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Discharge of recalcitrant pharmaceuticals into aquatic systems has caused severe impacts on public health and ecosystem. Advanced oxidation processes (AOPs) are effective for eliminating these refractory pollutants, for which single-atom catalysts (SACs) become the state-of-the-art materials owing to the maximized exposure of active metal sites. In this work, hollow spherical graphitic carbon nitride (hsCN) was fabricated to incorporate copper species to develop Fenton-like catalysts for acetaminophen (ACT) removal. Through pyrolysis of supramolecular assemblies derived from melamine-Cu complex and cyanuric acid, single atom Cu-N3 sites were anchored on hsCN by N-coordination to obtain SACu-hsCN. In virtue of the atomically dispersed Cu-N3 sites as well as the hollow structure of hsCN providing smooth channels for the interactions between single Cu atoms and reactants, the optimal 5.5SACu-hsCN removed 94.8% of ACT after 180 min of Fenton-like reactions, which was superior to that of 5.5AGCu-hsCN with aggregated Cu particles on hsCN (56.7% in 180 min). Moreover, 5.5SACu-hsCN was still active after four cycles of regeneration. The mechanism investigation demonstrated that both hydroxyl radicals (OH) and singlet oxygen (1O2) contributed to ACT degradation in 5.5SACu-hsCN/H202 system, in which non-radical 1O2 played the dominant role.

Membrane separation and sulfate radicals-based advanced oxidation processes (SR-AOPs) can be combined as an efficient technique for the elimination of organic pollutants. The immobilization of metal oxide catalysts on ceramic membranes can enrich the membrane separation technology with catalytic oxidation avoiding recovering suspended catalysts. Herein, nanostructured Co3O4 ceramic catalytic membranes with different Co loadings were fabricated via a simple ball-milling and calcination process. Uniform distribution of Co3O4 nanoparticles in the membrane provided sufficient active sites for catalytic oxidation of 4-hydroxybenzoic acid (HBA). Mechanistic studies were conducted to determine the reactive radicals and showed that both SO4•− and •OH were present in the catalytic process while SO4•− plays the dominant role. The anti-fouling performance of the composite Co@Al2O3 membranes was also evaluated, showing that a great flux recovery was achieved with the addition of PMS for the fouling caused by humic acid (HA).

Three-dimensional (3D) graphene-based macrostructures are being developed to combat the issues associated with two-dimensional (2D) graphene materials in practical applications. The 3D macrostructures (3DMs), for example, membranes, fibres, sponges, beads, and mats, can be formed by the self-assembly of 2D graphene-based precursors with exceptional surface area and unique chemistry. With rational design, the 3D macrostructures can then possess outstanding properties and exclusive structures. Thanks to various advantages, these macrostructures are competing in a variety of applications with promising performances unlike the traditional activated carbons, biochars and hydrochars, which have less flexibilities for modifications towards versatile applications. However, despite having such a wide range of applications, 3DMs remain applicable on laboratory scale due to the associated factors like cost and extensive research. This perspective provides an overview of available graphene-based macrostructures and their diverse synthesis protocols. In the synthesis, hydrothermal route, chemical vapor deposition (CVD), wet spinning, 3D printing, vacuum filtration, spray drying and emulsion methods are highlighted. In addition, the physio-chemical properties of these macrostructures are discussed with the relationship among the porosity, surface area and the bulk density. The perspective also highlights the versatile potentials of different 3DMs in wastewater remediation by adsorption, desalination, and catalytic oxidation, etc. Following the concluding remarks, future outlooks on commercial applications of 3DMs are also provided.