Biporous Metal-Organic Framework with Tunable CO2/CH4 Separation Performance Facilitated by Intrinsic Flexibility.

In this work, we report the synthesis of SION-8, a novel metal-organic framework (MOF) based on Ca(II) and a tetracarboxylate ligand TBAPy4- endowed with two chemically distinct types of pores characterized by their hydrophobic and hydrophilic properties. By altering the activation conditions, we gained access to two bulk materials: the fully activated SION-8F and the partially activated SION-8P with exclusively the hydrophobic pores activated. SION-8P shows high affinity for both CO2 ( Qst = 28.4 kJ/mol) and CH4 ( Qst = 21.4 kJ/mol), while upon full activation, the difference in affinity for CO2 ( Qst = 23.4 kJ/mol) and CH4 ( Qst = 16.0 kJ/mol) is more pronounced. The intrinsic flexibility of both materials results in complex adsorption behavior and greater adsorption of gas molecules than if the materials were rigid. Their CO2/CH4 separation performance was tested in fixed-bed breakthrough experiments using binary gas mixtures of different compositions and rationalized in terms of molecular interactions. SION-8F showed a 40-160% increase (depending on the temperature and the gas mixture composition probed) of the CO2/CH4 dynamic breakthrough selectivity compared to SION-8P, demonstrating the possibility to rationally tune the separation performance of a single MOF by manipulating the stepwise activation made possible by the MOF's biporous nature

Kinetic studies of oxidative coupling of methane on samarium oxide

Kinetic behaviour of three samples of samarium oxide (cubic (Sm-1 ), monoclinic (Sm-3) and mixed cubic-monoclinic (Sm 2) ) were studied in the oxidative coupling of methane using a gradientless flow circulation system. The specific rate of C2- product formation differed by a factor of 6-8 for Sm-1 and Sm-3. The specific activity for CO formation did not depend upon the crystal structure of samarium oxide while the rate of formation of CO2 was different for the samples studied. It is proposed that formation of CO and CO2 occurs via different reaction routes. The rate of CO2 formation at high CHJO2 ratio is limited by oxidant activation or surface CO2-complex decomposition

Ab initio data-analytics study of carbon-dioxide activation on semiconductor oxide surfaces

The excessive emissions of carbon dioxide (CO2) into the atmosphere threaten to shift the CO2 cycle planet-wide and induce unpredictable climate changes. Using artificial intelligence (AI) trained on high-throughput first principles based data for a broad family of oxides, we develop a strategy for a rational design of catalytic materials for converting CO2 to fuels and other useful chemicals. We demonstrate that an electron transfer to the π-antibonding orbital of the adsorbed molecule and the associated bending of the initially linear molecule, previously proposed as the indicator of activation, are insufficient to account for the good catalytic performance of experimentally characterized oxide surfaces. Instead, our AI model identifies the common feature of these surfaces in the binding of a molecular O atom to a surface cation, which results in a strong elongation and therefore weakening of one molecular C-O bond. This finding suggests using the C-O bond elongation as an indicator of CO2 activation. Based on these findings, we propose a set of new promising oxide-based catalysts for CO2 conversion, and a recipe to find more

Analysis and theory of gas transport in microporous sol-gel derived ceramic membranes

Sol-gel modification of mesoporous alumina membranes is a very successful technique to improve gas separation performance. Due to the formed microporous top layer, the membranes show activated transport and molecular sieve-like separation factors. This paper concentrates on the mechanism of activated transport (also often referred to as micropore diffusion or molecular sieving). Based on a theoretical analysis, results from permeation and separation experiments with H2, CO2, O2, N2, CH4 and iso-C4H10 on microporous sol-gel modified supported ceramic membranes are integrated with sorption data.\ud \ud Gas permeation through these membranes is activated, and for defect-free membranes the activation energies are in the order of 13¿15 kJ.mol¿1 and 5¿6 kJ.mol¿1 for H2 and CO2 respectively. Representative permeation values are in the order of 6×10¿7 mol.m¿2.s¿1.Pa¿1 and 20×10¿7 mol.m¿2.s¿1.Pa¿1 for H2 at 25°C and 200°C, respectively. Separation factors for H2/CH4 and H2/iso-butane are in the order of 30 and 200 at 200°C, respectively, for high quality membranes.\ud \ud Processes which strongly determine gas transport through microporous materials are sorption and micropore diffusion. Consequently, the activation energy for permeation is an apparent one, consisting of a contribution from the isosteric heat of adsorption and the activation energy for micropore diffusion. An extensive model is given to analyse these contributions.\ud \ud For the experimental conditions studied, the analysis of the gas transport mechanism shows that interface processes are not rate determining. The calculated activation energies for micropore diffusion are 21 kJ.mol¿1 and 32 kJ.mol¿1 for H2 and CO2, respectively. Comparison with zeolite diffusion data shows that these activation energies are higher than for zeolite 4A (dpore=4Å), indicating that the average pore size of the sol-gel derived membranes is probably smaller

A Simple Kinetic Analysis of Syngas During Steam Hydrogasification of Biomass Using a Novel Inverted Batch Reactor with Instant High Pressure Feeding

A newly designed inverted batch reactor equipped with a pressure-driven feeding system was built for investigating the kinetics of syngas during the steam hydrogasification (SHR) of biomass. The system could instantly load the feedstock into the reactor at high temperature and pressure, which simulated the way to transport the feedstock into a hot and pressurized gasifier. Experiments were conducted from 600 °C to 700 °C. The inverted reactor showed very high heating rate by enhancing the carbon conversion and syngas production. The kinetic study showed that the rates of CH4, CO and CO2 formation during SHR were increased when the gasification temperature went up. SHR had comparatively lower activation energy for CH4 production. The activation energies of CH4, CO and CO2 during SHR were 42.8, 51.8 and 14 kJ/mol, respectively

Surface-Plasmon-Assisted Photoelectrochemical Reduction of CO2 and NO3− on Nanostructured Silver Electrodes

Electrochemical reduction of carbon dioxide (CO2) typically suffers from low selectivity and poor reaction rates that necessitate high overpotentials, which impede its possible application for CO2 capture, sequestration, or carbon-based fuel production. New strategies to address these issues include the utilization of photoexcited charge carriers to overcome activation barriers for reactions that produce desirable products. This study demonstrates surface-plasmon-enhanced photoelectrochemical reduction of CO2 and nitrate (NO3−) on silver nanostructured electrodes. The observed photocurrent likely originates from a resonant charge transfer between the photogenerated plasmonic hot electrons and the lowest unoccupied molecular orbital (MO) acceptor energy levels of adsorbed CO2, NO3−, or their reductive intermediates. The observed differences in the resonant effects at the Ag electrode with respect to electrode potential and photon energy for CO2 versus NO3− reduction suggest that plasmonic hot-carriers interact selectively with specific MO acceptor energy levels of adsorbed surface species such as CO2, NO3−, or their reductive intermediates. This unique plasmon-assisted charge generation and transfer mechanism can be used to increase yield, efficiency, and selectivity of various photoelectrochemical processes

Permeation and separation studies on microporous sol-gel modified ceramic membranes

Permeation and separation experiments with H2, CO2, O2, N2, CH4 and isobutane with microporous sol-gel modified supported ceramic membranes were performed to determine the gas transport characteristics and the hydrogen separation performance of these membranes. It is found that the permeation is activated, and for defectfree membranes the apparent activation energies are in the ranges 13¿15 and 5¿6 kJ mol¿1 for H2 and CO2, respectively. Correction for the pressure drop over the support results in apparent activation energies for the silica top-layer on the order of 17¿22 and 10¿15 kJ mol¿1 for H2 and CO2 respectively. Due to the very thin top-layer, the permeation is relatively high, with representative values of 6·10¿7 and 20·10¿7 mol m¿2s¿1 Pa¿1 for H2 at 25 and 200°C, respectively. The H2 permeation is almost pressure-independent up to pressures of at least 5 bar. Typical separation factors for H2---CH4 and H2---isobutane are approximately ¿40 and ¿200, respectively, at 200°C for high-quality membranes. For moderate-quality membranes the H2---CH4 separation factor is around 10, while the H2---isobutane separation factor remains at a high value of around 100 at 200°C and 120 at 300°C

Shock-induced CO2 loss from CaCO3: Implications for early planetary atmospheres

Recovered samples from shock recovery experiments on single crystal calcite were subjected to thermogravimetric analysis to determine the amount of post-shock CO2, the decarbonization interval and the activation energy, for the removal of remaining CO2 in shock-loaded calcite. Comparison of post-shock CO2 with that initially present determines shock-induced CO2 loss as a function of shock pressure. Incipient to complete CO2 loss occurs over a pressure range of approximately 10 to approximately 70 GPa. Optical and scanning electron microscopy reveal structural changes, which are related to the shock-loading. The occurrence of dark, diffuse areas, which can be resolved as highly vesicular areas as observed with a scanning electron microscope are interpreted as representing quenched partial melts, into which shock-released CO2 was injected. The experimental results are used to constrain models of shock-produced, primary CO2 atmospheres on the accreting terrestrial planets