Interconnected porous hollow CuS microspheres derived from metal-organic frameworks for efficient adsorption and electrochemical biosensing
Graphical abstract
Introduction
Hierarchical micro/nanostructures with hollow features and porous textures represent a unique class of functional materials, which have important applications in various areas including catalysis, adsorption, energy conversion/storage, gas sensors, drug delivery, optoelectronics, and biomedicine [1], [2], [3], because of their characteristic merits such as well-defined interior cavities, lower density, larger specific surface area, and better permeation compared to the solid and/or bulk counterparts. Among the present available methods, the sacrificial template route is regarded as a versatile strategy to realize hollow structures due to the effective operability, good reproducibility and simplicity. Especially, rational utilization of different principles including the Kirkendall effect [4], [5], Ostwald ripening [6], [7], galvanic replacement [8], [9], chemical etching [10], [11], and ionic exchange [12], [13] to combine with sacrificial template facilitates the formation of hollow structures in diverse functional materials. Notwithstanding these advances, there is still a great challenge to exploit a facile and reliable strategy for simultaneously achieving the interior hollowing and shell pore creation.
Metal-organic frameworks (MOFs) are an intriguing class of porous crystalline inorganic-organic hybrid materials built from metal ions or clusters and polyfunctional organic ligands, and have attracted increasing attention in recent years, owing to both fundamental scientific interest and attractive applications [14]. Recently, MOFs have been demonstrated to be ideal sacrificial templates or precursors for the generation of porous hollow transition metal oxides, metal phosphides and porous carbon nanostructures by thermal decomposition under controllable atmospheres [15], [16], [17], [18], [19]. For example, porous α-Fe2O3 microboxes [20] and spindles [21] can be directly obtained by using Prussian blue and MIL-88-Fe as templates, respectively. Similarly, other porous hollow binary or multinary transition metal oxide (e.g. Co3O4 [22], CuO [23], CuO-Cu2O [24], ZnxCo3 -xO4 [25], Fe2O3@NiCo2O4 [26] and NiFe2O4/Fe2O3 [27]) micro/nanostructures have been prepared using the corresponding metal-organic frameworks for various applications. Porous carbon with high specific surface area can be also obtained by direct carbonization of different zeolitic imidazolate frameworks (ZIFs) [28], [29], [30]. Beyond the MOF-derived porous hollow oxides and carbons, polyhedral nanocages of ZnS [31] and CoS [32] were also accurately produced from the ZIFs in the presence of sulfidation agents. This interesting discovery undoubtedly suggests that the MOFs can be served as effective templates or precursors to construct hollow transition metal sulfides. However, to meet the application requirements, hollow metal sulfide structures with porous shells are of special attraction, because they can provide a large specific surface area for contact, abundant active sites for interaction, and multiple accessible channels for diffusion and transport. Unfortunately, there have been few reports on the design and fabrication of the micro/nanostructured metal sulfides with both hollow interior and shell porosity derived from MOFs so far.
In the present study, we report a facile and scalable strategy toward the fabrication of novel interconnected porous hollow CuS microspheres (HCMs) derived from Cu-BTC (BTC = benzene-1,3,5-tricarboxylate) MOFs. In the presence of thioacetamide (TAA), the low temperature sulfidation reaction could induce the effective chemical transformation of octahedral Cu-BTC to CuS HCMs. It is demonstrated that the concentration-gradient-driven outward diffusion of Cu-BTC during the anion-exchange reaction between Cu-BTC and S2 - anions is critical for the generation of hollow structures. The obtained CuS HCMs with hollow interior and shell porosity exhibit interesting properties for pollutant removal [33], [34], [35], [36], [37], [38], [39], [40], [41], [42], [43], [44], [45], [46], [47] and biosensing applications. As an efficient adsorbent, the CuS HCMs achieve an extremely fast adsorption rate with high removal efficiency for organic dye in water. When evaluated as a non-enzymatic biosensor, the CuS HCMs manifest a high sensitivity and low detection limit for electrochemical detection of glucose.
Section snippets
Materials
Cu(NO3)2 · 3H2O, thioacetamide (TAA), NaOH, methanol, ethanol, methylene blue (MB) and glucose were purchased from Kelong Chemical Reagents company (Chengdu, China). Benzene-1,3,5-tricarboxylic acid (BTC) were purchased from Aladin Ltd. (Shanghai, China). All chemicals used in this study were of commercially available analytical grade and used without further purification.
Synthesis of interconnected porous hollow CuS microspheres
A schematic diagram of the synthesis procedure is shown in Scheme 1. The synthesis of Cu-BTC MOFs followed Huang et al.’s
Results and discussion
Cu-BTC is one of the most well-known and easily obtainable Cu-based MOFs, which is constructed from Cu2 + ions and benzene-1,3,5-tricarboxylic acid (BTC) forming a three-dimensional architecture. In this study, Cu-BTC MOFs can be facilely produced in a large scale by mixing copper nitrate and BTC in methanol, and then served as the precursor to synthesize CuS products. The structure of the Cu-BTC precursor was determined by X-ray diffraction (XRD) and FTIR spectroscopy. Fig. 1a shows a typical
Conclusions
In summary, we have demonstrated a facile, effective, scalable route to synthesize the novel hierarchical porous CuS HCMs, which was realized by the mild sulfidation-induced chemical transformation of Cu-BTC MOFs. The tentative formation mechanism for the formation of the CuS HCMs was proposed on the basis of a series of designed experiments, which suggested that the concentration-gradient-driven outward diffusion of Cu-BTC during the anion-exchange reaction between Cu-BTC and S2 - anions was a
Acknowledgements
This work was supported by the National Natural Science Foundation of China (21207108), the Sichuan Youth Science and Technology Foundation (2013JQ0012), and the Research Foundation of CWNU (12B018, 14E016).
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