Photocatalytic Gold Recovery from Industrial Gold Plating Effluent by ZnO Nanoparticles: Optimum Condition and Possible Applications.

The comparative study of photocatalytic gold recovery from cyanide-based gold plating solution was explored via commercial and hydrothermally synthesized ZnO nanoparticles (NPs). The effects of hydrothermal temperatures on the properties and photocatalytic activities of synthesized ZnO NPs were investigated. In addition, the effects of operating parameters including types of hole scavenger, concentrations of the best hole scavenger, the initial pH of wastewater, and photocatalyst dosages were examined. The obtained results demonstrated that the commercial ZnO NPs exhibited a higher photocatalytic activity for gold recovery than that of the synthesized ones owing to their good crystal quality and the presence of non-lattice zinc ions and appropriate non-lattice oxygen ions. Via the commercial ZnO NPs, the gold ions were almost completely recovered from the cyanide-based gold plating effluent within 7 h at an initial pH of 11.0 in the presence of 10 vol % C2H5OH and 1.0 g/L of photocatalyst loading with a pseudo-first-order rate constant of 0.2637 h-1. Finally, the resultant gold-decorated ZnO NPs exhibited a higher photocatalytic property for color reduction from industrial wastewater and antibacterial activity than that of fresh ZnO NPs. The results obtained in this study possess benefits and pave the way for waste remediation and management for the plating industries.

Highly efficient ZnO/WO3 nanocomposites towards photocatalytic gold recovery from industrial cyanide-based gold plating wastewater.

Discharging the gold-contained wastewater is an economic loss. In this work, a set of ZnO/WO3 was facile synthesized by hydrothermal method in order to recover gold from the industrial cyanide-based gold plating wastewater by photocatalytic process. Effect of ZnO contents coupled with WO3 was first explored. Then, effects of operating condition including initial pH of wastewater, type of hole scavenger, concentration of the best hole scavenger and photocatalyst dose were explored. A series of experimental results demonstrated that the ZnO/WO3 nanocomposite with 5 wt% ZnO (Z5.0/WO3) depicted the highest photocatalytic activity for gold recovery due to the synergetic effect of oxygen vacancies, a well-constructed ZnO/WO3 heterostructure and an appropriate band position alignment with respect to the redox potentials of [Au(CN)2]- and hole scavengers. Via this ZnO/WO3 nanocomposite, approximately 99.5% of gold ions was recovered within 5 h using light intensity of 3.57 mW/cm2, catalyst dose of 2.0 g/L, ethanol concentration of 20 vol% and initial pH of wastewater of 11.2. In addition, high stability and reusability were observed with the best nanocomposite even at the 5th reuse. This work provides the guidance and pave the way for designing the ZnO/WO3 nanocomposite for precious metal recovery from a real industrial wastewater.

Glycerol photocatalytic oxidation to higher value-added compounds via bismuth oxyhalide photocatalysts.

Bismuth oxyhalides (BiOX) including BiOCl, BiOBr, and BiOI, were well synthesized using solvothermal technique and then used in the aqueous phase photooxidation of glycerol as a catalyst. The as-synthesized BiOBr could achieve the highest glycerol transformation of around 85.6% in 8 h under ultraviolet light (UV) irradiation among as-synthesized BiOXs. Moreover, the BiOBr/TiO2 heterojunction was also prepared through an ethylene glycol-assisted solvothermal process. This new BiOBr/TiO2 heterostructure exhibited excellent photocatalytic activity (97.4%) for the oxidation of glycerol compared with pure BiOBr (74%) under ultraviolet light irradiation at 6 h. This obtained behavior was confirmed by more produced OH• radicals of BiOBr/TiO2.

Innovative metal oxides (CaO, SrO, MgO) impregnated waste-derived activated carbon for biohydrogen purification.

In this work, a series of innovative metal oxide impregnated waste-derived activated carbons (MO/AC) was synthesized and used to purify the simulated biohydrogen based on the concept of CO2 removal from the gas stream. Effects of metal oxide types (CaO, SrO and MgO) and contents of the best metal oxides on the morphology and the CO2 adsorption capacity from the biohydrogen were investigated. It was found that both metal oxide types and contents played an important role on the adsorbent textural property and surface chemistry as well as the CO2 adsorption capacity. Among all synthesized adsorbent, the MgO-impregnated AC with 12 wt.% MgO (12MgO/AC) exhibited the highest CO2 adsorption capacity of around 94.02 mg/g. With this successive adsorbent, the biohydrogen with the H2 purity higher than 90 mol% can be achieved from the gas stream with 50 mol% CO2 for the first 2 min of adsorption period in a fixed bed reactor. The mechanism of CO2 adsorption occurred via a combined process of the physisorption and chemisorption. Besides, the 12MgO/AC exhibited a high recyclability after several repetitive adsorption/desorption cycles.

Photosynthesis of Au/TiO2 nanoparticles for photocatalytic gold recovery from industrial gold-cyanide plating wastewater.

A series of Aux/TiO2 nanoparticles (NPs) with different gold loadings (x = 0.1-1.0 wt%) was synthesized by the photodeposition and then employed as photocatalysts to recover precious component from the industrial gold-cyanide plating wastewater. Effects of Au loading, catalyst dosage and types of hole scavenger on the photocatalytic gold recovery were investigated under ultraviolet-visible (UV-Vis) light irradiation at room temperature. It was found that different Au loadings tuned the light absorption capacity of the synthesized photocatalysts and enhanced the photocatalytic activity in comparison with the bare TiO2 NPs. The addition of CH3OH, C2H5OH, C3H8O, and Na2S2O3 as a hole scavenger significantly promoted the photocatalytic activity of the gold recovery, while the H2O2 did not. Among different hole scavengers employed in this work, the CH3OH exhibited the highest capability to promote the photocatalytic gold recovery. In summary, the Au0.5/TiO2 NPs exhibited the best photocatalytic activity to completely recover gold ions within 30 min at the catalyst dosage of 0.5 g/L, light intensity of 3.20 mW/cm2 in the presence of 20 vol% CH3OH as hole scavenger. The photocatalytic activity slightly decreased after the 5th cycle of recovery process, indicating its high reusability.

Valorization of spent disposable wooden chopstick as the CO2 adsorbent for a CO2/H2 mixed gas purification.

A series of activated carbons (ACs) derived from spent disposable wooden chopsticks was prepared via steam activation and used to separate carbon dioxide (CO2) from a CO2/hydrogen (H2) mixed gas at atmospheric pressure. A factorial design was employed to investigate the effects of the activation temperature and time as well as their interactions on the production yield of ACs and their CO2 adsorption capacity. The activation temperature exhibited a much higher impact on both the production yield and the CO2 adsorption capacity of ACs than the activation time. The interaction of both parameters did not significantly affect the yield of ACs, but did affect the CO2 adsorption capacity. The optimal preparation condition provided ACs with a desirable yield of around 23.18% and a CO2 adsorption capacity of 85.19 mg/g at 25 °C and 1 atm and consumed the total energy of 225.28 MJ/kg AC or 116.4 MJ/g-mol CO2. A H2 purity of greater than 96.8 mol% was achieved from a mixed gas with low CO2 concentration (< 20 mol%) during the first 3 min of adsorption and likewise around 90 mol% from a mixed gas with a high CO2 concentration (> 30 mol%) during the first 2 min. The CO2 adsorption on the as-prepared ACs proceeded dominantly via multilayer physical adsorption and was affected by both the surface area and micropore volume of the ACs. The adsorption capacity was diminished by around 18% after six adsorption/desorption cycles. The regeneration of the as-prepared chopstick-derived ACs can be easily performed via heating at a low temperature and ambient pressure, suggesting their potential application in the temperature swing adsorption process.

Correction to "Ultrasound-Assisted Synthesis of Nonmetal-Doped Titanium Dioxide Photocatalysts for Simultaneous H2 Production and Chemical Oxygen Demand Removal from Industrial Wastewater".

[This corrects the article DOI: 10.1021/acsomega.1c03483.].

Photocatalytic Recovery of Gold from a Non-Cyanide Gold Plating Solution as Au Nanoparticle-Decorated Semiconductors.

In this work, a photocatalytic process was carried out to recover gold (Au) from the simulated non-cyanide plating bath solution. Effects of semiconductor types (TiO2, WO3, Nb2O3, CeO2, and Bi2O3), initial pH of the solution (3-10), and type of complexing agents (Na2S2O3 and Na2SO3) and their concentrations (1-4 mM each) on Au recovery were explored. Among all employed semiconductors, TiO2 exhibited the highest photocatalytic activity to recover Au from the simulated spent plating bath solution both in the absence and presence of complexing agents, in which Au was completely recovered within 15 min at a pH of 6.5. The presence of complexing agents remarkably affected the size of deposited Au on the TiO2 surface, the localized surface plasmon effect (LSPR) behavior, and the valence band (VB) edge position of the obtained Au/TiO2, without a significant change in the textural properties or the band gap energy. The photocatalytic activity of the obtained Au/TiO2 tested via two photocatalytic processes depended on the common reduction mechanism rather than the textural or optical properties. As a result, the Au/TiO2 NPs obtained from the proposed recovery process are recommended for use as a photocatalyst for the reactions occurring at the conduction band rather than at the valence band. Notably, they exhibited good stability after the fifth photocatalytic cycle for Au recovery from the actual cyanide plating bath solution.

Ultrasound-Assisted Synthesis of Nonmetal-Doped Titanium Dioxide Photocatalysts for Simultaneous H2 Production and Chemical Oxygen Demand Removal from Industrial Wastewater.

A series of nonmetal-doped titanium dioxide (Nm x /TiO2, where x is the weight fraction of nonmetal elements) photocatalysts was prepared via ultrasonic-assisted impregnation for simultaneous hydrogen (H2) production and chemical oxygen demand (COD) removal from industrial wastewater. Three types of Nm elements, carbon (C), silicon (Si), and phosphorus (P), were explored. The P1/TiO2 exhibited a higher photocatalytic activity for H2 production and COD removal than the C1/TiO2 and Si1/TiO2 photocatalysts. Approximately 6.43 mmol/g photocatalyst of H2 was produced, and around 26% COD removal was achieved at a P1/TiO2 loading of 4.0 g/L, a light intensity of 5.93 mW/cm2, and a radiation time of 4 h. This is because the P1/TiO2 photocatalyst exhibited lower point of zero charge values and a more appropriate band position compared with other Nm x /TiO2 photocatalysts to produce H+, which can consequently form H2, and reactive oxygen species (HO· and O2 · -), which serve as oxidizing agents to degrade the organic pollutants. Increasing the content of the P element doped into the TiO2-based material up to 7.0% by weight enhanced the H2 production and COD removal up to 8.34 mmol/g photocatalyst and 50.6%, respectively. This is attributed to the combined effect of the point of zero charge value and the S BET of the prepared photocatalysts. The photocatalytic activity of the P7/TiO2 photocatalyst was still higher than the TiO2-based material after the fourth use.

Enhancing the Antibacterial Properties of PVDF Membrane by Hydrophilic Surface Modification Using Titanium Dioxide and Silver Nanoparticles.

This work investigates polyvinylidene fluoride (PVDF) membrane modification to enhance its hydrophilicity and antibacterial properties. PVDF membranes were coated with nanoparticles of titanium dioxide (TiO2-NP) and silver (AgNP) at different concentrations and coating times and characterized for their porosity, morphology, chemical functional groups and composition changes. The results showed the successfully modified PVDF membranes containing TiO2-NP and AgNP on their surfaces. When the coating time was increased from 8 to 24 h, the compositions of Ti and Ag of the modified membranes were increased from 1.39 ± 0.13 to 4.29 ± 0.16 and from 1.03 ± 0.07 to 3.62 ± 0.08, respectively. The water contact angle of the membranes was decreased with increasing the coating time and TiO2-NP/AgNP ratio. The surface roughness and permeate fluxes of coated membranes were increased due to increased hydrophilicity. Antimicrobial and antifouling properties were investigated by the reduction of Escherichia coli cells and the inhibition of biofilm formation on the membrane surface, respectively. Compared with that of the original PVDF membrane, the modified membranes exhibited antibacterial efficiency up to 94% against E. coli cells and inhibition up to 65% of the biofilm mass reduction. The findings showed hydrophilic improvement and an antimicrobial property for possible wastewater treatment without facing the eminent problem of biofouling.

Comparative Study of the ORR Activity and Stability of Pt and PtM (M = Ni, Co, Cr, Pd) Supported on Polyaniline/Carbon Nanotubes in a PEM Fuel Cell.

The oxygen reduction reaction (ORR) activity and stability of platinum (Pt) and PtM (M = Ni, Co, Cr, Pd) supported on polyaniline/carbon nanotube (PtM/PANI-CNT) were explored and compared with the commercial Pt/C catalyst (ETEK). The Pt/PANI-CNT catalyst exhibited higher ORR activity and stability than the commercial Pt/C catalyst even though it had larger crystallite/particle sizes, lower catalyst dispersion and lower electrochemical surface area (ESA), probably because of its high electrical conductivity. The addition of second metal (M) enhanced the ORR activity and stability of the Pt/PANI-CNT catalyst, because the added M induced the formation of a PtM alloy and shifted the d-band center to downfield, leading to a weak chemical interaction between oxygenated species and the catalyst surface and, therefore, affected positively the catalytic activity. Among all the tested M, the addition of Cr was optimal. Although it improved the ORR activity of the Pt/PANI-CNT catalyst slightly less than that of Pd (around 4.98%) in low temperature (60 °C)/pressure (1 atm abs), it reduced the ESA loss by around 14.8% after 1000 cycles of repetitive cyclic voltammetry (CV). In addition, it is cheaper than Pd metal. Thus, Cr was recommended as the second metal to alloy with Pt on the PANI-CNT support.

Photoinduced Glycerol Oxidation over Plasmonic Au and AuM (M = Pt, Pd and Bi) Nanoparticle-Decorated TiO2 Photocatalysts.

In this study, sol-immobilization was used to prepare gold nanoparticle (Au NP)-decorated titanium dioxide (TiO2) photocatalysts at different Au weight % (wt. %) loading (Aux/TiO2, where x is the Au wt. %) and Au⁻M NP-decorated TiO2 photocatalysts (Au3M3/TiO2), where M is bismuth (Bi), platinum (Pt) or palladium (Pd) at 3 wt. %. The Aux/TiO2 photocatalysts exhibited a stronger visible light absorption than the parent TiO2 due to the localized surface plasmon resonance effect. Increasing the Au content from 1 wt. % to 7 wt. % led to increased visible light absorption due to the increasing presence of defective structures that were capable of enhancing the photocatalytic activity of the as-prepared catalyst. The addition of Pt and Pd coupled with the Au3/TiO2 to form Au3M3/TiO2 improved the photocatalytic activity of the Au3/TiO2 photocatalyst by maximizing their light-absorption property. The Au3/TiO2, Au3Pt3/TiO2 and Au3Pd3/TiO2 photocatalysts promoted the formation of glyceraldehyde from glycerol as the principle product, while Au3Bi3/TiO2 facilitated glycolaldehyde formation as the major product. Among all the prepared photocatalysts, Au3Pd3/TiO2 exhibited the highest photocatalytic activity with a 98.75% glycerol conversion at 24 h of reaction time.

Optimal Hydrogen Production Coupled with Pollutant Removal from Biodiesel Wastewater Using a Thermally Treated TiO2 Photocatalyst (P25): Influence of the Operating Conditions.

This work aimed to produce hydrogen (H2) simultaneously with pollutant removal from biodiesel wastewater by photocatalytic oxidation using a thermally-treated commercial titanium dioxide (TiO2) photocatalyst at room temperature (~30 °C) and ambient pressure. The effects of the operating conditions, including the catalyst loading level (1-6 g/L), UV light intensity (3.52-6.64 mW/cm²), initial pH of the wastewater (2.3-8.0) and reaction time (1-4 h), on the quantity of H2 production together with the reduction in the chemical oxygen demand (COD), biological oxygen demand (BOD) and oil and grease levels were explored. It was found that all the investigated parameters affected the level of H2 production and pollutant removal. The optimum operating condition for simultaneous H2 production and pollutant removal was found at an initial wastewater pH of 6.0, a catalyst dosage of 4.0 g/L, a UV light intensity of 4.79 mW/cm² and a reaction time of 2 h. These conditions led to the production of 228 µmol H2 with a light conversion efficiency of 6.78% and reduced the COD, BOD and oil and grease levels by 13.2%, 89.6% and 67.7%, respectively. The rate of pollutant removal followed a pseudo-first order chemical reaction with a rate constant of 0.008, 0.085 and 0.044 min-1 for the COD, BOD and oil and grease removal, respectively.

Treatment of biodiesel wastewater by adsorption with commercial chitosan flakes: parameter optimization and process kinetics.

The possibility of using commercial chitosan flakes as an adsorbent for the removal of pollutants from biodiesel wastewater was evaluated. The effect of varying the adsorption time (0.5-5 h), initial wastewater pH (2-8), adsorbent dose (0.5-5.5 g/L) and mixing rate (120-350 rpm) on the efficiency of pollutant removal was explored by univariate analysis. Under the derived optimal conditions, greater than 59.3%, 87.9% and 66.2% of the biological oxygen demand (BOD), chemical oxygen demand (COD) and oil & grease, respectively, was removed by a single adsorption. Nevertheless, the remaining BOD, COD and oil & grease were still higher than the acceptable Thai government limits for discharge into the environment. When the treatment was repeated, a greater than 93.6%, 97.6% and 95.8% removal of the BOD, COD and oil & grease, respectively, was obtained. The reusability of commercial chitosan following NaOH washing (0.05-0.2 M) was not suitable, with less than 40% efficiency after just one recycling and declining rapidly thereafter. The adsorption kinetics of all pollutant types by the commercial chitosan flakes was controlled by a mixed process of diffusion and adsorption of the pollutants during the early treatment period (0-1.5 h) and then solely controlled by adsorption after 2 h.

Treatment of wastewater from pulp and paper mill industry by electrochemical methods in membrane reactor.

The treatment of wastewater from a pulp and paper mill plant using electrochemical methods was performed at a laboratory bench-scale at ambient temperature (~30 °C). The effects of wastewater dilution (10- to 100-fold), circulating water flow rate (0-3.95 l/min), current density (1.90-3.80 mA/cm(2)) and sodium chloride concentration (0-3.75 g/l) were ascertained. The results demonstrated that this methods can facilitate the disappearance of the oxidative coupling unit of lignin as well as other organic and inorganic compounds, measured in terms of the removal of color, total biological- and total chemical oxygen demand (BOD and COD), and the total suspended and dissolved solids (TSS and TSD). In addition, the electrochemical method was more effective at reducing the pollutant levels, produced a smaller quantity of low-density sludge and had a low operating cost per unit quantity of COD. After optimization, the electrochemical method operating in a batch mode enhanced the removal of color, BOD and COD at around 98%, 98% and 97%, respectively, whilst in a continuous mode at the steady state condition (8 h after the start-up time) the color, BOD and COD levels were reduced by around 91%, 83% and 86%, respectively.

Remediation of biodiesel wastewater by chemical- and electro-coagulation: a comparative study.

The remediation of biodiesel wastewater was carried out using chemical and electrochemical techniques. Initially the fatty acid methyl esters (FAME or biodiesel) and free fatty acids (FFA) were chemically removed from the wastewater using three types of mineral acids, H(2)SO(4), HNO(3) and HCl, at different pH values within the range of 1.0-8.0. Optimally, approximately 24.3 ml/l of FAME/FFA were removed from the wastewater when using H(2)SO(4) to set a final pH of 2.5 for 7 min. All pollutant levels were markedly reduced during this step. That is, approximately 38.94%, 76.32% and 99.36% of COD, BOD5 and oil & grease were respectively removed. The acidic aqueous phase left after the removal of the FAME/FFA phase was then treated by chemical- and electro-coagulation processes. The results demonstrated that both investigated treatment processes were effective for treating wastewater from a biodiesel production plant. The chemical coagulation provided a lower operating cost (1.11 USD/m(3)) compared with the electro-coagulation process (1.78 USD/m(3)). However, the latter process provided a better quality of wastewater compared with the former process, with the exception of the BOD levels.

Treatment of distillery wastewater by the nano-scale zero-valent iron and the supported nano-scale zero-valent iron.

The treatment of wastewater from the distillery industry was carried out by using nano-scale- and supported nano-scale zero-valent iron at a laboratory scale and ambient temperature. Effects of dilution, pH, mixing rate, zero-valent iron dosage, and amount of support for the zero-valent iron were investigated. All parameters had a significant effect on the removal efficiency of all investigated pollutants. Increasing the number of dilutions and the nano-scale zero-valent iron dosage led to the increase of removal efficiency of pollutants. Higher removal efficiency was achieved in an acidic initial pH of wastewater. The reduction of all pollutants was limited by the kinetics of the pollutant destruction/reduction by nano-scale zero-valent iron particles at a mixing rate greater than 170 rpm. At optimum condition, greater than 95, 94, and 64% of color, chemical oxygen demand, and biochemical oxygen demand were removed, respectively, within 6 hours. Additionally, the presence of a support had a significant effect on pollutant removal.