PdCu Nanoalloy Electrocatalysts in Oxygen Reduction Reaction: Role of Composition and Phase State in Catalytic Synergy.

The catalytic synergy of nanoalloy catalysts depends on the nanoscale size, composition, phase state, and surface properties. This report describes findings of an investigation of their roles in the enhancement of electrocatalytic activity of PdCu alloy nanoparticle catalysts for oxygen reduction reaction (ORR). Pd(n)Cu(100-n) nanoalloys with controlled composition and subtle differences in size and phase state were synthesized by two different wet chemical methods. Detailed electrochemical characterization was performed to determine the surface properties and the catalytic activities. The atomic-scale structures of these catalysts were also characterized by high-energy synchrotron X-ray diffraction coupled with atomic pair distribution function analysis. The electrocatalytic activity and stability were shown to depend on the size, composition, and phase structure. With Pd(n)Cu(100-n) catalysts from both methods, a maximum ORR activity was revealed at Pd/Cu ratio close to 50:50. Structurally, Pd50Cu50 nanoalloys feature a mixed phase consisting of chemically ordered (body-centered cubic type) and disordered (face-centered cubic type) domains. The phase-segregated structure is shown to change to a single phase upon electrochemical potential cycling in ORR condition. While the surface Cu dissolution occurred in PdCu catalysts from the two different synthesis methods, the PdCu with a single-phase character is found to exhibit a tendency of a much greater dissolution than that with the phase segregation. Analysis of the results, along theoretical modeling based on density functional theory calculation, has provided new insights for the correlation between the electrocatalytic activity and the catalyst structures.

Catalytic activity of bimetallic catalysts highly sensitive to the atomic composition and phase structure at the nanoscale.

The ability to determine the atomic arrangement in nanoalloy catalysts and reveal the detailed structural features responsible for the catalytically active sites is essential for understanding the correlation between the atomic structure and catalytic properties, enabling the preparation of efficient nanoalloy catalysts by design. Herein we describe a study of CO oxidation over PdCu nanoalloy catalysts focusing on gaining insights into the correlation between the atomic structures and catalytic activity of nanoalloys. PdCu nanoalloys of different bimetallic compositions are synthesized as a model system and are activated by a controlled thermochemical treatment for assessing their catalytic activity. The results show that the catalytic synergy of Pd and Cu species evolves with both the bimetallic nanoalloy composition and temperature of the thermochemical treatment reaching a maximum at a Pd : Cu ratio close to 50 : 50. The nanoalloys are characterized structurally by ex situ and in situ synchrotron X-ray diffraction, including atomic pair distribution function analysis. The structural data show that, depending on the bimetallic composition and treatment temperature, PdCu nanoalloys adopt two different structure types. One features a chemically ordered, body centered cubic (B2) type alloy consisting of two interpenetrating simple cubic lattices, each occupied with Pd or Cu species alone, and the other structure type features a chemically disordered, face-centered cubic (fcc) type of alloy wherein Pd and Cu species are intermixed at random. The catalytic activity for CO oxidation is strongly influenced by the structural features. In particular, it is revealed that the prevalence of chemical disorder in nanoalloys with a Pd : Cu ratio close to 50 : 50 makes them superior catalysts for CO oxidation in comparison with the same nanoalloys of other bimetallic compositions. However, the catalytic synergy can be diminished if the Pd50Cu50 nanoalloys undergo phase segregation into distinct chemically-ordered (B2-type) and disordered (fcc-type) domains. This finding is significant since it provides a rational basis for streamlining the design and preparation of Pd-based nanoalloy catalysts in terms of atomic structure and phase state.

Nanoalloy Printed and Pulse-Laser Sintered Flexible Sensor Devices with Enhanced Stability and Materials Compatibility.

While conformal and wearable devices have become one of the most desired formats for printable electronics, it is challenging to establish a scalable process that produces stable conductive patterns but also uses substrates compatible with widely available wearable materials. Here, we describe findings of an investigation of a nanoalloy ink printed and pulsed-laser sintered conductive patterns as flexible functional devices with enhanced stability and materials compatibility. While nanoparticle inks are desired for printable electronics, almost all existing nanoparticle inks are based on single-metal component, which, as an electronic element, is limited by its inherent stabilities of the metal such as propensity of metal oxidation and mobility of metal ions, especially in sintering processes. The work here has demonstrated the first example in exploiting plasmonic coupling of nanoalloys and pulsed-laser energy with controllable thermal penetration. The experimental and theoretical results have revealed clear correlation between the pulsed laser parameters and the nanoalloy structural characteristics. The superior performance of the resulting flexible sensor device, upon imparting nanostructured sensing materials, for detecting volatile organic compounds has significant implications to developing stable and wearable sensors for monitoring environmental pollutants and breath biomarkers. This simple "nanoalloy printing-laser sintering-nanostructure printing" process is entirely general to many different sensor devices and nanostructured sensing materials, enabling the ability to easily construct sophisticated sensor array.

Design of functional nanoparticles and assemblies for theranostic applications.

Nanostructured materials have found increasing applications in medical therapies and diagnostics (theranostics). The main challenge is the ability to impart the nanomaterials with structurally tailored functional properties which can effectively target biomolecules but also provide signatures for effective detection. The harnessing of functional nanoparticles and assemblies serves as a powerful strategy for the creation of the structurally tailored multifunctional properties. This article highlights some of the important design strategies in recent investigation of metals (especially gold and silver), and magnetically functionalized nanoparticles, and molecularly assembled or biomolecularly conjugated nanoparticles with tunable optical, spectroscopic, magnetic, and electrical properties for applications in several areas of potential theranostic interests. Examples include colorimetric detection of amino acids and small peptides, surface-enhanced Raman scattering detection of biomolecular recognition of proteins and DNAs, delivery in cell transfection and bacteria inactivation, and chemiresistive detection of breath biomarkers. A major emphasis is placed on understanding how the control of the nanostructures and the molecular and biomolecular interactions impact these biofunctional properties, which has important implications for bottom-up designs of theranostic materials.

Solving the nanostructure problem: exemplified on metallic alloy nanoparticles.

With current technology moving rapidly toward smaller scales nanometer-size materials, hereafter called nanometer-size particles (NPs), are being produced in increasing numbers and explored for various useful applications ranging from photonics and catalysis to detoxification of wastewater and cancer therapy. Nature also is a prolific producer of useful NPs. Evidence can be found in ores on the ocean floor, minerals and soils on land and in the human body that, when water is excluded, is mostly made of proteins that are 6-10 nm in size and globular in shape. Precise knowledge of the 3D atomic-scale structure, that is how atoms are arranged in space, is a crucial prerequisite for understanding and so gaining more control over the properties of any material, including NPs. In the case of bulk materials such knowledge is fairly easy to obtain by Bragg diffraction experiments. Determining the 3D atomic-scale structure of NPs is, however, still problematic spelling trouble for science and technology at the nanoscale. Here we explore this so-called "nanostructure problem" from a practical point of view arguing that it can be solved when its technical, that is the inapplicability of Bragg diffraction to NPs, and fundamental, that is the incompatibility of traditional crystallography with NPs, aspects are both addressed properly. As evidence we present a successful and broadly applicable, 6-step approach to determining the 3D atomic-scale structure of NPs based on a suitable combination of a few experimental and computational techniques. This approach is exemplified on 5 nm sized Pd(x)Ni(100-x) particles (x = 26, 56 and 88) explored for catalytic applications. Furthermore, we show how once an NP atomic structure is determined precisely, a strategy for improving NP structure-dependent properties of particular interest to science and technology can be designed rationally and not subjectively as frequently done now.

Atomic-structural synergy for catalytic CO oxidation over palladium-nickel nanoalloys.

Alloying palladium (Pd) with other transition metals at the nanoscale has become an important pathway for preparation of low-cost, highly active and stable catalysts. However, the lack of understanding of how the alloying phase state, chemical composition and atomic-scale structure of the alloys at the nanoscale influence their catalytic activity impedes the rational design of Pd-nanoalloy catalysts. This work addresses this challenge by a novel approach to investigating the catalytic oxidation of carbon monoxide (CO) over palladium-nickel (PdNi) nanoalloys with well-defined bimetallic composition, which reveals a remarkable maximal catalytic activity at Pd:Ni ratio of ~50:50. Key to understanding the structural-catalytic synergy is the use of high-energy synchrotron X-ray diffraction coupled to atomic pair distribution function (HE-XRD/PDF) analysis to probe the atomic structure of PdNi nanoalloys under controlled thermochemical treatments and CO reaction conditions. Three-dimensional (3D) models of the atomic structure of the nanoalloy particles were generated by reverse Monte Carlo simulations (RMC) guided by the experimental HE-XRD/PDF data. Structural details of the PdNi nanoalloys were extracted from the respective 3D models and compared with the measured catalytic properties. The comparison revealed a strong correlation between the phase state, chemical composition and atomic-scale structure of PdNi nanoalloys and their catalytic activity for CO oxidation. This correlation is further substantiated by analyzing the first atomic neighbor distances and coordination numbers inside the nanoalloy particles and at their surfaces. These findings have provided new insights into the structural synergy of nanoalloy catalysts by controlling the phase state, composition and atomic structure, complementing findings of traditional density functional theory studies.

Nanoalloying and phase transformations during thermal treatment of physical mixtures of Pd and Cu nanoparticles.

Nanoscale alloying and phase transformations in physical mixtures of Pd and Cu ultrafine nanoparticles are investigated in real time with in situ synchrotron-based x-ray diffraction complemented by ex situ high-resolution transmission electron microscopy. The combination of metal-support interaction and reactive/non-reactive environment was found to determine the thermal evolution and ultimate structure of this binary system. At 300 °C, the nanoparticles supported on silica and carbon black intermix to form a chemically ordered CsCl-type (B2) alloy phase. The B2 phase transforms into a disordered fcc alloy at higher temperature (> 450 °C). The alloy nanoparticles supported on silica and carbon black are homogeneous in volume, but evidence was found of Pd surface enrichment. In sharp contrast, when supported on alumina, the two metals segregated at 300 °C to produce almost pure fcc Cu and Pd phases. Upon further annealing of the mixture on alumina above 600 °C, the two metals interdiffused, forming two distinct disordered alloys of compositions 30% and 90% Pd. The annealing atmosphere also plays a major role in the structural evolution of these bimetallic nanoparticles. The nanoparticles annealed in forming gas are larger than the nanoparticles annealing in helium due to reduction of the surface oxides that promotes coalescence and sintering.

DNA assembly and enzymatic cutting in solutions: a gold nanoparticle based SERS detection strategy.

The ability to monitor biomolecular recognition such as DNA hybridization and enzymatic reactivity in solutions with high sensitivity is important for developing effective bioassay strategies. Surface enhanced Raman scattering (SERS) based on use of solid substrates to produce the SERS effect for the detection often requires substrate preparation which is ineffective for rapid monitoring. This report describes a new strategy exploiting a gold nanoparticle (AuNP) based interparticle "hot-spot" for SERS monitoring of DNA mediated assembly and enzyme induced cleavage of the assembly in solution phase. The DNAs consist of two different complementary DNA strands with a thiol modification for attachment to AuNPs of selected sizes. In a solution containing AuNPs conjugated with one of the single-stranded (ss) DNA and other AuNPs labeled with a Raman reporter molecule, 4-mercaptobenzoic acid (MBA), the introduction of the complementary DNA strand leads to a linkage of the two types of AuNPs, producing double-stranded (ds) DNA-AuNP assembly (ds-DNA-AuNPs) with an interparticle "hot-spot" for SERS detection of the diagnostic bands of the reporter. Upon introducing a restriction enzyme (e.g. MspI) into the ds-DNA-AuNP assembly solution, the removal of the interparticle "hot-spot" due to restriction enzyme cleavage of the ds-DNA leads to a decrease of the SERS signals. While the detailed cleavage process may depend on the reaction time and the amount of enzyme, the viability of using gold nanoparticle "hot-spot" based SERS monitoring of DNA assembly and enzyme cleavage is clearly demonstrated, which has important implications for developing new strategies for bioassays.