The catalytic activity and hydrocarbon selectivity in electrochemical carbon dioxide (CO2) reduction on cuprous oxide (Cu2O) derived copper nanoparticles is discussed. Cuprous oxide films with [100], [110] and [111] orientation and variable thickness were electrodeposited by reduction of copper(ii) lactate on commercially available copper plates. After initiation of the electrochemical CO2 reduction by these oxide structures, the selectivity of the process was found to largely depend on the parent Cu2O film thickness, rather than on the initial crystal orientation. Starting with thin Cu2O films, besides CO and hydrogen, selective formation of ethylene is observed with very high ethylene-to-methane ratios (∼8 to 12). In addition to these products, thicker Cu2O films yield a remarkably large amount of ethane. Long term Faradaic efficiency analysis of hydrocarbons shows no sign of deactivation of the electrodes after 5 hours of continuous experiment. Online mass spectroscopy studies combined with X-ray diffraction data suggest the reduction of the Cu2O films in the presence of CO2, generating a nanoparticulate Cu morphology, prior to the production of hydrogen, CO, and hydrocarbons. Optimizing coverage, number density and size of the copper nanoparticles, as well as local surface pH, may allow highly selective formation of the industrially important product ethylene.

Aqueous-phase electrochemical reduction of carbon dioxide requires an active, earth-abundant electrocatalyst, as well as highly efficient mass transport. Here we report the design of a porous hollow fibre copper electrode with a compact three-dimensional geometry, which provides a large area, three-phase boundary for gas–liquid reactions. The performance of the copper electrode is significantly enhanced; at overpotentials between 200 and 400 mV, faradaic efficiencies for carbon dioxide reduction up to 85% are obtained. Moreover, the carbon monoxide formation rate is at least one order of magnitude larger when compared with state-of-the-art nanocrystalline copper electrodes. Copper hollow fibre electrodes can be prepared via a facile method that is compatible with existing large-scale production processes. The results of this study may inspire the development of new types of microtubular electrodes for electrochemical processes in which at least one gas-phase reactant is involved, such as in fuel cell technology.

P/n and n/p junctions with depths of 200 nm to several micrometers have been created in flat silicon substrates as well as on 3D microstructures by means of a variety of methods, including solid source dotation (SSD), low‐pressure chemical vapor deposition (LPCVD), atmospheric pressure chemical vapor deposition, and plasma‐enhanced chemical vapor deposition. Radial junctions in Si micropillars are inspected by optical and scanning electron micro­scopies, using a CrO3‐based staining solution, which enables visualization of the junction depth. When applying identical‐doping parameters to flat substrates, ball grooving, followed by staining and optical microscopy, yields similar junction depth values as high‐resolution scanning electron microscopy imaging on stained cross‐sections and secondary ion mass spectrometry depth profilometry. For the investigated 3D microstructures, doping based on SSD and LPCVD give uniform and conformal junctions. Junctions made with SSD‐boron doping and CVD‐phosphorus doping could be accurately predicted with a model based on Fick's diffusion law. 3D‐microstructured silicon pillar arrays show an increased efficiency for sunlight capturing. The functionality of micropillar arrays with radial junctions is evidenced by improved short‐circuit current densities and photovoltaic efficiencies compared with flat surfaces, for both n‐ and p‐type wafers (average pillar arrays efficiencies of 9.4% and 11%, respectively, compared with 8.3% and 6.4% for the flat samples).

No abstract