Synthesis, characterization, kinetics and modeling studies of new generation pollutant ketoprofen removal in water using copper nanoparticles

https://doi.org/10.1016/j.molliq.2020.115075Get rights and content

Highlights

  • Facile synthesis of Copper nanoparticles (new generation adsorbent).

  • Easy and fast removal of ketoprofen (new generation pollutant).

  • Developed method is environmental friendly and inexpensive.

  • May be used to remove propranolol drug residue from any water body.

Abstract

Copper nanoparticles were synthesized following their characterization by XRD, SEM-EDX and TEM techniques. These nanoparticles were used to remove new generation pollutant ketoprofen up to 89% at optimal conditions of 50 mg/L concentration, 50 min, 5.0 pH, 1.0 g/L dose and 25 °C. The adsorption followed the Langmuir, Temkin and Dubinin - Radushkevich models describing good adsorption of ketoprofen in water. The adsorption followed pseudo-first-order and liquid film diffusion mechanism. The adsorption was spontaneous and exothermic as proposed by the thermodynamics data. The supramolecular mechanism was purposed for the adsorption. Remarkably, the adsorption process was appropriate at low contact time. These properties of the adsorption made this development applicable to natural water resources, making the process economic and eco-friendly. So, this adsorption method may be used to remove ketoprofen in water easily at an inexpensive level.

Introduction

Nowadays, many water resources are being contaminated by emerging pollutants such as chemicals, metals, surfactants, pharmaceuticals, pesticides, and personal care products [1]. Among these pollutants, non-steroidal anti-inflammatory drugs (NSAIDs) are usually found in some water resources. It is because these medicines are made and utilized in big amounts and are released continuously into the environment even in very low concentrations by the industries, hospitals and domestic activities [2]. Ketoprofen (the chemical structure is given in supporting information as Fig. S1; MW 254.2806 g) is one of the most widely used NSAIDs to treat muscles and joints pain, inflammation, gout, osteoarthritis rheumatoid arthritis, etc. Moreover, ketoprofen is also used to cure pain due to strains, sprains, bone disorders, etc. Of course, it is good medicine for curing the above ailments but also has certain side effects. It shows digestive problems, diarrhea, constipation, gas, heartburn, unusual tiredness, bloating, etc. [3,4]. Ketoprofen contaminated water may create the above problems and, therefore, it is important to remove ketoprofen from water.

As a result of the extensive production and usage, ketoprofen is considered as new generation pollutant and discharged unceasingly into the environment and polluting various water bodies [5,6]. For instance, Santos et al. [7] reported the existence of ketoprofen (1.2 μg/L) in four water treatment plants in Seville, Spain. Lindqvist et al. [8] found 1.2 mg/L of ketoprofen in wastewater influent in Finland. Rabiet et al. [9] detected ketoprofen in influent and effluent wastewater samples of Mediterranean catchment (France) in the amount range of 0.38–3.15 mg/L. Similarly, ketoprofen has been found in various water resources across the world [[10], [11], [12], [13]].

Despite several methods that have been used to remove ketoprofen in water, the adsorption method is being considered as the best method owing to its advantages such as simple design, easy to handle, choice of adsorbents, simultaneous removal of various pollutants, and low-cost [[14], [15], [16], [17], [18], [19], [20]]. Recently, Ahmed [21] reviewed the adsorption of non-steroidal anti-inflammatory drugs from aqueous solutions using carbons. The author discussed various adsorption capacities of ketoprofen, ibuprofen, diclofenac and naproxen on activated carbon. The preparation of carbon from the different waste precursors is discussed and the adsorption was analyzed by various isotherms. The conclusion drawn is that NAISDs adsorption largely dependent on initial concentration and adsorbent dose rather than on pH and temperature. Most of the results obeyed Langmuir isotherm. As per this author, there is still a need for adsorption improvement by developing new adsorbent, fixed-bed studies, regeneration and pilot and full-scale studies. Some specific papers are cited herein and for instance, Gao and Marc [22] used activated carbon for the removal of ketoprofen. Ouasfi et al. [23] prepared porous carbon from Laminaria digitata algae and used it for the elimination of ketoprofen. Al-Khateeb et al. [24] stated the removal of ketoprofen in water using graphene as an adsorbent. By considering these articles, it was observed that the removal of ketoprofen is required more advancement. Some adsorbents have low adsorption capacity for ketoprofen while others are not working at the natural pH of the water and hence, such types of adsorbents cannot be applied to natural water resources for ketoprofen removal. Therefore, it was realized that there is a necessity to develop a fast and commercial method for ketoprofen removal. For this purpose, the copper nanoparticles were synthesized and used to remove ketoprofen in water.

Section snippets

Preparation of ketoprofen solutions

A precisely weighed amount of ketoprofen was used to prepare the stock solution (0.1 g/L) in methanol. This stock solution was then further diluted and used to prepare 5 to 70 mg/L for the adsorption and 1 to 10 mg/L for HPLC studies.

Synthesis of copper nanoparticles (CNPs)

A precisely weighed amount of copper sulfate (3.192 g) was dissolved in 100 mL of distilled water and stirred incessantly to obtain a blue color. This salt solution was then heated up to 85 °C followed by a 5.0 M sodium hydroxide solution was added dropwise into

Characterization of CNPs

The peaks in XRD at 2θ values of 34.5, 37.4, 46.5, 50.3, 55.4, 59.5, 64.6, 66.6, 70.4 and 73.5° are indexed as (400, 311, 220, 202, 200, 112, 111, 110), respectively. These values established the occurrence of two crystalline forms of Cu2O and CuO in the prepared CNPs and, these results are in good promise with those reported already in literature for CNPs [25]. Concisely, these XRD results established the crystallinity of the reported CNPs. This crystallinity is because of the occurrence of

Adsorption isotherms

The obtained adsorption data were assessed by using different isotherm models namely Langmuir, Freundlich, Temkin and Dubinin–Radushkevich (D-R) isotherms. The equations used for these models are given in the supplementary file (SI). The Langmuir isotherm assumes monolayer adsorption, and Freundlich isotherm assumes multilayer adsorption of the adsorbate onto adsorbent, while Temkin and D-R isotherm model describes the interaction between the adsorbate and the adsorbent, and the physio-chemical

Kinetics modeling

To understand the kinetics involved during the removal of ketoprofen by CNPs, following models were employed. The corresponding equations of these models are given in Table S2 in SI.

Thermodynamic study

The thermodynamic factors such as enthalpy (ΔH0), free energy (ΔG0), and entropy (ΔS0) values associated with the ketoprofen adsorption on CNPs were determined. The ΔG0 value was obtained by using Eq. (3), while Eq. (4) was used to calculate the equilibrium constant Ke0, which was later used to exploit for enthalpy and entropy of the adsorption process [27].ΔG0=RTlnKe0where R is the ideal gas constant (8.314 J/mol K), and T is the temperature (K).Ke0={(1000.bL/mg.MW.Adsorbate0}/γwhere b is the

Adsorption mechanism

The adsorption mechanism involved behind the adsorption of ketoprofen on CNPs is ascertained by intraparticle diffusion kinetic and liquid film diffusion kinetic models. The equations of these models are given in Table S2 in SI. The experimental data were analyzed by these models and are discussed in the following sub-section.

Supramolecular mechanism of adsorption

The determination of the supramolecular mechanism behind the ketoprofen adsorption is a very important aspect of the removal of other profens in the future. The experimental data gathered in this article were used to determine the mechanism of sorption at the supramolecular level. D - R isotherm has confirmed ketoprofen adsorption physical in nature. Keeping into consideration the experimental data, the prediction of D - R isotherm and outcomes of other models described in this article, efforts

Conclusions

CNPs were synthesized followed by characterized via XRD, SEM-EDX, and TEM techniques. The CNPs showed remarkable removal of ketoprofen. The adsorption followed the Langmuir model confirming monolayer adsorption. The applicability of the Temkin and D-R isotherm models is an indication of good interactions of ketoprofen molecules with CNPs and the physical nature of the adsorption. The adsorption followed pseudo-first-order kinetics and liquid film diffusion mechanism. The adsorption was

CRediT authorship contribution statement

Zeid A. ALOthman: Conceptualization, Methodology, Writing, reviewing, Validation and Investigation; Ahmad Yacine Badjah: Data curation, Formal analysis, Osamah M. Alduhaish: Data curation, Software, Karthik Rathinam: Visualization, Writing - review & editing, Stefan Panglisch: Visualization, Writing - review & editing, Imran Ali: Conceptualization, Methodology, Writing- reviewing and editing, Validation, Investigation and Supervision.

Declaration of Competing Interest

The authors of this manuscript do not have any interest in conflict.

Acknowledgment

The authors are grateful to the Deanship of Scientific Research, King Saud University for funding through Vice Deanship of Scientific Research Chairs.

References (29)

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