)∶Ni^(2+)荧光材料,该材料的激发波长为390 nm,发射峰位于1300 nm,覆盖了NIR-Ⅱ区域。半高宽约为220 nm的超宽带NIR发射是由于Ni^(2+)处于一个弱晶体场环境中,这种环境是由于MgAl_(x)Ga_(2-x)O_(4)基体中[(Al/Ga)O_(6)]八面体中心周围的高电荷极化导致的空间不对称畸变造成的。通过改变体系中Al^(3+)与Ga^(3+)的离子比例,将NIR-Ⅱ区的发射强度大大提高,发光强度提升为原来的9倍左右。着重研究了Ni^(2+)掺杂最优比例MgAl_(1.5)Ga_(0.5)O_(4)的光谱特性。探讨了体系的温度特性,使用掺Ni^(2+)的近红外荧光粉和商业高效紫外LED芯片(@395 nm)构建了NIR pc-LED,研究表明该材料体系可能在pc-LED光谱技术中展现出较大潜力。这种阳离子调制策略将给近红外发光材料的性能提升提供有效的方法。

Controllably partial removal of thiolate ligands from unsupported Au_(25) nanoclusters by rapid thermal treatments for electrochemical CO_(2)reduction

Colloidal synthesis of metal nanoclusters will inevitably lead to the blockage of catalytically active sites by organic ligands.Here,taking[Au_(25)(PET)_(18)]-(PET=2-phenylethanethiol)nanocluster as a model catalyst,this work reports a feasible procedure to achieve the controllably partial removal of thiolate ligands from unsupported[Au_(25)(PET)_(18)]-nanoclusters with the preservation of the core structure.This procedure shortens the processing duration by rapid heating and cooling on the basis of traditional annealing treatment,avoiding the reconfiguration or agglomeration of Au_(25)nanoclusters,where the degree of dethiolation can be regulated by the control of duration.This work finds that a moderate degree of dethiolation can expose the Au active sites while maintaining the suppression of the competing hydrogen evolution reaction.Consequently,the activity and selectivity towards CO formation in electrochemical CO_(2)reduction reaction of Au_(25)nanoclusters can be promoted.This work provides a new approach for the removal of thiolate ligands from atomically precise gold nanoclusters.

蓝光激发的KMgF_(3)∶Cr^(3+)/Ni^(2+)基透明微晶玻璃超宽带近红外发光

近红外光谱技术在食品科学、信息安全、生物医疗等重大国计民生领域的应用对近红外光源提出了越来越高的要求。研发具有高效超宽带发射的近红外光源因此成为一项重要且迫切的研究课题。本文采用熔融淬火法在氟硅酸盐玻璃体系SiO_(2)-K_(2)CO_(3)-KF·2H_(2)O-MgF_(2)中成功析出了钙钛矿型KMgF_(3)纳米晶体。通过改变玻璃组分和热处理温度可以调控氟化物纳米晶相的析出,得到析晶和透明度最佳的微晶玻璃样品。玻璃中KMgF_(3)纳米晶体为Cr^(3+)和Ni^(2+)提供了稳定的八面体配位和低声子能量发光环境,在450 nm蓝光激发下,基于Cr^(3+)到Ni^(2+)的能量传递实现了Cr^(3+)(700~1200 nm)和Ni^(2+)(1400~1700 nm)双宽带近红外发射,并且双宽带近红外发光强度随离子掺杂浓度而可调变化。荧光光谱和荧光衰减曲线表征证明了Cr^(3+)到Ni^(2+)的能量传递过程,对应的能量传递效率为52.2%,能量传递机制为电子偶极-四极相互作用。研究结果不仅可以为系统掌握透明光学材料的超宽带发光规律提供基础数据,同时有助于设计开发低成本、高效率的近红外宽带光源。

Highly Selective Electrocatalytic CuEDTA Reduction by MoS_(2) Nanosheets for Efficient Pollutant Removal and Simultaneous Electric Power Output

Electrocatalytic reduction of ethylenediamine tetraacetic acid copper(CuEDTA),a typical refractory heavy metal complexation pollutant,is an environmental benign method that operates at mild condition.Unfortunately,the selective reduction of CuEDTA is still a big challenge in cathodic process.In this work,we report a MoS_(2) nanosheet/graphite felt(GF)cathode,which achieves an average Faraday efficiency of 29.6%and specific removal rate(SRR)of 0.042 mol/cm^(2)/h for CuEDTA at−0.65 V vs SCE(saturated calomel electrode),both of which are much higher than those of the commonly reported electrooxidation technology-based removal systems.Moreover,a proofof-concept CuEDTA/Zn battery with Zn anode and MoS_(2)/GF cathode is demonstrated,which has bifunctions of simultaneous CuEDTA removal and energy output.This is one of the pioneer studies on the electrocatalytic reduction of heavy metal complex and CuEDTA/Zn battery,which brings new insights in developing efficient electrocatalytic reduction system for pollution control and energy output.

Salt-assisted Synthesis of Hollow Bi_2WO_6 Microspheres with Superior Photocatalytic Activity for NO Removal

Hollow Bi2WO6 microspheres are successfully synthesized by a facile ultrasonic spray pyrolysis（USP） method using NaCl as a salt template.The as-prepared hollow microspheres assembled as nanoplates with dimensions of approximately 41-148 nm and are dispersed with non-uniform pores on the template surface.By swapping the salt template with KC1 or Na2SO4,different morphologies of Bi2WO6 are obtained.The experimental results demonstrate that NaCl plays a key role on the formation of Bi2WO6 with hollow structures.The specific growth mechanism of hollow microspheres was studied in detail.The Bi2WO6 hollow microspheres exhibit an excellent photocatalytic efficiency for NO removal under solar light irradiation,which is 1.73 times higher than for the Bi2WO6 obtained in the absence of any salt template.This enhancement can be ascribed to the simultaneous improvement on the surface area and visible light-harvesting ability from the hollow structures.Electron spin resonance（ESR） results suggest that both radicals of ·OH and ·O2^- are involved in the photocatalytic process over the BWO-NaCl sample.The production of ·O2^- radicals offers better durability for NO removal.

活性炭电极的改性及对Co^(2+),Mn^(2+)和Ni^(2+)的电吸附性能

以商用活性炭(AC)为原料,分别采用磷酸和氢氧化钠改性的方法制备了两种不同的改性活性炭电极材料.采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、Brunauer-Emmett-Teller(BET)测试、傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)等手段以及电化学分析方法,对改性前后活性炭材料的表面性质和电化学性能进行了探究.结果表明,H_(3)PO_(4)改性使活性炭的孔隙分布更加密集,NaOH改性使活性炭表面的孔隙结构更加清晰均匀;H_(3)PO_(4)和NaOH改性均使活性炭的比表面积增加.循环伏安测试结果表明,改性前后活性炭电极在低扫描速率下均具备良好的双电层特性,并且两种改性处理均能提高活性炭电极的比电容;当扫描速率为5 mV/s时,未改性、H_(3)PO_(4)以及NaOH改性活性炭电极的比电容分别为36.51,77.25和85.19 F/g.电吸附实验结果证明,两种改性活性炭电极对Co^(2+),Mn^(2+)和Ni^(2+)均有较好的去除效果,电吸附过程均更加符合Langmuir模型,在初始浓度、电压和pH相同的条件下,NaOH改性电极对Co^(2+),Mn^(2+)和Ni^(2+)具有更高的去除率和吸附容量,去除率可分别达到96.84%,94.37%和96.90%,吸附容量分别为140.8,111.4和108.5 mg/g.

空间站CO_(2)去除系统节气技术研究

针对空间站CO_(2)去除系统周期性真空解吸会损失大量气体的问题,对系统的节气技术进行研究。从分子筛材料的吸附及解吸特性出发,研究影响系统气体损失量的关键因素。结合系统运行流程和运行周期,综合考虑节气泵工作特性、寿命要求和系统的CO_(2)去除性能,提出了满足指标要求的系统节气方案。采用对损失气体进行实测采样的方法对系统的气体损失量进行了试验验证。试验数据及空间站在轨运行数据表明:设计的节气方案可以控制系统的气体损失量小于45 g/d,提出方案满足设计指标要求。

Fe_(3)O_(4)/CS/EDTA对水溶液中Cu^(2+)和Ni^(2+)的吸附研究

分析了自制的Fe_(3)O_(4)/CS/EDTA纳米粒对水溶液中的重金属离子Cu^(2+)和Ni^(2+)的吸附性能和吸附机理。研究了pH值、溶液初始浓度、反应时间等对吸附性能的影响,结合红外、XPS和比表面分析结果确定了参与吸附配位的功能基团及可能发生的络合反应。结果表明:Fe_(3)O_(4)/CS/EDTA对Cu^(2+)和Ni^(2+)的吸附等温线均符合Langmuir模型,对Cu^(2+)的吸附效果要优于Ni^(2+),这可能与Ni^(2+)的离子半径较Cu^(2+)小以及Ni^(2+)与吸附剂形成的金属螯合物的稳定性较Cu^(2+)低有关;Fe_(3)O_(4)/CS/EDTA对Cu^(2+)和Ni^(2+)的吸附机理类似于N·O型螯合剂,并非一般的物理吸附,而是一种以金属离子为中心的吸附螯合。

采用温度梯度的干燥反应器H_(2)O穿透深度评估方法

针对空间站CO_(2)去除系统中干燥反应器对H_(2)O穿透深度缺乏直接评估手段的问题,提出利用干燥反应器内部温度传感器的温度梯度特性来间接评估的方法;根据硅胶材料吸附H_(2)O放热、脱附H_(2)O吸热的物理特性,结合温度传感器在干燥反应器中的深度位置,分析了不同边界条件下温度传感器数据曲线在吸附及解吸周期内的变化特性,提出反映干燥反应器H_(2)O穿透深度的指标集和评估方法;并对所提方法在系统的密闭舱试验中进行了验证,验证结果表明了指标集的合理性和所提方法的有效性。

5%Ag掺杂对MNO_(2)纳米棒和海胆微球形貌及其甲苯氧化性能的影响

采用水热法制备了MNO_(2)纳米棒和海胆微球,并原位掺杂5%Ag制备了Mn-Ag复合氧化物,利用SEM、XRD、BET、Raman等表征技术对其结构进行表征,并考察不同催化剂对甲苯的去除性能。结果表明:(NH_(4))_(2)S_(2)O_(8)的掺入量会对MNO_(2)的形貌产生影响,当其掺入量为2.28 g时,形成MNO_(2)纳米棒,当其掺入量为6.84 g时,形成MNO_(2)海胆微球;MNO_(2)纳米棒掺杂5%的Ag后,形貌未发生变化,但当MNO_(2)海胆微球掺杂5%Ag时,表面的纳米线较MNO_(2)海胆微球有所增长,且出现了缠绕现象,形成了空心鸟巢状结构;5%Ag掺杂后,对MNO_(2)纳米棒和MNO_(2)海胆微球的晶型未产生影响,均为α-MNO_(2),但5%Ag-MNO_(2)纳米棒出现了Mn2O_(3)的衍射峰;MNO_(2)海胆微球较MNO_(2)纳米棒的比表面积、孔径和孔容均增大,且Ag的掺杂进一步提高了MNO_(2)海胆微球的比表面积、孔径和孔容;MNO_(2)海胆微球比MNO_(2)纳米棒具有更好的甲苯去除性能,且5%Ag掺杂后,MNO_(2)海胆微球对甲苯的去除性能达到最好。

混凝强化型好氧颗粒污泥对Ni^(2+)吸附性能及机理研究

为强化好氧颗粒污泥(AGS)对重金属Ni^(2+)的吸附效能,利用聚合氯化铝(PAC)和天然混凝剂(SNC)的特性培养形成混凝强化型AGS,并探究AGS对Ni^(2+)的吸附性能及机理。结果表明:PAC型和SNC型AGS对Ni^(2+)均具有良好的吸附性能且存在特异性,Ni^(2+)质量浓度为0~25 mg/L时,PAC型AGS吸附效能较优;Ni^(2+)质量浓度为100~150 mg/L时,SNC型AGS吸附性能较优。模型拟合结果表明:混凝强化型AGS对Ni^(2+)的吸附以物理-化学吸附为主,对于吸附量及吸附速率,SNC型AGS均大于PAC型AGS。傅里叶红外变换光谱(FT-IR)结果表明,吸附过程中混凝强化型AGS存在大量羟基、羧基和氨基等基团与Ni^(2+)吸附结合,实现了Ni^(2+)的有效去除;同时,SNC能强化AGS中的官能团,提高吸附性能。

pH对δ-MnO_(2)吸附硫酸锰溶液中Co^(2+)、Ni^(2+)的影响

硫酸锰溶液中重金属离子的深度净化,一直是锰行业研究的热点和重点。利用X射线衍射(XRD)、扫描电镜(SEM)和红外光谱(FT-IR)等手段对所制备的δ-MnO_(2)进行表征,利用Visual Minteq软件模拟硫酸锰溶液中Mn、Co和Ni的离子形态随pH的变化关系,研究不同pH条件对δ-MnO_(2)吸附硫酸锰溶液中Co^(2+)、Ni^(2+)的影响。结果表明:δ-MnO_(2)结晶性较差,缺陷和空隙较多,表面羟基丰富。随着硫酸锰溶液pH升高,δ-MnO_(2)对于Co^(2+)和Ni^(2+)吸附率逐渐增加,Co^(2+)比Ni^(2+)更容易被吸附。在低pH下,δ-MnO_(2)吸附效果受结构缺陷和空隙影响,pH高于5时,在表面负电荷和羟基的共同作用下大量吸附Co^(2+)和Ni^(2+),Co^(2+)、Ni^(2+)吸附率最高达到99.98%、89.53%。对吸附后δ-MnO_(2)进行XRD和FT-IR分析进一步验证了吸附机理,为解决锰系电池原材料硫酸锰溶液中重金属杂质离子难去除问题提供一定基础。

改性多孔硅酸镁纳米材料对废水中Ni^(2+)的吸附性能

将十二烷基磺酸钠(SDS)改性的系列多级孔硅酸镁纳米材料(FMS)用于吸附工业废水中重金属离子Ni^(2+),采用电感耦合等离子发射光谱仪(ICP AES)测定吸附前后溶液中Ni^(2+)的浓度,对所测定的实验数据用动力学和Langmuir吸附模型进行拟合。根据系列改性材料表征数据和实验数据拟合结果,研究系列改性材料的吸附行为及其对Ni^(2+)的吸附效能与吸附材料比表面积、孔结构等性质之间的构效关系。结果表明:孔径和比表面积更大的5 FMS(FMS中添加5%(质量分数)SDS)对Ni^(2+)的平衡吸附量最大,可达231.62 mg/g;所有材料对Ni^(2+)的吸附行为均符合拟二级动力学模型,表明化学吸附在吸附过程中占主导地位;同时所有材料对Ni^(2+)的吸附较好地符合Langmuir吸附模型,即为单分子层均匀吸附,其中5 FMS理论吸附量最大,为280.40 mg/g;该系列材料主要是通过静电吸附、表面金属离子(Mg^(2+))和酸性基团与溶液中Ni^(2+)交换达到去除Ni^(2+)的目的。

改性纤维素对水中Ni^(2+)的吸附研究

从花生壳中提取纤维素,并对其进行柠檬酸改性,考查改性后纤维素对水中Ni^(2+)的吸附特性。实验考查了柠檬酸用量、酯化反应时间等因素对吸附的影响。结果表明:柠檬酸用量为0.16 g·g^(-1)、酯化时间为120 min时,改性后纤维素对镍离子有较高的吸附率。红外光谱分析发现,柠檬酸改性后纤维素的羟基吸收峰显著减弱且出现新的羧基峰。当溶液pH为7、吸附150 min时,对镍去除率为61.08%。等温吸附实验表明,柠檬酸改性纤维素对镍离子吸附可以用Langmuir等温模型表述。

一体式A^(2)O-MBR系统处理高速公路服务区污水的研究

为解决高速公路服务区污水中污染物浓度高、处理设施普遍存在效能低下等问题,采用一体式A^(2)O-MBR反应器处理该目标污水。在反应器启动成功的基础上,研究了不同溶解氧(DO)、硝化液回流比和C/N下A^(2)O-MBR工艺对污染物的去除性能。结果表明,在控制DO为4 mg/L,硝化液回流比为300%,C/N为6时,A^(2)O-MBR获得了最佳污染物去除效果,A^(2)O-MBR工艺的COD、BOD_5和TP去除率分别为90.57%、93.75%和93.00%。反应器稳定运行时,出水NH_(4)^(+)-N和SS分别为4.2 mg/L和4.5 mg/L,出水指标均达到了《城市污水再生利用城市杂用水水质》(GB/T 18920—2020)中冲厕、车辆冲洗的要求。一体式A^(2)O-MBR在一定程度上可以降低膜组件的污染程度,从而降低系统的维护运行成本,可为高速公路服务区污水处理实际工程改造提供参考。

Removal of nitrogen and phosphorus in a combined A^2/O-BAF system with a short aerobic SRT

A bench-scale anaerobic/anoxic/aerobic process-biological aerated filter （A^2/O-BAF） combined system was carded out to treat wastewater with lower C/N and C/P ratios. The A^2/O process was operated in a short aerobic sludge retention time （SRT） for organic pollutants and phosphorus removal, and denitrification. The subsequent BAF process was mainly used for nitrification. The BAF effluent was partially returned to anoxic zone of the A^2/O process to provide electron acceptors for denitrification and anoxic P uptake. This unique system formed an environment for reproducing the denitdfying phosphate-accumulating organisms （DPAOs）. The ratio of DPAOs to phosphorus accumulating organisms （PAOs） could be maintained at 28% by optimizing the organic loads in the anaerobic zone and the nitrate loads into the anoxic zone in the A^2/O process. The aerobic phosphorus over-uptake and discharge of excess activated sludge was the main mechanism of phosphorus removal in the combined system. The aerobic SRT of the A^2/O process should meet the demands for the development of aerobic PAOs and the restraint on the nitrifiers growth, and the contact time in the aerobic zone of the A^2/O process should be longer than 30 min, which ensured efficient phosphorus removal in the combined system. The adequate BAF effluent return rates should be controlled with 1--4 mg/L nitrate nitrogen in the anoxic zone effluent of A^2/O process to achieve the optimal nitrogen and phosphorus removal efficiencies.