Interfacial Assembly of Nanowire Arrays toward Carbonaceous Mesoporous Nanorods and Superstructures

Abstract

Synthesis of anisotropic carbonaceous nano‐ and micro‐materials with well‐ordered mesoporous structures has attracted increasing attention for a broad scope of applications. Although hard‐templating method has been widely employed, overcoming the viscous forces to prepare anisotropic mesoporous materials is particularly challenging via the universal soft‐templating method, especially from sustainable biomass as a carbon resource. Herein, the synthesis of biomass‐derived nanowire‐arrays based mesoporous nanorods and teeth‐like superstructures is reported, through a simple and straightforward polyelectrolyte assisted soft‐templating hydrothermal carbonization (HTC) approach. A surface energy induced interfacial assembly mechanism with the synergetic interactions between micelles, nanowire, nanorods, and polyelectrolyte is proposed. The polyelectrolyte acts not only as a stabilizer to decrease the surface energy of cylindrical micelles, nanowires and nanorods, but also as a structure‐directing agent to regulate the oriented attachment and anisotropic assembly of micelles, nanowires, and nanorods. After a calcination treatment, the carbon nanorod and teeth‐like superstructure are successfully coupled with Ru to directly produce supported catalysts for the hydrogen evolution reaction, exhibiting much better performance than the isotropic nanospheres based catalyst. This HTC approach will open up new avenues for the synthesis of anisotropic materials with various morphologies and dimensions, expanding the palette of materials selection for many applications.

Construction of shell-like carbon superstructures through anisotropically oriented self-assembly for distinct electromagnetic wave absorption

“…1, the shell-like superstructure carbon is designed and formed through an interfacial super-assembly process. 31 In this reaction, ribose is used as a carbon precursor, F127 is employed as a soft template, sulfuric acid is utilized as a catalyst, and PSSMA is selected as a structure-directing agent. First, triblock copolymer F127 and ribose self-assemble into 1D cylindrical F127/ribose micelles as subunits.…”

“…The specific preparation process was as follows according to our previous report: 31 6 g of ribose was added to 60 mL of 1.53 M sulfuric acid solution under continuous stirring, and then 3 g of F127 was added and stirred for 12 h until a clarified solution was formed. Subsequently, the solution was poured into a 100 mL PTFE liner and placed into a hydrothermal reactor and hydrothermally reacted in an oven at 140 °C for 4 h. After the reaction was completed, the reactor was cooled to room temperature with cold water and filtered through a Büchner funnel, washed with water and ethanol until the filtrate was clarified, and then the filtered product was dried in an oven at 70 °C for 24 h. Upon cooling, the resulting powder was labeled sphere-like carbonaceous material.…”

Morphological Control of Biochar with Emerging Functionalities by Thermodynamic and Kinetic Approaches

“…However, because of the complexity of the HTC process, although the sugars have similar chemical compositions, they can form products with largely different morphologies under almost the same HTC conditions. For example, when changing the carbon precursor from xylose to ribose, bivalvelike superstructures were transformed into teethlike superstructures assembled from mesoporous nanorods (Figure e–g). , For the additives, they have been proved to be an effective component in changing the packing parameters of the micelle composites. For example, 1,3,5-trimethylbenzene (TMB) was utilized as a swelling agent in the synthesis of carbonaceous nanostructures with tunable pore sizes, that is, TMB molecules aggregated into hydrophobic cores regulating the volume of micelle composites, for which the packing parameters were controlled. , More recently, TMB has been further demonstrated to be capable of strengthening the hydrophobic-end inter-reaction between micelle composites, which enhances the end-to-end assembly of cylindrical micelles and further generates longer and thinner nanofiber-based nanowires …”

“…(e–g) SEM and TEM images of carbonaceous teethlike superstructures assembled from mesoporous nanorods. Reproduced with permission from ref . Copyright 2022 John Wiley & Sons.…”

“…For example, when changing the carbon precursor from xylose to ribose, bivalvelike superstructures were transformed into teethlike superstructures assembled from mesoporous nanorods (Figure 8e−g). 37,51 For the additives, they have been proved to be an effective component in changing the packing parameters of the micelle composites. For example, 1,3,5trimethylbenzene (TMB) was utilized as a swelling agent in the synthesis of carbonaceous nanostructures with tunable pore sizes, that is, TMB molecules aggregated into hydrophobic cores regulating the volume of micelle composites, for which the packing parameters were controlled.…”