Methane Conversion to Methanol by Platinum Catalysts By: Sean W. Hanley

Platinum Catalysts Platinum (II) Chloride (bpyrm)PtCl 2 PtCl 2 H 2 PtCl 6 (NH 3 ) 2 PtCl 2 All of these catalyst have been studied to see which catalyst has the best percent yield of methanol with the least amount of catalytic death. (bpym)PtCl 2 with oleum has been recently found to have 72% yield. This catalyst will be the major catalyst looked at. This reaction has the most hope in industry but also a crucial problem arises. Past catalysts have had 40% yield using mercury which is not environmentally friendly. K 2 PtCl 4

Overall Reactions Overall Reaction Hydrolysis Reaction 220C Application Reaction

Catalytic Interaction Platinum (II)Platinum (IV) Catalytic interaction mechanism to form methanol Activating step of methane

Catalytic Interaction cont. Suggested mechanism for the oxidation step

Catalytic Interaction cont. Final product then undergoes hydrolysis and turns into methanol Purposed mechanism for functionalization step

Overall Proposed Mechanism

Different Solvent Interactions H 2 SO 4 Sulfuric Acid –Concentrated Sulfuric Acid –Dilute Sulfuric Acid HF/SbF 5 – Causes Fluorination rather then oxidation of methane Methanol and H 2 O Interacts with catalyst- causing catalytic death

Using Different Catalysts (bpym)PtCl 2 soluble and good interaction with sulfuric acid PtCl 2 and PtO 2 insoluble in H 2 O or other organic solvents PtCl 4, K 2 PtCl 4, and H 2 PtCl 6 soluble but not compatible with sulfuric acid This leads us to believe only (bpym)PtCl 2 is the only catalyst that works Yet Ionic Liquids allow these other catalysts to dissolve readily upon heating

Ionic Liquids (IL)

Ionic Liquids Interactions

Ionic Liquids Interactions Cont. Better percent yield (Concentration) from the Ionic Liquids then with (bpym)PtCl 2 by itself Ionic liquids are more water-tolerant “Green” Chemistry due to low volatility and good thermal stability

Applications Industry applications to produce natural gas to liquid products in milder conditions (T < 300 o c) Use in hydrogen cars to produce a hydrogen yielding reaction from methanol Safer fuels Environmentally friendly reaction

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Problems Facing Industry (bpym)PtCl 2 is extremely sensitive to small amounts of water present in the reaction Methanol is very hard to extract from the sulfuric acid/ water solution There is also severe inhibition from the sulfuric acid/ water solution- causing catalytic death

Future Experiments Differing acids may lead to a more accessible way of extracting Methanol as a product Using Ionic Liquids to create a higher yield in less concentrated sulfuric acid Different Platinum catalysts that are more water-tolerant

Highlights (bpym)PtCl 2 is a very good catalyst at producing methanol approximately 70% yield The problems are that methanol is very hard to extract from the sulfuric acid/ water solution HF/SbF 5 is not a reasonable system to convert methane to methanol Ionic liquids increase yield and are more water- tolerant Realize how this catalyst could be used to further Hydrogen “Car” applications

References Cheng, J.; Li, Z.; Haught. M.; Tang. Y. Chem. Commun. 2006, 4617 Kua, J.; Xu X.; Perenia, R. A.; Goddard, W. A., III. Organometallics 2002, 21, 511. Kua, J.; Goddard III, W. J. Am. Chem. Soc. 1999, 121, Seidel, S.; Seppelt, K. Inorg. Chem. 2003, 42,

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