CM1417- Green Chemistry Ezra Ho Su Han A0080957U Greening The Grid: Growing Artificial Leaves It is the best of times;

in the history of the world, never has so much people have access to such an abundance of energy, and enhancing our lives. It is also the worst of times; an extreme gulf exists between the global North and South. Today, at least 1.5 billion people worldwide lacks access to electricity and at least 3 billion still use biomass for fuel, hindering development and exacerbating public health problems (IEA, 2010). Closer to home, in the developed world, more than 80% of our energy comes from fossil fuels (US EIA, 2011), constituting more than 50% of global greenhouse gas (GHG) emissions. While the transmutation of fossil fuels into energy has tremendously improved our lives, it has also contributed to rapid rises in GHG atmospheric concentrations that are very likely causing disruptive changes in climatic and ecological systems on a global scale (IPCC, 2007). As global energy demands mount, and barring a paradigm shift in energy consumption, the planet is on a road to complete ecosystemic collapse. Having gotten into this predicament due to our separation from nature, it is time we recognise our mistake. Fortunately, the emerging field of biomimetics is beginning to tap on nature's library of 4 billion years of natural selection. In this, the leaf, humble and ubiquitous, offers a solution. A ray of hope that is revealed through the dance of molecules to the tune of the sustainable paradigm. At the very fundamental level of life organisation, it is the Sun that sustains all life. Through the formation of carbohydrates and oxygen gas from carbon dioxide gas and water in the presence of sunlight [Equation 1], life thrives. In order to unlock the secret of the artificial leaf, we must first examine the inner workings of the photosynthetic process. 2n CO2 (g) + 4n H2O (l) + photons 2(CH2O)n (l) + 2n O2 (g) + 2n H2O (l) [Equation 1] With reference to Figure 1A below, the light-dependent reaction of photosynthesis is activated when photon particles from the Sun hits Photosystem II (abbreviated as PSII in Figure 1]. The proton causes a cascading wave of electron excitation that begins from PSII, through the various protein complexes in the thylakoid membrane, driving hydrogen ion movement from the stroma into the lumen. Finally, powered by a proton gradient, flow of hydrogen ions through ATP (adenosine

triphosphate) synthase produces the universal cellular energy currency, ATP (Hall & Rao, 1999). The products, NADPH (the reduced form of NADP+ - nicotinamide adenine dinucleotide phosphate) and ATP, then transition to the Calvin Cycle to be catalysed into carbohydrates. More significant to this analysis, as photons energise the PSII complex, they also simultaneously oxide water into hydrogen protons, electrons and oxygen gas [Equation 2]. H2O 4H+ + 4e- + O2 [Equation 2]

Figure1 A: The photosynthetic complex; Source: Wikipedia

This process, which takes place in what is known as the oxygen-evolving complex (OEC) in PSII, replaces the excited electrons driving light-dependent photosynthesis. More crucially, such a mechanism is able to oxidise oxygen- a highly electronegative element, from hydrogen; something which would require a disproportionate amount of energy and resources to mimic through conventional electrolysis. While the exact mechanism of this labyrinthine process is still shrouded in mystery, research suggests that the OEC is a Manganese-Calcium-Oxide cubane cluster (Ferreira et al, 2004). Should an artificial catalytic mechanism be found that imitates the plant's OEC, the hydrogen gas produced could then be catalysed in a fuel cell, together with oxygen gas, to produce clean energy, alleviating the energy crisis and lifting millions out of poverty (Cook et al, 2010). Although electrolysis of water is not novel, conventional catalysts like platinum are too expensive to be commercially viable. Moreover, in a plant's OEC, the oxidative stress induced by the splitting of water causes the entire structure to degenerate every 30 minutes during photosynthesis. Amazingly, proteins in PSII constantly regenerate the OEC (Birch, 2009). Inspired by this, in 2008, researchers reported a breakthrough where a cobalt-phosphate catalyst succeeded in forming an artificial OEC on a indium tin oxide electrode (Kanan & Nocera, 2008). The implications of this are staggering. Based on their results, the cobalt-phosphate catalyst was able to produce as much oxygen as photosynthesis. Should this mechanism be completely fine -tuned to

split water, the equivalent of an Olympic-sized swimming pool would suffice to satisfy global energy demand in 2050 [Equation 3]. H2O 4H+ + 4e- + O2 (H= 237 KJ/Mol = 13 MJ/L) 3.2 x 10^6 L x 13 MJ = 41 TW [Equation 3] (Nocera, 2010) This breakthrough offers a decentralised energy supply where sunlight is captured via photovoltaic (PV) cells and used to electrolyse water with the artificial OEC. The produced hydrogen and oxygen is then fed into a fuel cell to generate electricity. The by-product, water, is then pumped back to the artificial OEC to be reused [Figure 2A]. This effectively guarantees a pollution-free and renewable energy supply to sustain a world with increasing population pressures. With rapidly falling costs, and improving performances for PV cells (Barbose et al, 2011) and fuel cells (US DoE, 2011), there is no reason why in as soon as a decade, it would be technically impossible to power the world in a safe, renewable and emission-free way. Imagine a world where dropping a piece of metal in a glass of water produces electricity. No more fossil fuels. No more pollution. No more poor people not being able to afford electricity. Indeed, the future promises to be a bright one.

Figure2 A: Decentralised energy system; Source: Nocera, 2010

References Barbose, G., Darghouth, N., Wiser, R., Seel, J. (2011). Tracking the Sun IV: An Historical Summary of the Installed Cost of Photovoltaics in the United States from 1998 to 2010. Lawrence Berkeley National Laboratory. Retrieved from http://eetd.lbl.gov/ea/emp/reports/lbnl-5047e.pdf Birch, H. (2009, May). The Artificial Leaf. Chemistry World, 42-45.

Cook, T. R., Dogutan, D. K, Reece, S. Y, Surendranath, Y, Teets, T. S, & Nocera, D. G. (2010). Solar Energy Supply and Storage for the Legacy and Nonlegacy worlds. Chemical Review, 110(11), 6474-6502. Ferreira, K. N., Iverson, T. M, Maghlaoui, K. Barber, J, & Iwata, S. (2004). Architecture of the Photosynthetic Oxygen-Evolving Center. Science, 303, 1831-1838. Hall, D.O and Rao K.K. (1999) Photosynthesis. 6Th ed. United Kingdom: Cambridge University Press Kanan, M. W., & Nocera, D. G. (2008). In Situ Formation Of An Oxygen-evolving Catalyst In Neutral Water Containing Phosphate and Co2 . Science, 321, 1072-1075. Nocera, D. G. (Speaker). (2010, February 18). Personalized Energy for 1 (x 6 billion) [Video podcast]. IHMC Pensacola Evening Lecture Series. Retrieved from http://www.youtube.com/watch?v=ZAkM_dV6CFs US Department of Energy (DoE)/ Breakthrough Technologies Institute Inc. 2011. 2010 Fuel Cell Technologies Market Report. Retrieved from http://www1.eere.energy.gov/hydrogenandfuelcells/pdfs/2010_market_report.pdf U.S Energy Information Administration (US EIA). 2011. International Energy Outlook 2011. Retrieved from http://www.eia.gov/forecasts/ieo/pdf/0484(2011).pdf International Energy Agency (IEA). 2010. World Energy Outlook: Energy Poverty - How to make modern energy access universal? Retrieved from http://www.iea.org/weo/docs/weo2010/weo2010_poverty.pdf Intergovernmental Panel on Climate Change (IPCC). 2007. Climate Change 2007: Synthesis Report. Retrieved from https://www.ipcc.ch/pdf/assessment-report/ar4/syr/ar4_syr.pdf