Herein, through supramolecular gel assisted pre-configuration, a novel bamboo-like porous graphitic carbon nitride (g-C3N4) deposited with single-atom Fe was successfully prepared and used for sulfite (S(IV)) activation. Unexpectedly, owing to the presence of single-atom Fe, hybrid material with only 2.5‰ of Fe exhibited 16 times higher S(IV) activation efficiency for diclofenac removal than pure g-C3N4 under visible light irradiation. Moreover, a synergetic effect of Fe and g-C3N4 was found to play the dominate role, and the synergetic factor was calculated to be 0.84. The synergetic mechanism mainly related to the generation of surface Fe-S(IV) complex, which could be affected by S(IV) species or the presence of H2PO4−. DCF removal was significantly enhanced at alkaline condition, but the enhancement was mainly attributed to photocatalysis but not synergetic effect. Decarboxylation, hydroxylation, chlorine abstraction and cleavages at bridging N atom were the main degradation pathways of DCF, which agreed well with Fukui index prediction. The toxicity of DCF was alleviated during the degradation process through successful mineralization of chlorine atoms.
V-Fe concentrate ore was applied to activate peroxydisulfate (PDS) for carbamazepine (CBZ) degradation. The excellent performance of V-Fe concentrate ore was mainly ascribed to the quick electron transfer from surface ≡V(III) and ≡V (IV) to ≡Fe(III) for ≡Fe(II) regeneration, which was confirmed by XPS and XAS analyses. This accelerated ≡Fe(II) regeneration could thus lead to quick formation of HO, SO4−, O2− and effective degradation of CBZ. The degradation rate of CBZ could be also expressed by a kinetic model, i.e., −d[CBZ]/dt = (0.83 mM-0.55 min-1(g/L)-0.65) [CBZ]0.29[PDS]1.26[V-Fe]0.65. Combined with the measured intermediates and the results of DFT calculation, CBZ degradation pathway was proposed systematically. Moreover, this catalyst displayed excellent recyclability and general applicability for a broad substrate scope. This study suggests low valent vanadium makes crucial contributions to the high activity of V-Fe-based catalysts, and improves the understanding of electron transfer mechanism between V and Fe in PDS activation process.
Pharmaceuticals and personal care products (PPCPs) are of great concern due to their increasing health effects, so advanced treatment technologies for PPCPs removal are urgently needed. In this study, titanate nanotubes decorated Co(OH)2 hollow microsphere (CoM/TNTs) composites were synthesized by a two-step solvothermal method, and used to activate peroxymonosulfate (PMS) through heterogenous catalysis for acetaminophen (ACE) degradation in water. The optimum material (CoM/TNTs0.5) activated PMS system exhibited high ACE removal efficiency and quick kinetic, as 93.0% ACE was degraded even within 10 min. The two components in CoM/TNTs showed a synergetic effect on PMS activation for radicals production: Co(OH)+ from CoM was the primary active species to active PMS, while TNTs could offer abundant –OH groups for Co(OH)+ formation. Density functional theory (DFT) calculation further interpreted the mechanism of Co(OH)+ for PMS activation by means of reaction potential energy surface (PES) analysis. Both the scavenger quenching tests and electron paramagnetic resonance analysis revealed that the sulfate radical (SO4-·) played a dominant role in ACE degradation. Moreover, DFT calculation also suggested that the ACE atoms with high Fukui index (f -) represented the active sites for electrophilic attack by SO4-·. The toxicity analysis based on quantitative structure-activity relationship (QSAR) verified the reduced toxicity of transformation products. Furthermore, CoM/TNTs also had good reusability and stability over five cycles. This work provides deep insights into the reaction mechanisms of radical production and organics attack in cobalt-based PMS activation system.
Bifunctional Bi12O17Cl2/MIL-100(Fe) composite (BMx) was firstly constructed via facile ball-milling method. The optimal BM200 was highly efficient for Cr(VI) sequestration and activation of persulfate (PS) for bisphenol A (BPA) decomposition under white light illumination, which was much more remarkable than the pristine MIL-100(Fe) and Bi12O17Cl2, respectively. Furthermore, the photocatalytic reduction efficiency can be significantly improved via the addition of some green small organic acids (SOAs). As well, the BPA degradation can be achieved over an extensive initial pH range of 3.0–11.0. When the PS concentration increased to more than 2.0 mM, the BPA degradation efficiency decreased due to the SO4−• self-scavenging effect. It was also found that the co-existence of inorganic anions like H2PO4−, HCO3−, SO42−, Cl− and NO3− could decelerate the BPA degradation. The excellent photocatalytic Cr(VI) reduction and persulfate activation performances originated from both MIL-100(Fe) with excellent PS activation ability and Bi12O17Cl2 with a favorable band position, which not only enabled the efficient separation of charges but also accelerated the formation of SO4−• radicals. The BM200 displayed prominent stability and recyclability. More importantly, the credible degradation pathway was proposed based on UHPLC-MS analysis and DFT calculation. This research revealed that the Fe-based MOFs/bismuth-rich bismuth oxyhalides (BixOyXz, X = Cl, Br and I) composites possessed great potential in wastewater remediation.
Developing efficient pharmaceuticals and personal care products (PPCPs) degradation technologies is of scientifical and practical importance to restrain their discharge into natural water environment. This study fabricated and applied a composite material of amorphous MnO2 nanoparticles in-situ anchored titanate nanotubes (AMnTi) to activate peroxymonosulfate (PMS) for efficient degradation and mineralization of carbamazepine (CBZ). The degradation pathway and toxicity evolution of CBZ during elimination were deeply evaluated through produced intermediates identification and theoretical calculations. AMnTi with a composition of (0.3MnO2)•(Na1.22H0.78Ti3O7) offered high activation efficiency of PMS, which exhibited 21- and 3-times degradation rate of CBZ compared with the pristine TNTs and MnO2, respectively. The high catalytic activity can be attributed to its unique structure, leading to a lattice shrinkage and small pores to confine the PMS molecule onto the interface. Therefore, efficient charge transfer and catalytic activation through MnOTi linkage occurred, and a MnTi cycle mediating catalytic PMS activation was found. Both hydroxyl and sulfate radicals played key roles in CBZ degradation. Theoretical calculations, i.e., density functional theory (DFT) and computational toxicity calculations, combined with intermediates identification revealed that CBZ degradation pathway was hydroxyl addition and NC cleavage. CBZ degradation in this system was also a toxicity-attenuation process.
Exploring the specific characteristics of pharmaceuticals and personal care products (PPCPs) via adsorption and degradation are scientific and practical significance to control their release to water matrix. In this work, a good adsorbent and ion-exchange material, i.e., titanate nanotubes (TNTs), was employed for adsorption of ciprofloxacin (CIP, a model PPCPs). The adsorption behaviors and mechanisms of CIP with different dissociated species by TNTs were studied through both experimental and theoretical calculations. The multilayered TNTs with high BET surface area (272.3 m2/g) and large pore volume (1.26 cm3/g) exhibited good adsorption property for CIP. The CIP species (i.e., CIP+, CIP±, CIP−) at various pH exhibited significantly different adsorption favorability. Adsorption kinetics and isotherms data revealed that TNTs offered the high uptake for CIP+ (Qmax = 464.47 μmol/g or 153.90 mg/g at pH 5) than CIP± and CIP−. Characterizations indicated the formation of Ti−O−N linkage between CIP molecules and TNTs after adsorption, suggesting the chemical interaction between CIP and TNTs. Density functional theory (DFT) calculations reveal variation on pH affects the protonation/deprotonation state of CIP, and then changes the distribution of molecular orbitals and the electrostatic potential (ESP) energy of CIP. ESP follows the trend as: CIP+ (180.57 kcal/mol) > CIP± (146.78 kcal/mol) > CIP− (12.30 kcal/mol), indicating the side of piperazine ring in CIP oriented to TNTs dominates the CIP adsorption. The integrated experimental and theoretical results, for the first time, suggest that ESP energy can serve as the indicator and predictor of adsorption ability for the PPCPs molecules with various speciation, and can help to deeply describe the adsorption mechanism of PPCPs. In addition, TNTs have great application for the removal of PPCPs through adsorption in practical wastewater treatment area.
Mixtures of U(VI) and chlorinated compounds have been detected at many radionuclides-contaminated sites. Yet, simultaneous removal of the two classes of contaminants is still challenging. Herein, we prepared a new type of composite material (TNTs/ACF) based on commercial TiO2 and activated carbon fiber (ACF) through a hydrothermal approach and tested it for simultaneous removal of U(VI) and 2-Chlorophenol (2-CP). The hydrothermal treatment converted TiO2 into titanate nanotubes (TNTs), a cation exchanger, which are not only supported by bulk ACF, but also modified by carbon nanoparticles. TNTs/ACF exhibited fast sorption kinetics and high adsorption capacities for both U(VI) (Langmuir Qmax = 188.0 mg/g) and 2-CP (Qmax = 122.1 mg/g). Moreover, higher adsorption was observed when both solutes are co-present than in the single-solute systems. An extended dual-mode model, which considers adsorption and other specific mechanisms well interpreted the adsorption isotherms. The optimal working pH for U(VI) ranged from 6.0 to 8.0, while the sorption of 2-CP remained high over a broader pH range. The presence of 1.0–10.0 mg/L humic acid as TOC increased the adsorption of both chemicals. The key adsorption mechanism for U(VI) is ion-exchange at the –O− functional sites in the interlayers of TNTs, while 2-CP was taken up via hydrophobic interactions with ACF and capillary condensation. The adsorption synergy of U(VI) and 2-CP in the binary systems resulted from the complexation between U(VI) ions and phenolic groups of 2-CP and the cation–π interactions. TNTs/ACF appears promising for simultaneous removal of radionuclides and chlorinated chemicals from contaminated water.