This paper reports the synthesis of two-dimensional, hierarchical, porous, and (001)-faceted metal (Ag, Zn, and Al)-doped TiO2 nanostructures (TNSs) and the study of their photocatalytic activity. Two-dimensional metal-doped TNSs were synthesized using the hydrolysis of ammonium hexafluorotitanate in the presence of hexamethylenetetramine and metal precursors. Typical morphology of metal-doped TNSs is a hierarchical nanosheet that is composed of randomly stacked nanocubes (dimensions of up to 5 μm and 200 nm in edge length and thickness, respectively) and has dominant (001) facets exposed. Raman analysis and X-ray photoelectron spectroscopy results indicated that the Ag doping, compared to Zn and Al, much improves the crystallinity degree and at the same time dramatically lowers the valence state binding energy of the TNS and provides an additional dopant oxidation state into the system for an enhanced electron-transfer process and surface reaction. These are assumed to enhance the photocatalytic of the TNS. In a model of photocatalytic reaction, that is, rhodamine B degradation, the AgTNS demonstrates a high photocatalytic activity by converting approximately 91% of rhodamine B within only 120 min, equivalent to a rate constant of 0.018 m-1 and ToN and ToF of 94 and 1.57 min-1, respectively, or 91.1 mmol mg-1 W-1 degradation when normalized to used light source intensity, which is approximately 2 times higher than the pristine TNS and several order higher when compared to Zn- and Al-doped TNSs. Improvement of the crystallinity degree, decrease in the defect density and the photogenerated electron and hole recombination, and increase of the oxygen vacancy in the AgTNS are found to be the key factors for the enhancement of the photocatalytic properties. This work provides a straightforward strategy for the preparation of high-energy (001) faceted, two-dimensional, hierarchical, and porous Ag-doped TNSs for potential use in photocatalysis and photoelectrochemical application.
Perovskite solar cells have emerged as a potential energy alternative due to their low cost of fabrication and high power conversion efficiency. Unfortunately, their poor ambient stability has critically limited their industrialization and application in real environmental conditions. Here, we show that by introducing hexamine molecules into the perovskite lattice, we can enhance the photoactive phase stability, enabling high-performance and air-processable perovskite solar cells. The unencapsulated and freshly prepared perovskite solar cells produce a power conversion efficiency of 16.83% under a 100 mW cm-2 1.5G solar light simulator and demonstrate high stability properties when being stored for more than 1500 h in humid air with relative humidity ranging from 65 to 90%. We envisage that our findings may revolutionize perovskite solar cell research, pushing the performance and stability to the limit and bringing the perovskite solar cells toward industrialization.
The crystallinity properties of perovskite influence their optoelectrical performance in solar cell applications. We optimized the grain shape and crystallinity of perovskite film by annealing treatment from 130 to 170 °C under high humidity (relative humidity of 70%). We found that the grain size, grain interface, and grain morphology of the perovskite are optimized when the sample was annealed at 150 °C for 1 h in the air. At this condition, the perovskite film is composed of 250 nm crystalline shape grain and compact inter-grain structure with an invincible grain interface. Perovskite solar cells device analysis indicated that the device fabricated using the samples annealed at 150 °C produced the highest power conversion efficiency, namely 17.77%. The open circuit voltage (Voc), short-circuit current density (Jsc), and fill factor (FF) of the device are as high as 1.05 V, 22.27 mA/cm2, and 0.76, respectively. Optoelectrical dynamic analysis using transient photoluminescence and electrochemical impedance spectroscopies reveals that (i) carrier lifetime in the champion device can be up to 25 ns, which is almost double the carrier lifetime of the sample annealed at 130 °C. (ii) The interfacial charge transfer resistance is low in the champion device, i.e., ~20 Ω, which has a crystalline grain morphology, enabling active photocurrent extraction. Perovskite's behavior under annealing treatment in high humidity conditions can be a guide for the industrialization of perovskite solar cells.