Usman Farooq

An efficient catalytic degradation of trichloroethene in a percarbonate system catalyzed by ultra-fine heterogeneous zeolite supported zero valent iron-nickel bimetallic composite

Zeolite supported nano iron-nickel bimetallic composite (Z-nZVI-Ni) was prepared using a liquid-phase reduction process. The corresponding surface morphologies and physico-chemical properties of the Z-nZVI-Ni composite were determined using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Energy dispersive X-ray spectra (EDS), Brunauer Emmett Teller (BET) adsorption, wide angle X-ray diffractometry (WA-XRD), and Fourier transform infrared spectroscopy (FTIR). The results indicated high dispersion of iron and nickel nano particles on the zeolite sheet with an enhanced surface area. Complete destruction of trichloroethene (TCE) and efficient removal of total organic carbon (TOC) were observed by using Z-nZVI-Ni as a heterogeneous catalyst for a Fenton-like oxidation process employing sodium percarbonate (SPC) as an oxidant. The electron spin resonance (ESR) of Z-nZVI-Ni verified the generation and intensity of hydroxyl radicals (OH•). The quantification of OH• elucidated by using p-chlorobenzoic acid, a probe indicator, confirmed the higher intensity of OH•. The transformation products were identified using GC-MS. The slow iron and nickel leaching offered higher stability and better catalytic activity of Z-nZVI-Ni, demonstrating its prospective long term applications in groundwater for TCE degradation.

Enhanced degradation of benzene by percarbonate activated with Fe(II)-glutamate complex

Effective degradation of benzene was achieved in sodium percarbonate (SPC)/Fe(II)-Glu system. The presence of glutamate (Glu) could enhance the regeneration of Fe(III) to Fe(II), which ensures the benzene degradation efficiency at wider pH range and eliminate the influence of HCO3− in low concentration. Meanwhile, the significant scavenging effects of high HCO3− concentration could also be overcome by increasing the Glu/SPC/Fe(II)/benzene molar ratio. Free radical probe compound tests, free radical scavenger tests, and electron paramagnetic resonance (EPR) analysis were conducted to explore the reaction mechanism for benzene degradation, in which hydroxyl radical (HO•) and superoxide anion radical (O2•−) were confirmed as the predominant species responsible for benzene degradation. In addition, the results obtained in actual groundwater test strongly indicated that SPC/Fe(II)-Glu system is applicable for the remediation of benzene-contaminated groundwater in practice.

Degradation of trichloroethylene in aqueous solution by rGO supported nZVI catalyst under several oxic environments

The reduced graphene oxide (rGO) supported nano zero-valent iron (nZVI) (nZVI-rGO) was synthesized successfully and applied in the several oxic environments to remove trichloroethylene (TCE). The nZVI-rGO had a better catalytic performance than bare nZVI for the TCE removal. Both aggregation of nZVI and agglomeration of rGO were in part prevented by loading the nZVI nanoparticles on the rGO sheet. Among all the oxic environments, the better removal of TCE was followed as the order of PMS > SPS > H2O2. Chemical scavenger tests were carried out to identify the reactive oxygen species (ROSs) generated in the removal of TCE, showing that in PMS and SPS systems, SO4- and HO were main radicals responsible for TCE removal, while HO and O2- were main radicals in H2O2 system. The possible mechanisms were proposed with nZVI-rGO under several oxic environments. The recyclability of nZVI-rGO, dechlorination and mineralization of TCE were investigated. These fundamental data confirmed the effectiveness of nZVI-rGO to remove TCE and could help selecting the suitable oxidants to use with nZVI-rGO in the actual field groundwater remediation.

Efficient transformation in characteristics of cations supported-reduced graphene oxide nanocomposites for the destruction of trichloroethane

Experiments were conducted to investigate the use of graphene-oxide supported metallic nanocomposites for improving the degradation of trichloroethane (TCA) by sodium percarbonate (SPC). Two methods of production, chemical reduction (CR) and solvo-thermal (ST), were tested for preparation of single (Fe) and binary (Fe-Cu) nanocomposites supported by reduced graphene oxide (rGO). A variety of analytical techniques including N2 adsorption Brunauer-Emmett-Teller (BET), x-ray diffraction (XRD), fourier-transfrom infrared spectroscopy (FTIR), and transmisison electron microscopy (TEM) were applied to characterize the physicochemical and microstructural properties of the synthesized nanocomposites. The characterization indicated that the CR method produced nanocomposites that comprised only mesoporous structure. Conversely, both micro and mesoporous structures were present for samples produced with the ST method. The synthesized single and bimetallic composites produced from the ST method showed higher surface areas, i.e. 93.6 m2/g and 119.2 m2/g as compared to the ones synthesized via the CR method, i.e. 13.8 m2/g and 38.0 m2/g respectively. The results of FTIR and XRD analyses confirmed that the ST method produced highly crystalline nanocomposites. SEM and TEM analysis validated that metallic particles with definite morphology well distributed on the surface of rGO. X-ray photoelectron spectroscopy (XPS) analysis confirmed the homogeneity nanocomposites and occurrence of variation in copper oxidation states during degradation process. EDS mapping validate the homogeneous distribution of Cu and Fe at reduced graphene oxide surface. The Fe-Cu/rGO (ST) activated SPC system effectively degraded TCA (92%) in 2.5 h at low nanocomposite dose compared to the Fe-Cu/rGO (CR) and only Fe, for which the maximum degradation efficiencies achieved were 81% and 34%. In conclusion, excellent catalytic characteristics were observed for the ST-synthesized single and bimetallic (Fe/rGO, Fe-Cu/rGO) catalysts. These catalysts were successful in improving the degradation of TCA via activated SPC.

The impact of surface properties and dominant ions on the effectiveness of G-nZVI heterogeneous catalyst for environmental remediation

The surface properties of nanocomposites are influenced by the existence of inorganic species that may affect its performance for specific catalytic applications. The impact of different ionic species on particular catalytic activity had not been investigated to date. In this study, the surface charge (zeta potential) of graphene-oxide-supported nano zero valent iron (G-nZVI) was tested in definitive cationic (Na+, K+, Ca2+ and Mg2+) and anionic (Br-, Cl-, NO3-, SO42-, and HCO3-) environments. The efficiency of G-nZVI catalyst was inspected by measuring the generation of reactive oxygen species (ROS) for the degradation of 1,1,1-trichloroethane (TCA) in sodium percarbonate (SPC) system. Tests conducted using probe compounds confirmed the generation of OH and O2- radicals in the system. In addition, the experiments performed using scavenging agents certified that O2- were primary radicals responsible for TCA removal, along with prominent contribution from OH radicals. The study confirmed that G-nZVI catalytic capability for TCA degradation is notably affected by various cationic species. The presence of Ni2+ and Cu2+ significantly enhanced (94%), whereas Na+ and K+ had minor effects on TCA removal. Overall, the results indicated that groundwater ionic composition may have low impact on the effectiveness of G-nZVI-catalyzed peroxide TCA treatment.

Enhanced degradation of trichloroethylene in oxidative environment by nZVI/PDA functionalized rGO catalyst

Nano zero-valent iron (nZVI) particles with higher reactivity have been recognized as more efficient catalysts than Fe(II) for the groundwater remediation. The rapid emergence of novel catalyst supports efficiently prevent the rapid aggregation of nZVI and further improve catalytic reactivity. However, the lack of ability to avoid the potential oxidation of bare nZVI-support structure in air environment hinders its wider application in the actual contaminated sites. In this study, nZVI on reduced graphene oxide (rGO) functionalized by polydopamine (PDA) (nZVI-PDA@rGO) was synthesized successfully and applied into sodium persulfate (SPS), potassium monopersulfate (PMS) and H2O2 oxidative environments to remove trichloroethylene (TCE). For comparison, nZVI supported on solely rGO was prepared. The XRD test displayed the stronger stability of α-Fe(0) in nZVI-PDA@rGO catalyst against oxidation exposed to air. Compared with nZVI-rGO, a core shell structure of nZVI-PDA@rGO was observed in TEM image obviously. The dosage tests showed nZVI-PDA@rGO had a better catalytic reactivity than nZVI-rGO for TCE removal at lower catalyst and oxidant dosages, i.e. PMS dosage: 0.3 mM, catalyst dosage: 50 mg L-1, TCE removal: 45.0% (nZVI-rGO) up to 99.6% (nZVI-PDA@rGO). TCE removal mechanisms were revealed through radical scavenger tests, demonstrating sulfate radicals played more important role in nZVI-PDA@rGO catalyzed-oxidant systems.

Adsorption dynamics and mechanism of aqueous sulfachloropyridazine and analogues using the root powder of recyclable long-root Eichhornia crassipes

In this study, we reclaimed the root powder of long-root Eichhornia crassipes (L.R.E.C.) as a biosorbent to remove aqueous sulfachloropyridazine (SCP) and other sulfonamides. The adsorption processes were investigated dependent on multiple measurements, including FT-IR and XPS analysis. The results confirmed that the basic amine group of neutral SCP molecules and the carboxyl hydroxyl on the surface of the root powder played the leading role in adsorption processes. Additionally, the experiments of ionic strength effect validated the involvement of electrostatic interaction in adsorption. Meanwhile, the adsorption data were fitted by various models and the results indicated that the Pseudo-second-order model and Freundlich model could well describe the adsorption processes, indicating the existence of physisorption and chemisorption as multi-layer adsorption. The maximum capacities of root powder for SCP were calculated to be 226.757 μg g-1 (288.15 K), 182.815 μg g-1 (303.15 K) and 163.132 μg g-1 (318.15 K) at pH of 3.0. The thermodynamic results revealed that the adsorption was a spontaneous and exothermic process. Moreover, the accordance with intra-particle diffusion presented that the adsorption processes could be divided into three steps and the reaction constant had a negatively linear relationship with the thickness of the boundary layer. The results proved that root powder of L.R.E.C. has great potential to remediate sulfonamides at practical level.