Defects of Metal Halide Perovskites in Photocatalytic Energy Conversion: Friend or Foe?

Photocatalytic solar-to-fuel conversion over metal halide perovskites (MHPs) has recently attracted much attention, while the roles of defects in MHPs are still under debate. Specifically, the mainstream viewpoint is that the defects are detrimental to photocatalytic performance, while some recent studies show that certain types of defects contribute to photoactivity enhancement. However, a systematic summary of why it is contradictory and how the defects in MHPs affect photocatalytic performance is still lacking. In this review, the innovative roles of defects in MHP photocatalysts are highlighted. First, the origins of defects in MHPs are elaborated, followed by clarifying certain benefits of defects in photocatalysts including optical absorption, charge dynamics, and surface reaction. Afterward, the recent progress on defect-related MHP photocatalysis, i.e., CO2 reduction, H2 generation, pollutant degradation, and organic synthesis is systematically discussed and critically appraised, putting emphasis on their beneficial effects. With defects offering peculiar sets of merits and demerits, the personal opinion on the ongoing challenges is concluded and outlining potentially promising opportunities for engineering defects on MHP photocatalysts. This critical review is anticipated to offer a better understanding of the MHP defects and spur some inspiration for designing efficient MHP photocatalysts.

Pseudohalide Anions to Suppress Oxidative Degradation for Efficient Formamidinium-Based Sn-Pb Halide Perovskite Solar Cells.

Although binary Sn-Pb perovskites possess optimal band gap approaching to the Shockley-Queisser limit efficiency, the enhancement on power conversion efficiency (PCE) of Sn-Pb perovskite solar cells (PSCs) is impeded by the detrimental oxidation of Sn2+. Herein, a novel and effective strategy is developed to introduce pseudohalide anion thiocyanate (SCN-) with similar ionic radius to iodide to occupy the X-site of the perovskite lattice, thus restraining the rapid oxidation of Sn2+ to Sn4+. The incorporation of SCN- into perovskite stabilizes the perovskite crystal structure thermodynamically and increases the adsorption-energy-barrier of oxygen molecules. The coordination between Sn2+ and SCN- can reduce the defect density by healing the undercoordinated Sn2+ and suppressing the Sn and I vacancies. With the incorporation of SCN-, the ion migration behavior and lattice strain associated with the defects are remarkably relaxed. The study on carrier dynamics based on steady-state and time-resolved photoluminescence suggests that the carrier lifetime and non-radiative recombination rate of SCN- PSCs can be remarkably prolonged and depressed, respectively. As a result, FASn0.5Pb0.5I3-based PSCs achieve a 14.5% increase in PCE, reaching 13.74% under AM 1.5G illumination. This strategy takes a noteworthy step toward high efficiency and high stability FA-based Sn-Pb PSCs.

The Importance of the Interfacial Contact: Is Reduced Graphene Oxide Always an Enhancer in Photo(Electro)Catalytic Water Oxidation?

Optimizing interfacial contact between graphene and a semiconductor has often been proposed as essential for improving their charge interactions. Herein, we fabricated bismuth vanadate-reduced graphene oxide (BiVO4/rGO) composites with tailored interfacial contact extents and revealed their disparate behavior in photoelectrochemical (PEC) and powder suspension (PS) water oxidation systems. BiVO4/rGO with a high rGO coverage on the BiVO4 surface (BiVO4/rGO HC) exhibited an 8-fold enhancement in the PEC photocurrent density with respect to neat BiVO4 at 0 V versus Ag/AgCl, while BiVO4/rGO with a low rGO coverage (BiVO4/rGO LC) gave a lesser 3-fold enhancement. In contrast, BiVO4/rGO HC delivered a detrimental effect, while BiVO4/rGO LC exhibited an enhanced performance for oxygen evolution in the PS system. The phenomenon is attributed to changes in the hydrophobicity of the BiVO4/rGO composite in conjunction with the interfacial contact configuration. A better BiVO4/rGO interfacial contact was found to improve the charge separation efficiency and charge transfer ability of the composite material, explaining the superior PEC performance of BiVO4/rGO HC. Additionally, optimization of the interfacial contact extent was revealed to further improve the energetics of the composite material, as evidenced by a Fermi level shift to a more negative potential. However, the high hydrophobicity of BiVO4/rGO HC arising from the higher rGO reduction extent triggered poor water miscibility, reducing the surface wettability and therefore hampering the photocatalytic O2 evolution activity of the sample. The study underlines water miscibility as a governing issue in the PS system.

Manipulation of Charge Transport by Metallic V13 O16 Decorated on Bismuth Vanadate Photoelectrochemical Catalyst.

Conductive metal oxides represent a new category of functional material with vital importance for many modern applications. The present work introduces a new conductive metal oxide V13 O16 , which is synthesized via a simplified photoelectrochemical procedure and decorated onto the semiconducting photocatalyst BiVO4 in controlled mass percentages ranging from 25% to 37%. Owing to its excellent conductivity and good compatibility with oxide materials, the metallic V13 O16 -decorated BiVO4 hybrid catalyst shows a high photocurrent density of 2.2 ± 0.2 mA cm-2 at 1.23 V versus reversible hydrogen electrode (RHE). Both experimental characterization and density functional theory calculations indicate that the superior photocurrent derives from enhanced charge separation and transfer, resulting from ohmic contact at the interface of mixed phases and superior electrical conductivity from V13 O16 . A Co-Pi coating on BiVO4 -V13 O16 further increases the photocurrent to 5.0 ± 0.5 mA cm-2 at 1.23 V versus RHE, which is among the highest reported for BiVO4 -based photoelectrodes. Surface photovoltage and transient photocurrent measurements suggest a charge-transfer model in which photocurrents are enhanced by improved surface passivation, although the barrier at the Co-Pi/electrolyte interface limits the charge transfer.

Cu2ZnSnS4 Nanoparticle Sensitized Metal-Organic Framework Derived Mesoporous TiO2 as Photoanodes for High-Performance Dye-Sensitized Solar Cells.

We present a facile hot injection and hydrothermal method to synthesize Cu2ZnSnS4 (CZTS) nanoparticles sensitized metal-organic frameworks (MOFs)-derived mesoporous TiO2. The MOFs-derived TiO2 inherits the large specific surface area and abundantly porous structures of the MOFs structure, which is of great benefit to effectively enhance the dye loading capacity, prolong the incident light traveling length by enhancing the multiple interparticle light-scattering process, and therefore improve the light absorption capacity. The sensitization of CZTS nanoparticles effectively enlarges the photoresponse range of TiO2 to the visible light region and facilitates photoinduced carrier transport. The formed heterostructure between CZTS nanoparticles and MOFs-derived TiO2 with matched band gap structure effectively suppresses the recombination rates of photogenerated electron/hole pairs and prolongs the lifespan of the carriers. Photoanodes based upon CZTS/MOFs-derived TiO2 photoanodes can achieve the maximal photocurrent of 17.27 mA cm(-2) and photoelectric conversion performance of 8.10%, nearly 1.93 and 2.21 times higher than those of TiO2-based photoanode. The related mechanism and model are investigated. The strikingly improved photoelectric properties are ascribed to a synergistic action between the MOFs-derived TiO2 and the sensitization of CZTS nanoparticles.