Bulk-Processed Plasmonic Plastic Nanocomposite Materials for Optical Hydrogen Detection

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 sensors with response times in the 2 s range and an LoD of few 10 ppm of H2. To put plasmonic plastics in a wider perspective, we also report their implementation using different polymer matrix materials that can be used for 3D printing and (an)isotropic Au nanoparticles that enable the manufacturing of macroscopic plasmonic objects with, if required, dichroic optical properties and in amounts that can be readily upscaled. We advertise that melt processing of plasmonic plastic nanocomposites is a viable route toward the realization of plasmonic objects and sensors, produced by scalable colloidal synthesis and additive manufacturing techniques.