This paper demonstrates that nanospace engineering of KOH activated carbon is possible by controlling the degree of carbon consumption and metallic potassium intercalation into the carbon lattice during the activation process. High specific surface areas, porosities, sub-nanometer (<1 nm) and supra-nanometer (1-5 nm) pore volumes are quantitatively controlled by a combination of KOH concentration and activation temperature. The process typically leads to a bimodal pore size distribution, with a large, approximately constant number of sub-nanometer pores and a variable number of supra-nanometer pores. We show how to control the number of supra-nanometer pores in a manner not achieved previously by chemical activation. The chemical mechanism underlying this control is studied by following the evolution of elemental composition, specific surface area, porosity, and pore size distribution during KOH activation and preceding H(3)PO(4) activation. The oxygen, nitrogen, and hydrogen contents decrease during successive activation steps, creating a nanoporous carbon network with a porosity and surface area controllable for various applications, including gas storage. The formation of tunable sub-nanometer and supra-nanometer pores is validated by sub-critical nitrogen adsorption. Surface functional groups of KOH activated carbon are studied by microscopic infrared spectroscopy.
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http://dx.doi.org/10.1088/0957-4484/23/1/015401 | DOI Listing |
ACS Nano
January 2025
Creative Research Initiative Center for Nanospace-confined Chemical Reactions (NCCR), Pohang University of Science and Technology (POSTECH), Pohang 37673, Korea.
Unlike homogeneous metal complexes, achieving absolute control over reaction selectivity in heterogeneous catalysts remains a formidable challenge due to the unguided molecular adsorption/desorption on metal-surface sites. Conventional organic surface modifiers or ligands and rigid inorganic and metal-organic porous shells are not fully effective. Here, we introduce the concept of "ligand-porous shell cooperativity" to desirably reaction selectivity in heterogeneous catalysis.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Light-driven spin hyperpolarization of organic molecules is a crucial technique for spin-based applications such as quantum information science (QIS) and dynamic nuclear polarization (DNP). Synthetic chemistry provides the design of spins with atomic precision and enables the scale-up of individual spins to hierarchical structures. The high designability and extended pore structure of metal-organic frameworks (MOFs) can control interactions between spins and guest molecules.
View Article and Find Full Text PDFACS Nano
January 2025
Department of Chemical and Biomolecular Engineering, National University of Singapore, 117585 Singapore.
C aromatic isomers, namely para-xylene (PX), meta-xylene (MX), ortho-xylene (OX), and ethylbenzene (EB), are essential industrial chemicals with a wide range of applications. The effective separation of these isomers is crucial across various sectors, including petrochemicals, pharmaceuticals, and polymer manufacturing. Traditional separation methods, such as distillation and solvent extraction, are energy-intensive.
View Article and Find Full Text PDFAdv Mater
December 2024
Department of Materials Science and Engineering, Korea University, Seoul, 02841, Republic of Korea.
Graph theory has been widely used to quantitatively analyze complex networks of molecules, materials, and cells. Analyzing the dynamic complex structure of extracellular matrix can predict cell-material interactions but has not yet been demonstrated. In this study, graph theory-based mathematical modeling of RGD ligand graph inter-relation is demonstrated by differentially cutting off RGD-to-RGD interlinkages with flexibly conjugated magnetic nanobars (MNBs) with tunable aspect ratio.
View Article and Find Full Text PDFChemistry
December 2024
Department of Applied Chemistry, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
Two-dimensional (2D) polymer network monolayers with novel block architectures were fabricated via sequential copolymerization within a pillared-layer metal-organic framework (MOF) that served as the reaction template. The MOF provides a confined 2D nanospace, restricting the crosslinking copolymerization of vinyl monomers to two dimensions. Sequential crosslinking copolymerization of methyl methacrylate and styrene, regulated by the reversible addition-fragmentation chain transfer (RAFT) process, resulted in the formation of 2D block architectures with 'patchy' domains consisting of crosslinked poly(methyl methacrylate) and polystyrene segments.
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