氧化还原-配位滴定法测定热镀锌助镀剂中的Fe^(2+)和ZnCl_2含量

助镀剂中Fe2+和Zn Cl2含量对热镀锌影响很大,目前测定方法如配位滴定法存在指示剂变化不明显等缺点。助镀剂经处理后,利用重铬酸钾酸性条件下的氧化性滴定Fe2+,以Cu-PAN为指示剂用EDTA配位滴定测定Zn2+。结果表明:该方法原理新颖,终点显色敏锐,操作简便,所需仪器少,成本低廉,Fe2+的加标回收率为99.17%,Zn Cl2的加标回收率为97.94%,准确度较高,可满足一般车间测定需要。

基于一氧化碳、二氧化碳和氧气分子吸附为探针的碳化钼、碳化钨、氮化钼和氮化钨的表面化学性质:密度泛函理论分析（英文）

作为具有吸引力的电极材料,过渡金属碳化物与氮化物被应用在许多电化学储能及能量转换领域.本工作中,通过密度泛函理论计算,以及一氧化碳(CO)、二氧化碳(CO_2)和氧气(O_2)分子的吸附来表征钼和钨的碳化物及氮化物,如碳化钼(Mo_2C)、碳化钨(W2C)、氮化钼(Mo_2N)和氮化钨(Mo_2C)的表面化学性质.这些探针分子可为研究钼和钨的碳化物及氮化物表面在酸性/碱性的氧化还原性质提供衡量方法.计算结果表明,CO_2分子的吸附发生在路易斯碱位,其碱性降低顺序为α-W_2C(001)>α-W_2N(001)>β-Mo_2C(001)>γ-Mo_2N(100).此外,CO和O_2分子吸附可用于评估上述碳化物及氮化物的还原能力,其还原性减小顺序为β-W_2C(100)>α-Mo_2C(100)>α-W_2N(001)>α-W_2C(001)>β-Mo_2C(001)>γ-Mo_2N(100).由于还原本性,使得上述这些碳化物和氮化物成为在各种催化反应中有可能取代贵金属的良好候选材料.

酸性金属氧化物对锰铈氧化物催化剂脱硝温度窗口的调控作用(英文)

利用溶胶-凝胶法,采用三种酸性金属氧化物(氧化铌、氧化钨和氧化钼)对锰铈复合氧化物催化剂进行了改性.测试了催化剂的氮氧化物选择性催化还原(SCR)活性,以筛选对应不同温度窗口的合适酸性氧化物改性剂.同时评价了催化剂的NO氧化和NH3氧化活性.利用X射线衍射、BET比表面积测试、H2程序升温还原、NH3/NOx程序升温脱附和NH3/NOx吸附红外光谱等手段对催化剂进行了表征.MnOx-CeO2催化剂表现出良好的低温(100-150°C)活性.酸性金属氧化物的添加削弱了催化剂的氧化还原特性,从而抑制了NH3的活化和NO2辅助的快速SCR反应.与此同时,相对高温(250-350°C)区NH3的氧化也受到了抑制,B酸和L酸上的NH3吸附得以增强.因此,催化剂的SCR脱硝温度窗口向高温移动,改性效果Nb2O5<WO3<MoO3.

Relationship and effect of redox potential,jarosites and extracellular polymeric substances in bioleaching chalcopyrite by acidithiobacillus ferrooxidans

The changes of pH,redox potential,concentrations of soluble iron ions and Cu^2＋ with the time of bioleaching chalcopyrite concentrates by acidithiobacillus ferrooxidans were investigated under the different conditions of initial total-iron amount as well as mole ratio of Fe（III） to Fe（II） in the solutions containing synthetic extracellular polymeric substances （EPS）.When the solution potential is lower than 650 mV （vs SHE）,the inhibition of jarosites to bioleaching chalcopyrite is not vital as EPS produced by bacteria can retard the contamination through flocculating jarosites even if concentration of Fe（III） ions is up to 20 g/L but increases with increasing the concentration of Fe（III） ions;jarosites formed by bio-oxidized Fe3＋ ions are more easy to adhere to outside surface of EPS space on chalcopyrite;the EPS layer with jarosites acts as a weak diffusion barrier to further rapidly create a high redox potential of more than 650 mV by bio-oxidizing Fe^2＋ ions inside and outside EPS space into Fe^3＋ ions,resulting in a rapid deterioration of ion diffusion performance of the EPS layer to inhibit bioleaching chalcopyrite severely and irreversibly.

Promotional roles of ZrO_2 and WO_3 in V_2O_5-WO_3/TiO_2-ZrO_2 catalysts for NO_x reduction by NH_3:Catalytic performance,morphology,and reaction mechanism

V2O5/TiO2-ZrO2 catalysts containing various amounts of WO3 were synthesized.The catalyst morphologies,catalytic performances,and reaction mechanisms in the selective catalytic reduction of NOx by NH3 were investigated using in situ diffuse-reflectance infrared Fourier-transform spectroscopy,temperature-programmed reduction（TPR）,X-ray diffraction,and the Brunauer-Emmett-Teller（BET） method.The BET surface area of the triple oxides increased with increasing ZrO2 doping but gradually decreased with increasing WO3 loading.Addition of sufficient WO3 helped to stabilize the pore structure and the combination of WO3 and ZrO2 improved dispersion of all the metal oxides.The mechanisms of reactions using V2O5-9%WO3/TiO2-ZrO2 and V2O5-9%WO3/TiO2were compared by using either a single or mixed gas feed and various pretreatments.The results suggest that both reactions followed the Eley-Ridel mechanism;however,the dominant acid sites,which depended on the addition of WO3 or ZrO2,determined the pathways for NOx reduction,and involved[NH4^＋-NO-Bronsted acid site]^＊ and[NH2-NO-Lewis acid site]^＊ intermediates,respectively.NH3-TPR and H2-TPR showed that the metal oxides in the catalysts were not reduced by NH3 and O2did not reoxidize the catalyst surfaces but participated in the formation of H2O and NO2.

Influence of transition metal modification of oxide-derived Cu electrodes in electroreduction of CO_2

The modification of oxide-derived Cu electrode with Ni, Zn, and Au was examined to improve the catalytic activity of COz electroreduction. The experimental results showed that Ni modification increased the Faraday efficiency of the formation of formic acid and n-propanol. The Faraday effi- ciency relating to the formation of the liquid products was as high as 34.3% at -1.5 V versus the saturated calomel electrode reference potential. In contrast, modification with Zn reduced the for- mic acid formation efficiency but enhanced the alcohol formation efficiency. Finally, modification with Au suppressed the selectivity toward the formation of both formic acid and alcohols.

Nitrite Accumulation during the Denitrification Process in SBR for the Treatment of Pre-treated Landfill Leachate

The nitrite accumulation in the denitrification process is investigated with sequencing batch reactor （SBR） treating pre-treated landfill leachate in anoxic/anaerobic up-flow anaerobic sludge bed I（UASB）. Nitrite accumulates obviously at different initial nitrate concentrations （64.9,54.8,49.3 and 29.5 mg·L^-1 ） and low temperatures, and the two break points on the oxidation-reduction potential （ORP） profile indicate the completion of nitrate and nitrite reduction. Usually, the nitrate reduction rate is used as the sole parameter to characterize the denitrification rate, and nitrite is not even measured. For accuracy, the total oxidized nitrogen （nitrate ＋ nitrite） is used as a measure, though details characterizing the process may be overlooked. Additionally, batch tests are conducted to investigate the effects of C/N ratios and types of carbon sources on the nitrite accumulation during the denitrification. It is observed that carbon source is sufficient for the reduction of nitrate to nitrite, but for further reduction of nitrite to nitrogen gas, is deficient when C/N is below the theoretical critical level of 3.75 based on the stoichiometry of denitrification. Five carbon sources used in this work, except for glucose, may cause the nitrite accumulation. From experimental results and cited literature, it is concluded that Alcaligene species may be contained in the SBR activated-sludge system.

Grey relational analysis on the relation between marine environmental factors and oxidation-reduction potential

The effects of marine environmental factors-temperature （T）, dissolved oxygen （DO）, salinity （S） and pH--on the oxidation-reduction potential （ORP） of natural seawater were studied in laboratory. The results show an indistinct relationship between these four factors and the ORE but they did impact the ORP. Common mathematical methods were not applicable for describing the relationship. Therefore, a grey relational analysis （GRA） method was developed. The degrees of correlation were calculated according to GILA and the values of T, pH, DO and S were 0.744, 0.710, 0.692 and 0.690, respectively. From these values, the relations of these factors to the ORP could be described and evaluated, and those of T and pH were relatively major. In general, ORP is influenced by the synergic effect of T, DO, pH and S, with no single factor having an outstanding role.

Leaching of chalcopyrite: An emphasis on effect of copper and iron ions

Many researchers found that the Fe2+together with less amount of Cu2+can accelerate the leaching of chalcopyrite.In this work,the leaching of chalcopyrite with Cu2+was investigated.The leaching residuals were examined by Raman spectroscopy.Based on the leaching experiments,the chemical equilibrium in solution was calculated using Visual MINTEQ.The results showed that the Fe in chalcopyrite lattice was replaced by Cu2+;therefore,the chalcopyrite transformed into covellite.Furthermore,the formation of chalcocite occurred when Fe2+and Fe3+were added to the solution containing Cu2+.The copper extraction increased with a decrease of the initial redox potential(or the ratio of Fe3+/Fe2+).

Kinetics and Modeling of Chemical Leaching of Sphalerite Concentrate Using Ferric Iron in a Redox-controlled Reactor

This work presents a study for chemical leaching of sphalerite concentrate under various constant Fe3+ concentrations and redox potential conditions. The effects of Fe3+ concentration and redox potential on chemical leaching of sphalerite were investigated. The shrinking core model was applied to analyze the experimental results. It was found that both the Fe3+ concentration and the redox potential controlled the chemical leaching rate of sphalerite. A new kinetic model was developed, in which the chemical leaching rate of sphalerite was proportional to Fe3+ concentration and Fe3+ /Fe2+ ratio. All the model parameters were evaluated from the experimental data. The model predictions fit well with the experimental observed values.

Bioleaching and electrochemical properties of chalcopyrite by pure and mixed culture of Leptospirillum ferriphilum and Acidthiobacillus thiooxidans

The bioleaching of chalcopyrite was investigated using a pure and mixed culture consisting of iron-oxidizing Leptospirillum ferriphilum （L. ferriphilum） and sulfur-oxidizing Acidthiobacillus thiooxidans （.4. thiooxidans）. The electrochemical tests were conducted to investigate the bioleaching behavior of chalcopyrite by various bacteria. Bioleaching efficiency of chalcopyrite in mixed culture is higher than that in the pure culture of L.ferriphilum alone. The iron-oxidizing L.ferriphilum plays a dominant role during bioleaching of chalcopyrite in the mixed culture of L. ferriphilum and A. thiooxidans. During bioleaching, certain values of redox potential are beneficial to the decomposition of chalcopyrite. Jarosite and sulfur are observed as products of bioleaching. The addition of A. thiooxidans during leaching by L. ferriphilum can change the electrochemical control steps of leaching. The corrosion current density is substantially promoted in the culture involving bacteria, especially in the mixed culture.

Insights into facet-dependent reactivity of CuO–CeO2 nanocubes and nanorods as catalysts for CO oxidation reaction

Copper–ceria(Cu O–CeO2) catalysts have been known to be very effective for the oxidation of CO, and their chemical behavior has been extensively studied during the last decades. However, the effect of different CeO2 crystal surfaces on the catalytic activity of Cu O–CeO2 for the oxidation of CO is still unclear and should be further elucidated. In this study, we deposited 1 wt% Cu on mostly {100}-exposed CeO2 nanocubes(1 Cu Ce NC) and mostly {110}-exposed CeO2 nanorods(1 Cu Ce NR), respectively. Both 1 Cu Ce NC and 1 Cu Ce NR have been used as catalysts for the oxidation of CO and achieved 100% and 50% CO conversion at 130 ℃, respectively. The differences in the catalytic activity of 1 Cu Ce NC and 1 Cu Ce NR were analyzed using temperature-programmed reduction of H2 and temperature-programmed desorption of CO techniques. The results confirmed the excellent reducibility of the 1 Cu Ce NC catalyst, which was attributed to the weak interactions between Cu and the CeO2 support. Moreover, in situ diffuse reflectance infrared Fourier-transform spectroscopy studies indicated that the {100} planes of 1 Cu Ce NC facilitated the generation of active Cu(I) sites, which resulted in the formation of highly reactive Cu(I)-CO species during the oxidation of CO. Both the excellent redox properties and effective CO adsorption capacity of the 1 Cu Ce NC catalyst increased its catalytic reactivity.

Thermal coupled photoconductivity as a tool to understand the photothermal catalytic reduction of CO2

Photocatalysis shows great promise in the field of solar energy conversion.One of the reasons for this is because it promotes the development of multi-field-coupled catalysis.In order to explore the principles of multi-field-coupled catalytic reactions,an in situ multi-field-coupled characterization technique is required.In this study,we obtained hydrogenated ST-01 TiO2 and observed enhanced catalytic activity by thermal coupled photocatalysis.In situ photoconductivity was employed to understand the activity enhancement.The effects of the reaction temperature,reaction atmosphere,and oxygen vacancy(Ov)on the photoconductivity of TiO2 were studied.After coupling thermal into photoconductivity measurement,highly active Ov-TiO2 displayed rapid decay of photoconductivity in a CO2 atmosphere and slow decay of photoconductivity in a N2 atmosphere.These phenomena revealed that photothermal coupling assisted the detrapping of electrons at the Ov surface and promoted electron transfer to CO2,which clearly explained the high photothermal catalytic activity of Ov-TiO2.This study demonstrated that photoconductivity is a useful tool to help understand photothermal catalytic phenomena.

Effect of Sludge Retention Time on Nitrite Accumulation in Real-time Control Biological Nitrogen Removal Sequencing Batch Reactor

In this study,four sequencing batch reactors(SBR),with the sludge retention time(SRT)of 5,10,20 and 40 d,were used to treat domestic wastewater,and the effect of SRT on nitrite accumulation in the biological nitrogen removal SBR was investigated.The real-time control strategy based on online parameters,such as pH,dissolved oxygen(DO)and oxidation reduction potential(ORP),was used to regulate the nitrite accumulation in SBR. The model-based simulation and experimental results showed that with the increase of SRT,longer time was needed to achieve high level of nitritation.In addition,the nitrite accumulation rate(NAR)was higher when the SRT was relatively shorter during a 112-day operation.When the SRT was 5 d,the system was unstable with the mixed liquor suspended solids(MLSS)decreased day after day.When the SRT was 40 d,the nitrification process was significantly inhibited.SRT of 10 to 20 d was more suitable in this study.The real-time control strategy combined with SRT control in SBR is an effective method for biological nitrogen removal via nitrite from wastewater.

Selection of Chelated Fe(Ⅲ)/Fe(Ⅱ) Catalytic Oxidation Agents for Desulfurization Based on Iron Complexation Method

Optimization of factors influencing the experiments on reactions involving 8 different chelating agents and soluble Fe(III)/Fe(II) salts was carried out to yield chelated iron complexes. A combination of optimized influencing factors has resulted in a Fe chelating capacity of the iron-based desulfurization solution to be equal to 6.83—13.56 g/L at a redox potential of 0.185—0.3. The desulfurization performance of Fe(III)/Fe(II) chelating agents was investigated on a simulated sulfur-containing industrial gas composed of H2 S and N2 in a cross-flow rotating packed bed. Test results have revealed that the proposed iron-based desulfurization solution showed a sulfur removal efficiency of over 99% along with a Fe chelating capacity exceeding 1.35 g/L. This desulfurization technology which has practical application prospect is currently in the phase of commercial scale-up study.

On-line Monitoring for Phosphorus Removal Process and Bacterial Community in Sequencing Batch Reactor

For efficient energy consumption and control of effluent quality, the cycle duration for a sequencing batch reactor (SBR) needs to be adjusted by real-time control according to the characteristics and loading of waste-water. In this study, an on-line information system for phosphorus removal processes was established. Based on the analysis for four systems with different ecological community structures and two operation modes, anaerobic-aerobic process and anaerobic-anaerobic process, the characteristic patterns of oxidation-reduction potential (ORP) and pH were related to phosphorous dynamics in the anaerobic, anoxic and aerobic phases, for determination of the end of phosphorous removal. In the operation mode of anaerobic-aerobic process, the pH profile in the anaerobic phase was used to estimate the relative amount of phosphorous accumulating organisms (PAOs) and glycogen accumulat-ing organisms (GAOs), which is beneficial to early detection of ecology community shifts. The on-line sensor val-ues of pH and ORP may be used as the parameters to adjust the duration for phosphorous removal and community shifts to cope with influent variations and maintain appropriate operation conditions.

Effect of Return Sludge Pre-concentration on Biological Phosphorus Removal in a Novel Oxidation Ditch

A pilot-scale,pre-anoxic-anaerobic oxidation ditch was used in this study to treat municipal wastewater with limited carbon source.A novel return activated sludge(RAS) pre-concentration tank was adopted for improv-ing the phosphorus removal efficiency and the effects of RAS pre-concentration ratio were studied.Under the opti-mal operational condition,the suspended total phosphorus(STP) and the total phosphorus(TP) removal efficiencies were around 58.9% and 63.9% respectively and the effluent-P was lower than 0.8 mg·L-1.The reason is that with the optimal RAS pre-concentration ratio,nitrate is completely removed with endogenous carbon source and the secondary phosphorus release is strictly restrained in the pre-anoxic tank.Therefore,the anaerobic phosphorus release and the carbon source uptake by phosphorus accumulation organisms(PAOs) in the sludge,which are ex-tremely important to the phosphorus removal process,can be fully satisfied.Furthermore,the oxidation-reduction potential is proved to be suitable for controlling the RAS pre-concentration ratio due to influent fluctuation and varied conditions.The novel modified system is also beneficial for PAO accumulation.

Sustainable copper extraction from mixed chalcopyrite–chalcocite using biomass

This paper elaborated on the sustainability of the copper extraction process. In fact, an alternative copper extraction route from mixed sulphide ores, chalcopyrite and chalcocite using mesophilic biomass consortium at 33.3 °C and ferric leaching process were attempted. Bioleaching experiments were settled with a fraction size of-75+53 μm. Bacteria were used as the catalyst. A copper yield of 65.50% was obtained. On the other hand, in ferric leaching process, with a fraction size of-53+38 μm, when the temperature was increased to 70 °C, the copper leaching rate increased to 78.52%. Thus, comparatively, the mesophilic bioleaching process showed a more obvious advantage in copper extraction than leaching process with a high temperature. However, it has been resolved from the characterization performed using SEM-EDS, FTIR and XRD observations coupled with different thermodynamic approaches that, the indirect mechanism is the main leaching mechanism, with three transitory mechanisms(polysulphide, thiosulphate and elemental sulphur mechanisms) for the mixed chalcopyrite-chalcocite ore. Meanwhile, the speciation turns into Cu2 S-Cu S-Cu5 Fe S4-Cu2 S before turning into Cu SO4. While ferrous oxidation and the formation of ferric sulphate occur, and there is a formation of strong acid as bacteria digest sulphide minerals into copper sulphate at low temperature, which is why this copper production scenario requires a redox potential more than 550 m V at room temperature for high copper leaching rate.

Stepwise dissolution of chalcopyrite bioleaching by thermophile A.manzaensis and mesophile L. ferriphilum

Chalcopyrite dissolution was evaluated by bioleaching and electrochemical experiments with thermophile A. manzaensis（Acidianus manzaensis） and mesophile L. ferriphilum（Leptospirillum ferriphium） cultures at 65 ℃ and 40 ℃, respectively. It was investigated that the bioleaching of chalcopyrite was stepwise. It was reduced to Cu2 S at a lower redox potential locating in the whole bioleaching process by A. manzaensis at high temperature while only at initial days of bioleaching by L. ferriphilum at a relative low temperature. No reduced product was detected when the redox potential was beyond a high level（e.g., 550 m V（vs SCE）） bioleached by L. ferriphilum. Chalcopyrite bioleaching efficiency was substantially improved bioleached by A. manaensis compared to that by L. ferriphilum, which was mainly attributed to the reduction reaction occurring during bioleaching. The reductive intermediate Cu2 S was more amenable to oxidation than chalcopyrite, causing enhanced copper extraction.

Solar‐energy‐driven photothermal catalytic C–C coupling from CO_(2) reduction over WO_(3–x)

Solar‐energy‐driven catalytic CO_(2) reduction for the production of value‐added carbon‐based materials and chemical raw materials has attracted great interest to alleviate the global climate change and energy crisis.The production of multicarbon(C2)products through CO_(2) reduction is extremely attractive,however,the yield and selectivity of C2 products remain low because of the low reaction temperature required and the low photoelectron density of the substrate.Here,we introduce WO3–x,which contains oxygen vacancies and exhibits an excellent photothermal conversion efficiency,to improve the generation of C2 products(C2H4 and C2H6)under simulated sunlight(UV‐Vis‐IR)irradiation.WO3–x produced 5.30 and 0.93μmol·g^(–1)C2H4 and C2H6,respectively,after 4 h,with a selectivity exceeding 34%.In situ Fourier transform infrared spectra and theoretical calculations showed that the oxygen vacancies enhanced the water activation and hydrogenation of adsorbed CO for the formation of C2 products via C–C coupling from CH2/CH3 intermediates.The findings of this study could assist in the design of highly active solar‐energy‐driven catalysts to produce C–C coupling products through CO2 reduction.