Controlling the Pore Size and Connectivity of Alumina-Particle-Stabilized Foams Using Sodium Dodecyl Sulfate: Role of Surfactant Concentration.

Herein, alumina foams were prepared from particle-stabilized foams, fabricated by direct foaming methods, that varied according to the concentration of sodium dodecyl sulfate (SDS). To confirm the formation mechanism of pore structures in alumina ceramic foams with varying SDS concentrations, the adsorption density, contact angle, ζ-potential, and surface tension of the alumina particles dispersed in SDS were analyzed. Additionally, model analysis was performed to confirm the interaction between alumina and air bubbles by applying the extended Derjaguin-Landau-Verwey-Overbeek model. The attachment of alumina particles to bubble surfaces at different SDS concentrations affected the pore structure of the ceramic foams; this confirmed that the attachment was significantly affected by the electrostatic interaction energy rather than hydrophobic interaction. Therefore, the pore size and connectivity of alumina foams could be controlled by varying the electrostatic interaction energy between alumina particles and air bubbles, which is determined by the SDS concentration.

Synthesis of hierarchical MoO2/MoS2 nanofibers for electrocatalytic hydrogen evolution.

Perpendicularly attached MoS2 nanosheets on MoO2 conductive nanofibers were synthesized by combining electrospinning, calcination, and sulfurization processes. Compared to randomly stacked MoS2 nanosheets on MoO2 nanofiber, they show greater hydrogen evolution reaction (HER) performance (i.e., onset potential of -180 mV versus normal hydrogen electrode with the Tafel slope of 59 mV dec-1). HER performance decreases with increasing MoS2 nanocrystal size.

Bioleaching of arsenic from highly contaminated mine tailings using Acidithiobacillus thiooxidans.

The behavior of arsenic (As) bioleaching from mine tailings containing high amount of As (ca. 34,000 mg/kg) was investigated using Acidithiobacillus thiooxidans to get an insight on the optimal conditions that would be applied to practical heap and/or tank bioleaching tests. Initial pH (1.8-2.2), temperature (25-40 °C), and solid concentration (0.5-4.0%) were employed as experimental parameters. Complementary characterization experiments (e.g., XRD, SEM-EDS, electrophoretic mobility, cell density, and sulfate production) were also carried out to better understand the mechanism of As bioleaching. The results showed that final As leaching efficiency was similar regardless of initial pH. However, greater initial As leaching rate was observed at initial pH 1.8 than other conditions, which could be attributed to greater initial cell attachment to mine tailings. Unlike the trend observed when varying the initial pH, the final As leaching efficiency varied with the changes in temperature and solid concentration. Specifically, As leaching efficiency tended to decrease with increasing temperature due to the decrease in the bacterial growth rate at higher temperature. Meanwhile, As leaching efficiency tended to increase with decreasing solid concentration. The results for jarosite contents in mine tailings residue after bioleaching revealed that much greater amount of the jarosite was formed during the bioleaching reaction at higher solid concentration, suggesting that the coverage of the surface of the mine tailings by jarosite and/or the co-precipitation of the leached As with jarosite could be a dominant factor reducing As leaching efficiency.

Effect of Poly(vinyl alcohol) Concentration on the Micro/Mesopore Structure of SBA15 Silica.

In this work, a series of micro/mesoporous SBA15 silica materials were synthesized using P123 and poly(vinyl alcohol) (PVA) as co-templates. The pore structure of the prepared SBA15 was observed to be a function of the PVA concentration. When the amount of PVA was relatively small, the specific surface area, micropore volume, and pore wall thickness of the synthesized SBA15 were considerably large. By contrast, when a large amount of PVA was added, the pore wall thickness was greatly reduced, but the mesopore volume and size increased. This is because the added PVA interacted with the polyethylene oxide (PEO) in the shells of the P123 micelles. Furthermore, when the amount of PVA was increased, the core polypropylene oxide (PPO) block also increased, owing to the enhanced aggregation of the P123/PVA mixed micelles. This research contributes to a basic comprehension of the cooperative interactions and formation process underlying porous silica materials, assisting in the rational design and synthesis of micro/mesoporous materials.

3-D porous cellulose nanofibril aerogels with a controllable copper nanoparticle loading as a highly efficient non-noble-metal catalyst for 4-nitrophenol reduction.

Nitrophenols(NPs) are highly toxic compounds that occur in various industrial effluents. Herein, we investigated Cu nanoparticle-loaded cellulose nanofibril (CNF/PEI-Cu) aerogels as a catalyst for degrading 4-nitrophenol (4NP) in the wastewater. Non-noble metal based low-cost catalyst material and easily scalable preparation method make CNF/PEI-Cu aerogel as an appropriate catalyst for practical application in 4NP wastewater treatment. Our strategy to improve the loading amount of homogeneously distributed Cu nanoparticles was to functionalize a CNF aerogel using polyethylene imine (PEI), which can bind Cu2+ ions. Porous CNF aerogels with homogenously distributed 20-40 nm Cu nanoparticles were obtained by adsorbing Cu2+ ions and chemically reducing them to Cu metal. The FTIR, XRD, SEM, XPS and ICP-OES analysis were used to confirm the in-situ formation of Cu nanoparticles. In the presence of the CNF/PEI-Cu aerogels, 4NP was effectively reduced to 4-aminophenol (4AP) without loss of the Cu nanoparticles. The activation energy (Ea) and reaction rate constant (kapp) of the catalytic 4NP reduction reaction by the CNF/PEI2-Cu aerogels were calculated to be Ea = 39.56 kJ mol-1 and kapp = 0.770 min-1, respectively. The Ea is similar or even smaller than the Ea values of the corresponding reactions involving noble-metal catalysts, demonstrating that the CNF/PEI-Cu aerogels developed in the present study have strong potential as practical and economical catalysts.

Modified cellulose nanofibril aerogel: Tunable catalyst support for treatment of 4-Nitrophenol from wastewater.

4-Nitrophenol (4-NP) is a hazardous aromatic compound widely used for various industries. Catalytic reduction of 4-NP using metal nanoparticles (NPs) is a highly effective method to treat 4-NP from waste effluent. Even though lots of methods have investigated to prepare efficient metal NPs composites, the nano and/or micro size of composites makes it hard to recover after wastewater treatment, limiting its practical use. Here, we fabricate 3-dimensional polyethylene imine grafted cellulose nanofibril (CNF-PEI) aerogel as a porous support material for platinum (Pt) NPs to practically and effectively treat 4-NP from wastewater. The Pt NPs are formed in-situ mode on cylindrical CNF-PEI aerogel by adsorption reaction with amine groups of PEI and subsequently reduction with NaBH4. Control of PEI grafting density and the initial concentration of Pt ions allows manipulation of the loading mass, size, and distribution of Pt NPs on 3D scaffold of CNF-PEI aerogel. The composite aerogel shows high catalytic activity for conversion of 4-NP. The 4-NP conversion activity is strongly affected by the size of Pt NPs and effective surface area of aerogels. The 2.74 nm size Pt NPs with even distribution in the aerogel show fast reaction kinetics (k = 0.12 min-1). Finally, 4-NP reduction efficiency does not decrease during 5 times reuse cycle of Pt NPs loaded CNF-PEI aerogel. This CNF-PEI aerogel loaded with Pt NPs is recovered easily from wastewater after treatment, so it is reusable and offers high potential as a practical recyclable environmental catalyst.

Mesoporous Silica Derived from Municipal Solid Waste Incinerator (MSWI) Ash Slag: Synthesis, Characterization and Use as Supports for Au(III) Recovery.

In this study, the effect of NaOH on the synthesis of mesoporous silica (MS) by using municipal solid-waste incinerator (MSWI) ash slag was investigated. Moreover, the prepared MS was used as a support to evaluate its potential for the recovery of gold ions (Au(III)) from aqueous solution. The extraction process for the MSWI ash slag activated through mechanical grinding entailed alkali treatment, using varying concentrations of NaOH. The content of Si extracted from MSWI ash slag increased with the increasing grinding time and NaOH concentration. As the NaOH concentration increased, the pore structure (e.g., Brunauer-Emmett-Teller (BET) surface area and pore volume) of the synthesized MS improved. In addition, the amount of adsorbed Au(III) increased with increasing sulfur content immobilized on the support, and the sulfur content was in turn governed by the silanol content of the MS support. The adsorbent prepared by using the MS-3M support exhibited the highest Au(III) adsorption capacity (110.3 mg/g), and its adsorption-desorption efficiency was not significantly affected even after five adsorption-desorption cycles.

Processable high internal phase Pickering emulsions using depletion attraction.

High internal phase emulsions have been widely used as templates for various porous materials, but special strategies are required to form, in particular, particle-covered ones that have been more difficult to obtain. Here, we report a versatile strategy to produce a stable high internal phase Pickering emulsion by exploiting a depletion interaction between an emulsion droplet and a particle using water-soluble polymers as a depletant. This attractive interaction facilitating the adsorption of particles onto the droplet interface and simultaneously suppressing desorption once adsorbed. This technique can be universally applied to nearly any kind of particle to stabilize an interface with the help of various non- or weakly adsorbing polymers as a depletant, which can be solidified to provide porous materials for many applications.

Transport, retention, and long-term release behavior of ZnO nanoparticle aggregates in saturated quartz sand: Role of solution pH and biofilm coating.

The transport, retention, and long-term release of zinc oxide nanoparticle aggregates (denoted below as ZnO-NPs) were investigated in saturated, bare and biofilm (Pseudomonas putida) coated sand packed columns. Almost complete retention of ZnO-NPs occurred in bare and biofilm coated sand when the influent solution pH was 9 and the ionic strength (IS) was 0.1 or 10 mM NaCl, and the retention profiles were always hyper-exponential. Increasing the solution IS and biofilm coating produced enhanced retention of ZnO-NPs near the column inlet. The enhanced NPs retention at high IS was attributed to more favorable NP-silica and NP-NP interactions; this was consistent with the interaction energy calculations. Meanwhile, the greater NPs retention in the presence of biofilm was attributed to larger roughness heights which alter the mass transfer rate, the interaction energy profile, and lever arms associated with the torque balance; e.g., scanning electron and atomic force microscopy was used to determine roughness heights of 33.4 nm and 97.8 nm for bare sand and biofilm-coated sand, respectively. Interactions between NPs and extracellular polymeric substances may have also contributed to enhanced NP retention in biofilm-coated sand at low IS. The long-term release of retained ZnO-NPs was subsequently investigated by continuously injecting NP-free solution at pH 6, 9, or 10 and keeping the IS constant at 10 mM. The amount and rate of retained ZnO-NP removal was strongly dependent on the solution pH. Specifically, almost complete removal of retained ZnO-NPs was observed after 627 pore volumes when the solution pH was 6, whereas much less Zn was recovered when the eluting solution pH was buffered to pH = 9 and especially 10. This long-term removal was attributed to pH-dependent dissolution of retained ZnO-NPs because: (i) the solubility of ZnO-NPs increases with decreasing pH; and (ii) ZnO-NPs were not detected in the effluent. The presence of biofilm also decreased the initial rate and amount of dissolution and the subsequent transport of Zn(2+) due to the strong Zn(2+) re-adsorption to the biofilm. Our study indicates that dissolution will eventually lead to the complete removal of retained ZnO-NPs and the transport of toxic Zn(2+) ions in groundwater environments with pH ranges of 5-9.

Porous Ca-based bead sorbents for simultaneous removal of SO2, fine particulate matters, and heavy metals from pilot plant sewage sludge incineration.

In this study, a porous calcium-based sorbent was prepared for simultaneous removal of SO2, particulate matter (PM), and heavy metals generated during incineration of sewage sludge. The prepared sorbent was confirmed to have a 3-dimensional-network pore structure, a high specific surface area of 68.5m(2)/g, and gas permeability of 1.12 × 10(-10)m(2). Laboratory-scale tests indicated that there was an improvement in the performance of SO2 removal as the porosity and the specific surface area of the sorbent increased. Additionally, increasing reaction temperature led to greater SO2 removal. Meanwhile, the SL-4 and LS-3 sorbents prepared in this study were installed for operation during pilot tests treating the sewage sludge combustion gas generated by a fluidized incinerator in order to compare and evaluate their feasibility for use in industrial applications. The results showed that the reactivity between SO2 and the starting material of the sorbent (Ca(OH)2>CaCO3), as well as the high specific surface area of the sorbent, were confirmed to be critical factors that improved the performance of SO2 removal. Notably, the results confirmed that both fine PM (≤ 1 µm) and heavy metals were simultaneously removed with increasing efficiency over the time of operation.

Transport of carboxyl-functionalized carbon black nanoparticles in saturated porous media: Column experiments and model analyses.

The aim of this study was to investigate the transport behavior of carboxyl-functionalized carbon black nanoparticles (CBNPs) in porous media including quartz sand, iron oxide-coated sand (IOCS), and aluminum oxide-coated sand (AOCS). Two sets of column experiments were performed under saturated flow conditions for potassium chloride (KCl), a conservative tracer, and CBNPs. Breakthrough curves were analyzed to obtain mass recovery and one-dimensional transport model parameters. The first set of experiments was conducted to examine the effects of metal (Fe, Al) oxides and flow rate (0.25 and 0.5 mL min(-1)) on the transport of CBNPs suspended in deionized water. The results showed that the mass recovery of CBNPs in quartz sand (flow rate=0.5 mL min(-1)) was 83.1%, whereas no breakthrough of CBNPs (mass recovery=0%) was observed in IOCS and AOCS at the same flow rate, indicating that metal (Fe, Al) oxides can play a significant role in the attachment of CBNPs to porous media. In addition, the mass recovery of CBNPs in quartz sand decreased to 76.1% as the flow rate decreased to 0.25 mL min(-1). Interaction energy profiles for CBNP-porous media were calculated using DLVO theory for sphere-plate geometry, demonstrating that the interaction energy for CBNP-quartz sand was repulsive, whereas the interaction energies for CBNP-IOCS and CBNP-AOCS were attractive with no energy barriers. The second set of experiments was conducted in quartz sand to observe the effect of ionic strength (NaCl=0.1 and 1.0mM; CaCl2=0.01 and 0.1mM) and pH (pH=4.5 and 5.4) on the transport of CBNPs suspended in electrolyte. The results showed that the mass recoveries of CBNPs in NaCl=0.1 and 1.0mM were 65.3 and 6.4%, respectively. The mass recoveries of CBNPs in CaCl2=0.01 and 0.1mM were 81.6 and 6.3%, respectively. These results demonstrated that CBNP attachment to quartz sand can be enhanced by increasing the electrolyte concentration. Interaction energy profiles demonstrated that the interaction energy profile for CBNP-quartz sand was compressed and that the energy barrier decreased as the electrolyte concentration increased. Furthermore, the mass recovery of CBNPs in the presence of divalent ions (CaCl2=0.1 mM) was far lower than that in the presence of monovalent ions (NaCl=0.1 mM), demonstrating a much stronger effect of Ca(2+) than Na(+) on CBNP transport. Mass recovery of CBNPs at pH 4.5 was 55.6%, which was lower than that (83.1%) at pH 5.4, indicating that CBNP attachment to quartz sand can be enhanced by decreasing the pH. The sticking efficiencies (α) calculated from the mass recovery by colloid filtration theory were in the range from 2.1×10(-2) to 4.5×10(-1), which were far greater than the values (2.56×10(-6)-3.33×10(-2)) of theoretical sticking efficiencies (αtheory) calculated from the DLVO energy by the Maxwell model.