Methods for enzyme-enhanced CO2 capture include contacting a CO2-containing gas with an aqueous absorption solution at process conditions—such as high temperature, high pH, and/or using carbonate-based solutions—in the presence of Thermovibrio ammonificans carbonic anhydrase (TACA) or functional derivative thereof for catalyzing the hydration reaction of CO2 into bicarbonate and hydrogen ions and/or catalyzing the desorption reaction to produce a CO2 gas. The TACA may be provided to flow with the solution to cycle through a CO2 capture system that includes an absorber and a stripper.