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Cychosz K.A.,Quantachrome Instruments | Guillet-Nicolas R.,Quantachrome Instruments | Garcia-Martinez J.,University of Alicante | Thommes M.,Quantachrome Instruments
Chemical Society Reviews | Year: 2017

This review focuses on important aspects of applying physisorption for the pore structural characterization of hierarchical materials such as mesoporous zeolites. During the last decades major advances in understanding the adsorption and phase behavior of fluids confined in ordered nanoporous materials have been made, which led to major progress in the physisorption characterization methodology (summarized in the 2015 IUPAC report on physisorption characterization). Here we discuss progress and challenges for the physisorption characterization of nanoporous solids exhibiting various levels of porosity from micro- to macropores. While physisorption allows one to assess micro- and mesopores, a widely employed method for textural analysis of macroporous materials is mercury porosimetry and we also review important insights associated with the underlying mechanisms governing mercury intrusion/extrusion experiments. Hence, although the main focus of this review is on physical adsorption, we strongly emphasize the importance of combining advanced physical adsorption with other complementary experimental techniques for obtaining a reliable and comprehensive understanding of the texture of hierarchically structured materials. © 2017 The Royal Society of Chemistry.


Gor G.Y.,Rutgers University | Gor G.Y.,Princeton University | Thommes M.,Quantachrome Instruments | Cychosz K.A.,Quantachrome Instruments | Neimark A.V.,Rutgers University
Carbon | Year: 2012

Quenched solid density functional theory (QSDFT) model for characterization of mesoporous carbons using nitrogen adsorption is extended to cylindrical and spherical pore geometries. The kernels of theoretical isotherms in the range from 0.4 to 50 nm are constructed accounting for different possible variations of the pore shapes in micropore and mesopore regions. The results of QSDFT method are illustrated with experimental data on adsorption on novel CMK-3 and 3DOm carbons. The proposed method is recommended for pore size distribution calculations for micro-mesoporous carbons obtained through various templating mechanisms. © 2011 Elsevier Ltd. All rights reserved.


Xu Y.,University of Maryland University College | Wen Y.,University of Maryland University College | Zhu Y.,University of Maryland University College | Gaskell K.,University of Maryland University College | And 4 more authors.
Advanced Functional Materials | Year: 2015

The use of sulfur in the next generation Li-ion batteries is currently precluded by its poor cycling stability caused by irreversible Li2S formation and the dissolution of soluble polysulfides in organic electrolytes that leads to parasitic cell reactions. Here, a new C/S cathode material comprising short-chain sulfur species (predominately S2) confined in carbonaceous subnanometer and the unique charge mechanism for the subnano-entrapped S2 cathodes are reported. The first charge-discharge cycle of the C/S cathode in the carbonate electrolyte forms a new type of thiocarbonate-like solid electrolyte interphase (SEI). The SEI coated C/S cathode stably delivers ≈600 mAh g-1 capacity over 4020 cycles (0.0014% loss cycle-1) at ≈100% Coulombic efficiency. Extensive X-ray photoelectron spectroscopy analysis of the discharged cathodes shows a new type of S2 species and a new carbide-like species simultaneously, and both peaks disappear upon charging. These data suggest a new sulfur redox mechanism involving a separated Li+/S2- ion couple that precludes Li2S compound formation and prevents the dissolution of soluble sulfur anions. This new charge/discharge process leads to remarkable cycling stability and reversibility. © 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.


Min B.-H.,Inha University | Jeong E.-Y.,Inha University | Thommes M.,Quantachrome Instruments | Park S.-E.,Inha University
Chemical Communications | Year: 2011

Plugged mesoporous SBA-15 having a 2-D hexagonal pore structure could be directly synthesized under acidic conditions using P123 as a supramolecular template, sodium metasilicate and alcoholamines. The use of alcoholamines seemed to play roles as capturing agents for silica sources that could form internal porous plugs. © The Royal Society of Chemistry 2011.


Kleitz F.,Laval University | Berube F.,Laval University | Guillet-Nicolas R.,Laval University | Yang C.-M.,National Tsing Hua University | Thommes M.,Quantachrome Instruments
Journal of Physical Chemistry C | Year: 2010

In order to investigate the details of the process of pore condensation and hysteresis mechanisms in three-dimensional (3-D) pore networks, we performed a systematic study of the adsorption and pore condensation behavior of N 2 (77.4 K) and Ar (77.4 and 87.3 K) in a 3-D ordered pore system, i.e., cubic Ia3̄d mesoporous KIT-6 silica materials with mode pore diameters ranging from ca. 5 nm up to 11 nm. KIT-6 silica is a porous material composed of two intertwined mesoporous subnetworks similar as in MCM-48, but this material can be prepared with much larger mean pore diameters. Accurate pore size analysis was performed by X-ray diffraction modeling and by state-of the art application of nonlocal density functional theory (NLDFT) on N 2 (77.4 K) and Ar (87.3 K) sorption data. Furthermore, our data suggest that the width of the adsorption/desorption hysteresis loop observed for 3-D KIT-6 silica can be narrower as compared to that of pseudo-one-dimensional SBA-15 silica of the same pore size (i.e., in the pore diameter range from 6 to 8 nm). This specific behavior correlates well with the existence of the highly interconnected 3-D pore network of the KIT-6 material. Moreover, the results of our investigations are also consistent with previous observations that the SBA-15 pore system becomes more and more interconnected with increasing aging temperatures, i.e., SBA-15 changes from being a material with a pseudo-one-dimensional mesopore system to a material exhibiting a three-dimensional pore system resembling KIT-6 silica. These results provide new insights into the effects of pore interconnectivity on pore condensation and hysteresis behavior in both KIT-6 and SBA-15 silica materials and enable a more thorough understanding of the pore structure and textural properties of these materials. © 2010 American Chemical Society.


Thommes M.,Quantachrome Instruments | Morell J.,University of Hamburg | Cychosz K.A.,Quantachrome Instruments | Froba M.,University of Hamburg
Langmuir | Year: 2013

Ordered mesoporous CMK carbons and periodic mesoporous organosilica (PMO) materials have been characterized by combining nitrogen (77.4 K) and argon (87.3 K) adsorption with recently developed quenched solid density functional theory (QSDFT). Systematic, high-resolution water adsorption experiments have been performed in the temperature range from 298 to 318 K in order to ascertain the effect of surface chemistry (using periodic mesoporous organosilicas (PMOs) of given pore size) and pore size/pore geometry (using CMK-3, CMK-8 carbons) on the adsorption, pore filling, condensation and hysteresis behavior. These data reveal how the interplay between confined geometry effects and the strength of the adsorption forces influence the adsorption, wetting, and phase behavior of pore fluids. Further, our results indicate that water adsorption is quite sensitive to both small changes in pore structure and surface chemistry, showing the potential of water adsorption as a powerful complementary tool for the characterization of nanoporous solids. © 2013 American Chemical Society.


Silvestre-Albero J.,Instituto Universitario Of Materiales | Silvestre-Albero A.,Instituto Universitario Of Materiales | Rodriguez-Reinoso F.,Instituto Universitario Of Materiales | Thommes M.,Quantachrome Instruments
Carbon | Year: 2012

In order to get more insight into the characterization of nanoporous carbons by gas adsorption, the use of different probe molecules has been compared. A series of activated carbons with ranging porosity (burn-off) have been prepared from olive stones using CO 2 as activating agent and characterized using nitrogen and argon adsorption at low temperature (77.4 K for N 2 and 87.3 K for Ar) together with CO 2 adsorption at 273 K and immersion calorimetry into liquids of different molecular dimensions. Experimental results show that argon adsorption in narrow carbon micropores takes place at a higher relative pressure compared to nitrogen due to a weaker effective adsorption potential (lower strength of dispersion forces), including the absence of specific interactions of argon with the adsorbent surface. We show further that application of advanced theoretical approaches based on the density functional theory (NLDFT and QSDFT) provides an accurate description of the pore-size distribution (PSD). The PSD obtained from the argon adsorption data at 87.3 K is in good agreement with immersion calorimetry measurements. Our results demonstrate that argon adsorption at 87.3 K in combination with the application of advanced DFT methods (e.g. QSDFT) allows for a reliable characterization of the narrow microporosity in highly heterogeneous activated carbons. © 2011 Elsevier Ltd. All rights reserved.


Thommes M.,Quantachrome Instruments | Mitchell S.,Institute for Chemical and Bioengineering | Perez-Ramirez J.,Institute for Chemical and Bioengineering
Journal of Physical Chemistry C | Year: 2012

Advanced physicochemical characterization of the pore structure of hierarchical zeolites, including the precise knowledge of pore size, interconnectivity, and surface properties, is crucial in order to interpret their superior performance in catalytic and adsorption applications. Postsynthetic mesopore formation by alkaline treatment of zeolites leads to simultaneous compositional changes due to the selective dissolution of silicon. By careful tuning of these effects through subsequent acid treatment, the Si/Al ratio can be restored to that of the parent zeolite. We evaluate the application of argon (87.3 K) and water (298.5 K) adsorption to assess the porous properties of mesoporous ZSM-5 zeolites with equivalent porosity, but differing composition. An accurate and combined micro/mesopore size analysis is obtained by applying NLDFT (nonlocal density functional theory) analysis on the argon isotherms. The argon adsorption data clearly reveal the two different relative pressure regions of micro- and mesopore filling of hierarchical zeolites. In contrast, the two filling regions overlap upon adsorption of water due to the hydrophobic nature of the ZSM-5 micropores and the much more hydrophilic nature of the mesopores. This indicates that water adsorption is sensitive to the Si/Al ratio, the distribution of aluminum species in the zeolite, and to the presence of polar groups on the mesopore surface. Thus, further insights into the surface and structural properties of the pores in hierarchical zeolites prepared by desilication can be gained. Based on our results, we put forward a hydrophilicity index capable of identifying differences in surface chemistry between distinct porous materials, and also between the micro- and mesopores present within hierarchically structured nanoporous materials. © 2012 American Chemical Society.


Thommes M.,Quantachrome Instruments | Cychosz K.A.,Quantachrome Instruments
Adsorption | Year: 2014

Within the last two decades major progress has been achieved in understanding the adsorption and phase behavior of fluids in ordered nanoporous materials and in the development of advanced approaches based on statistical mechanics such as molecular simulation and density functional theory (DFT) of inhomogeneous fluids. This progress, coupled with the availability of high resolution experimental procedures for the adsorption of various subcritical fluids, has led to advances in the structural characterization by physical adsorption. It was demonstrated that the application of DFT based methods on high resolution experimental adsorption isotherms provides a much more accurate and comprehensive pore size analysis compared to classical, macroscopic methods. This article discusses important aspects of major underlying mechanisms associated with adsorption, pore condensation and hysteresis behavior in nanoporous solids. We discuss selected examples of state-of-the-art pore size characterization and also reflect briefly on the existing challenges in physical adsorption characterization. © 2014 Springer Science+Business Media New York.


Peterson G.R.,Texas Tech University | Cychosz K.A.,Quantachrome Instruments | Thommes M.,Quantachrome Instruments | Hope-Weeks L.J.,Texas Tech University
Chemical Communications | Year: 2012

We describe the simple preparation of nitrocellulose gels and high surface area (300 + m 2 g -1) aerogels and their hierarchical pore structures. The solvent in which the gels form greatly influences the pore geometry and size distribution of the gels in both the macro- and mesopore domains. © 2012 The Royal Society of Chemistry.

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