Computational Design of Alloy Nanostructures for Optical Sensing of Hydrogen

Ekborg-Tanner, Pernilla; Rahm, J. Magnus; Rosendal, Victor; Bancerek, Maria; Rossi, Tuomas P.; Antosiewicz, Tomasz J.; Erhart, Paul

doi:10.1021/acsanm.2c01189

Cited by 8 publications

(6 citation statements)

References 55 publications

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“…This enabled the measurement of optical pressure composition isotherms (Figure 2c). Later studies 33,34,47 and first-principles calculations 56,57 revealed direct proportionality between the H concentration in Pd and Δλ peak .…”

Section: Plasmonic Hydrogen Sensingmentioning

confidence: 99%

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: Plasmonic Hydrogen Sensingmentioning

confidence: 99%

Bulk-Processed Plasmonic Plastic Nanocomposite Materials for Optical Hydrogen Detection

et al. 2023

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“…Moreover, the increase in the number of holes is greatest between 0 and 50%, echoing the composition dependence observed for the spectra. As discussed in more detail in refs and , one can understand this trend with composition as being the result of the gradual filling/depletion of the d-band when starting from the pure group-10/group-11 element. This analysis thus demonstrates that the trends observed here are not strongly affected by NP size or shape and largely represent the behavior of the surface (as opposed to the full NP).…”

Section: Resultsmentioning

confidence: 99%

Tailoring Hot-Carrier Distributions of Plasmonic Nanostructures through Surface Alloying

Fojt,

Rossi,

Kumar

et al. 2024

ACS Nano

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Alloyed metal nanoparticles are a promising platform for plasmonically enabled hot-carrier generation, which can be used to drive photochemical reactions. Although the non-plasmonic component in these systems has been investigated for its potential to enhance catalytic activity, its capacity to affect the photochemical process favorably has been underexplored by comparison. Here, we study the impact of surface alloy species and concentration on hot-carrier generation in Ag nanoparticles. By first-principles simulations, we photoexcite the localized surface plasmon, allow it to dephase, and calculate spatially and energetically resolved hot-carrier distributions. We show that the presence of non-noble species in the topmost surface layer drastically enhances hot-hole generation at the surface at the expense of hot-hole generation in the bulk, due to the additional d-type states that are introduced to the surface. The energy of the generated holes can be tuned by choice of the alloyant, with systematic trends across the d-band block. Already low surface alloy concentrations have a large impact, with a saturation of the enhancement effect typically close to 75% of a monolayer. Hot-electron generation at the surface is hindered slightly by alloying, but here a judicious choice of the alloy composition allows one to strike a balance between hot electrons and holes. Our work underscores the promise of utilizing multicomponent nanoparticles to achieve enhanced control over plasmonic catalysis and provides guidelines for how hot-carrier distributions can be tailored by designing the electronic structure of the surface through alloying.

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“…As our model system we use the AuPd alloy system, which we have widely used and characterized in the context of plasmonic hydrogen sensors. ,,,, Such sensors are based on the principle that hydrogen absorption into interstitial sites of metallic hosts, such as Pd and its alloys but also other systems like Ni, Mg, Y, Hf, , and Ta, and their alloys with Pd, induces distinct changes in their electronic structure, and thus optical response in general and LSPR in particular. Importantly, these changes are proportional to the hydrogen concentration/partial pressure in their surroundings. − From the application perspective, such sensors are attractive since their optical signal transducing mechanism generates no sparks and since the entire sensor, in principle, can be miniaturized down to a single nanoparticle. ,− The former aspect is especially important since hydrogen–oxygen mixtures are highly flammable above the 4% H 2 lower explosive limit.…”

Section: Resultsmentioning

confidence: 99%

A Microshutter for the Nanofabrication of Plasmonic Metal Alloys with Single Nanoparticle Composition Control

et al. 2023

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Alloying offers an increasingly important handle in nanomaterials design in addition to the already widely explored size and geometry of nanostructures of interest. As the key trait, the mixing of elements at the atomic level enables nanomaterials with physical or chemical properties that cannot be obtained by a single element alone, and subtle compositional variations can significantly impact these properties. Alongside the great potential of alloying, the experimental scrutiny of its impact on nanomaterial function is a challenge because the parameter space that encompasses nanostructure size, geometry, chemical composition, and structural atomic-level differences among individuals is vast and requires unrealistically large sample sets if statistically relevant and systematic data are to be obtained. To address this challenge, we have developed a microshutter device for spatially highly resolved physical vapor deposition in the lithography-based fabrication of nanostructured surfaces. As we demonstrate, it enables establishing compositional gradients across a surface with single nanostructure resolution in terms of alloy composition, which subsequently can be probed in a single experiment. As a showcase, we have nanofabricated arrays of AuAg, AuPd, and AgPd alloy nanoparticles with compositions systematically controlled at the level of single particle rows, as verified by energy dispersive X-ray and single particle plasmonic nanospectroscopy measurements, which we also compared to finite-difference time-domain simulations. Finally, motivated by their application in state-of-the-art plasmonic hydrogen sensors, we investigated PdAu alloy gradient arrays for their hydrogen sorption properties. We found distinctly compositiondependent kinetics and hysteresis and revealed a composition-dependent contribution of a single nanoparticle response to the ensemble average, which highlights the importance of alloy composition screening in single experiments with single nanoparticle resolution, as offered by the microshutter nanofabrication approach.

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Computational Design of Alloy Nanostructures for Optical Sensing of Hydrogen

Cited by 8 publications

References 55 publications

Bulk-Processed Plasmonic Plastic Nanocomposite Materials for Optical Hydrogen Detection

Bulk-Processed Plasmonic Plastic Nanocomposite Materials for Optical Hydrogen Detection

Tailoring Hot-Carrier Distributions of Plasmonic Nanostructures through Surface Alloying

A Microshutter for the Nanofabrication of Plasmonic Metal Alloys with Single Nanoparticle Composition Control

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