No abstract

While electrochemical water splitting is one of the most promising methods to store light/electrical energy in chemical bonds, a key challenge remains in the realization of an efficient oxygen evolution reaction catalyst with large surface area, good electrical conductivity, high catalytic properties, and low fabrication cost. Here, a facile solution reduction method is demonstrated for mesoporous Co3O4 nanowires treated with NaBH4. The high‐surface‐area mesopore feature leads to efficient surface reduction in solution at room temperature, which allows for retention of the nanowire morphology and 1D charge transport behavior, while at the same time substantially increasing the oxygen vacancies on the nanowire surface. Compared to pristine Co3O4 nanowires, the reduced Co3O4 nanowires exhibit a much larger current of 13.1 mA cm‐2 at 1.65 V vs reversible hydrogen electrode (RHE) and a much lower onset potential of 1.52 V vs RHE. Electrochemical supercapacitors based on the reduced Co3O4 nanowires also show a much improved capacitance of 978 F g‐1 and reduced charge transfer resistance. Density‐functional theory calculations reveal that the existence of oxygen vacancies leads to the formation of new gap states in which the electrons previously associated with the Co‐O bonds tend to be delocalized, resulting in the much higher electrical conductivity and electrocatalytic activity.

Longevity has been a long-standing concern for hybrid perovskite photovoltaics. We demonstrate high-resilience positive-intrinsic-negative perovskite solar cells by incorporating a piperidinium-based ionic compound into the formamidinium-cesium lead-trihalide perovskite absorber. With the bandgap tuned to be well suited for perovskite-on-silicon tandem cells, this piperidinium additive enhances the open-circuit voltage and cell efficiency. This additive also retards compositional segregation into impurity phases and pinhole formation in the perovskite absorber layer during aggressive aging. Under full-spectrum simulated sunlight in ambient atmosphere, our unencapsulated and encapsulated cells retain 80 and 95% of their peak and post-burn-in efficiencies for 1010 and 1200 hours at 60° and 85°C, respectively. Our analysis reveals detailed degradation routes that contribute to the failure of aged cells.

We demonstrate for the first time the controlled Sn-doping in TiO(2) nanowire (NW) arrays for photoelectrochemical (PEC) water splitting. Because of the low lattice mismatch between SnO(2) and TiO(2), Sn dopants are incorporated into TiO(2) NWs by a one-pot hydrothermal synthesis with different ratios of SnCl(4) and tetrabutyl titanate, and a high acidity of the reactant solution is critical to control the SnCl(4) hydrolysis rate. The obtained Sn-doped TiO(2) (Sn/TiO(2)) NWs are single crystalline with a rutile structure, and the incorporation of Sn in TiO(2) NWs is well controlled at a low level, that is, 1-2% of Sn/Ti ratio, to avoid phase separation or interface scattering. PEC measurement on Sn/TiO(2) NW photoanodes with different Sn doping ratios shows that the photocurrent increases first with increased Sn doping level to >2.0 mA/cm(2) at 0 V vs Ag/AgCl under 100 mW/cm(2) simulated sunlight illumination up to ~100% enhancement compared to our best pristine TiO(2) NW photoanodes and then decreases at higher Sn doping levels. Subsequent annealing of Sn/TiO(2) NWs in H(2) further improves their photoactivity with an optimized photoconversion efficiency of ~1.2%. The incident-photon-to-current conversion efficiency shows that the photocurrent increase is mainly ascribed to the enhancement of photoactivity in the UV region, and the electrochemical impedance measurement reveals that the density of n-type charge carriers can be significantly increased by the Sn doping. These Sn/TiO(2) NW photoanodes are highly stable in PEC conversion and thus can serve as a potential candidate for pure TiO(2) materials in a variety of solar energy driven applications.

We developed a postgrowth modification method of two-dimensional WO3 nanoflakes by a simultaneous solution etching and reducing process in a weakly acidic condition. The obtained dual etched and reduced WO3 nanoflakes have a much rougher surface, in which oxygen vacancies are created during the simultaneous etching/reducing process for optimized photoelectrochemical performance. The obtained photoanodes show an enhanced photocurrent density of ∼1.10 mA/cm(2) at 1.0 V vs Ag/AgCl (∼1.23 V vs reversible hydrogen electrode), compared to 0.62 mA/cm(2) of pristine WO3 nanoflakes. The electrochemical impedance spectroscopy measurement and the density functional theory calculation demonstrate that this improved performance of dual etched and reduced WO3 nanoflakes is attributed to the increase of charge carrier density as a result of the synergetic effect of etching and reducing.