Varying the Hydrogen Bonding Strength in Phenolic/PEO‐b‐PLA Blends Provides Mesoporous Carbons Having Large Accessible Pores Suitable for Energy Storage

Abstract

as efficient electron transfer media to improve the performance of electric double-layer capacitors (EDLCs). [9] Furthermore, the blending of a self-assembled block copolymer with the carbon source (e.g., phenolic resin) is becoming more widespread. This method has the advantage of providing well-ordered mesoporous structures that can be used efficiently in various applications. [10,11] Typically, a block copolymer that forms a self-assembled structure is mixed with a carbon source to obtain various dimensional carbon structures. The blending of a commercial Pluronic-type triblock copolymer, such as poly(ethylene oxide-b-propylene oxideb-ethylene oxide), as the template is the method used most widely to prepare mesoporous materials. [12][13][14][15][16][17][18][19] Because of limitations in molecular weight and composition, it can, however, be difficult to prepare mesoporous materials having pore sizes of greater than 10 nm when using Pluronic-type triblock copolymers. Block copolymers featuring long hydrophobic segments and high molecular weight-for instance, poly(ethylene oxideb-styrene) (PEO-b-PS) [20,21] and poly(ethylene oxide-b-methyl methacrylate) (PEO-b-PMMA) [22] -are promising candidates as templates to prepare large-pore-size mesoporous carbons. For example, Zhao et al. prepared mesoporous carbons with long-range order, large surface areas (>1500 m 2 g −1 ), and large pores (≈23 nm) when using PEO 125 -b-PS 230 as the template as displayed in Scheme S1a-c in the Supporting Information. [21] With PEO 125 -b-PMMA 114 as the template, they obtained mesoporous carbons having large surface areas (>1500 m 2 g −1 ) and pores (≈10 nm) [22] when applying resol as the carbon source. Mesoporous carbons with smaller pores but thicker walls were obtained when using PEO-b-PMMA as the template, rather than PEO-b-PS, because the phenolic OH units could interact strongly with the PEO segment (interassociation equilibrium constant (K A ) = 286) [23] and weakly with the PMMA CO units (K A = 20) [24,25] through hydrogen bonding, but not with the hydrophobic PS segment. Indeed, the PS block segment would undergo complete microphase In this study, mesoporous carbons are prepared by using a resol-type phenolic resin as the carbon source and poly(ethylene oxide-b-lactic acid) (PEO-b-PLA) copolymer as the template, with a process of thermal curing, calcination, carbonization, and activation. The structures of these mesoporous carbons are strongly influenced by the self-assembled structures formed from phenolic/PEO-b-PLA blends, varying from double-gyroid, to cylinder, and finally to spherical micelle structures upon increasing the phenolic concentrations. The large pores (>20 nm) and high surface areas (>1000 m 2 g −1 ) of these activated mesoporous carbons arise because the phenolic resin interacts only with the PEO segment (i.e., not with the PLA segment) through hydrogen bonding; thus, the relative wall thickness of the phenolic matrix decreases after template removal (thereby increasing the pore size), similar to the beha...

Multifunctional Polyhedral Oligomeric Silsesquioxane (POSS) Based Hybrid Porous Materials for CO2 Uptake and Iodine Adsorption

“…The preparation of porous organic polymers (POPs) has become a hot topic in the academic and industry fields due to their interesting features, such as high physicochemical stability, porous character, low density, facile preparation, low regeneration energy, and good thermal and chemical stabilities [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 ]. Porous organic polymers have been applied in different applications such as light harvesting, chemical sensors, catalysis, iodine uptake, H 2 production from water, water treatment, optoelectronic devices, carbon dioxide reduction, nanofiltration, enantioseparation, energy storage, gas separation, and adsorption [ 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 ]. The synthesis of POPs was successfully achieved using various synthetic methods, including Friedel–Crafts arylation, Schiff base reactions, Suzuki reactions, Yamamoto reactions, Heck reactions, and Sonogashira reactions [ 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 ].…”

Meso/Microporous Carbons from Conjugated Hyper-Crosslinked Polymers Based on Tetraphenylethene for High-Performance CO2 Capture and Supercapacitor

“…Nowadays, the preparation of porous carbon materials has attracted much attention due to their interesting properties such as excellent electrical conductivity, high surface areas and high pore volumes, and good chemical, thermal, and mechanical stabilities [ 55 , 56 , 57 , 58 , 59 ]. Therefore, porous carbonaceous materials have been applied in many real-life applications, for example catalysis, gas separation, gas capture, energy storage in supercapacitors and batteries, fuel cells, water treatment and purification, and electromagnetic interface shielding [ 60 , 61 , 62 , 63 , 64 ]. As reported, the preparation of porous carbonaceous materials with high surface area and excellent porosity nature can be achieved by chemical activation for many polymers’ precursors, for example conjugated microporous polymers (CMPs), metal-organic frameworks (MOFs), HCPs, and porous aromatic frameworks (PAFs) [ 62 , 63 , 64 ].…”

Advances in porous organic polymers: syntheses, structures, and diverse applications

“…[2][3][4][5][6][7][8][9][10][11][12][13][14] Based on the IUPAC classification, porous materials can be divided, based on their pore diameters, into microporous (<2 nm), mesoporous (>2 nm and <50 nm), and macroporous (>50 nm) materials. [15][16][17][18][19][20][21][22] Many various porous materials have been constructed from metal-organic frameworks (MOFs) and porous organic polymers (POPs). 1,[23][24][25][26][27][28] MOFs are typically crystalline porous materials or porous coordination polymers obtained through the formation of coordinate bonds between organic ligands and clusters or metal ions to form voids within the framework structure, thereby resulting in porosity.…”