Materials for low cost, scalable,

thermochemical hydrogen production

Engineers in Prof. Arunava Majumdar's laboratory have formulated high-entropy phase-change
materials that can split water to produce hydrogen at moderate temperatures using a
scalable, carbon-free process. The hydrogen is produced through a two-step solar-powered
thermochemical redox reaction. Then it can be harnessed to
reduce carbon dioxide and produce chemicals such as
plastics, syngas or transportation fuel.
The reaction is compatible with the existing infrastructure of
the chemical industry reaction because it proceeds at
moderate temperatures (~1200oC or lower) with
extremely fast oxygen release kinetics. In addition, the
materials used for the reaction are in powder form,
allowing the process to be scaled volumetrically in well-
known chemical reactor designs (e.g. fluidized bed). This
water-splitting technology is designed to potentially
produce carbon-free hydrogen at prices competitive with
steam methane reforming (SMR). Furthermore, it may
turn CO2 from an environmental liability to an asset by
converting it CO feedstock for chemical and renewable fuel production.
Schematic diagram of two-step thermochemical water splitting reactions using the proposed
high-entropy mixed oxides.

Stage of Research
The inventors have formulated the entropy stabilized material, verified that it can produce
hydrogen at 1200oC or lower (lower temperature than current state of the art), and performed
repeatability studies to ensure that it can be cycled continuously to produce hydrogen.

Applications
 Hydrogen production
 Carbon sequestration - H2 can reduce CO2 to CO, which can be used for feedstock in
downstream reactions
 Synthesis of carbon-based chemicals such as:
o syngas
o plastics
o transportation fuel
 Thermal energy storage

Advantages
 Moderate operation temperature:
o thermochemical redox reactions take place at ~ 1200 oC or lower
o compatible with existing infrastructure to convert CO and H 2 to a variety of
chemicals, including liquid fuels
 Scalable - metal oxide materials are in powder form that can be scaled up
volumetrically
 Carbon-free pathways:
o thermochemical reaction can be driven by solar power
o unlike SMR, these materials enable H2 production without CO2 waste
 o H2 can be used to reduce CO2 to carbon CO for downstream chemical reactions
 High performance material - extremely fast oxygen release kinetics that are
comparable to state-of-the art materials such as ceria, even at reduced temperatures.
In principle, if we simply heat up enough, we can split water into hydrogen (H2) and oxygen
(O2). However, such direct water thermolysis requires temperatures >2500ºC, which makes it
unsuitable for real-life applications. This main problem is solved using a certain number of
chemical reactions to divide the water decompositions into more steps. The reactants are
regenerated in a closed loop while the overall chemical reaction remains that of direct water
thermolysis. The result is what is commonly called as thermochemical water splitting cycle
(TWSC). Thanks to TWSCs operating temperature decreases, and hydrogen and oxygen are
produced in different steps, which eliminates the need for high-temperature gas separation
and reduces the risk of accidents.
This trick is anything but new. The idea behind TWSCs dates to 1966. The interest in this
technology then increased during the 70´s and the 80´s due to the oil crisis. At that time, a
huge amount of TWSCs was proposed with the main idea of producing hydrogen from nuclear
energy. Since their conception, TWSCs have been considered the natural alternative to water
electrolysis for large-scale H2 production. One of the main advantages presented by TWCSs is
that they are catalyst-free and do not rely on expensive and rare elements.
The research on TWSCs boomed at the beginning of the 21 st century when climate change
awareness grew rapidly among the scientific community. Nowadays, the technological
advances achieved in solar energy collectors and concentrators make coupling TWSCs with
concentrated solar energy particularly interesting for green hydrogen production. Moreover,
the utilization of waste heat has great potential for decentralized hydrogen production in
proximity of industries or power plants. Creating TWSCs modules could help to decrease the
overall CO2 footprint of the industrial process and find application in smart grids, together with
electrolyzes and thermal energy storage (TES) units.

Many candidates for a (still) green technology. More than 300 thermochemical water splitting
cycles have been proposed, but only a few have been extensively investigated. Moreover,
despite the 50 years-long history and the high potential, the technology readiness level (TRL)
of TWSCs is still quite low, especially if compared to electrolyzes. The thermochemical cycles
can involve 2 to 5-6 steps with operating temperatures between 500ºC and 2000ºC. In
general, the lower the number of steps, the higher the required temperature and vice versa.
The multistep cycles (nº steps ≥ 3) are the oldest and the more studied. This is due to their
relatively low operating temperatures (T < 900 ºC), which made them attractive when the
research on TWSCs was mainly focused on the nuclear sector.

Electro-thermochemical Li Cycling for NH3 Synthesis from N2 and

H2O
Stanford researchers at the Jaramillo, Nørskov, and Cargnello Labs have developed an
improved system to generate NH3 (ammonia) from N2 and H2O via a low-pressure, electro-
thermochemical, sustainable alternative to the conventional Haber-Bosch process.
The prevalent Haber-Bosch manufacturing technique, which reacts N 2 with H2, has a number
of drawbacks. It consumes large amounts of natural gas to obtain H 2, emits carbon dioxide,
and requires high-pressure conditions that force the use of expensive centralized factories.
The new technology resolves a number of these concerns. The use of water in place of
H2 obviates the need for fossil fuels, the technique emits only H 2O and O2 as byproducts, and
less rigorous pressure requirements reduce the cost of running the process. Moreover, this
technique could allow for the local production of ammonia that would then be put
immediately into the soil, reducing the cost of fertilizer and maximizing nitrogen utilization
efficiency. Thus, this technology could allow for cheaper, less energy-consuming, and more
environmentally friendly production and use of ammonia, compared to current standards.
Figure description - A schematic of one possible set-up for an ammonia-producing system;
given N2 and H2O inputs, the system releases ammonia and byproducts H 2O and O2.
Stage of Research as of October 2016
 Proof-of-concept completed
 88.5% current efficiency to
ammonia demonstrated

Applications
 Ammonia production from
water and N2 for use as:
 Fertilizer
 Chemical precursor
to many nitrogen-
containing
chemicals
 Fuel alternative
 Energy storage from renewable sources (wind, solar, etc.)

Advantages
 Ammonia production without the use of H 2 and fossil fuels
 Energy-efficient May provide a means by which to resolve energy concerns with the
Haber-Bosch process, which requires over 1% of the entire global energy and 3-5 % of
the natural gas supply for pre-requisite hydrogen production
 Lower-cost less high-pressure requirements than Haber-Bosch, allowing for less
equipment and operational costs
 Enables local manufacturing- could be produced locally instead of inside large
factories, reducing distribution costs and maximizing nitrogen utilization efficiency
 Environmentally-friendly: unlike Haber-Bosch, does not emit CO2.
Photocatalytic water splitting is a process that uses photocatalysis for
the dissociation of water (H2O) into hydrogen (H2) and oxygen (O2). The inputs are light energy
(photons), water, and a catalyst(s). The process is inspired by Photosynthesis, which converts
water and carbon dioxide into oxygen and carbohydrates. Water splitting using solar radiation
has not been commercialized. Photocatalytic water splitting is done by dispersing
photocatalyst particles in water or depositing them on a substrate,
unlike Photoelectrochemical cell, which are assembled into a cell with a
photoelectrode. Hydrogen fuel production using water and light (photocatalytic water
splitting), instead of petroleum, is an important renewable energy strategy.
Two moles of H2O is split into 1 mole O2 and 2 mole H2 using light in the process shown below.

A photon with an energy greater than 1.23 eV is needed to generate an electron–hole pairs,
which react with water on the surface of the photocatalyst. The photocatalyst must have a
bandgap large enough to split water; in practice, losses from material internal resistance and
the overpotential of the water splitting reaction increase the required bandgap energy to 1.6–
2.4 eV to drive water splitting
Water splitting is driven by the electron-hole pair generated by a
photon. The bandgap is the energy difference between the conduction
band minimum (CB) and the valence band maximum (VB).
Electrocatalysts are added to reduce the overpotential of water
splitting. The process of water-splitting is a
highly endothermic process (ΔH > 0). Water splitting occurs
naturally in photosynthesis when the energy of four
photons is absorbed and converted into
chemical energy through a complex
biochemical pathway (Dolai's or Kok's
S-state diagrams). The oxygen-evolving complex (OEC), also
known as the water-splitting complex, is a water-oxidizing enzyme involved in the photo-
oxidation of water during the light reactions of photosynthesis. OEC is surrounded by 4 core
proteins of photosystem II at the membrane-lumen interface. The mechanism for splitting
water involves absorption of three photons before the fourth provides sufficient energy for
water oxidation. Based on a widely accepted theory from 1970 by Kok, the complex can exist
in 5 states, denoted S0 to S4, with S0 the most reduced and S4 the most oxidized. Photons
trapped by photosystem II move the system from state S0 to S1 to S2 to S3 and finally to S4.
S4 reacts with water producing free oxygen:
2 H2O → O2 + 4 H+ + 4 e−
This conversion resets the catalyst to the S 0 state.
The active site of the OEC consists of a cluster of manganese and calcium with the formula
Mn4Ca1OxCl1–2(HCO3)y. This cluster is bound to D1 and CP43 subunits and stabilized by peripheral
membrane proteins. Many characteristics of it have been examined by flash
photolysis experiments, electron paramagnetic resonance (EPR), and X-ray spectroscopy.
O–H bond homolysis in water requires energy of 6.5 - 6.9 eV (UV photon). Infrared light has
sufficient energy to mediate water splitting because it technically has enough energy for the
net reaction. However, it does not have enough energy to mediate the elementary reactions
leading to the various intermediates involved in water splitting (this is why there is still
water on Earth). Nature overcomes this challenge by absorbing four visible photons. In the
laboratory, this challenge is typically overcome by coupling the hydrogen production reaction
with a sacrificial reductant other than water.
Materials used in photocatalytic water splitting fulfill the band requirements and typically
have dopants and/or co-catalysts added to optimize their performance. A
sample semiconductor with the proper band structure is titanium dioxide (TiO2) and is
typically used with a co-catalyst such as platinum (Pt) to increase the rate of H2 production. A
major problem in photocatalytic water splitting is photocatalyst decomposition and corrosion.