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1. Remote controlled optical manipulation of bimetallic nanoparticle catalysts using peptides

   https://doi.org/10.1039/D1CY00189B  

   Lawrence, Randy L.; Olagunju, Mary O.; Liu, Yang; Mahalingam, Krishnamurthy; Slocik, Joseph M.; Naik, Rajesh R.; Frenkel, Anatoly I.; Knecht, Marc R. (April 2021, Catalysis Science & Technology)

   null (Ed.)

   Bimetallic nanoparticles remain a promising avenue to achieve highly reactive catalysts. In this contribution, we demonstrate the use of a photoswitchable peptide for the production of PdAu bimetallic nanoparticles at a variety of Pd : Au ratios. Using this peptide, the biomolecular overlayer structure can be switched between two different conformations ( cis vs. trans ) via light irradiation, thus accessing two different surface structures. The composition and arrangement of the materials was fully characterized, including atomic-level analyses, after which the reactivity of the bimetallic materials was explored using the reduction of 4-nitrophenol as a model system. Using these materials, it was demonstrated that the reactivity was maximized for the particles prepared at a Pd : Au ratio of 1 : 3 and with the peptide in the cis conformation. Such results present routes to a new generation of catalysts that could be remotely activated for on/off reactivity as a function of the ligand overlayer conformation. 

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2. Plasmonic Response of Light-Activated, Nano-Gold Doped Polymers

   https://doi.org/10.1557/adv.2019.286  

   Andriolo, Jessica M.; Joseph, McKenzie L.; Brockway, Molly C.; Skinner, Jack L. (January 2019, MRS Advances)

   Abstract Incorporation of metallic nanoparticles (NPs) in polymer matrix has been used to enhance and control dissolution and release of drugs, for targeted drug delivery, as antimicrobial agents, localized heat sources, and for unique optoelectronic applications. Gold NPs in particular exhibit a plasmonic response that has been utilized for photothermal energy conversion. Because plasmonic nanoparticles typically exhibit a plasmon resonance frequency similar to the visible light spectrum, they present as good candidates for direct photothermal conversion with enhanced solar thermal efficiency in these wavelengths. In our work, we have incorporated ∼3-nm-diameter colloidal gold (Au c ) NPs into electrospun polyethylene glycol (PEG) fibers to utilize the nanoparticle plasmonic response for localized heating and melting of the polymer to release medical treatment. Au c and Au c in PEG (PEG+Au c ) both exhibited a minimum reflectivity at 522 nm or approximately green wavelengths of light under ultraviolet-visible (UV-Vis) spectroscopy. PEG+Au c ES fibers revealed a blue shift in minimum reflectivity at 504 nm. UV-Vis spectra were used to calculate the theoretical efficiency enhancement of PEG+Au c versus PEG alone, finding an approximate increase of 10 % under broad spectrum white light interrogation, and ∼14 % when illuminated with green light. Au c enhanced polymers were ES directly onto resistance temperature detectors and interrogated with green laser light so that temperature change could be recorded. Results showed a maximum increase of 8.9 °C. To further understand how gold nanomaterials effect the complex optical properties of our materials, spectroscopic ellipsometry was used. Using spectroscopic ellipsometry and modeling with CompleteEASE® software, the complex optical constants of our materials were determined. The complex optical constant n (index of refraction) provided us with optical density properties related to light wavelength divided by velocity, and k (extinction coefficient) was used to show the absorptive properties of the materials. 

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3. Transforming Noble‐Metal Nanocrystals into Complex Nanostructures through Facet‐Selective Etching and Deposition

   https://doi.org/10.1002/cnma.201900378  

   Ahn, Jaewan; Zhang, Luo; Qin, Dong (August 2019, ChemNanoMat)

   Abstract Facet‐selective etching and deposition, as determined by the landscape of surface energy, represent two powerful methods for the transformation of noble‐metal nanocrystals into nanostructures with complex shapes or morphologies. This review highlights the use of these two methods, including integration of them, for the fabrication of novel monometallic and bimetallic nanostructures with enhanced properties. We start with an introduction to the role of surface capping in controlling the facet‐selective etching or deposition on the surface of Ag nanocrystals, followed by a case study of how to maneuver etching and deposition at different facets of Pd nanocrystals for the fabrication of nanoframes. We then introduce the use of galvanic replacement to accomplish selective etching and deposition on two different facets in an orthogonal manner, transforming Pd nanocubes into Pd−Pt octapods. By complementing galvanic replacement with a chemical reduction reaction, it is also feasible to control the rates of these two reactions for the conversion of Ag nanocubes into Ag@Ag−Au concave nanocubes and Ag@Au core‐shell nanocubes. These transformation methods not only greatly increase the shape diversity of metal nanocrystals but also offer nanocrystals with enhanced plasmonic and/or catalytic properties. 

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4. Catalytic oxidation of propane over palladium alloyed with gold: an assessment of the chemical and intermediate species

   https://doi.org/10.1039/c8cy01704b  

   Kareem, Haval; Shan, Shiyao; Wu, Zhi-Peng; Velasco, Leslie; Moseman, Kelli; O'Brien, Casey P.; Tran, Dat T.; Lee, Ivan C.; Maswadeh, Yazan; Yang, Lefu; et al (November 2018, Catalysis Science & Technology)

   Understanding the catalytic oxidation of propane is important for developing catalysts not only for catalytic oxidation of hydrocarbons in emission systems but also for selective oxidation in the chemical processing industry. For palladium-based catalysts, little is known about the identification of the chemical or intermediate species involved in propane oxidation. We describe herein findings of an investigation of the catalytic oxidation of propane over supported palladium nanoalloys with different compositions of gold (Pd n Au 100−n ), focusing on probing the chemical or intermediate species on the catalysts in correlation with the bimetallic composition and the alloying phase structure. In addition to an enhanced catalytic activity, a strong dependence of the catalytic activity on the bimetallic composition was revealed, displaying an activity maximum at a Pd : Au ratio of 50 : 50 in terms of reaction temperature. This dependence is also reflected by its dependence on the thermochemical treatment conditions. While the activity for nanoalloys with n ∼ 50 showed little change after the thermochemical treatment under oxygen, the activities for nanoalloys with n < 50 and n > 50 showed opposite trends. Importantly, this catalytic synergy is linked to the subtle differences of chemical and intermediate species which have been identified for the catalysts with different bimetallic compositions by in situ measurements using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). For the catalytic oxidation of propane over the highly-active catalyst with a Pd : Au ratio of 50 : 50, the major species identified include acetate and bicarbonate, showing subtle differences in comparison with the identification of bicarbonate and formate for the catalyst with <50% Au (with a lower activity) and the absence of apparent species for the catalyst with >50% Au (activity is largely absent). The alloying of 50% Au in Pd is believed to increase the oxophilicity of Pd, which facilitates the first carbon–carbon bond cleavage and oxygenation of propane. The implications of the findings on the catalytic synergy of Pd alloyed with Au and the design of active Pd alloy catalysts are also discussed. 

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5. Coupling the chemical reactivity of bimetallic surfaces to the orientations of liquid crystals

   https://doi.org/10.1039/d1mh00035g  

   Szilvási, Tibor; Yu, Huaizhe; Gold, Jake I.; Bao, Nanqi; Wolter, Trenton J.; Twieg, Robert J.; Abbott, Nicholas L.; Mavrikakis, Manos (July 2021, Materials Horizons)

   null (Ed.)

   The development of responsive soft materials with tailored functional properties based on the chemical reactivity of atomically precise inorganic interfaces has not been widely explored. In this communication, guided by first-principles calculations, we design bimetallic surfaces comprised of atomically thin Pd layers deposited onto Au that anchor nematic liquid crystalline phases of 4′- n -pentyl-4-biphenylcarbonitrile (5CB) and demonstrate that the chemical reactivity of these bimetallic surfaces towards Cl 2 gas can be tuned by specification of the composition of the surface alloy. Specifically, we use underpotential deposition to prepare submonolayer to multilayers of Pd on Au and employ X-ray photoelectron and infrared spectroscopy to validate computational predictions that binding of 5CB depends strongly on the Pd coverage, with ∼0.1 monolayer (ML) of Pd sufficient to cause the liquid crystal (LC) to adopt a perpendicular binding mode. Computed heats of dissociative adsorption of Cl 2 on PdAu alloy surfaces predict displacement of 5CB from these surfaces, a result that is also confirmed by experiments revealing that 1 ppm Cl 2 triggers orientational transitions of 5CB. By decreasing the coverage of Pd on Au from 1.8 ± 0.2 ML to 0.09 ± 0.02 ML, the dynamic response of 5CB to 1 ppm Cl 2 is accelerated 3X. Overall, these results demonstrate the promise of hybrid designs of responsive materials based on atomically precise interfaces formed between hard bimetallic surfaces and soft matter. 

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