Importance of carbon structure for nitrogen and sulfur co-doping to promote superior ciprofloxacin removal via peroxymonosulfate 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.

Promotional effect of Ca doping on Bi2Fe4O9 as peroxymonosulfate activator for gatifloxacin removal.

A series of Ca-doped bismuth ferrite was prepared at various %w/w of Ca via a facile hydrothermal method to obtain Bi2XCa2(1-X)Fe4O9 (denoted as BFOCa-X, where X = 1, 0.95, 0.90, 0.80, 0.50). The BFOCa-X catalysts were characterized, and the results showed that they consist of pure phase BFO with nanosheet-like morphology. The as-prepared BFOCa-X catalysts were used as peroxymonosulfate (PMS) activator for gatifloxacin (GAT) removal. It was found that the catalytic activity decreased in the following order: BFOCa-0.8 (90.2% GAT removal efficiency in 45 min, kapp = 0.084 min-1)>BFOCa-0.95 > BFOCa-0.9 > BFOCa-0.5 > BFO indicating that BFOCa-0.8 has the optimized active sites for catalysis. The Ca dopant contributed to the increased oxygen vacancies and surface hydroxyl groups, promoting the catalytic PMS activation process. The kapp value increased gradually with increasing catalyst loading and PMS dosage while pH 9 presented the highest GAT removal rate. The GAT degradation rate was inhibited by PO43-, humic acid and NH4+ but promoted in the presence of Cl-, NO3- and HCO3-. It was also found that the GAT can undergo several degradation pathways in the catalytic PMS system, which eventually mineralized into innocuous compounds. The dominant reactive oxygen species (ROS) were identified using chemical scavengers, revealing that SO4•-, 1O2 and •OH contributed significantly to GAT degradation. Based on the XPS study, PMS was activated by the Fe2+/Fe3+ redox cycling and oxygen vacancies to produce SO4•-/•OH and 1O2, respectively. Overall, the BFOCa-0.8 also showed excellent reusability up to at least 4 cycles with low Bi and Fe leaching (<7 and 62 µg L-1, respectively), indicating that it has promising potential for application as PMS activator for antibiotics removal.

Can biochar and hydrochar be used as sustainable catalyst for persulfate activation?

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.