Direct synthesis of ordered mesoporous materials from thermoplastic elastomers

Abstract

The ability to manufacture ordered mesoporous materials using low-cost precursors and scalable processes is essential for unlocking their enormous potential to enable advancement in nanotechnology. While templating-based methods play a central role in the development of mesoporous materials, several limitations exist in conventional system design, including cost, volatile solvent consumption, and attainable pore sizes from commercial templating agents. This work pioneers a new manufacturing platform for producing ordered mesoporous materials through direct pyrolysis of crosslinked thermoplastic elastomer-based block copolymers. Specifically, olefinic majority phases are selectively crosslinked through sulfonation reactions and subsequently converted to carbon, while the minority block can be decomposed to form ordered mesopores. We demonstrate that this process can be extended to different polymer precursors for synthesizing mesoporous polymer, carbon, and silica. Furthermore, the obtained carbons possess large mesopores, sulfur-doped carbon framework, with tailorable pore textures upon varying the precursor identities.

Precursor design for efficient synthesis of large-pore, sulfur-doped ordered mesoporous carbon through direct pyrolysis

“…SEBS required 4 h of reaction at 150 °C to achieve a fully MSDE Paper crosslinked state, confirmed by mass gain, gel fraction, and FTIR results. 26 The enhanced sulfonation-induced crosslinking reaction kinetics of the SBS precursors can be attributed to the presence of alkenes within their backbones. These functionalities can readily react to form intermolecular crosslinks, as double bonds are known to be more reactive than single bonds due to their more electron rich nature, which can also facilitate the installation of sulfonic acid groups along the polymer backbone.…”

“…Specifically, XPS survey scans in Fig. 7(A and B) depict sulfur contents of 0.6 at% and 1.4 at% for SBS100 and SBS150 samples, respectively, which are in a similar range compared to SEBS-derived OMCs, 26 as well as other functional carbon materials derived from semicrystalline polyolefin precursors, including polypropylene and polyethylene. 50,51 The level of sulfur content at 1.4 at% is close to other reports of synthesizing sulfur-doped OMCs through the use of dopants, such as benzyl disulfide, 52 thiophenol, 53 sulfur powders.…”

“…18 The application of thermoplastic elastomers (TPEs) as a new type of OMC precursor through direct pyrolysis approach has been very recently reported, providing an exciting new avenue to synthesize OMC using low-cost and widely available chemicals. 26 Generally, TPE-based BCPs contain a polyolefin majority phase and some high glass transition temperature (T g ) minority components, such as polystyrene.…”

Synergistic Adsorption and In Situ Catalytic Conversion of SO2 by Transformed Bimetal-Phenolic Functionalized Biomass

“…The N 2 adsorption–desorption isotherms were used to determine the specific surface area and pore size of the obtained materials. The Ti/Co–C NF nanofibers exhibited the characterization of a mixed type of I and IV, indicating that the Ti/Co–C NF samples have the multistage pore structure of micropores and mesopores (Figure b) . The pore size distributions of the Ti/Co–C NF nanofibers prepared by different mole ratios of Ti 4+ /Co 2+ ions were calculated by the Horvath–Kawazoe method (Figure c).…”

“…The Ti/Co−C NF nanofibers exhibited the characterization of a mixed type of I and IV, indicating that the Ti/Co−C NF samples have the multistage pore structure of micropores and mesopores (Figure 2b). 46 The pore size distributions of the Ti/Co−C NF nanofibers prepared by different mole ratios of Ti 4+ /Co 2+ ions were calculated by the Horvath−Kawazoe method (Figure 2c). Pore size distributions of all Ti/Co−C NF were found to be concentrated in the regions of micropores (1.2−2.0 nm) and mesopores (2.2−3.5 nm).…”