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1. 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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2. 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)
3. Dioxygen Activation Kinetics over Distinct Cu Site Types in Cu-Chabazite Zeolites

   https://doi.org/10.1021/acscatal.1c03471  

   Bregante, Daniel T.; Wilcox, Laura N.; Liu, Changming; Paolucci, Christopher; Gounder, Rajamani; Flaherty, David W. (October 2021, ACS Catalysis)
4. Uneven Oxidation and Surface Reconstructions on Stepped Cu(100) and Cu(110)

   https://doi.org/10.1021/acs.nanolett.1c04124  

   Li, Meng; Curnan, Matthew T.; Saidi, Wissam A.; Yang, Judith C. (February 2022, Nano Letters)
5. 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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