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ConspectusLead halide perovskites are under the spotlight of current research due to their potential for efficient and cost-effective next-generation optoelectronic devices. The unique photonic and electronic properties of these solution-processable materials brought them to the forefront of materials science. However, the toxicity and instability of lead-based perovskites are the major hurdles for their commercialization. These issues initiated an effort towards the development of environmentally friendly, lead-free perovskites. In this context, bismuth halide perovskites (BHPs) were ideal rivals for lead-based congeners due to their excellent chemical stability, lower toxicity, and structural versatility. Understanding the crystal structure and optoelectronic properties of BHPs is crucial for designing them for specific, tailor-made applications. This Account aims to review our recent research progress on the role of functional organic spacer cations in modulating the electronic confinements, optical properties, and photoconductivity of BHPs. We have employed a comprehensive experimental and theoretical investigation to probe the intriguing optical and electronic properties of these materials. Our findings on the structure-optoelectronic property correlations will be valuable guidelines for the rational selection of organic spacer cations in designing BHPs featuring low exciton binding energy, narrow optical bandgap, enhanced visible light absorption, and high photoconductivity. One of our key findings is that by increasing the electron affinity of the organic spacer ligands, photoconductivity and visible light absorption of BHPs could be significantly enhanced. We hope that the fundamental level understanding of the photophysical properties discussed in this Account will lead to new design rules for developing high-performance BHP materials.

An effective heterojunction with robust charge separation and enormous degradation efficiency is the major task for photocatalyst preparation. In this study, we have prepared the FeCo 2 O 4 -loaded g-C 3 N 4 nanosheet by the sol-gel-assisted calcination method for photo-Fenton-like degradation under visible-light irradiation by activating persulfate. The nanocomposite exhibits a higher charge separation efficiency than pure g-C 3 N 4 and FeCo 2 O 4 for the degradation reaction against naproxen drugs. An effective interaction between the nanoparticles increases the degradation efficiency up to 91% with a synergistic index of 73.62%. Moreover, the nanocomposite exhibits a 78% mineralization efficiency against the naproxen pollutant under visible-light irradiation. For practical implementation, the degradation reaction was tested with various pH values, different water sources (DI, lake, and tap water), and light sources (LED (visible)/direct sunlight (UV-visible)). Moreover, the possible degradation mechanism predicted by the elemental trapping experiment and the recycling experiment clearly revealed that the heterojunction composite has a high enough degradation stability., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Bismuth-based zero-dimensional perovskites garner high research interest because of their advantages, such as excellent moisture stability and lower toxicity in comparison to lead-based congeners. However, the wide optical bandgap (>2 eV) and poor photoconductivity of these materials are the bottlenecks for their optoelectronic applications. Herein, we report a combined experimental and theoretical study of the structural features and optoelectronic properties of two novel and stable zero-dimensional bismuth perovskites: (biphenyl bis(methylammonium)) 1.5 BiI 6 ·2H 2 O (BPBI) and (naphthalene diimide bis(ethylammonium)) 1.5 BiI 6 ·2H 2 O (NDBI). NDBI features a remarkably narrower bandgap (1.82 eV) than BPBI (2.06 eV) because of the significant orbital contribution of self-assembled naphthalene diimide cations at the band edges of NDBI. Further, the FP-TRMC analysis revealed that the photoconductivity of NDBI is about 3.7-fold greater than that of BPBI. DFT calculations showed that the enhanced photoconductivity in NDBI arises from its type-IIa band alignment, whereas type-Ib alignment was seen in BPBI.

Bismuth-based perovskites are attracting intense scientific interest due to low toxicity and excellent moisture stability compared to lead-based analogues. However, high exciton binding energy, poor charge carrier separation, and transport efficiencies lower their optoelectronic performances. To address these issues, we have integrated an electronically active organic cation, naphthalimide ethylammonium, between the [BiI 5 2- ] n chains via crystal engineering to form a novel perovskite-like material (naphthalimide ethylammonium) 2 BiI 5 (NBI). Single crystal analysis revealed a one-dimensional quantum-well structure for NBI in which inter-inorganic well electronic coupling is screened by organic layers. It exhibited anisotropic photoconductivity and long-lived charge carriers with milliseconds lifetime, which is higher than that of CH 3 NH 3 PbI 3 . Density functional theory calculations confirmed type-IIa band alignment between organic cations and inorganic chains, allowing the former to electronically contribute to the overall charge transport properties of the material.

Perovskite nanocrystals are promising luminescent materials with synthetic feasibility and band gap tunability. Nonetheless, application of the perovskite nanocrystals to light-emitting devices has been challenging because of the intrinsic poor colloidal stability and environmental vulnerability issues. Here, we introduce a new protocol for highly air-stable perovskite nanocrystal layers with a tunable band gap via a simple nanocrystal pinning process. The nanocrystals were composed of CH 3 NH 3 PbBr 3 (MAPbBr 3 ) mixed with (vinylbenzylamine) 2 PbBr 4 ((VBzA) 2 PbBr 4 ), which contains a photopolymerizable structure-directing ligand. Along with the compostion of (VBzA) 2 PbBr 4 , the band gap of the perovskite layer continuously increased with the reduction of the nanocrystal size and also lattice distortion. The nanocrystal film readily polymerized upon exposure to visible light was highly stable under humid air more than 15 days. Its application to bluish-green light-emitting diodes is demonstrated.

Symmetrical electrochemical capacitors are attracting immense attention because of their fast charging-discharging ability, high energy density, and low cost of production. The current research in this area is mainly focused on exploring novel low-cost electrode materials with higher energy and power densities. In the present work, we fabricated an electrochemical double-layer capacitor using methylammonium bismuth iodide (CH 3 NH 3 ) 3 Bi 2 I 9 , a lead-free, zero-dimensional hybrid perovskite material. A maximum areal capacitance of 5.5 mF/cm 2 was obtained, and the device retained 84.8% of its initial maximum capacitance even after 10 000 charge-discharge cycles. Impedance spectroscopy measurements revealed that the active layer provides a high surface area for the electrolyte to access. As a result, the charge transport resistance is reasonably low, which is advantageous for delivering excellent performance., Competing Interests: The authors declare no competing financial interest.