Nanoplasmonic Alloy Hydrogen Sensors
Doktorsavhandling, 2018

The hydrogen economy proposes hydrogen gas as the main energy carrier thanks to its high energy density and the possibility to produce it in a sustainable way without CO2 emission. However, the wide flammability range of hydrogen-air mixtures dictates that hydrogen sensors will be a mandatory accessory to any appliance or vehicle fueled by hydrogen. Exploiting a phenomenon occurring at the nanoscale, a new type of hydrogen sensor based on the strong interaction of light with metal nanoparticles has rapidly developed in the past years. These so-called nanoplasmonic hydrogen sensors rely on hydride-forming metal nanoparticles that sustain localized surface plasmon resonance (LSPR); a collective oscillation of electrons in the nanoparticles induced by irradiated light. The energy at which the resonance occurs depends on the permittivity, as well as size and shape of the nanoparticles. Since both size and permittivity change significantly when a metal transforms into a metal hydride upon absorption of hydrogen, this effect can be used to detect it. To this date, palladium (Pd) has been the prototype material for both fundamental studies related to hydrogen sorption mechanisms in metals and in next-generation hydrogen detection devices across all sensing platforms. Specifically for the hydrogen detection, however, pure Pd does not satisfy the required sensing performance standard due to its inherent hysteresis during hydrogen absorption and desorption and slow kinetics. Furthermore it is also prone to deactivation by species like carbon monoxide and nitric oxides.

To address these limitations, in this thesis a new class of plasmonic hydrogen sensors based on noble metal alloy nanoparticles comprised of Pd, Gold (Au) and Copper (Cu) is explored. To enable such sensors, we first developed a nanofabrication method to produce alloy nanoparticles with precise control of their composition, size and shape. Investigating the fundamental properties of these alloy systems upon interaction with hydrogen, we found a universal correlation between the amount of hydrogen absorbed and the optical response, independent of alloy composition. Moreover, we demonstrated how segregation of Au atoms to surface of PdAu nanoparticles can be measured as a distinct change in the plasmonic response. Focusing on the optical hydrogen sensor application, we then studied in detail the performance of various PdAu, PdCu and PdAuCu alloys, as well as the use of thin polymer selective membrane coatings to prevent sensor deactivation by poisoning gases. As the main result, we created sensors with hysteresis-free sub-second response with sub-5 ppm sensitivity that meet or exceed stringent performance targets. To push the concept closer to application, we also demonstrated the integration of alloy nanoparticles with optical fibers for hydrogen sensing.

indirect nanoplasmonic sensing

plasmonic sensors

hydrogen sensors

polymers

fiber optics

nanofabrication

localized surface plasmon resonance

alloy nanoparticles

carbon capture and storage

sensors

palladium

PJ-salen, Fysikgården 2B, Chalmers.
Opponent: Prof. Reginald Penner, University of Californa, Irvine, USA

Författare

Ferry Nugroho

Chalmers, Fysik, Kemisk fysik

Bottom-Up Nanofabrication of Supported Noble Metal Alloy Nanoparticle Arrays for Plasmonics

ACS Nano,; Vol. 10(2016)p. 2871-2879

Artikel i vetenskaplig tidskrift

Nugroho, F. A. A., Zhdanov, V. P., Langhammer C. Universal Scaling and Design Rules of Hydrogen-Induced Optical Properties in Pd and Pd-Alloy Nanoparticles

Hysteresis-Free Nanoplasmonic Pd-Au Alloy Hydrogen Sensors

Nano Letters,; Vol. 15(2015)p. 3563-3570

Artikel i vetenskaplig tidskrift

Darmadi, I., Nugroho, F. A. A., Kadkhodazadeh, S., Wagner, J. B., Langhammer, C. Rationally Designed Binary and Ternary Alloy Nanoparticles for Poisoning-Resistant Nanoplasmonic Hydrogen Sensors with Hysteresis-Free Sub-Second Response

Nugroho, F. A. A., Darmadi, I., Schreuders, H., Susarrey-Arce, A., da Silva Fanta, A. B., Bannenberg, L., Kadkhodazadeh, S., Wagner, J. B., Zhdanov, V. P., Antosiewicz, T., Dam, B., Langhammer, C. Nanoparticle – Polymer Hybrid Optical Hydrogen Sensors

Nugroho, F. A. A., Eklund, R., Nilsson, S., Langhammer, C. A Fiber-Optic Nanoplasmonic Hydrogen Sensor via Pattern-Transfer of Nanofabricated PdAu Alloy Nanostructures

Nugroho, F. A. A., Susarrey-Arce, A., Kadkhodazadeh, S., Wagner, J. B., Langhammer, C. Probing Surface Segregation in Metal Alloy Nanoparticles using Plasmonic Sensing

UV–Visible and Plasmonic Nanospectroscopy of the CO2 Adsorption Energetics in a Microporous Polymer

Analytical Chemistry,; Vol. 87(2015)p. 10161-10165

Artikel i vetenskaplig tidskrift

Imagine driving a car for hours, travelling along the beautiful coasts of Sweden, and what is coming out of the exhaust pipe are not toxic and polluting gases but only water. How fun and relieving would it be? This scenario may sound like imagination but, in fact, it is not. It happens now as you read this, with the rise of a hydrogen energy system. Hydrogen, the smallest and most abundant element in the universe, is wonderful. It carries three times more energy than gasoline of the same mass and possesses high energy conversion efficiency. Even better, hydrogen can be produced from water and therefore enables a truly sustainable energy cycle, free from polluting and greenhouse gas emissions.

With these fantastic facts, one may then wonder: “Why don’t we see it being used more often now?” Apparently, there are a lot of reasons. To fully integrate the concept into our lives, there are still a lot of technological advances that have to be accomplished in multiple sectors, from the creation of hydrogen gas, its storage, to its distribution and usage. Most importantly, in each of these sectors, the process has to be done safely as hydrogen is actually a quite dangerous gas: it is flammable! Just a mere 4% of hydrogen gas in a room is enough to start a fire if a tiny spark ignites the hydrogen-air mixture. In fact, the trauma of the Hindenburg disaster in 1937, where a zeppelin balloon filled with hydrogen caught fire and crashed, killing 35 people, hinders to some extent the wide use of hydrogen fuel still today. To move forward, it is thus imperative to have a hydrogen detection system to signal a leak before a flammable hydrogen concentration is reached. As a guideline for this development, many institutions and stakeholders of a hydrogen energy system have released demanding performance standards for hydrogen sensors. In general, they have to be fast, sensitive and stable for many years of application.

Current hydrogen sensors mostly use palladium (often mixed with gold to produce “white gold”) since it can absorb a lot of hydrogen spontaneously, accompanied by the change in its characteristics. However, in this respect palladium hydrogen sensors are commonly characterized by slow response with low sensitivity. Even worse, palladium’s ability to absorb hydrogen disappears when it is exposed to some pollutant gases such as carbon monoxide and nitrogen dioxide, which we find readily in the (urban) air. To fulfill the requirements above, finding new type of sensors with novel materials is thus necessary.

In this thesis I present a hydrogen-sensing platform using light and extremely small particles of alloys of palladium and other metals. To do so, I would like to bring the reader into a world thousand times smaller than a strand of hair, a scale where materials may behave significantly different than how they are commonly known to. For example, in this size regime, palladium particles exhibit a color that depends on their shape and size. I will discuss how these small palladium alloy particles are produced and how they absorb hydrogen, which later modifies their color. Finally I show how we can make use of this phenomenon to realize an optical hydrogen sensor by measuring the color change induced by hydrogen. By combining palladium with other metals such as gold and copper, as well as covering it with different types of polymers (one is the polymer we use in our non-stick frying pans!), I created a fast, sensitive and stable hydrogen sensor. As the key highlight of this thesis, I succeeded to detect as low as 1 hydrogen molecule per 1000 gas molecules in less than 1 second, that is, the fastest hydrogen sensor in the world! And best of all, it still works even under exposure to carbon monoxide and nitrogen dioxide. So sit back, get a drink and enjoy the reading!

Styrkeområden

Nanovetenskap och nanoteknik

Materialvetenskap

Ämneskategorier

Materialteknik

Fysik

Materialkemi

Nanoteknik

ISBN

978-91-7597-717-1

Doktorsavhandlingar vid Chalmers tekniska högskola. Ny serie: 4398

Utgivare

Chalmers tekniska högskola

PJ-salen, Fysikgården 2B, Chalmers.

Opponent: Prof. Reginald Penner, University of Californa, Irvine, USA

Mer information

Senast uppdaterat

2018-04-27