Crystal orientation-dependent etching and trapping in thermally-oxidised Cu₂O photocathodes for water splitting

Ammonia solution etching was carried out on thermally-oxidised cuprous oxide (TO-Cu2O) in photocathode devices for water splitting. The etched devices showed increased photoelectrochemical (PEC) performance compared to the unetched ones as well as improved reproducibility. -8.6 mA cm-2 and -7 mA cm-2 photocurrent density were achieved at 0 V and 0.5 V versus the reversible hydrogen electrode (VRHE), respectively, in the champion sample with an onset potential of 0.92 VRHE and a fill factor of 44 %. An applied bias photon-to-current efficiency of 3.6 % at 0.56 VRHE was obtained, which represents a new record for Cu2O-based photocathode systems. Capacitance-based profiling studies showed a strong pinning effect from interfacial traps in the as-grown device, and these traps were removed by ammonia solution etching. Moreover, the etching procedure gave rise to a diverse morphology of Cu2O crystals based on the different crystallographic orientations. The distribution of crystallographic orientations and the relationship between the crystal orientation and the morphology after etching were examined by electron backscatter diffraction (EBSD) and scanning electron microscopy (SEM). The high-index crystal group showed a statistically higher PEC performance than the low-index group. X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) revealed metallic copper at the Cu2O/Ga2O3 interface, which we attribute as the dominant trap that limits the PEC performance. It is concluded that the metallic copper originates from the reduction of the CuO impurity layer on the as-grown Cu2O sample during the ALD process, while the reduction from Cu2O to Cu is not favorable

Clean Carbon Cycle via High‐Performing and Low‐Cost Solar‐Driven Production of Freshwater

While renewable power available worldwide costs increasingly less than the least expensive option based on fossil fuels, countries continue to increase their coal-fired capacity, which should conversely fall by 80% within a decade to limit global warming effects. To address the challenges to the implementation of such an aim, here, a path is explored that leverages on a previously unrecognized aspect of coal, opening to a new solar-driven carbon cycle that is environmentally friendly. By engineering the porosity matrix of coal into a suitably designed compressed volumetric structure, and by coupling it with a network of cotton fibers, it is possible to create a record performing device for freshwater production, with a desalination rate per raw material cost evaluated at 1.39 kg h − 1 $ − 1 at one sun intensity. This value is between two and three times higher than any other solar desalination device proposed to date. These results could envision a clean and socially sustainable cycle for carbon materials that, while enabling an enhanced water economy with global access to freshwater and sanitation, poses zero risks of reinjecting C O 2 into the environment through competing economies in the fossil's market