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Fenton Like Catalysis and Oxidation/Adsorption Performances of Acetaminophen and Arsenic Pollutants in Water on a Multi-metal Cu-Zn-Fe-LDH Hongtao Lu, Zhiliang Zhu, Hua Zhang, Jianyao Zhu, Yanling Qiu, LinYan Zhu, and Stephan Küppers ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b08933 • Publication Date (Web): 02 Sep 2016 Downloaded from http://pubs.acs.org on September 6, 2016

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ACS Applied Materials & Interfaces

Fenton Like Catalysis and Oxidation/Adsorption Performances of Acetaminophen and Arsenic Pollutants in Water on a Multi-metal Cu-Zn-Fe-LDH

Hongtao Lua, Zhiliang Zhua,*, Hua Zhanga, Jianyao Zhua, Yanling Qiub , Linyan Zhuc, Stephan Küppersc a

State Key Laboratory of Pollution Control and Resource Reuse, Tongji University,

Shanghai 200092, China； b

Key Laboratory of Yangtze River Water Environment, Ministry of Education, Tongji

University, Shanghai 200092, China； c

Research Center Jülich, ZEA-3, Jülich 52425, Germany

Correspondence information: Zhiliang Zhu, Professor State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, 1239 Siping Road, Shanghai, 200092, China. E-mail: [email protected] Phone: +86-21-6598 2426, Fax: +86-21-6598 4626

ACS Paragon Plus Environment

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Abstract The acetaminophen can increase the risk of arsenic-mediated hepatic oxidative damage, therefore, the decontamination of water polluted with the coexistent acetaminophen and arsenic brings new challenge for purification of drinking water. In this work, a three metal layered double hydroxide Cu-Zn-Fe-LDH was synthesized and applied as a heterogeneous Fenton-like oxidation catalyst and adsorbent to simultaneously remove acetaminophen (Paracetamol, PR) and arsenic. The results showed that the degradation of acetaminophen was accelerated with decrease of pH or increase of H2O2 concentrations. Under the condition of 0.5 g•L-1 catalyst dosage

and 30 mmol•L−1 H2O2 concentration, the

acetaminophen in a water sample was totally degraded within 24h by a Fenton like reaction. The synthesized Cu-Zn-Fe-LDH also exhibited a high efficiency for arsenate removal from aqueous solutions, the calculated maximum adsorption capacity was 126.13 mg•g-1. In the presence of hydrogen peroxide, the more toxic arsenite can be gradually oxidized into arsenate and adsorbed at the same time by Cu-Zn-Fe-LDH. For the simulated water samples with coexistent arsenic and acetaminophen pollutants, after the treatment with Cu-Zn-Fe-LDH and H2O2, the residual arsenic concentration in water was below 10 µg•L-1 and the acetaminophen not detected in the solution. It indicated that the obtained CuZn-Fe-LDH is an efficient material for the decontamination of combined pollution with acetaminophen and arsenic.

Keywords: layered double hydroxides; heterogeneous catalysis; acetaminophen; arsenic; adsorption


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1. Introduction The coexistance of pharmaceuticals and arsenic and possible effect on human being’s health in water environment have attracted more attentions in recent years, coexistent arsenic and pharmaceuticals are found in different natural water bodies sucn as Taihu Lake, Dainchi Lake in China and the Columbia River at Warrendale in Uited States1-4. It brings a new challenge to the purification of polluted water. Pharmaceutical contamination in water environment has been a public concern5. A lot of studies and evaluations show that chemicals with pharmaceutical activities are widely found in natural surface water and groundwater systems as drinking water sources6-8. Acetaminophen (Paracetamol), as a common antipyretic and analgesic medicine, has been used all over the world 9. Usually, it can’t be totally metabolized and is excreted through urine and stool, then enter into wastewater system. It may also be discharged during manufacture or discarded from unused and expired medicines. After the conventional biological treatment process for water, it cann’t be completely removed and a certain amount of acetaminophen will still remain in the water as a pollutant 10. Acetaminophen is well known as one of pharmaceutical active compounds (PACs) 11, its continuous release poses potential danger to animals and people even in very low concentrations12, and its existence is likely to cause aquatic toxicity, genotoxicity and endocrine disruption13. Advanced oxidation processes (AOPs), such as photo catalysis, ozonation and Fenton oxidation, are important technologies for the degradation of refractory contaminants in water and wastewater oxidation

9, 17-18

14-16

. Various advanced oxidation processes such as photo catalysis

, electrochemical

19

and Fenton process

20

have been employed to remove

acetaminophen in polluted water. The advantage of a suitable heterogeneous catalyst is


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that it can be easily separated from the stream and doesn’t cause disposal problems21. Amongst these, the heterogeneous Fenton method is an attractive technique to remove various organic substances in aqueous solutions22. Arsenic (As) is both toxic and carcinogenic. Arsenic pollution and its control has got great concern in the world. Ingestion of arsenic can lead to seriously detrimental influences on human health including cancers, neurological disorders and muscular weakness 23. The World Health Organization has set a limit of 10 µg·L-1 for arsenic in drinking water 24. In a natural water environment, inorganic arsenic usually occurs in states of As(III) and As(V) 25-27

. As(V) species predominate in oxygen enriched environments, but As(III) is more

stable in groundwater systems because of anoxic and near neutral pH conditions

28

.

Arsenite species was found higher toxicity than arsenate 29. A lot of possible technologies have been investigated, for instance, sedimentation and coagulation phytoremediation

33

30-31

, filtration

32

,

and adsorption34-36 . In many available methods, adsorption is

considered as an promising and practical approache. Usually, As(V) species are easier to be adsorbed on the surfaces of adsorbent materials than As(III). Several researches have followed with interest on the adsorption after oxidation in order to remove As(III) substances

37

. Several methods have been reported such as O2/O3 38, manganese oxides

39

,

iron oxides 40 and H2O2 41-42, photochemical and photocatalytic oxidation 43-44. In recent years, the study on the toxicology of arsenic and acetaminophen has attracted scientists’ attention

45-48

. Several investigations indicated that the acetaminophen can

increase the risk of arsenic-mediated hepatic oxidative damage

49-50

, it brings a new

challenge to the purification of drinking water. However, to the best of our knowledge, the simultaneous decontamination of water with the coexistent arsenic and acetaminophen has


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not been reported. Considering the characteristics of the arsenic and acetaminophen, the most likely way is to use a catalytic/adsorption method to simultaneously remove the organic pollutant and arsenic. Layered double hydroxides (LDHs) materials are useful multi-functional anionic clays with general form represented by [MII1-xMIIIx(OH)2]x+(An)x/n·mH2O. Here, MII, MIII are ions of divalent and trivalent metals, respectively. The intercalated anion is expressed with An-. The number of interlayer water is denoted as m and the ratio of MIII/(MII + MIII) is represented by x 51. In recent years, more researches on the synthesis and application of different functional LDHs and related composite materials have been reported 52-53. The main purpose of this study is to find an efficient way to decontaminate the combined water pollution of acetaminophen and arsenic. In this work, a multi-metal Cu-ZnFe-LDH material with the layer composition including three transition metal ions and intercalation of sulfate has been developed, and used to study the catalytic oxidation and adsorption performances for single and mixed pollutants of acetaminophen and arsenic in water. Based on the preliminary experimental result of catalysis efficiency with the synthesized Cu-Zn-Fe-LDH, further studies for heterogeneous Fenton process of acetaminophen in aqueous solution, identification of the major degradation intermediates, and

possible

catalysis

mechanism

were

investigated.

Then,

the

catalytic

oxidation/adsorption of arsenite were studied. Finally, the Cu-Zn-Fe-LDH material was successfully applied to deal with the simulated water samples containing coexistent acetaminophen and arsenite pollutants, and it was found that the result can meet the requirement of drinking water for arsenic and the acetaminophen was not detected.


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2 Materials and methods 2.1 Chemicals Acetaminophen (Paracetamol, PR) was bought from Sinopharm Chemical Regent Co with >98% purity and used for test samples. Acetaminophen standard substance (purity >99.5%) was bought from Sigma Aldrich solution

of

the

compound.

Acetaminophen-D4

and used for preparing a standard standard

solution,

arsenic

salt

Na2HAsO4·7H2O and NaAsO2 (purity >98%) were purchased from Sigma Aldrich. The stock solution with 1000 mg·L-1 As(V) was prepared with the pure water from Milli-Q device (18.2 MΩ·cm at 25°C). All experimental solutions were made from the stock solution with the dilution of de-ionized water. The experimental solutions of As(III) were freshly made. Other chemicals were all analytical grade with no more purification before use. 2.2 Synthesis of Cu-Zn-Fe-LDH material The Cu-Zn-Fe-LDH material with intercalation of sulfate ions was synthesized using coprecipitation method in aqueous solutions. At first, 1 mol·L-1 NaOH and 100 ml mixed solution containing Cu(SO4)2·5H2O (2.49 g), Fe(SO4)2·7H2O (8.34 g) and Zn(SO4)2·7H2O (17.25 g) were slowly dropped into a glass reactor which contained 100 ml de-ionized water. The pH value of above mixed solution was controlled at about 7 by addition of dilute sulfuric acid or sodium hydroxide solutions. After reaction, the suspensions were aged at 313K for 24h. The suspensions were filtered and the solid part was washed with de-ionized water. Then, the obtained material was dried at 313K to get the final product Cu-Zn-FeLDH which was used in the following experiments. 2.3 Characterization of Cu-Zn-Fe-LDH material


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The synthesized Cu-Zn-Fe-LDH material was dissolved in hydrogen nitrate to prepare the chemical analysis solution. The analysis method and instruments for characterization of the materials were same as described in details in our previous publications 54-55, which include ICP-OES (Agilent 720, USA), XRD (Bruker D-8 Advance), FTIR (Nicolet, USA), SEM with EDS (Hitachi S-4800, Japan), TEM (JEM2011, Japan), XPS (PHI, USA) and so on. 2.4 Determination of acetaminophen and arsenic concentrations The acetaminophen concentrations in solution were measured using Ultra Performance Liquid Chromatography (UPLC) with a UV–vis photo diode array detector, and equipped with ACQUITY UPC² BEH (C18), 100 × 3.0 mm, 1.7µm particle size column. The acetonitrile and water were used as the mobile phases, the ratio of acetonitrile: water was 10:90. The flow rate was 0.35 mL·min−1. Sample injection volume and retention time were 5.00 µL and 0.7 min, respectively. The degradation intermediates were determined using high performance chromatography-time of flight mass spectrography (HPLC-TOFMS), using a Waters ACQUITY UPLC I-Class equipped with ACQUITY UPLC BEH (C18), 100 × 3.0 mm, 1.7µm particle size column. Mobile phases were acetonitrile and water with 0.1% formic acid. The concentrations of arsenic were determined by the instruments of ICP-MS and atomic fluorescence spectrometry. 2.5 Catalytic activity tests 2.5.1 Degradation of acetaminophen by Cu-Zn-Fe-LDH with H2O2 The catalytic oxidation experiments of acetaminophen degradation were conducted in Erlenmeyer flask (250 mL). The catalyst material of Cu-Zn-Fe-LDH was added into 100 mL acetaminophen aqueous solution (pH 7.0), unless otherwise specified. The pH value of the solution was not adjusted during the experiments. The initial acetaminophen


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concentration was taken as C0. By adding the solution of H2O2 under a dark condition, the reaction of degradation was initiated, and the flask was shaken in a thermostatic shaker at 150 rpm, 25℃. The required samples were taken out and filtered with the 0.22 µm membranes to remove the solid material during the reaction at a set time intervals. The residual acetaminophen concentration in the supernatant was then determined by UPLC. The blank test without the addition of H2O2 was carried out at the same time. 2.5.2 Adsorption and oxidation of arsenic Adsorption experiments were conducted with the batch equilibrium sorption method at 298 K. The experiments were triplicate and the average results were adopted. The effect of original solution pH, sorption isotherm and kinetics on arsenic adsorption were studied. When the Cu-Zn-Fe-LDH material had been added into the system, the flask was shaken at 150 rpm in a thermostatic shaker for a set time. Then, the solution was filtered with a 0.22 µm membrane and analyzed. The kinetics of As(III) oxidation and adsorption process were investigated at 298K, pH=7.0. The initial concentrations of hydrogen peroxide and arsenite were 0.4 mmol·L-1and 1 mg·L-1, respectively. The added amount of Cu-Zn-Fe-LDH material was set in the range of 0.1 g·L-1 to 0.4 g·L-1. 3 Results and discussions 3.1 Characterization 3.1.1 Chemical composition of Cu-Zn-Fe-LDH From the chemical analysis result, the metal ratio of the synthesized Cu-Zn-Fe-LDH was determined. It is shown in Table1. According to the general structure and composition of LDHs, the chemical formula of [Cu0.13Zn0.51Fe0.36(OH)2](SO4)0.18·mH2O was assumed. It


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shows that the metal molar ratio in the synthesized material was similar to the proportion of the starting reactants. Table 1 Chemical composition of the Cu-Zn-Fe-LDH

Chemical Analysis Result a

M(Cu/Zn/Fe)a

m (Cu)b/%

1::4.09:2.89

5.68

m (Zn)/%

m (Fe)/%

23.95

14.43

Molar ratio of Cu/Zn/Fe, bMass content of Cu in material

3.1.2 XRD analysis The XRD result of the Cu-Zn–Fe-LDH material is shown in Fig. 1a. The reflection of LDH material’s characteristic peaks of was high intensity. It was found that the material was in a state of high-crystalline. The peaks of (001), (002), (003), (110) and (113) have been observed obviously, and no peaks of other crystalline phases found. The FULLPROF program was used to analyze the structure

56

. Based on the diffraction data, the sample of

Cu-Zn–Fe-LDH was indexed as hexagonal lattice, the parameters of unit cell (a) and (c) were 0.5410 nm and 1.0914 nm, respectively. The spacing of basal lamina (d(001)) was 1.0914 nm. It was similar with the SO42- intercalated LDHs of previous report 51.

Fig. 1 a.XRD pattern of Cu-Zn-Fe-LDH, b. FTIR spectrum of Cu-Zn-Fe-LDH


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3.1.3 FTIR spectroscopy analysis Fig. 1b was the FTIR spectrum of the materials. The broad and strong absorbance peak around position 3412 cm-1 was related to the hydroxide layers and interlayer waters’ hydrogen-bond stretching vibration. The absorbance peak at 1624 cm-1 was vibration of adsorbed water 57. The peaks which appear in the range of 450-650 cm-1 may attributed the bonds of metal hydrogen or metal oxygen 58. The Zn–O lattice vibrations presented at 513 cm-1 59. The peak around 1113 cm-1 attributed to sulfate that had been consistent with the similar XRD analysis 60-61. 3.1.4 Specific surface and zero potential analysis The result of N2 adsorption–desorption isotherm for the synthesized materials is shown in Fig.S1. The isotherm data was in accordance with the IV type of adsorption isotherms of IUPAC classification. The isotherm exhibited an H3 type hysteresis loop which was relevant to the type of wedge shaped pores. It may be generated with plate-like particles packed. The results indicated the material had a layer structure, which were consistent with the other report

62

. The specific surface area was 29.7 m2·g-1 (calculated with Multi-Point

BET method, C=472.51). The pore size distribution based on adsorption data was worked out by BJH method. The total pore volume was 0.439 cc·g-1 and the average pore diameter was 33.4 nm. It showed that the material belonged to the category of mesoporous material. The pHzpc of the Cu-Zn-Fe-LDH material was 9.6, which was determined by the zeta potential of its dispersions under the pH range of 4 to10 (Fig. S2). 3.1.5 Surface morphology analysis The micrograph of TEM is shown in Fig.2a. The synthesized Cu-Zn-Fe-LDH was general hexagonal and schistose. That result was consistent with the XRD index. The Cu-


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Zn-Fe-LDH SEM images were presented in Fig.2b. It can be found that the material aggregated in lamellar structure. Irregular accumulation of sheet laminate produced pores which were in accordance with pore size analysis. The electron diffraction (SAED) pattern of the selected area was shown in Fig.2c, where the crystal plane indices were consistent with the XRD pattern of (110), (300) and (302). (d(110)=0.2705 nm, d(300)= 0.1545 nm, d(302)=0.1500 nm) . Fig 2d was the image of HRTEM (High Resolution Transmission Electron Microscopy) for the Cu-Zn-Fe-LDH. It can be seen that the spacing of interplanar was about 0.254 nm, which is in agreement with the crystal structure data of lattice plane (113) determined from the XRD pattern. It also supported that the Cu-Zn-Fe-LDH material existed in a layered structure. The Energy Dispersive Spectroscopy of Cu-Zn-Fe-LDH was shown in Fig.3, The presence of sulfur peaks further proved that the results of XRD and FTIR analysis.


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Fig.2 a. TEM image of Cu-Zn-Fe-LDH, b. SEM images of Cu-Zn-Fe-LDH, c. Selected area electron diffraction (SAED) pattern of Cu-Zn-Fe-LDH d. High Resolution Transmission Electron Microscopy (HRTEM) image of the Cu-Zn-Fe-LDH


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Fig.3 EDS spectrum of Cu-Zn-Fe-LDH

3.2 Heterogeneous Fenton degradation test 3.2.1 Effect of hydrogen peroxide dosage on acetaminophen degradation The aqueous solution of 0.1 mmol·L-1 acetaminophen was prepared, then the required amount of Cu-Zn-Fe-LDH (0.5 g·L-1) added. The H2O2 dosage range was from 0.5 mmol·L-1 to 50 mmol·L-1. Under the condition without adding the Cu-Zn-Fe-LDH catalyst material, with the increment of H2O2 concentrations, the acetaminophen’s degradation rate was nearly unchanged, there was almost no degradation occurred as shown in Fig.4a, 4b. In the presence of Cu-Zn-Fe-LDH, acetaminophen degradation rate increased gradually with the increasement of H2O2 concentrations. When the catalyst dosage was 0.5 g·L-1 with initial H2O2 of 30 mmol•L−1 (mM), after 10 hours, the degradation rate of acetaminophen


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reached 99%. Iron and copper ions were not detected in the solution after degradation reaction. The results showed that Cu-Zn-Fe-LDH could be used as an effective catalyst for the heterogeneous oxidation of acetaminophen.

Fig. 4 a, b The effect of hydrogen peroxide dosage on acetaminophen (PR) degradation ([PR]0 = 0.1 mmol·L−1; [Cu-Zn-Fe-LDH] =0.5 g·L−1 ; T=25℃) c. The effect of catalyst dosage on acetaminophen (PR) degradation ([PR]0 = 0.1 mmol·L−1; [H2O2] =30 mmol·L−1 or 50 mmol·L−1 ; T=25℃) d. The effect of pH on acetaminophen (PR) degradation ([PR]0 = 0.1 mmol·L−1; [H2O2]=20 mmol·L−1 ; [Cu-Zn-FeLDH]=0.5g·L−1 ; T=25℃)


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3.2.2 Effect of catalyst dosage on acetaminophen degradation The effect of catalyst dosage on acetaminophen degradation was shown on Fig.4c The initial concentration of acetaminophen in aqueous solution was 0.1 mmol·L-1. The dosages of the catalyst were set as 0.25 g·L-1, 0.5 g·L-1 and 1.0 g·L-1, respectively. The initial H2O2 concentrations of 30 and 50 mmol·L-1 were set. With the same hydrogen peroxide concentration, it was found that the degradation rate of acetaminophen was enhanced obviously with the increase of the catalyst dosage. 3.2.3 Effect of pH on acetaminophen degradation The solution pH effect on acetaminophen degradation was studied under different initial pH values in range of 6.0 to 9.0. The result was shown in Fig. 4d. It showed that under the weak acid condition, the degradation efficiency of acetaminophen was higher. It is related to the relationship between the REDOX potential of H2O2 and the hydrogen ions concentration. The higher concentration of hydrogen ions will increase the REDOX potential of H2O2. 3.3 Adsorption and heterogeneous oxidation of arsenic 3.3.1 Effect of solution pH The initial solution pH effect on As(V) adsorption by Cu-Zn-Fe-LDH was studied. The pH values range is from 3.0 to 10.0. As shown in Fig. S3, high removal efficiencies of As(V) were observed at pH range of 3~8. Nevertheless, it declined when the initial solution pH value was above 8. The cause may be explained with the different existent forms of As(V) species in a aqueous solution under various pH values. The H2AsO4- was major species at the pH ranges from 2.1 to 6.7. However, when the pH value of the aqueous solution is higher than 6.7, the divalent negative ion form (HAsO42-) will be the dominant 26.


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Because the pHzpc of the Cu-Zn-Fe-LDH was 9.6, the surface will be negatively charged under the condition of pH > 9.6. The electrical rejection may be stronger than a low pH condition between the negatively charged sites of the surface and the species of HAsO42-. 3.3.2 Adsorption kinetics Two kinetics models (pseudo-first-order and pseudo-second-order) were used to fit the batch experiments data. These two models can be expressed by the following two equations. ln(Qe − Qt ) = ln Qe − K 1t

(1)

t 1 t = + 2 Qt K 2 Qe Qe

(2)

As shown in Fig.S4, the adsorption was fast in the initial 8h, and then slowed down and finally reached equilibrium after 24 h. The kinetics parameters of fitting curves are presented in Table.S1. It showed that the experiment data can be excellently described by the pseudo-second-order for the value of correlation coefficient close to 1. 3.3.3 Adsorption isotherms Langmuir, Freundlich and Sips isotherms models were applied to the analysis of adsorption data of arsenite and arsenate on the Cu-Zn-Fe-LDH material, respectively. These models can be expressed by the following equations. Langmuir:

Qe =

Qm K L C e 1 + K LCe

(3)

Freundlich: 1

(4)

Qe = K F C e n


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Sips:

Qe =

K s Qm C e

m

1 + K s Ce

m

(5)

. Fig.S5 shows the adsorption isotherms of arsenate and arsenite on the Cu-Zn-Fe-LDH materials and the constants were determined by non-linear regression.

The obtained

parameters and constants of the isotherm models are summarized in Table S2. Based on the R2 (correlation coefficient) values, it showed that the adsorption data of As(V) are better conform to the Sips isotherm equation than others. The maximum adsorption capacity for arsenate was 126.13 mg·g-1. The adsorption data of As(III) can be described well by the Langmuir isotherm equation. The maximum adsorption capacity for arsenite was 51.56 mg·g-1. It indicated that this synthesized Cu-Zn-Fe-LDH is an efficient material for arsenic decontamination by adsorption from aqueous solutions. 3.3.4 Heterogeneous oxidation of As(III) The kinetics of arsenite oxidation and adsorption were

shown in Fig.5. The

concentrations of As(III) in solution gradually decreased with time, but the concentration of As(V) species increased in the first 1 hour, then decreased and kept stable at a very low concentration level. This indicated that the arsenite was gradually oxidized into arsenate and adsorbed at the same time onto the Cu-Zn-Fe-LDH. When the material dosage is 0.4 g·L-1, after 8 hours, the residual arsenic in the solution was below 10 µg·L-1, which can meet the demand of drinking water for arsenic by WHO.


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Fig. 5 The kinetics of As(III) oxidation and adsorption. T=298K, pH=7.0. [H2O2]= 0.4 mmol·L-1. The concentration of As(III) was 1 mg·L-1 and the dosages of catalyst Cu-ZnFe-LDH were set in a range from 0.1 g·L-1 to 0.4 g·L-1. a) As (III) concentration change with time in solution. b) As (V) concentration change with time in solution.

3.4 Simultaneous removal of acetaminophen and arsenic The batch experiments for the removal of coexistent arsenic and acetaminophen in simulated water samples have been carried out in the aqueous solution of pH 7.0 which contained As(III) (5 mg·L-1) and acetaminophen (15 mg·L-1). The Cu-Zn-Fe-LDH material dosage was 0.5 g·L-1, and the hydrogen peroxide concentration was 50 mmol·L-1. The result showed that, after 24 hours, the remaining concentration of arsenic was below 10 µg·L-1, and the acetaminophen was not detected in the solution by UPLC. The AFS fluorescence spectra for As after treatment of the coexist arsenic and acetaminophen was shown in Fig.S6. Besides, Fig. S7 is the time-varied chromatogram for acetaminophen when treating the coexist arsenic and acetaminophen. 3.5 Cyclic utilization and stability of Cu-Zn-Fe-LDH


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The materials of Cu-Zn-Fe-LDH before and after adsorption of arsenic were used to study cycling utilization and stability as a Fenton catalyst for six round, respectively. The initial concentration of acetaminophen was 15 mg·L-1. The concentration of hydrogen peroxide was 50 mmol·L-1 and catalyst dosage was 0.5 g·L-1. The reaction time of each cycle was 24 hours. The concentration of acetaminophen, arsenic, copper and iron in the solution were detected after each cycle of the reaction. There is no release of arsenic found in the solution during each cycle. After each cycle, no copper or iron species were found leaching into the solution. As shown in Fig.S8, the degradation efficiency of acetaminophen keeps almost unchangeable in six cycles. It indicated that the Cu-Zn-FeLDH material as a heterogeneous Fenton catalyst can be reused. Arsenic adsorbed on the material had no effect on the catalytic degradation of acetaminophen, and the process of the degradation did not cause the release of arsenic. 3.6 Mechanism of catalytic oxidation and adsorption As stated in section 3.2, the Cu-Zn-Fe-LDH showed good activity for catalytic oxidation of acetaminophen by H2O2. This is a Fenton like reaction, where the LDH materials act as the source of Fe2+ ions. Since the Zn-Fe-LDH material without copper composition had shown little catalytic activity for degradation of acetaminophen in our experiment. It can be inferred that Cu2+ might activate and enhance the catalytic activity of the material

63-64

. Generally, hydrogen peroxide is believed to have an inclined chain

structure. According to the bond energies, it can be speculated that the bond O-O was more likely broken. The layered structure of Cu-Zn-Fe-LDH was shown in Fig S9. The surface of Cu-Zn-Fe-LDH may experience a cyclic process of iron or copper, and the active species


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like ·OH that play the role of oxidation is produced in that process. The H2O2 molecules might form Cu(II)-OOH with Cu2+ and transfer electrons to produce Cu(I)-OH and •OH51, 65-66

.

In order to understand the mechanism more clearly, the surface states of the Cu-Zn-FeLDH material before and after the reactions were determined by XPS analysis method. The XPS full-range spectra are shown in Fig. S10. Further details about XPS spectra of S2p3, As3d, O1s, Cu2p and Fe2p before and after oxidation/adsorption are shown in Fig.6a, Fig.6b, Fig.S11 and Fig.S12, respectively. As shown in Fig.6a, ions exchanged between arsenate and sulfate species lead to the shift of binding energy of S2p to a less negative level after oxidation and sorption of arsenite. As shown in Fig.6b, the binding energy peaks of As3d after oxidation/adsorption of As(III) are 47.6 eV and 46.4 eV, respectively. It is attributed to the bonding of As(V)–O, reveling that the arsenic species existed on the surface of material were As(V) only after oxidation/adsorption of As(III) in a single or coexistence system. The Fig. S11 is O1s spectra of the material. The binding energy of O 1s moved to a less positive level after oxidation/adsorption, and the similar oxygen state of the Cu-Zn-Fe-LDH material surface was found after oxidation/adsorption of arsenite and catalytic degradation of acetaminophen, respectively. After the As(III) oxidation/adsorption and acetaminophen degradation, the spectra of Cu2p and Fe2p for the Cu-Zn-Fe-LDH also exhibited little change, which are shown in Fig. S12. The change of Cu2p in binding energy after catalytic oxidation of acetaminophen is more obvious, which indicated that the activity of copper ions are related. For Fe2p, the shift from 716.2 to 715.8 eV related with catalytic oxidation of acetaminophen occurred mainly at about 716 eV.


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Fig.6 a. XPS spectra of S2p3 of Cu-Zn-Fe-LDH before and after oxidation/adsorption b. XPS spectra of As3d of Cu-Zn-Fe-LDH after oxidation/adsorption arsenite, coexistent acetaminophen (PR) and arsenite

The degradation intermediates of acetaminophen were also identified in our experiment, which are shown in Table 2.


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Table 2 Identified intermediates during degradation of acetaminophen Structures

Intermediates

m/z(M+H)

Acetamide

60.044

Oxalic acid

91.003

N-(1-hydroxyethyl)acetamide

104.071

3-Acetamidohexa-2,4-dienedioic acid

200.090

N-(3,4-dihydroxyphenyl)acetamide

168.066

According to the determined intermediates, the degradation reaction mechanism was speculated. At the beginning of the reaction, HPLC-TOFMS analysis showed the presence of N-(3,4-dihydroxyphenyl) acetamide and acetamide. It indicated that the attack of OH radicals to the aromatic ring proceeds through addition mechanism67.


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The possible schematic diagram of degradation reaction process of acetaminophen is shown in Fig.7.

Fig.7 The schematic diagram of degradation reaction process of acetaminophen

Based on above results, the possible removal mechanism of acetaminophen and arsenite with the Cu-Zn-Fe-LDH material could be described as Fig.8.


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Fig.8 Diagrammatic sketch of simultaneous removal mechanism of acetaminophen and arsenite by Cu-Zn-Fe-LDH

4. Conclusions A multi-metal Cu-Zn-Fe-LDH material was synthesized and used as a heterogeneous Fenton-like oxidation catalyst and adsorbent. The degradation of acetaminophen (PR) and oxidation/adsorption of arsenic were studied in aqueous solutions. Degradation of acetaminophen was accelerated with decrease pH or increase in H2O2 concentration. When the catalyst dosage was 0.5 g·L-1 and H2O2 dosage of 30 mmol•L−1 (mM), the degradation of acetaminophen reached 99%. The Cu-Zn-Fe-LDH is also a potential efficient adsorbent for the removal of arsenic from water with the maximum adsorption capacity of 126.13


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mg·g-1. In the presence of hydrogen peroxide, the arsenite was gradually oxidized into arsenate and adsorbed by Cu-Zn-Fe-LDH at the same time. For the simulated water sample with coexistent arsenic and acetaminophen, after treatment by Cu-Zn-Fe-LDH and H2O2, the remaining concentration of arsenic was below 10 µg·L-1 and the acetaminophen not detected in the solution. The obtained Cu-Zn-Fe-LDH material in this work might be used for simultaneous efficient removal of acetaminophen and arsenic (As(III)/As(V)). This study focused only on the coexistence of acetaminophen and arsenic, for more application of catalytic oxidation and adsorption process to treat other coexistent pollutants, further researches are needed and it can expand the application of this functional material in decontamination of complexed pollution systems.

Supporting Information : The specific surface area and zeta potential analysis figures, the adsorption performance of arsenic on the materials (Effect of pH, isotherm and kinetics), AFS fluorescence spectra for Arsenic, UPLC chromatogram for acetaminophen, reutilization of material, XPS characterization spectra and diagram of the material’s layered structure have been included in the supporting materials.

Acknowledgements This work was supported by the National Natural Science Foundation of China (No. 41372241).


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Table of Contents/Abstract Graphic


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Adsorption Performances of

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