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Plasmonic hydrogen sensors are promising safety monitoring devices for the emerging hydrogen economy provided a fast response time and poisoning resistance can be achieved. Nanocomposites composed of palladium nanoparticles embedded in a polymer matrix facilitate rapid hydrogen diffusion if a fluorinated polymer is used, while a denser polymer such as atactic poly(methyl methacrylate) (PMMA) facilitates a high degree of gas selectivity. However, nanocomposites that combine a fast response with poisoning resistance have not yet been realized. Here, these two properties are achieved simultaneously by modifying the surface of a fluorinated polymer nanocomposite with a thin PMMA coating, which functions as a molecular sieve that effectively blocks carbon monoxide. The resulting surface passivated nanocomposite shows a high degree of poisoning resistance without compromising a fast sensing response of 2-3 seconds upon exposure to 100 mbar of hydrogen. The sensor signal and response are preserved over 55 cycles of synthetic air containing 5% hydrogen and 500 ppm of carbon monoxide, indicating that nanocomposites are a viable approach for the realization of robust hydrogen sensors.

Cationic surfactants are widely used in the colloidal synthesis of noble metal nanoparticles in general, and of Pd nanoparticles in particular, to stabilize them toward aggregate formation in solution and to promote shape-specific particle growth. Despite the benefits at the synthesis stage, these surfactants can be problematic once the nanoparticles are to be applied as they may both geometrically block and electronically alter surface sites that are important for surface chemical reactions. This is particularly relevant in applications like bio- and chemosensors where analyte-nanoparticle surface interactions constitute the actual sensing event. Here, H2sensors based on Pd and its alloys are no exception since the dissociation of H2on the particle surface is the first step toward hydride formation and thus hydrogen detection, and it has been demonstrated that the presence of surfactant molecules detrimentally affects the hydrogen sorption rate. Here, we therefore develop a scheme to remove cationic surfactants from Pd nanoparticle surfaces by means of subsequent O2and H2plasma treatment, whose effectiveness we verify by X-ray photoelectron spectroscopy. Furthermore, we find that the plasma treatment both alters the surface structure of the Pd nanoparticles at the atomic level and leads to surface contamination by so-called H2plasma swift chemical sputtering of Al, Si and F species present in the plasma chamber, which in combination significantly reduce hydrogen sorption rates and increase apparent activation energies, as revealed by plasmonic hydrogen sorption kinetic measurements. Finally, we show that both these effects can be reversed by mild thermal annealing and that after the complete plasma cleaning-thermal annealing sequence hydrogen sorption rates essentially identical to the ones of neat Pd particles never exposed to cationic surfactants can be achieved. This advertises tailored plasma cleaning and mild heat treatments as an effective recipe for the remo

ConspectusSensors are ubiquitous, and their importance is only going to increase across many areas of modern technology. In this respect, hydrogen gas (H2) sensors are no exception since they allow mitigation of the inherent safety risks associated with mixtures of H2 and air. The deployment of H2 technologies is rapidly accelerating in emerging energy, transport, and green steel-making sectors, where not only safety but also process monitoring sensors are in high demand. To meet this demand, cost-effective and scalable routes for mass production of sensing materials are required. Here, the state-of-the-art often resorts to processes derived from the microelectronics industry where surface-based micro- and nanofabrication are the methods of choice and where (H2) sensor manufacturing is no exception.In this Account, we discuss how our recent efforts to develop sensors based on plasmonic plastics may complement the current state-of-the-art. We explore a new H2 sensor paradigm, established through a series of recent publications, that combines (i) the plasmonic optical H2 detection principle and (ii) bulk-processed nanocomposite materials. In particular, plasmonic plastic nanocomposite sensing materials are described that comprise plasmonic H2-sensitive colloidally synthesized nanoparticles dispersed in a polymer matrix and enable the additive manufacturing of H2 sensors in a cost-effective and scalable way. We first discuss the concept of plasmonic plastic nanocomposite materials for the additive manufacturing of an active plasmonic sensing material on the basis of the three key components that require individual and concerted optimization: (i) the plasmonic sensing metal nanoparticles, (ii) the surfactant/stabilizer molecules on the nanoparticle surface from colloidal synthesis, and (iii) the polymer matrix. We then introduce the working principle of plasmonic H2 detection, which relies on the selective absorption of H species into hydride-forming metal nanoparticles

Cationic surfactants are widely used in the colloidal synthesis of noble metal nanoparticles in general, and of Pd nanoparticles in particular, to stabilize them toward aggregate formation in solution and to promote shape-specific particle growth. Despite the benefits at the synthesis stage, these surfactants can be problematic once the nanoparticles are to be applied as they may both geometrically block and electronically alter surface sites that are important for surface chemical reactions. This is particularly relevant in applications like bio- and chemosensors where analyte-nanoparticle surface interactions constitute the actual sensing event. Here, H2 sensors based on Pd and its alloys are no exception since the dissociation of H2 on the particle surface is the first step toward hydride formation and thus hydrogen detection, and it has been demonstrated that the presence of surfactant molecules detrimentally affects the hydrogen sorption rate. Here, we therefore develop a scheme to remove cationic surfactants from Pd nanoparticle surfaces by means of subsequent O2 and H2 plasma treatment, whose effectiveness we verify by X-ray photoelectron spectroscopy. Furthermore, we find that the plasma treatment both alters the surface structure of the Pd nanoparticles at the atomic level and leads to surface contamination by so-called H2 plasma swift chemical sputtering of Al, Si and F species present in the plasma chamber, which in combination significantly reduce hydrogen sorption rates and increase apparent activation energies, as revealed by plasmonic hydrogen sorption kinetic measurements. Finally, we show that both these effects can be reversed by mild thermal annealing and that after the complete plasma cleaning–thermal annealing sequence hydrogen sorption rates essentially identical to the ones of neat Pd particles never exposed to cationic surfactants can be achieved. This advertises tailored plasma cleaning and mild heat treatments as an effective recipe for the, Peer Reviewed, Postprint (published version)

Sensors are ubiquitous, and their importance is only going to increase across many areas of modern technology. In this respect, hydrogen gas (H2) sensors are no exception since they allow mitigation of the inherent safety risks associated with mixtures of H2 and air. The deployment of H2 technologies is rapidly accelerating in emerging energy, transport, and green steel-making sectors, where not only safety but also process monitoring sensors are in high demand. To meet this demand, cost-effective and scalable routes for mass production of sensing materials are required. Here, the state-of-the-art often resorts to processes derived from the microelectronics industry where surface-based micro- and nanofabrication are the methods of choice and where (H2) sensor manufacturing is no exception. In this Account, we discuss how our recent efforts to develop sensors based on plasmonic plastics may complement the current state-of-the-art. We explore a new H2 sensor paradigm, established through a series of recent publications, that combines (i) the plasmonic optical H2 detection principle and (ii) bulk-processed nanocomposite materials. In particular, plasmonic plastic nanocomposite sensing materials are described that comprise plasmonic H2-sensitive colloidally synthesized nanoparticles dispersed in a polymer matrix and enable the additive manufacturing of H2 sensors in a cost-effective and scalable way. We first discuss the concept of plasmonic plastic nanocomposite materials for the additive manufacturing of an active plasmonic sensing material on the basis of the three key components that require individual and concerted optimization: (i) the plasmonic sensing metal nanoparticles, (ii) the surfactant/stabilizer molecules on the nanoparticle surface from colloidal synthesis, and (iii) the polymer matrix. We then introduce the working principle of plasmonic H2 detection, which relies on the selective absorption of H species into hydride-forming metal nanoparticles that, in, We acknowledge financial support from the Swedish Foundation for Strategic Research framework project RMA15-0052 and the Knut and Alice Wallenberg Foundation project 2016.0210. The authors also acknowledge the Paul Scherrer Institute, Villigen PSI, Switzerland for provision of synchrotron radiation beam-time at the beamline cSAXS of the SLS, Dr. Barbara Berke and Prof. Marianne Liebi for the SAXS experiments and corresponding data analysis, and Dr. Amir Pourrahimi and Dr. Robson Rosa da Silva for assistance with nanoparticle synthesis and the preparation of nanocomposites. We also thank Johan Landberg at RISE Research Institutes of Sweden AB for the compounding and pelletizing of several kilograms of Au:PMMA composite and gratefully acknowledge Add:north, especially Eric Bengtsson, for the production of the Au:PMMA 3D-printer filament in their extrusion line. Part of this work was carried out at the Chalmers MC2 Cleanroom Facility and at the Chalmers Materials Analysis Laboratory (CMAL). We thank Gabriel Danielsson for the design of a CAD model of the Vinga lighthouse and Dr. Christopher Tiburski for the Au nanorod FDTD simulations., Peer Reviewed, Postprint (published version)

Hydrogen-air mixtures are highly flammable. Hydrogen sensors are therefore of paramount importance for timely leak detection during handling. However, existing solutions do not meet the stringent performance targets set by stakeholders, while deactivation due to poisoning, for example by carbon monoxide, is a widely unsolved problem. Here we present a plasmonic metal-polymer hybrid nanomaterial concept, where the polymer coating reduces the apparent activation energy for hydrogen transport into and out of the plasmonic nanoparticles, while deactivation resistance is provided via a tailored tandem polymer membrane. In concert with an optimized volume-to-surface ratio of the signal transducer uniquely offered by nanoparticles, this enables subsecond sensor response times. Simultaneously, hydrogen sorption hysteresis is suppressed, sensor limit of detection is enhanced, and sensor operation in demanding chemical environments is enabled, without signs of long-term deactivation. In a wider perspective, our work suggests strategies for next-generation optical gas sensors with functionalities optimized by hybrid material engineering.

Hydrogen sensors are a prerequisite for the implementation of a hydrogen economy due to the high flammability of hydrogen-air mixtures. They are to comply with the increasingly stringent requirements set by stakeholders, such as the automotive industry and manufacturers of hydrogen safety systems, where sensor deactivation is a severe but widely unaddressed problem. In response, we report intrinsically deactivation-resistant nanoplasmonic hydrogen sensors enabled by a rationally designed ternary PdAuCu alloy nanomaterial, which combines the identified best intrinsic attributes of the constituent binary Pd alloys. This way, we achieve extraordinary hydrogen sensing metrics in synthetic air and poisoning gas background, simulating real application conditions. Specifically, we find a detection limit in the low ppm range, hysteresis-free response over 5 orders of magnitude hydrogen pressure, subsecond response time at room temperature, long-term stability, and, as the key, excellent resistance to deactivating species like carbon monoxide, notably without application of any protective coatings. This constitutes an important step forward for optical hydrogen sensor technology, as it enables application under demanding conditions and provides a blueprint for further material and performance optimization by combining and concerting intrinsic material assets in multicomponent nanoparticles. In a wider context, our findings highlight the potential of rational materials design through alloying of multiple elements for gas sensor development, as well as the potential of engineered metal alloy nanoparticles in nanoplasmonics and catalysis.