Electro-oxidation of Ni (II)-citrate complexes at BDD electrode and simultaneous recovery of metallic nickel by electrodeposition

The simultaneous electro-oxidation of Ni (II)-citrate and electrodeposition recovery of nickel metal were attempted in a combined electro-oxidation-electrodeposition reactor with a boron-doped diamond (BDD) anode and a polished titanium cathode. Effects of initial nickel citrate concentration, current density, initial pH, electrode spacing, electrolyte type, and initial electrolyte dosage on electrochemical performance were examined. The efficiencies of Ni (II)-citrate removal and nickel metal recovery were determined to be 100% and over 72%, respectively, under the optimized conditions (10 mA/cm², pH 4.09, 80 mmol/L Na₂SO₄, initial Ni (II)-citrate concentration of 75 mg/L, electrode spacing of 1 cm, and 180 min of electrolysis). Energy consumption increased with increased current density, and the energy consumption was 0.032 kWh/L at a current density of 10 mA/cm² (pH 6.58). The deposits at the cathode were characterized by scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). These characterization results indicated that the purity of metallic nickel in cathodic deposition was over 95%. The electrochemical system exhibited a prospective approach to oxidize metal complexes and recover metallic nickel.     

Dechlorination of carbon tetrachloride by the catalyzed Fe-Cu process

The electrochemical reduction characteristics of carbon tetrachloride (CT) were investigated using cyclic voltammetry in this study. In addition, the difference in reduction mechanisms of CT between Master Builders' iron and the catalyzed Fe-Cu process was discussed. The results showed that CT was reduced directly on the surface of copper rather than by atomic hydrogen produced at the cathode in the catalyzed Fe-Cu process. The reduction was realized largely by atomic hydrogen in Master Builders' iron. The entire CT in 350 ml aqueous solution with 320 mgL was reduced to trichloromethane and dichloromethane in 2.25 h when 100 g of scrap iron with FeCu ratio of 10:1 (ww) were used. Moreover, the reduction rate slowed with time. CT could be reduced at acidic, neutral and alkaline pH from solution by Fe-Cu bimetallic media, but the mechanisms were di?erent. The degradation rate was not significantly in?uenced by pH in the catalyzed Fe-Cu process; in Master Builders' iron it clearly increased with decreasing pH. The kinetics of the reductions followed pseudo-first order in both cases. Furthermore, the reductions under acidic conditions proceeded faster than that under the neutral and alkaline conditions. The catalyzed Fe-Cu process was superior to Master Builders' iron in treating CT-containing water and this advantage was particularly noticeable under alkaline conditions. The reduction was investigated in the cathode (Cu) and anode (Fe) compartments respectively, the results showed that the direct reduction pathway played an important role in the reduction by the catalyzed Fe-Cu process. The catalyzed Fe-Cu process is of practical value.     

阳极COD对榨菜生产废水MDC产电、脱盐的影响及氨氮去除的微生物群落分析

构建了3室榨菜生产废水微生物脱盐燃料电池系统(microbial desalination cell,MDC),探讨了其阳极COD对榨菜废水MDC产电、脱盐的影响;通过微生物群落分析,探查了脱盐室${{\rm{NH}}_4^ + }$-N的去除途径。结果表明：在产电性能方面,MDC阳极COD为900 mg·L⁻¹时较400 mg·L⁻¹与1 400 mg·L⁻¹时更优,在1 000 Ω的外电阻负载下,其输出电压、最大功率密度、库仑效率分别为550 mV、2.91 W·m⁻³、(15.7±0.5)%;在脱盐方面,阳极COD为400 mg·L⁻¹时,较其他2种情况更优,MDC的脱盐时间、脱盐速率、电子利用效率分别为910.5 h、5.15 mg·h⁻¹、111%。阳极COD不同的MDC脱盐室,其${{\rm{NH}}_4^ + }$-N的去除途径基本相同。脱盐室部分${{\rm{NH}}_4^ + }$-N转化为${{\rm{NO}}_3^ - }$-N后,通过自身的反硝化或以NO₃形式迁移至阳极得以去除,剩余的大部分${{\rm{NH}}_4^ +} $-N以${{\rm{NH}}_4^ + }$形式迁移至阴极,在碱性环境下转化为NH₃并排出。高通量测序分析结果表明,水解发酵菌属(总丰度为33.21%)为MDC阳极的核心微生物群落。阳极生物膜中的电化学活性菌(总丰度为11.78%)可实现电池的产电功能,反硝化菌属(总丰度为14.61%)的存在证明,脱盐室盐室${{\rm{NO}}_3^ - }$-N迁移至阳极室后进行了反硝化并得以去除。在脱盐室水体中检测到了氨氧化菌属(总丰度为6.93%)及反硝化菌属(总丰度为15.82%),这也是脱盐室中${{\rm{NO}}_3^ - }$-N快速产生和随后浓度陡降的原因。     

正交法设计Fe、N共掺杂TiO2/Ti液膜可见光光催化处理染料废水

采用溶胶-凝胶法制备了Fe、N共掺杂TiO_2膜电极(Fe,N-TiO_2/Ti),并设计三因素五水平正交试验对电极制备条件进行优化.结果表明,各因素影响主次顺序为:煅烧温度Fe掺杂量N掺杂量;最优制备条件为:煅烧温度550℃,Fe掺杂量0.3%(质量分数),N掺杂量0.3%(质量分数);共掺杂电极光催化活性优于单掺杂和未掺杂电极.紫外-可见漫反射和光电性能测试表明,催化剂有可见光响应;XRD表征结果表明,Fe、N共掺杂细化了晶粒,有效抑制了金红石相的形成,其晶型为锐钛矿型,粒径为11.48 nm.利用Fe,N-TiO_2/Ti与Cu阴极组装成斜置双极液膜反应器,可见光激发光催化降解苋菜红,考察了主要影响因素.结果发现,最佳条件为:初始pH 2.50,废水流量5.1 L·h~(-1),在此条件下处理20mg·L~(-1)苋菜红80 min,脱色率达到91.6%.电极重复使用10次,每次60 min,脱色率下降了12.99%,说明电极稳定性较好.     

抛石环境中铝合金阳极性能评价及其对海底隧道钢壳保护效果评估

目的 解决埋覆介质中牺牲阳极电化学性能评价的不确定性,实现非匀质介质中牺牲阳极电容量测试结果的评价和对比.方法 模拟沉管隧道埋覆的环境介质,对铝合金牺牲阳极的电容量和溶解形貌进行评测.为区别于现有的海水等匀质介质中阳极的检测方法,建立非匀质介质中铝阳极电化学性能评价方法.另外,在上述埋覆介质中,测定阳极和阴极的极化曲线...     

石墨烯掺杂聚苯胺阳极提高微生物燃料电池性能

微生物燃料电池（microbial fuel cell,MFC）技术可分解代谢污染物质并同步输出电能,在环境及能源领域吸引了越来越多的关注.但是,输出功率密度较低、成本较高、底物降解率低等特点限制了其实际应用,其中阳极是主要限制因素之一.本研究选取具有优异导电性、大比表面积的石墨烯和生物相容性较好的聚苯胺（polyaniline,PANI）,并优化二者比例关系,制备得到石墨烯掺杂PANI复合材料.将复合材料涂覆在玻碳电极表面分析电化学性能,循环伏安（cyclic voltammetry,CV）和线性伏安扫描（linear sweep voltammetry,LSV）测试结果均显示石墨烯含量占比20%的复合电极（20%石墨烯）电化学性能最好.将复合材料修饰在碳布表面作为MFC阳极时以石墨烯含量占比5%的复合电极（5%石墨烯）生物电化学性能最佳,LSV得到最大输出功率密度为（831±45）mW·m^-2,分别是20%石墨烯、1%石墨烯、石墨烯、PANI、碳布阳极的1.2、1.3、1.3、1.5、1.8倍.最大输出电压、开路电压、化学需氧量去除率、库仑效率、生物量密度均以5%石墨烯电极最高.电化学阻抗分析表明5%石墨烯电极极化内阻仅为（24±2）Ω,是碳布电极的19.8%.电化学和生物电化学性能并不完全一致,说明电极材料的生物相容性是影响MFC性能的主要因素之一.5%石墨烯阳极充分发挥了石墨烯和聚苯胺的优点,提高了MFC的产电性能.     

Preparation of Ti species coating hydrotalcite by chemical vapor deposition for photodegradation of azo dye

TiO_2 in anatase crystal phase is a very effective catalyst in the photocatalytic oxidation of organic compounds in water. To improve its photocatalytic activity, the Ti-coating Mg Al hydrotalcite(Ti–Mg Al–LDH) was prepared by chemical vapor deposition(CVD) method.Response surface method(RSM) was employed to evaluate the effect of Ti species coating parameters on the photocatalytic activity, which was found to be affected by the furnace temperature, N2 flow rate and influx time of precursor gas. Application of RSM successfully increased the photocatalytic efficiency of the Ti–Mg Al–LDH in methylene blue photodegradation under UV irradiation, leading to improved economy of the process.According to the results from X-ray diffraction, scanning electron microscopy, Brunner–Emmet–Teller and Barrett–Joyner–Hallender, thermogravimetric and differential thermal analysis, UV–vis diffuse reflectance spectra analyses, the Ti species(TiO_2or/and Ti~(4+)) were successfully coated on the Mg Al–LDH matrix. The Ti species on the surface of the Ti–Mg Al–LDH lead to a higher photocatalytic performance than commercial TiO_2-P25. The results suggested that CVD method provided a new approach for the industrial preparation of Ti-coating Mg Al–LDH material with good photocatalytic performances.     

以养殖废水为底料的微生物燃料电池产电性能与水质净化效果

以养殖场沼泥为接种物,构建了乙二胺、三氯化铁改性碳毡阳极的单室无膜微生物燃料电池,探讨了2种阳极改性电池的产电规律,考察了其去除养殖废水中COD、氨氮的效果以及臭味的表观性状变化。结果表明,以葡萄糖为底物时,乙二胺、三氯化铁改性阳极微生物燃料电池在启动20 d和22 d后分别达到稳定,输出电压分别为0.514 V和0.527V(外阻为500Ω),对应输出功率密度分别为332 mW/m2和349 mW/m2。逐渐增大废水投加比例至原水时,2个电池的最大功率密度分别为208 mW/m2和158 mW/m2,COD去除率分别为85%和78%,氨氮去除率分别为52%和45%。此外,养殖废水的臭味去除效果明显。因此,构建的2种改性阳极微生物燃料电池可以利用养殖废水产电,同时使水质得到一定程度的净化。     

Al-Zn-Sn-Ce牺牲阳极干湿交替环境电化学性能研究

目的 为满足高强钢装备的阴极保护要求,开展新型干湿交替环境牺牲阳极电化学性能测试,评价材料的阴极保护效果。方法 采用高温熔炼方法,制备Al-Zn-Sn-Ce低电位牺牲阳极试样,进行不同浸水率下(干湿态环境时间比为1:1、3:1和7:1)的干湿交替环境牺牲阳极电化学性能试验、电化学表征测试及腐蚀微观形貌表征,通过对比试验数据和材料形貌表征结果,综合分析铝合金牺牲阳极在干湿交替环境下的电化学性能,探究干湿交替环境因素对阳极溶解行为的影响。结果 Al-Zn-Sn-Ce牺牲阳极在多种试验环境下的工作电位为‒0.70~‒0.81 V(vs. SCE),符合高强钢阴极保护电位需求,阳极表面溶解形貌相对均匀,表面阴阳极电化学微区分布均匀。随着干湿态试验环境时间比的增加,阳极工作电位出现正移,干态环境下表面腐蚀产物的沉积和结壳导致阳极活化溶解能力下降,而干湿态环境时间比最大时,阳极自腐蚀反应得到一定的抑制,阳极电流效率均保持在75%以上。结论 随着干湿态试验环境时间比的增加,牺牲阳极在干湿交替试验环境中的工作电位出现正移。由于干态环境下表面腐蚀产物的沉积和结壳,导致阳极活化溶解能力下降,但自腐蚀反应得到抑制。Al-0.7Zn-0.1Sn-0.1Ce低电位牺牲阳极在复杂干湿交替环境中表现出良好的阴极保护性能。