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The Metrohm Poster Award was initially introduced 29 years ago during the Conference for Electroanalytical Chemistry (ELACH) and has become a longstanding tradition. The most recent edition of this award was given to two winners at Electrochemistry 2022 in Berlin, Germany. The conference, themed «At the Interface between Chemistry and Physics», attracted over 600 scientists specializing in diverse electrochemistry disciplines. Electrochemistry 2022 served as a post-pandemic platform for participants to explore cutting-edge trends and applications, and to share advancements in vital areas such as sensor technology, energy storage, CO2 reduction, photoelectrochemistry, bioelectrochemistry, electrosynthesis, corrosion, electrochemical analytics, and electrocatalysis.

Metrohm Poster Award 2022 winners

More than 300 poster presentations took place, and the poster committee (members of the scientific panel) carefully chose the top two. The winners were then honored with a prize of €500 each at the award ceremony.

Winners of the Metrohm Poster Award 2022 from left to right: Marko Malinović (Technical University of Darmstadt) and Dr. Gumaa A El-Nagar (Helmholtz-Zentrum, Berlin).

The research of Marko Malinović is presented in this article. His poster was titled: «Size controlled synthesis of crystalline IrO2 nanoparticles for oxygen evolution reaction in acidic environment».

Doctoral candidate Mr. Marko Malinović, joint winner of the Metrohm Poster Award at Electrochemistry 2022 in Berlin.
Doctoral candidate Mr. Marko Malinović Joint winner of the Metrohm Poster Award at Electrochemistry 2022 in Berlin.

Meet Mr. Marko Malinović

Marko Malinović is a Ph.D. student at the Technical University of Darmstadt. He received his Bachelor’s degree with Honors (2016) and his Master’s degree (2017) in Materials Science and Engineering from the University of Novi Sad, Serbia

Before pursuing his doctoral studies, Mr. Malinović gained industrial experience as a Process, Research, and Development Engineer at Tarkett, a multinational company specialized in flooring production. Currently, Mr. Malinović is in the final year of his doctoral studies focusing on iridium-based electrocatalysts for water oxidation in polymer electrolyte membrane (PEM) water electrolysis.

CO2, climate change, and cars

Implementing strategies to mitigate climate change is of the utmost importance. The consequences of excessive CO2 emissions and subsequent influence on regional climates is already being felt, resulting in the more frequent occurrence of natural disasters with inevitable human casualties.

Heavy reliance of the transport sector on fossil fuels consequently generated 37% of total CO2 emissions in 2021 [1]. Despite the increasing number of electric cars on the road, additional environmentally friendly technological solutions are needed to tackle the challenge of CO2 emission reduction. 

Recently, more attention has been given to hydrogen-powered cars as a partial solution. This class of vehicles is based on fuel cell technology where hydrogen (in a reaction with oxygen) generates the electricity needed to power the vehicle, with only water and heat as the side products. Even though this sounds ideal, hydrogen can only be considered climate neutral if it is produced using renewable energy sources. In 2020, a total of 57 TWh of hydrogen was produced in Germany, a third of which resulting from the steam reforming of fossil fuels, and therefore directly linked to high CO2 emissions [2]. The global share of hydrogen derived from renewable energy sources known as «green hydrogen» less than 1%, alarmingly indicating where the focus must be shifted to make an impact.

Water electrolysis

The proposed solution to circumvent excessive CO2 emission during the production of hydrogen is via electrochemical water splitting. The electrical energy required for the endothermic reaction of water splitting is provided from renewable sources, resulting in the production of green hydrogen.

Among different electrolysis technologies available for industrial scale production, alkaline water electrolyzers and polymer electrolyte membrane (PEM) water electrolyzers are most commonly used. Of these two, the latter provides up to four times higher current density and is more adaptable to the sometimes rather unpredictable electrical input from renewable power sources [3]. When compared to the actual price expansion of fossil fuels, green hydrogen has become fully cost-competitive, and in some parts of the world even cheaper than hydrogen derived from fossil fuel sources.

This brings up the following question: What is keeping this technology from holding a larger share of global hydrogen production?

Can green hydrogen decarbonize the mobility sector in the future?

To answer this question, we will focus on PEM water electrolyzers (PEM-WE). These electrolyzers can conveniently operate under dynamic conditions, enabling their coupling with renewable energy sources. Ultimately, excess electricity can be stored in the form of hydrogen.

In order to make this happen, two electrochemical reactions must take place in the PEM cell. At the anode, water is oxidized to generate oxygen, electrons, and protons in the reaction known as the oxygen evolution reaction (OER). Consequently, protons are conducted through the membrane and reduced at the cathode to form hydrogen (Figure 1). 

Figure 1. Schematic overview of green hydrogen production via PEM water electrolysis and its potential application with an emphasis on catalyst designs for anodic water oxidation.

Despite hydrogen being the desired product, the bottleneck of this process is the sluggish OER which directly influences the overall efficiency of the water electrolyzer. High potentials are applied to overcome the kinetic problem of OER that, together with the acidic environment originating from a polymer electrolyte membrane, creates rather harsh conditions in the cell, thus limiting the choice of catalysts for this reaction mostly to noble metals. 

Iridium to the rescue, at a cost

Out of several researched materials, iridium-based catalysts have offered the best compromise between catalytic activity and durability [4]. However, this is also where the main problem lies regarding the successful scale-up of PEM water electrolysis. The estimated availability of iridium is approximately seven tons per year, making it one of the scarcest metals in the world [5]. Low amounts of available iridium, together with volatile supply-demand trends and force majeure factors related to the main mining sites, are reflected in its price which has skyrocketed in 2023 to approximately €150,000 per kg (down from a high point of €172,200 per kg at the end of April 2022) [6].

Keeping in mind the high and unpredictable cost and availability of iridium, a major scientific challenge is to find a way to reduce the loading of iridium-based catalyst used in PEM-WE while maintaining high performance and durability. Intriguingly, Bernt et al. [7] calculated that if the transportation sector was to be decarbonized by 2100 using hydrogen-powered vehicles, the iridium-specific power density must be reduced by a factor of 50 compared to the current state. 

Nanomaterials for sustainable energy conversion

The gravity of this challenge is the driving force behind Marko Malinović’s research conducted in the group of Prof. Dr. Marc Ledendecker. Designing an efficient and durable iridium-based catalyst with a reduced amount of noble metal is not a trivial task. Numerous catalyst designs (Figure 1) are reported in the literature addressing this challenge, comprising bare metal iridium, metal oxides, mixed metal oxides, core-shell structures, leached oxides, and nanostructured materials [8]. Marko’s research is focused on iridium oxide materials as they can potentially offer metal-like conductivity but also enhanced durability compared to their metallic counterparts.

To ensure maximized utilization of the catalyst, Marko’s research aims to synthesize nanomaterials that possess high surface-to-volume ratios as only the surface of the catalyst actively participates in catalysis. Even though amorphous iridium oxide (IrO2) is well known for its superior activity towards OER, the durability is still not sufficient to ensure longer operation times [9]. Crystalline iridium oxide obtained at temperatures ≥400 °C has a positive influence on the stability of the catalyst [10]. However, high calcination temperatures inevitably lead to a decrease in catalytically active surface area.

The novel synthesis route developed in the Ledendecker research group offers the possibility to synthesize IrO2 nanoparticles with preserved particle size and morphology even after the thermal treatment at high temperatures [11]. What makes this method unique is the fact that improvement in durability is not traded at the expense of catalytically active surface area. Thus, the primary goal of maximized utilization of the catalyst is ensured.

Marko Malinović (center) hard at work in the laboratory with colleagues Ezra S. Koh (left) and Jisik Choi (right).

The next steps

Further reduction of the amount of this precious noble metal is called for. This could be secured through the introduction of an earth-abundant material as a core material which is consequently coated with a thin layer of IrO2, creating a structure known as «core-shell» (Figure 1) [12].

Selecting the right core material could have a crucial impact on the final electrochemical properties of the active iridium oxide shell. Besides thermodynamic compatibility between core and shell material, the main preconditions that core materials must fulfill in order to be considered are their metallic conductivity and resistance to corrosion in an acidic medium [13]. Bearing in mind that corrosion resistance of the non-noble metals under the operational conditions of PEM-WE is questionable, this task is of major importance and will have special attention in Marko’s future research plans. 

Marko Malinović and Sandro Haug (Deutsche METROHM GmbH & Co. KG) at the Electrochemistry 2022 Best Poster Award ceremony.
Marko Malinović and Sandro Haug (Deutsche METROHM GmbH & Co. KG) at the Electrochemistry 2022 Best Poster Award ceremony.

Conclusion

From the electrocatalysis point of view, the strategy in scaling up PEM water electrolyzers to GW level would strongly depend on the performance of state-of-the-art catalysts. The low availability of noble metals in conjunction with their high cost shifts research efforts to create catalysts with improved efficiency and prolonged lifetime while reducing the amounts of noble metals used. Mutual collaboration between science and industry is of paramount importance for arguably the biggest mission of the 21st century.

Given the urgency to address climate change, numerous researchers concentrate on electrochemical applications such as electrocatalysis, energy conversion, and energy storage. The essential requirement for this work is reliable electrochemical instrumentation, such as potentiostats/galvanostats like VIONIC powered by INTELLO from Metrohm.

We are proud to award our best poster award prize to Mr. Marko Malinović for his outstanding research in this field and wish him good luck in his future endeavors. His research contributes to the development of cost-effective catalysts for greener production of hydrogen for various purposes including decarbonization of the transport sector.

Key take-aways:

  1. PEM water electrolyzers can be coupled to renewable energy sources, storing excess electricity as hydrogen.
  2. The OER which directly influences the overall PEM cell efficiency is slow and is considered the bottleneck of the process.
  3. Only a limited choice of (mostly noble metal) catalysts can withstand the harsh PEM cell conditions used.
  4. Iridium-based catalysts are an excellent candidate but are extremely costly and scarce.
  5. Synthesis of durable and efficient catalysts based on iridium oxide nanomaterials to maximize noble metal utilization shows promise.

[1] International Energy Agency. Transport – Improving the sustainability of passenger and freight transport. IEA. https://www.iea.org/topics/transport (accessed 2023-06-29).

[2] Statista Research Department. Produktion von Wasserstoff nach Prozess in Deutschland im Jahr 2020. Statista. https://de.statista.com/statistik/daten/studie/1194793/umfrage/produktion-von-wasserstoff-nach-prozess/ (accessed 2023-06-29).

[3] Babic, U.; Suermann, M.; Büchi, F. N.; et al. Critical Review—Identifying Critical Gaps for Polymer Electrolyte Water Electrolysis Development. J. Electrochem. Soc. 2017, 164 (4), F387. DOI:10.1149/2.1441704jes

[4] Danilovic, N.; Subbaraman, R.; Chang, K.-C.; et al. Activity-Stability Trends for the Oxygen Evolution Reaction on Monometallic Oxides in Acidic Environments. J Phys Chem Lett 2014, 5 (14), 2474–2478. DOI:10.1021/jz501061n

[5] Cowley, A. PGM Market Report - May 2023; Johnson Matthey PLC, 2023; p 52.

[6Iridium. Umicore Precious Metals Management. https://pmm.umicore.com/en/prices/iridium/ (accessed 2023-06-29).

[7] Bernt, M.; Siebel, A.; Gasteiger, H. A. Analysis of Voltage Losses in PEM Water Electrolyzers with Low Platinum Group Metal Loadings. J. Electrochem. Soc. 2018, 165 (5), F305. DOI:10.1149/2.0641805jes

[8] Malinovic, M.; Ledendecker, M. Whittling Iridium down to Size. Nat Energy 2022, 7 (1), 7–8. DOI:10.1038/s41560-021-00963-x

[9] Geiger, S.; Kasian, O.; Shrestha, B. R.; et al. Activity and Stability of Electrochemically and Thermally Treated Iridium for the Oxygen Evolution Reaction. J. Electrochem. Soc. 2016, 163 (11), F3132. DOI:10.1149/2.0181611jes

[10] Geiger, S.; Kasian, O.; Ledendecker, M.; et al. The Stability Number as a Metric for Electrocatalyst Stability Benchmarking. Nat Catal 2018, 1 (7), 508–515. DOI:10.1038/s41929-018-0085-6

[11] Malinovic, M.; Paciok, P.; Koh, E. S.; et al. Size-Controlled Synthesis of IrO2 Nanoparticles at High Temperatures for the Oxygen Evolution Reaction. Advanced Energy Materials 2023, 13 (28), 2301450. DOI:10.1002/aenm.202301450

[12] Ledendecker, M.; Geiger, S.; Hengge, K.; et al. Towards Maximized Utilization of Iridium for the Acidic Oxygen Evolution Reaction. Nano Res. 2019, 12 (9), 2275–2280. DOI:10.1007/s12274-019-2383-y

[13] Hunt, S. T.; Román-Leshkov, Y. Principles and Methods for the Rational Design of Core-Shell Nanoparticle Catalysts with Ultralow Noble Metal Loadings. Acc Chem Res 2018, 51 (5), 1054–1062. DOI:10.1021/acs.accounts.7b00510

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Haug

Sandro Haug

Head of Electrochemistry
Deutsche METROHM GmbH & Co. KG, Filderstadt, Germany

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