Renewable Hydrogen Technologies: Production, Purification, Storage, Applications and Safety

1

Renewable Hydrogen Energy

An Overview

Luis M. Gandía, Gurutze Arzamendi and Pedro M. Diéguez,    Escuela Técnica Superior de Ingenieros Industriales y de Telecomunicación, Universidad Pública de Navarra, Campus de Arrosadía, E-31006 Pamplona, Spain

Outline

1.1 Setting the Context: Climate Change and Energy Security

1.1.1 International Energy Outlook

1.1.1.1 Oil and Liquid Fuels

1.1.1.2 Natural Gas and Coal

1.1.1.3 Electricity

1.1.1.4 CO2 Emissions

1.1.2 Toward Decarbonization

1.2 Is A New Energy Carrier Necessary?

1.2.1 The Hydrogen Economy

1.2.2 The Efficiency Issue

1.2.3 Hydrogen Contribution to Transportation and the Electric Grid

1.2.3.1 Hydrogen in Transportation

1.2.3.2 Hydrogen and the Electric Grid

1.3 Hydrogen Production

1.3.1 Pathways

1.3.1.1 Nonrenewable Hydrogen

1.3.1.2 Renewable Hydrogen

1.3.2 Status and Prospects of Renewables

1.4 Hydrogen Today

Acknowledgments

References

1.1 Setting the Context: Climate Change and Energy Security

The experience gained from over a decade of sustained research, development and demonstration projects corroborates that hydrogen and fuel cell technologies have strong potential to play a significant role in the new energy system that must be defined in the coming years. This energy system should provide adequate and prompt responses to the threats posed by the climate change and energy security issues.

The leaders of the Group of Eight (G8) recognized during the summit held in L’Aquila (Italy), July 2009 that, as for the dangers of climate change, the costs of inaction far outweigh the costs of moving toward low-carbon societies. But at the same time, it is obvious that secure energy availability is indispensable for social and economic development, so it is essential to ensure global energy access. It was also recognized, in agreement with the work of the United Nations (UN) Intergovernmental Panel on Climate Change,¹ that the increase in global average temperature above preindustrial levels should not exceed 2 °C. To this end, global CO2 emissions must peak and then start to decline rapidly within the next 5–10 years to have a reasonable chance of avoiding the worst impact of climate change. The global atmospheric CO2 concentration was about 330 ppm in 1970 and after 40 years it has increased at least 60 ppm, reaching over 390 ppm by the end of 2010. It has been projected that if atmospheric CO2 levels increase up to about 450 ppm, a critical point could be reached at which warming exacerbated by strong positive feedbacks will seriously disrupt climate.² At the rate at which CO2 emissions are currently growing, the critical point could be attained well before the next 40 years. In response to this serious threat, the G8 leaders expressed their willingness to share with all countries the goal of achieving at least a 50% reduction of global emissions by 2050 and to support a goal of developed countries reducing greenhouse gas (GHG) emissions by 80% or more by 2050 compared to 1990.

Regrettably, results from the most recent studies lead to discouraging perspectives. The International Energy Agency (IEA) has estimated that 80% of the total CO2 emissions permissible by 2035 in order to achieve a stabilization in 450 ppm are already locked-in by our current energy-related infrastructure.³ In the IEA central scenario, the so-called New Policies Scenario, in which the governments’ commitments are assumed to be implemented in a cautious manner, the trend of global emissions is consistent with a long-term average temperature increase of more than 3.5 °C. But the situation could even become much worse under the IEA Current Policies Scenario, which assumes that no new policies are added to those in force as of mid-2011. In this case, we would run the dangerous risk that the mean temperature rises 6 °C or more.³ Despite the almost generalized concern about the consequences of climate change, it is disappointing that policy makers are often faced with continuous difficulties in reaching clear compromises on the reduction of GHG emissions. The most recent demonstration occurred during the UN Climate Change Conference 2011 held in Durban (South Africa). Fortunately in this occasion, the world’s three largest pollutant emitters (United States, China and India) have agreed for the first time to sign up to a legal treaty to reduce GHG emissions. To elaborate an instrument with legal force applicable to all parties, it has been decided to create the so-called Ad Hoc Working Group on the Durban Platform for Enhanced Action.⁴ The problem is that it has been scheduled that the Working Group completes its mission no later than 2015 and that the resulting legal instrument comes into effect from 2020. This may be too late. In fact, in the absence of stringent new actions by 2017, the energy-related infrastructure in place by that year will it make impossible to accomplish the CO2 stabilization objective without extremely high costs.³

Previous analysis gives an idea of the risks associated to the difficulties of reaching international agreements on the reduction of GHG emissions. However, to better appreciate the magnitude of the challenge posed by the energy security issue and the need of transforming the energy system, a brief international energy outlook and a summary of the milestones that have to be achieved by a decarbonized economy are presented in the following subsections. Regrettably, we will see that the role assigned to hydrogen in the current energy policies is, at least in Europe, little relevant at the moment.

1.1.1 International Energy Outlook

According to the U.S. Energy Information Administration (EIA), under the conditions of a reference case that does not contemplate the incorporation of legislation or policies affecting energy markets, the world marketed energy consumption grows by 53% from 2008 to 2035.⁵ This means that the world primary energy consumption increases from 12,726 Mtoe in 2008 to 15,599 Mtoe in 2020 and 19,404 Mtoe in 2035a. The projected increase is modest in the case of the countries that are part of the Organization for Economic Cooperation and Development (OECD) (18%). Much of the growth takes place in non-OECD nations that increase by 85% their primary energy use during that period. The reason for this big difference mainly lies in the very different economic growth pace of these world regions. The recovery from the 2008 to 2009 worldwide economic recession makes uneven progresses. In the developed countries, the recovery is slow compared with previous economic crises; it seems that this situation will continue, at least in the short term, as suggested by the high unemployment figures and debt levels of some economies as well as financial turbulences existing within the OECD. In contrast, economic growth will remain robust in the main emerging economies due to strong capital incomes. According to the U.S. EIA reference case, China and India will continue to lead the world economic growth and the growth of the energy demand. The projected average annual gross domestic product (GDP) increase of the OECD countries during the 2008–2035 period is 2.1%, led by the OECD Americas with 2.6%. The annual energy consumption growth for the whole OECD region is 0.6% over this 27-year period. In the case of the non-OECD nations, the average annual GDP increase is much higher, up to 4.6%, led by the non-OECD Asia with a mean 5.3% GDP growth. This impressive sustained economic development is consistent with the projected average annual energy consumption growth for the non-OECD nations of 2.3% and 2.9% for the non-OECD Asia region.⁵ It is very relevant that the combined energy use of China and India more than doubles over the 2008–2035 period, reaching 31% of the world energy consumption, whereas the percentage of the OECD region amounts up to 37.4%.

In the following subsections, a more detailed outlook by energy sources as well as prospects for electricity and the energy-related CO2 emissions will be presented.

1.1.1.1 Oil and Liquid Fuels

The U.S. EIA projections show that liquid fuels, mainly from fossil origin, will remain the largest primary energy source with a market share that decreases from 34% to 29% between 2008 and 2035. Global consumption of petroleum-derived fuels and other liquids as biodiesel, bioethanol and synthetic fuels obtained from coal and gas increase altogether from 85.7 million barrels per day (bpd) in 2008 to 112.2 million bpd in 2035. Great part of this important increase corresponds to the transport sector which, in the absence of significant technological advances and despite the rising oil prices, increases the use of liquid fuels by 46%.⁵ The evolution of the monthly average prices of the Brent and West Texas Intermediate (WTI) crude oils since June 1995 is shown in Fig. 1.1. As can be seen, Brent crude oil price peaked at U.S. $145.9 per barrel (bbl) on 7th July 2008 and then decreased abruptly to initiate again a progressive increase characterized by a marked volatility, reaching $111/bbl by the end of January 2012. The average annual price in 2011 was $113/bbl, which almost coincided with that of 2008 ($112/bbl). Similarly, the WTI crude oil price peaked at $145/bbl in July 2008, and then decreased markedly to increase again reaching $98.5/bbl by the end of January 2012. Annual average prices for WTI oil crude were $98.3, $38.9 and $90.7 per barrel in 2008, 2009 and 2011, respectively. According to the EIA reference case projections, the average WTI oil crude price will reach $125/bbl in 2035. In a recent and thorough study, Sorrell et al.⁶ report that, as a result of a series of geological, technological and even definitional aspects, there is a real increase of the global average oil reserve that can be observed since 1995. The reserve growth is higher for the older (discovered before 1986) and larger onshore fields and the main contributions to this growth come from Saudi Arabia (37%), Iran (15%), Venezuela (12%) and Qatar (9%). Despite this positive finding from the point of view of the future global oil supply, as the decline rate of all currently producing fields is at least 4% per year, more than two thirds of the current oil production capacity may need to be replaced by 2030 simply in order to keep the production constant.⁶ Within this context, it is expected that during the coming decades, an important development of the exploitation of unconventional resources of liquid fuels as oil sands, extraheavy oil, shale oil, biofuels, and coal-to-liquids and gas-to-liquids technologies takes place. Global production of unconventional liquid fuels reached 3.9 million bpd in 2008 and it is projected that it increases up to 13.1 million bpd by 2035, accounting for 12% of the world’s fuel liquids supply. Main future contributions are expected to come from Canadian oil sands (4.8 million bpd), biofuels from the USA and Brazil (2.2 and 1.7 million bpd, respectively) and extraheavy oil from Venezuela (1.4 million bpd).⁵ Despite the good perspectives for this sector, especially for the Canadian oil sands (over 7 million bpd of capacity), it should be noted that these unconventional resources are characterized by significantly higher energy intensity and GHG emissions than conventional light oil.⁷

FIGURE 1.1 Evolution of the monthly average prices of the Brent and WTI crude oils since June 1995. (For color version of this figure, the reader is referred to the online version of this book.)

1.1.1.2 Natural Gas and Coal

World consumption of natural increases by 52% according to the EIA projections, that is, from 3.141 × 10⁶ million m³ in 2008 to 4.783 × 10⁶ million m³ in 2035. It is expected that natural gas continues being the preferred fuel for electric power production due to its advantages in terms of relatively low capital costs and energy efficiency associated to the use of combined cycle gas turbines. The strong position of natural gas within the energy market will be reinforced by the growth of liquefied natural gas production capacity and the recent advances in drilling technologies such as horizontal drilling and hydraulic fracturing that make now profitable to exploit many sources of unconventional natural gas as shale gas basins. It is expected that the natural gas reserve growth helps to control the gas price and increases the demand for this energy source likely above the projections. Initial estimates rise the shale gas reserve above 187 trillion m³. This figure is very significant taking into account that world-proven gas natural reserve and world technically recoverable gas resources (excluding shale oil) were 189 trillion m³ and 453 trillion m³, respectively, by January 2011.⁵ Coinciding with the shale gas production boom, concern has arisen about the environmental impact of the new drilling techniques. In a recent life cycle analysis, Burnham et al.,⁸ from the Argonne National Laboratory (IL, USA) found similar GHG emissions from shale gas and conventional natural gas production and use, which were 23% and 33% lower than for gasoline and coal, respectively. This study has alerted to the importance of controlling the upstream methane leakage and venting, which are key contributors to the total GHG from natural gas (conventional or unconventional) and can significantly reduce its benefits compared to oil or coal from the point of view of GHG emissions.

Regarding coal, world consumption increases by 50% according to the EIA reference case projections from 3502 Mtoe in 2008 to 5289 Mtoe in 2035. This remarkable consumption growth corresponds to that in the non-OECD Asia countries because the use of coal in the rest of the world remains almost unchanged. Especially China and India, having large domestic reserves of coal, increase its use for power generation and industrial sector by 70–100%. World projections of coal consumption are subjected to significant uncertainty in relation with the final feasibility and deployment of carbon capture and storage (CCS). This subject is treated with more detail in Section 1.3.1.1.

1.1.1.3 Electricity

World net generation of electricity increases by 84% in the EIA reference case, from 19.1 million GWh in 2008 to 35.2 million GWh in 2035.⁵ This impressive growth is led by the non-OECD Asia region with an annual average increase of 4.0% from 2008 to 2035, whereas it is only 1.2% per year for the OECD region due to the maturity of the market in the developed countries. Coal remains the main primary energy source for electricity generation although its share decreases from 40% in 2008 to 36.6% in 2035. Natural gas shows an opposite trend, with its share increasing from 21.8% to 23.8%. However, the most important growth corresponds to power generation from renewables with a share rising from 19.3% in 2008 to 23.4% in 2035. More than 82% of this increase is due to hydroelectric and wind energy which, by the end of the projection period, contribute with further 2.5 million GWh and 1.3 million GWh, respectively. Electricity from nuclear power maintains an almost constant share of about 14%, with a generation that increases from 2.6 million GWh in 2008 to 4.9 million GWh in 2035. Nuclear energy is considered a key piece of the future energy mix because it can contribute significantly to achieving a high degree of decarbonization of the energy system. However, the possible long-term implications of the incidents that occurred at the Fukushima Daiichi (Japan) nuclear power plant in March 2011 have given rise to considerable uncertainty about the future evolution of nuclear power generation. It is then likely that the projected figures are somewhat overestimated. The EIA projections show that 75% of the nuclear power-installed capacity growth takes place in non-OECD countries, led by China, Russia and India, which add 106, 28 and 24 GW, respectively, of new generation capacity.

1.1.1.4 CO2 Emissions

Under the current policies assumption, global energy-related CO2 emissions are projected to increase by 43% over the period between 2008 and 2035.⁵ This implies passing from 30,200 million metric tons in 2008 to 43,200 million metric tons in 2035. Much of this big increase is associated to the robust economic growth exhibited by the largest non-OECD developing nations. Coal accounts for the main share of CO2 emissions that increases slightly from 44.1% in 2008 to 44.9% in 2035. On the other hand, whereas the share of liquid fuels decreases from 35.3% to 33.2%, that of natural gas increases from 20.6% to 21.9% over the 27-year projection period. With regard to carbon intensity, whereas it improves (decreases) worldwide when referred to the unit of economic output due to more efficient energy transformation processes, different trends arise when considering CO2 emissions per capita. In this case, emissions from the OECD countries fall slightly from 11.1 metric tons per person in 2008 to 10.6 metric tons per person in 2035. In contrast, the emissions intensity increases in the non-OECD countries, especially China, where the increase is from 5.1 to 9.3 metric tons per person during the 2008–2035 period. This gives an idea of the magnitude of the expected energy consumption increase in the most populated country on earth.

1.1.2 Toward Decarbonization

The international energy outlook presented in the previous section makes it clear that under a scenario dominated by the current policies, the energy-related CO2 emissions increase remarkably, just the opposite to what is needed in order to possibly limit the increase in global average temperature below 2 °C. Strongly determined policies are required to remedy this situation. First and foremost, the overall energy consumption has to be reduced. Forecasts by the IEA according to the 450 PS scenario (based on a plausible post-2012 climate policy framework to stabilize the GHG concentration at 450 ppm CO2-equivalent) projects a global primary energy consumption of 14,920 Mtoe by 2035.⁹ This figure contrasts clearly with the above-mentioned 19,404 Mtoe projected by the U.S. EIA for 2035 under current policies assumption. The gap should be even higher because the U.S. EIA forecasts include only marketed energy, whereas those by the IEA also include biomass, such as fuelwood, charcoal and agricultural waste used for cooking and heating in developing countries, that accounts for about 10% of world primary energy demand. In Fig. 1.2, the world consumption of primary energy by sources in 2009 and in 2035 according to the IEA 450 PS scenario is compared. It can be seen that the achievement of the GHG concentration stabilization goal (450 PS) requires doubling the contribution of both renewables and nuclear power in the energy mix. Their share should increase from 13.2% in 2009 to 26.8% in 2035 in the case of renewables and from 5.8% in 2009 to 11.2% in 2035 for nuclear power. According to the 450 PS scenario, the combined share of fossil fuels should decrease from 81% in 2009 to 62% in 2035; nevertheless, the natural gas consumption increases by 17%. On the other hand, whereas the required oil consumption decreases is small, that of coal is about 25%. This constitutes a very challenging goal owing to the strong implantation of coal use for electricity generation, especially in the USA, China and India that have large domestic reserves.

FIGURE 1.2 Primary energy consumption by source in 2009 and in 2035 according to the projections of the IEA 450 PS scenario compatible with the stabilization of the GHG concentration at 450 ppm CO2-equivalent. (For color version of this figure, the reader is referred to the online version of this book.)

The European Union (EU), in response to the commitment expressed by the G8 leaders in 2009 in order to achieve a significant reduction of the GHG emissions by 2050, has launched a series of ambitious initiatives. In support of the European Council’s abatement objectives for Europe, the European Climate Foundation (ECF) has elaborated the Roadmap 2050: a practical guide to a prosperous, low-carbon Europe.¹⁰ This document outlines plausible ways to achieve a reduction target of GHG emissions of at least 80% compared to 1990 levels. Among the findings of this study it can be emphasized that the GHG emission reduction objectives will be hard to realize if a transition to a new energy system both in the way the energy is used and in the way it is produced is not started before 2015. This has also important implications from the economic point of view. Having begun the transition in 2010, the capital spent in the power sector would have increased from €30 000 million in the first year to €65 000 million in 2025. If delayed by 10 years, the capital spent in 2035 would increase up to €90 000 million. However, apart from technical and economic issues, the feasibility of implementation of the decarbonization pathways is considered the biggest challenge. The following milestones have to be achieved by a European decarbonized economy between now and 2050¹⁰:

1. Installation of about 5000 km² of solar panels over 40 years is required; this means equaling 0.1% of the EU area assuming that half of the new capacity corresponds to rooftop panels. Installation and replacement of close to 100,000 wind turbines (of which half could be offshore) is also required. This implies between 2000 and 4000 new turbines per year, a pace similar to that exhibited by the wind energy sector in the last years although the new turbines should be significantly larger (up to 7–10 MW).

2. An overall expansion of electric grid interconnection between and across regions in Europe that is an increase of factor three from today’s level of transmission capacity is needed. Moreover, between 190 and 270 GW of backup generation capacity is required to maintain the reliability of the electric system, of which 120 GW is already in the baseline. This represents 10–15% of total generation capacity by 2050 that would be run at load factors between less than 5% up to a maximum of 8% depending of the degree of penetration of renewables.

3. The implementation of CCS for power generation and the industrial sector is required. This implies building the corresponding infrastructure for transporting and storing the captured CO2. It should be noted that the ECF’s roadmap has been designed under the assumption of a carbon tax of at least € 20–30 per metric ton of CO2 over 40 years.

4. Under the assumption of a penetration of renewables of 40%, about 1.5 million GWh per year of nuclear power is required, compared with approximately 1 million GWh per year today. About 200 GW of new nuclear power would be required, representing over a 100 of new nuclear plants entering into operation. In contrast, a degree of penetration of renewables of 80% would lead to the replacement of half the current level of nuclear power production.

5. Potentially up to 200 million electric and fuel cell vehicles and around 100 million heat pumps for buildings and city districts need to be deployed.

Along the lines of the ECF work, on 15 December 2011 the European Commission (EC) adopted the Communication Energy Roadmap 2050¹¹ where the EC explores the challenges posed by delivering the EU’s decarbonization objective of reducing GHG emissions to 80–95% below 1990 levels by 2050 while ensuring security of energy supply and competitiveness. Within this context, it should be noted that the EU has as the starting point the Directive on the Promotion of the Use of Energy from Renewable Sources.¹² This Directive establishes as general objectives to achieve a 20% share of energy from renewable sources in the EU’s gross final consumption of energy and a 10% share of energy from renewables in each member state’s transport energy consumption by 2020. These objectives are ambitious but insufficient because they would lead to less than half of the decarbonization goal for 2050. The Energy Roadmap 2050 is the basis for developing a long-term European framework in order to guarantee a high degree of decarbonization of the European economy. According to this document, a secure, competitive and decarbonized energy system in 2050 is possible.¹¹ To this end, a transition is necessary from the current system, characterized by high fuel and operational costs, to a system based on higher capital expenditure but lower fuel costs. Cumulative grid investment costs alone could amount to €1.5 × 10⁶ to 2.2 × 10⁶ million between 2011 and 2050. These large figures result from the fact that electricity will have to play an increasingly important role, doubling its share in final demand energy to 36–39% in 2050, and contributing to the decarbonization of transport and heating/cooling needs. It should be taken into account that in the coming few years an important number of power plants will reach the end of their useful life. This can be viewed as an opportunity for performing the structural change that needs the power generation system. Another key point is the need for reducing the primary energy demand through energy saving and improved efficiency strategies. Primary energy demand should decrease by 16–20% by 2030 and 32–41% by 2050 as compared to consumption peaks in 2005–2006.

However, as important as the above objectives is the need to transmit a new sense of urgency and collective responsibility to the public and private sectors as well as to the general public in order to suitably address the challenges posed by the climate change and the transformation of our energy system.

1.2 Is a New Energy Carrier Necessary?

At this point, the reader will have perceived the minor role assigned to hydrogen in the current energy policies. The same conclusion was reached by Bleischwitz and Bader after a thorough review of the EU energy and regulatory and spending policies.¹³ It can be said that the current EU policy framework does not hinder hydrogen development but it does not constitute a strong push factor either.

In the European Energy Roadmap 2050, probably the world’s most ambitious decarbonization strategy designed until now, hydrogen appears only in the section entitled Smart technology, storage and alternative fuels.¹¹ Regarding alternative fuels and electric vehicles, it is mentioned that they have to be supported by regulatory developments, standardization, infrastructure policy and further research and demonstration efforts, particularly on batteries, fuel cells and hydrogen, which together with smart grids can multiply the benefits of electromobility both for decarbonization of transport and development of renewable energy.

The fact that the role assigned to hydrogen in the current policies is little relevant despite the progresses made in the recent years suggests that perhaps we have to ask the question: Is a new energy carrier really necessary?

In the following subsections, we will try to answer this question discussing on the evolution of the Hydrogen Economy concept, the issue of the energy efficiency and the interactions between hydrogen and electricity.

1.2.1 The Hydrogen Economy

The roots of the hydrogen economy concept have been established by Dunn in his History of Hydrogen.¹⁴ It should be remembered that hydrogen has traditionally important applications in the chemical industry such as ammonia and methanol syntheses, oil refining and several petrochemical processes. However, a series of cases can be found that illustrate the interest for other uses of hydrogen from the start of the twentieth century. At that time, for example, the first big commercial units of water electrolysis were built and put into operation in Canada taking advantage of its large hydroelectric resources. Hydrogen and oxygen were mainly used in steel-cutting procedures. The German zeppelins used hydrogen for air travel during the 1920s and 1930s. During World War II, numerous cars, delivery vans and trucks were adapted to run on hydrogen in Germany and England. The U.S. space program led to the start of the development of fuel cells in the 1950s and 1960s. But the origin of the concept of a hydrogen economy corresponds to the electrochemist John Bockris in 1970. At that time, Bockris was a consultant to General Motors (GM) and, in his book Energy: The Solar Hydrogen Alternative (1975), he traces the coining of the term to a discussion at GM about possible alternatives to gasoline where it was agreed that hydrogen would be the eventual fuel for all types of transport in the future. Along with Bockris,¹⁵ T. Nejat Veziroglu, who has been president of the International Association for Hydrogen Energy (IAHE) since its beginning in 1974, has also had a prominent role in the development and dissemination of the hydrogen economy concept.¹⁶,¹⁷ It seems no coincidence that the birth of the hydrogen economy concept in the 1970s coincides with the first oil crisis that marked the beginning of the end of cheap oil. The hydrogen economy pursues the final objective of a new energy system where human civilization is primarily powered by hydrogen. However, hydrogen is not an alternative fuel but an energy carrier that has to be produced consuming primary energy. This constitutes the central, but not unique, problem of the hydrogen economy.¹⁸

McDowall and Eames carried out an extensive review of the literature available until 2005 with the aim of capturing the diversity of published studies dealing with the future of hydrogen as an energy carrier and the hydrogen economy.¹⁹ Despite divergent views on the factors that will shape the future of hydrogen energy, four main issues stand out in the early studies as thedrivers of a hydrogen economy: climate change, energy security, local air quality and international competitiveness. A series of barriers to the development of a hydrogen economy have also been identified. Among the most outstanding are the difficulties involved in establishing a market for hydrogen and fuel cells in the absence of a hydrogen distribution and refueling infrastructure, and vice versa, without a market for hydrogen, there are no incentives for investments in very expensive new infrastructures. There is also agreement that the high cost of fuel cells as well as of hydrogen produced from low-carbon routes is a big hurdle for the deployment of hydrogen as an energy carrier in the sustainable future. A series of technological barriers are also recognized: difficulties for onboard storage of hydrogen, which limits the driving range of fuel cell vehicles, limited lifetime and reliability of fuel cells, uncertainty over the feasibility, costs and environmental impact of CCS, safety issues, public acceptance and the lack of specific legislation, codes and standards. Under these circumstances, the exploratory studies project that the hydrogen economy emerges very slowly, or not at all, in business as usual scenarios. However, a rapid deployment is predicted under conditions of strong governmental support combined, or as a result, of technological breakthroughs that allow greatly reducing costs, marked oil price increases, shifts in social values, or a rapid intensification of the problems associated to climate change. Several policy measures are usually recommended to support the hydrogen economy: increased R&D funding, infrastructure development, tax incentives for hydrogen fuel production and fuel cell vehicles purchase, support for renewables and targets for low carbon vehicles.

Taking the transition to fuel cell vehicles as the key step toward a hydrogen economy introduction, as it is usually considered in the early hydrogen futures studies, one can find a broad temporal distribution covering the period between 2010 and 2050 when the hydrogen economy emerges; this illustrates the diversity of views in this regard.¹⁹ Once emerged, there is considerable agreement that the evolution of the hydrogen economy is from decentralized to centralized schemes. At first, a decentralized scheme based on the local (onsite) production of hydrogen from water electrolysis and biomass processing or steam reforming of natural gas facilitates overcoming the big barrier posed by the lack of a suitable infrastructure to the transition to hydrogen. Later, a gradual shift to centralized architectures allows introducing a wider variety of energy sources as coal and nuclear thermal energy for hydrogen generation at large scale and lower costs provided that a dedicated hydrogen distribution infrastructure is available. There is also agreement that in the short to medium term hydrogen production will rely on methane steam reforming, preferably with CCS, whereas the ultimate hydrogen economy is based on renewables. Fossil fuels as natural gas and coal and nuclear energy are frequently considered as transitional technologies.

McDowall and Eames identified a series of problems with the majority of the early literature.¹⁹ Many of the studies make assumptions about the effects of policies on innovation and diffusion of new technologies but without a theoretical background or making explicit the basis of the assumptions. Predictions, forecasts and targets are recycled, deployed as arguments to confirm particular views of the future. Many of the descriptive futures display a prohydrogen bias, and there is also a tendency to analyze the prospective developments in hydrogen relatively isolated rather than integrated in a global and dynamic energy system.

In our opinion, another important weakness of many studies related to hydrogen energy is that the key issue of the efficiency, that is, the overall energy balance of hydrogen use is very often not clearly addressed.

1.2.2 The Efficiency Issue

Primary energy is consumed in all the steps of the hydrogen economy chain: production, storage, distribution, delivery and end use. Bossel²⁰ and Bossel et al.²¹ have performed an analysis of the energy losses associated to these steps adopting water electrolysis for hydrogen production, as it allows the direct use of renewable sources as hydroelectric, wind or solar energy. Starting from 100 kWh of AC renewable electricity, Bossel estimated and compared the overall efficiency between the electricity source and wheel motion for two types of cars: a hydrogen fuel cell electric vehicle (FCEV) and a battery electric vehicle (BEV) with regenerative braking.²⁰ The results for the FCEV case when hydrogen is distributed, stored and transferred to the vehicle as compressed gas are summarized in Fig. 1.3A. As can be seen, there is a cascade of energy losses that begins with the AC–DC conversion of electricity to feed the water electrolyzer. Bossel assumed efficiencies for these steps of 95 and 75%, respectively. As for the electrolysis, the figure seems reasonable in view of the performance of the modern alkaline bipolar filter press-type water electrolyzers, although it is significantly lower (50–65%) for the polymer electrolyte membrane (PEM) electrolyzers.²²,²³ Transmission electricity losses were not present, in accordance with a plant for hydrogen production directly from the renewable electricity source. Regarding hydrogen delivery, in this example, it was considered that hydrogen was first compressed to 20 MPa and distributed by road to filling stations where it was stored at 10 MPa, and finally compressed to 40 MPa for rapid transfer to vehicles where it is stored at 35 MPa. The aggregate efficiency of this delivery scheme is 72%. As for the fuel cell, 50% efficiency was assumed that along with a 90% efficiency for the rest of the vehicle system yields an efficiency of the fuel cell-based powertrain of 45%. This results in 23 kWh of final useful energy, that is, an estimated overall efficiency of only 23%. The 50% efficiency assigned for the fuel cell seems today to be somewhat low. According to the Fuel Cells Technology Program of the U.S. Department of Energy, a PEM fuel cell yields 60% efficiency for transportation. Taking this value into account, the overall efficiency would increase up to about 28% (27.7 kWh of final energy available). Obviously, the final result is also dependent on the way hydrogen is stored and delivered. Presently, compressed and liquefied hydrogen are the only options commercially available. According to Bossel, the energy efficiency of the delivery scheme based on liquid hydrogen is 65% for the liquefaction process and 90% for its road transport, storage and vehicle transfer steps resulting in an aggregate 58%. In this case, the useful energy finally available, 22.5 kWh (22.5% overall efficiency assuming 60% efficiency for the fuel cell), is lower than when considering the use of hydrogen as compressed gas.

FIGURE 1.3 Energy losses for an FCEV fueled with hydrogen from water electrolysis and a BEV. (For color version of this figure, the reader is referred to the online version of this book.) Source: Data taken from Bossel.²⁰

In the case of the BEV (Figure 1.3B), the losses correspond to the electricity transmission through the grid (90%), AC–DC conversion and battery charging (85%) and the electric powertrain (90%). The final overall efficiency of the BEV, 69%, is much higher than that for the FCEV. Obviously, the production of hydrogen from electricity (and water) to reconvert it back to electricity in a hydrogen fuel cell will be always much less efficient that the direct use of the original electric resource regardless of the way hydrogen is stored and delivered. From this example, it can be said that about one fourth of the electric power obtained from a renewable resource is finally put to service when using hydrogen produced from water electrolysis as energy carrier. It should be noted that water electrolysis has the advantage that produces very pure hydrogen, suitable for direct use in a PEM fuel cell. This is in contrast with the hydrogen production pathways from biomass, natural gas or coal that produce a mixture of hydrogen and carbon oxides (CO and CO2). As PEM fuel cells do not tolerate CO concentrations in the feed above 10–50 ppm, it is necessary to further process the hydrogen stream to convert CO into CO2 and then separate the carbon dioxide. Although the reforming of natural gas is a very efficient process that can achieve 90% for large-scale centralized plants, the need for hydrogen purification represents a significant energy penalty. Methane can be obtained from renewables resources as biomass gasification or the anaerobic digestion of organic wastes to produce biogas to further produce hydrogen, but at the expense of additional energy losses. It is interesting to mention at this point that hydrogen can be used in internal combustion engines (ICEs). Of course the efficiency is low compared with a fuel cell, although thermal efficiencies up to 35% can be achieved, which are better than the typical values for gasoline engines. However, ICEs do not require high-purity hydrogen that can offset to some extent the lower efficiency. Hydrogen-fueled ICE vehicles can be considered a transitional or bridging technology that would allow a faster introduction of hydrogen in the transport sector. This is mainly due to their lower cost, immediate availability and the possibility of using the current manufacture infrastructure of the automotive industry.²⁴

The analysis of the parasitic energy losses led Bossel to state that a hydrogen economy will never make sense because it is an extremely inefficient proposition for the distribution of electricity from renewables. He also affirmed that, despite some niche markets tolerating high energy losses, it is unlikely that hydrogen will ever become a relevant energy carrier in an energy system relying on renewables and energy efficiency.²⁰ Although much less categorical in their conclusions, Rand and Dell also indicated that it would be very inefficient and uneconomic under most conditions to convert renewable electricity to a chemical fuel to be used in an ICE or reconverted back to electricity in a fuel cell.²⁵ According to these authors, it would be generally better to utilize directly renewable electricity since energy losses during electricity distribution are comparatively small. Two possible exceptions are highlighted. On the one hand is the case of islands or isolated communities with large renewable resources but without storing means that could produce hydrogen with surplus energy and reconvert it to electricity during periods of peak demand or insufficient renewable resource. On the other hand are countries such as Iceland or Norway that have abundant and cheap geothermal or hydroelectricity that could be used to produce hydrogen for use in transport. Rand and Dell also mentioned that without taking account of the losses incurred in compressing and distributing hydrogen, about 45% of the original electricity used to generate hydrogen by water electrolysis may be recovered with fuel cells. This figure is in line with the previous analysis of energy losses of an FCEV if one considers 75% efficiency for water electrolysis and 60% efficiency for the fuel cell.

Armaroli and Balzani also expressed a critical view.¹⁸ Due to the environmental issues posed by the production of hydrogen from the currently available procedures, these authors described that talking about a hydrogen economy is at least in part a futile exercise before having developed the exploitation of renewables. They also described as irrational the use of water electrolysis to produce hydrogen that will be used in fuel cells to generate electricity again. The only reason to do it would be related to the capacity of hydrogen to store energy, but this practice is far from the dream of a global energy economy because it may become only a part of a future new energy system.

As discussed previously (see Section 1.1.2), the reduction of the primary energy consumption should be one of the pillars supporting this system. Energy efficiency will play a key role to achieve this goal. In fact, it should be noted that current energy losses during the whole energy conversion process amount to about two thirds of the primary energy used in power plants, kilns, thermal engines, high-temperature chemical processes, etc.²⁶ Electrolysis and fuel cell combinations may be employed for temporary storage of energy but only in situations where convenience outweighs inefficiency, as in the case of the FCEVs. In the very long term, when renewable electricity may be the main source of energy, efficiency considerations will dictate that it should be transmitted directly and not by chemical carriers as hydrogen. A sustainable energy system cannot be built on the basis of inefficiency, and this principle has to also be applied to the hydrogen economy. Therefore, the original hydrogen energy concept needs to be redesigned.

1.2.3 Hydrogen Contribution to Transportation and the Electric Grid

In a recent essay by Andrews and Shabani, it is affirmed that the time for a vision of the future in which hydrogen is the exclusive fuel has passed because the trend is toward the extensive use of electricity and batteries.²⁷ This does not imply that its future role has to be irrelevant. There are important areas of application in which hydrogen can still make significant contributions, but in cooperation with electricity, not as competitors. This is the case of the use of hydrogen in the transportation sector and as energy storage means for the support of electric grids relying extensively on renewables.²⁷ These applications will be briefly commented on in the next subsections.

1.2.3.1 Hydrogen in Transportation

Our standard of living is in great part due to an easy access to the effective and fast transport of passengers, raw materials and manufactured goods. For this reason, as well as due to the strong implications of transport from the environmental and energy security points of view, this sector will continue playing a key role in the future energy system.²⁸,²⁹

Contrary to what happens today, that oil-derived fuels cover almost 95% of the energy demand of the transport sector, it is expected that in the coming decades there is a remarkable diversification of the energy sources used for transportation. Although the share of oil (including unconventional resources) will presumably continue to be predominant until at least 2035–2050, it seems reasonable that synthetic fuels from natural gas and coal, compressed and liquefied natural gas as well as biofuels gradually increase their contribution. Nevertheless, these options should also face their own challenges. This is the case, for example, of biofuels, which due to the possible negative impact of their extensive production on sustainability, have a maximum estimated future share of 20–30%.²⁹ All the alternatives mentioned so far are fuels for ICEs (note that methane can also feed some high-temperature fuel cells suitable for stationary applications). But what may lead to a revolution of the transport sector is its electrification, a revolution that perhaps has already started. Several car manufacturers are now commercializing a series of electric vehicles that, although with a small market share at the moment, are expected to grow their sales at a rapid pace in the coming years. These vehicles can be ranked according to an increased involvement of the battery in the powertrain, and thus extended electric driving range, as follows²⁹: hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs) and pure BEVs. Both HEVs and PHEVs incorporate an ICE whereas the BEVs include an electric engine. The FCEVs can be considered an alternative to the PHEVs and HEVs. Electrification has important advantages:

1. It is an effective way of decarbonizing the transport sector provided that electricity from renewables is used to recharge the batteries.

2. The energy efficiency is much higher compared to the use of liquid fuels or even FCEVs; nevertheless, further development of batteries technology is still required.

3. There is only need for a network of recharging stations but, in contrast to hydrogen, the distribution infrastructure already exists, the electric grid. Of course, a transformation of the grid management system will be required to permit a high degree of penetration of renewables in the electricity mix.

Despite the optimistic perspectives for the electric vehicles, perhaps the main challenge they have to face is that of customer acceptance regarding their limited driving range, as well as the availability, accessibility and user convenience of the recharging stations. According to the current status of the battery technology, it seems that BEV will be suitable only for short-distance transport, for example in urban areas, due to their limited driving range. In order to increase the range to large distances PHEVs can be used, but they depend on the availability of liquid fuels. This is where the hydrogen FCEVs become more competitive because these vehicles cover the entire driving range; moreover, refueling is much faster than in the case of the electric vehicles.²⁹ The drawbacks are the higher cost of FCEVs and the complexity and cost of a completely new hydrogen distribution infrastructure.

The degree of success of the BEVs and FCEVs will depend to a great extent on the future technological progress and cost evolution of batteries and fuel cells. A significant breakthrough in battery technology allowing BEVs to cover the entire driving range would likely make the FCEVs largely unnecessary. In contrast, the consequences of a breakthrough in fuel cells technology leading to a substantial reduction of the FCEV cost is much less clear due to the uncertainties about the feasibility of a supporting hydrogen infrastructure. It may also happen that BEVs and FCEVs reach their corresponding market shares that can differ depending on different regional or national determining factors such as the grid characteristics, hydrogen costs, renewables deployment and liquid fuels availability.

Finally, the potential of the hydrogen-fueled ICE vehicles to dynamize an early hydrogen market that can catalyze the integration of hydrogen in the transport sector should not be forgotten.

1.2.3.2 Hydrogen and the Electric Grid

The electric grid accumulates over a century of reliable service but aging of the infrastructure is challenging the ability of the electric grid to continue performing suitably. One of the main challenges is the management of an increasing share of intermittent generation capacity associated to renewables as wind and solar energy. The fluctuations of these sources are more pronounced than fluctuations in electricity demand and compensating for these variations is complex. The smart grid concept is very promising regarding the solution of these problems.³⁰ A smart grid consists in the application of modern communications infrastructure to various segments of the electric grid. This enables the system operator to better monitor the high-voltage transmission grid and control the energy flows more precisely. The load control capacity offered by a smart grid could help to compensate for wind and solar variability by managing energy storage systems, as for example, thermal storage units based on electric water heaters, compressed air facilities or hydropumping. Hydrogen produced from water electrolysis offers also the possibility of storing renewable energy during overgeneration periods. The Spanish case constitutes a good example of the potential of hydrogen to balance the grid loads.³¹ The current power generation capacity in Spain is over 90 GW while the peak demand reaches about 45 GW. Clearly, the Spanish power system is dramatically underutilized. Part of this overcapacity, even those corresponding to nonrenewable energy sources, could be considered for hydrogen production, as suggested for other world regions.³² Moreover, an analysis of the data from the Spanish power operator shows that annual power generation exceeds the electricity demand in an amount that in 2009 reached 3.25% (8170 GWh), with a daily average surplus of 22.4 GW. The study carried out by Gutiérrez-Martín and Guerrero-Hernández is based on the analysis of the deployment of 53 water electrolysis plants of a rated capacity of 50 MW each during the period 2011–2020.³¹ It was concluded that, by starting the operation in 2011 with 23 electrolysis units, a positive cash flow is obtained from 2014 with net income of €1863 million in the whole period considered. It is possible in this way to attain up to 42.2% share of renewable power generation in Spain by 2020. The total surplus energy would amount up to 126,013 GWh, being about 61% off-peak generated energy. The energy back generated with hydrogen would be 11,674 GWh ≈ 1 Mtoe, or the energy content equivalent of about 297,000 tons of hydrogen. The study serves to illustrate that it is technically and economically feasible to improve the management of the electric grid using the excess power during overgeneration periods for producing hydrogen from water electrolysis.

1.3 Hydrogen Production

Hydrogen is an energy carrier so its production is the first step of its possible contribution to the energy system. Moreover, this step greatly influences its environmental and carbon footprints because hydrogen can be obtained whatever the type (fossil, nuclear or renewable) of primary energy used.

This section will start with a series of simple calculations with the aim of illustrating the order of magnitude that represents the amount of hydrogen that can be needed in the future. The analysis is limited to the foreseeable needs for transportation since, as discussed previously, the transport sector is one of the most likely areas of application of hydrogen. According to the U.S. EIA reference case, the primary energy demanded by the transport sector will increase from 2470 Mtoe in 2008 to 3578 Mtoe in 2035.⁵ This is equivalent to an increase from 103 to 150 EJ. It should be noted these enormous amounts of energy include all transport means (road, rail, air, water and even pipeline). As a first approximation, only road transport with light-duty vehicles will be considered. Even with a significant electrification of the transportation, the share attained by the FCEVs could reach 30–70%.²⁹ Therefore, the energy that would be demanded in the form of hydrogen in 2035 can be estimated between 6 and 14 EJ. The higher heating value of hydrogen is 141.6 MJ/kg so the amount of hydrogen required would be between 42.4 and 98.9 million tons. The current annual world production of hydrogen is about 60 million tons that are mainly used for ammonia synthesis (51%), oil refining (35%) and methanol synthesis (8%).³³ This implies that by 2035, the global production capacity of hydrogen would have to be between two and three times the current one. Achieving this figure looks challenging but not impossible, especially if there is a dynamic market stimulating the production and consumption of hydrogen. These calculations can be considered conservative compared to what would be the hydrogen-equivalent of the total world energy demanded by the transportation sector. One can realize in this way the unattainable implications of a hydrogen economy fully powered with hydrogen.

In the following subsections, the main routes for hydrogen production will be presented, with emphasis on the use of renewables.

1.3.1 Pathways

One of the attractive features of hydrogen as an energy carrier is that it can be obtained from virtually any energy source. This topic has been profusely treated in the literature so here we will limit to provide a general overview distinguishing between routes leading to the production of nonrenewable and renewable hydrogen.³³–³⁵

1.3.1.1 Nonrenewable Hydrogen

The main pathways for hydrogen from nonrenewable energy sources are schematized in Fig. 1.4. Nuclear power has been included in this category because the available nuclear fuel reserves are limited. These routes have great importance because they are currently used to produce over 96% of the total hydrogen. About 48% is obtained from methane, mainly by steam reforming, 30% from petroleum fractions in refineries (through steam reforming and partial oxidation) and 18% from coal gasification.¹⁸,³³ The share of water electrolysis to hydrogen production is 4% and only the contribution of renewables to the electricity mix could be considered capable of producing renewable hydrogen. This contribution was about 20% in 2010.³⁶

FIGURE 1.4 Scheme of the main hydrogen production pathways from fossil fuels and nuclear power. (For color version of this figure, the reader is referred to the online version of this book.)

Hydrogen production from fossil fuels is carried out through a series of thermochemical processes involving several catalytic steps. These processes are commercially available and, in the case of the steam reforming of methane (SRM), especially mature. As long as natural gas remains at moderate prices, even including a carbon tax, SRM will prevail as the technology of choice for massive hydrogen production.³⁷ There is almost general agreement that the huge amounts of hydrogen required for its introduction in the transportation sector could only be obtained in the short and medium terms by means of SRM. Recent developments in the field of coal gasification such as the entrained flow gasifiers used in the Integrated Gasification Combined Cycle (IGCC) systems indicate that this technology will play an increasingly important role for hydrogen production.³⁸–⁴⁰ Power plants based on IGCC could efficiently coproduce hydrogen and electricity. However, in order that fossil fuels can contribute to hydrogen production within an energy system compatible with the stabilization of the GHG concentration in the atmosphere, the development and deployment of CCS technologies are indispensable.

Regarding CO2 and CCS, Benson and Surles made an interesting analogy with other environmental problems.⁴¹ In the same manner as pollutants such as SO2 or NOx from power plants or municipal wastes are no longer released into the environment, these authors wonder whether it could be the same with the CO2 emissions from fossil fuels. In previous occasions, avoiding pollutant emissions was initially believed to be too costly. However, once the requirements to limit the emissions are established, technological innovation in competitive markets resulted in effective solutions at acceptable costs. This is also expected for CCS, also known as carbon sequestration. The process starts with the separation and concentration to a nearly pure form of the CO2 contained in flue gases at the industrial source. Then it is compressed to about 10 MPa and pumped as liquid into deep geological formations where it is stored. Suitable underground formations are depleted oil and gas wells, brine-filled formations or deep unmineable coal beds. Consideration was also given to the injection and storage of CO2 in the ocean, but concerns about possible unknown environmental impacts have led to loss of interest in this option. Potential storage capacity is estimated to be over 3 × 10⁶ million tons of CO2 and a few industrial-scale projects have been operated.⁴¹ There are different types of CCS systems: postcombustion, precombustion and oxyfuel combustion. The flue gas pressure, its CO2 content and the type of fuel (solid or gas) are important factors in selecting the capture system. There is relatively little experience in combining CO2 capture, transport and storage into a fully integrated system.⁴² In addition to the technological challenges that still remain, numerous life cycle assessment studies are being performed in order that the decision to deploy CCS at a large scale is based on robust information on its overall costs and benefits.⁴³

As mentioned earlier, water electrolysis constitutes a minority pathway to hydrogen production. The technology is mature; moreover, there are commercial units available with rated powers up to 3.5 MW that are capable of producing up to about 600 hydrogen tons per year.²³ The main drawbacks are economic; the operating costs are especially much higher than for the thermochemical routes. High-temperature heat available, for example, at nuclear power plants could be used in conjunction with electricity to perform the electrolysis of steam with the advantage that at high temperature it is thermodynamically feasible to lower the fraction of energy supplied to the electrolyzer in the form of electricity, thus reducing production costs. This technology is not commercially available yet, although promising progresses have been made in recent years.

As indicated in Fig.1.4, high-temperature heat can be used to obtain hydrogen from water by means of thermochemical cycles. This pathway consists in a series of chemical reactions forming a closed cycle in which water is decomposed and all other chemical compounds are recycled. Typically, thermochemical cycles require heat at temperatures of at least 850–900 °C. For this reason, the feasibility of these cycles is typically linked to nuclear power, although the concept also shows potential to be performed with geothermal resources.⁴⁴ At present, the most promising cycles are the so-called sulfur–iodine (S–I), Br–Ca–Fe and copper-chloride (Cu-Cl). None of them is commercially available yet.

The cost of hydrogen is obviously a key factor that will markedly influence the role a given technology will play for future hydrogen production. Bartels et al. performed a literature review on this issue.⁴⁵ Even including CCS, the cheapest hydrogen can be obtained from coal (U.S. $1.05–1.83/kg) and natural gas ($2.48–3.17/kg). Although the initial capital cost of the coal plants are much higher than that fueled with natural gas, the coal ones benefit from a significantly cheaper and more abundant feedstock.

Hydrogen costs are much higher for the remaining production routes. Regarding, for example, water electrolysis combined with the current nuclear reactors technology, the cost of hydrogen is within the $4.36–7.36/kg range. These figures can be compared with the price of gasoline taking into account that 1 kg of hydrogen has approximately the same energy content as a U.S. gallon (3.78  l) of gasoline.

1.3.1.2 Renewable Hydrogen

The main pathways for hydrogen from renewable energy sources are schematized in Fig. 1.5. Biomass can be used for hydrogen production through thermochemical processes. Among the several possible options, gasification is expected to be commercially available in the near future with very attractive hydrogen costs (U.S. $1.44–2.83/kg).³³,⁴⁵ Anaerobic digestion is also an appealing route to hydrogen production because it allows the valorization of organic wastes. Low production rate is one of the main challenges of this process.⁴⁶ In Fig. 1.5, wind, hydroelectric, geothermal, wave and tidal energies have been grouped because their contribution to hydrogen production would be almost exclusively based on water electrolysis. Hydrogen from wind power and water electrolysis could be obtained at prices of $5.55–6.77/kg. Of course, solar photovoltaic (PV) energy can also be used to obtain hydrogen from water electrolysis. PV panels have experienced remarkable cost reductions in the last years; however, hydrogen produced from water electrolysis driven with PV electricity is still much more expensive ($23.27/kg) than hydrogen from wind power.⁴⁵ Nevertheless, the evolution is favorable and it is expected that in the future the costs of hydrogen produced from both solar PV and wind power are similar. Concentrated solar power also allows generating electricity that can be used for water electrolysis; hydrogen costs are estimated at $6.46/kg.⁴⁵

FIGURE 1.5 Scheme of the main hydrogen production pathways from renewables. (For color version of this figure, the reader is referred to the online version of this book.)

It is apparent from Fig. 1.5 that solar energy is the most versatile form of renewable energy regarding hydrogen production. In fact, in addition to solar electricity-driven water electrolysis, there are many other options.⁴⁶–⁴⁸ Solar–thermal water splitting, also known as solar thermolysis, is receiving considerable attention. The idea of the direct decomposition of water driven by concentrated solar heat is attractive. However, the process is unfavored thermodynamically; at temperatures as high as 2200 °C, a maximum water (steam) dissociation of 25% can be achieved. Moreover, the necessity of separating hydrogen of the coproduced oxygen, radiation losses and challenges associated to the availability of materials for reactor construction capable of withstanding these extremely high temperatures are issues that may make this process technically and economically unfeasible. As a result, the interest is now placed on the thermochemical cycles that, as discussed in the previous section, can operate at much lower temperatures.⁴⁹,⁵⁰

Photocatalytic water splitting under visible light irradiation allows obtaining hydrogen from the irradiation of sunlight on water in the presence of a suitable catalyst that reduces the high activation energy of the decomposition reaction.⁵¹,⁵² The process can be carried out more easily by an indirect route, using water in combination with a so-called sacrificial reducing agent, typically, and alcohol such as methanol. Noble metals such as Pd, Pt, Ir and Au supported on a semiconductor such as TiO2 are active catalysts for this process. The use of a sacrificial agent compromises the sustainability of the indirect route since whereas hydrogen gas is liberated,