A high pressure semi-continuous batch electrolyzer is used to convert CO2 to formic acid/formate on a tin-based cathode using bipolar membranes (BPMs) and cation ex- change membranes (CEMs). The effects of CO2 pressure up to 50 bar, electrolyte concentration, flow rate, cell potential, and the two types of membranes on the cur- rent density (CD) and Faraday efficiency (FE) for formic acid/formate are investigated. Increasing the CO2 pressure yields a high FE up to 90% at a cell potential of 3.5 V and a CD of ∼30 mA/cm2. The FE decreases significantly at higher cell potentials and current densities, and lower pressures. Up to 2 %wt formate was produced at a cell potential of 4 V, a CD of ∼100 mA/cm2, and a FE of 65%. The advantages and disadvantages of using BPMs and CEMs in electrochemical cells for CO2 conversion to formic acid/formate are discussed.

We use a high pressure semi-continuous batch electrochemical reactor with a tin- based cathode to demonstrate that it is possible to efficiently convert CO2 to formic acid (FA) in low pH (i.e., pH < pKa) electrolyte solutions. The effect of CO2 pressure (up to 50 bar), bipolar membranes, and electrolyte (K2SO4) concentration on the current density (CD) and the Faraday efficiency (FE) of formic acid were investigated. The highest FE (∼80%) of FA was achieved at a pressure of around 50 bar at a cell potential of 3.5 V and a CD of ∼30 mA/cm2. To suppress the hydrogen evolution reaction (HER), the electrochemical reduction of CO2 in aqueous media is typically performed at alkaline conditions. The consequence of this is that products like formic acid, which has a pKa of 3.75, will almost completely dissociate into the formate form. The pH of the electrolyte solution has not only a strong influence on the electrochemical reduction process of CO2, but also on the downstream separation of (dilute) acid products like formic acid. The selection of separation processes depends on the dissociation state of the acids. A review of separation technologies for formic acid/formate removal from aqueous dilute streams is provided. By applying common separation heuristics, we have selected liquid-liquid extraction and electrodialysis for formic acid and formate separation, respectively. An economic evaluation of both separation processes shows that the formic acid route is more attractive than the formate one. These results urge for better design of (1) CO2 electrocatalysts that can operate at low pH without affecting the selectivity of the desired products, and (2) technologies for efficient separation of dilute products from (photo)electrochemical reactors.

Direct electrochemical reduction of CO₂ to C₂ products such as ethylene is more efficient in alkaline media, but it suffers from parasitic loss of reactants due to (bi)carbonate formation. A two-step process where the CO₂ is first electrochemically reduced to CO and subsequently converted to desired C₂ products has the potential to overcome the limitations posed by direct CO₂ electroreduction. In this study, we investigated the technical and economic feasibility of the direct and indirect CO₂ conversion routes to C₂ products. For the indirect route, CO₂ to CO conversion in a high temperature solid oxide electrolysis cell (SOEC) or a low temperature electrolyzer has been considered. The product distribution, conversion, selectivities, current densities, and cell potentials are different for both CO₂ conversion routes, which affects the downstream processing and the economics. A detailed process design and techno-economic analysis of both CO₂ conversion pathways are presented, which includes CO₂ capture, CO₂ (and CO) conversion, CO₂ (and CO) recycling, and product separation. Our economic analysis shows that both conversion routes are not profitable under the base case scenario, but the economics can be improved significantly by reducing the cell voltage, the capital cost of the electrolyzers, and the electricity price. For both routes, a cell voltage of 2.5 V, a capital cost of $10,000/m², and an electricity price of <$20/MWh will yield a positive net present value and payback times of less than 15 years. Overall, the high temperature (SOEC-based) two-step conversion process has a greater potential for scale-up than the direct electrochemical conversion route. Strategies for integrating the electrochemical CO₂/CO conversion process into the existing gas and oil infrastructure are outlined. Current barriers for industrialization of CO₂ electrolyzers and possible solutions are discussed as well.

We present a new plugin for LAMMPS for on-the-fly computation of transport properties (OCTP) in equilibrium molecular dynamics. OCTP computes the self- and Maxwell-Stefan diffusivities, bulk and shear viscosities, and thermal conductivities of pure fluids and mixtures in a single simulation. OCTP is the first implementation in LAMMPS that uses the Einstein relations combined with the order-n algorithm for the efficient sampling of dynamic variables. OCTP has low computational requirements and is easy to use because it follows the native input file format of LAMMPS. A tool for calculating the radial distribution function (RDF) of the fluid beyond the cutoff radius, while taking into account the system size effects, is also part of the new plugin. The RDFs computed from OCTP are needed to obtain the thermodynamic factor, which relates Maxwell-Stefan and Fick diusivities. To demonstrate the efficiency of the new plugin, the transport properties of an equimolar mixture of water-methanol were computed at 298 K and 1 bar.

Hydrogen is one of the most popular alternatives for energy storage. Because of its low volumetric energy density, hydrogen should be compressed for practical storage and transportation purposes. Recently, electrochemical hydrogen compressors (EHCs) have been developed that are capable of compressing hydrogen up to P = 1000 bar, and have the potential of reducing compression costs to 3 kWh/kg. As EHC compressed hydrogen is saturated with water, the maximum water content in gaseous hydrogen should meet the fuel requirements issued by the International Organization for Standardization (ISO) when refuelling fuel cell electric vehicles. The ISO 14687–2:2012 standard has limited the water concentration in hydrogen gas to 5 μmol water per mol hydrogen fuel mixture. Knowledge on the vapor liquid equilibrium of H₂O–H₂ mixtures is crucial for designing a method to remove H₂O from compressed H₂. To the best of our knowledge, the only experimental high pressure data (P > 300 bar) for the H₂O–H₂ phase coexistence is from 1927 [J. Am. Chem. Soc., 1927, 49, 65–78]. In this paper, we have used molecular simulation and thermodynamic modeling to study the phase coexistence of the H₂O–H₂ system for temperatures between T = 283 K and T = 423 K and pressures between P = 10 bar and P = 1000 bar. It is shown that the Peng-Robinson equation of state and the Soave Redlich-Kwong equation of state with van der Waals mixing rules fail to accurately predict the equilibrium coexistence compositions of the liquid and gas phase, with or without fitted binary interaction parameters. We have shown that the solubility of water in compressed hydrogen is adequately predicted using force-field-based molecular simulations. The modeling of phase coexistence of H₂O–H₂ mixtures will be improved by using polarizable models for water. In the Supporting Information, we present a detailed overview of available experimental vapor–liquid equilibrium and solubility data for the H₂O–H₂ system at high pressures.

We performed H-cell and flow cell experiments to study the electrochemical reduction of CO₂ to oxalic acid (OA) on a lead (Pb) cathode in various nonaqueous solvents. The effects of anolyte, catholyte, supporting electrolyte, temperature, water content, and cathode potential on the Faraday efficiency (FE), current density (CD), and product concentration were investigated. We show that a high FE for OA can be achieved (up to 90%) at a cathode potential of -2.5 V vs Ag/AgCl but at relatively low CDs (10-20 mA/cm²). The FE of OA decreases significantly with increasing water content of the catholyte, which causes byproduct formation (e.g., formate, glycolic acid, and glyoxylic acid). A process design and techno-economic evaluation of the electrochemical conversion of CO₂ to OA is presented. The results show that the electrochemical route for OA production can compete with the fossil-fuel based route for the base case scenario (CD of 100 mA/cm², OA FE of 80%, cell voltage of 4 V, electrolyzer CAPEX of $20000/m², electricity price of $30/MWh, and OA price of $1000/ton). A sensitivity analysis shows that the market price of OA has a huge influence on the economics. A market price of at least $700/ton is required to have a positive net present value and a payback time of less than 10 years. The performance and economics of the process can be further improved by increasing the CD and FE of OA by using gas diffusion electrodes and eliminating water from the cathode, lowering the cell voltage by increasing the conductivity of the electrolyte solutions, and developing better OA separation methods.