Carbon-based dots (CDs) are a novel class of luminescent carbon nanomaterials that have attracted much attention as promising alternatives for cadmium-based quantum dots and fluorescent organic dyes. Although different strategies have been proposed to produce CDs with intense and tuneable one-photon excited fluorescence (OPEF), the case of analogous two-photon excited fluorescence (TPEF) has not been fully explored yet. By varying the synthesis conditions, we produced three types of phloroglucinol-based carbon nanodots (PG CNDs). Their remarkable OPEF and TPEF properties can be tuned by (Ia) the conjugated aromatic domains and (Ib) the content of oxygenous moieties. In addition, the emission colour of the PG CNDs is strongly responsive to (II) the hydrogen-bonding network, enabling colour-switching while maintaining excellent fluorescence yields (both OPEF and TPEF). These three factors were evaluated for their suitability for the tuning of the emission colour. Our studies point out the advantages of the tuneable PG CNDs to be used in optoelectronics and biological application domains.

We report a microscopic model of the phonon-adsorption correlations in flexible metal−organic framework materials. We analyze the mechanism of the gate opening deformation using the notion of coupled phonon- and adsorption-induced structural transformation. Using the ZIF-8 structure as an example, we perform an analysis of transformation-related, low-frequency phonon modes of the framework.On the basis of structure-related quantities such as pore limiting diameter, void fraction, and adsorption uptake, we determine the conditions which lead to the gate opening transformation in ZIF-8. Energetic landscape of the deformation process is analyzed using grand thermodynamic potential of adsorption. We generalize our conclusions to other flexible ZIF structures with the same topology.

Competitive adsorption of water is an important issue in the adsorption-based industrial processes of bio- and flue gases separation. The dehumidification of gases prior to separation would increase process complexity and lower its economic interest. In this work, large-scale computational screening was applied to identify Metal-Organic Frameworks (MOFs) structures which exhibit high CO2/CH4 selectivity and total loading higher than 0.5 mol/kg (in the presence of water). High-throughput Grand Canonical Monte Carlo (GCMC) screening of nearly 3000 existing MOF materials was carried out. Initial selection assumed fixed values of pore limiting diameter (PLD) and Henry's constant for water and allowed one to preselect 764 structures. After GCMC simulations carried for 50/50 CO2/CH4 mixture, at ambient conditions (p = 1 bar, T = 298 K), and variable gas humidity (0%, 5%, 30% and 40%) the final selection revealed 13 most promising MOFs structures. We focused on analysis of the correlations between the properties of the selected MOFs and the separation selectivity. We show that the selectivity is a complex function of the porous materials characteristics and finding selective sorbent, performing well in dry and wet conditions requires careful analysis of available MOFs.

Soft porous crystals undergo large structural transformations under a variety of physical stimuli. Breathing-like transformations, occurring with a large volume change, have been associated with an existence of bi-stable or multi-stable crystal structures. Here, we provide a detailed, multiscale qualitative and quantitative analysis of the adsorption-induced “breathing” transformations in two metal organic frameworks (MOFs): MIL-53(Al) which is a reference case of our approach, and recently synthetized JUK-8, which does not show any bistability without adsorbate. The proposed approach is based on atomistic simulations and does not require any empirical or adjustable parameters. It allows for a prediction of potential structural transformations in MOF and, in the case of adsorption-induced deformations, a calculation of the adsorption stress. We also show that the quantitative agreement between calculated and experimental results critically depends on the quality of the dispersion energy correction.

We discuss the mechanism of the structural transformations of gas adsorbed in microporous crystalline solids. We show that it is possible to induce structural transformations in a confined system by simply varying the number of molecules adsorbed in the pore. We found that the mechanism of these novel, adsorption-induced structural transformation in nano-pores differs from the capillary condensation. First, the structure of the confined gas is determined by a competition between adsorption sites attractive forces and intermolecular interaction. Second, at low temperature, the transformation is discontinuous because it is defined by limited number of accessible adsorption sites [1,2]. In the case of methane adsorbed in IRMOFs porous structures the character of transformation depends on temperature but also on the IRMOF structure: it changes from strongly discontinuous (especially at low temperatures), to continuous transition. The mechanism of the transformation is also modified by the size of the gas molecules and the strength of interaction. However, even discontinuous transition can produce continuous isotherms. We will show that the continuous isotherm can be the effect of statistical dynamical switching between two phase, characterized by different number of adsorbed molecules. We show the simulated microscopic mechanism and experimental observations support such statistical interpretation. This work was supported by the Polish National Science Centre (NCN, grant no. 2015/17/B/ST8/00099). The calculations have been partially performed at the WCSS computer center of The Wroclaw University of Science and Technology, grant no 33.References[1] Heterogeneous melting of methane confined in nano-pores. Dundar, E.; Boulet, P.; Wexler, C.; et al. J. Chem. Phys. 145, 144704 (2016)[2] Adsorption-Induced Structural Phase Transformation in Nanopores. Kuchta, Bogdan; Dundar, Ege; Formalik, Filip; et al. Angewandte Chimie In. Ed. 56, 16243–16246. (2017)