Patterned Carbon Nitride–Based Hybrid Aerogel Membranes via 3D Printing for Broadband Solar Wastewater Remediation

Abstract

Controlled scalable assembly of 2D building blocks into macroscopic 3D architectures is highly significant. However, the assembly of g‐C3N4 into tailored, 3D architectures is not yet reported. Here, a 3D printing methodology to enable the programmable construction of carbon nitride–based hybrid aerogel membranes with patterned macroscopic architectures is proposed. g‐C3N4 nanosheets (CNNS) are used as the building block, and sodium alginate (SA) increases the viscosity of the ink to obtain the desired rheological properties. Three printing routes, including printing directly in air and in the supporting reservoirs composed of CaCl2/glycerol solution or Pluronic F127, are demonstrated for printing versatility. The printed Au nanobipyramid–CNNS–SA hybrid aerogels exhibit broadband visible‐light absorption and superior solar wastewater remediation performance with excellent cyclic stability and easy manipulation features. Remarkably, the activity of the 3D‐printed aerogel is about 2.5 times of that of the contrast sample, attributing to the enhanced liquid velocity and solution diffusion efficiency because of the 3D‐printed structure, which is demonstrated by experimental and theoretical simulations. This approach can be extended to the macroscopic assembly of other 2D materials for myriad applications.

Graphitic carbon nitride and polymers: a mutual combination for advanced properties

“…(b) Optical image of a woodpile structure (mass ratio CN : SA = 1 : 2) printed via Pluronic F127 (Route 3) and (c) a cross-sectional SEM image (Reprinted with permission. 205 Copyright 2018 John Wiley and Sons).…”

“…13a). 205 Hence, 3D hydrogel scaffolds were obtained that could be utilized for photocatalytic tasks. A carbon nitride nanosheet/sodium alginate (CNNS-SA)-based ink was printed and crosslinked in CaCl 2 /glycerol solution ( Fig.…”

Photo‐Induced Hydrogel Formation Based on g‐C3N4 Nanosheets with Self‐Cross‐Linked 3D Framework for UV Protection Application

“…[13] It has been successfully used to reinforce hydrogels, and meanwhile bestowed additional properties on the obtained composite hydrogels. [14][15][16][17][18][19][20][21] Nevertheless, the current synthetic process is relatively complex and needs external initiators or cross-linkers. For example, Jiang et al triggered the polymerization of aniline by ammonium persulfate (APS) in presence of cross-linker and carbon nitride.…”

“…Recently, graphitic carbon nitride (g‐C 3 N 4 ) as metal‐free semiconductor has attracted extensive attention . It has been successfully used to reinforce hydrogels, and meanwhile bestowed additional properties on the obtained composite hydrogels . Nevertheless, the current synthetic process is relatively complex and needs external initiators or cross‐linkers.…”

In-situ Construction of Superhydrophilic g-C3N4 Film by Vapor-Assisted Confined Deposition for Photocatalysis

“…All these properties make g-C 3 N 4 a promising candidate for catalytic and conventional applications in the last decade (Thomas et al, 2008;Wang et al, 2012;Liu et al, 2016b;Ong et al, 2016). Numerous studies were put into improving the catalytic efficiencies of g-C 3 N 4 through strategies including nanoarchitectures design, functionalization through molecular engineering and modification with other semiconductors or metals (Sun et al, 2012;Jun et al, 2013;Liu and Antonietti, 2013;Huang et al, 2014Huang et al, , 2018Liu et al, 2014aLiu et al, ,b, 2015aLiu et al, , 2016cLiu et al, , 2017aLiu et al, ,b, 2018Shalom et al, 2014;Cao et al, 2015a;Han et al, 2015;Yang et al, 2015b;Xiong et al, 2016;Zhou et al, 2016;Ong, 2017;Xia et al, 2017;Xu et al, 2017;Yu et al, 2017;Chen et al, 2018aChen et al, ,b, 2019Choi et al, 2018;He et al, 2018;Zhao et al, 2018;Zhang et al, 2019). The heterogeneous nature of the g-C 3 N 4 powder necessitates the development of the film for further practical device use (Cazelles et al, 2015;Chen et al, 2018b;Xiao et al, 2019;Xu and Shalom, 2019).…”