Ionothermal Synthesis and Structure Analysis of an Open‐Framework Zirconium Phosphate with a High CO₂/CH₄ Adsorption Ratio

Abstract

Less is more: an open-framework zirconium phosphate with unusual 7-ring channels was synthesized ionothermally from a deep-eutectic solvent. This small-pore material displays a CO(2)/CH(4) adsorption ratio (17.3 at 1 bar) that is significantly higher than that of typical 8-ring materials, making it highly attractive for CO(2)/CH(4) separations.

Synthesis, structure and characterization of ZrPOF-DEA, a microporous zirconium phosphate framework material

“…Although ZrPOF-DEA displays an adsorption capacity for CO 2 that is significantly higher than that for CH 4 (CO 2 /CH 4 adsorption ratio of 11.7 at 1 bar), this value is less than that found for the closely related ZrPOF-EA material (CO 2 /CH 4 = 17.3 [2]). The amount of CH 4 adsorbed at 1 bar is comparable for the two samples (0.058 mmol/g for ZrPOF-DEA and 0.054 mmol/g for ZrPOF-EA), but ZrPOF-DEA adsorbs only 0.679 mmol/g of CO 2 at 1 bar while ZrPOF-EA adsorbs 0.934 mmol/g.…”

“…3.8 Å), such as SAPO-34 (framework type CHA [1]), are used for this purpose. However, we recently reported the ionothermal synthesis of a microporous zirconium phosphate material, ZrPOF-EA, that can discriminate between CO 2 and CH 4 very well [2]. The structure analysis of that material showed that it has both 7-and 8-ring pore openings, and this clarifies why its adsorption capacity is markedly higher for the smaller CO 2 than for the larger CH 4 .…”

Quantum Chemical Insight into the Interactions and Thermodynamics Present in Choline Chloride Based Deep Eutectic Solvents

“…This salt is economically produced in large quantities and can be used with a variety of HDBs such as amides, carboxylic acids, glycols and phenols, thus offering a wide range of options. 10 The flexibility in DES composition and "the sustainable" nature of DES systems have broadened their applications into nanochemistry, 11 electrochemistry, 12,13 3 catalysis, 14 polymer synthesis, 15 gas separation, 16,17 generation of mesoporous carbons, 18 with chloride anion, and significant moderation in urea-urea and choline-chloride interaction energies, which resulted in a significant melting point depression for the DES mixture. 23 Similarly, Perkins et al made observations using MD simulations and infrared spectroscopy that suggested the presence of strong trans-type hydrogen-bonding interactions between the Cl -and urea to maximize the number of hydrogen bonds, leading to the low-melting nature of this DES.…”

Optimizing the input parameters for powder charge flipping

“…We have now tested this procedure on several data sets (Table 11), collected on both organic and inorganic materials, and it seems to work. The straightforward approach with = 0.3, B iso = 0-1, HM = 20-5, = AUTO , 500 cycles and 100 runs produced interpretable maps that could be identified with the R SF value for a Ba phenylboronate (novel structure, sample kindly provided by Danielle Laurencin, University of Montpellier, France), for the molecular sieve ZrPOF-EA (Liu et al, 2011), for two tricyanomethane derivatives (Š išak, McCusker, Buckl et al, 2010), and for the sugars dl-ribose (sample kindly provided by J. D. Dunitz, ETH Zurich) and d-arabinose (Takagi & Jeffrey, 1977). Three organic structures, all crystallizing in the space group P2 1 like d-ribose, required starting phases from an approximate model.…”

“…For example, phase information derived from high-resolution transmission electron microscopy (HRTEM) images can be added in reciprocal space, or a structure envelope (Brenner et al, 1997) can be imposed on the electron density map in real space. Although most applications to date have involved inorganic materials, in particular microporous solids (Dong et al, 2007;Liu et al, 2009Liu et al, , 2011Massü ger et al, 2007;Sun et al, 2009;Xie et al, 2009;Kubli et al, 2012), some organic compounds have also been studied (Baerlocher, McCusker & Palatinus, 2007;Š išak, McCusker, Buckl et al, 2010). Because the program is relatively new, the selection of input parameter values for the powder charge-flipping (pCF) algorithm in Superflip has necessarily been rather subjective and arbitrary.…”