Comprehensive insights into the application of graphene-based aerogels for metals removal from aqueous media: Surface chemistry, mechanisms, and key features

Efficient removal of heavy metals and other toxic metal pollutants from wastewater is essential to protect human health and the surrounding vulnerable ecosystems. Therefore, significant efforts have been invested in developing practical and sustainable tools to address this issue, including high-performance adsorbents. In this respect, within the last few years, graphene-based aerogels/xerogels/cryogels (GBAs) have emerged and drawn significant attention as excellent materials for removing and recovering harmful and valuable metals from different aqueous media. Such an upward trend is mainly due to the features of the aerogel materials combined with the properties of the graphene derivatives within the aerogel's network, including the GBAs' unique threedimensional (3D) porous structure, high porosity, low density, large specific surface area, exceptional electron mobility, adjustable and rich surface chemistry, remarkable mechanical features, and tremendous stability. This review offers a comprehensive analysis of the fundamental and practical aspects and phenomena related to the application of GBAs for metals removal. Herein, we cover all types of (bottom-up) synthesized GBAs, including true microporous graphene-based aerogels as well as other 3D graphene-based open-cell interconnected mesoporous and macroporous aerogels, foams, and sponges. Indeed, we provide insights into the fundamental understanding of the GBAs' suitability for such an important application by revealing the mechanisms involved in metals removal and the factors inducing and controlling the highly selective behavior of these distinctive adsorbents. Besides conventional adsorptive pathways, we critically analyzed the ability of GBAs to electrochemically capture metal pollutants (i.e., electrosorption) as well as their efficiency in metals detoxification through reductive mechanisms (i.e., adsorption-reduction-readsorption). We also covered the reusability aspect of graphene aerogels (GAs)-based adsorbents, which is strongly linked to the GBAs' outstanding stability and efficient desorption of captured metals. Furthermore, in view of their numerous practical and environmental benefits, the development and application of magnetically recoverable GAs for metals removal is also highlighted. Moreover, we shed light on the potential practical and scalable implementation of GBAs by evaluating their performance in continuous metals removal processes while highlighting the GBAs' versatility demonstrated by their ability to remove multiple contaminants along with metal pollutants from wastewater media. Finally, this review provides readers with an accessible overview and critical discussion of major recent achievements regarding the development and applications of GAs-based adsorbents for metal ions removal. Along with our recommendations and suggestions for potential future work and new research directions and opportunities, this review aims to serve as a valuable resource for researchers in the field of wastewater treatment and inspire further progress towards developing next-generation high-performance GBAs and expanding their application.