We developed a new chemical strategy to enhance the stability of lead selenide nanocrystals (PbSe NCs) against oxidation through the surface passivation by P-O- moieties. In the synthesis of PbSe NCs, tris(diethylamino)phosphine (TDP) selenide (Se) was used as a Se precursor, and the resulting PbSe NCs withstood long-term air exposure while showing nearly no sign of oxidation. Nuclear magnetic resonance (NMR) spectroscopy reveals that TDP derivatives passivate the surface of PbSe NC. Through a series of ligand cleavage reactions, we found that the TDP derivatives are bound on NC surface through the P-O- moiety. Based on such understanding, it turned out that direct addition of various PAs during the synthesis of PbSe NCs also results in the NCs whose absorption spectrum remains nearly intact after air exposure for weeks. The P-O- moieties render the NCs stable in the operation of field effect transistors, suggesting that our findings can enable the use of air stable PbSe NCs in wider array of optoelectronic applications.

Growth of monodisperse indium phosphide (InP) quantum dots (QDs) represents a pressing demand in display applications, as size uniformity is related to color purity in display products. Here, we report the colloidal synthesis of InP QDs in the presence of Zn precursors in which size uniformity is markedly enhanced as compared to the case of InP QDs synthesized without Zn precursors. Nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, and mass spectrometry analyses on aliquots taken during the synthesis allow us to monitor the appearance of metal− phosphorus complex intermediates in the growth of InP QDs. In the presence of zinc carboxylate, intermediate species containing Zn−P bonding appears. The Zn−P intermediate complex with P(SiMe 3 ) 3 exhibits lower reactivity than that of the In−P complex, which is corroborated by our prediction based on density functional theory and electrostatic potential charge analysis. The formation of a stable Zn−P intermediate complex results in lower reactivity, which enables slow growth of QDs and lowers the extreme reactivity of P(SiMe 3 ) 3 , hence monodisperse QDs. Insights from experimental and theoretical studies advance mechanistic understanding and control of nucleation and growth of InP QDs, which are key to the preparation of monodisperse InP-based QDs in meeting the demand of the display market.

We report the photocatalytic conversion of CO2 to CH4 using CuPt alloy nanoclusters anchored on TiO2. As the size of CuPt alloy nanoclusters decreases, the photocatalytic activity improves significantly. Small CuPt nanoclusters strongly bind CO2 intermediates and have a stronger interaction with the TiO2 support, which also contributes to an increased CH4 generation rate. The alloying and size effects prove to be the key to efficient CO2 reduction, highlighting a strategic platform for the design of photocatalysts for CO2 conversion.

We examine the effects of chlorine-passivation of Cd surface atoms on photocatalytic H 2 O reduction by CdSe NCs. Transient absorption spectroscopy reveals that Cl passivation removes electron trap states in CdSe NCs, which is also reflected in an increase of photoluminescence quantum yield, e.g., from 9 to 22% after the Cl treatment. Size-tunable energy states in CdSe NCs enable the systematic investigation of surface defects and their effect on the photocatalytic hydrogen generation rate. It turns out that, depending on band-edge energy levels, the surface trap states may enhance or inhibit photocatalysis. Cl-treated CdSe NCs larger than 2.7 nm show a higher hydrogen evolution rate than untreated CdSe NCs of the same size as Cl treatment removes trap states with energy below the H 2 O reduction potential. In contrast, the same Cl treatment does not increase the photocatalytic rate of CdSe NCs smaller than 2.7 nm because both the conduction band edge and trap states are above the water reduction potential. The size-dependence of the effect of Cl treatment suggests that electron trap states in CdSe may promote photocatalytic activity by enhancing charge separation.

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In this study, we designed and synthesized photocatalysts for hydrogen evolution from water by coating a thin layer of amorphous TiO2 (a-TiO2) on CdSe nanocrystals (NCs). The thin shell of a-TiO2 serves as a channel for charge carriers otherwise unutilized. Albeit a previous notion that a-TiO2 is a poor photocatalyst, the enhanced photocatalytic activity in the presence of a-TiO2 suggests that the material helps utilize the photogenerated charge carriers when it is in a form of thin shell on CdSe NCs. Type II band offset in CdSe/a-TiO2 appears to allow the electron in the conduction band of CdSe NCs to migrate over to that of a-TiO2, and the electron participates in the hydrogen production from water. Size of CdSe NCs influences the photocatalytic hydrogen evolution rate as the energy difference between the conduction bands of semiconductors becomes larger. Electron transfer from CdSe NCs to a-TiO2 layer is influenced by the level of the conduction-band edge of CdSe NCs: the size dependence indicates that electron injection to TiO2 is facilitated with energy level offset between CdSe and TiO2, while smaller NCs have larger band gap and thus narrower spectral range of absorption. The interplay between charge-transfer rate and absorption cross-section should be considered in designing heterostructure NC-based photocatalysts for water splitting.

We demonstrate photocatalytic reduction of methylene blue in the infrared region, using PbSe/CdSe/CdS core/shell/shell heterostructure nanocrystals (HNCs) with type II or quasi-type II band offsets. Varying deposition rates of the CdS shell result in nanocrystals of diverse morphologies ranging from spheres to pyramids to tetrapods. The faceted shapes enable the selective growth of Au tips, which help increase photocatalytic activity since the Au tips serve as an electron sink. Comparative studies reveal that the photocatalytic activity appears to correlate with the integral overlap of electron and hole wave functions. Tetrapod-shaped HNCs with Au tips show considerably higher photocatalytic activity for the reduction of methylene blue than sphere or pyramid-shaped HNCs of equivalent composition arrangement.

We present facile synthesis of bright CdS/CdSe/CdS@SiO nanoparticles with 72% of quantum yields (QYs) retaining ca 80% of the original QYs. The main innovative point is the utilization of the highly luminescent CdS/CdSe/CdS seed/spherical quantum well/shell (SQW) as silica coating seeds. The significance of inorganic semiconductor shell passivation and structure design of quantum dots (QDs) for obtaining bright QD@SiO is demonstrated by applying silica encapsulation via reverse microemulsion method to three kinds of QDs with different structure: CdSe core and 2 nm CdS shell (CdSe/CdS-thin); CdSe core and 6 nm CdS shell (CdSe/CdS-thick); and CdS core, CdSe intermediate shell and 5 nm CdS outer shell (CdS/CdSe/CdS-SQW). Silica encapsulation inevitably results in lower photoluminescence quantum yield (PL QY) than pristine QDs due to formation of surface defects. However, the retaining ratio of pristine QY is different in the three silica coated samples; for example, CdSe/CdS-thin/SiO shows the lowest retaining ratio (36%) while the retaining ratio of pristine PL QY in CdSe/CdS-thick/SiO and SQW/SiO is over 80% and SQW/SiO shows the highest resulting PL QY. Thick outermost CdS shell isolates the excitons from the defects at surface, making PL QY relatively insensitive to silica encapsulation. The bright SiO-coated SQW sample shows robustness against harsh conditions, such as acid etching and thermal annealing. The high luminescence and long-term stability highlights the potential of using the SQW/SiO nanoparticles in bio-labeling or display applications.