Aerosol Jet Printed Surface-Enhanced Raman Substrates: Application for High-Sensitivity Detection of Perfluoroalkyl Substances.

Printing technologies offer an attractive means for producing low-cost surface-enhanced Raman spectroscopy (SERS) substrates with high-throughput methods. The development of these substrates is especially important for field-deployable detection of environmental contaminants. Toward this end, we demonstrate SERS-based substrates fabricated through aerosol jet printing of silver nanoparticles and graphene inks on Kapton films. Our printed arrays exhibited measurable intensities for fluorescein and rhodamine dyes down to concentrations of 10-7 M, with the highest SERS intensities obtained for four print passes of Ag nanoparticles. The substrates also exhibited an excellent shelf life, with little reduction in fluorescein intensities after 9 months of shelf storage. We also demonstrated the capability of our substrates to sense perfluoroalkyl substances (PFAS), the so-called forever chemicals that resist degradation due to their strong C-F bonds and persist in the environment. Interestingly, the addition of graphene to the Ag nanoparticles greatly enhanced the SERS intensity of the perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) molecules under basic conditions (pH ∼ 9) compared to that of fluorescein and rhodamine. We were able to successfully detect SERS spectra from nano- and picomolar (∼0.4 ppt) concentrations of PFOA and PFOS, respectively, demonstrating the viability of deploying our SERS sensors in the environment for the ultrasensitive detection of contaminants.

Precision Modification of Monolayer Transition Metal Dichalcogenides via Environmental E-Beam Patterning.

Layered Transition Metal Dichalcogenides (TMDs) are an important class of materials that exhibit a wide variety of optoelectronic properties. The ability to spatially tailor their expansive property-space (e.g., conduction behavior, optical emission, surface interactions) is of special interest for applications including, but not limited to, sensing, bioelectronics, and spintronics/valleytronics. Current methods of property modulation focus on the modification of the basal surfaces and edge sites of the TMDs by the introduction of defects, functionalization with organic or inorganic moieties, alloying, heterostructure formation, and phase engineering. A majority of these methods lack the resolution for the development of next-generation nanoscale devices or are limited in the types of functionalities useful for efficient TMD property modification. In this study, we utilize electron-beam patterning on monolayer TMDs (MoSe2, WSe2 and MoS2) in the presence of a pressure-controlled atmosphere of water vapor within an environmental scanning electron microscope (ESEM). A series of parametric studies show local optical and electronic property modification depending on acceleration voltage, beam current, pressure, and electron dose. The ultimate pattern resolution achieved is 67 ± 9 nm. Raman and photoluminescence spectroscopies coupled with Kelvin Probe Force Microscopy reveal electron dose-dependent p-doping in the patterned regions, which we attribute to functionalization from the products of water vapor radiolysis (oxygen and hydroxyl groups). The modulation of the work function through patterning matches well with Density Functional Theory modeling. Finally, post-functionalization of the patterned areas with an organic fluorophore demonstrates a robust method to achieve nanoscale functionalization with high fidelity.

Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies.

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.

Solvent-Induced Assembly of Microbial Protein Nanowires into Superstructured Bundles.

Protein-based electronic biomaterials represent an attractive alternative to traditional metallic and semiconductor materials due to their environmentally benign production and purification. However, major challenges hindering further development of these materials include (1) limitations associated with processing proteins in organic solvents and (2) difficulties in forming higher-order structures or scaffolds with multilength scale control. This paper addresses both challenges, resulting in the formation of one-dimensional bundles composed of electrically conductive protein nanowires harvested from the microbes Geobacter sulfurreducens and Escherichia coli. Processing these bionanowires from common organic solvents, such as hexane, cyclohexane, and DMF, enabled the production of multilength scale structures composed of distinctly visible pili. Transmission electron microscopy revealed striking images of bundled protein nanowires up to 10 µm in length and with widths ranging from 50-500 nm (representing assembly of tens to hundreds of nanowires). Conductive atomic force microscopy confirmed the presence of an appreciable nanowire conductivity in their bundled state. These results greatly expand the possibilities for fabricating a diverse array of protein nanowire-based electronic device architectures.

Degradation of Organic Cations under Alkaline Conditions.

Understanding the degradation mechanisms of organic cations under basic conditions is extremely important for the development of durable alkaline energy conversion devices. Cations are key functional groups in alkaline anion exchange membranes (AAEMs), and AAEMs are critical components to conduct hydroxide anions in alkaline fuel cells. Previously, we have established a standard protocol to evaluate cation alkaline stability within KOH/CD3OH solution at 80 °C. Herein, we are using the protocol to compare 26 model compounds, including benzylammonium, tetraalkylammonium, spirocyclicammonium, imidazolium, benzimidazolium, triazolium, pyridinium, guanidinium, and phosphonium cations. The goal is not only to evaluate their degradation rate, but also to identify their degradation pathways and lead to the advancement of cations with improved alkaline stabilities.

Polyene-Free Photoluminescent Polymers via Hydrothermal Hydrolysis of Polyacrylonitrile in Neutral Water.

We report the hydrothermally enhanced hydrolysis of polyacrylonitrile (PAN) in neutral water, which generates photoluminescent polymers with low unsaturation degrees. Despite the hydrophobic nature of PAN, the product can be dissolved in water at a high concentration (≥100 g/L). The product exhibits complete absence of alkenes or aromatic structures, and photoluminescence originates from newly formed N- and O-containing groups. The presence of both n to π* and π to π* transitions is confirmed by time-dependent density functional theory (TD-DFT) calculations. The efficient transformation of PAN benefits from the enhanced hydrolysis of nitrile groups. While similar reactions have been reported previously under alkaline environments, we demonstrate that efficient hydrolysis can also occur in neutral water under the hydrothermal condition. Two additional methods based on different mechanisms are discussed to demonstrate the simplicity and efficiency of the hydrothermal reaction.

Synthesis of Zwitterionic Pluronic Analogs.

Novel polymer amphiphiles with chemical structures designed as zwitterionic analogs of Pluronic block copolymers were prepared by controlled free radical polymerization of phosphorylcholine (PC) or choline phosphate (CP) methacrylate monomers from a difunctional poly(propylene oxide) (PPO) macroinitiator. Well-defined, water-dispersible zwitterionic triblock copolymers, or "zwitteronics", were prepared with PC content ranging from 5 to 47 mol percent and composition-independent surfactant characteristics in water, which deviate from the properties of conventional Pluronic amphiphiles. These PC-zwitteronics assembled into nanoparticles in water, with tunable sizes and critical aggregation concentrations (CACs) based on their hydrophilic-lipophilic balance (HLB). Owing to the lower critical solution temperature (LCST) miscibility of the hydrophobic PPO block in water, PC-zwitteronics exhibited thermoreversible aqueous solubility tuned by block copolymer composition. The chemical versatility of this approach was demonstrated by embedding functionality, in the form of alkyne groups, directly into the zwitterion moieties. These alkynes proved ideal for cross-linking the zwitteronic nanoparticles and for generating nanoparticle-cross-linked hydrogels using UV-initiated thiol-yne "click" chemistry.

Bithiazolidinylidene polymers: synthesis and electronic interactions with transition metal dichalcogenides.

We describe the synthesis of electron acceptors consisting of bithiazolidinylidene (BT) derivatives incorporated into solution processible polymers. Novel BT-containing polymers displayed p-doping behavior when in contact with the n-type transition metal dichalcogenide (TMDC) MoS2. A work function (WF) increase of MoS2, resulting from contact with BT polymers, was measured by Kelvin probe force microscopy (KPFM), representing the first example of polymer p-doping of MoS2, which is beneficial for advancing the design of electronically tailored TMDCs.

Lithographically Patterned Functional Polymer-Graphene Hybrids for Nanoscale Electronics.

Two-dimensional (2D) materials are believed to hold significant promise in nanoscale optoelectronics. While significant progress has been made in this field over the past decade, the ability to control charge carrier density with high spatial precision remains an outstanding challenge in 2D devices. We present an approach that simultaneously addresses the dual issues of charge-carrier doping and spatial precision based on a functional lithographic resist that employs methacrylate polymers containing zwitterionic sulfobetaine pendent groups for noncovalent surface doping of 2D materials. We demonstrate scalable approaches for patterning these polymer films via electron-beam lithography, achieving precise spatial control over carrier doping for fabrication of high-quality, all-2D, lateral p-n junctions in graphene. Our approach preserves all of the desirable structural and electronic properties of graphene while exclusively modifying its surface potential. The functional polymer resist platform and concept offers a facile route toward lithographic doping of graphene- and other 2D material-based optoelectronic devices.

Tetrathiafulvalene-containing polymers for simultaneous non-covalent modification and electronic modulation of MoS2 nanomaterials.

Transition metal dichalcogenides (TMDCs) such as MoS2 comprise an important class of 2D semiconductors with numerous interesting electronic and mechanical features. Full utilization of TMDCs in materials and devices, however, necessitates robust functionalization methods. We report well-defined tetrathiafulvalene (TTF)-based polymers, exploiting synthetic routes that overcome challenges previously associated with these systems. These platforms enable basal plane coordinative interactions with MoS2, conceptually in parallel with pyrene-containing platforms for graphene and carbon nanotube modification. Not yet reported for TMDCs, these non-covalent interactions are universal and effective for MoS2 irrespective of the lattice structure, affording significantly enhanced solution stabilization of the nanosheets. Additionally, the TTF-functionalized polymers offer electronic structure modulation of MoS2 by ground state charge transfer and work function reduction, demonstrated using Kelvin probe force microscopy (KPFM). Notably, coordination and electronic effects are amplified for the TTF-polymers over TTF itself. Experiments are supported by first-principles density functional theory (DFT) calculations that probe polymer-TTF surface interactions with MoS2 and the resultant impact on electronic properties.