Scalable and simultaneous generation of homogeneous acid Co(III) and base Co(I) electrocatalysts using a divided electrolyzer

G. Muthuraman; S. Balaji; I.-S. Moon

Journal of Industrial and Engineering Chemistry, Vol.58, 240-245, February, 2018

DOI10.1016/j.jiec.2017.09.032 Export Citation

Scalable and simultaneous generation of homogeneous acid Co(III) and base Co(I) electrocatalysts using a divided electrolyzer

G. Muthuraman, S. Balaji, and I.-S. Moon^†

Department of Chemical Engineering, Sunchon National University, #255 Jungang-ro, Suncheon 57922, Jeollanam-do, Republic of Korea

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A scalable and simultaneous synthesis of Co(III) (Co2(SO4)3) and Co(I) ([Co(I)(CN)5]4-) electrocatalysts using a divided electrolyzer is reported for the first time. The overpotential gain of oxygen evolution reaction (OER) by high concentration of an acid and hydrogen evolution reaction (HER) by high concentration of a base was utilized for this new state-of-the art electro-syntheses. Difference in generation rate between acid electrocatalyst Co(III) and base electrocatalyst Co(I) was minimized by controlling the flow of H3O+ ions from anode to cathode. Also, variation in the nature of cathode materials was found to influence the formation rate of both acid Co(III) and base Co(I) electrocatalysts. We have shown that by selecting a suitable combination of electrode pair and controlling the presence of H3O+ ions it becomes possible to synthesize 3.5 mM of Co(III) and 2.5 mM of Co(I) simultaneously in both compartments of a divided electrolytic cell. This achievement on the hitherto unreported development in electrocatalyst synthesis strategy is the first of its kind in divided electrolytic cells.

Keywords:Homogeneous electrocatalyst;Simultaneous generation;Potential window widening;Paired electrolysis

[References]

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[1] Zhang G, Scott BL, Hanson SK, Angew. Chem.-Int. Edit., 51, 12102 (2012)

[2] Xiaohui D, Harun T, ACS Catal., 4, 3701 (2014)

[3] Priest HF, Inorg. Synth., 3, 171 (1950)

[4] Cox B, Sharpe AG, J. Chem. Soc., 1798 (1954).

[5] Meyers MD, Cotton FA, J. Am. Chem. Soc., 82, 5027 (1960)

[6] Muthuraman G, Chung SJ, Moon IS, ACS Comb. Sci., 14, 359 (2012)

[7] Warnqvist B, Inorg. Chem., 9, 682 (1970)

[8] McCrory CCL, Uyeda C, Peters JC, J. Am. Chem. Soc., 134(6), 3164 (2012)

[9] Thompson MR, Day VW, Tau KD, Muetterties EL, Inorg. Chem., 20, 1237 (1981)

[10] Knijnenburg Q, Horton AD, van der Heijden H, Kooistra TM, Hetterscheid DGH, Smits JMM, de Bruin B, Budzelaar PHM, Gal AW, J. Mol. Catal. A-Chem., 232(1-2), 151 (2005)

[11] Amezquita-Valencia M, Cabrera A, J. Mol. Catal. A-Chem., 366, 17 (2013)

[12] Zuo WW, Lough AJ, Li YF, Morris RH, Science, 342(6162), 1080 (2013)

[13] Sonnenberg JF, Coombs N, Dube PA, Morris RH, J. Am. Chem. Soc., 134(13), 5893 (2012)

[14] Morales-Guio CG, Liardet L, Mayer MT, Tilley SD, Gratzel M, Hu X, Angew. Chem.-Int. Edit., 54, 664 (2015)

[15] Fabbri E, Habereder A, Waltar K, Kotz R, Schmidt TJ, Catal. Sci. Technol., 4, 3800 (2014)

[16] Lakadamyali F, Kato M, Muresan MM, Reisner E, Angew. Chem.-Int. Edit., 51, 9381 (2012)

[17] Agarwal J, Shaw TW, Stanton CJ, Majetich GF, Bocarsly AB, Schaefer HF, Angew. Chem.-Int. Edit., 53, 5152 (2014)

[18] Hayashi T, Kikuchi S, Asano Y, Endo Y, Yamada T, Org. Process Res. Dev., 16, 1235 (2012)

[19] Nakazono T, Parentab AR, Sakai K, Chem. Commun., 49, 6325 (2013)

[20] Fleming CA, Hydrometallurgy, 30, 127 (1992)

[21] Spitzer M, Bertazzoli R, Hydrometallurgy, 74, 233 (2004)

[22] Hanzlik J, Vlcek J, J. Chem. Soc. D, 47 (1969).

[23] Adamson AW, J. Am. Chem. Soc., 73, 5710 (1951)

[24] Bard AJ, Parsons R, Jordan J, Standard Potentials in Aqueous Solutions, Marcel Dekker, New York, 1985.

[25] Simons R, Nature, 280, 824 (1979)

[26] Kovalevsky AY, Hanson BL, Mason SA, Yoshida T, Fisher SZ, Mustyakimov M, Forsyth VT, Blakeley MP, Keen DA, Langan P, Angew. Chem.-Int. Edit., 50, 7520 (2011)

[27] Spalek O, Balej J, Paseka I, J. Chem. Soc.-Faraday Trans., 78, 2349 (1982)

[28] Inczedy J, Erday L, J. Period. Polytech., 6, 195 (1962)

[29] Garver TM, Yuan H, Determination of the Property of a Solution or Solid Using Raman Ratios. U.S. Patent, No. US 6,774,992 B1, 10 August 2004.

[30] Miltzarek GL, Sampaio CH, Cortina JL, Miner. Eng., 15(1-2), 75 (2002)