Robust Colloidal Synthesis of Palladium–Gold Alloy Nanoparticles for Hydrogen Sensing

Lerch, Sarah; Stolaś, Alicja; Darmadi, Iwan; Wen, Xin; Strach, Michał; Langhammer, Christoph; Moth‐Poulsen, Kasper

doi:10.1021/acsami.1c15315

Cited by 12 publications

(11 citation statements)

References 71 publications

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“…As hydrogen-sensitive plasmonic nanoparticles, we initially selected CTAB-stabilized colloidal Pd nanocubes due to their robust synthesis protocol before changing the surfactant and taking the step to colloidal PdAu alloy nanoparticles synthesized according to protocols we have optimized for H 2 sensing. 2,32 Using PMMA, we created a nanocomposite in which the cubic shape of the Pd nanocrystals was well preserved (Figure 5a) and for which s-SAXS analysis revealed a homogeneous distribution and isotropic arrangement of the particles. 3 Exposure to H 2 revealed an overall response characteristic for Pd.…”

Section: D-printed Plasmonic Plastic Hydrogen Sensorsmentioning

confidence: 99%

“…In this Account, which is based on a series of papers that we have published during the last 4 years, − ,− we will discuss our key discoveries, as well as the rational design and optimization of plasmonic plastic nanocomposites and their constituents, i.e., colloidal plasmonic nanoparticles and the polymer matrix, with respect to bulk processing, optical/plasmonic properties, and application in the area of optical H 2 sensing. In developing this story, we focus on materials design based on a fundamental understanding of the limiting factors for the targeted application.…”

Section: Introductionmentioning

confidence: 99%

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Bulk-Processed Plasmonic Plastic Nanocomposite Materials for Optical Hydrogen Detection

et al. 2023

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Conspectus 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 turn, induces distinct changes in their optical plasmonic signature in proportion to the H2 concentration in the local atmosphere. Subsequently, we assess the roles of the key components of a plasmonic plastic for H2 sensing, where we have established that (i) alloying Pd with Au and Cu eliminates hysteresis and introduces intrinsic deactivation resistance at ambient conditions, (ii) surfactant/stabilizer molecules can significantly accelerate and decelerate H2 sorption and thus sensor response, and (iii) polymer coatings accelerate sensor response, reduce the limit of detection (LoD), and enable molecular filtering for sensor operation in chemically challenging environments. Based on these insights, we discuss the rational development and detailed characterization of bulk-processed plasmonic plastics based on glassy and fluorinated matrix polymers and on tailored flow-chemistry-based synthesis of Pd and PdAu alloy colloidal nanoparticles with optimized stabilizer molecules. In their champion implementation, they enable highly stable H2 sen...

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Section: D-printed Plasmonic Plastic Hydrogen Sensorsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Bulk-Processed Plasmonic Plastic Nanocomposite Materials for Optical Hydrogen Detection

et al. 2023

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“…At the nanoscale, alloying is widely used in heterogeneous catalysis to engineer activity and selectivity of surface reactions, in hydrogen sensors, in electrochemical desalination, and in biological applications like bioimaging or photothermal therapy . Here, the increasing availability of colloidal synthesis routes of alloy nanoparticles − is an important driver of this development. Returning to the application of the alloying concept in nano-optics and plasmonics, we have recently reported a systematic first-principles calculations based study of the complex dielectric functions of late transition-metal alloys, and Jian et al reported a first-principles study of non-radiative LSPR decay in the AgCu alloy system .…”

Section: Introductionmentioning

confidence: 99%

Engineering Optical Absorption in Late Transition-Metal Nanoparticles by Alloying

Tiburski

Langhammer

2022

ACS Photonics

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Alloying is an increasingly important handle to engineer the optical properties of metal nanoparticles that find applications in, for example, optical metamaterials, nanosensors, and plasmon-enhanced catalysis. One advantage of alloying over traditionally used particle size and shape engineering is that it, in principle, enables tuning of optical properties without a spectral shift of the localized surface plasmon resonance, which is important for applications where a specific spectral band is targeted. A second advantage is that alloying simultaneously enables adjustment of nanoparticle electronic, chemical, mechanical, and light absorption properties. However, a systematic survey of the impact of alloying on light absorption in metal nanoparticles does not exist, despite its key role in applications that include photothermal therapy, plasmonic heat generation, and plasmon catalysis. Therefore, we present here the systematic screening of the light absorption properties of binary late transition-metal alloys composed of Au, Ag, Cu, Pd, and Pt in the visible spectral range, based on a combination of experiments and finite-difference time-domain simulations, and discuss in detail the underlying physics. By studying these 10 alloy systems for 14 different nanoparticle sizes, we find that most nanoparticles experience a maximal absorption efficiency at around 80 nm particle diameter, and that most alloy systems outperform their neat constituents, with integrated absorption enhancement factors of up to 200%. This highlights the untapped potential of alloying for the engineering of light absorption in nanoparticles, and the presented material screening constitutes a resource for the rational selection of alloy systems with tailored absorption properties.

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“…Pd films and nanoparticles, and their derivatives in terms of alloys, find wide application in processes and technologies where the interaction of molecules with their surfaces is a key step, such as in heterogeneous catalysis, − gas storage, , gas separation membranes, , and gas sensors. − In this context, the interaction of Pd surfaces with hydrogen gas is an interesting subcategory, ,,, where many applications exploit the exceptional ability of Pd to efficiently dissociate molecular hydrogen (H 2 ) at ambient conditions and absorb H into its lattice in interstitial sites, eventually forming a hydride . In many of these applications, the kinetics of H 2 dissociation and/or absorption and desorption into/from the interstitial sites in the Pd lattice is a crucial aspect of the targeted performance because it determines, for instance, kinetics of a catalytic reaction, , response times of hydrogen sensors, ,− or the loading time of a hydrogen storage medium .…”

Section: Introductionmentioning

confidence: 99%

Plasma Cleaning of Cationic Surfactants from Pd Nanoparticle Surfaces: Implications for Hydrogen Sorption

Darmadi

Piella

Stolaś

et al. 2023

ACS Appl. Nano Mater.

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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 removal of surfactant molecules from nanoparticle surfaces.

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Robust Colloidal Synthesis of Palladium–Gold Alloy Nanoparticles for Hydrogen Sensing

Cited by 12 publications

References 71 publications

Bulk-Processed Plasmonic Plastic Nanocomposite Materials for Optical Hydrogen Detection

Bulk-Processed Plasmonic Plastic Nanocomposite Materials for Optical Hydrogen Detection

Engineering Optical Absorption in Late Transition-Metal Nanoparticles by Alloying

Plasma Cleaning of Cationic Surfactants from Pd Nanoparticle Surfaces: Implications for Hydrogen Sorption

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