Carbon dioxide to methanol

Kuwabata S, Nishida K, Tsuda R, Inoue H, Yoneyama H (1994) Photochemical reduction of carbon dioxide to methanol using ZnS microcrystaUite as a photocatalyst in the presence of methanol dehydrogenase. J Electrochem Soc 141 1498-1503... 

Scheme 103 Catalytic reduction of carbon dioxide to methanol.

Liu Y, et al. Efficient conversion of carbon dioxide to methanol using copper catalyst by a new low-temperature hydrogenation process. Chem Lett. 2007 36 1182-3. 

Seshadri G, Chao L, Bocarsly AB. A new homogeneous electrocatalyst for the reduction of carbon dioxide to methanol at low overpotential. J Electroanal Chem. 1994 372 145-50. 

Arena F, et al. Synthesis, characterization and activity pattern of Cu-ZnO/Zr02 catalysts in the hydrogenation of carbon dioxide to methanol. J Catal. 2007 249(2) 185-94. 

Hydrogenation of carbon dioxide to methanol was investigated over Cu/ZnO catalysts prepared by mechanical alloying(MA) method, which is suitable for excellent mixing of different materials to make alloys or composites. The catalytic activity increases with mechanical milling time, and methanol yield over the catalyst milled for 120 hour is about 1.5 times higher than that of conventional coprecipitated Cu/ZnO catalyst. The reason for increasing catalytic activity by MA method can be attributed to the preparation of well mixed structure of Cu and ZnO nanocrystals. 

We present results on the catalytic hydrogenation of carbon dioxide to methanol in a conventional tubular packed-bed reactor filled with a copper based catalyst. In addition, results of an alternative approach using a dielectric-barrier discharge (DBD) reactor with and without the aid of a catalyst are presented. 

To make fuels that are storable and transportable, there are two primary chemical transformations to consider. One is the conversion of carbon dioxide to methanol, and the other is splitting water. Methanol could be used in a fuel cell where it is converted to carbon dioxide. This must be converted back to methanol to close the carbon loop. Alternatively, if hydrogen is used as a replacement fuel for carbon-based fuel, a hydrogen fuel cell that utilizes the product of solar or electrical water splitting would be available for transportation. 

Regarding suitable cathodes for the electrocatalytic reduction of carbon dioxide to methanol, indium, and tin have good prospects because each has a high overpotential for hydrogen evolution, the chief competitor in aqueous solution for carbon dioxide reduction to methanol ... 

However, Hori (1986) found the electrocatalytic reduction of carbon dioxide to methane on a molybdenum cathode to be electrocatalytic [11]. One hundred percent reduction of carbon dioxide to methanol at 0°C was reported. What remains open to research is the use of nonaqueous solvents, for example, acetonitrile, because there would be then no competition from hydrogen evolution. Carbon dioxide does undergo electrochemical reduction in acetonitrite to glycolic acid. Here is a research topic, which could have world consequences and cost very little (about 105 per year per researcher, even a dozen would make a great difference in five years). 

Ganesh, I. Conversion of Carbon Dioxide to Methanol Using Solar Energy. Mater. Sci. Appl., 2011, 2, 1407—1415. 

Homogeneous hydrogenation of carbon dioxide to methanol is catalyzed by ruthenium cluster anions in the presence of halide anions. The catalyst system was Ru3(CO)i2 and alkyl iodides in A -methylpyrrolidone (NMP) solution at 513 K. Some methane was also formed. FT-IR spectra of the reactions allowed identification of several ruthenium carbonyl anions. 

Obert, R. and Dave, B.C. (1999) Enzymatic conversion of carbon dioxide to methanol enhanced methanol production in silica sol-gel matrices. / Am. Chem. Soc., 121, 12192-12193. 

Ogura, K. and H. Uchida (1987). Electrocatalytic reduction of carbon dioxide to methanol. Part 5. Relationship between the ability of metal complexes to engage in homogeneous catalysis and their coordination chemistry. J. Chem. Soc. Dalton Trans. 6, 1377-1380. 

Olah, G. A., Goeppert, A., Suiya Prakash, G. K. (2009). Chemical recycling of carbon dioxide to methanol and dimethyl ether from greenhouse gas to renewable, environmentally carbon neutral fuels and synthetic hydrocarbons. Journal of Organic Chemistry, 74, 487—498. http //dx.doi.org/10.1021/jo801260f. 

Canfield, D. and Frese, K.W. reduction of carbon-dioxide to methanol on n-gaas andp-gaas and p-inp - effect of crystal-face, electrolyte and current-density. Journal of the Electrochemical Society, 1983. 130(8) p. 1772-1773. 

Yan Y, Gu J, Bocarsly AB (2014) Hydrogen bonded pyridine dimer a possible intermediate in the electrocatalytic reduction of carbon dioxide to methanol. Aerosol Air Qual Res 14 515-521... 

Aurian-Blajeni B, Taniguchi I, Bockris JOM (1983) Photoelectrochemical reduction of carbon dioxide using polyaniline-coated silicon. J Electroanal Chem Interf Electrochem 149 291-293 Ogura K, Yoshida I (1987) Electrocatalytic reduction of carbon dioxide to methanol. VI. Use of a solar cell and comparison with that of carbon monoxide. Electrochim Acta 32 1191-1195... 

Jiang Z, Xu S, Wu H (2003) Novel conversion of carbon dioxide to methanol catalyzed by sol-gel immobilized dehydrogenases. Intemational conference on carbon dioxide utilization ICCDU VII, Seoul-Korea... 

Sahibzada, M., ChadwickD., and Metcalfe, l.S. Hydrogenation of carbon dioxide to methanol over palladium-promoted Cu/Zn0/Al203 catalysts. Catal Today 1996, 29, 361-311. 

Hydrogenation of carbon dioxide to methanol is slightly exergonic, and to methane to a greater extent, because of the favorable thermodynamics of water formation (see Figure 5.5). 

Olah, G. A. Goeppert, A. Surya Prakash, G. K. Chemical Recycling of Carbon Dioxide to Methanol and Dimethyl Ether From Greenhouse Gas to Renewable, Environmentally Carbon Neutral Fuels and Synthetic Hydrocarbons. J. Org. Chem. 2009,74, 487 98. 

Arena, F. Barbera, K. Italiano, G. Bonura, G. Spadaro, L. Fmsteri, F. Synthesis, Characterization and Activity Pattern of Cu-ZnO/ZrOj Catalysts in the Hydrogenation of Carbon dioxide to Methanol. J. Catal. 2007,249,185-194. 

Liu, Y. Zhang, Y. Wang, T. J. Tsubaki, N. Efficient Conversion of Carbon Dioxide to Methanol Using Copper Catalyst by a New Low-temperature Hydrogenation Process. Chem. Lett. 2007,36,1182-1183. 

The same catalysts and conditions may operate for both reaction directions, that is, either towards the synthesis of methanol or towards its oxidation. Again, CO2 reduction must be able to compete with the electrochemical reduction of water-yielding hydrogen gas. Thermodynamically, the reduction of CO2 to CH3OH is slightly more favourable than the reduction of water. Kinetically, CO2 reduction can be favoured by electrodes, which act as poor catalysts for water reduction, including metallic Mo, Cu, In, Sn and Sb. Using nearly neutral electrolytes, rather than acidic ones, rendered CO2 reduction kinetically more favourable [148]. A detailed mechanism of the mediated electroreduction of carbon dioxide to methanol is addressed in the next section. 

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