Facet-Dependent Selectivity of Cu Catalysts in Electrochemical CO2 Reduction at Commercially Viable Current Densities.

Despite substantial progress in the electrochemical conversion of CO2 into value-added chemicals, the translation of fundamental studies into commercially relevant conditions requires additional efforts. Here, we study the catalytic properties of tailored Cu nanocatalysts under commercially relevant current densities in a gas-fed flow cell. We demonstrate that their facet-dependent selectivity is retained in this device configuration with the advantage of further suppressing hydrogen production and increasing the faradaic efficiencies toward the CO2 reduction products compared to a conventional H-cell. The combined catalyst and system effects result in state-of-the art product selectivity at high current densities (in the range 100-300 mA/cm2) and at relatively low applied potential (as low as -0.65 V vs RHE). Cu cubes reach an ethylene selectivity of up to 57% with a corresponding mass activity of 700 mA/mg, and Cu octahedra reach a methane selectivity of up to 51% with a corresponding mass activity of 1.45 A/mg in 1 M KOH.

Size dependent selectivity of Cu nano-octahedra catalysts for the electrochemical reduction of CO2 to CH4.

Octahedral Cu nanocrystals in the size range of 75-310 nm are synthesized and investigated for electrochemical CO2 reduction. The smallest nanocrystals show the best selectivity for CO2, particularly methane, which is explained by geometric effects.

Potential-induced nanoclustering of metallic catalysts during electrochemical CO2 reduction.

In catalysis science stability is as crucial as activity and selectivity. Understanding the degradation pathways occurring during operation and developing mitigation strategies will eventually improve catalyst design, thus facilitating the translation of basic science to technological applications. Herein, we reveal the unique and general degradation mechanism of metallic nanocatalysts during electrochemical CO2 reduction, exemplified by different sized copper nanocubes. We follow their morphological evolution during operation and correlate it with the electrocatalytic performance. In contrast with the most common coalescence and dissolution/precipitation mechanisms, we find a potential-driven nanoclustering to be the predominant degradation pathway. Grand-potential density functional theory calculations confirm the role of the negative potential applied to reduce CO2 as the main driving force for the clustering. This study offers a novel outlook on future investigations of stability and degradation reaction mechanisms of nanocatalysts in electrochemical CO2 reduction and, more generally, in electroreduction reactions.

Enzyme-responsive multifunctional surfaces for controlled uptake/release of (bio)molecules.

The current trend in the development of biomaterials is towards bioactive and biodegradable systems. In particular, enzyme-responsive structures are useful tools to realize biodegradable surfaces for the controlled delivery of biomolecules/drugs through a triggered surface erosion process. Up to now, enzyme-responsive structures have been designed by covalent linkage between synthetic polymers and biodegradable functionalities that are responsive to chemical and biological cues (i.e. proteases or pH) [1-4]. Here, we present a novel approach to achieve enzyme-responsive surface-attached networks by exploiting the non-covalent interaction between streptavidin and biotin. The functional component of this three-dimensional (3D) structure is a layer of biotinylated peptides that are degraded by the action of specific proteases. The system was stable under typical physiological conditions; however, it was efficiently degraded upon enzyme exposure. Further, the controlled release of biomolecules and drugs--previously entrapped into the surface-attached network--was demonstrated to occur as a consequence of the enzymatic cleavage. This versatile approach does not require complex chemical procedures. Interestingly, it can be easily adapted to different enzyme-peptide partners and therefore is very attractive for tissue replacement, drug delivery and biosensing.

Highly stable gel electrolytes for dye solar cells based on chemically engineered polymethacrylic hosts.

Four different species of ionically conductive polymers were synthesized and successfully implemented to formulate novel quasi-solid electrolytes for dye solar cells. A power conversion efficiency superior to 85% of the correspondent liquid electrolyte as well as an excellent cell's stability was demonstrated after 500 days of storage.

Ultra lightweight PMMA-based composite plates with robust super-hydrophobic surfaces.

Extremely lightweight plates made of an engineered PMMA-based composite material loaded with hollow glass micro-sized spheres, nano-sized silica particles and aluminum hydroxide prismatic micro-flakes were realized by cast molding. Their interesting bulk mechanical properties were combined to properly tailored surface topography compatible with the achievement of a superhydrophobic behavior after the deposition of a specifically designed hydrophobic coating. With this aim, we synthesized two different species of fluoromethacrylic polymers functionalized with methoxysilane anchoring groups to be covalently grafted onto the surface protruding inorganic fillers. By modulating the feed composition of the reacting monomers, it was possible to combine the hydrophobic character of the polymer with an high adhesion strength to the substrate and hence to maximize both the water contact angle (up to 157°) and the durability of the easy-to-clean effect (up to 2000 h long outdoor exposure).