FUTURE GREEN POWER: SOLAR FUELS FROM CARBON DIOXIDE

Very recently, Prof. Robert H. Crabtree from Yale University: New Haven, CT, US, wrote a scientific letter on “Alternate Strategies for Solar Fuels from Carbon Dioxide” in ACS Energy Letters [1].

In his letter, he mentioned that the timing mismatch between the supply and demand for solar electricity would require energy storage, for which conversion to a storable chemical fuel is one option. Beyond that, sectors such as marine navigation, aviation, etc. may still need liquid fuels, exported from the solar facility. These might also serve as one input into a future renewable chemicals industry.

Dihydrogen is hard to store; therefore, converting CO₂ into liquids such as methanol or ethanol is a leading option and also methanation to form “solar methane”.

U. Ulmer et al., mentioned in their recent review article titled on “Fundamentals and applications of photocatalytic CO2 methanation” [2], that is one of the recent research efforts, “solar methane” can now be produced through the photocatalytic conversion of carbon dioxide and water to methane and oxygen. This approach could play an integral role in realizing a sustainable energy economy by closing the carbon cycle and enabling the efficient storage and transportation of intermittent solar energy within the chemical bonds of methane molecules.

Sustainable production of“synthetic” natural gas (SNG) is possible through the conversion of CO₂ and water (H₂O) into CH₄ and oxygen (O₂) using renewable energy such as sunlight.

The advantages of this approach are threefold, which are reported in Nature Communications on July 2019:

1. The infrastructure required for the storage, distribution, and use of (S)NG is already established and readily available.

2. The high energy density of SNG makes it an efficient storage medium for excess renewable energy.

3. The high abundance and relatively low cost of CO₂ and H₂O feedstocks make SNG a significantly value-added product.

A research group reviewed from some of the recent articles that the best-case solar-to-methane efficiency is 13.0% (22.5% for solar cells [3]; 90% for CO₂ capture from flue gas [4,5]; 80% for water electrolysis [6] and 80% for CO₂ methanation [7]). The most recent developments regarding the various solar methanation schemes are in Figure 1. The artificial photosynthesis and photobiorefinery are the advanced techniques for the production of solar fuels.

Figure 1. Schematic depiction of the solar methanation process and the various methods [2].

The advantages of solar methane technology:

Solar CH₄ technology could relatively seamlessly integrate into existing energy infrastructure (such as storage, pipeline, and distribution facilities) at low cost and with minimal impact on the environment and landscape.
In this regard, solar CH₄ technology seems inclined toward public acceptance, providing a strong contribution towards ameliorating global warming and relieving climate change.

The electrochemical (EC) or photoelectrochemical cell (PEC) production of H2 or synthesis gas is convenient for product separation but problematic for storage while production of MeOH makes separation somewhat harder.

Another interesting solar fuel is methyl formate:

One plausible compromise candidate is methyl formate (bp = 31 °C), which should self-separate under only slightly elevated temperature, yet be easily liquefied for storage.
Its heat of vaporization is also low (29 versus 37.6 kJ/mol for MeOH) and it is a good fuel for internal combustion engines (octane number 115) and a useful fuel additive.
In one rare case, Lucas et al. report the electroreduction of CO2 over a Cu electrocatalyst to MeOCHO as the main product [8].
MeOCHO was also the principal product in a PEC reduction of CO2 with lignin-stabilized Cu2O under a Xe−Hg lamp (300−580 nm emission) [9].

Prof. Robert H. Crabtree has mainly proposed that methyl formate act as a main solar fuel. However, conversion of methyl formate to methanol may not even be required. Because MeOCHO is recognized as an intermediate in the operation of MeOH fuel cells it is likely be a viable fuel cell substrate on its own, although methyl formate itself is not electrochemically active and initial hydrolysis to formic acid and methanol precedes electrooxidation [10]. If MeOCHO proves able to stand in for methanol in fuel applications, MeOCHO might have a wider role in a future fuel and solar energy storage economy.

The main advantage of methyl formate solar fuel:

The more volatile methyl formate may have advantages as a CO₂ reduction product in being relatively easily separated from the electrochemical (EC) or PEC product mixture, yet be relatively easy to store as a liquid and use as a fuel.

References

[1]. Crabtree, R. H. ACS Energy Lett. 5, 2505−2507 (2020).

[2]. Ulmer, U., Dingle, T., Duchesne, P. N., Morris, R. H., Tavasoli, A., Wood, T., & Ozin, G. A. Nat. Commun., (2019) 10, 3169.

[3]. Albrecht, S. & Rech, B. Nat. Energy 2, 1-2 (2017).

[4]. Veawab, A. & Aroonwilas, A. Fuel Chem. Div. Prepr. 47, 49–50 (2002).

[5]. Brethomé, F. M., Williams, N. J., Seipp, C. A. & Kidder, M. K. Nat. Energy 3, 553 – 559 (2018).

[6]. Carmo, M., Fritz, D. L., Mergel, J. & Stolten, D. Int. J. Hydrog. Energy 38, 4901–4934 (2013).

[7]. Götz, M. et al. Renew. Energy 85, 1371–1390 (2016).

[8]. de Lucas-Consuegra, A., Serrano-Ruiz, J. C., Gutierrez-Guerra, N., & Valverde, J. L. Catalysts 2018, 8, 340−351.

[9]. Robatjazi, H. et al. Nat. Commun. 8, 1–9 (2017).

[10]. Abd-El-Latif, A. A. & Baltruschat, H. J. Electroanal. Chem. 662, 204−212 (2011).

Blog Written By

Dr. A. S. GANESHRAJA

National College, Thiruchirappalli

Tamilnadu, India

Blog Editors

Dr. S. Chanrasekar

Dr. K. Rajkumar

Dr. K. Vaithinathan

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