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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

Catalyst activity can depend distinctly on nanoparticle size and shape. Therefore, understanding the structure sensitivity of catalytic reactions is of fundamental and technical importance. Experiments with single-particle resolution, where ensemble-averaging is eliminated, are required to study it. Here, we implement the selective trapping of individual spherical, cubic, and octahedral colloidal Au nanocrystals in 100 parallel nanofluidic channels to determine their activity for fluorescein reduction by sodium borohydride using fluorescence microscopy. As the main result, we identify distinct structure sensitivity of the rate-limiting borohydride oxidation step originating from different edge site abundance on the three particle types, as confirmed by first-principles calculations. This advertises nanofluidic reactors for the study of structure-function correlations in catalysis and identifies nanoparticle shape as a key factor in borohydride-mediated catalytic reactions.

We have investigated the effects of high-energy electronirradiationon the oxidation of copper nanoparticles in environmental scanningtransmission electron microscopy (ESTEM). The hemispherically shapedparticles were oxidized in 3 mbar of O-2 in a temperaturerange 100-200 & DEG;C. The evolution of the particles was recordedwith sub-nanometer spatial resolution in situ in ESTEM. The oxidationencompasses the formation of outer and inner oxide shells on the nanoparticles,arising from the concurrent diffusion of copper and oxygen out ofand into the nanoparticles, respectively. Our results reveal thatthe electron beam actively influences the reaction and overall acceleratesthe oxidation of the nanoparticles when compared to particles oxidizedwithout exposure to the electron beam. However, the extent of thiselectron beam-assisted acceleration of oxidation diminishes at highertemperatures. Moreover, we observe that while oxidation through theoutward diffusion of Cu+ cations is enhanced, the electronbeam appears to hinder oxidation through the inward diffusion of O2- anions. Our results suggest that the impact of thehigh-energy electrons in ESTEM oxidation of Cu nanoparticles is mostlyrelated to kinetic energy transfer, charging, and ionization of thegas environment, and the beam can both enhance and suppress reactionrates., Funding Agencies|VILLUM FONDEN [36155]; Knut and Alice Wallenberg Foundation [2015.0055]; Swedish Research Council (VR) [2018-00329]

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)

Grain boundaries determine physical properties of bulk materials including ductility, diffusivity, and electrical conductivity. However, the role of grain boundaries in nanostructures and nanoparticles is much less understood, despite the wide application of nanoparticles in nanophotonics, nanoelectronics, and heterogeneous catalysis. Here, we investigate the role of high-angle grain boundaries in the oxidation of Cu nanoparticles, using a combination of in situ single particle plasmonic nanoimaging and postmortem transmission electron microscopy image analysis, together with ab initio and classical electromagnetic calculations. We find an initial growth of a 5-nm-thick Cu2O shell on all nanoparticles, irrespective of different grain morphologies. This insensitivity of the Cu2O shell on the grain morphology is rationalized by extraction of Cu atoms from the metal lattice being the rate limiting step, as proposed by density functional theory calculations. Furthermore, we find that the change in optical scattering intensity measured from the individual particles can be deconvoluted into one contribution from the oxide layer growth and one contribution that is directly proportional to the grain boundary density. The latter contribution signals accumulation of Cu vacancies at the grain boundaries, which, as corroborated by calculations of the optical scattering, leads to increased absorption losses and thus a decrease of the scattering, thereby manifesting the role of grain boundaries as vacancy sinks and nuclei for Kirkendall void formation at a later stage of the oxidation process.

Chemical reactions involving nanoparticles often follow complex processes. In this respect, real-time probing of single nanoparticles under reactive conditions is crucial for uncovering the mechanisms driving the reaction pathway. Here, we have captured in situ the oxidation of single Cu nanoparticles to unravel a sequential competitive activation of different mechanisms at temperatures 50-200 °C. Using environmental scanning transmission electron microscopy, we monitor the evolution of oxide formation with sub-nanometre spatial resolution, and show how the prevalence of oxide island nucleation, Cabrera-Mott, Valensi-Carter and Kirkendall mechanisms under different conditions determines the morphology of the particles. Moreover, using in situ electron energy-loss spectroscopy, we probe the localised surface plasmons of individual particles during oxidation, and with the aid of finite-difference time-domain electrodynamic simulations investigate the signature of each mechanism in their plasmonic response. Our results shed light on the rich and intricate processes involved in the oxidation of nanoparticles, and provide in-depth insight into how these processes govern their morphology and optical response, beneficial for applications in catalysis, sensing, nanomedicine and plasmonics.

Grain boundaries determine physical properties of bulk materials including ductility, diffusivity, and electrical conductivity. However, the role of grain boundaries in nanostructures and nanoparticles is much less understood, despite the wide application of nanoparticles in nanophotonics, nanoelectronics, and heterogeneous catalysis. Here, we investigate the role of high-angle grain boundaries in the oxidation of Cu nanoparticles, using a combination of in situ single particle plasmonic nanoimaging and postmortem transmission electron microscopy image analysis, together with ab initio and classical electromagnetic calculations. We find an initial growth of a 5-nm-thick Cu2O shell on all nanoparticles, irrespective of different grain morphologies. This insensitivity of the Cu2O shell on the grain morphology is rationalized by extraction of Cu atoms from the metal lattice being the rate limiting step, as proposed by density functional theory calculations. Furthermore, we find that the change in optical scattering intensity measured from the individual particles can be deconvoluted into one contribution from the oxide layer growth and one contribution that is directly proportional to the grain boundary density. The latter contribution signals accumulation of Cu vacancies at the grain boundaries, which, as corroborated by calculations of the optical scattering, leads to increased absorption losses and thus a decrease of the scattering, thereby manifesting the role of grain boundaries as vacancy sinks and nuclei for Kirkendall void formation at a later stage of the oxidation process.

Grain boundaries determine physical properties of bulk materials including ductility, diffusivity, and electrical conductivity. However, the role of grain boundaries in nanostructures and nanoparticles is much less understood, despite the wide application of nanoparticles in nanophotonics, nanoelectronics, and heterogeneous catalysis. Here, we investigate the role of high-angle grain boundaries in the oxidation of Cu nanoparticles, using a combination of in situ single particle plasmonic nanoimaging and postmortem transmission electron microscopy image analysis, together with ab initio and classical electromagnetic calculations. We find an initial growth of a 5-nm-thick Cu2O shell on all nanoparticles, irrespective of different grain morphologies. This insensitivity of the Cu2O shell on the grain morphology is rationalized by extraction of Cu atoms from the metal lattice being the rate limiting step, as proposed by density functional theory calculations. Furthermore, we find that the change in optical scattering intensity measured from the individual particles can be deconvoluted into one contribution from the oxide layer growth and one contribution that is directly proportional to the grain boundary density. The latter contribution signals accumulation of Cu vacancies at the grain boundaries, which, as corroborated by calculations of the optical scattering, leads to increased absorption losses and thus a decrease of the scattering, thereby manifesting the role of grain boundaries as vacancy sinks and nuclei for Kirkendall void formation at a later stage of the oxidation process.