As methyltheobromine (MTB) has been increasingly detected in wastewater, it would be necessary to develop more intensive and effective approaches to remove MTB. As Co species immobilized on carbonaceous materials appears as a promising catalyst, doping carbon with nitrogen has been also validated to significantly enhance catalytic activities for Oxone activation. Therefore, it is desired to develop a composite of immobilizing Co species on N-doped carbonaceous supports for activating Oxone to degrade MTB. Unfortunately, very few studies have demonstrated such composites for activating Oxone to degrade MTB as this type of composites are conventionally prepared via complex procedures. Alternatively, this study aims to develop such a composite conveniently by using a cobaltic coordination polymer (CP) as a precursor. Specifically Co2+ and 4,4-bipyridine (BIPY) are selected for formulating a special one-dimensional CP, which is then carbonized to convert Co to Co nanoparticles (NPs) and transform BIPY to carbon nitride (CN) matrices. Because of 1-D coordinated structure of CoBIPY, the resulting magnetic Co NPs are well-distributed and protected within CN to form a magnetic Co-embedded carbon nitride composite (MCoCN). In comparison to pristine CN and Co3O4, MCoCN exhibits much higher catalytic activities to activate Oxone for degrading MTB completely within 7 min. MCoCN also shows a much lower activation energy of 24.6 kJ/mol than other reported catalysts for activating Oxone to degrade MTB. The findings of this study validate that the 1-D coordination polymer of CoBIPY is a useful precursor to prepare MCoCN for effectively activating Oxone to degrade MTB.
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.
As cobalt (Co) represents an effective transition metal for activating Oxone to degrade contaminants, tricobalt tetraoxide (Co3O4) is extensively employed as a heterogeneous phase of Co for Oxone activation. Since Co3O4 can be manipulated to exhibit various shapes, 2-dimensional plate-like morphology of Co3O4 can offer large contact surfaces. If the large plate-like surfaces can be even porous, forming porous nanoplate Co3O4 (PNC), such a PNC should be a promising catalyst for Oxone activation. Therefore, a facile but straightforward method is proposed to prepare such a PNC for activating Oxone to degrade pollutants. In particular, a cobaltic coordination polymer with a morphology of hexagonal nanoplate, which is synthesized through coordination between Co2+ and thiocyanuric acid (TCA), is adopted as a precursor. Through calcination, CoTCA could be transformed into hexagonal nanoplate-like Co3O4 with pores to become PNC. This PNC also shows different characteristics from the commercial Co3O4 nanoparticle (NP) in terms of surficial reactivity and textural properties. Thus, PNC exhibits a much higher catalytic activity than the commercial Co3O4 NP towards activation of Oxone to degrade a model contaminant, salicylic acid (SA). Specifically, SA was 100% degraded by PNC activating Oxone within 120 min, and the Ea of SA degradation by PNC-activated Oxone is 70.2 kJ/mol. PNC can also remain stable and effective for SA degradation even in the presence of other anions, and PNC could be reused over multiple cycles without significant loss of catalytic activity. These features validate that PNC is a promising and useful Co-based catalyst for Oxone activation.
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.
Since 5-sulfosalicylic acid (SFA) has been increasingly released to the environment, SO4--based oxidation processes using Oxone have been considered as useful methods to eliminate SFA. As Co3O4 has been a promising material for OX activation, the four 3D Co3O4 catalysts with distinct morphologies, including Co3O4-C (with cubes), Co3O4-P (with plates), Co3O4-N (with needles) and Co3O4-F (with floral structures), are fabricated for activating OX to degrade SFA. In particular, Co3O4-F not only exhibits the highest surface area but also possesses the abundant Co2+ and more reactive surface, making Co3O4-F the most advantageous 3D Co3O4 catalyst for OX activation to degrade SFA. The mechanism of SFA by this 3D Co3O4/OX is also investigated and the corresponding SFA degradation pathway has been elucidated. The catalytic activities of Co3O4 catalysts can be correlated to physical and chemical properties which were associated with particular morphologies to provide insights into design of 3D Co3O4-based catalysts for OX-based technology to degrade emerging contaminants, such as SFA.
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.
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.
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 cobalt (Co) has been the most useful element for activating Oxone to generate SO4•-, this study aims to develop a hierarchical catalyst with nanoscale functionality and macroscale convenience by decorating nanoscale Co-based oxides on macroscale supports. Specifically, a facile protocol is proposed by utilizing Cu mesh itself as a Cu source for fabricating CuCo2O4 on Cu mesh. By changing the dosages of the Co precursor and carbamide, various nanostructures of CuCo2O4 grown on a Cu mesh can be afforded, including nanoscale needles, flowers, and sheets. Even though the Cu mesh itself can be also transformed to a Cu-Oxide mesh, the growth of CuCo2O4 on the Cu mesh significantly improves its physical, chemical, and electrochemical properties, making these CuCo2O4@Cu meshes much more superior catalysts for activating Oxone to degrade the Azo toxicant, Acid Red 27. More interestingly, the flower-like CuCo2O4@Cu mesh exhibits a higher specific surface area and more superior electrochemical performance, enabling the flower-like CuCo2O4@Cu mesh to show the highest catalytic activity for Oxone activation to degrade Acid Red 27. The flower-like CuCo2O4@Cu mesh also exhibits a much lower Ea of Acid Red 27 degradation than the reported catalysts. These results demonstrate that CuCo2O4@Cu meshes are advantageous heterogeneous catalysts for Oxone activation, and especially, the flower-like CuCo2O4@Cu mesh appears as the most effective CuCo2O4@Cu mesh to eliminate the toxic Acid Red 27.