Surface-Engineered Cesium Lead Bromide Perovskite Nanocrystals for Enabling Photoreduction Activity.

In recent years, colloidal lead halide perovskite (LHP) nanocrystals (NCs) have exhibited such intriguing light absorption properties to be contemplated as promising candidates for photocatalytic conversions. However, for effective photocatalysis, the light harvesting system needs to be stable under the reaction conditions propaedeutic to a specific transformation. Unlike photoinduced oxidative reaction pathways, photoreductions with LHP NCs are challenging due to their scarce compatibility with common hole scavengers like amines and alcohols. In this contribution, it is investigated the potential of CsPbBr3 NCs protected by a suitably engineered bidentate ligand for the photoreduction of quinone species. Using an in situ approach for the construction of the passivating agent and a halide excess environment, quantum-confined nanocubes (average edge length = 6.0 ± 0.8 nm) are obtained with a low ligand density (1.73 ligand/nm2) at the NC surface. The bifunctional adhesion of the engineered ligand boosts the colloidal stability of the corresponding NCs, preserving their optical properties also in the presence of an amine excess. Despite their relatively short exciton lifetime (τAV = 3.7 ± 0.2 ns), these NCs show an efficient fluorescence quenching in the presence of the selected electron accepting quinones (1,4-naphthoquinone, 9,10-phenanthrenequinone, and 9,10-anthraquinone). All of these aspects demonstrate the suitability of the NCs for an efficient photoreduction of 1,4-naphthoquinone to 1,4-dihydroxynaphthalene in the presence of triethylamine as a hole scavenger. This chemical transformation is impracticable with conventionally passivated LHP NCs, thereby highlighting the potential of the surface functionalization in this class of nanomaterials for exploring new photoinduced reactivities.

In Situ Formation of Zwitterionic Ligands: Changing the Passivation Paradigms of CsPbBr3 Nanocrystals.

CsPbBr3 nanocrystals (NCs) passivated by conventional lipophilic capping ligands suffer from colloidal and optical instability under ambient conditions, commonly due to the surface rearrangements induced by the polar solvents used for the NC purification steps. To avoid onerous postsynthetic approaches, ascertained as the only viable stability-improvement strategy, the surface passivation paradigms of as-prepared CsPbBr3 NCs should be revisited. In this work, the addition of an extra halide source (8-bromooctanoic acid) to the typical CsPbBr3 synthesis precursors and surfactants leads to the in situ formation of a zwitterionic ligand already before cesium injection. As a result, CsPbBr3 NCs become insoluble in nonpolar hexane, with which they can be washed and purified, and form stable colloidal solutions in a relatively polar medium (dichloromethane), even when longly exposed to ambient conditions. The improved NC stability stems from the effective bidentate adsorption of the zwitterionic ligand on the perovskite surfaces, as supported by theoretical investigations. Furthermore, the bidentate functionalization of the zwitterionic ligand enables the obtainment of blue-emitting perovskite NCs with high PLQYs by UV-irradiation in dichloromethane, functioning as the photoinduced chlorine source.

Size-tunable and stable cesium lead-bromide perovskite nanocubes with near-unity photoluminescence quantum yield.

Stable cesium lead bromide perovskite nanocrystals (NCs) showing a near-unity photoluminescence quantum yield (PLQY), narrow emission profile, and tunable fluorescence peak in the green region can be considered the ideal class of nanomaterials for optoelectronic applications. However, a general route for ensuring the desired features of the perovskite NCs is still missing. In this paper, we propose a synthetic protocol for obtaining near-unity PLQY perovskite nanocubes, ensuring their size control and, consequently, a narrow and intense emission through the modification of the reaction temperature and the suitable combination ratio of the perovskite constituting elements. The peculiarity of this protocol is represented by the dissolution of the lead precursor (PbBr2) as a consequence of the exclusive complexation with the bromide anions released by the in situ SN2 reaction between oleylamine (the only surfactant introduced in the reaction mixture) and 1-bromohexane. The obtained CsPbBr3 nanocubes exhibit variable size (ranging from 6.7 ± 0.7 nm to 15.2 ± 1.2 nm), PL maxima between 505 and 517 nm, and near-unity PLQY with a narrow emission profile (fwhm of 17-19 nm). Additionally, the NCs synthesized with this approach preserve their high PLQYs even after 90 days of storage under ambient conditions, thus displaying a remarkable optical stability. Through the rationalization of the obtained results, the proposed synthetic protocol provides a new ground for the direct preparation of differently structured perovskite NCs without resorting to any additional post-synthetic treatment for improving their emission efficiency and stability.

A new route for the shape differentiation of cesium lead bromide perovskite nanocrystals with near-unity photoluminescence quantum yield.

The ongoing interest in all-inorganic cesium lead bromide perovskite nanocrystals (CsPbBr3 NCs) is mainly due to their optical properties, in particular their high photoluminescence quantum yields (PLQYs). Three-precursor synthetic methods, in which the sources of the three elements (cesium, lead and bromine) constituting the perovskite scaffold are chemically independent, often succeed in the achievement of near-unity PLQY perovskite NCs. However, this class of synthetic approaches precludes the accessibility to crystal morphologies different from the traditional cuboidal ones. In order to upgrade three-precursor synthetic schemes to obtain more sophisticated morphologies - such as rods - we propose a conceptually original synthetic methodology, in which a potentially controllable stage of the reaction anticipates the fast crystallization promoted by cesium injection. To this purpose, lead oxide, 1-bromohexane (at different molar ratios with respect to lead) and the ligands (oleic acid and a suitable amine) in 1-octadecene are reacted at 160 °C for an incubation period of 30 min before cesium injection. During this stage and at high C6H13Br/PbO molar ratios, the bromide release from reactions between the ligands and 1-bromohexane promotes the evolution of [PbBr(2+n)]n- species as well as of two-dimensional [(RNH3)2(PbBr4)]n structures with a rod-like shape (aspect ratios ∼10). These structures act as the templating agents for the subsequent crystallization promoted by cesium injection, ensuring the formation of near-unity PLQY nanorods in the presence of decylamine. Conversely, the pronounced decomposition of the preformed [(RNH3)2(PbBr4)]n structures preludes to the formation of near-unity PLQY nanocubes in the presence of hexylamine. The amine choice exerts also an important role in the emission stability of the corresponding NCs, since the nanocubes prepared in the presence of hexylamine maintain their near-unity PLQYs up to 90 days under ambient conditions. In addition to the long-term PLQY stability, the nanorods prepared with decylamine also exhibit a remarkable resistance to the presence of water, due to the compact and hydrophobic organic shell passivating the NC surface. These findings can contribute to the development of innovative synthetic methodologies for controlling the shape and stability of near-unity PLQY perovskite NCs.