As the search for efficient catalysts for CO 2 photoreduction continues, nanostructured perovskite oxides have emerged as a class of high-performance photocatalytic materials. The perovskite oxide candidates for CO 2 photoreduction are primarily nanostructured forms of titanates, niobates, tantalates and cobaltates. These materials form the focus of this review article because they are much sought-after due to their nontoxic nature, adequate chemical stability, and tunable crystal structures, bandgaps and surface energies. As compared to conventional semiconductors and nanomaterial catalysts, nanostructured perovskite oxides also exhibit an extended optical-absorption edge, longer charge carrier lifetimes, and favorable band-alignment with respect to reduction potential of activated CO 2 and reduction products of the same. While CO 2 reduction product yields of several hundred μ mol −1 h −1 are observed with many types of perovskite oxide nanomaterials in stand-alone forms, yield of such quantities are not common with semiconductor nanomaterials of other types. In this review, we present current state-of-the-art synthesis methods to form perovskite oxide nanomaterials, and procedures to engineer their bandgaps. This review also presents a comprehensive summary and discussion on crystal structures, defect distribution, morphologies and electronic properties of the perovskite oxides, and correlation of these properties to CO 2 photoreduction performance. This review offers researchers key insights for developing advanced perovskite oxides in order to further improve the yields of CO 2 reduction products.
1 April 2019 in Applied Catalysis B: Environment and Energy
This is the first report of a 17.6% champion efficiency solar cell architecture comprising monocrystalline TiO 2 nanorods (TNRs) coupled with perovskite, and formed using facile solution processing without non-routine surface conditioning. Vertically oriented TNR ensembles are desirable as electron transporting layers (ETLs) in halide perovskite solar cells (HPSCs) because of potential advantages such as vectorial electron percolation pathways to balance the longer hole diffusion lengths in certain halide perovskite semiconductors, ease of incorporating nanophotonic enhancements, and optimization between a high contact surface area for charge transfer (good) versus high interfacial recombination (bad). These advantages arise from the tunable morphology of hydrothermally grown rutile TNRs, which is a strong function of the growth conditions. Fluorescence lifetime imaging microscopy of the HPSCs demonstrated a stronger quenching of the perovskite PL when using TNRs as compared to mesoporous/compact TiO 2 thin films. Due to increased interfacial contact area between the ETL and perovskite with easier pore filling, charge separation efficiency is dramatically enhanced. Additionally, solid-state impedance spectroscopy results strongly suggested the suppression of interfacial charge recombination between TNRs and perovskite layer, compared to other ETLs. The optimal ETL morphology in this study was found to consist of an array of TNRs ∼300 nm in length and ∼40 nm in width. This work highlights the potential of TNR ETLs to achieve high performance solution-processed HPSCs.
The electron diffusion length (Ln) is smaller than the hole diffusion length (Lp) in many halide perovskite semiconductors meaning that the use of ordered one-dimensional (1D) structures such as nanowires (NWs) and nanotubes (NTs) as electron transport layers (ETLs) is a promising method of achieving high performance halide perovskite solar cells (HPSCs). ETLs consisting of oriented and aligned NWs and NTs offer the potential not merely for improved directional charge transport but also for the enhanced absorption of incoming light and thermodynamically efficient management of photogenerated carrier populations. The ordered architecture of NW/NT arrays affords superior infiltration of a deposited material making them ideal for use in HPSCs. Photoconversion efficiencies (PCEs) as high as 18% have been demonstrated for HPSCs using 1D ETLs. Despite the advantages of 1D ETLs, there are still challenges that need to be overcome to achieve even higher PCEs, such as better methods to eliminate or passivate surface traps, improved understanding of the hetero-interface and optimization of the morphology (i.e., length, diameter, and spacing of NWs/NTs). This review introduces the general considerations of ETLs for HPSCs, deposition techniques used, and the current research and challenges in the field of 1D ETLs for perovskite solar cells.