Data for a new spinel catalyst to activate peroxymonosulfate for highly efficient degrading organic contaminants in water based on non-radical process

Abstract

The aim of this research is to degrade organic contaminants in aqueous solution via lead ferrite (PbFe₂O₄) as a catalyst to activate peroxymonosulfate (PMS). PbFe₂O₄ was synthesized by a citrate combustion method and analyzed by SEM, TEM and XRD. A simulated solution including thionine were used, with different conditions tested to optimize the degradation process, including comparing PbFe₂O₄ to other catalysts, PbO and Fe₂O₃, and tracking active oxygen species. The concentrations of thionine and PMS were tracked with a UV-Vis spectrophotometer in the treatment process. The data are presented as graphs and tables. A detailed analyses of this report can be found in the article “New insight into the mechanism of peroxymonosulfate activation by nanoscaled lead-based spinel for organic matters degradation: a singlet oxygen-dominated oxidation process” published in Journal of colloid and interface science.

Specifications Table

Subject	Environmental engineering
Specific subject area	Advanced oxidation process
Type of data	Table Figure
How data were acquired	Field emission scanning electron microscope (FESEM, Hitachi SU-8010, 5kV, Japan), field emission transmission electron microscope (FETEM, Hitachi HT-7700, 120kV, Japan), X-ray diffraction (XRD, Bruker D8 Advance, Germany), Electron paramagnetic resonance spectrometer (EPR, Bruker Biospin GmbH E500-9.5/12, Germany), Atomic Absorption Spectrophotometer (AAS, TAS-990, China), UV-Vis spectrophotometer (TU-1901, China), and high-performance liquid chromatography (HPLC, Shimadzu LC-20AT, Japan)
Data format	Raw and analyzed data
Parameters for data collection	The effect of initial thionine concentration, solution pH, catalysts and peroxymonosulfate dosages was evaluated during the experiments of organic degradation. Experiments were done in triplicates in separate reactors and room temperature (25±2°C) was maintained throughout the reactions.
Description of data collection	HPLC coupled with UV detector was used to track tetracyclines antibiotics concentrations throughout the degradation reaction, and the thionine concentration of different time intervals were detected by UV-Vis spectrophotometer.
Data source location	Anhui Normal University Wuhu China
Data accessibility	With the article
Related research article	Author's name Fu Liu, Wenwen Li, Dechang Wu, Tong Tian, Jian-Feng Wu, Zong-Mu Dong, Guang-Chao Zhao * * Corresponding author: E-mail: gczhao@mail.ahnu.edu.cn Title New insight into the mechanism of peroxymonosulfate activation by nanoscaled lead-based spinel for organic matters degradation: a singlet oxygen-dominated oxidation process Journal Journal of Colloid and Interface Science DOI/In Press https://doi.org/10.1016/j.jcis.2020.03.116

Value of the data

• •The data reveal that a new spinel material, PbFe₂O₄, can be used as catalyst to activate PMS generating active oxygen species for organic contaminants degradation in aqueous with a non-radical process.
• •Researchers involved in advanced oxidation processes (AOPs) and treatment of organic contaminants in water can benefit from the data.
• •The data can be used as a comparison for other researchers interested in developing new catalysts to activate peroxymonosulfate for organic contaminants degradation in aqueous. It also helps the researchers to understand the corresponding catalytic mechanism in degradation process.
• •The data can also be utilized to develop a real treatment system for organic (dye and pharmaceutical) effluents by improving and perfecting the various parameters design. Additionally, effect of chlorides (Cl⁻) and phosphates in real effluents can provide useful information in this process.

1. Data Description

Data presented in this paper described the microstructure and morphology of the synthesized catalysts and effectiveness of PbFe₂O₄/PMS system in thionine and tetracyclines antibiotics degradation.

The virgin and used catalysts were analyzed by SEM, TEM, and XRD, and depicted in Fig. 1, Fig. 2. The thionine removal by PbFe₂O₄, PMS, or PbFe₂O₄/PMS systems, and thionine removal efficiency in catalytic PMS by PbFe₂O_4, Fe₂O₃ and PbO are depicted in Fig. 3. The effect of pH on the removal efficiency of thionine in PbFe₂O₄/PMS system is presented in Fig. 4. The concentrations of lead and ferric ions leached from PbFe₂O₄/PMS system after every cycle use of PbFe₂O₄ are shown in Fig. 5. The observed rate constants (k), obtained for pseudo-first order fitting, for degradation of thionine with different catalyst dosages in PMS oxidation system are presented in Table 1, and the variation of k with the joining of coexisting anions are presented in Table 2. A simple review on the different reactive species responsible for removing contaminants by advanced oxidation processes based on persulfates catalytic oxidation are presented in Table 3.

Fig. 1.

XRD spectra of virgin PbFe₂O₄ prepared with different calcination temperature (400-600°C)

Fig. 2.

SEM (a), TEM (b) images of the used PbFe₂O₄.

Fig. 3.

(a) Thionine removal efficiency in different systems, (b) thionine removal efficiency in catalytic PMS by PbFe₂O_4, Fe₂O₃ and PbO. General conditions: [PMS]₀=400μM, Catalyst dosage=400mg•L⁻¹, [Thionine]₀=10μM, pH=9.0, T=25°C.

Fig. 4.

Thionine removal efficiency in using PbFe₂O₄/PMS system under different pH in 20min. Conditions: [Thionine]₀=10μM, [PMS]₀=400μM, Catalyst dosage=400mg•L⁻¹, T=25°C.

Fig. 5.

Concentrations of lead and ferric ions leached from PbFe₂O₄/PMS system after every cycle use of PbFe₂O₄.

Table 1.

Variation of the pseudo-first order rate constant of thionine degradation with catalyst dosages in PMS oxidation system.

Oxide dose (mg/L)	k of first order kinetics (min−1)	R2
① PbFe2O4	−	−
200	0.2002	0.967
400	0.2048	0.970
600	0.1477	0.981
800	0.1347	0.984
② Fe2O3	−	−
200	0.1172	0.983
400	0.1235	0.996
600	0.0716	0.992
800	0.0526	0.960
③ PbO	−	−
200	0.1027	0.989
400	0.1068	0.985
600	0.0332	0.913
800	0.0234	0.922

Table 2.

Variation of the pseudo-first order rate constant of thionine degradation with coexisting anions concentration in PbFe₂O₄/PMS system.

Coexisting anions (mM)	k of first order kinetics (min−1)	R2
① Cl−	−	−
0	0.2048	0.970
5	0.2133	0.955
20	0.2724	0.950
50	0.4231	0.987
100	0.5970	0.981
② NO3−	−	−
0	0.2048	0.970
20	0.1906	0.975
50	0.1991	0.972
③ HCO3−	−	−
0	0.2048	0.970
20	0.2108	0.965
50	0.2016	0.975
④ H2PO4−	−	−
0	0.2048	0.970
20	0.2176	0.977
50	0.2445	0.994

Table 3.

Contaminants removal by advanced oxidation processes based on different catalyst/persulfates catalytic oxidation system.

Advanced oxidation process	Target pollutant	Main reactive species	Reference
CuFe2O4/peroxymonosulfate	Arsenic(Ⅲ)	SO4•− and •OH	[1]
CuFe2O4/peroxymonosulfate	Norfloxacin	SO4•− and •OH	[2]
CuFe2O4/kaolinite/peroxymonosulfate	Bisphenol A	SO4•− and •OH	[3]
Benzoquinone/Peroxymonosulfate	sulfamethoxazole	1O2	[4]
CuO@CHFMs/Peroxymonosulfate	Bisphenol A	1O2	[5]
MWCNTS/peroxymonosulfate	Methylene blue and phenol	charge transfer	[6]
α-MnO2/Peroxymonosulfate	ciprofloxacin	SO4•−, •OH and 1O2	[7]
Graphitized nanodiamonds/persulfates	Various organic compounds	charge transfer	[8]
Cu/CuFe2O4//persulfate	Tetracycline	SO4•− and •OH	[9]
Fe3O4/sepiolite/persulfate	Atrazine	SO4•− and SO5•−	[10]
CuO/peroxydisulfate	2,4-dichlorophenol	charge transfer	[11]
PbFe2O4/peroxymonosulfate	Thionine and tetracyclines	1O2	This work

EPR spectra, used with DMPO and TMP as a spin trap agent, are shown in Fig. 6. Moreover, the Fig. 7 presents the degradation of tetracyclines antibiotics by PbFe₂O₄/PMS system in different water samples. The raw data of all degradation experiments are shared as supplementary material.

Fig. 6.

EPR spectra of TMP−¹O₂ and DMPO-SO₄^•−/^•OH/O₂^•−.

Conditions: [PMS]₀=1mM, [PbFe₂O₄]=400mg•L⁻¹, pH=9.0, T=25°C, 3min, [TMP]₀=25mM, [DMPO]₀=25mM.

Fig. 7.

Remvoal efficiency of Tetracycline (a) and Metacycline (b) by PbFe₂O₄/PMS system in different water samples. General conditions: [Tetracyclines]₀=5mg•L⁻¹, [PMS]₀=400μM, Catalyst dosage=400mg•L⁻¹, pH=9.0, T=25°C.

2. Experimental Design, Materials, and Methods

2.1. Experimental materials

The PbFe₂O₄ catalyst was synthesized by a citrate combustion method according to the modified previous reports [12]. Briefly, the stoichiometric ratio 1:2 of Pb(NO₃)₂ (0.01M) and Fe(NO₃)₂ (0.02M) were dissolved in 100 mL of ultrapure water under magnetic stirring to form a mixed solution. After that, the specific amount of C₆H₈O₇•H₂O (0.03M) was added to above solution with continuous stirring for 2h. The pH of solution was adjusted to 5 with concentrated NH₃•H₂O. The obtained homogeneous solution was constant stirred at 90°C until the formation of sticky gel, and then calcined at 600°C for 2h. Finally, the resulted brown products were ground, washed three times with ultrapure water and dried at 80°C for 24h.

Pure PbO and Fe₂O₃ catalysts were used as a comparison in this work and were prepared according to the aforementioned methods used for PbFe₂O₄, but without Pb(NO₃)₂ and Fe(NO₃)₂, respectively.

2.2. Experimental procedure

A common stock solution of each reactant was prepared and aliquots of the stock solutions were combined to achieve the initial experimental conditions. Batch experiments were carried out in 100mL brown glass vials. Specific amounts of PbFe₂O₄ were initially dispersed into 80mL organic contaminants solution (thionine or tetracyclines antibiotics). After mixing for 1min, a certain dosage of PMS solution was added to start the reaction. The suspension was stirring at room temperature (25 ± 2°C) with the rate 120 rpm under exposure to air and samples were withdrawn through 0.45μm filters at different time intervals.

To accurately analyze the concentration of organic compounds, excess sodium nitrite was immediately introduced into the filtrate to quench residual PMS. The residual concentration of thionine in the solution was measured by a UV–vis spectrophotometer (TU-1901, China) at maximum absorbance wavelength of 602 nm, and the tetracyclines antibiotics concentration were determined using a high-performance liquid chromatography (HPLC, Shimadzu LC-20AT, Japan) equipped with Agilent ZORBAX extend 80A C-18 column (4.6 mm × 250 mm with i.d. 5 μm) and a UV detector at a wavelength of 272 nm. The degradation of tetracyclines antibiotics in practical water samples were conducted. Water samples were prepared through adding tetracyclines antibiotics to tap water, river water and self-made water in lab (containing HCO₃⁻:10 mM; H₂PO₄⁻:10 mM; SO₄²⁻:10 mM and NO₃⁻:10 mM) to form a simulated waste water sample for degradation experiments. After finished the thionine degradation experiment, the dissolved metal ions in solution was determined by Atomic Absorption Spectrophotometer (AAS, TAS-990, China).

All of the degradation experiments were performed in triplicate, with error bars in figures representing one standard deviation. Thionine degradation data in PbFe₂O₄/PMS, PbO/PMS, and Fe₂O₃/PMS system were fitted by pseudo-first order kinetics (Eq. (1), R²>0.97).

$$1\mathrm{n}({\mathrm{C}}_{\mathrm{t}}/{\mathrm{C}}_0)=-k\mathrm{t}$$ (1)

where C₀ and C_t represent the initial thionine concentration and the concentration at time t (min) respectively, k (min⁻¹) is the first order reaction rate constant.