At the nanoscale the positions of coexistence lines on the phase diagrams are shifted and their new locations depend mainly on the size and shape of the nano-confinement, the structure of the confining walls, and their interaction with the confined substance. Here 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 adsorption sites [1,2]. The confined, equilibrium structures are not characterized by mean positions of molecules but rather by a probability distribution of molecular positions around adsorption centres. This distribution changes when the number of molecules in the pore increases. The character of transformation is temperature dependent: strongly discontinuous at low temperature, it evolves into a continuous transition when the temperature increases. The mechanism of the transformation is also modified when the size of the gas molecules and types of interaction change. In particular, we report the existence of the intermediate phase, observed only above a critical strength of the attractive interactions. 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.

Unlike macroscopic objects, any system of nanometric size shows characteristics that strongly depend on its size and geometric form. It is the consequence of the fact that the major part of atoms (or molecules) of nano-object is located at its surface, and their cohesive energy is smaller than for the atoms in the bulk. Here we show that when a fluid is confined in nano-volume, delimited by non-interacting pore walls, its density is heterogeneous, decreases close to the pore wall, and, on average, is smaller than the density of bulk fluid. The heterogeneity of distribution of fluid density, resulting from the nano-confinement, progressively weakens when the pore size increases, and totally disappears for pores larger than 5 nm. On the other side, in the limit of very small pores, the fluid density approaches the ideal gas value. This effect should be distinguished from the well know heterogeneity of density of fluids adsorbed in nanopores, driven by the difference between the strength of fluid-fluid and fluid-pore wall interactions, that varies with the distance from the pore wall. The reported observation has non-trivial influence on evaluation of excess/total adsorption in nanopores, as these two quantities are calculated assuming the known – and homogeneous – bulk density of gas in the pore. Additionally, the gas density in the pores depends on the definition of the pore volume which is neither straightforward nor unique. The right estimation of both: pore volume and gas density is essential for quantitative interpretation of experimental adsorption isotherms: evaluation of pore size distribution and of the amount of adsorbed gas. We analyze this problem on an example of five gases: H2, CH4, the two intensively studied energy vectors, and N2, Ar, and Kr, commonly used for characterization of porous structures. For H2, the distributions of densities of gas confined in adsorbing and not adsorbing pores are compared and commented. This work was supported by the French National Research Agency ANR, grant HYSTOR no. ANR-14-CE05-0009.

Unlike macroscopic objects, any system of nanometric size shows characteristics that strongly depend on its size and geometric form. It is the consequence of the fact that the major part of atoms (or molecules) of nano-object is located at its surface, their cohesive energy is smaller than for the atoms in the bulk. Here we show that when a fluid is confined in nano-volume, delimited by non-interacting pore walls, its density is heterogeneous, decreases close to the pore wall, and, on average, is smaller than the density of bulk fluid. The heterogeneity of distribution of fluid density, resulting from the nano-confinement, progressively weakens when the pore size increases, and totally disappears for pores larger than 5 nm. On the other side, in the limit of very small pores, the fluid density approaches the ideal gas value. This effect should be distinguished from the well know heterogeneity of density of fluids adsorbed in nanopores, driven by the difference between the strength of fluid-fluid and fluid-pore wall interactions, that varies with the distance from the pore wall. The reported observation has non-trivial influence on evaluation of excess/total adsorption in nanopores, as these two quantities are calculated assuming the known – and homogeneous – bulk density of gas in the pore. Additionally, the gas density in the pores depends on the definition of the pore volume which is neither straightforward nor unique. The right estimation of both: pore volume and gas density is essential for quantitative interpretation of experimental adsorption isotherms: evaluation of pore size distribution and of the amount of adsorbed gas. We analyze this problem on an example of five gases: H2, CH4, the two intensively studied energy vectors, and N2, Ar, and Kr, commonly used for characterization of porous structures. For H2, the distributions of densities of gas confined in adsorbing and not adsorbing pores are compared and commented.

At the nanoscale the positions of coexistence lines on the phase diagrams are shifted and their new locations depend mainly on the size and shape of the nano-confinement, the structure of the confining walls, and their interaction with the confined substance. Here 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 adsorption sites1,2.The confined, equilibrium structures are not characterized by mean positions of molecules but rather by a probability distribution of molecular positions around adsorption centres. This distribution transforms when the number of molecules in the pore increases. The character of transformation depends on temperature: it is strongly discontinuous at low temperature but evolves into a continuous transition when the temperature increases. Here we show how the mechanism of the transformation is modified by temperature and also by different types of interaction and the size of the gas molecules. In particular, the existence of the intermediate phase is observed only above a critical strength of the attractive interactions.

Phase changes are ubiquitous in nature, and transformations between solid structures represent a large group of them. They are usually reported on phase diagrams, as coexistence lines between different structures. The phase diagrams, well established for macroscopic 3-dimensional (3D) materials, change drastically when the material’s dimensions are reduced to few nanometers, or if the material is confined in a nano-pore. At the nanoscale the positions of coexistence lines on the phase diagrams are shifted and their new locations depend mainly on the size and shape of the nano-confinement, the structure of the confining walls, and their interaction with the confined substance. Here 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 that of well-known capillary condensation. The confined, equilibrium structures are not characterized by mean positions of molecules but rather by a probability distribution of molecular positions around adsorption centres. The character of transformation depends on temperature: it is strongly discontinuous at low temperature but evolves into a continuous transition when the temperature increases.

A molecular machine, or nanomachine, refers to any nano-sized system that produces quasi-mechanical movements (output) in response to a specific stimuli (input). Nano-engineering is today a rapidly growing, innovative field of science and technology. The 2016 Nobel Prize in Chemistry recompensing the chemical research effort in this area confirmed that engineering of the nano-machines is not any more an object of science-fiction stories. We are at the advent of new engineering methodology, in which the nano-systems can be numerically designed and chemically synthesized. In order to construct a complex machine, several challenging problems must be solved. First, a number of pre-assembled building blocks have to be prepared, as the function of the device is intended to be a consequence of their assembly. Furthermore, to obtain a predetermined function of the machine, this assembly should provide a possibility to precisely controlled translational and rotational movements of the machine components, stimulated by an inflow of external energy. The machine also needs an interface with its environment. Ultimately, it should be able to overcome thermal fluctuation (Brownian motion) that influences its mechanical action, and to operate out of equilibrium in dissipative systems, when controlled and driven by an external fueling, by light or other energy source.Starting from Richard Feynman prediction from 1984 that it would be possible to build machines with nanometric dimensions we show how the notion of the nano-machine has evolved during the last century. In 1983 chemists succeeded to produce molecular chains, catenanes, in which ring-shaped molecules were linked together by mechanical bonds, but the interlocked molecules did not form any intermolecular, strong covalent bonds. The catenanes were not only a new class of macromolecules: they also represented the first step towards creating a molecular machine. Then, in 1994 a rotaxane, a ring-shaped molecule that is mechanically attached to an axle has been created. The first molecular motor was proposed in 1999. Since then the rotaxane has been used to construct numerous molecular machines, including a molecular elevator, which can raise itself 0.7 nanometers above a surface, and an artificial muscle (2000), that is able to bend a very thin gold lamina. Many new ideas have been published and many new systems have been already synthesized. This presentation will be focused on the nanomachines in which the light is used as a photonic factor actuating and allowing control of the nano-machines movements.