Low-Temperature Wastewater Electrolysis for H2 and Clean Water Generation
Authors: Lopez-Ruiz Juan A. , Boruah Bhanupriya , Strange Lyndi E. , Riedel Nickolas W 
Published: August 2024

Water electrolysis represents a sustainable approach to produce green hydrogen (H2); however, the high energy cost (H2O → 2H+ + 2e- + ½O2, ∆H° = 275 kJ/mol H2, E° = −1.18 V) associated with water electrolysis and electricity cost (>$50/MWh) results in a minimum H2 selling price ≈$4/kg H2. Hence, we need to find alternative process to generate H2 to meet the current U.S. Department of Energy's (DOE's) Energy Earthshots of $1/kg H2 in one decade.
Wastewater electrolysis represents an alternative approach to generate H2 with renewable sources by electrochemically oxidizing organic molecules to generate H2 (e.g., CH3COOH + 2H2O → 2CO2 + 8e- + 8H+, ∆H° = 53 kJ/mol, E° = −0.02 V,) which has up to 5 times lower energy requirement than water electrolysis. As opposed to water electrolysis that requires clean water streams, wastewater electrolysis uses readily available waste streams that need cleanup anyway to generate H2; hence, integrating a second application in addition to H2 generation.1-3

In this work, we compare the performance of heterogeneous electrocatalysts for the electrocatalytic oxidation (ECO) of organic molecules present in wastewater as well as electrocatalysts for the H2 evolution reaction (HER) at room temperature. ECO electrocatalysts were developed and tested using real wastewaters derived from several sources including the hydrothermal liquefaction (HTL) of food waste. We synthesized the ECO electrocatalysts using both platinum-group metals (PGM) as well as base-group metals (BGM) with equimolar loadings and tested them as a function of half-cell potential. Our results show that both PGM- and BGM-based bimetallics improve the activity and stability compared to the baseline RuO2-based catalysts4-6. We performed a preliminary techno-economic analysis and showed that the levelized costs of using this technology to process the wastewater alone is equivalent to that of traditional wastewater processing. The sale of the produced H2 co-product will decrease the levelized processing cost below that of current wastewater processing.

References

Andrews, E.; Lopez-Ruiz, J. A.; Egbert, J. D.; Koh, K.; Sanyal, U.; Song, M.; Li, D.; Karkamkar, A. J.; Derewinski, M. A.; Holladay, J.; Gutiérrez, O. Y.; Holladay, J. D., Performance of Base and Noble Metals for Electrocatalytic Hydrogenation of Bio-Oil-Derived Oxygenated Compounds. ACS Sustainable Chemistry &amp; Engineering
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Lopez-Ruiz, J. A.; Qiu, Y.; Andrews, E.; Gutiérrez, O. Y.; Holladay, J. D., Electrocatalytic valorization into H2 and hydrocarbons of an aqueous stream derived from hydrothermal liquefaction. Journal of Applied Electrochemistry
2021,
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Lopez-Ruiz, J. A.; Andrews, E.; Akhade, S. A.; Lee, M.-S.; Koh, K.; Sanyal, U.; Yuk, S. F.; Karkamkar, A. J.; Derewinski, M. A.; Holladay, J.; Glezakou, V.-A.; Rousseau, R.; Gutiérrez, O. Y.; Holladay, J. D., Understanding the Role of Metal and Molecular Structure on the Electrocatalytic Hydrogenation of Oxygenated Organic Compounds. ACS Catalysis
2019,
9 (11), 9964-9972.

Qiu, Y.; Lopez-Ruiz, J. A.; Zhu, G.; Engelhard, M. H.; Gutiérrez, O. Y.; Holladay, J. D., Electrocatalytic decarboxylation of carboxylic acids over RuO2 and Pt nanoparticles. Appl. Catal. B-Environ.
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Lopez-Ruiz, J. A.; Qiu, Y.; Andrews, E.; Gutiérrez, O. Y.; Holladay, J. D., Electrocatalytic valorization into H2 and hydrocarbons of an aqueous stream derived from hydrothermal liquefaction. J. Appl. Electrochem.
2021,
51 (1), 107-118.

Qiu, Y.; Lopez-Ruiz, J. A.; Sanyal, U.; Andrews, E.; Gutiérrez, O. Y.; Holladay, J. D., Anodic electrocatalytic conversion of carboxylic acids on thin films of RuO2, IrO2, and Pt. Appl. Catal. B-Environ.
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Figure 1