Uncovering the Dynamics of Urease and Carbonic Anhydrase Genes in Ureolysis, Carbon Dioxide Hydration, and Calcium Carbonate Precipitation.

The hydration of CO2 suffers from kinetic inefficiencies that make its natural trapping impractically sluggish. However, CO2-fixing carbonic anhydrases (CAs) remarkably accelerate its equilibration by 6 orders of magnitude and are, therefore, "ideal" catalysts. Notably, CA has been detected in ureolytic bacteria, suggesting its potential involvement in microbially induced carbonate precipitation (MICP), yet the dynamics of the urease (Ur) and CA genes remain poorly understood. Here, through the use of the ureolytic bacteriumSporosarcina pasteurii, we investigate the differing role of Ur and CA in ureolysis, CO2 hydration, and CaCO3 precipitation with increasing CO2(g) concentrations. We show that Ur gene up-regulation coincides with an increase in [HCO3-] following the hydration of CO2 to HCO3- by CA. Hence, CA physiologically promotes buffering, which enhances solubility trapping and affects the phase of the CaCO3 mineral formed. Understanding the role of CO2 hydration on the performance of ureolysis and CaCO3 precipitation provides essential new insights, required for the development of next-generation biocatalyzed CO2 trapping technologies.

Kinetic and Thermodynamic Enhancement of Low-Temperature Oxygen Release from Strontium Ferrite Perovskites Modified with Ag and CeO2.

The redox behavior of the nonstoichiometric perovskite oxide SrFeO3-δ modified with Ag, CeO2, and Ce was assessed for chemical looping air separation (CLAS) via thermogravimetric analysis and by cyclic release and uptake of O2 in a packed bed reactor. The results demonstrated that the addition of ∼15 wt % Ag at the surface of SrFeO3-δ lowers the temperature of oxygen release in N2 by ∼60 °C (i.e., from 370 °C for bare SrFeO3-δ to 310 °C) and more than triples the amount of oxygen released per CLAS cycle at 500 °C. Impregnation of SrFeO3-δ with Ag increased the concentration of oxygen vacancies at equilibrium, lowering (3 - δ) under all investigated oxygen partial pressures. The addition of CeO2 at the surface or into the bulk of SrFeO3-δ resulted in more modest changes, with a decrease in temperature for O2 release of 20-25 °C as compared to SrFeO3-δ and a moderate increase in oxygen yield per reduction cycle. The apparent kinetic parameters for reduction of SrFeO3-δ, with Ag and CeO2 additives, were determined from the CLAS experiments in a packed bed reactor, giving activation energies and pre-exponential factors of Ea,reduction = 66.3 kJ mol-1 and Areduction = 152 mol s-1 m-3 Pa-1 for SrFeO3-δ impregnated with 10.7 wt % CeO2, 75.7 kJ mol-1 and 623 molO2 s-1 m -3 Pa-1 for SrFeO3-δ mixed with 2.5 wt % CeO2 in the bulk, 29.9 kJ mol-1 and 0.88 molO2 s-1 m-3 Pa-1 for Sr0.95Ce0.05FeO3-δ, and 69.0 kJ mol-1 and 278 molO2 s-1 m-3 Pa-1 for SrFeO3-δ impregnated with 12.7 wt % Ag, respectively. Kinetics for reoxidation were much faster and were assessed for two materials with the slowest oxygen uptake, SrFeO3-δ, giving the activation energy Ea,oxidation = 177.1 kJ mol-1 and pre-exponential factor Aoxidation = 3.40 × 1010 molO2 s-1 m-3 Pa-1, and Sr0.95Ce0.05FeO3-δ, giving the activation energy Ea,oxidation = 64.0 kJ mol-1, and pre-exponential factor Aoxidation = 584 molO2 s-1 m-3 Pa-1.

Production of Acetaldehyde via Oxidative Dehydrogenation of Ethanol in a Chemical Looping Setup.

A novel chemical looping (CL) process was demonstrated to produce acetaldehyde (AA) via oxidative dehydrogenation (ODH) of ethanol. Here, the ODH of ethanol takes place in the absence of a gaseous oxygen stream; instead, oxygen is supplied from a metal oxide, an active support for an ODH catalyst. The support material reduces as the reaction takes place and needs to be regenerated in air in a separate step, resulting in a CL process. Here, strontium ferrite perovskite (SrFeO3-δ) was used as the active support, with both silver and copper as the ODH catalysts. The performance of Ag/SrFeO3-δ and Cu/SrFeO3-δ was investigated in a packed bed reactor, operated at temperatures from 200 to 270 °C and a gas hourly space velocity of 9600 h-1. The CL capability to produce AA was then compared to the performance of bare SrFeO3-δ (no catalysts) and materials comprising a catalyst on an inert support, Cu or Ag on Al2O3. The Ag/Al2O3 catalyst was completely inactive in the absence of air, confirming that oxygen supplied from the support is required to oxidize ethanol to AA and water, while Cu/Al2O3 gradually got covered in coke, indicating cracking of ethanol. The bare SrFeO3-δ achieved a similar selectivity to AA as Ag/SrFeO3-δ but at a greatly reduced activity. For the best performing catalyst, Ag/SrFeO3-δ, the obtained selectivity to AA reached 92-98% at yields of up to 70%, comparable to the incumbent Veba-Chemie process for ethanol ODH, but at around 250 °C lower temperature. The CL-ODH setup was operated at high effective production times (i.e., the time spent producing AA to the time spent regenerating SrFeO3-δ). In the investigated configuration with 2 g of the CLC catalyst and 200 mL/min feed flowrate ∼5.8 vol % ethanol, only three reactors would be required for the pseudo-continuous production of AA via CL-ODH.