Preparation of an electrochemical sensor utilizing graphene-like biochar for the detection of tetracycline.

Tetracycline (TC), which is ubiquitous in the aquatic environment, can cause ecological imbalance and adversely affect human health. Therefore, a quick, inexpensive, and easy method for the detection of TC in water systems is highly desirable. This study reports the development of a novel electrochemical sensor from waste peanut shell for the quick detection of TC in water. Raman and TEM lattice mapping analyses confirmed the successful preparation of graphene -like biochar from waste peanut shells (PSs) via hydrothermal and pyrolysis processes. An electrochemical sensor, PS@glassy carbon electrode (PS@GCE), was then developed by coating the prepared graphene-like biochar on the surface of a glass electrode to enhance its conductivity. The feasibility of using this sensor for the detection of TC in the aqueous system was investigated. The PS@GCE sensor exhibited excellent sensitivity with a low detection limit of 3.6 × 10--9 nM and a linear range of 10-10-102 µM. These results were attributed to the large specific surface area and high conductivity, of the PS biochar. The stability of the PS@GCE sensor was also investigated in the presence of TC (10-4 M) and interfering species (10-2 M) and recovery rates in the range of 86.4%-116.0% were achieved, thus indicating the absence of an interference range of range of 84.3%-98.2% with relative standard deviation lower than 6% were achieved upon the detection of TC in natural water samples using the designed sensor, thus confirming the superior repeatability of the PS@GCE sensor. Consequently, the designed electrode has a high potential for application in the detection of TC in natural aqueous systems.

Sputter-Deposited High Entropy Alloy Thin Film Electrocatalyst for Enhanced Oxygen Evolution Reaction Performance.

Thin film catalysts, giving a different morphology, provide a significant advantage over catalyst particles for the gas evolution reaction. Taking the advantages of sputter deposition, a high entropy alloy (HEA) thin film electrocatalyst is hereby reported for the oxygen evolution reaction (OER). The catalyst characteristics are investigated not only in its as-deposited state, but also during and after the OER. For comparison, unary, binary, ternary, and quaternary thin film catalysts are prepared and characterized. The surface electronic structure modification due to the addition of a metal is studied experimentally and theoretically using density functional theory calculation. It is demonstrated that sputtered FeNiMoCrAl HEA thin film exhibits OER performance superior to all the reported HEA catalysts with robust electrocatalytic activity having a low overpotential of 220 mV at 10 mA cm-2 , and excellent electrochemical stability at different constant current densities of 10 and 100 mA cm-2 for 50 h. Furthermore, the microstructure transformation is investigated during the OER, which is important for the understanding of the OER mechanism provided by HEA electrocatalyst. Such a finding will contribute to future catalyst design.

Production of Mesoporous Magnetic Carbon Materials from Oily Sludge by Combining Thermal Activation and Post-Washing.

In this work, the oily sludge (OS) from a local waste oil recycling plant was reused as a precursor for producing porous magnetic carbon composites (CC) by pyrolysis, followed by carbon dioxide activation. Based on the thermogravimetric analysis (TGA) of the OS feedstock, the preparation experiments were performed at 800−900 °C. From the pore analysis of the CC products, it indicated an increasing trend, as the BET surface area greatly increased from about 1.0 to 44.30 m2/g. In addition, the enhancement effect on the pore properties can be consistently obtained from the acid-washed CC products because the existing and new pores were reformed due to the leaching-out of inorganic minerals. It showed an increase from 32.27 to 94.45 m2/g and 44.30 to 94.52 m2/g at 850 and 900 °C, respectively, showing their mesoporous features. These porous and iron-containing features were also observed by the scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS). In addition, the adsorption removal of total organic carbon (TOC) in the raw wastewater, by the CC product, showed its high performance (>80%).

Reuse of the Materials Recycled from Renewable Resources in the Civil Engineering: Status, Achievements and Government's Initiatives in Taiwan.

Growing concerns about the circular economy and sustainable waste management for civil applications of non-hazardous mineral industrial waste have increased in recent years. Therefore, this study presents a trend analysis of industrial waste generation and treatment during the years of 2010-2020, and focused on promotion policies and regulatory measures for mandatory renewable resources from industrial sources in Taiwan, including reclaimed asphalt pavement (RAP) material, water-quenched blast furnace slag, and ilmenite chlorination furnace slag. According to the official database of the online reported statistics during the period of 2010-2020, approximately three million metric tons per year of renewable resources were totally reused in civil engineering or related cement products, reflecting a balanced supply chain in the domestic market. Among these, water-quenched blast furnace slag accounted for about 90% (about 2.7 million metric tons) in Taiwan. Currently, the legislative framework of sustainable waste management in Taiwan is based on the Waste Management Act and the Resource Recycling Act, but there are some problems with them. In order to effectively reduce environmental loadings and conserve natural resources to mitigate climate change, some recommendations are addressed from different points of view.

The use of ultrasound-assisted anaerobic compost tea washing to remove poly-chlorinated dibenzo-p-dioxins (PCDDs), dibenzo-furans (PCDFs) from highly contaminated field soils.

The remediation of dioxin-contaminated soil of a specific coastal area previously employed for the manufacture of pentachlorophenol (PCP) in southern Taiwan's Tainan City has attracted much attention of researchers there. This work addresses the possibility of providing an effective and environmentally friendly option for removing PCDD/Fs from soil in that field. Soil screening/sieving was first conducted to assess particle distribution. Fine sand was observed to be the major component of the soil, accounting for more than 60% of the total mass. A combination of ultrasonification and mechanical double-blade agitation was used to facilitate the washing of the soil using the biosurfactant anaerobic compost tea. More than 85 and 95% of total removal efficiencies were achieved for moderately and highly contaminated soils after 6 and 10 washing cycles, respectively, under ambient temperature, a soil/liquid ratio 1:2.5, 700 rpm, and over a relatively short duration. These results were achieved through the collision and penetration effects of this combined treatment as well as PCDD/F partitioning between the particles and anaerobic compost tea. This study represents the first to report the use of anaerobic compost tea solvent to wash soil highly contaminated by dioxin. It was concluded that anaerobic compost tea, rich in non-toxic bio-surfactants (e.g., alcohols, humic acids), can be used to improve bioavailability and bioactivity of the soil making bio-attenuation and full remediation more efficient.

Removal of chloride from MSWI fly ash.

The high levels of alkali chloride and soluble metal salts present in MSWI fly ash is worth noting for their impact on the environment. In addition, the recycling or reuse of fly ash has become an issue because of limited landfill space. The chloride content in fly ash limits its application as basis for construction materials. Water-soluble chlorides such as potassium chloride (KCl), sodium chloride (NaCl), and calcium chloride hydrate (CaCl(2) · 2H(2)O) in fly ash are easily washed away. However, calcium chloride hydroxide (Ca(OH)Cl) might not be easy to leach away at room temperature. The roasting and washing-flushing processes were applied to remove chloride content in this study. Additionally, air and CO(2) were introduced into the washing process to neutralize the hazardous nature of chlorides. In comparison with the water flushing process, the roasting process is more efficient in reducing the process of solid-liquid separation and drying for the reuse of Cl-removed fly ash particles. In several roasting experiments, the removal of chloride content from fly ash at 1050°C for 3h showed the best results (83% chloride removal efficiency). At a solid to liquid ratio of 1:10 the water-flushing process can almost totally remove water-soluble chloride (97% chloride removal efficiency). Analyses of mineralogical change also prove the efficiency of the fly ash roasting and washing mechanisms for chloride removal.

Removal of chloride from electric arc furnace dust.

Electric arc furnace (EAF) dust with high chloride content increases the threat of dioxin emissions and the high chloride content reduces the value of recycled zinc oxide produced by EAF dust recycling plants. This study conducts a number of laboratory experiments to determine the technical feasibility of a new dechlorination method. These methods consist of a series of roasting processes and water washing processes. In the roasting process, EAF dust was heated in a tube furnace to evaluate the parameters of atmospheric conditions, roasting temperature, and roasting time. Results indicate that sulfation roasting is more efficient in reducing chloride content than other roasting processes. The water washing process can totally remove water-soluble chloride at a solid to liquid ratio of 1:10. However, the remaining water-insoluble substance is difficult to dechlorinate. For example, lead chloride forms a hydroxyl-halide (PbOHCl) and lead chloride carbonate (Pb(2)CO(3)Cl(2)) agglutinative matrix that is hard to wash away.

The characteristics of organic sludge/sawdust derived fuel.

A fundamental study of the characteristics of a sludge refuse-derived fuel (RDF) and the combustion behaviors were done. The test data demonstrate good results for the development of energy recovery technology of organic sludge or waste. The ash deposit formation propensity has been based on pretreatment, temperature and the ratio of organic sludge to sawdust. The usage of organic sludge and waste as an alternative fuel is cost effective and has environmental benefits.

Remediation of oil-contaminated sand by coal agglomeration using ball milling.

The mechanical shear force provided by a less energy intensive device (usually operating at 20-200 rpm), a ball mill, was used toperform coal agglomeration and its effects on remediation of a model fuel oil-contaminated sand were evaluated. Important process parameters such as the amount of coal added, milling time, milling speed and the size of milling elements are discussed. The results suggested that highly hydrophobic oil-coal agglomerates, formed by adding suitable amounts of coal into the oil-contaminated sand, could be mechanically liberated from cleaned sand during ball milling and recovered as a surface coating on the steel balls. Over 90% removal of oil from oil-contaminated sand was achieved with 6 wt% of coal addition and an optimum ball milling time of 20 min and speed of 200 rpm. This novel process has considerable potential for cleaning oil-contaminated sands.

Treatment of ammonia by catalytic wet oxidation process over platinum-rhodium bimetallic catalyst in a trickle-bed reactor: effect of pH.

This work adopted aqueous solutions of ammonia for use in catalytic liquid-phase reduction in a trickle-bed reactor with a platinum-rhodium bimetallic catalyst, prepared by the co-precipitation of chloroplatinic acid (H2PtCl6) and rhodium nitrate [Rh(NO3)3]. The experimental results demonstrated that a minimal amount of ammonia was removed from the solution by wet oxidation in the absence of any catalyst, while approximately 97.0% of the ammonia was removed by wet oxidation over the platinum-rhodium bimetallic catalyst at 230 degrees C with an oxygen partial pressure of 2.0 MPa. The oxidation of ammonia has been studied as a function of pH, and the main reaction products were determined. A synergistic effect is manifest in the platinum-rhodium bimetallic structure, in which the material has the greatest capacity to reduce ammonia. The reaction pathway linked the oxidizing ammonia to nitric oxide, nitrogen, and water.

Adsorption of poly(ethylene oxide) on smectite: Effect of layer charge.

The adsorption of polymers on clay is important in many applications. However the mechanisms of poly(ethylene oxide) (PEO) adsorption on smectite is not well elucidated at present. The aim of this study was to investigate the effect of layer charge density on the adsorption of PEO by smectite. The results indicated that both the hydrophobic interaction (between CH(2)CH(2) groups and siloxane surface) and the hydrogen bonding (between ether oxygen of PEO and structure OH of smectite) lead to PEO preferential adsorption on the surface of low-charge smectite. In addition, the delamination of low-charge smectite in water is enhanced upon PEO adsorption presumably due to the hydrophilic ether oxygen of adsorbed PEO.

Preparation of coal slurry with organic solvents.

In this study, various organic solvents were used to prepare coal slurries and the rheological and thermal properties of coal-organic solvent slurries were examined. Solvents with molecules containing unpaired electrons (high basicity) show high extraction power and cause swelling of coal. Therefore, coal-organic solvent slurries usually showed higher viscosities compared to coal-water slurry. In addition, coal slurries prepared by alcohols and cyclohexanone demonstrated lower settling rates but a high specific sedimentation volume presumably because these solvents swelled coal particles well and led to the formation of weak gel structures in the bulk. In addition, ethanol and cyclohexanone are capable of breaking a considerable amount of hydrogen bonds in coal and subsequently opening up the structures. Thus, more surface area is available for combustion and the combustion rate of coal slurries was increased.

Preparation of coal slurry with 2-propanol.

This study explored the feasibility of using waste organic solvents as substitutes for water to prepare coal slurries. The rheological properties of coal-2-propanol slurries were examined and compared with that of coal-water slurry (CWS). The good compatibility between coal particles and 2-propanol resulted in stable particle suspension in slurry which usually exhibit Newtonian behaviour. However, coal-2-propanol slurries usually shown higher viscosities comparing to CWSs at a fixed solid loading due to swelling of coal by 2-propanol. In addition, coal-2-propanol slurries demonstrated lower settling rates (higher stability) compared to CWSs presumably due to good compatibility between coal particles and 2-propanol. Finally, coal-2-propanol slurries formed bulky sediment with loose structure even coal particles suspended in 2-propanol were more stable than coal particles in CWSs.

Determination of the surface area of smectite in water by ethylene oxide chain adsorption.

This study investigates the feasibility of using ethylene oxide (EO) chain adsorption to determine the surface area of smectite in water. Experimental results indicate that high-molecular-weight poly(ethylene oxide) (PEO) should be used to provide reasonable estimations for monolayer capacity of PEO on smectite. The surface areas of smectites in water are calculated from the monolayer capacity of PEO adsorbed on smectite by taking the area per EO unit as 8.05 A(2). The method measures the actual surface area of smectite exposed when dispersed in water, which is important to applications of smectite under aqueous conditions.

Estimation of surface area of montmorillonite by ethylene oxide chain adsorption.

This study investigates the feasibility of using ethylene oxide chain adsorption to determine the surface area of an expandable clay, montmorillonite. Experimental results indicate that high molecular weight poly(ethylene oxide) or nonionic surfactant with long ethylene oxide chain should be used to provide reasonable estimations for monolayer capacity. The method has advantages over Brunauer, Emmett, and Teller method in that it is readily applicable to a wide range of areas, particularly to 2:1 layer silicates under aqueous conditions.

Removal of phenol from water by adsorption-flocculation using organobentonite.

Bentonite modified with short chain cationic surfactant might be the basis of a new approach to removing organic pollutants from water. The treatment process involves dispersing bentonite to the contaminated water and then adding a small cationic surfactant so as to result in flocs which are agglomerates of organobentonite and bound organic pollutants. The flocs are then removed from the solution by sedimentation. Experimental results indicate that BTMA-bentonite displays a high affinity for phenol, possibly because phenol molecules interact favorably with the benzene ring in BTMA ion through increased pi-pi type interactions. Under appropriate operating conditions, 90% phenol removal and nearly 100% bentonite recovery could be achieved by the adsorption flocculation process using BTMA-bentonite. Additionally, the insensitivity of the process to the changing ionic strength of the solution and rapid adsorption kinetics made adsorption-flocculation with BTMA-bentonite attractive for continuous treatment of large volumes of industrial wastewater. The bentonite may function as a recyclable surfactant support for the adsorption and subsequent combustion of organic pollutants.

Sorption of benzene and naphthol to organobentonites intercalated with short chain cationic surfactants.

This work studies the sorption of benzene and naphthol by bentonites exchanged with quaternary ammonium surfactants tetramethylammonium (TMA) ion, benzyltrimethylammonium (BTMA) ion, tetraethylammonium (TEA) ion, and benzyltriethylammonium (BTEA) ion to elucidate how exchanged short chain organic cations affect the mechanistic function of the modified bentonite. Local high charge density areas are found at interlamellar surfaces of bentonite and intercalated short chain organic cations aggregate preferentially at these sites to form organic carbon phase effective in nonionic organic compounds (NOC) uptake. Experimental results indicate that the amount of benzene uptake decreases as the size of intercalated organic cation increases from TMA to BTMA to TEA to BTEA, presumably due to the different structures of organic carbon phase formed in organobentonite. In addition, benzene sorption capacity of organobentonite modified with short chain organic cation is highly sensitive to the cation exchange capacities (CEC) of bentonite used.