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11 pre-treatmentandvoltagecyclingpretreatment.Metha nol formation continues during extended electrolysis though a drop in faradaic ef?ciency is observed. From spectroscopicanalysisoftheelectrolyteforsoluble molybdenum species and electrochemical analysis of the surface for insoluble molybdenum compounds itis concluded that the formation of corrosion products is inhibited under electrolysis conditions. By contrast, open circuit corrosion of molybdenum can lead to carbon monoxide or methanol depending on whether the electrode has been voltage cycled. The equivalentfreecorrosioncurrentisél uA cm’Z,well below typical electrolysis current densities. 12 from about —l.2 V and plus 0.2 V, relative to SCE, over 100% faradaicefficiencyforproductionofmetha nol from carbon dioxide results, but, this is apparently duetocorrosionofthecathode. INDUSTRIAL APPLICABILITY The method of the present invention is useful for convertingcarbondioxidetomethanolwherebyenergy such as solar energy can be readily converted to stor= able form, namely, by providing a fuel which can be burned to recapture the energy. While the invention has been described with respect to certain speci?c embodiments thereof itwill be under stoodthatmany variationsarepossiblewithinthescope and spirit of the invention as de?ned by the appended Voltage cycled electrodes are much more susceptible to corrosion under electrolysis conditions. In this case carbondioxidereactsrapidlywithmolybdenummetal , claims. to form methanol selectively. It was also shown that molybdenum bronzes are a chemical reducing agent for methanol synthesis from aqueous carbon dioxide. We claim: 1. A method of producing methanol from carbon dioxide, comprising; electrolyzing a solution of carbon dioxide in an aque“ ous solvent having an electrolyte therein and utiliz ing a cathode which comprises molybdenum to producemethanol. 4,609,441 More generally, and as supported by the extensive 20 data in the examples set forth above, carbon dioxide can be efficiently converted to produce methanol. Gener ally,thepH ofthesolutionshouldfalwithintherange fromabout0toabout7.IfthepH isintherangefrom about 5 to about 7, it is necessary to have an added 25 the solution falls within the range from about 0 to about electrolyte.IfthepHisbelowabout5,theacidprovides suf?cient electrolyte. Generally, the cathode is con= trolled to have a voltage from about —0.5 V to about —1.1V relativetoSCE.Furthermore,ifthecathodeis cycled between two voltages which fall in the range 7. 3.A methodassetforthinclaim1,whereinthecath ode iscontrolled to have a voltage from about -0.5 V to about — 1.1 V relative to SCE. * 1* * * it 35 45 55 60 65 2.A methodassetforthinclaim1,whereinthepH ofPDF Image | ELECTROCHEMICAL REDUCTION OF AQUEOUS CO2 TO METHANOL
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