Heat capacities and spontaneous enthalpy-relaxation effects of the benzene confined in silica MCM-41 and SBA-15 pores with uniform diameters were measured by high-precision adiabatic calorimetry. The fusion temperatures and fusion enthalpies determined were compared with the literature results of benzene confined within pores of CPG glasses. It was confirmed, from the observed spontaneous heat-release or -absorption effects, that there exists a non-crystallizing amorphous component of confined benzene, as reported previously. The pore-diameter dependence of fusion enthalpy observed was inconsistent with the previously proposed model which suggested that the non-crystallizing amorphous component is located on the pore wall in the form of a shell-like structure of a few nm in thickness. A very slow relaxation process corresponding to a translational-diffusion motion of molecule was observed, indicating that the benzene fills the pores incompletely along the pore channel. In addition, we found that the fusion enthalpy as a function of inverse pore-diameter dependence decreases steeply in the range of 60-10 nm in diameter while gradually in the range around 5 nm.
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http://dx.doi.org/10.1088/0953-8984/27/10/105101 | DOI Listing |
Phys Chem Chem Phys
January 2025
School of Mechanical & Vehicle Engineering, Linyi University, Linyi, Shandong 276000, China.
Molecular dynamics simulations demonstrate that regular conical helices of poly(-phenylene) (PPP) chains can be constructed inside the confined space of single-walled carbon nanocones (CNCs). The translocation displacement of the PPP chain combined with the change of the system total potential energy including each energy component and structural parameters of the formed conical helix is discussed to deeply explore the microstructure evolution, driving forces and dynamic mechanisms. In addition, the influence of chain length, cone angle, temperature, chain number, linked position of benzene rings and the form of Lennard-Jones potential on the helical encapsulation is further studied.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
School of Engineering, Westlake University, Hangzhou 310024, Zhejiang Province, China.
The Friedel-Crafts reaction has been extensively applied to the preparation of various porous organic polymers because of its simple operation and abundant building blocks. However, due to its poor reversibility and excessive random reactive sites, the synthesis of crystalline organic polymers/frameworks by Friedel-Crafts reaction has never been realized so far. Herein, we develop a molecular confined Friedel-Crafts reaction strategy to achieve rapid preparation (within only 30 minutes) of highly crystalline covalent triazine frameworks (CTFs) with tailorable functionality for the first time.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
State Key Laboratory of Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 500, Dongchuan Road, Shanghai, 200241, China.
JACS Au
November 2024
Materials Discovery Laboratory, Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, United States.
Capturing carbon dioxide from diluted streams, such as flue gas originating from natural gas combustion, can be achieved using recyclable, humidity-resistant porous materials. Three such materials were synthesized by chemically modifying the pores of metal-organic frameworks (MOFs) with Lewis basic functional groups. These materials included aluminum 1,2,4,5-tetrakis(4-carboxylatophenyl) benzene (Al-TCPB) and two novel MOFs: Al-TCPB(OH), and Al-TCPB(NH), both isostructural to Al-TCPB, and chemically and thermally stable.
View Article and Find Full Text PDFSmall
January 2025
Department of Environmental Science, Zhejiang University, Hangzhou, 310058, China.
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