LDRD final report on light-powered nanovehicles.

We have investigated the possibility of constructing nanoscale metallic vehicles powered by biological motors or flagella that are activated and powered by visible light. The vehicle's body is to be composed of the surfactant bilayer of a liposome coated with metallic nanoparticles or nanosheets grown together into a porous single crystal. The diameter of the rigid metal vesicles is from about 50 nm to microns. Illumination with visible light activates a photosynthetic system in the bilayer that can generate a pH gradient across the liposomal membrane. The proton gradient can fuel a molecular motor that is incorporated into the membrane. Some molecular motors require ATP to fuel active transport. The protein ATP synthase, when embedded in the membrane, will use the pH gradient across the membrane to produce ATP from ADP and inorganic phosphate. The nanoscale vehicle is thus composed of both natural biological components (ATPase, flagellum; actin-myosin, kinesin-microtubules) and biomimetic components (metal vehicle casing, photosynthetic membrane) as functional units. Only light and storable ADP, phosphate, water, and weak electron donor are required fuel components. These nano-vehicles are being constructed by self-assembly and photocatalytic and autocatalytic reactions. The nano-vehicles can potentially respond to chemical gradients and other factors such as light intensity and field gradients, in a manner similar to the way that magnetic bacteria navigate. The delivery package might include decision-making and guidance components, drugs or other biological and chemical agents, explosives, catalytic reactors, and structural materials. We expected in one year to be able only to assess the problems and major issues at each stage of construction of the vehicle and the likely success of fabricating viable nanovehicles with our biomimetic photocatalytic approach. Surprisingly, we have been able to demonstrate that metallized photosynthetic liposomes can indeed be made. We have completed the synthesis of metallized liposomes with photosynthetic function included and studied these structures by electron microscopy. Both platinum and palladium nanosheeting have been used to coat the micelles. The stability of the vehicles to mechanical stress and the solution environment is enhanced by the single-crystalline platinum or palladium coating on the vesicle. With analogous platinized micelles, it is possible to dry the vehicles and re-suspend them with full functionality. However, with the liposomes drying on a TEM grid may cause the platinized liposomes to collapse, although probably stay viable in solution. It remains to be shown whether a proton motive force across the metallized bilayer membrane can be generated and whether we will also be able to incorporate various functional capabilities including ATP synthesis and functional molecular motors. Future tasks to complete the nanovehicles would be the incorporation of ATP synthase into metallized liposomes and the incorporation of a molecular motor into metallized liposomes

DOE/BES/NSET annual report on growth of metal and semiconductor nanostructures using localized photocatalysts.

Our overall goal is to understand and develop a novel light-driven approach to the controlled growth of unique metal and semiconductor nanostructures and nanomaterials. In this photochemical process, bio-inspired porphyrin-based photocatalysts reduce metal salts in aqueous solutions at ambient temperatures to provide metal nucleation and growth centers. Photocatalyst molecules are pre-positioned at the nanoscale to control the location and morphology of the metal nanostructures grown. Self-assembly, chemical confinement, and molecular templating are some of the methods used for nanoscale positioning of the photocatalyst molecules. When exposed to light, the photocatalyst molecule repeatedly reduces metal ions from solution, leading to deposition and the synthesis of the new nanostructures and nanostructured materials. Studies of the photocatalytic growth process and the resulting nanostructures address a number of fundamental biological, chemical, and environmental issues and draw on the combined nanoscience characterization and multi-scale simulation capabilities of the new DOE Center for Integrated Nanotechnologies, the University of New Mexico, and Sandia National Laboratories. Our main goals are to elucidate the processes involved in the photocatalytic growth of metal nanomaterials and provide the scientific basis for controlled synthesis. The nanomaterials resulting from these studies have applications in nanoelectronics, photonics, sensors, catalysis, and micromechanical systems. The proposed nanoscience concentrates on three thematic research areas: (1) the creation of nanoscale structures for realizing novel phenomena and quantum control, (2) understanding nanoscale processes in the environment, and (3) the development and use of multi-scale, multi-phenomena theory and simulation. Our goals for FY03 have been to understand the role of photocatalysis in the synthesis of dendritic platinum nanostructures grown from aqueous surfactant solutions under ambient conditions. The research is expected to lead to highly nanoengineered materials for catalysis mediated by platinum, palladium, and potentially other catalytically important metals. The nanostructures made also have potential applications in nanoelectronics, nanophotonics, and nanomagnetic systems. We also expect to develop a fundamental understanding of the uses and limitations of biomimetic photocatalysis as a means of producing metal and semiconductor nanostructures and nanomaterials. The work has already led to a relationship with InfraSUR LLC, a small business that is developing our photocatalytic metal reduction processes for environmental remediation. This work also contributes to science education at a predominantly Hispanic and Native American university

Fault Diagnosis and Prediction System for Metal Wire Feeding Additive Manufacturing

In the process of metal wire and additive manufacturing, due to changes in temperature, humidity, current, voltage, and other parameters, as well as the failure of machinery and equipment, a failure may occur in the manufacturing process that seriously affects the current situation of production efficiency and product quality. Based on the demand for monitoring of the key impact parameters of additive manufacturing, this paper develops a parameter monitoring and prediction system for the additive manufacturing feeding process to provide a basis for future fault diagnosis. The fault diagnosis and prediction system for metal wire supply and additive manufacturing utilizes STM 32 as its core, enabling the capture and transmission of temperature, humidity, current, and voltage data. The upper computer system, designed on the LabVIEW 2019 virtual instrument platform, incorporates an LSTM neural network model and facilitates a connection between LabVIEW and MATLAB 2019 to achieve the prediction function. The monitoring and prediction system established in this study is intended to provide basic research assistance in the field of fault diagnosis

Mild pyrolysis of ionic self-assembled cobalt porphyrins on carbon toward efficient electrochemical conversion of CO2 to CO

We report ionic self-assembly of two oppositely charged cobalt(QIII) porphyrins (CoPs) on carbon coupled with subsequent mild pyrolysis at 350 degrees C, making CoPs lose some peripheral groups and become tightly adsorbed on the carbon with a high faradaic efficiency of 88 +/- 1.5% and a current density of 8 mA cm(-2) at a low overpotential of 430 mV toward electrochemical conversion of CO2 to CO

Three-point bending performances of integral-forming aluminum foam sandwich

In the course of service, integral-forming aluminum foam sandwich (IFAFS) needed to bear three-point bending loads in different directions, however, its deformation mechanism and failure modes were still unclear. In this work, three-point bending performances of IFAFS under flatwise and edgewise bending conditions were investigated by experiment, in-situ micro X-ray tomography and digital volume correlation (DVC) calculation. The results showed that three-point bending performance was more stable under edgewise bending condition, and with the decrease of span length IFAFS presented three different failure modes of oblique core shear, asymmetric and symmetrical surface fracture. In addition, porosity mutation was a significant reason for crack initiation, and optimizing pore homogeneity was important to improve the performance and predictability of failure location. Different strengthening effect of sandwich structure anisotropy and different internal deformation evolutions caused by internal strain vortex were two main reasons which lead to performance difference of IFAFS with different solid panel directions. Connection of pre-existing micropores with dimple-like micropores generated during deformation process leads to the failure of IFAFS. The key factors to further optimize three-point bending performance and predictability of IFAFS was to homogenize the pore distribution of IFAFS

Uniform PdH0.33 nanodendrites with a high oxygen reduction activity tuned by lattice H

We report the synthesis of β-palladium hydride nanodendrites (PdH0.33 NDs). The uniform PdH0.33 NDs are 36.3 ± 5.0 nm in diameter and selectively expose (111) planes decorated with (221) and (331) high-indexed steps. The PdH0.33 NDs show a high mass activity of 0.719 A/mgPd at 0.9 V (vs. reversible hydrogen electrode-RHE) toward alkaline oxygen reduction reaction (ORR), which is 3.7 and 6.3 times that of commercial Pt/C and house-made Pd/C, respectively. This study exemplifies the possibility of using special morphology and lattice H to modify the strain and electronic effect of metal for the optimization of functionalities. Keywords: Palladium hydride, Nanodendrites, Oxygen reduction reaction, Oxygen adsorption energ