Adsorption and reduction of nitrate in water on hydrotalcite-supported Pd-Cu catalyst

The hydrotalcite-supported Pd-Cu catalysts were successfully prepared by the impregnation or coprecipitation method, and their adsorption and catalytic reduction activity for nitrate in water were evaluated. The catalysts were characterized by X-ray diffraction (XRD) and surface area (BET) analysis. The results demonstrated that hydrotalcite-supported Pd-Cu catalysts could significantly adsorb nitrate ions, and then, effectively catalytically reduce them. The excellent adsorption ability for nitrate resulted from the regenerated layer structure of calcined hydrotalcite catalyst in nitrate aqueous solution. Nitrate was forced into the interlayer space and adsorbed on the external surface. The adsorption kinetics and the adsorption isotherm could be well described by pseudo-second-order model and the Langmuir model, respectively. The comparison of catalytic reduction with the adsorption for nitrate indicated that catalytic hydrogenation activity for nitrate increased with increasing adsorption capacity; nitrate reduction on hydrotalcite-supported Pd-Cu catalysts was a consecutive and dynamic adsorption and catalytic hydrogenation process. In addition, the catalyst obtained by coprecipitation method, with intact regeneration of hydrotalcite structure and a high dispersion of active metals, hold higher adsorption and catalytic activity than that prepared by co-impregnation method.     

Catalytic reduction of nitrates using Pt/CeO2 catalysts in a continuous reactor

The increasing pollution of natural sources of drinking water encourages the development of new emerging technologies and processes for water remediation. The present study demonstrates that monometallic Pt catalysts provide high conversion on the nitrate reduction reaction when ceria is used as support. However, the presence of ammonium was detected in all the catalysts. In order to control the formation of ammonium, the acid–base character of the support was modified, introducing several fluoride species into the CeO₂, using two different methods: impregnation and combustion. The introduction of fluoride species in the CeO₂ support by combustion produces a slight decrease in the reduction of nitrates. However, an important decrease in ammonium formation was observed. The capability of the reduction of surface CeO₂ and the acid–base properties of the support, after the addition of fluoride species, play an important role in the control of both activity and selectivity. The incorporation of fluoride species into the CeO₂, represents an alternative way to improve the selectivity of nitrate reduction toward nitrogen without the use of additional molecules such as CO₂ to control pH.     

Catalytic wet air oxidation of phenol using active carbon: performance of discontinuous and continuous reactors

Catalytic wet air oxidation (CWAO) of an aqueous phenol solution using active carbon (AC) as catalytic material was compared for a slurry and trickle bed reactor. Semi‐batchwise experiments were carried out in a slurry reactor in the absence of external and internal mass transfer. Trickle‐bed runs were conducted under the same conditions of temperature and pressure. Experimental results from the slurry reactor study showed that the phenol removal rate significantly increased with temperature and phenol concentration, whereas partial oxygen pressure had little effect. Thus, at conditions of 160 °C and 0.71 MPa of oxygen partial pressure, almost complete phenol elimination was achieved within 2 h for an initial phenol concentration of 2.5 g dm^?3. Under the same conditions of temperature and pressure, the slurry reactor performed at much higher initial rates with respect to phenol removal than the trickle bed reactor, both for a fresh active carbon and an aged active carbon, previously used for 50 h in the trickle bed reactor, but mineralisation was found to be much lower in the slurry reactor. Mass transfer limitations, ineffective catalyst wetting or preferential flow in the trickle bed alone cannot explain the drastic difference in the phenol removal rate. It is likely that the slurry system also greatly favours the formation of condensation polymers followed by their irreversible adsorption onto the AC surface, thereby progressively preventing the phenol molecules to be oxidised. Thus, the application of this type of reactor in CWAO has to be seriously questioned when aiming at complete mineralisation of phenol. Furthermore, any kinetic study of phenol oxidation conducted in a batch slurry reactor may not be useful for the design and scale‐up of a continuous trickle bed reactor. © 2001 Society of Chemical Industry     

The influence of activated carbon support on nitrate reduction by Fe(0) nanoparticles

Activated Carbon supported Fe(0) nanoparticles (AC-Fe(0)) were applied to the reductive removal of nitrate to investigate the effects of AC support on the reactivity of Fe(0) nanoparticle. XRD, SEM and EDS, XPS analyses on AC-Fe(0) revealed that AC-Fe(0) is more susceptible to oxidation compared to the unsupported Fe(0) nanoparticles, and that the extent of oxidation of the AC-Fe(0) particles will vary depending on the ratios of AC to Fe(0). Nitrate reduction rate of AC-Fe(0) was much slower than that of unsupported Fe(0) nanoparticles. AC-Fe(0) (0.5: 1) particles reduced the nitrate to ca. 40% of the initial concentration, and AC-Fe(0) (5: 1) particles performed poorly with only 10% removal of the nitrate. Besides the deactivation of AC-Fe(0) due to corrosion of Fe(0), the mass transport limitation caused by the thick layering of Fe(0) on porous AC seemed to be another negative factor for the decreased reactivity of AC-Fe(0).     

Catalytic conversion of low-density polyethylene using a continuous screw kiln reactor

Both thermal and catalytic cracking of low-density polyethylene (LDPE) have been investigated using a screw kiln reactor. Thermal degradation gives rise to a broad product distribution, whereas catalytic cracking over Al-MCM-41 leads mainly to hydrocarbons within the gasoline range (C₅–C₁₂) with selectivities up to 80%. The increase of the screw speed between 3 and 15 rpm in the catalytic experiments allows the plastic feed rate to be varied in the range 20–41 g h⁻¹. The changes observed in the TOF values when varying the screw speed point out a decrease of the activity per site with increasing residence times, which may be due to the catalyst deactivation or to a contribution of the degradative extrusion at higher screw speeds. Likewise, a certain increase in the selectivity towards the gasoline fraction is observed at short residence times. On the other hand, PIONA analyses indicate that, regardless of the screw speed, the main components of the gasoline are olefins (50%) and isoparaffins (20%), whereas the aromatic content is always below 6%, with a proportion of benzene lower than 0.1%.     

Electrocatalytic reduction of nitrate on copper electrode in alkaline solution

This work is devoted to the study of the kinetics and reaction mechanism of nitrate reduction on a copper electrode in 0.1 M NaOH, which acts as the supporting electrolyte. The experimental methods include cyclic voltammetry (CV), cronoamperometry (CA), controlled-potential electrolysis (CPE), and coulometry. In CV, there are three potential regions where charge transfer reactions take place, reactions which are associated with NO₃⁻ and/or intermediates reduction. Two isopotential points observed in CV indicate the existence of some competitive adsorption processes at the electrode surface.The three charge transfer steps were also made evident in the CA, CPE and coulometry studies. The correlation of the experimental results with the literature data led to the conclusion that NO₃⁻ reduction on a copper electrode in 0.1 M NaOH has an intermediate (N₂O₂²⁻) species, which reduces to N₂ at a potential of about −1.3 V and to NH₄OH at potential values lower than −1.4 V (both values are vs. SCE).     

The reduction of nitrate at a copper cathode in aqueous acid

It is confirmed that nitrate reduces to ammonia in high yield at a copper cathode in aqueous acidic perchlorate and sulphate media. At pH below 2, well formed reduction waves are observed; the process is irreversible but in the plateau region it is mass transfer controlled. Above pH 3, no reduction occurs. It is also shown that chloride, bromide and iodide ions inhibit the reduction causing the half wave potential for nitrate to be shifted to more negative potentials.     

Pulse-mode electrochemical reduction of carbon dioxide using copper and copper oxide electrodes for selective ethylene formation

Although the electrochemical reduction of CO₂ at a copper electrode produces hydrocarbons, the activity for the conversion of CO₂ is significantly reduced after several tens of minutes by the deposition of poisoning species on the electrode. In order to solve the poisoning species problem, the electrochemical reduction of CO₂ was carried out using a copper electrode in the pulse electrolysis mode by anodic as well as cathodic polarization. The anodic polarization intervals suppressed the deposition of the poisoning species on the electrode, and the amount of two hydrocarbons produced, CH₄ and C₂H₆, decreased only slightly even after one hour. By choosing the appropriate anodic potential and time duration the selectivity for C₂H₆ formation was significantly enhanced. The enhancement was found to be due to the copper oxide formed on the copper electrode. The selectivity was further improved when the electrochemical reduction was carried out using a copper oxide electrode. The highest efficiency of about 28% was obtained at −3.15 V.     

Catalytic dehydrogenative coupling of methane on active carbon. Effect of metal supported on active carbon

Ethane, ethene, ethyne and hydrogen are obtained in good yields via dehydrogenative coupling of methane in the presence of active carbon as a catalyst. The product yield is increased by supporting metal on active carbon.     

Simultaneous removal of atrazine and nitrate using a biological granulated activated carbon (BGAC) reactor

The objective of this research was to characterize the performance of granulated activated carbon (GAC) as a carrier for Pseudomonas ADP in a non‐sterile continuous fluidized bed reactor for atrazine degradation under anoxic conditions. The GAC was compared with two non‐adsorbing carriers: non‐adsorbing carbon particles (‘Baker product’) having the same surface area available for biofilm growth as the GAC, and sintered glass beads. The initial atrazine degradation efficiency was higher than 90% in the reactors with the non‐adsorbing carriers, but deteriorated to 20% with time due to contamination by foreign denitrifying bacteria. In contrast, no deterioration was observed in the biological granulated activated carbon (BGAC) reactor. A maximal atrazine volumetric and specific degradation rate of 0.820 ± 0.052 g atrazine dm^?3 day^?1 and 1.7 ± 0.4 g atrazine g^?1 protein day^?1 respectively were observed in the BGAC reactor. Concurrent atrazine biodegradation and desorption from the carrier was shown and an effluent concentration of 0.002 mg dm^?3 (below the EPA standard) was achieved in the BGAC reactor. The advantages of the BGAC reactor over the non‐adsorbing carrier reactors can probably be explained by the adsorption–desorption mechanism providing favorable microenvironmental conditions for atrazine–degrading bacteria. Copyright © 2004 Society of Chemical Industry     

Enhanced degradation of reactive dyes using a novel carbon ceramic electrode based on copper nanoparticles and multiwall carbon nanotubes

A novel carbon ceramic electrode consisting of CuNPs and MWCNT was developed to treat reactive orange 84 (RO84) wastewater using ultrasound-assisted electrochemical degradation. The proposed electrode generated more hydroxyl radicals than non-nanoparticle electrodes did. In addition, a new electrochemical sensor was applied to determine residue RO84 in an aqueous medium during discoloration. This sensor is based on a glassy carbon electrode modified with gold nanourchins and graphene oxide and can detect RO84 concentration in the range of 1.0-1200 μmol·L^-1 with the detection limit of 0.03 μmol·L^-1. The degradation effects of the modified electrode on RO84 were evaluated systematically with different initial pH values, time durations, and amounts of CuNPs and MWCNT. The results suggested that the removal efficiency of RO84 was approximately 83% after 120 min of electrolysis in a phosphate buffer with pH 8.0 using a carbon ceramic electrode made with 4.0 wt% CuNPs and 4.0 wt% MWCNT. The possible mechanism of RO84 degradation was monitored by gas chromatography-mass spectrometry, and degradation pathways were proposed.     

Environmental remediation of aqueous nitrate solutions by photocatalytic reduction using Pd/NaTaO3 nanoparticles

NaTaO₃ nanoparticles were prepared by an ultrasonic method, and Pd was deposited onto the surface of NaTaO₃ via photoassisted deposition. The resulting samples were characterised by X-ray diffraction, ultraviolet and visible spectroscopy, photoluminescence emission spectroscopy, transmission electron microscopy, extended X-ray absorption fine structure analysis, and surface area measurements. The catalytic performance of the samples in the photoreduction of nitrate under visible light was determined. The UV–vis analysis indicated that a red shift occurred after Pd was loaded onto NaTaO₃. The maximum reduction efficiency was 100%, which was obtained using 0.6 wt% Pd/NaTaO₃ after a reaction time of 50 min.     

Catalytic reduction of nitrate in water: Promoted palladium catalysts supported in resin

The reactive properties of Pd–Cu and Pd–In catalysts over weak anionic exchange resin as support was investigated in the catalytic nitrate reduction. Pd–Cu/resin catalysts were prepared upon different copper fixation procedures (ion exchange method and controlled surface reaction). The samples were tested in a batch reactor with H₂ bubbling and constant pH. The fresh and reacted catalysts were characterized by TEM, EPMA, XRD and XPS. The results demonstrated a higher activity of the Pd–Cu/resin catalyst prepared upon controlled surface reaction due to a high concentration of binary sites in the external surface. On the other hand, the XRD and TEM analyses indicated that sinterization occurs during reaction, leading to an increase in the average particle size.In the same way, a Pd–In/resin was investigated showing more activity and less selectivity than the Pd–Cu/resin sample.     

碳纤维表面连续镀铜工艺及性能研究

采用电化学沉积的方法在聚丙烯腈基碳纤维表面连续镀铜。利用CHI660电化学工作站测定了不同镀液的阴极极化曲线,以此优化镀液配方,并研究了工艺参数对镀层质量的影响。结果表明,以P2O74?与Cu2+质量比为7的镀液为基础镀液,加入20g/L柠檬酸铵,在温度40°C,pH=8.2～8.8和电流0.6A的条件下电镀60～150s,可以消除"黑心"和"结块"现象,得到均匀、细致、界面结合力良好的碳纤维表面镀铜层。镀后碳纤维导电性提高了150倍,但力学性能有所下降。     

Alloy ratio effect of Pd/Pt nanoparticles on carbon nanotubes for catalysing methanol-tolerant oxygen reduction

Pd₁Pt₃, Pd₁Pt₁, and Pd₃Pt₁ nanoparticles supported on multi-wall carbon nanotubes (CNTs) were prepared by the self-regulation reduction of sodium n-dodecyl sulphate and used as catalysts in oxygen reduction reactions (ORRs). The crystal properties of these alloy nanoparticles on the CNT were measured by X-ray diffraction spectroscopy (XRD) and high-resolution transmission electron microscopy (HRTEM). The angle shifting of the XRD peak and the lattice spacing of the nanoparticles measured by HRTEM increased with an increase in Pd amount, indicating a regulable Pd-Pt ratio for the alloy nanoparticle composition. Rotating ring-disk electrode (RRDE) measurements indicate that the number of electrons catalysed by the Pd₁Pt₃/CNT, Pd₁Pt₁/CNT, and Pd₃Pt₁/CNT nanocatalysts in the ORRs were 3.98, 3.97, and 3.93, respectively. These results show that these ORRs occur via a 4-electron pathway. Linearly scanned voltammetry in the electrolyte with methanol revealed that Pd₃Pt₁/CNT has high methanol tolerance during ORRs.     

Modelling of a continuous parallel plate plug flow electrochemical reactor: electrowinning of copper

Journal of Applied Electrochemistry - On the basis of copper winning in a sulphuric acid medium this paper presents an original calculation method for the design of a continuous parallel plate...     

Catalyst optimization and reduction condition of continuous growth of carbon nanotubes on carbon fiber surface

Carbon nanotubes (CNTs)/carbon fiber (CF) reinforcements were synthesized under different catalyst compositions and reduction conditions. The effects of the catalyst, reduction temperature and reduction time on the surface morphology, graphitization, and single filament tensile strength of the prepared CNTs/CF samples were investigated. When nickel was used as the catalyst and copper as the catalyst promoter, with the increase of copper concentration, the catalytic activity increased. Thus, the carbon source was consumed more completely, improving the abundance of CNTs with good graphitization. And the effect of repairing CF defects was more obvious, hence the single filament tensile strength accordingly increased. Besides, the increase of catalyst reduction temperature and reduction time intensified the etching of CF by catalyst, and decreased the single filament tensile strength of CF. With the deposition of CNTs, the tensile strength of CF was enhanced in varying degrees. When the concentration of cooper was 0.01 mol/L with the reduction time of 10 min and reduction temperature of 450 °C, CNTs/CF had the highest tensile strength, which can reach up to 4.51 GPa. We determined that bimetallic catalysts could adjust the catalytic activity of nickel. The change of reduction time and temperature would affect the quality of CNTs, which was helpful to obtain high quality CNTs on CF surface and improve the mechanical properties of CNTs/CF and its composites.     

硝酸铋和活性炭催化的水合肼还原芳香族硝基化合物制芳胺

研究了以硝酸铋和活性炭催化水合肼还原芳香族硝基化合物制备芳胺的反应.以硝基苯为底物,考察了硝酸铋和活性炭用量对反应的影响.结果表明,还原1 mmol硝基苯,Bi(NO3)3·5H2O和活性炭的适宜用量分别为0.06和0.1 g.在适宜的条件下,9种芳香族硝基化合物被还原为芳胺的收率为78%～99%.芳香族硝基化合物中取代基对反应结果有较大影响.催化剂的活性随使用次数的增加而下降,其活性下降的原因是硝酸铋的流失.