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The process of carbon capture and sequestration has been proposed as a method of mitigating the build-up of greenhouse gases in the atmosphere. If implemented, the cost of electricity generated by a fossil fuel-burning power plant would rise substantially, owing to the expense of removing CO 2 from the effluent stream. There is therefore an urgent need for more efficient gas separation technologies, such as those potentially offered by advanced solid adsorbents. Here we show that diamine-appended metal-organic frameworks can behave as ‘phase-change’ adsorbents, with unusual step-shaped CO 2 adsorption isotherms that shift markedly with temperature. Results from spectroscopic, diffraction and computational studies show that the origin of the sharp adsorption step is an unprecedented cooperative process in which, above a metal-dependent threshold pressure, CO 2 molecules insert into metal-amine bonds, inducing a reorganization of the amines into well-ordered chains of ammonium carbamate. As a consequence, large CO 2 separation capacities can be achieved with small temperature swings, and regeneration energies appreciably lower than achievable with state-of-the-art aqueous amine solutions become feasible. The results provide a mechanistic framework for designing highly efficient adsorbents for removing CO 2 from various gas mixtures, and yield insights into the conservation of Mg 2+ within the ribulose-1,5-bisphosphate carboxylase/oxygenase family of enzymes. A cooperative insertion mechanism for CO 2 adsorption is shown to generate highly efficient adsorbents for carbon capture applications. Efficient CO 2 absorption in a metal-organic framework Advanced solid adsorbents are being investigated as potential agents for efficient gas separation technologies that could help make carbon capture technologies more economical. This paper probes the mechanism of carbon dioxide adsorption of a previously reported diamine-appended metal-organic framework. This material demonstrates unusual and potentially practically useful adsorption properties. The authors find that CO 2 adsorbs through insertion into the highly stable metal-amine bonds of the metal-organic framework. As a consequence of the homogenous and perfect spacing of amines, as dictated by the framework's topology, the insertion of a single CO 2 molecule induces neighbouring sites to also adsorb CO 2 in an unprecedented chain reaction process.

The inevitable nexus between energy use and CO2 emission necessitates the development of sustainable energy systems. The conversion of CO2 to CH4 using green H2 in power-to-gas applications in such energy systems has attracted much interest. In this context, the present study provides a thermodynamic insight into the effect of water removal on CO2 conversion and irreversibility within a CO2 methanation reactor. A fixed-bed reactor with one intermediate water removal point, representing two reactors in series, was modeled by a one-dimensional pseudo-homogeneous model. Pure CO2 or a mixture of CO2 and methane, representing a typical biogas mixture, were used as feed. For short reactors, both the maximum conversion and the largest irreversibilities were observed when the water removal point was located in the middle of the reactor. However, as the length of the reactor increased, the water removal point with the highest conversion was shifted towards the end of the reactor, accompanied by a smaller thermodynamic penalty. The largest irreversibilities in long reactors were obtained when water removal took place closer to the inlet of the reactor. The study discusses the potential benefit of partial water removal and reactant feeding for energy-efficient reactor design.

Kirkwood-Buff (KB) integrals provide a connection between microscopic properties and thermodynamic properties of multicomponent fluids. The estimation of KB integrals using molecular simulations of finite systems requires accounting for finite size effects. In the small system method, properties of finite subvolumes with different sizes embedded in a larger volume can be used to extrapolate to macroscopic thermodynamic properties. KB integrals computed from small subvolumes scale with the inverse size of the system. This scaling was used to find KB integrals in the thermodynamic limit. To reduce numerical inaccuracies that arise from this extrapolation, alternative approaches were considered in this work. Three methods for computing KB integrals in the thermodynamic limit from information of radial distribution functions (RDFs) of finite systems were compared. These methods allowed for the computation of surface effects. KB integrals and surface terms in the thermodynamic limit were computed for Lennard–Jones (LJ) and Weeks–Chandler–Andersen (WCA) fluids. It was found that all three methods converge to the same value. The main differentiating factor was the speed of convergence with system size L. The method that required the smallest size was the one which exploited the scaling of the finite volume KB integral multiplied by L. The relationship between KB integrals and surface effects was studied for a range of densities.

The ideal gas model is an important and useful model in classical thermodynamics. This remains so for small systems. Molecules in a gas can be adsorbed on the surface of a sphere. Both the free gas molecules and the adsorbed molecules may be modeled as ideal for low densities. The adsorption energy, Us, plays an important role in the analysis. For small adsorbents this energy depends on the curvature of the adsorbent. We model the adsorbent as a sphere with surface area Ω=4πR2, where R is the radius of the sphere. We calculate the partition function for a grand canonical ensemble of two-dimensional adsorbed phases. When connected with the nanothermodynamic framework this gives us the relevant thermodynamic variables for the adsorbed phase controlled by the temperature T, surface area Ω, and chemical potential μ. The dependence of intensive variables on size may then be systematically investigated starting from the simplest model, namely the ideal adsorbed phase. This dependence is a characteristic feature of small systems which is naturally expressed by the subdivision potential of nanothermodynamics. For surface problems, the nanothermodynamic approach is different, but equivalent to Gibbs’ surface thermodynamics. It is however a general approach to the thermodynamics of small systems, and may therefore be applied to systems that do not have well defined surfaces. It is therefore desirable and useful to improve our basic understanding of nanothermodynamics.

It is known that thermodynamic properties of a system change upon confinement. To know how, is important for modelling of porous media. We propose to use Hill’s systematic thermodynamic analysis of confined systems to describe two-phase equilibrium in a nanopore. The integral pressure, as defined by the compression energy of a small volume, is then central. We show that the integral pressure is constant along a slit pore with a liquid and vapor in equilibrium, when Young and Young–Laplace’s laws apply. The integral pressure of a bulk fluid in a slit pore at mechanical equilibrium can be understood as the average tangential pressure inside the pore. The pressure at mechanical equilibrium, now named differential pressure, is the average of the trace of the mechanical pressure tensor divided by three as before. Using molecular dynamics simulations, we computed the integral and differential pressures, p ^ and p, respectively, analysing the data with a growing-core methodology. The value of the bulk pressure was confirmed by Gibbs ensemble Monte Carlo simulations. The pressure difference times the volume, V, is the subdivision potential of Hill, ( p − p ^ ) V = ϵ . The combined simulation results confirm that the integral pressure is constant along the pore, and that ϵ / V scales with the inverse pore width. This scaling law will be useful for prediction of thermodynamic properties of confined systems in more complicated geometries.

The process of carbon capture and sequestration has been proposed as a method of mitigating the build-up of greenhouse gases in the atmosphere. If implemented, the cost of electricity generated by a fossil fuel-burning power plant would rise substantially, owing to the expense of removing C[O.sub.2] from the effluent stream. There is therefore an urgent need for more efficient gas separation technologies, such as those potentially offered by advanced solid adsorbents. Here we show that diamine-appended metal-organic frameworks can behave as 'phase-change' adsorbents, with unusual step-shaped C[O.sub.2] adsorption isotherms that shift markedly with temperature. Results from spectroscopic, diffraction and computational studies show that the origin of the sharp adsorption step is an unprecedented cooperative process in which, above a metal-dependent threshold pressure, C[O.sub.2] molecules insert into metal-amine bonds, inducing a reorganization of the amines into well-ordered chains of ammonium carbamate. As a consequence, large C[O.sub.2] separation capacities can be achieved with small temperature swings, and regeneration energies appreciably lower than achievable with state-of-the-art aqueous amine solutions become feasible. The results provide a mechanistic framework for designing highly efficient adsorbents for removing C[O.sub.2] from various gas mixtures, and yield insights into the conservation of [Mg.sup.2+] within the ribulose-1,5-bisphosphate carboxylase/oxygenase family of enzymes.

Biomethane production from biogas can be increased by methanation of carbon dioxide with hydrogen through the Sabatier reaction. In this work, the performance of the methanation process is investigated under isothermal and adiabatic conditions for different temperature and pressure levels. The processes were modelled assuming equilibrium conditions, minimizing the Gibbs free energy. The results indicate that the exergy of heat removed from the process, and thereby the integration potential, increases with increasing temperature. The internal irreversibility is smaller and the heat integration potential larger for adiabatic reactors than for isothermal reactors.