Active sites of atomically dispersed Pt supported on Gd-doped ceria with improved low temperature performance for CO oxidation.

"Single - atom" catalysts (SACs) have been the focus of intense research, due to debates about their reactivity and challenges toward determining and designing "single - atom" (SA) sites. To address the challenge, in this work, we designed Pt SACs supported on Gd-doped ceria (Pt/CGO), which showed improved activity for CO oxidation compared to its counterpart, Pt/ceria. The enhanced activity of Pt/CGO was associated with a new Pt SA site which appeared only in the Pt/CGO catalyst under CO pretreatment at elevated temperatures. Combined X-ray and optical spectroscopies revealed that, at this site, Pt was found to be d-electron rich and bridged with Gd-induced defects via an oxygen vacancy. As explained by density functional theory calculations, this site opened a new path via a dicarbonyl intermediate for CO oxidation with a greatly reduced energy barrier. These results provide guidance for rationally improving the catalytic properties of SA sites for oxidation reactions.

Biomimetic and Biologically Compliant Soft Architectures via 3D and 4D Assembly Methods: A Perspective.

Recent progress in soft material chemistry and enabling methods of 3D and 4D fabrication-emerging programmable material designs and associated assembly methods for the construction of complex functional structures-is highlighted. The underlying advances in this science allow the creation of soft material architectures with properties and shapes that programmably vary with time. The ability to control composition from the molecular to the macroscale is highlighted-most notably through examples that focus on biomimetic and biologically compliant soft materials. Such advances, when coupled with the ability to program material structure and properties across multiple scales via microfabrication, 3D printing, or other assembly techniques, give rise to responsive (4D) architectures. The challenges and prospects for progress in this emerging field in terms of its capacities for integrating chemistry, form, and function are described in the context of exemplary soft material systems demonstrating important but heretofore difficult-to-realize biomimetic and biologically compliant behaviors.

Aliovalent Doping of CeO2 Improves the Stability of Atomically Dispersed Pt.

Atomically dispersed supported catalysts hold considerable promise as catalytic materials. The ability to employ and stabilize them against aggregation in complex process environments remains a key challenge to the elusive goal of 100% atom utilization in catalysis. Herein, using a Gd-doped ceria support for atomically dispersed surface Pt atoms, we establish how the combined effects of aliovalent doping and oxygen vacancy generation provide dynamic mechanisms that serve to enhance the stability of supported single-atom configurations. Using correlated, in situ X-ray absorption, photoelectron, and vibrational spectroscopy methods for the analysis of samples on the two types of support (with and without Gd doping), we establish that the Pt atoms are located proximal to Gd dopants, forming a speciation that serves to enhance the thermal stability of Pt atoms against aggregation.

Silicon Heterojunction Microcells.

We report the design, fabrication, and characterization of silicon heterojunction microcells, a new type of photovoltaic cell that leverages high-efficiency bulk wafers in a microscale form factor, while also addressing the challenge of passivating microcell sidewalls to mitigate carrier recombination. We present synthesis methods exploiting either dry etching or laser cutting to realize microcells with native oxide-based edge passivation. Measured microcell performance for both fabrication processes is compared to that in simulations. We characterize the dependence of microcell open-circuit voltage (Voc) on the cell area-perimeter ratio and examine synthesis processes that affect edge passivation quality, such as sidewall damage removal, the passivation material, and the deposition technique. We report the highest Si microcell Voc to date (588 mV, for a 400 µm × 400 µm × 80 µm device), demonstrate Voc improvements with deposited edge passivation of up to 55 mV, and outline a pathway to achieve microcell efficiencies surpassing 15% for such device sizes.

3D Particle Free Printing of Biocompatible Conductive Hydrogel Platforms for Neuron Growth and Electrophysiological Recording.

Electrically conductive 3D periodic microscaffolds are fabricated using a particle-free direct ink writing approach for use as neuronal growth and electrophysiological recording platforms. A poly (2-hydroxyethyl methacrylate) (pHEMA)/pyrrole ink, followed by chemical in situ polymerization of pyrrole, enables hydrogel printing through nozzles as small as 1 µm. These conductive hydrogels can pattern complex 2D and 3D structures and have good biocompatibility with test cell cultures (~94.5% viability after 7 days). Hydrogel arrays promote extensive neurite outgrowth of cultured Aplysia californica pedal ganglion neurons. This platform allows extracellular electrophysiological recording of steady-state and stimulated electrical neuronal activities. In summation, this 3D conductive ink printing process enables preparation of biocompatible and micron-sized structures to create customized in vitro electrophysiological recording platforms.

Dynamic structure of active sites in ceria-supported Pt catalysts for the water gas shift reaction.

Oxide-supported noble metal catalysts have been extensively studied for decades for the water gas shift (WGS) reaction, a catalytic transformation central to a host of large volume processes that variously utilize or produce hydrogen. There remains considerable uncertainty as to how the specific features of the active metal-support interfacial bonding-perhaps most importantly the temporal dynamic changes occurring therein-serve to enable high activity and selectivity. Here we report the dynamic characteristics of a Pt/CeO2 system at the atomic level for the WGS reaction and specifically reveal the synergistic effects of metal-support bonding at the perimeter region. We find that the perimeter Pt0 - O vacancy-Ce3+ sites are formed in the active structure, transformed at working temperatures and their appearance regulates the adsorbate behaviors. We find that the dynamic nature of this site is a key mechanistic step for the WGS reaction.

Biocompliant Composite Au/pHEMA Plasmonic Scaffolds for 3D Cell Culture and Noninvasive Sensing of Cellular Metabolites.

The field of 3D printing is an area of active research, with a substantial focus given to the design and construction of customized tools for applications in technology. There exists a particular need in these developing areas of opportunity for new multi-functional soft materials that are biologically compatible for the growth and directed culturing of cells. Herein, a composite material consisting of gold nanoparticles with useful plasmonic properties embedded within a highly hydrophilic poly-2-hydroxyethylmethacrylate matrix is described and characterized. This composite material serves dual functions as both host framework scaffold for cell lines such as pre-osteoblasts as well as a plasmonic biosensor for in situ measurements of living cells. The plasmonic properties of this system are characterized as a function of the material properties and related to compositional features of the material through a proposed light-directed mechanism. This chemistry provides a tunable, 3D printable plasmonic composite material of encapsulated gold nanoparticles in a biologically-compliant, acrylate-based hydrogel matrix. Surface-enhanced Raman scattering studies of 3D-microcultures supported by the scaffolds are carried out and the strong influence of perm-selective molecular diffusion in its analytical responses is established. Most notably, specific, largely hydrophilic, cellular metabolites are detected within the supported live cultures.

3D-Printed Hydrogel Composites for Predictive Temporal (4D) Cellular Organizations and Patterned Biogenic Mineralization.

Materials chemistries for hydrogel scaffolds that are capable of programming temporal (4D) attributes of cellular decision-making in supported 3D microcultures are described. The scaffolds are fabricated using direct-ink writing (DIW)-a 3D-printing technique using extrusion to pattern scaffolds at biologically relevant diameters (≤ 100 µm). Herein, DIW is exploited to variously incorporate a rheological nanoclay, Laponite XLG (LAP), into 2-hydroxyethyl methacrylate (HEMA)-based hydrogels-printing the LAP-HEMA (LH) composites as functional modifiers within otherwise unmodified 2D and 3D HEMA microstructures. The nanoclay-modified domains, when tested as thin films, require no activating (e.g., protein) treatments to promote robust growth compliances that direct the spatial attachment of fibroblast (3T3) and preosteoblast (E1) cells, fostering for the latter a capacity to direct long-term osteodifferentiation. Cell-to-gel interfacial morphologies and cellular motility are analyzed with spatial light interference microscopy (SLIM). Through combination of HEMA and LH gels, high-resolution DIW of a nanocomposite ink (UniH) that translates organizationally dynamic attributes seen with 2D gels into dentition-mimetic 3D scaffolds is demonstrated. These analyses confirm that the underlying materials chemistry and geometry of hydrogel nanocomposites are capable of directing cellular attachment and temporal development within 3D microcultures-a useful material system for the 4D patterning of hydrogel scaffolds.

Solution processes for ultrabroadband and omnidirectional graded-index glass lenses with near-zero reflectivity in high concentration photovoltaics.

Concentrator photovoltaic (CPV) systems, where incident direct solar radiation is tightly concentrated onto high-efficiency multi-junction solar cells by geometric optical elements, exhibit the highest efficiencies in converting the sun's energy into electric power. Their energy conversion efficiencies are greatly limited, however, due to Fresnel reflection losses occurring at three air/optics interfaces in the most sophisticated dual-stage CPV platforms. This paper describes a facile one-step wet-etching process to create a nanoporous surface with a graded-index profile on both flat and curved glasses, with capabilities of achieving ~99% average transmission efficiency in a wide wavelength range from 380 nm to 1.3 µm and for a wide range of incident angles up to ±40° regardless of the polarization state of incident sunlight. The simplicity of the etching process remarkably increases their versatility in various optical elements that require unconventional form factors such as Fresnel lenses and microlens arrays, and/or demanding curvatures along with much reduced dimensions such as ball lenses. Etched glass surfaces on two-stage optical concentrating systems yield enhancements in total optical transmission efficiencies by 13.8% and in the photocurrent by 14.3%, as experimentally determined by measurements on microscale triple-junction solar cells. The presented strategy can be widely adapted in a variety of applications such as image sensors, display systems, and other optoelectronic devices.

Semiconductor Nanomembrane Materials for High-Performance Soft Electronic Devices.

The development of methods to synthesize and physically manipulate extremely thin, single-crystalline inorganic semiconductor materials, so-called nanomembranes, has led to an almost explosive growth of research worldwide into uniquely enabled opportunities for their use in new "soft" and other unconventional form factors for high-performance electronics. The unique properties that nanomembranes afford, such as their flexibility and lightweight characteristics, allow them to be integrated into electronic and optoelectronic devices that, in turn, adopt these unique attributes. For example, nanomembrane devices are able to make conformal contact to curvilinear surfaces and manipulate strain to induce the self-assembly of various 3D nano/micro device architectures. Further, thin semiconductor materials (e.g., Si-nanomembranes, transition metal dichalcogenides, and phosphorene) are subject to the impacts of quantum and other size-dependent effects that in turn enable the manipulation of their bandgaps and the properties of electronic and optoelectronic devices fabricated from them. In this Perspective, nanomembrane synthesis techniques and exemplary applications of their use are examined. We specifically describe nanomembrane chemistry exploiting high-performance materials, along with precise/high-throughput techniques for their manipulation that exemplify their growing capacities to shape outcomes in technology. Prominent challenges in the chemistry of these materials are presented along with future directions that might guide the development of next generation nanomembrane-based devices.

Solid-Liquid Lithium Electrolyte Nanocomposites Derived from Porous Molecular Cages.

We demonstrate that solid-liquid nanocomposites derived from porous organic cages are effective lithium ion electrolytes at room temperature. A solid-liquid electrolyte nanocomposite (SLEN) fabricated from a LiTFSI/DME electrolyte system and a porous organic cage exhibits ionic conductivity on the order of 1 × 10-3 S cm-1. With an experimentally measured activation barrier of 0.16 eV, this composite is characterized as a superionic conductor. Furthermore, the SLEN displays excellent oxidative stability up to 4.7 V vs Li/Li+. This simple three-component system enables the rational design of electrolytes from tunable discrete molecular architectures.

Refractive index sensing and surface-enhanced Raman spectroscopy using silver-gold layered bimetallic plasmonic crystals.

Herein we describe the fabrication and characterization of Ag and Au bimetallic plasmonic crystals as a system that exhibits improved capabilities for quantitative, bulk refractive index (RI) sensing and surface-enhanced Raman spectroscopy (SERS) as compared to monometallic plasmonic crystals of similar form. The sensing optics, which are bimetallic plasmonic crystals consisting of sequential nanoscale layers of Ag coated by Au, are chemically stable and useful for quantitative, multispectral, refractive index and spectroscopic chemical sensing. Compared to previously reported homometallic devices, the results presented herein illustrate improvements in performance that stem from the distinctive plasmonic features and strong localized electric fields produced by the Ag and Au layers, which are optimized in terms of metal thickness and geometric features. Finite-difference time-domain (FDTD) simulations theoretically verify the nature of the multimode plasmonic resonances generated by the devices and allow for a better understanding of the enhancements in multispectral refractive index and SERS-based sensing. Taken together, these results demonstrate a robust and potentially useful new platform for chemical/spectroscopic sensing.

Three-dimensional mesostructures as high-temperature growth templates, electronic cellular scaffolds, and self-propelled microrobots.

Recent work demonstrates that processes of stress release in prestrained elastomeric substrates can guide the assembly of sophisticated 3D micro/nanostructures in advanced materials. Reported application examples include soft electronic components, tunable electromagnetic and optical devices, vibrational metrology platforms, and other unusual technologies, each enabled by uniquely engineered 3D architectures. A significant disadvantage of these systems is that the elastomeric substrates, while essential to the assembly process, can impose significant engineering constraints in terms of operating temperatures and levels of dimensional stability; they also prevent the realization of 3D structures in freestanding forms. Here, we introduce concepts in interfacial photopolymerization, nonlinear mechanics, and physical transfer that bypass these limitations. The results enable 3D mesostructures in fully or partially freestanding forms, with additional capabilities in integration onto nearly any class of substrate, from planar, hard inorganic materials to textured, soft biological tissues, all via mechanisms quantitatively described by theoretical modeling. Illustrations of these ideas include their use in 3D structures as frameworks for templated growth of organized lamellae from AgCl-KCl eutectics and of atomic layers of WSe2 from vapor-phase precursors, as open-architecture electronic scaffolds for formation of dorsal root ganglion (DRG) neural networks, and as catalyst supports for propulsive systems in 3D microswimmers with geometrically controlled dynamics. Taken together, these methodologies establish a set of enabling options in 3D micro/nanomanufacturing that lie outside of the scope of existing alternatives.

3D-Printed pHEMA Materials for Topographical and Biochemical Modulation of Dorsal Root Ganglion Cell Response.

Understanding and controlling the interactions occurring between cells and engineered materials are central challenges toward progress in the development of biomedical devices. In this work, we describe materials for direct ink writing (DIW), an extrusion-based type of 3D printing, that embed a custom synthetic protein (RGD-PDL) within the microfilaments of 3D-hydrogel scaffolds to modify these interactions and differentially direct tissue-level organization of complex cell populations in vitro. The RGD-PDL is synthesized by modifying poly-d-lysine (PDL) to varying extents with peptides containing the integrin-binding motif Arg-Gly-Asp (RGD). Compositional gradients of the RGD-PDL presented by both patterned and thin-film poly(2-hydroxyethyl) methacrylate (pHEMA) substrates allow the patterning of cell-growth compliance in a grayscale form. The surface chemistry-dependent guidance of cell growth on the RGD-PDL-modified pHEMA materials is demonstrated using a model NIH-3T3 fibroblast cell line. The formation of a more complex cellular system-organotypic primary murine dorsal root ganglion (DRG)-in culture is also achieved on these scaffolds, where distinctive forms of cell growth and migration guidance are seen depending on their RGD-PDL content and topography. This experimental platform for the study of physicochemical factors on the formation and the reorganization of organotypic cultures offers useful capabilities for studies in tissue engineering, regenerative medicine, and diagnostics.

Anomalous Structural Disorder in Supported Pt Nanoparticles.

Supported Pt nanocatalysts generally exhibit anomalous behavior, including negative thermal expansion and large structural disorder. Finite temperature DFT/MD simulations reproduce these properties, showing that they are largely explained by a combination of thermal vibrations and low-frequency disorder. We show here that a full interpretation is more complex and that the DFT/MD mean-square relative displacements (MSRD) can be further separated into vibrational disorder, "dynamic structural disorder" (DSD), and long-time equilibrium fluctuations of the structure dubbed "anomalous structural disorder" (ASD). We find that the vibrational and DSD components behave normally, increasing linearly with temperature while the ASD decreases, reflecting the evolution of mean nanoparticle geometry. As a consequence the usual procedure of fitting the MSRD to normal vibrations plus temperature-independent static disorder results in unphysical bond strengths and Grüneisen parameters.

Quantitative Reflection Imaging for the Morphology and Dynamics of Live Aplysia californica Pedal Ganglion Neurons Cultured on Nanostructured Plasmonic Crystals.

We describe a reflection imaging system that consists of a plasmonic crystal, a common laboratory microscope, and band-pass filters for use in the quantitative imaging and in situ monitoring of live cells and their substrate interactions. Surface plasmon resonance (SPR) provides a highly sensitive method to monitor changes in physicochemical properties occurring at metal-dielectric interfaces. Polyelectrolyte thin films deposited using the layer-by-layer (LBL) self-assembly method provide a reference system for calibrating the reflection contrast changes that occur when the polyelectrolyte film thickness changes and provide insight into the optical responses that originate from the multiple plasmonic features supported by this imaging system. Finite-difference time-domain (FDTD) simulations of the optical responses measured experimentally from the polyelectrolyte reference system are used to provide a calibration of the optical system for subsequent use in quantitative studies investigating live cell dynamics in cultures supported on a plasmonic crystal substrate. Live Aplysia californica pedal ganglion neurons cultured in artificial seawater were used as a model system through which to explore the utility of this plasmonic imaging technique. Here, the morphology of cellular peripheral structures ≲80 nm in thickness were quantitatively analyzed, and the dynamics of their trypsin-induced surface detachment were visualized. These results illustrate the capacities of this system for use in investigations of the dynamics of ultrathin cellular structures within complex bioanalytical environments.

Deterministic Integration of Biological and Soft Materials onto 3D Microscale Cellular Frameworks.

Complex 3D organizations of materials represent ubiquitous structural motifs found in the most sophisticated forms of matter, the most notable of which are in life-sustaining hierarchical structures found in biology, but where simpler examples also exist as dense multilayered constructs in high-performance electronics. Each class of system evinces specific enabling forms of assembly to establish their functional organization at length scales not dissimilar to tissue-level constructs. This study describes materials and means of assembly that extend and join these disparate systems-schemes for the functional integration of soft and biological materials with synthetic 3D microscale, open frameworks that can leverage the most advanced forms of multilayer electronic technologies, including device-grade semiconductors such as monocrystalline silicon. Cellular migration behaviors, temporal dependencies of their growth, and contact guidance cues provided by the nonplanarity of these frameworks illustrate design criteria useful for their functional integration with living matter (e.g., NIH 3T3 fibroblast and primary rat dorsal root ganglion cell cultures).

Concentrator photovoltaic module architectures with capabilities for capture and conversion of full global solar radiation.

Emerging classes of concentrator photovoltaic (CPV) modules reach efficiencies that are far greater than those of even the highest performance flat-plate PV technologies, with architectures that have the potential to provide the lowest cost of energy in locations with high direct normal irradiance (DNI). A disadvantage is their inability to effectively use diffuse sunlight, thereby constraining widespread geographic deployment and limiting performance even under the most favorable DNI conditions. This study introduces a module design that integrates capabilities in flat-plate PV directly with the most sophisticated CPV technologies, for capture of both direct and diffuse sunlight, thereby achieving efficiency in PV conversion of the global solar radiation. Specific examples of this scheme exploit commodity silicon (Si) cells integrated with two different CPV module designs, where they capture light that is not efficiently directed by the concentrator optics onto large-scale arrays of miniature multijunction (MJ) solar cells that use advanced III-V semiconductor technologies. In this CPV+ scheme ("+" denotes the addition of diffuse collector), the Si and MJ cells operate independently on indirect and direct solar radiation, respectively. On-sun experimental studies of CPV+ modules at latitudes of 35.9886° N (Durham, NC), 40.1125° N (Bondville, IL), and 38.9072° N (Washington, DC) show improvements in absolute module efficiencies of between 1.02% and 8.45% over values obtained using otherwise similar CPV modules, depending on weather conditions. These concepts have the potential to expand the geographic reach and improve the cost-effectiveness of the highest efficiency forms of PV power generation.

Programming Mechanical and Physicochemical Properties of 3D Hydrogel Cellular Microcultures via Direct Ink Writing.

3D hydrogel scaffolds are widely used in cellular microcultures and tissue engineering. Using direct ink writing, microperiodic poly(2-hydroxyethyl-methacrylate) (pHEMA) scaffolds are created that are then printed, cured, and modified by absorbing 30 kDa protein poly-l-lysine (PLL) to render them biocompliant in model NIH/3T3 fibroblast and MC3T3-E1 preosteoblast cell cultures. Spatial light interference microscopy (SLIM) live cell imaging studies are carried out to quantify cellular motilities for each cell type, substrate, and surface treatment of interest. 3D scaffold mechanics is investigated using atomic force microscopy (AFM), while their absorption kinetics are determined by confocal fluorescence microscopy (CFM) for a series of hydrated hydrogel films prepared from prepolymers with different homopolymer-to-monomer (Mr ) ratios. The observations reveal that the inks with higher Mr values yield relatively more open-mesh gels due to a lower degree of entanglement. The biocompatibility of printed hydrogel scaffolds can be controlled by both PLL content and hydrogel mesh properties.

Biomimetic 4D printing.

Shape-morphing systems can be found in many areas, including smart textiles, autonomous robotics, biomedical devices, drug delivery and tissue engineering. The natural analogues of such systems are exemplified by nastic plant motions, where a variety of organs such as tendrils, bracts, leaves and flowers respond to environmental stimuli (such as humidity, light or touch) by varying internal turgor, which leads to dynamic conformations governed by the tissue composition and microstructural anisotropy of cell walls. Inspired by these botanical systems, we printed composite hydrogel architectures that are encoded with localized, anisotropic swelling behaviour controlled by the alignment of cellulose fibrils along prescribed four-dimensional printing pathways. When combined with a minimal theoretical framework that allows us to solve the inverse problem of designing the alignment patterns for prescribed target shapes, we can programmably fabricate plant-inspired architectures that change shape on immersion in water, yielding complex three-dimensional morphologies.