Moses O. Tadé

Novel Applications of Red Mud as Coagulant, Adsorbent and Catalyst for Environmentally Benign Processes

Red mud (RM) is a by-product of bauxite processing via the Bayer process. Its disposal remains an issue of great importance with significant environmental concerns. In the past decades, a lot of research has been done to utilize red mud for environmental-benign applications such as a building material additive and for metal recovery. In recent years, red mud has also been explored for gas cleaning and wastewater treatment. In this paper, we review varying novel applications of red mud as a coagulant and adsorbent for water and gas treatment as well as catalyst for some industrial processes. The environmental compatibility of red mud is discussed. Some directions of future research are also proposed. Red mud presents a promising application in water treatment for removal of toxic heavy metal and metalloid ions, inorganic anions such as nitrate, fluoride, and phosphate, as well as organics including dyes, phenolic compounds and bacteria. In addition, red mud can also be employed as catalysts for hydrogenation, hydrodechlorination and hydrocarbon oxidation. Moreover, leaching and eco-toxicological tests indicate that red mud does not present high toxicity to the environment before or after reuse.

Synthesis of Nitrogen‐Doped Mesoporous Carbon Spheres with Extra‐Large Pores through Assembly of Diblock Copolymer Micelles

The synthesis of highly nitrogen-doped mesoporous carbon spheres (NMCS) is reported. The large pores of the NMCS were obtained through self-polymerization of dopamine (DA) and spontaneous co-assembly of diblock copolymer micelles. The resultant narrowly dispersed NMCS possess large mesopores (ca. 16 nm) and small particle sizes (ca. 200 nm). The large pores and small dimensions of the N-heteroatom-doped carbon spheres contribute to the mass transportation by reducing and smoothing the diffusion pathways, leading to high electrocatalytic activity.

Reduced Graphene Oxide for Catalytic Oxidation of Aqueous Organic Pollutants

We discovered that chemically reduced graphene oxide, with an I(D)/I(G) >1.4 (defective to graphite) can effectively activate peroxymonosulfate (PMS) to produce active sulfate radicals. The produced sulfate radicals (SO(4)(•-)) are powerful oxidizing species with a high oxidative potential (2.5-3.1 vs 2.7 V of hydroxyl radicals), and can effectively decompose various aqueous contaminants. Graphene demonstrated a higher activity than several carbon allotropes, such as activated carbon (AC), graphite powder (GP), graphene oxide (GO), and multiwall carbon nanotube (MWCNT). Kinetic study of graphene catalyzed activation of PMS was carried out. It was shown that graphene catalysis is superior to that on transition metal oxide (Co(3)O(4)) in degradation of phenol, 2,4-dichlorophenol (DCP) and a dye (methylene blue, MB) in water, therefore providing a novel strategy for environmental remediation.

SrNb0.1Co0.7Fe0.2O3−δ Perovskite as a Next-Generation Electrocatalyst for Oxygen Evolution in Alkaline Solution†

The perovskite SrNb0.1 Co0.7 Fe0.2 O3-δ (SNCF) is a promising OER electrocatalyst for the oxygen evolution reaction (OER), with remarkable activity and stability in alkaline solutions. This catalyst exhibits a higher intrinsic OER activity, a smaller Tafel slope and better stability than the state-of-the-art precious-metal IrO2 catalyst and the well-known BSCF perovskite. The mass activity and stability are further improved by ball milling. Several factors including the optimized eg orbital filling, good ionic and charge transfer abilities, as well as high OH(-) adsorption and O2 desorption capabilities possibly contribute to the excellent OER activity.

Nano-Fe0 Encapsulated in Microcarbon Spheres: Synthesis, Characterization, and Environmental Applications

Nanoscaled zerovalent iron (ZVI) encapsulated in carbon spheres (nano-Fe⁰@CS) were prepared via a hydrothermal carbonization method, using glucose and iron(III) nitrate as precursors. The properties of the nano-Fe⁰@CS were investigated by X-ray diffraction (XRD), thermogravimetric analysis-differential scanning calorimetry (TGA-DSC), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen adsorption/desorption isotherms. Nano-Fe⁰@CS was demonstrated, for the first time, as an effective material in activating Oxone (peroxymonosulfate, PMS) for the oxidation of organic pollutants. It was found that the efficiency of nano-Fe⁰@CS was higher than ZVI particles, iron ions, iron oxides, and a cobalt oxide. The mechanism of the high performance was discussed. The structure of the nano-Fe⁰@CS not only leads to high efficiency in the activation of PMS, but also good stability. This study extended the application of ZVI from reductive destruction of organics to oxidative degradation of organics by providing a green material for environmental remediation.

Recent advances in non-metal modification of graphitic carbon nitride for photocatalysis: a historic review

Photocatalysis is a green, feasible and versatile technology that has been widely used for energy conversion and environmental applications. As photocatalysis bears a great potential for solar energy utilization, enormous investigations have been implemented in the past decades. The fundamental mechanism and some applications were well addressed in the last century. Currently, the major focus in photocatalysis research is the design and development of photocatalyst materials. This review firstly introduces the historic milestones in photocatalysis studies and then a comprehensive survey is conducted on the metal-based photocatalysts, including TiO2-based photocatalysts, ZnO and other metal oxides, metal sulfides, metal nitrides, and plasmon photocatalysts. From a historical viewpoint, particular attention is paid to metal-free graphitic carbon nitride (g-C3N4), a novel visible-light photocatalyst. Various modification techniques for g-C3N4 are summarized and analyzed. In terms of its metal-free nature, the fabrication of a porous structure, shape-control synthesis and non-metal doping are discussed in detail. Photocatalytic studies on g-C3N4-based catalysts are introduced. Some emerging elemental photocatalysts are also introduced. Finally, perspectives on non-metal photocatalyst design and development are provided.

A comparative study of spinel structured Mn3O4, Co3O4 and Fe3O4 nanoparticles in catalytic oxidation of phenolic contaminants in aqueous solutions

Spinel structured Mn3O4, Co3O4 and Fe3O4 nanoparticles were prepared, characterized, and tested in degradation of aqueous phenol in the presence of peroxymonosulfate. It was found that Mn3O4 and Co3O4 nanoparticles are highly effective in heterogeneous activation of peroxymonosulfate to produce sulfate radicals for phenol degradation. The activity shows an order of Mn3O4>Co3O4>Fe3O4. Mn3O4 could fast and completely remove phenol in about 20 min, at the conditions of 25 ppm phenol, 0.4 g/L catalyst, 2 g/L oxone®, and 25 °C. A pseudo first order model would fit to phenol degradation kinetics and activation energies on Mn3O4 and Co3O4 were obtained as 38.5 and 66.2 kJ/mol, respectively. In addition, Mn3O4 exhibited excellent catalytic stability in several runs, demonstrating that Mn3O4 is a promising catalyst alternative to toxic Co3O4 for water treatment.

Coal fly ash supported Co3O4 catalysts for phenol degradation using peroxymonosulfate

Several fly ash (FA) samples derived from Australian (FA-WA) and Brazilian coals (FA-JL and FA-CH) were used as supports to prepare Co oxide (Co)-based catalysts. These Co/FA catalysts were tested in peroxymonosulfate activation for sulphate radical generation and phenol degradation in aqueous solution. The physicochemical properties of FA supports and Co/FA catalysts were characterised by N2 adsorption, X-ray diffraction (XRD), scanning electron microscopy coupling with energy dispersive spectroscopy (SEM-EDS), elemental mapping, and UV-vis diffuse reflectance spectroscopy. It was found that the FA supports did not show adsorption of phenol and could not activate peroxymonosulfate for sulphate radical generation. However, fly ash supported Co oxide catalysts (Co/FA) presented higher activities in the activation of peroxymonosulfate for phenol degradation than bulk Co oxide and their activities varied depending on the properties of the fly ash supports. Co/FA-JL showed the highest activity while Co/FA-WA showed the lowest. Activation energies of phenol degradation on three Co/FA catalysts were obtained to be 47.0, 56.5, 56.0 kJ mol−1 for Co/FA-WA, Co/FA-JL and Co/FA-CH, respectively.

Two-Point Control of a Reactive Distillation Column for Composition and Conversion

Abstract Reactive distillation is a hybrid process with dual process objectives: reactant conversion and product composition. Control schemes for reactive distillation frequently neglect the effect of the principal operating parameters on the reactant conversion, and this has a detrimental effect on the overall process profitability. An ETBE reactive distillation column has been used as a case study to show how a two-point control configuration, which recognises the importance of both composition and conversion, can be developed and implemented for a reactive distillation process. The combined composition and conversion control configuration was tested using SpeedUp dynamic simulations and proved to be effective in maintaining a high isobutylene conversion despite process disturbances. The two-point control scheme also had superior disturbance rejection capability, especially for feed rate changes, and composition set-point sensitivity compared with a one-point control scheme.

Adsorption of CH4 and CO2 on Zr-metal organic frameworks.

Zirconium-metal organic frameworks (Zr-MOFs) were synthesized with or without ammonium hydroxide as an additive in the synthesis process. It was found that addition of ammonium hydroxide would change the textural structure of Zr-MOF. The BET surface area, pore volume, and crystal size of Zr-MOF were reduced after addition of ammonium hydroxide. However, the crystalline structure and thermal stability were maintained and no functional groups were formed. Adsorption tests showed that Zr-MOF presented much higher CO(2) adsorption than CH(4). Zr-MOF exhibited CO(2) and CH(4) adsorption of 8.1 and 3.6 mmol/g, respectively, at 273 K, 988 kPa. The addition of ammonium hydroxide resulted in the Zr-MOF with a slight lower adsorption of CO(2) and CH(4), however, the selectivity of CO(2)/CH(4) is significantly enhanced.