Electrochemical reduction of carbon dioxide on pyrite as a pathway for abiogenic formation of organic molecules.
A wide spectrum of electrode potentials of minerals that compose sulfide ores enables the latter, when in contact with hydrothermal solutions, to form galvanic pairs with cathode potentials sufficient for electrochemical reduction of CO2. The experiments performed demonstrated the increase of cathode current on the rotating pyrite disc electrode in a range of potentials more negative than -800 mV in presence of CO2. In high-pressure experiments performed in a specially designed electrochemical cell equipped with a pyrite cathode and placed into autoclave, accumulation of formate was demonstrated after 24 hr passing of CO2 (50 atm, room temperature) through electrolyte solution. The formation of this product started on increasing the cathode potential to -800 mV (with respect to saturated silver chloride electrode). The yield grew exponentially upon cathode potential increase up to -1200 mV. The maximum current efficiency (0.12%) was registered at cathode potentials of about -1000 mV. No formate production was registered under normal atmospheric pressure and in the absence of imposed cathode potential. Neither in experiments, nor in control was formaldehyde found. It is proposed that the electrochemical reduction of CO2 takes part in the formation of organic molecules in hydrothermal solutions accompanying sulfide ore deposits and in 'black smokers' on the ocean floor.
A. N. Bach Institute of Biochemistry, Russian Academy of Sciences, Leninsky Prospect 33, Moscow, Russia. mgv@inbi.ras.ru
M G
MG
Vladimirov
Y F
YF
Ryzhkov
V A
VA
Alekseev
V A
VA
Bogdanovskaya
V A
VA
Otroshchenko
M S
MS
Kritsky
D002245:Carbon Dioxide / Q000737:chemistry*; D004563:Electrochemistry / Q000295:instrumentation / Q000379:methods; D004566:Electrodes; D005561:Formates / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D009930:Organic Chemicals / Q000737:chemistry / Q000378:metabolism*; D010084:Oxidation-Reduction; D011312:Pressure; D013440:Sulfides / Q000737:chemistry*; D013696:Temperature
D005561:Formates; D009930:Organic Chemicals; D013440:Sulfides; C030544:formic acid; C011342:pyrite; D002245:Carbon Dioxide; D007501:Iron