不同Cu2+浓度下热再生氨电池产电及Cu2+去除特性

热再生氨电池（thermally regenerative ammonia-based battery,TRAB）在废弃资源回收方面展现出独特优势和良好应用前景。通过构建TRAB来处理含Cu²⁺废液并回收电能和铜资源,实验中研究了不同Cu²⁺浓度对电池产电性能和废液Cu²⁺去除效果的影响。研究结果表明,当阴极废液Cu²⁺浓度低于0.2 mol/L时,随着Cu²⁺浓度的增加,电池最大输出功率不断增加,电池输出电压和产电周期不断增加,促使批次获得电量和能量密度也不断增加。同时采用TRAB技术去除废液中铜离子具有较高的去除效率,而且去除率随着废液中铜离子浓度的增加而增加。后续研究采用TRAB结合电凝法的两步处理法有望进一步提高处理效果,具有较好的经济性和应用前景。     

双室MFC对含Cu（Ⅱ）废水处理效能及其产电性能的影响

微生物燃料电池(microbial fuel cells,MFCs)可利用微生物将化学能转化为电能,并实现重金属的去除与还原回收。本研究构建了一种双室MFC用于处理含Cu²⁺的重金属废水,以探究不同初始浓度及阴极电极材料下MFC的产电性能和Cu²⁺的去除效果。结果表明,当阴极电极材料为不锈钢且阴极中Cu²⁺的初始浓度由10 mg/L增大至200 mg/L时,Cu²⁺的去除率由85.37%增大至98.16%(120 h),最大输出电压和功率密度分别为257 mV和36.75 mW/m2。当阴极电极材料为石墨板、钛片时,Cu²⁺的去除率分别为99.02%、98.27%,此时的最大输出电压和功率密度分别是不锈钢的1.45倍、1.18倍和1.71倍1.28倍。对阴极上附着的产物进行扫描电镜分析,Cu²⁺在阴极发生了还原反应,生成了单质铜。本研究可以为实现MFC高效回收重金属提供理论依据,对利用MFC解决环境污染和能源短缺问题有重要意义。     

不同Cu~(2+)浓度下热再生氨电池产电及Cu~(2+)去除特性

热再生氨电池(thermally regenerative ammonia-based battery,TRAB)在废弃资源回收方面展现出独特优势和良好应用前景。通过构建TRAB来处理含Cu~(2+)废液并回收电能和铜资源,实验中研究了不同Cu~(2+)浓度对电池产电性能和废液Cu~(2+)去除效果的影响。研究结果表明,当阴极废液Cu~(2+)浓度低于0.2 mol/L时,随着Cu~(2+)浓度的增加,电池最大输出功率不断增加,电池输出电压和产电周期不断增加,促使批次获得电量和能量密度也不断增加。同时采用TRAB技术去除废液中铜离子具有较高的去除效率,而且去除率随着废液中铜离子浓度的增加而增加。后续研究采用TRAB结合电凝法的两步处理法有望进一步提高处理效果,具有较好的经济性和应用前景。     

MFC-MEC耦合系统产电性能及处理含镉重金属废水的研究

以厌氧活性污泥为阳极菌种,乙酸钠为阳极底物,硫酸铜和重铬酸钾溶液为微生物燃料电池（MFC）阴极液,人工模拟含镉重金属废水为微生物电解池（MEC）阴极液,构建MFC-MEC耦合系统,利用MFC的产电驱动MEC运行,在不消耗外部能源的情况下,实现含镉重金属废水中Cd²⁺的去除。实验研究了MFC反应器容积、MFC堆栈、MEC电极材料、MEC阴极液pH对MFC-MEC耦合系统电性能及含镉重金属废水处理效果的影响。结果表明：MFC反应容积的扩大可以提高其产电性能,但与此同时会造成MFC的内阻升高,随着MFC容积的增加,MEC中Cd²⁺去除率逐渐增加,但同时MFC阴极Cr⁶⁺去除率逐渐下降;MFC堆栈可以提高工作组两端电压,串联时最大输出电压为1509 mV,Cd²⁺去除率为69.3%;以钛板作为MEC电极时,微生物能有效附着在阳极表面,MFC阳极COD去除率为85%,MEC中Cd²⁺去除率为51.5%;MEC阴极液pH在3~5时,有利于含镉重金属废水的处理,Cd²⁺去除率80%以上。经XRD分析,MEC阴极还原产物为CdCO₃。     

胶原多肽基表面活性剂对废水中Cu(Ⅱ)的沉淀浮选性能

以低浓度Cu²⁺水溶液模拟重金属离子废水,研究了胶原多肽基表面活性剂（阴离子型CBS和阳离子型C-CBS）对重金属离子废水的沉淀浮选性能。通过单因素实验考察了pH、气速、表面活性剂质量浓度、气浮时间、Cu²⁺初始浓度等因素对废水中Cu²⁺沉淀浮选效果的影响。结果表明,CBS和C-CBS均适用于在碱性条件下对金属离子废水进行沉淀浮选,Cu²⁺的去除率达到90%左右;且随着气速的升高,Cu²⁺的去除率增加而后趋于不变;随着表面活性剂用量的增加,对CBS,Cu²⁺的去除率增加,而对C-CBS,Cu²⁺的去除率反而下降;随气浮时间延长,Cu²⁺去除率逐渐增加而后趋于不变。研究表明,胶原多肽基表面活性剂可用于重金属离子废水的沉淀浮选。     

超重力强化电沉积去除废水中镉离子

采用阴极电沉积去除废水中重金属Cd²⁺,并进行过程强化提高Cd²⁺去除率,解决废水中重金属Cd²⁺永久残留问题,同时回收Cd资源。结果表明,电沉积去除废水中Cd²⁺过程受扩散控制,磁力搅拌强化电沉积使Cd²⁺去除率达85.4%。在相同条件下,超重力强化使Cd²⁺去除率达99.4%,比磁力搅拌电沉积提高了14%。动力学研究表明,两种强化电沉积去除废水中Cd²⁺过程均符合表观一级反应动力学规律。SEM和XRD分析表明,两种强化获得的沉积物均由Cd和Cd（OH）₂组成,超重力使其形貌由不稳定生长的枝晶结构变为稳定生长的片状结构。     

FeCl_3蚀刻Cu的废液的再生研究

用阴极除杂-阳极氧化三氯化铁蚀刻废液的电化学方法再生三氯化铁蚀刻铜的废液。结果表明,8 V为较合适的电解槽压,温度为25℃,极距为80 mm时ORP转化情况最好。由于电解实验中Fe⁽²⁺⁾的转化率比较低,因此对再生液的蚀刻能力进行研究,得出可循环使用次数最少为3次。总铜离子含量检测表明,再生一次后的溶液中的Cu(2+)的转化率比较低,因此对再生液的蚀刻能力进行研究,得出可循环使用次数最少为3次。总铜离子含量检测表明,再生一次后的溶液中的Cu⁽²⁺⁾去除率为68.5%。由于Cu(2+)去除率为68.5%。由于Cu⁽²⁺⁾去除率比较低,进而探究Cu(2+)去除率比较低,进而探究Cu⁽²⁺⁾含量对蚀刻能力的影响,表明当Cu(2+)含量对蚀刻能力的影响,表明当Cu⁽²⁺⁾浓度为0.119 g/mL是蚀刻能力的一个临界值,浓度升高溶液的蚀刻能力变低。因此实际应用中,以8 V电压25℃、80 mm极距可最大化的提高循环利用率,实现废液的再生利用。     

具有高浓度氨腔室的立式热再生氨电池性能特性

热再生电池（thermally regenerative ammonia-based battery,TRAB）可有效地将低温热能转化为电能,但其较为严重的氨渗透现象严重影响电池的产电稳定性。本文通过可视化证明了TRAB阳极氨与电解液的自分层现象,基于此构建了一种具有高浓度氨腔室的立式热再生氨电池,通过构建高浓度氨腔室和阳极氨传输阻挡层来调控氨分布,从而缓解电池中氨渗透过程。研究结果表明,与常规结构的热再生氨电池相比,具有氨腔室的热再生电池通过调控阳极氨分布解决了氨渗透的问题,在较高氨浓度（6mol/L）条件下获得了更高的输出功率、产电量以及更稳定的产电性能。此外,多孔泡沫铜阳极可以阻挡氨向下传输,进一步缓解氨渗透。具有合适孔隙密度（80PPI）的多孔电极在获得较大反应面积的同时保证了其内部良好的物质传输,使电池获得最佳的输出功率（10.8mW）。     

交联淀粉负载氢氧化镁复合材料对Cu2+的吸附性能

以交联淀粉和MgSO₄·7H₂O为原料，NaOH为碱化剂，制备了交联淀粉负载氢氧化镁复合材料IStMg(OH)₂，采用FTIR、SEM、EDS、XRD对其进行了表征，并将其用于对模拟废水中Cu²⁺的吸附去除，考察了IStMg(OH)₂投加量、pH、Cu²⁺初始浓度等因素对ISt-Mg(OH)₂吸附Cu²⁺性能的影响。结果表明，当Cu²⁺质量浓度为20mg/L,pH=5.32,ISt-Mg(OH)₂投加量为300 mg/L，吸附温度为25 ℃时，Cu²⁺的去除率可达91.7%。吸附等温线拟合结果表明，ISt-Mg(OH)₂对水中Cu²⁺的吸附过程符合Langumir吸附模型，为单分子层吸附过程，在25 ℃时，拟合饱和吸附量为82.78 mg/g。吸附动力学数据拟合结果表明，吸附过程符合准二级动力学模型，属于...     

电极对微生物燃料电池同时处理有机废水和含铜重金属废水产电性能的影响

实验以有机废水为阳极底物,以活性污泥中的混合菌为阳极接种微生物,以含铜废水为阴极液,构建双室MFC,探讨电极对MFC同时处理有机废水和含铜重金属废水产电性能的影响.结果表明:MFC对阳极有机废水COD的去除率最高为79.1%,对阴极液中Cu²⁺的去除率最高为95.6%.活性炭/石墨棒电极MFC产电性能最优,开路电压最高为800mV,是石墨棒电极MFC的1.25倍,是活性炭/碳纸电极MFC的1.3倍,是碳纸电极MFC的1.5倍.当电极距离为2cm时,MFC开路电压580mV,内阻为181Ω,产电性能最优.电极表面积为75cm²时,MFC的开路电压470mV,是电极表面积为50cm²的MFC的1.1倍,是电极表面积为30cm²的MFC的2.1倍.当A_An/A_cat=0.4时MFC产能最佳,MFC的开路电压最高为600mV,最大功率密度48.2mW/m².     

采用泡沫铜电极的热再生氨电池性能数值模拟

以采用泡沫铜电极的热再生氨电池（thermally regenerative ammonia-based battery，TRAB）为研究对象，建立了多孔介质内物质传输与电化学反应耦合的稳态模型，计算获得了电池性能及多孔电极内物质传输特性，并研究了电解质浓度和电极孔隙率对电池性能的影响。研究结果表明，从主流区界面到多孔电极内部，阳极氨和阴极铜离子浓度逐渐降低，存在一定的浓度梯度，而且随着反应电流的增大，浓度梯度明显增大。在一定的范围内分别增大阳极氨浓度和阴极铜离子浓度，从主流区向多孔电极内物质传输增强，电池性能均能不断提升；随着硫酸铵浓度的增大，电解质电导率增大，电池性能逐渐提升，但增幅逐渐减小。此外，多孔电极孔隙率也会影响电池性能，本研究中TRAB在电极孔隙率为0.6时获得最高的最大功率(15.3 mW)。     

喷射床电沉积法处理铜镍混合废水

以实验室模拟酸性铜镍废水为研究对象,采用自制喷射床电沉积实验装置在恒电流条件下对铜镍混合酸性废水进行了沉积实验,研究了pH、电流值、温度和鼓入氮气对沉积效果和电解液DO的影响规律。实验结果表明,在前210 min控制pH为3,后270 min为4.5,电流值15 A,温度25℃,鼓入氮气的条件下,沉积480 min,铜镍离子沉积率可以分别达到99.88%和85.21%;实验过程中DO先迅速增大至最大值,之后缓慢降低;鼓入氮气可以有效降低溶液中溶解氧,提高金属的沉积率;由于Ni和Cu²⁺之间置换反应的存在,削弱了沉积铜的腐蚀但加剧了镍的腐蚀,使得铜镍混合电沉积在宏观上表现出一定的顺序性,这说明在特定条件下采用喷射床电沉积法分类回收废水中的混合金属是可行的。     

One-electron reducibility of isolated copper oxide on alumina for selective NO–CO reaction

The H₂-TPR (temperature-programmed reduction) study was performed for supported copper oxide catalysts with low loading (0.5 wt% as copper). Among the various kinds of support materials (γ-Al₂O₃, TiO₂, ZrO₂, SiO₂, ZSM-5), alumina-supported copper oxide indicated a one-electron reduction behavior of Cu²⁺ into Cu⁺ ions in the presence of H₂. The reduction of the isolated Cu²⁺ species in a tetragonally distorted octahedral symmetry into the low coordinated Cu⁺ ions was identified by means of X-ray absorption spectroscopy (XANES and EXAFS). The isolated Cu⁺ ions hosted by γ-Al₂O₃ surface were prevented from further reduction into metallic Cu⁰ state under reducing condition with H₂ at 773 K. Less dispersed supported copper oxide species were easily reduced to Cu⁰ metal particles with H₂ at 573 K regardless of the kinds of support materials. It is suggested that the one-electron redox behavior of the isolated copper oxide species over γ-Al₂O₃ promotes the catalytic reduction of NO with CO in the presence of oxygen on the basis of redox-type mechanism between Cu²⁺ and Cu⁺ in atomically dispersed state.     

氧化铈-二氧化硅介孔材料制备及对铜离子的吸附性能

采用共沉淀法和沉淀浸渍法制备了纳米氧化铈-二氧化硅（CeO₂-SiO₂）介孔材料吸附剂,主要考察了其对水中铜离子（Cu²⁺）的吸附行为。通过X射线衍射（XRD）、扫描电镜（SEM）和氮吸附（BET）等手段对合成的介孔材料进行了性能表征,并通过静态吸附实验分析了溶液pH、溶液初始金属离子质量浓度、吸附剂用量、吸附时间等条件对介孔材料吸附Cu²⁺性能的影响。结果表明：共沉淀法制备的纳米CeO₂-SiO₂介孔材料对Cu²⁺的去除效果较沉淀浸渍法要好;当溶液pH=7.0时CeO₂-SiO₂介孔材料对Cu²⁺的吸附效果最好,20 min时基本达到吸附平衡;溶液初始Cu²⁺浓度增大Cu²⁺去除率降低,Cu²⁺累计吸附量增大;随着吸附剂用量增加Cu²⁺去除率增大,当CeO₂-SiO₂吸附剂用量为0.15 g/L时对Cu²⁺的去除率趋于稳定;CeO₂-SiO₂吸附剂对不同金属离子吸附性能由大到小的顺序为Cu²⁺、Fe²⁺、Mn²⁺,该吸附过程均符合准二级动力学模型。     

羧甲基纤维素钠螯合Cu(Ⅱ)的稳定常数测定及螯合效果分析

为了考察羧甲基纤维素钠(CMC)对重金属离子 的螯合能力,利用紫外分光光度法测定了不同c(Cu²⁺)/c(-COO^-)浓度比下CMC与 形成螯合物的吸收光谱,探讨了螯合物的组成,并计算其稳定常数。结果表明:CMC对 有螯合作用,当c(Cu²⁺)/c(-COO^-)小于0.6,螯合物在237 nm处出现最大吸收峰,-COO^-为主要配体,与 按物质的量比为2:1进行螯合,此时,螯合物稳定常数为1.88×10¹⁰;c(Cu²⁺)/c(-COO^-)为0.6～1.0时,214、237 nm处出现最大吸收峰,-COO^-、-OH都参与螯合反应并形成新的螯合物;c(Cu²⁺)/ c(-COO^-)大于1.0时,214 nm存在最大吸收峰,-OH为主要配体。考察了利用CMC螯合去除溶液中 的效果,实验表明,CMC-Cu螯合物可在溶液中直接析出,析出物为絮状沉淀。当c(Cu²⁺)/c(-COO^-)等于0.5时为最佳CMC用量,此时上清液中 去除率可以达到96%以上。     

Surface and bulk properties of Cu–ZSM-5 and Cu/Al2O3 solids during redox treatments. Correlation with the selective reduction of nitric oxide by hydrocarbons

This paper deals with the redox properties of Cu ions implanted in ZSM-5 and supported on Al₂O₃, catalysts active in the selective reduction of NO by hydrocarbons such as propane. Data on the reducibility of the Cu systems in various atmospheres (vacuum, CO, H₂, O₂) and on their DeNO_x activity are presented. The methods used to obtain informations on the surface and bulk transformations (and their link with catalytic behaviour) are complementary: UV–visible diffuse reflectance spectroscopy being useful to detect the presence of Cu²⁺ and Cu⁰, while Cu⁺ is detected indirectly by the analysis of the IR spectrum of CO bound selectively to this cation.

The main contributions to the previous knowledge are the following: it is possible to distinguish CO bound to isolated and non-isolated Cu⁺ ions; the isolated Cu²⁺ ions are reducible under vacuum without participation of organic impurities; the more active solids for the NO reduction into N₂ are characterized by the presence of isolated Cuⁿ⁺ ions beside the additional influence of the zeolitic framework; after the formation of Cu⁺ ions the redox cycles are reversible but, after the formation of Cu⁰, the reversibility or irreversibility of the redox cycles and the restoration of the SCR activity are function of the copper content; the activity decreases after agglomeration into bulk oxides; there is no formation of bulk CuO during the reaction and, with reducing and moderate oxidizing mixtures, part of the copper remains as cuprous ions.     

Identification of copper(II) and copper(I) and their interconversion in Cu/ZSM-5 De-NOx catalysts

A combined Fourier transform IR (FT-IR) and electron paramagnetic resonance (EPR) study shows that copper in ‘excessively exchanged’ Cu/ZSM-5 is initially present as OH bridged Cu²⁺ dimers, besides isolated Cu²⁺ ions. Upon heating, the dimers lose water and become oxygen bridged [Cu---O---Cu]²⁺ complexes. These are ‘EPR-silent’, presumably as a consequence of antiferromagnetic coupling of the unpaired electrons in each Cu²⁺; they are, however, detectable by their perturbation of the lattice vibrations, detected by a FT-IR band at 918–923 cm⁻¹. Reduction by hydrogen or carbon monoxide converts the [Cu---O---Cu]²⁺ complexes to pairs of Cu⁺ ions, while the color changes from green to grey. Reductive adsorption of nitrogen monoxide on Cu²⁺ results in the formation of Cu⁺---NO⁺. Destructive thermal desorption of nitrogen monoxide at 100°C not only restores the Cu²⁺ ions, but also appears to regenerate the [Cu---O---Cu]²⁺ complex. The results suggest that pairs of copper ions are instrumental in the catalytic decomposition of nitrogen monoxide.     

Polymerization of methyl methacrylate in the presence of molecular oxygen — a kinetic study

Methyl methacrylate was polymerized in aqueous medium initiated by a copper(II)-ascorbic acidoxygen system at 40°C and a kinetic study of the reaction is presented. The rate of polymerization, R_p showed an increase, constancy and then a decrease with increase in the [Cu²⁺]. The order with respect to [Cu²⁺] was 0.5 in the rate increase region. The order in monomer concentration changed gradually from 1.0 to 2.0 with increase in [Cu²⁺]. R_p became independent of ascorbic acid (AA) concentration and oxygen concentration at high concentrations. These results indicate that termination by mutual interaction of chain radicals predominates at low [Cu²⁺] while termination was exclusively by metal ions at high [Cu²⁺]. R_p was also observed to increase with temperature and ionic strength and to K_p/K_t^1/2 value was calculated and compared with literature values. Chain lengths were determined by viscometry for the polymers obtained under various experimental conditions.