Amino-functionalized MIL-101(Cr) photodegradation enhancement by sulfur-enriched copper sulfide nanoparticles: An experimental and DFT study
Introduction
The increase in urban and industrial activities of our societies has led to growing amounts of pollutants being released into the environment, which causes severe problems for water quality. The presence of organic dyes in water resources, used for example, in industrial processes for textiles, food, leather, paint or coatings, leads to many problems such as non-aesthetic, eutrophication, and they also endanger human health [1,2]. There are several traditional techniques for the remediation of dye molecules in wastewater, including physical and biological technologies that are, however, incapable of achieving efficient degradation of the dye molecules [[3], [4], [5], [6], [7], [8]]. In recent years, interest has grown into the use of solar energy and semiconductor photocatalysis in water purification, e.g., the pollutants degradation process, the photocatalytic green fuel production, and the conversion of greenhouse molecules into fuels or chemicals [[9], [10], [11], [12]]. Also, the specific functionalization of compounds for specific roles in their environment and targeting using green surfactants has a bright future [13,14]. Several photocatalytic materials, including metal oxides, metal sulfides, metal phosphides, and metal-organic frameworks (MOFs), have been studied for water purification through the photodegradation of pollutants molecules [[15], [16], [17], [18], [19]]. Some innovative findings include in the study on the composite products with enhanced morphology as well as the improved Z-scheme- charge-carriers separation and plasmon-induced injection for the photocatalytic process [20,21], increasing the utilization efficiency of visible light by doping [22], and the new combination of the process like the interaction between photocatalysts and microorganisms [23].
Copper (II) sulfide (CuS) is one of the most promising semiconductor materials with excellent optical, electronic, chemical, and thermal properties [[24], [25], [26], [27], [28], [29], [30], [31]]. It is a p-type semiconductor with a broad reported range for its bandgap (1.63–2.56 eV) [32,33]. CuS has attracted much attention as a co-catalyst to improve the photocatalytic performance of a wide range of materials, e.g., in combination with metal oxides and metal sulfides, as well as carbonaceous graphitic carbon nitride (g-CN), and also for the fabrication of efficient hybrid/composite materials with carbon-based materials like graphene oxide for energy conversion applications [[34], [35], [36], [37]].
Metal-organic frameworks define as hybrid inorganic/organic crystalline materials designed as metal clusters and organic linkers, which have the potential application of impurity removal in aqueous solutions [[38], [39], [40], [41]]. Flexibility in the linker design of MOFs, their high surface area and porosity have led to the use of MOFs in various scientific and technological fields, including gas storage, gas separation, drug delivery, sensors, supercapacitors, heat transfer, water adsorption, catalytic and photocatalytic applications [8,[42], [43], [44]]. Alvaro et al. [45] first proposed MOF-5 as a catalyst for the photodegradation of water contaminants, and after that, many types of research studies have focused on MOFs as photoactive materials for energy applications [[45], [46], [47], [48]]. However, pure MOFs have drawbacks as photocatalysts, corresponding to a high electron-hole recombination rate and partial adsorption of UV–visible irradiation [[49], [50], [51]]. Different groups of materials, including conventional semiconductor materials (TiO2, ZnO, CdS, ZnS), carbon-based materials (graphene oxide, g-CN), and even diverse types of MOFs have been used to fabricate active hybrid/composite photocatalysts with enhanced photocatalytic performance compared to pure MOFs and other parent materials [[52], [53], [54], [55]]. Among these diverse strategies for developing efficient hybrid/composite photocatalysts, semiconductor@MOF photocatalysts have shown considerable advantages, resulting from the synergistic effect between MOFs and conventional semiconductors [56]. Many semiconductor nanoparticles have been used for developing semiconductor@MOF systems to date, including CdS@MIL-101(Cr), ZnO@ZIF-8, TiO2@UiO-66, ZnO@MOF-5, CdS@MIL-53(Fe), CdS@MIL-100(Fe), and Bi2S3@MIL-100(Fe) [[56], [57], [58], [59], [60]]. Recently, the main focus of researchers for developing new semiconductor@MOF photocatalysts is to identify new combinations of MOFs and semiconductor materials that use a direct Z-scheme charge separation mechanism, which, compared to traditional type-II band-to-band charge separation, shows higher redox capacity and more efficient charge carrier separation [61,62].
The primary purpose of this study was to explore the use of copper sulfide nanoparticles to enhance the photocatalytic efficiency of MOFs. The novel direct Z-scheme NH2-MIL-101(Cr)@CuS composite with different weight percentages of copper sulfide was developed for the operative photodegradation of RhB in the visible light irradiation. The high surface area amino-functionalized MIL-101(Cr) with water-stable structure was used as a matrix to disperse the nanoparticles of copper sulfide, reduce their agglomeration, and also reduce the electron-hole recombination rate in the resulting composite structures compared to the parent materials [63]. In the photocatalytic degradation of RhB, electrochemical and photoelectrochemical experiments showed the excellent photocatalytic activity of the composite, owing to the effective interactions with NH2-MIL-101(Cr) and copper sulfide nanoparticles, which may introduce these nanoparticles as a cost-effective, innocuous and operative co-catalyst for the development of photocatalytic composite systems based on MOFs.
Section snippets
Materials
All the chemicals (AR grade) were used without any further purification. Cu(NO3)2.6H2O (98%), thioacetamide (98%), Cr(NO3)3·9H2O (99%) were purchased from Sigma Aldrich. Ethylene glycol (98%), NaOH (98%), and 2-Aminoterephthalic acid (99%) were purchased from Merck Company. Nafion solution (5%) was purchased from Alfa Aesar Company.
Synthesis of CuS nanoparticles
The CuS nanoparticles are synthesized via the hydrothermal approach [64]. For this purpose, about 0.1215 g (0.41 mmol) of Cu(NO3)2.6H2O and 0.0765 g (1 mmol) of
Characterization of NM@CuS composites
The PXRD patterns of the pure NH2-MIL-101(Cr), the composite series, and pure CuS are presented in Fig. 1. The peak positions and diffraction intensities of NH2-MIL-101 match the observed patterns, as well as the simulated XRD for MIL-101(Cr), reported in the literature [63,78,79]. The PXRD patterns of the CuS nanoparticles confirm the presence of CuS in the structure of the obtained composite samples. The main peaks of CuS nanoparticles appeared at 2θ = 28°, 29°, 30°, 48°, 52°, and 58°. In the
Conclusion
In summary, a series of the NM@CuS composite photocatalyst samples were fabricated via a conventional solvothermal approach. The photocatalytic elimination of RhB has demonstrated that the sample containing 0.15 g NH2-MIL-101(Cr) in the precursor suspension exhibits higher photocatalytic ability compared to other samples, which can be attributed to the following factors: effective visible light absorption in the composite samples compared to pure NH2-MIL-101(Cr); higher surface area of the
CRediT authorship contribution statement
Mr. Soheil Abdpour: Conceptualization Ideas, Methodology, Writing - Original Draft, Formal analysis, Investigation. Prof. Elaheh Kowsari: Supervision, Writing - Review & Editing. Dr. Behrouz Bazri: Formal analysis, Writing - Review & Editing, Investigation. Prof. Mohammad Reza Alavi Moghaddam: Supervision, Writing - Review & Editing. Dr. Saeedeh SarabadaniTafreshi: Formal analysis, simulation section. Dr. Nora H. de Leeuw: Formal analysis, simulation section. Mrs. Ilka Simon: Formal analysis.
Declaration of competing interest
All authors have participated in (a) conception and design, or analysis and interpretation of the data; (b) drafting the article or revising it critically for important intellectual content; and (c) approval of the final version.
This manuscript has not been submitted to, nor is under review at, another journal or other publishing venue.
The authors have no affiliation with any organization with a direct or indirect financial interest in the subject matter discussed in the manuscript.
Acknowledgment
We wish to express our gratitude to the Iran National Science Foundation (INSF) (Project no. 96001364) and Research Affairs Division at the Amirkabir University of Technology of Tehran (AUT) (Grant no. 1235/40) for financial support. This work has used computational facilities of the Advanced Research Computing @ Cardiff (ARCCA) Division, Cardiff University, UK.
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2023, Applied Surface ScienceCitation Excerpt :Although, the broad energy band gap of MOFs has limited their application in photocatalytic processes. One practical solution to overcome this disadvantage is to synthesize the composite structure of MOFs [14,16]. Numerous studies have been performed on the fabrication of MOF composite with other semiconductors.