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1. Synthesis and Characterization of Cu(II) and Mixed-Valence Cu(I)Cu(II) Clusters Supported by Pyridylamide Ligands

   https://doi.org/10.1021/acs.inorgchem.0c00008  

   Schneider, Joseph D.; Smith, Brett A.; Williams, Grant A.; Powell, Douglas R.; Perez, Felio; Rowe, Gerard T.; Yang, Lei (April 2020, Inorganic Chemistry)
2. Fabrication of Cu-CNT Composite and Cu Using Laser Powder Bed Fusion Additive Manufacturing

   https://doi.org/10.3390/powders1040014  

   Ladani, Leila; Razmi, Jafar; Sadeghilaridjani, Maryam (December 2022, Powders)

   Additive manufacturing (AM) as a disruptive technique has offered great potential to design and fabricate many metallic components for aerospace, medical, nuclear, and energy applications where parts have complex geometry. However, a limited number of materials suitable for the AM process is one of the shortcomings of this technique, in particular laser AM of copper (Cu) is challenging due to its high thermal conductivity and optical reflectivity, which requires higher heat input to melt powders. Fabrication of composites using AM is also very challenging and not easily achievable using the current powder bed technologies. Here, the feasibility to fabricate pure copper and copper-carbon nanotube (Cu-CNT) composites was investigated using laser powder bed fusion additive manufacturing (LPBF-AM), and 10 × 10 × 10 mm3 cubes of Cu and Cu-CNTs were made by applying a Design of Experiment (DoE) varying three parameters: laser power, laser speed, and hatch spacing at three levels. For both Cu and Cu-CNT samples, relative density above 90% and 80% were achieved, respectively. Density measurement was carried out three times for each sample, and the error was found to be less than 0.1%. Roughness measurement was performed on a 5 mm length of the sample to obtain statistically significant results. As-built Cu showed average surface roughness (Ra) below 20 µm; however, the surface of AM Cu-CNT samples showed roughness values as large as 1 mm. Due to its porous structure, the as-built Cu showed thermal conductivity of ~108 W/m·K and electrical conductivity of ~20% IACS (International Annealed Copper Standard) at room temperature, ~70% and ~80% lower than those of conventionally fabricated bulk Cu. Thermal conductivity and electrical conductivity were ~85 W/m·K and ~10% IACS for as-built Cu-CNT composites at room temperature. As-built Cu-CNTs showed higher thermal conductivity as compared to as-built Cu at a temperature range from 373 K to 873 K. Because of their large surface area, light weight, and large energy absorbing behavior, porous Cu and Cu-CNT materials can be used in electrodes, catalysts and their carriers, capacitors, heat exchangers, and heat and impact absorption. 

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3. Progression of the dealloying front in bilayer Cu–Al and Cu–Zn nanoporous foams

   https://doi.org/10.1557/s43578-023-01069-8  

   Hemmendinger, Karina D.; Hodge, Andrea M. (June 2023, Journal of Materials Research)

   Abstract The role of interfaces and the controlling synthesis parameters of graded dealloyed nanoporous metallic materials are investigated, focusing on the dealloying front progression in complex precursor materials with multiple alloy compositions. Specifically, the effects of relative density and chemical potential on the dealloying front in sputtered bilayer copper alloy films are explored with two case studies: Cu–Al/Cu–Al and Cu–Al/Cu–Zn. Cross-sectional scanning electron (SEM) micrographs and energy-dispersive X-ray spectroscopy mapping trace the dealloying front across three time intervals, while top-surface and cross-sectional SEM probes the final dealloyed foam morphology. Final ligament sizes were found to be independent of the synthesis parameters (21–28 nm), due to a combination of fast reaction times and phosphate-inhibited surface diffusion of Cu atoms. The chemical potential gradient yielded faster reaction times, whereas slower reaction times and a higher at.% of Cu in the top layer of precursor material produced a more uniform morphology. Graphical abstract 

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4. Synthesis of Core@Shell Cu‐Ni@Pt‐Cu Nano‐Octahedra and Their Improved MOR Activity

   https://doi.org/10.1002/anie.202014144  

   Li, Can; Chen, Xiaobo; Zhang, Lihua; Yan, Shaohui; Sharma, Anju; Zhao, Bo; Kumbhar, Amar; Zhou, Guangwen; Fang, Jiye (February 2021, Angewandte Chemie International Edition)

   Abstract Fabrication of 3dmetal‐based core@shell nanocatalysts with engineered Pt‐surfaces provides an effective approach for improving the catalytic performance. The challenges in such preparation include shape control of the 3dmetallic cores and thickness control of the Pt‐based shells. Herein, we report a colloidal seed‐mediated method to prepare octahedral CuNi@Pt‐Cu core@shell nanocrystals using CuNi octahedral cores as the template. By precisely controlling the synthesis conditions including the deposition rate and diffusion rate of the shell‐formation through tuning the capping ligand, reaction temperature, and heating rate, uniform Pt‐based shells can be achieved with a thickness of <1 nm. The resultant carbon‐supported CuNi@Pt‐Cu core@shell nano‐octahedra showed superior activity in electrochemical methanol oxidation reaction (MOR) compared with the commercial Pt/C catalysts and carbon‐supported CuNi@Pt‐Cu nano‐polyhedron counterparts. 

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5. Encapsulation of tricopper cluster in a synthetic cryptand enables facile redox processes from Cu ^I Cu ^I Cu ^I to Cu ^II Cu ^II Cu ^II states

   https://doi.org/10.1039/D0SC05441K  

   Zhang, Weiyao; Moore, Curtis E.; Zhang, Shiyu (March 2021, Chemical Science)

   null (Ed.)

   One-pot reaction of tris(2-aminoethyl)amine (TREN), [Cu I (MeCN) 4 ]PF 6 , and paraformaldehyde affords a mixed-valent [ TREN4 Cu II Cu I Cu I (μ 3 -OH)](PF 6 ) 3 complex. The macrocyclic azacryptand TREN4 contains four TREN motifs, three of which provide a bowl-shape binding pocket for the [Cu 3 (μ 3 -OH)] 3+ core. The fourth TREN caps on top of the tricopper cluster to form a cryptand, imposing conformational constraints and preventing solvent interaction. Contrasting the limited redox capability of synthetic tricopper complexes reported so far, [ TREN4 Cu II Cu I Cu I (μ 3 -OH)](PF 6 ) 3 exhibits several reversible single-electron redox events. The distinct electrochemical behaviors of [ TREN4 Cu II Cu I Cu I (μ 3 -OH)](PF 6 ) 3 and its solvent-exposed analog [ TREN3 Cu II Cu II Cu II (μ 3 -O)](PF 6 ) 4 suggest that isolation of tricopper core in a cryptand enables facile electron transfer, allowing potential application of synthetic tricopper complexes as redox catalysts. Indeed, the fully reduced [ TREN4 Cu I Cu I Cu I (μ 3 -OH)](PF 6 ) 2 can reduce O 2 under acidic conditions. The geometric constraints provided by the cryptand are reminiscent of Nature's multicopper oxidases (MCOs). For the first time, a synthetic tricopper cluster was isolated and fully characterized at Cu I Cu I Cu I ( 4a ), Cu II Cu I Cu I ( 4b ), and Cu II Cu II Cu I ( 4c ) states, providing structural and spectroscopic models for many intermediates in MCOs. Fast electron transfer rates (10 5 to 10 6 M −1 s −1 ) were observed for both Cu I Cu I Cu I /Cu II Cu I Cu I and Cu II Cu I Cu I /Cu II Cu II Cu I redox couples, approaching the rapid electron transfer rates of copper sites in MCO. 

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