A kinetic model incorporating adsorption, desorption and biodegradation processes was developed to describe the bioregeneration of granular activated carbon (GAC) loaded with 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP), respectively, in simultaneous adsorption and biodegradation processes. The model was numerically solved and the results showed that the kinetic model was well-fitted (R(2)>0.83) to the experimental data at different GAC dosages and at various initial 4-CP and 2,4-DCP concentrations. The rate of bioregeneration in simultaneous adsorption and biodegradation processes was influenced by the ratio of initial chlorophenol concentration to GAC dosage. Enhancement in the rate of bioregeneration was achieved by using the lowest ratio under either one of the following experimental conditions: (1) increasing initial chlorophenol concentration at constant GAC dosage and (2) increasing GAC dosage at constant initial chlorophenol concentration. It was found that the rate enhancement was more pronounced under the second experimental condition.
The objectives of this study are to obtain the time courses of the amount of chlorophenol adsorbed onto granular activated carbon (GAC) in the simultaneous adsorption and biodegradation processes involving 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP), respectively, and to quantify the bioregeneration efficiency of GAC loaded with 4-CP and 2,4-DCP by direct measurement of the amount of chlorophenol adsorbed onto GAC. Under abiotic and biotic conditions, the time courses of the amount of chlorophenol adsorbed onto GAC at various GAC dosages for the initial 4-CP and 2,4-DCP concentrations below and above the biomass acclimated concentrations of 300 and 150 mg/L, respectively, were determined. The results show that the highest bioregeneration efficiency was achieved provided that the initial adsorbate concentration was lower than the acclimated concentration. When the initial adsorbate concentration was higher than the acclimated concentration, the highest bioregeneration efficiency was achieved if excess adsorbent was used.
Engineered biochar is increasingly regarded as a cost-effective and eco-friendly peroxymonosulfate (PMS) activator. Herein, biochar doped with nitrogen and sulfur moieties was prepared by pyrolysis of wood shavings and doping precursor. The doping precursor consists of either urea, thiourea or 1:1 w/w mixture of urea and thiourea (denoted as NSB-U, NSB-T and NSB-UT, respectively). The physicochemical properties of the NSBs were extensively characterized, revealing that they are of noncrystalline carbon with porous structure. The NSBs were employed as PMS activator to degrade organic pollutants particularly methylene blue (MB). It was found that NSB-UT exhibited higher MB removal rate with kapp = 0.202 min-1 due to its relatively high surface area and favorable intrinsic surface moieties (combination of graphitic N and thiophenic S). The effects of catalyst loading, PMS dosage and initial pH were evaluated. Positive enhancement of the MB removal rate can be obtained by carefully increasing the catalyst loading or PMS dosage. Meanwhile, the MB removal rate is greatly influenced by pH due to electrostatic interactions and pH dependent reactions. The NSB-UT can be reused for several cycles to some extent and its catalytic activity can be restored by thermal treatment. Based on the radical scavenger study and XPS analysis, the nonradical pathway facilitated by the graphitic N and thiophenic S active sites are revealed to be the dominant reaction pathway. Overall, the results of this study show that engineered biochar derived from locally available biowaste can be transformed into PMS activator for environmental applications.
Over the past decade, there has been a surge of interest in using char (hydrochar or biochar) derived from biomass as persulfate (PS, either peroxymonosulfate or peroxydisulfate) activator for anthropogenic pollutants removal. While extensive investigation showed that char could be used as a PS activator, its sustainability over prolonged application is equivocal. This review provides an assessment of the knowledge gap related to the sustainability of char as a PS activator. The desirable char properties for PS activation are identified, include the high specific surface area and favorable surface chemistry. Various synthesis strategies to obtain the desirable properties during biomass pre-treatment, hydrochar and biochar synthesis, and char post-treatment are discussed. Thereafter, factors related to the sustainability of employing char as a PS activator for anthropogenic pollutants removal are critically evaluated. Among the critical factors include performance uncertainty, competing adsorption process, char stability during PS activation, biomass precursor variation, scalability, and toxic components in char. Finally, some potential research directions are provided. Fulfilling the sustainability factors will provide opportunity to employ char as an economical and efficient catalyst for sustainable environmental remediation.
In this study, a facile hydrothermal method was employed to prepare Me-doped Bi2Fe4O9 (Me = Zn, Cu, Co, and Mn) as peroxymonosulfate (PMS) activator for ciprofloxacin (CIP) degradation. The characteristics of the Me-doped bismuth ferrites were investigated using various characterization instruments including SEM, TEM, FTIR and porosimeter indicating that the Me-doped Bi2Fe4O9 with nanosheet-like square orthorhombic structure was successfully obtained. The catalytic activity of various Me-doped Bi2Fe4O9 was compared and the results indicated that the Cu-doped Bi2Fe4O9 at 0.08 wt.% (denoted as BFCuO-0.08) possessed the greatest catalytic activity (kapp = 0.085 min-1) over other Me-doped Bi2Fe4O9 under the same condition. The synergistic interaction between Cu, Fe and oxygen vacancies are the key factors which enhanced the performance of Me-doped Bi2Fe4O9. The effects of catalyst loading, PMS dosage, and pH on CIP degradation were also investigated indicating that the performance increased with increasing catalyst loading, PMS dosage, and pH. Meanwhile, the dominant reactive oxygen species was identified using the chemical scavengers with SO4•-, •OH, and 1O2 playing a major role in CIP degradation. The performance of BFCuO-0.08 deteriorated in real water matrix (tap water, river water and secondary effluent) due to the presence of various water matrix species. Nevertheless, the BFCuO-0.08 catalyst possessed remarkable stability and can be reused for at least four successive cycles with >70% of CIP degradation efficiency indicating that it is a promising catalyst for antibiotics removal.
Zero valent iron-loaded biochar (Fe0-BC) has shown promise for the removal of various organic pollutants, but is restricted by reduced specific surface area, low utilization efficiency and limited production of reactive oxygen species (ROS). In this study, iron carbide-loaded activated biochar (Fe3C-AB) with a high surface area was synthesized through the pyrolysis of H3PO4 activated biochar with Fe(NO3)3, tested for removing bisphenol A (BPA) and elucidated the adsorption and degradation mechanisms. As a result, H3PO4 activated biochar was beneficial for the transformation of Fe0 to Fe3C. Fe3C-AB exhibited a significantly higher removal rate and removal capacity for BPA than that of Fe0-BC within a wide pH range of 5.0-11.0, and its performance was maintained even under extremely high salinity and different water sources. Moreover, X-ray photoelectron spectra and density functional theory calculations confirmed that hydrogen bonds were formed between the COOH groups and BPA. 1O2 was the major reactive species, constituting 37.0% of the removal efficiency in the degradation of BPA by Fe3C-AB. Density functional reactivity theory showed that degradation pathway 2 of BPA was preferentially attacked by ROS. Thus, Fe3C-AB with low cost and excellent recycling performance could be an alternative candidate for the efficient removal of contaminants.
Three specific catalysts, namely ZIF-67 (zeolitic imidazolate framework-67), Co@NCF (Co@Nitrogen-Doped Carbon Framework), and 3D NCF (Three-Dimensional Nitrogen-Doped Carbon Framework), were prepared and studied for pulp and paper mill effluent degradation using heterogeneous activation of peroxymonosulfate (PMS). Numerous characterizations, including scanning electron microscopy (SEM), X-ray diffraction (XRD), and N2 adsorption, were used to characterize the properties of three different catalysts. 3D NCF is remarkably effective at heterogeneous activation of PMS to generate sulfate radicals to degrade pulp and paper mill effluent (PPME) compared to the other as-prepared catalysts. The catalytic activity reveals a sequence of 3D NCF > Co@NCF > ZIF-67.3D NCF could degrade organic pollutants in 30 min at an initial COD concentration of 1146 mg/L of PPME, 0.2 g/L catalysts, 2 g/L PMS, and 50 °C. Consequently, it was observed that the degradation of PPME using 3D NCF followed first-order kinetics, with an activation energy of 40.54 kJ mol-1. Overall, 3D NCF/PMS system reveals promising performance for PPME removal.
The escalation of global water pollution due to emerging pollutants has gained significant attention. To address this issue, catalytic peroxymonosulfate (PMS) activation technology has emerged as a promising treatment approach for effectively decontaminating a wide range of pollutants. Recently, modified biochar has become an increasingly attractive as PMS activator. Metal-heteroatom-co-doped biochar (MH-BC) has emerged as a promising catalyst that can provide enhanced performance over heteroatom-doped and metal-doped biochar due to the synergism between metal and heteroatom in promoting PMS activation. Therefore, this review aims to discuss the fabrication pathways (i.e., internal vs external doping and pre-vs post-modification) and key parameters (i.e., source of precursors, synthesis methods, and synthesis conditions) affecting the performance of MH-BC as PMS activator. Subsequently, an overview of all the possible PMS activation pathways by MH-BC is provided. Subsequently, Also, the detection, identification, and quantification of several reactive species (such as, •OH, SO4•-, O2•-, 1O2, and high valent oxo species) generated in the catalytic PMS system by MH-BC are also evaluated. Lastly, the underlying challenges associated with poor stability, the lack of understanding regarding the interaction between metal and heteroatom during PMS activation and quantification of radicals in multi-ROS system are also deliberated.
Herein, we report a detailed study on creating heterojunction between graphitic carbon nitride (g-C3N4) and bismuth phosphate (BiPO4), enhancing the unpaired free electron mobility. This leads to an accelerated photocatalysis of 2,4-dichlorophenols (2,4-DCPs) under sunlight irradiation. The heterojunction formation was efficaciously conducted via a modest thermal deposition technique. The function of g-C3N4 plays a significant role in generating free electrons under sunlight irradiation. Together, the generated electrons at the g-C3N4 conduction band (CB) are transferred and trapped by the BiPO4 to form active superoxide anion radicals (•O2-). These active radicals will be accountable for the photodegradation of 2,4-DCPs. The synthesized composite characteristics were methodically examined through several chemical and physical studies. Due to the inimitable features of both g-C3N4 and BiPO4, its heterojunction formation, 2.5wt% BiPO4/g-C3N4 achieved complete 2,4-DCP removal (100%) in 90 min under sunlight irradiation. This is due to the presence of g-C3N4 that enhanced electron mobility through the formation of heterojunctions that lengthens the electron-hole pairs' lifetime and maximizes the entire solar spectrum absorption to generate active electrons at the g-C3N4 conduction band. Thus, this formation significantly draws the attention for future environmental remediation, especially in enhancing the entire solar spectrum's harvesting.
In this study, chitosan/porous carbon composite (C-PC) modified in 1-Allyl-3-methyl imidazolium bromide [AMIM][Br] under airtight condition was prepared for the removal of Acid Blue-25 dye (AB-25) from aqueous medium. For comparison of adsorption efficiency of C-PC, chitosan-activated carbon composite (C-AC) was also prepared in 1% acetic acid. The adsorbents were characterised using SEM, EDX, XRD, BET, TGA and FTIR. The micrograph of C-PC revealed cavities and slightly rough surfaces dominated with similar sized and irregular shaped stone-like materials which differ from the precursors' micrograph. BET analysis revealed the domination of mesopores on the C-PC and C-AC surfaces, as the hydroxyl and amino group on C-PC are the main active sites for AB-25 dye uptake. The dye was better adsorbed onto C-PC at pH 2 and C-AC at pH 4. The adsorption capacity obtained for C-PC, C-AC, activated carbon (AC) and chitosan (CH) using Langmuir isotherm model are 3333.33 mg/g, 909.90 mg/g, 909.09 mg/g and 833.33 mg/g, respectively. The experimental data are well described by Langmuir and Fruendlich isotherms for adsorption of the dye onto C-PC, AC and CH. C-AC fitted into Langmuir isotherm only. The kinetics of the adsorption fitted into pseudo-second order indicating the possibility of chemical interactions in the adsorption process.
The primary aim of this study is to develop an economical, stable, and effective heterogeneous catalyst for wastewater remediation via the Fenton oxidation process. For this purpose, Fe3O4-montmorillonite alginate (FeMA) composite beads were synthesized by entrapping Fe3O4-montmorillonite in calcium alginate beads. The performance of the catalysts was evaluated via the Fenton degradation of ofloxacin (OFL), an antibiotic that is frequently detected in water bodies. The physiochemical properties of the FeMA composite beads were characterized using X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscope/energy dispersive X-ray (FESEM/EDX), Brunauer-Emmett-Teller (BET) analysis, Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA). FeMA composite beads were found to have a higher surface area, higher porosity, and better thermal stability compared to pristine alginate beads. The composite beads were subsequently used for Fenton degradation of ofloxacin (OFL) in an aqueous solution. The effects of Fe3O4-montmorillonite loading on alginate, FeMA composite beads dosage, initial solution pH, initial OFL concentration, different oxidants, H2O2 dosage, reaction temperature, and inorganic salts on Fenton degradation of OFL in aqueous solution was investigated. The results revealed that the percentage of OFL degradation reached about 80 % under optimized conditions, while the total organic carbon (TOC) removal reached about 53 %. The entrapment of Fe3O4-montmorillonite in alginate beads results in less iron ions leaching compared to previous observation, and the efficiency remains constant over the five cycles investigated. The kinetics of the Fenton degradation process are best fitted to the pseudo-first-order kinetic model. It is therefore believed that FeMA composite beads can be a promising material for wastewater remediation via the Fenton oxidation process.
Adsorption efficiency of a duo-material blend featuring the fabrication of modified chitosan adsorbents (powder (C-emimAc), bead (CB-emimAc) and sponge (CS-emimAc)) for the removal of Cd(II) from aqueous solution was investigated. The chitosan@activated carbon (Ch/AC) blend was developed in a green ionic solvent, 1-ethyl-3-methyl imidazolium acetate (EmimAc) and its characteristics was examined using FTIR, SEM, EDX, BET and TGA. The possible mechanism of interaction between the composites and Cd(II) was also predicted using the density functional theory (DFT) analysis. The interactions of various blend forms (C-emimAc, CB-emimAc and CS-emimAc) with Cd(II) gave better adsorption at pH 6. The composites also present excellent chemical stability in both acidic and basic conditions. The monolayer adsorption capacities obtained (under the condition 20 mg/L [Cd], adsorbent dosage 5 mg, contact time 1 h) for the CB-emimAc (84.75 mg/g) > C-emimAc (72.99 mg/g) > CS-emimAc (55.25 mg/g), as this was supported by their order of increasing BET surface area (CB-emimAc (120.1 m2/g) > C-emimAc (67.4 m2/g) > CS-emimAc (35.3 m2/g)). The feasible adsorption interactions between Cd(II) and Ch/AC occurs through the O-H and N-H groups of the composites, as supported by DFT analysis in which an electrostatic interactions was predicted as the dominant force. The interaction energy (-1309.35 eV) calculated via DFT shows that the Ch/AC with amino (-NH) and hydroxyl (-OH) groups are more effective with four significant electrostatic interactions with the Cd(II) ion. The various form of Ch/AC composites developed in EmimAc possess good adsorption capacity and stability for the adsorption Cd(II).
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.
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 (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.
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.
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.
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.
While transition metals are useful for activating monopersulfate (MPS) to degrade contaminants, bimetallic alloys exhibit stronger catalytic activities owing to several favorable effects. Therefore, even though Co is an efficient metal for MPS activation, CoFe alloys are even more promising heterogeneous catalysts for MPS activation. Immobilization/embedment of CoFe alloy nanoparticles (NPs) onto hetero-atom-doped carbon matrices appears as a practical strategy for evenly dispersing CoFe NPs and enhancing catalytic activities via interfacial synergies between CoFe and carbon. Herein, N-doped carbon-embedded CoFe alloy (NCCF) is fabricated here to exhibit a unique hollow-engineered nanostructure and the composition of CoFe alloy by using Co-ZIF as a precursor after the facile etching and Fe doping. The Fe dopant embeds CoFe alloy NPs into the hollow-structured N-doped carbon substrate, enabling NCCF to possess the higher mesoscale porosity, active N species as well as more superior electrochemical properties than its analogue without Fe dopants, carbon matrix-supported cobalt (NCCo). Thus, NCCF exhibits a considerably larger activity than NCCo and the benchmark catalyst, Co3O4 NP, for MPS activation to degrade an environmental hormone, dihydroxydiphenyl ketone (DHPK). Besides, NCCF + MPS shows an even lower activation energy for DHPK degradation than literatures, and retains its high efficiency for eliminating DHPK in different water media. DHPK degradation pathway and ecotoxicity assessment are unraveled based on the insights from the computational chemistry, demonstrating that DHPK degradation by NCCF + MPS did not result in the formation of toxic and highly toxic by-products. These features make NCCF a promising heterogeneous catalyst for MPS activation to degrade DHPK.
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.