Search

Extraordinary self-healing efficiency is rarely observed in mechanically strong hydrogels, which often limits the applications of hydrogels in biomedical engineering. We have presented an approach to utilize a special type of graphene oxide-based crosslinker (GOBC) for the simultaneous improvement of toughness and self-healing properties of conventional hydrogels. The GOBC has been prepared from graphene oxide (GO) by surface oxidation and further introduction of vinyl groups. It has been designed in such a way that the crosslinker is able to form both covalent bonds and noncovalent interactions with the polymer chains of hydrogels. To demonstrate the efficacy of GOBC, it was incorporated in a conventional polyacrylamide (PAM) and polyacrylic acid (PAA) hydrogel matrix, and the mechanical and self-healing properties of the prepared hydrogels were investigated. In PAM-GOBC hydrogels, it has been observed that the mechanical properties such as tensile strength, Young's modulus, and toughness are significantly improved by the incorporation of GOBC without compromising the self-healing efficiency. The PAM-GOBC hydrogel with a modulus of about 0.446 MPa exhibited about 70% stress healing efficiency after 40 h. Whereas, under the same conditions a PAM hydrogel with commonly used crosslinker

The mechanical performances of hydrogels are greatly influenced by the functionality of cross-linkers and their covalent and non-covalent interactions with the polymer chains. Conventional chemical cross-linkers fail to meet the demand of large toughness and high extensibility for their immediate applications as artificial tissues like ligaments, blood vessels, and cardiac muscles in human or animal bodies. Herein, we synthesized a new graphene oxide-based two-dimensional (2D) cross-linker (GOBC) and exploited the functionality of the cross-linker for the enhancement of toughness and stretchability of a poly(acrylic acid) (PAA) hydrogel. The 2D nanosheets of GO were modified in such a way that they could provide multifunctional sites for both physical and chemical bonding with the polymer chains. Carboxylic acid groups at the surfaces of the GO sheets were coupled with the acrylate functional groups for covalent cross-linking, while the other oxygen-containing functional groups are responsible for physical cross-linking with polymers. The GOBC had been successfully incorporated into the PAA hydrogel and the mechanical properties of the GOBC cross-linked PAA hydrogel (PAA-GOBC) were investigated at various compositions of cross-linker. Seven times enhancement in both toughness and elongation at break has been achieved without compromising on the modulus for the as-synthesized PAA-GOBC compared to the conventional N,N′-methylenebis(acrylamide) (MBA) cross-linked PAA hydrogel. This facile and efficient way of GO modification is expected to lead the development of a high-performance nanocomposite for cutting-edge applications in biomedical engineering.

A combination of strong load-bearing capacity and high swelling degree is desired in hydrogels for many applications including drug delivery, tissue engineering, and biomedical engineering. However, a compromising relationship exists between these two most important characteristics of hydrogels. Improving both of these important properties simultaneously in a single hydrogel material is still beyond the satisfactory limit. Herein, we report a novel approach to address this problem by introducing a silica-based bi-functional 3D crosslinker. Our bi-functional silica nanoparticles (BF-Si NPs) possess amine groups that are able to offer pseudo-crosslinking effects induced by inter-cohesive bonding, and acrylate groups that can form conventional covalent crosslinking in the same hydrogel. We fabricated polyacrylic acid (PAc-Si) and polyacrylamide (PAm-Si) hydrogels using our BF-Si NPs via free radical polymerization to demonstrate this concept. Incorporation of the BF-Si crosslinkers into the hydrogels has resulted in a large enhancement in the mechanical properties compared to conventional hydrogel crosslinked with N,N′-methylene bisacrylamide (MBA). For instance, tensile strength and the toughness increased by more than 6 times and 10 times, respectively, upon replacing MBA with BF-Si in polyacrylamide hydrogel. Moreover, the hydrogels crosslinked with BF-Si exhibited a remarkably elevated level of swelling capacity in the aqueous medium. Our facile yet smart strategy of employing the 3D bi-functional crosslinker for combining high swelling degree and strong mechanical properties in the same hydrogels can be extended to the fabrication of many similar acrylate or vinyl polymer hydrogels.

The development of safe and cost-effective methods for the treatment of dye polluted wastewater has been a great concern among researchers. Herein, we developed a nanocomposite (M3D–PAA–CCN) based on polyacrylic acid (PAA) crosslinked with magnetic 3D crosslinkers (M3D) and carboxylated cellulose nanocrystals (CCN), for the removal of cationic dyes from aqueous solutions. Acrylic-functionalized Fe3O4 nanoparticles were covalently linked to the polymer chains via the form of the 3D crosslinker to introduce magnetic properties into the as-synthesized nanocomposite. The addition of highly dispersive CCN reduced the gel-like properties of the nanocomposite and instead incorporated a diffusive nature, which was more desirable for adsorbents. The surface morphology of the nanocomposite was analyzed by FESEM and the size of the nanocomposite particles was found to be in the range of 60–90 nm. The chemical functionalities and compositions were determined by XPS, FTIR, and EDX analyses whereas TGA confirmed the thermal stability of M3D–PAA–CCN. The maximum adsorption capacity of the M3D–PAA–CCN (332 mg g−1) was measured higher than that of M3D–PAA (114 mg g−1) to a cationic methylene blue (MB) dye indicating the significant contribution of CCN. The adsorption capacity of the as-synthesized M3D–PAA–CCN was found to be highly pH-dependent and the adsorption capacity increased with the increase of pH owing to the greater negative charge as indicated by the higher zeta potential. The adsorption kinetics of MB on the composites was found to follow the pseudo-second-order model. The adsorption capacity was also investigated as a function of concentration to figure out the adsorption mechanism using Langmuir and Freundlich isotherm models. The Langmuir model fitted the adsorption process better as suggested by the relatively smaller nonlinear chi-square value obtained from the fitting parameters.

Bimetallic nanocatalysts have been gaining huge research attention in the heterogeneous catalysis community recently owing to their tunable properties and multifunctional characteristics. In this work, we fabricated a bimetallic core–shell nanocomposite catalyst by employing a mussel-inspired strategy for immobilizing gold nanoparticles (AuNP) on the surface of nickel nanoparticles (NiNP). NiNPs obtained from the reduction of Ni(II) were first coated with polydopamine to provide the anchoring sites towards the robust immobilization of AuNPs. The as-synthesized nanocomposite (Ni–PD–Au) exhibited outstanding catalytic activity while reducing methylene blue (MB) and 4-nitrophenol (4-NP) yielding rate constants 13.11 min−1 and 4.21 min−1, respectively, outperforming the catalytic efficiency of its monometallic counterparts and other similar reported catalysts by large margins. The superior catalytic efficiency of the Ni–PD–Au was attributed to the well-known synergistic effect, which was experimentally investigated and compared with prior reports. Similar bio-inspired immobilization of AuNPs was also applied on graphene-wrapped NiNPs (Ni-G) instead of bare NiNPs to synthesize another composite catalyst (Ni-G–PD–Au), which yet again exhibited synergistic catalytic activity. A comparative study between the two nanocomposites suggested that Ni–PD–Au excelled in catalytic activity but Ni-G–PD–Au provided noteworthy stability showing ∼100% efficiency over 17 repeated cycles. However, along with excellent synergistic performance, both nanocomposites demonstrated high magnetization and thermal stability up to 350 °C ascertaining their easy separation and sustainability for high-temperature applications, respectively.

A polyacrylic acid (PAA) functionalized magnetic Fe3O4 nanoparticle-graphene oxide nanocomposite (PAA/MGO) was synthesized by a facile method. The structure and surface properties of MGO and PAA/MGO composites were characterized by infrared (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM), thermogravimetric analysis (TGA) and zeta potential measurements. The adsorption of a model dye pollutant, methylene blue (MB), on MGO and PAA/MGO was investigated in batch tests. The functionalization of PAA to MGO significantly enhances the maximum adsorption capacity of MB (at pH = 7) from ∼70 mg g−1 (on MGO) to ∼291 mg g−1 (PAA/MGO). The adsorption of MB on MGO and PAA/MGO was mainly driven by the electrostatic attraction between positively charged MB molecules and negatively charged nanocomposite surfaces, and the higher adsorption capacity of PAA/MGO is mainly attributed to the functionalization of PAA and its higher content of charged carboxyl groups than MGO. The adsorption capacity of MB on both MGO and PAA/MGO adsorbents also increases with increasing solution pH from 3 to 11, due to enhanced electrostatic attraction at high pH conditions. The limited adsorption capacity of MB on MGO and PAA/MGO at pH 3, when electrostatic attraction is almost negligible, indicates that π–π interaction between the GO surface and MB also plays a role in the adsorption process. The PAA/MGO shows a rapid adsorption rate and high adsorption capacity of MB with magnetic properties for easy separation and excellent recyclability, which endows the nanocomposite with great potential for the removal of cationic organic pollutants in wastewater treatment.