Nitrogen-doped carbon materials prepared using different organic precursors as catalysts of peroxymonosulfate to degrade sulfamethoxazole: First-time performance leading to the incorrect selection of the best catalyst.

Nitrogen-doped carbon materials are effective catalysts for peroxymonosulfate (PMS) activation to eliminate organic contaminants. In this research, the activity of nitrogen-doped carbon materials was significantly improved by optimizing the carbon source, and the reusability of the catalyst is used to select the best catalyst instead of depending on the performance in the first use, for avoiding the "short-life" catalyst with great initial activity. Fixing ferric nitrate nonahydrate and melamine as the metal and nitrogen sources, four catalysts were prepared using glucose, glucosamine hydrochloride, dopamine, and trimesic acid as the carbon sources, respectively. Based on the performance in PMS activation for sulfamethoxazole (SMX) removal, in the first use, the activity was Fe-DA-CN (carbon source: dopamine) > Fe-BTC-CN (carbon source: trimesic acid) > Fe-GLU-CN (carbon source: glucosamine) > Fe-DGLU-CN (carbon source: glucose). With no washing for the second time use, the activity was Fe-BTC-CN (0.135 min-1) â‰« Fe-DA-CN (0.037 min-1) > Fe-GLU-CN (0.032 min-1) > Fe-DGLU-CN (0.017 min-1). The large specific surface area, superior graphitization, and high CO/C-N group content endow Fe-BTC-CN with high ability in PMS activity. Surface-bound radicals are responsible for SMX elimination, and most of the SMX degradation intermediates have lower ecotoxicity than SMX.

Copper oxides activate peroxymonosulfate for degradation of methylene blue via radical and nonradical pathways: surface structure and mechanism.

A one-step hydrothermal method for preparation of copper oxides with different valences using ascorbic acid as a reducing reagent was developed for environmental remediation. The results suggested that the notable degradation performance of CuO0 may be attributable to the abundant active sites, such as Cu or Cu-O, and was not significantly related to the Cu valence state. In contrast to direct degradation of pollutants by traditional superoxide radicals (O2•-), O2•- played an important role in the reduction of high-valence Cu ions (Cu(III)). In addition, a series of radical quenching, electron paramagnetic resonance (EPR), and electrochemical experiments validated the existence of direct electron transfer between methylene blue (MB) and PMS mediated by CuO0 and surface-bound radicals. The results suggested that the CuO0/PMS system may be less susceptible to diverse ions and natural organic matter other than dihydrogen phosphate anions. The mechanism of MB degradation under alkaline conditions was different from that under acidic conditions in that it was not reliant on radicals or charge transfer but direct oxidation by PMS. This study provides new insights into the heterogeneous processes involved in PMS activation by the copper oxides. Furthermore, this paper devotes to providing theoretical basis on pollutant removal via PMS activated by copper oxides and developing low-cost and high-efficiency catalysts.

Electro-Induced Carbon Nanotube Discrete Electrodes for Sustainable Persulfate Activation.

In electrochemical advanced oxidation processes (EAOPs), the rate-limiting step is the mass transfer of pollutants to the electrodes due to the limited active surface areas. To this end, we established a three-dimensional (3D) EAOP system by coupling conventional graphite electrodes with dispersed carbon nanotubes (CNTs). The electrodes (particularly the anode) induced electric field spontaneously polarized CNTs into dispersed reactive particle electrodes (CNT-PEs) in the solution, which remarkably promoted electrochemical activation of peroxydisulfate (PDS) to generate surface CNT-PDS* complexes and surface-bound radicals (SBRs). Based on the excited potential (ECNT-PEs) at different positions in the 3D electric field, CNT-PEs were activated into three states. (i) ECNT-PEs < Eorganic, CNT-PEs are chemically inert toward DCP oxidation; (ii) Eorganic < ECNT-PEs < Ewater, CNT-PEs will oxidize DCP via an electron-transfer process (ETP); (iii) ECNT-PEs > Ewater, both CNT-PDS* complexes and the anode will oxidize water to produce SBRs. Thus, DCP could be oxidized by CNT-PDS* complexes via ETP to form polychlorophenols on the CNT surface, causing rapid deactivation of the micro-electrodes. In contrast, SBRs attack DCP directly into chloride ions and hydroxylated products, maintaining the surface cleanliness and activity of CNT-PEs for long-term operations.

Multifunctional capacity of CoMnFe-LDH/LDO activated peroxymonosulfate for p-arsanilic acid removal and inorganic arsenic immobilization: Performance and surface-bound radical mechanism.

Organoarsenic contaminants existing in water body threat human health and ecological environment due to insufficient bifunctional treatment technologies for organoarsenic degradation and inorganic arsenic immobilization. In order to safely and efficiently treat organoarsenic contaminants discharged into the aquatic environment, Co-Mn-Fe layered double hydroxide (CoMnFe-LDH) and Co-Mn-Fe layered double oxide (CoMnFe-LDO) were fabricated and employed as peroxymonosulfate (PMS) activator for organoarsenic degradation and inorganic arsenic immobilization, and p-arsanilic acid (p-ASA) was selected as target pollutant. Results demonstrated that the satisfactory removal of p-ASA (100.0%) in both CoMnFe-LDH/PMS and CoMnFe-LDO/PMS systems was obtained within 30 min, and substantial inorganic arsenic adsorption could be achieved (below 0.5 mg/L) in two systems with converting major inorganic arsenic species to arsenate. As XPS, ESR and quenching experiment revealed, the existence and generation of surface-bound radicals in two systems were identified. Based on density functional theory calculation and XPS analysis, the catalytic mechanism of CoMnFe-LDO/PMS system that PMS could be activated via direct electron transfer from adsorbed p-ASA was clarified, which differed from PMS activation via coupling with surface hydroxyl groups in CoMnFe-LDH/PMS system. Catalytic performance assessment under various critical operation parameters indicated that CoMnFe-LDH presented more stable ability of p-ASA removal in a wide pH range and complex aquatic environment. The recycle experiment demonstrated the excellent stability and reusability of CoMnFe-LDH(LDO). Besides, seven degradation products of p-ASA in CoMnFe-LDH/PMS system including phenolic compounds, azophenylarsonic acid, nitrobenzene and benzoquinne were identified by UV-Vis spectra and LC-TOF-MS analysis, and the corresponding degradation pathway was proposed. In summary, compared to CoMnFe-LDO/PMS, CoMnFe-LDH/PMS holds great promise for the development of an oxidation-adsorption process for efficient control of organoarsenic pollutant.

Thiourea-assisted one-step fabrication of a novel nitrogen and sulfur co-doped biochar from nanocellulose as metal-free catalyst for efficient activation of peroxymonosulfate.

The N, S co-doped biochar (N, S-BC) with multistage pore structure was successfully synthesized from nanocellulose and thiourea by one-step pyrolysis, which could effectively activate peroxymonosulfate (PMS) to degrade sulfamethoxazole (SMX) in water. Moreover, the removal efficiency of SMX by this oxidation system was 2.3-3.1 times than that of other systems activated by common metal oxides (such as Fe3O4、Fe2O3, and MnO2). More importantly, the mechanism of the N, S-BC/PMS process was deduced by reactive oxygen species (ROS) quenching experiment and electron paramagnetic resonance (EPR) test, which exhibited that surface-bound free radicals and singlet oxygen (1O2) played an essential role in the SMX degradation. Surprisingly, the sulfate radical (SO4•-) and hydroxyl radical (•OH) produced in this system existed in a bound state on the surface of the carbon catalyst to react with SMX, rather than dispersed in the aqueous solution. This particular form of free radicals could resist the influence of background substances and pH changes in water, and maintain excellent SMX degradation efficiency under different water matrices and pH. This study provides a new insight into the application of carbon catalyst in actual water pollution control.

Surface-bound radical control rapid organic contaminant degradation through peroxymonosulfate activation by reduced Fe-bearing smectite clays.

Heterogeneously activated peroxymonosulfate (PMS)-based advanced oxidation technologies (AOTs) have received increasing attention in contaminated water remediation. However, PMS activation by reduced clay minerals (e.g., reduced Fe-bearing smectite clays) has rarely been explored. Herein, PMS decomposition by reduced Fe-bearing smectite clays was investigated, and the hydroxyl radical (OH) and sulfate radical (SO4-) formation mechanisms were elucidated. Reduced nontronite NAu-2 (R-NAu-2) activated PMS efficiently to induce rapid degradation of diethyl phthalate (DEP) within 30 s. Mössbauer spectroscopy, FTIR and XPS analyses substantiated that distorted trans-coordinated Fe(II)Fe(II)Fe(II)OH entities were mainly responsible for rapid electron transfer to regenerate clay surface Fe(II) for PMS activation. Chemical probe, radical quenching, and electron paramagnetic resonance (EPR) results confirmed that OH and SO4- were mainly bound to the clay surface rather than in bulk solution, which resulted in the rapid degradation of organic compounds such as DEP, sulfamethoxazole, phenol, chlortetracycline and benzoic acid. Anions such as Cl- and NO3- had a limited effect on DEP degradation, while HCO3- inhibited the DEP degradation due to the increase of reaction pH. This study provides a new PMS activation strategy using reduced Fe-bearing smectite clays that will contribute to rapid degradation of organic contaminants using PMS-based AOTs.

Surface-bound sulfate radical-dominated degradation of 1,4-dioxane by alumina-supported palladium (Pd/Al2O3) catalyzed peroxymonosulfate.

Sulfate radicals have been demonstrated as an alternative to hydroxyl radicals in advanced oxidation processes. Unfortunately, the efficient activation of peroxymonosulfate (PMS), one of the most commonly used oxidants for the generation of sulfate radicals, still relies heavily on cobalt-bearing materials that are potential carcinogens. Although copper-iron bimetallic materials are promising activators, stoichiometric amounts of metals are required to achieve satisfactory performance. In this study, we propose a real catalytic process that is capable of degrading extremely recalcitrant 1,4-dioxane using a combination of alumina-supported metallic palladium (Pd/Al2O3) with PMS. The metal loading-normalized pseudo-first-order constant for 1,4-dioxane degradation with Pd/Al2O3 was more than 16,800 times that with copper-iron bimetallic materials. Complementary to Fenton reagents, Pd/Al2O3-PMS had a wide effective pH range from 4.0 to 8.5. In the absence of a substrate, PMS underwent more rapid decomposition under all conditions investigated, which suggests that its activation did not likely proceed via the previously proposed non-radical mechanism. On the basis of the strong inhibitory effects of common scavengers, we instead propose that surface-bound sulfate radicals were probably the dominant active species. A near-100% conversion rate of PMS to radicals was achieved with the Pd/Al2O3 catalyst.