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Elucidation of stoichiometric efficiency, radical generation and transformation pathway during catalytic oxidation of sulfamethoxazole via peroxymonosulfate activation

Bao Y, Oh WD, Lim TT, Wang R, Webster RD, Hu X

Water Res, 2019 03 15;151:64-74.
PMID: 30594091 DOI: 10.1016/j.watres.2018.12.007

In this work, nano-bimetallic Co/Fe oxides with different stoichiometric Co/Fe ratios were prepared using a novel one-step solution combustion method. The nano-bimetallic Co/Fe oxides were used for sulfamethoxazole (SMX) degradation via peroxymonosulfate (PMS) activation. The stoichiometric efficiencies of the as-prepared nano-bimetallic catalysts were calculated and compared for the first time. The radical generation was identified by electron paramagnetic resonance (EPR) as well as chemical quenching experiments, in which different scavengers were used and compared. The catalytic PMS activation mechanism in the presence of catalyst was examined by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The results showed that besides SO4•- and •OH, •OOH was also detected in the PMS/CoFeO2.5 system. Meanwhile, in addition to the previously proposed radical oxidation pathway, the results showed that SMX degradation also involved a non-radical oxidation, which could be verified by the degradation experiment without catalyst as well as the detection of 1O2. In the PMS activation process, cobalt functioned as the active site on CoFeO2.5 while Fe oxide functioned as the adsorption site. The electron transfer mechanism was proposed based on the XPS and metal leaching results. Additionally, via the detection of transformation products, different SMX transformation pathways involving nitration, hydroxylation and hydrolysis in the PMS/CoFeO2.5 system were proposed.
Fulltext The role of ubiquitous metal ions in degradation of microplastics in hot-compressed water

Vo TP, Rintala J, Dai L, Oh WD, He C

Water Res, 2023 Oct 15;245:120672.
PMID: 37783176 DOI: 10.1016/j.watres.2023.120672

Hydrothermal processing (HTP) is an efficient thermochemical technology to achieve sound treatment and resource recovery of sewage sludge (SS) in hot-compressed subcritical water. However, microplastics (MPs) and heavy metals can be problematic impurities for high-quality nutrients recovery from SS. This study initiated hydrothermal degradation of representative MPs (i.e., polyethylene (PE), polyamide (PA), polypropylene (PP)) under varied temperatures (180-300 °C) to understand the effect of four ubiquitous metal ions (i.e., Fe3+, Al3+, Cu2+, Zn2+) on MPs degradation. It was found that weight loss of all MPs in metallic reaction media was almost four times of that in water media, indicating the catalytic role of metal ions in HTP. Especially, PA degradation at 300 °C was promoted by Fe3+ and Al3+ with remarkable weight loss higher than 95% and 92%, respectively, which was ca. 160 °C lower than that in pyrolysis. Nevertheless, PE and PP were more recalcitrant polymers to be degraded under identical condition. Although higher temperature thermal hydrolysis reaction induced severe chain scission of polymers to reinforce degradation of MPs, Fe3+ and Al3+ ions demonstrated the most remarkable catalytic depolymerization of MPs via enhanced free radical dissociation rather than hydrolysis. Pyrolysis gas chromatography-mass spectrometry (Py GC-MS) was further complementarily applied with GC-MS to reveal HTP of MPs to secondary MPs and nanoplastics. This fundamental study highlights the crucial role of ubiquitous metal ions in MPs degradation in hot-compressed water. HTP could be an energy-efficient technology for effective treatment of MPs in SS with abundant Fe3+ and Al3+, which will benefit sustainable recovery of cleaner nutrients in hydrochar and value-added chemicals or monomers from MPs.
Fulltext The potential use of Azolla pinnata as an alternative bio-insecticide

Ravi R, Rajendran D, Oh WD, Mat Rasat MS, Hamzah Z, Ishak IH, et al.

Sci Rep, 2020 11 06;10(1):19245.
PMID: 33159109 DOI: 10.1038/s41598-020-75054-0

Four different tests showed the effectiveness of Azolla pinnata plant extracts against Aedes aegypti and Aedes albopictus mosquitoes. In the adulticidal test, there was a significant increase in mortality as test concentration increases and A. pinnata extracts showed LC50 and LC95 values of 2572.45 and 6100.74 ppm, respectively, against Ae. aegypti and LC50 and LC95 values of 2329.34 and 5315.86 ppm, respectively, against Ae. albopictus. The ovicidal test showed 100% eggs mortality for both species tested for all the concentrations tested at 1500 ppm, 1000 ppm, 500 ppm, 250 ppm and 125 ppm. Both tested samples of Ae. aegypti and Ae. albopictus did not lay any eggs in the plastic cups filled with the A. pinnata extract but instead opted to lay eggs in the plastic cups filled with water during the oviposition deterrence test. Similarly, the non-choice test of Ae. aegypti mosquitoes laid eggs on the sucrose solution meant for the nutrient source of the mosquitoes instead of in the plastic cup that was designed to facilitate oviposition filled with the extract. This clearly indicates the presence of bioactive compounds which are responsible in adulticidal and ovicidal activity in Aedes mosquitoes and at the same time inducing repellence towards the mosquitoes. The LC-MS results showed mainly three important chemical compounds from A. pinnata extracts such as 1-(O-alpha-D-glucopyranosyl)-(1,3R,25R)-hexacosanetriol, Pyridate and Nicotinamide N-oxide. All these chemicals have been used for various applications such as both emulsion and non-emulsion type of cosmetics, against mosquito vector such as Culex pipens and Anopheles spp. Finally, the overall view of these chemical components from A. pinnata extracts has shown the potential for developing natural product against dengue vectors.
Fulltext Analysis of chemical compositions and larvicidal activity of nut extracts from Areca catechu Linn against Aedes (Diptera: Culicidae)

Bharathithasan M, Ravindran DR, Rajendran D, Chun SK, Abbas SA, Sugathan S, et al.

PLoS One, 2021;16(11):e0260281.
PMID: 34843539 DOI: 10.1371/journal.pone.0260281

BACKGROUND: There is a growing need to use green alternative larvicidal control for Aedes larvae compared to chemical insecticides. Substantial reliance on chemical insecticides caused insecticide resistance in mosquito populations. Thus, research for alternate chemical compounds from natural products is necessary to control Aedes larvae. This study explores the analysis of chemical compositions from Areca catechu nut as a potential larvicide for Aedes (Diptera: Culicidae).
METHODS: The Areca catechu nut collected from Ipoh, Perak, Malaysia was grounded into powder and used for Soxhlet extraction. The chemical analysis of the extracts and their structures were identified using the GCMS-QP2010 Ultra (Shimadzu) system. National Institute of Standards and Technology (NIST) Chemistry WebBook, Standard Reference Database 69 (https://webbook.nist.gov/chemistry/) and PubChem (https://pubchem.ncbi.nlm.nih.gov/), the two databases used to retrieve the synonyms, molecular formula, molecular weight, and 2-dimensional (2D) structure of chemical compounds. Next, following WHO procedures for larval bioassays, the extracts were used to asses larvicidal activity against early 4th instar larvae of Aedes aegypti and Aedes albopictus.
RESULTS: The larvicidal activities were observed against early 4th stage larvae with different concentrations in the range from 200 mg/L to 1600 mg/L. The LC50 and LC95 of Aedes aegypti were 621 mg/L and 2264 mg/L respectively; whereas the LC50 and LC95 of Aedes albopictus were 636 mg/L and 2268 mg/L respectively. Mortality was not observed in the non-target organism test. The analysis using gas chromatography and mass spectrometer recovered several chemical compounds such as Arecaidine, Dodecanoic acid, Methyl tetradecanoate, Tetradecanoic acid , and n-Hexadecanoic acid bioactive components. These chemical constituents were used as additive formulations in pesticides, pest control, insect repellent, and insecticidal agents.
CONCLUSIONS: Our study showed significant outcomes from the extract of Areca catechu nut and it deserves further investigation in relation to chemical components and larvicidal actions between different species of Aedes mosquitoes. Even though all these findings are fundamental, it may have some interesting potentials to be developed as natural bio-larvicidal products.
Fulltext Comparison of the Surface Properties of Hydrothermally Synthesised Fe3O4@C Nanocomposites at Variable Reaction Times

Sani S, Adnan R, Oh WD, Iqbal A

Nanomaterials (Basel), 2021 Oct 16;11(10).
PMID: 34685183 DOI: 10.3390/nano11102742

The influence of variable reaction time (tr) on surface/textural properties (surface area, total pore volume, and pore diameter) of carbon-encapsulated magnetite (Fe3O4@C) nanocomposites fabricated by a hydrothermal process at 190 °C for 3, 4, and 5 h was studied. The properties were calculated using the Brunauer-Emmett-Teller (BET) isotherms data. The nanocomposites were characterised using Fourier transform infrared spectroscopy, X-ray diffraction analysis, thermogravimetry, and scanning and transmission electron microscopies. Analysis of variance shows tr has the largest effect on pore volume (F value = 1117.6, p value < 0.0001), followed by the surface area (F value = 54.8, p value < 0.0001) and pore diameter (F value = 10.4, p value < 0.001) with R2-adjusted values of 99.5%, 88.5% and 63.1%, respectively. Tukey and Fisher tests confirmed tr rise to have caused increased variations in mean particle sizes (11-91 nm), crystallite sizes (5-21 nm), pore diameters (9-16 nm), pore volume (0.017-0.089 cm3 g-1) and surface area (7.6-22.4 m2 g-1) of the nanocomposites with individual and simultaneous confidence limits of 97.9 and 84.4 (p-adj < 0.05). The nanocomposites' retained Fe-O vibrations at octahedral (436 cm-1) and tetrahedral (570 cm-1) cubic ferrite sites, modest thermal stability (37-60 % weight loss), and large volume-specific surface area with potential for catalytic application in advanced oxidation processes.
Fulltext Systematic Performance Comparison of Fe3+/Fe0/Peroxymonosulfate and Fe3+/Fe0/Peroxydisulfate Systems for Organics Removal

Oh WD, Ho YC, Mohamad M, Ho CD, Ravi R, Lim JW

Materials (Basel), 2021 Sep 14;14(18).
PMID: 34576510 DOI: 10.3390/ma14185284

Activated zero-valent iron (Ac-ZVI) coupled with Fe3+ was employed to activate peroxymonosulfate (PMS) and peroxydisulfate (PDS) for acid orange 7 (AO7) removal. Fe3+ was used to promote Fe2+ liberation from Ac-ZVI as an active species for reactive oxygen species (ROS) generation. The factors affecting AO7 degradation, namely, the Ac-ZVI:Fe3+ ratio, PMS/PDS dosage, and pH, were compared. In both PMS and PDS systems, the AO7 degradation rate increased gradually with increasing Fe3+ concentration at fixed Ac-ZVI loading due to the Fe3+-promoted liberation of Fe2+ from Ac-ZVI. The AO7 degradation rate increased with increasing PMS/PDS dosage due to the greater amount of ROS generated. The degradation rate in the PDS system decreased while the degradation rate in the PMS system increased with increasing pH due to the difference in the PDS and PMS activation mechanisms. On the basis of the radical scavenging study, sulfate radical was identified as the dominant ROS in both systems. The physicochemical properties of pristine and used Ac-ZVI were characterized, indicating that the used Ac-ZVI had an increased BET specific surface area due to the formation of Fe2O3 nanoparticles during PMS/PDS activation. Nevertheless, both systems displayed good reusability and stability for at least three cycles, indicating that the systems are promising for pollutant removal.
Chitosan modifications for adsorption of pollutants - A review

Saheed IO, Oh WD, Suah FBM

J Hazard Mater, 2021 04 15;408:124889.
PMID: 33418525 DOI: 10.1016/j.jhazmat.2020.124889

In recent times, research interest into the development of biodegradable, cost-effective and environmental friendly adsorbents with favourable properties for adsorption of pollutants is a challenge. Modification of chitosan via different physical and chemical methods have gained attention as a promising approach for removing organic (such as dyes and pharmaceuticals) and inorganic (such as metal/metal ions) pollutants from aqueous medium. In this regard, researchers have reported grafting and cross-linking approach among others as a potentially useful method for chitosan's modification for improved adsorption efficiency with respect to pollutant uptake. This article reviews the trend in chitosan modification, with regards to the summary of some recently published works on modification of chitosan and their adsorption application in pollutants (metal ion, dyes and pharmaceuticals) removal from aqueous medium. The review uniquely highlights some common cross-linkers and grafting procedures for chitosan modification, their influence on structure and adsorption capacity of modified-chitosan with respect to pollutants removal. Findings revealed that the performance of modified chitosan for adsorption of pollutants depends largely on the modification method adopted, materials used for the modification and adsorption experimental conditions. Cross-linking is commonly utilized for improving the chemical and mechanical stabilities of chitosan but usually decreases adsorption capacity of chitosan/modified-chitosan for adsorption of pollutants. However, literature survey revealed that adsorption capacity of cross-linked chitosan based materials have been enhanced in recently published works either by grafting, incorporation of solid adsorbents (e.g metals, clays and activated carbon) or combination of both prior to cross-linking.
Metal-organic frameworks for pesticidal persistent organic pollutants detection and adsorption - A mini review

Wagner M, Andrew Lin KY, Oh WD, Lisak G

J Hazard Mater, 2021 07 05;413:125325.
PMID: 33601143 DOI: 10.1016/j.jhazmat.2021.125325

The global population growth demands intensification of anthropogenic processes, thus leading to inter alia pollution of both land and aquatic environments with toxic organic compounds. Particularly harmful synthetic compounds are classified as persistent organic pollutants (POPs). Their relatively high chemical resistance resulted in a worldwide ban or strict control on the use of POPs. The majority of POPs were commonly used as pesticides, and unfortunately, some of them are still utilized as an aid in agricultural practices. Therefore, environmental monitoring in terms of reliable detection and quantification of pesticidal POPs is an ever-increasing need. Chemical sensors and adsorption materials crafted for specific pesticide operate on host-guest interactions should provide selectivity and sensitivity, thus leading to the detection of target molecule down to the nanomolar range. This could be achieved with materials exhibiting a very large active surface area, well-defined structure, and high stability. The novel materials studied in that context are metal-organic frameworks (MOFs). The structure of various MOFs can be functionalized to provide desired host-guest interactions. In this mini-review, we critically discuss the application of MOFs for the detection and adsorption of selected pesticides that are classified as POPs according to the Stockholm Convention.
High-sulfur capacity and regenerable Zn-based sorbents derived from layered double hydroxide for hot coal gas desulfurization

Wu M, Chang B, Lim TT, Oh WD, Lei J, Mi J

J Hazard Mater, 2018 Oct 15;360:391-401.
PMID: 30130697 DOI: 10.1016/j.jhazmat.2018.08.015

The Zn-Al mixed metal oxide (ZnAl-MMO) with a plate-like structure was derived from Zn-Al layered double hydroxide. The ZnAl-MMO with a Zn/Al molar ratio of 3:1 exhibits superior absorption ability for H2S in a simulated coal gas at 600 ℃ due to the special structure of the ZnAl-MMO. Besides ZnS, elemental sulfur is also produced during the desulfurization process. The deactivation model could well simulate the absorption behavior of H2S. The sulfidation reaction over the sorbent shows large initial reaction rate constants (1110-5390 m3 min-1 kg-1) and low activation energy (29.5 kJ mol-1). The regeneration rate of the used sorbent can reach 99.8% under the optimum conditions. The regenerated sorbents still show high sulfur capacity (ca. 30%), implying its great application potential for industrial-scale desulfurization of the hot coal gas.
Processing of flexible plastic packaging waste into pyrolysis oil and multi-walled carbon nanotubes for electrocatalytic oxygen reduction

Veksha A, Yin K, Moo JGS, Oh WD, Ahamed A, Chen WQ, et al.

J Hazard Mater, 2020 04 05;387:121256.
PMID: 31951979 DOI: 10.1016/j.jhazmat.2019.121256

Flexible plastic packaging waste causes serious environmental issues due to challenges in recycling. This study investigated the conversion of flexible plastic packaging waste with 11.8 and 27.5 wt.% polyethylene terephthalate (PET) (denoted as PET-12 and PET-28, respectively) into oil and multi-walled carbon nanotubes (MWCNTs). The mixtures were initially pyrolyzed and the produced volatiles were processed over 9.0 wt.% Fe2O3 supported on ZSM-5 (400 °C) to remove oxygenated hydrocarbons (catalytic cracking of terephthalic and benzoic acids) that deteriorate oil quality. The contents of oxygenated hydrocarbons were decreased in oil from 4.6 and 9.4 wt.% per mass of PET-12 and PET-28, respectively, to undetectable levels. After catalytic cracking, the oil samples had similar contents of gasoline, diesel and heavy oil/wax fractions. The non-condensable gas was converted into MWCNTs over 0.9 wt.% Ni supported on CaCO3 (700 °C). The type of plastic packaging influenced the yields (2.4 and 1.5 wt.% per mass of PET-12 and PET-28, respectively) and the properties of MWCNTs due to the differences in gas composition. Regarding the electrocatalytic application, both MWCNTs from PET-12 and PET-28 outperformed commercial MWCNTs and Pt-based electrodes during oxygen evolution reaction, suggesting that MWCNTs from flexible plastic packaging can potentially replace conventional electrode materials.
Multi-heteroatom-doped carbocatalyst as peroxymonosulfate and peroxydisulfate activator for water purification: A critical review

Choong ZY, Lin KA, Lisak G, Lim TT, Oh WD

J Hazard Mater, 2022 03 15;426:128077.
PMID: 34953256 DOI: 10.1016/j.jhazmat.2021.128077

Catalytic activation of peroxymonosulfate (PMS) and peroxydisulfate (PDS) (or collectively known as persulfate, PS) using carbocatalyst is increasingly gaining attention as a promising technology for sustainable recalcitrant pollutant removal in water. Single heteroatom doping using either N, S, B or P is widely used to enhance the performance of the carbocatalyst for PS activation. However, the performance enhancement from single heteroatom doping is limited by the type of heteroatom used. To further enhance the performance of the carbocatalyst beyond the limit of single heteroatom doping, multi-heteroatom doping can be conducted. This review aims to provide a state-of-the-art overview on the development of multi-heteroatom-doped carbocatalyst for PS activation. The potential synergistic and antagonistic interactions of various heteroatoms including N and B, N and S, N and P, and N and halogen for PS activation are evaluated. Thereafter, the preparation strategies to develop multi-heteroatom-doped carbocatalyst including one-step and multi-step preparation approaches along with the characterization techniques are discussed. Evidence and summary of the performance of multi-heteroatom-doped carbocatalyst for various recalcitrant pollutants removal via PS activation are also provided. Finally, the prospects of employing multi-heteroatom-doped carbocatalyst including the need to study the correlation between different heteroatom combination, surface moiety type, and amount of dopant with the PS activation mechanism, identifying the best heteroatom combination, improving the durability of the carbocatalyst, evaluating the feasibility for full-scale application, developing low-cost multi-heteroatom-doped carbocatalyst, and assessing the environmental impact are also briefly discussed.
A novel real-time monitoring and control system for waste-to-energy gasification process employing differential temperature profiling of a downdraft gasifier

Chan WP, Veksha A, Lei J, Oh WD, Dou X, Giannis A, et al.

J Environ Manage, 2019 Mar 15;234:65-74.
PMID: 30616190 DOI: 10.1016/j.jenvman.2018.12.107

A novel, cost-effective and real-time process monitoring and control system was developed to maintain stable operation of waste-to-energy gasification process. It comprised a feedback loop control that utilized the differential temperatures of the oxidation and reduction zones in the gasifier to determine the regional heat-flow (endothermic or exothermic), to assess the availability of oxidizing agent (for instance, air or O2) at the char bed and to calculate the fuel feeding rate. Based on the correlations developed, the air-to-fuel ratio or the equivalence air ratio (ER) for air gasification could be instantaneously adjusted to maintain stable operation of the gasifier. This study demonstrated a simplification of complex reaction dynamics in the gasification process to differential temperature profiling of the gasifier. The monitoring and control system was tested for more than 70 h of continuous operation in a downdraft fixed-bed gasifier with refuse-derived fuel (RDF) prepared from municipal solid wastes (MSW). With the system, fuel feeding rate could be adjusted accurately to stabilize the operating temperature and ER in the gasifier and generate syngas with consistent properties. Significant reductions in the fluctuations of temperature profiles at oxidation and reduction zones (from higher than 100 °C to lower than 50 °C), differential temperatures (from ±200 to ±50 °C) in gasifier and the flow rate (from 16 ± 6.5 to 12 ± 1.8 L/min), composition of main gas components, LHV (from 6.2 ± 3.1 to 5.7 ± 1.6 MJ/Nm3) and tar content (from 8.0 ± 9.7 to 7.5 ± 4.2 g/Nm3) of syngas were demonstrated. The developed gasifier monitoring and control system is adaptable to various types (updraft, downdraft, and fluidized-bed) and scales (lab, pilot, large scale) of gasifiers with different types of fuel.
Palatability of black soldier fly larvae in valorizing mixed waste coconut endosperm and soybean curd residue into larval lipid and protein sources

Lim JW, Mohd-Noor SN, Wong CY, Lam MK, Goh PS, Beniers JJA, et al.

J Environ Manage, 2019 Feb 01;231:129-136.
PMID: 30340132 DOI: 10.1016/j.jenvman.2018.10.022

The black soldier fly larvae (BSFL) have been widely extolled for the application in managing various solid organic wastes. Owing to the saprophagous nature of BSFL, a rapid valorization of solid organic wastes can be accomplished with the simultaneous production of valuable biochemical compounds derived from larval biomass. In the present works, the mixed waste coconut endosperm (w-CE) and soybean curd residue (SC-r) substrates with increasing protein nutritional constituent were administered to BSFL. The correlations between protein from larval feed substrates and nutritional profiles of BSFL biomasses were ultimately unveiled. The protein from larval feed substrates could be increased by increasing of SC-r portion against w-CE. At the w-CE:SC-r ratio of 3:2, the highest larval total weight gained and growth rate were attained; indicating an optimum protein nutritional constituent in mixed organics (12.4%) that could enhance the BSFL palatability. Further increment of protein nutritional constituent in mixed organics was found acidifying the residual larval feed substrate progressively, undermining the growth of BSFL. By feeding the BSFL with optimum mixed organics, the maximum accumulations of larval lipid and protein could be achieved. Transesterification of extracted lipid had demonstrated high in monounsaturated fatty acids (73%) which was suitable for biodiesel. The BSFL palatability was finally confirmed from the bioconversion viewpoint of mixed organic wastes. Again, achieving the highest bioconversion efficiency of 14% into larval biomass after accounting the metabolic loss of 54%. Therefore, a total of 68% of mixed w-CE and SC-r could be successfully bioconverted.
Fulltext Sustainable utilization of Sedum plumbizincicola as superior hydrochar for efficient nutrients recovery

Zhang R, Zhang Y, Goei R, Oh WD, Zhang Z, He C

J Environ Manage, 2023 Oct 15;344:118441.
PMID: 37379626 DOI: 10.1016/j.jenvman.2023.118441

To realize sound disposal of hyperaccumulator harvested from phytoremediation, hydrothermal carbonization (HTC) has been employed to obtain superior hydrochar adsorbents for removal of phosphate and ammonium from water body. A series of hydrochars have been prepared under tuned HTC conditions to tailor hydrochar with desired properties. Generally, increased temperature and prolonged reaction time facilitated acidic oxygen functional groups on hydrochars, thereby improving adsorption capacity of hydrochar. In single solute system, a superior hydrochar, derived from HTC under 260 °C for 2 h, achieved a maximum phosphate and ammonium adsorption capacity of 52.46 mg/g and 27.56 mg/g at 45 °C, respectively. In binary system, synergistic adsorption was observed only in lower solute concentration, whereas competitive adsorption occurred under higher solute concentration. Characterization and adsorption kinetics suggested chemisorption may dominate the adsorption process, thus the adsorption capacity could be improved by tuning pHpzc of hydrochar. This study firstly demonstrates the sustainable utilization of hyperaccumulators into nutrients-enriched hydrochar as fertilizer for in-situ phytoremediation of contaminated sites with minimized environmental risks towards circular economy.
Co3O4 nanocube-decorated nitrogen-doped carbon foam as an enhanced 3-dimensional hierarchical catalyst for activating Oxone to degrade sulfosalicylic acid

Lin XR, Kwon E, Hung C, Huang CW, Oh WD, Lin KA

J Colloid Interface Sci, 2021 Feb 15;584:749-759.
PMID: 33176929 DOI: 10.1016/j.jcis.2020.09.104

As sulfosalicylic acid (SUA) is extensively used as a pharmaceutical product, discharge of SUA into the environment becomes an emerging environmental issue because of its low bio-degradability. Thus, SO4--based advanced oxidation processes have been proposed for degrading SUA because of many advantages of SO4-. As Oxone represents a dominant reagent for producing SO4-, and Co is the most capable metal for activating Oxone to generate SO4-, it is critical to develop an effective but easy-to-use Co-based catalysts for Oxone activation to degrade SUA. Herein, a 3D hierarchical catalyst is specially created by decorating Co3O4 nanocubes (NCs) on macroscale nitrogen-doped carbon form (NCF). This Co3O4-decorated NCF (CONCF) is free-standing, macroscale and even squeezable to exhibit interesting and versatile features. More importantly, CONCF consists of Co3O4 NCs evenly distributed on NCF without aggregation. The NCF not only serves as a support for Co3O4 NCs but also offers additional active sites to synergistically enhance catalytic activities towards Oxone activation. Therefore, CONCF exhibits a higher catalytic activity than the conventional Co3O4 nanoparticles for activating Oxone to fully eliminate SUA in 30 min with a rate constant of 0.142 min-1. CONCF exhibits a much lower Ea value of SUA degradation (35.2 kJ/mol) than reported values, and stable catalytic activities over multi-cyclic degradation of SUA. The mechanism of SUA degradation is also explored, and degradation intermediates of SUA degradation are identified to provide a possible pathway of SUA degradation. These features validate that CONCF is certainly a promising 3D hierarchical catalyst for enhanced Oxone activation to degrade SUA. The findings obtained here are also insightful to develop efficient heterogeneous Oxone-activating catalysts for eliminating emerging contaminants.
Metal-complexed covalent organic frameworks derived N-doped carbon nanobubble-embedded cobalt nanoparticle as a magnetic and efficient catalyst for oxone activation

Nguyen HT, Lee J, Kwon E, Lisak G, Thanh BX, Oh WD, et al.

J Colloid Interface Sci, 2021 Jun;591:161-172.
PMID: 33601102 DOI: 10.1016/j.jcis.2021.01.108

While Cobalt nanoparticles (Co NPs) are useful for catalytic Oxone activation, it is more advantageous to embed/immobilize Co NPs on nitrogen-doped carbon substrates to provide synergy for enhancing catalytic performance. Herein, this study proposes to fabricate such a composite by utilizing covalent organic frameworks (COF) as a precursor. Through complexation of COF with Co, a stable product of Co-complexed COF (Co-COF) can be synthesized. This Co-COF is further converted through pyrolysis to N-doped carbon in which cobaltic NPs are embedded. Owing to its well-defined structures of Co-COF, the pyrolysis process transforms COF into N-doped carbon with a bubble-like morphology. Such Co NP-embedded N-doped carbon nanobubbles (CoCNB) with pores, magnetism and Co, shall be a promising catalyst. Thus, CoCNB shows a much stronger catalytic activity than commercial Co3O4 NPs to activate Oxone to degrade toxic Amaranth dye (AMD). CoCNB-activated Oxone also achieves a significantly lower Ea value of AMD degradation (i.e., 27.9 kJ/mol) than reported Ea values in previous literatures. Besides, CoCNB is still effective for complete elimination of AMD in the presence of high-concentration NaCl and surfactants, and CoCNB is also reusable over five consecutive cycles.
Aerobic oxidation of 5-hydroxymethylfurfural into 2,5-diformylfuran using manganese dioxide with different crystal structures: A comparative study

Lin KA, Oh WD, Zheng MW, Kwon E, Lee J, Lin JY, et al.

J Colloid Interface Sci, 2021 Jun 15;592:416-429.
PMID: 33691223 DOI: 10.1016/j.jcis.2021.02.030

Aerobic oxidation of 5-Hydroxymethylfurfural (HMF) to 2,5-Diformylfuran (DFF) using O2 gas represents a sustainable approach for valorization of lignocellulosic compounds. As manganese dioxide (MnO2) is validated as a useful oxidation catalyst and many crystalline forms of MnO2 exist, it is critical to explore how the crystalline structures of MnO2 influence their physical/chemical properties, which, in turn, determine catalytic activities of MnO2 crystals for HMF oxidation to DFF. In particular, six MnO2 crystals, α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, ε-MnO2, and λ-MnO2 are prepared and investigated for their catalytic activities for HMF oxidation to DFF. With different morphologies and crystalline structures, these MnO2 crystals possess very distinct surficial chemistry, redox capabilities, and textural properties, making these MnO2 exhibit different catalytic activities towards HMF conversion. Especially, β-MnO2 can produce much higher DFF per surface area than other MnO2 crystals. β-MnO2 could achieve the highest CHMF = 99% and YDFF = 97%, which are much higher than the reported values in literature, possibly because the surficial reactivity of β-MnO2 appears to be highest in comparison to other MnO2 crystals. Especially, β-MnO2 could exhibit YDFF > 90% over 5 cycles of reusability test, and maintain its crystalline structure, revealing its advantageous feature for aerobic oxidation of HMF to DFF. Through this study, the relationship between morphology, surface chemistry, and catalytic activity of MnO2 with different crystal forms is elucidated for providing scientific insights into design, application and development of MnO2-based materials for aerobic oxidation of bio-derived molecules to value-added products.
Hierarchical ZIF-decorated nanoflower-covered 3-dimensional foam for enhanced catalytic reduction of nitrogen-containing contaminants

Lin JY, Lee J, Oh WD, Kwon E, Tsai YC, Lisak G, et al.

J Colloid Interface Sci, 2021 Nov 15;602:95-104.
PMID: 34118608 DOI: 10.1016/j.jcis.2021.05.098

Metal Organic Frameworks (MOFs) represent a promising class of metallic catalysts for reduction of nitrogen-containing contaminants (NCCs), such as 4-nitrophenol (4-NP). Nevertheless, most researches involving MOFs for 4-NP reduction employ noble metals in the form of fine powders, making these powdered noble metal-based MOFs impractical and inconvenient for realistic applications. Thus, it would be critical to develop non-noble-metal MOFs which can be incorporated into macroscale and porous supports for convenient applications. Herein, the present study proposes to develop a composite material which combines advantageous features of macroscale/porous supports, and nanoscale functionality of MOFs. In particular, copper foam (CF) is selected as a macroscale porous medium, which is covered by nanoflower-structured CoO to increase surfaces for growing a cobaltic MOF, ZIF-67. The resultant composite comprises of CF covered by CoO nanoflowers decorated with ZIF-67 to form a hierarchical 3D-structured catalyst, enabling this ZIF-67@Cu foam (ZIF@CF) a promising catalyst for reducing 4-NP, and other NCCs. Thus, ZIF@CF can readily reduce 4-NP to 4-AP with a significantly lower Ea of 20 kJ/mol than reported values. ZIF@CF could be reused over 10 cycles and remain highly effective for 4-NP reduction. ZIF@CF also efficiently reduces other NCCs, such as 2-nitrophenol, 3-nitrophenol, methylene blue, and methyl orange. ZIF@CF can be adopted as catalytic filters to enable filtration-type reduction of NCCs by passing NCC solutions through ZIF@CF to promptly and conveniently reduce NCCs. The versatile and advantageous catalytic activity of ZIF@CF validates that ZIF@CF is a promising and practical heterogeneous catalyst for reductive treatments of NCCs.
Coordination polymer-derived cobalt-embedded and N/S-doped carbon nanosheet with a hexagonal core-shell nanostructure as an efficient catalyst for activation of oxone in water

Tuan DD, Oh WD, Ghanbari F, Lisak G, Tong S, Andrew Lin KY

J Colloid Interface Sci, 2020 Nov 01;579:109-118.
PMID: 32574728 DOI: 10.1016/j.jcis.2020.05.033

As sulfate-radical (SR)-based advanced oxidation processes are increasingly implemented, Oxone has been frequently-used for generation of SR. While Co3O4 nanoparticle (NP) has been widely-accepted as a promising catalyst for activating Oxone, Co3O4 NPs tend to aggregate in water, losing their reactivity. Thus, many attempts have immobilized Co3O4 NPs on supports, especially carbonaceous substrates, because combination of Co NPs with carbon substrates offers synergistic effects for boosting catalytic activities. Moreover, carbon substrates doped with hetero-atoms (N and S) further increase electron transfer and reactivity. Therefore, it is even promising to immobilize Co NPs onto N/S-doped carbon (NSC) to form Co-embedded NSC (denoted as CoNSC) for enhancing Oxone activation. In this study, a convenient and facile technique is proposed to prepare such a CoNSC via a simple carbonization treatment of a coordination polymer of Co and trithiocyanuric acid (TTCA). The resulting CoNSC exhibits the sheet-like hexagonal morphology with the core-shell configuration, and Co NPs are well-embedded into the N/S-doped carbonaceous matrix, making it an advantageous heterogeneous catalyst for Oxone activation. As Azorubine S (ARS) decolorization is employed as a model reaction of Oxone activation, CoNSC exhibits a higher catalytic activity than pristine Co3O4 and NSC for Oxone activation to decolorize ARS. In comparison to the other reported catalysts, CoNSC also possesses a much lower Ea for ARS decolorization. CoNSC can be also reusable and stable for Oxone activation over multiple cycles without loss of catalytic activity. These features validate that CoNSC is a promising and useful Co-based catalyst for Oxone activation.
Importance of carbon structure for nitrogen and sulfur co-doping to promote superior ciprofloxacin removal via peroxymonosulfate activation

Gasim MF, Veksha A, Lisak G, Low SC, Hamidon TS, Hussin MH, et al.

J Colloid Interface Sci, 2023 Mar 15;634:586-600.
PMID: 36549207 DOI: 10.1016/j.jcis.2022.12.072

Herein, five N, S-co-doped carbocatalysts were prepared from different carbonaceous precursors, namely sawdust (SD), biochar (BC), carbon-nanotubes (CNTs), graphite (GP), and graphene oxide (GO) and compared. Generally, as the graphitization degree increased, the extent of N and S doping decreased, graphitic N configuration is preferred, and S configuration is unaltered. As peroxymonosulfate (PMS) activator for ciprofloxacin (CIP) removal, the catalytic performance was in order: NS-CNTs (0.037 min-1) > NS-BC (0.032 min-1) > NS-rGO (0.024 min-1) > NS-SD (0.010 min-1) > NS-GP (0.006 min-1), with the carbonaceous properties, rather than the heteroatoms content and textural properties, being the major factor affecting the catalytic performance. NS-CNTs was found to have the supreme catalytic activity due to its remarkable conductivity (3.38 S m-1) and defective sites (ID/IG = 1.28) with high anti-interference effect against organic and inorganic matter and varying water matrixes. The PMS activation pathway was dominated by singlet oxygen (1O2) generation and electron transfer regime between CIP and PMS activated complexes. The CIP degradation intermediates were identified, and a degradation pathway is proposed. Overall, this study provides a better understanding of the importance of selecting a suitable carbonaceous platform for heteroatoms doping to produce superior PMS activator for antibiotics decontamination.

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