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.
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.
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.