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Plasmonic Cu@semiconductor heteronanocrystals (HNCs) have many favorable properties, but the synthesis of solid structures is often hindered by the nanoscale Kirkendall effect. Herein, we present the use of an atomically thin Au 3 Cu palisade interlayer to reduce lattice mismatch and mediate the Kirkendall effect, enabling the successive topological synthesis of Cu@Au 3 Cu@Ag, Cu@Au 3 Cu@Ag 2 S, and further transformed solid Cu@Au 3 Cu@CdS core-shell HNCs via cation exchange. The atomically thin and intact Au 3 Cu palisade interlayer effectively modulates the diffusion kinetics of Cu atoms as demonstrated by experimental and theoretical investigations and simultaneously alleviates the lattice mismatch between Cu and Ag as well as Cu and CdS. The Cu@Au 3 Cu@CdS HNCs feature exceptional crystallinity and atomically organized heterointerfaces between the plasmonic metal and the semiconductor. This results in the efficient plasmon-induced injection of hot electrons from Cu@Au 3 Cu into the CdS shell, enabling the Cu@Au 3 Cu@CdS HNCs to achieve high activity and selectivity for the photocatalytic reduction of CO 2 to CO.

Cation exchange (CE) in metal oxides under mild conditions remains an imperative yet challenging goal to tailor their composition and enable practical applications. Herein, we first develop an amorphization-induced strategy to achieve room-temperature CE for universally synthesizing single-atom doped In 2 O 3 nanosheets (NSs). Density functional theory (DFT) calculations elucidate that the abundant coordination-unsaturated sites present in a-In 2 O 3 NSs are instrumental in surmounting the energy barriers of CE reactions. Empirically, a-In 2 O 3 NSs as the host materials successfully undergo exchange with unary cations (Cu 2+ , Co 2+ , Mn 2+ , Ni 2+ ), binary cations (Co 2+ Mn 2+ , Co 2+ Ni 2+ , Mn 2+ Ni 2+ ), and ternary cations (Co 2+ Mn 2+ Ni 2+ ). Impressively, high-loading single-atom doped (over 10 atom %) In 2 O 3 NSs were obtained. Additionally, Cu/a-In 2 O 3 NSs exhibit an excellent ethanol yield (798.7 μmol g -1 h -1 ) with a high selectivity of 99.5% for the CO 2 photoreduction. This work offers a new approach to induce CE reactions in metal oxides under mild conditions and constructs scalable single-atom doped catalysts for critical applications.

We have designed a facile synthetic strategy for the selective deposition of Au metal on all-inorganic CsPbBr3 perovskite nanocrystals that includes the addition of PbBr2 salt along with AuBr3 salt. PbBr2 is necessary because the addition of Au3+ to solutions of CsPbBr3 nanocrystals otherwise results in the exchange of Au3+ ions from solution with Pb2+ cations within the nanocrystal lattice to produce Cs2AuIAuIIIBr6 nanocrystals with a tetragonal crystal structure and a band gap of about 1.6 eV, in addition to Au metal deposition. Including excess Pb2+ ions in solution prevents the exchange reaction. Au metal deposits on the surface of the nanocrystals to produce the Au-CsPbBr3 heterostructure nanoparticles with an Au particle diameter determined by the Au3+ ion concentration. Fluorescence quenching caused by Au deposition monotonically increases with deposition size, but the fluorescence quantum yield (QY) is significantly greater than if any cation exchange has occurred. An optimized synthesis can produce Au-CsPbBr3 nanoparticles with 70% QY and no evidence of cation exchange. [ABSTRACT FROM AUTHOR]

Nonclassical growth mechanisms such as self-assembly and oriented attachment are effective ways to build complex nanostructures from simpler ones. In the latter case, the nanoparticle components are electronically coupled; however, control over the attachment between nanoparticles is highly challenging and generally requires a delicate balance between dipole-, ligand-, and solvent-based interactions. To this end, we perform incomplete cation exchange with Ag+ (Cu+) on CdSe-seeded CdS nanorods and tetrapods to exclusively convert their tips into small Ag2S (Cu2S) domains. Selective removal of the ligands from these inorganic domains results in spontaneous, site-specific bridging of the nanoparticles. Using this method, we demonstrate the fabrication of polymer-like linear and branched nanoparticles with enhanced electrical properties, as well as the stoichiometric formation of nanoparticle homo- and heterodimers and tetramers. We show that linked structures can then be completely cation exchanged with Pb2+ to generate PbSe/PbS-based nanostructured photodetector media with enhanced properties. [ABSTRACT FROM AUTHOR]

Indium phosphide (InP) nanocrystals are emerging as an alternative to heavy metal containing nanocrystals for optoelectronic applications but lag behind in terms of synthetic control. Herein, luminescent wurtzite InP nanocrystals with narrow size distribution were synthesized via a cation exchange reaction from hexagonal Cu 3 P nanocrystals. A comprehensive surface treatment with NOBF 4 was performed, which removes excess copper while generating stoichiometric In/P nanocrystals with fluoride surface passivation. The attained InP nanocrystals manifest a highly resolved absorption spectrum with a narrow emission line of 80 meV, and photoluminescence quantum yield of up to 40%. Optical anisotropy measurements on ensemble and single particle bases show the occurrence of polarized transitions directly mirroring the anisotropic wurtzite lattice, as also manifested from modeling of the quantum confined electronic levels. This shows a green synthesis path for achieving wurtzite InP nanocrystals with desired optoelectronic properties including color purity and light polarization with potential for diverse optoelectronic applications.

For realizing scalable solar hydrogen synthesis, the development of visible-light-absorbing photocatalysts capable of overall water splitting is essential. Metal sulfides can capture visible light efficiently; however, their utilization in water splitting has long been plagued by the poor resilience against hole oxidation. Herein, we report that the ZnIn 2 S 4 monolayers with dual defects (Ag dopants and nanoholes) accessed via cation exchange display stoichiometric H 2 and O 2 evolution in pure water under visible light irradiation. In-depth characterization and modeling disclose that the dual-defect structure endows the ZnIn 2 S 4 monolayers with optimized light absorption and carrier dynamics. More significantly, the dual defects cooperatively function as active sites for water oxidation (Ag dopants) and reduction (nanoholes), thus leading to steady performance in photocatalytic overall water splitting without the assistance of cocatalysts. This work demonstrates a feasible way for fulfilling "all-in-one" photocatalyst design and manifests its great potential in addressing the stability issues associated with sulfide-based photocatalysts.

Lead halide perovskite nanocrystals, whether formed by their own nucleation and growth or by ion diffusion into the lattice of others, are still under investigation. Moreover, beyond isotropic nanocrystals, fabricating anisotropic perovskite nanocrystals by design has remained difficult. Exploring the lattice of orthorhombic-phase Cs 2 ZnBr 4 with the complete replacement of Zn tetrahedra by Pb octahedra, dimension-tunable anisotropic nanocrystals of CsPbBr 3 are reported. This B-site ion introduction led to CsPbBr 3 nanorods having [100] as major axis, in contrast with all reports on rods/wires where the lengths were along the [001] direction. This was possible by using derivatives of α-bromo ketones, which helped in tuning the shape of Cs 2 ZnBr 4 and also the facets of transformed CsPbBr 3 . While similar experiments are extended to orthorhombic Cs 2 HgBr 4 , standard nanorods with [001] as the major axis were observed. From these results, it is further concluded that anisotropic perovskite nanocrystals might not follow any specific rules for directional growth and instead might depend on the structure of the parent lattice.

Plasmonic semiconductors are an emerging class of low-cost plasmonic materials, and the presence of a bandgap and band-bending in these materials offer new opportunities to overcome some of the limitations of plasmonic metals. Here, we demonstrate that in a plasmonic p-n heterojunction (Cu 2-x Se-CdSe) the near-IR excitation (1.1 eV) of the hole plasmon in the p-Cu 2- x Se phase results in rapid hot electron transfer to n-CdSe, with an energy 2.2 eV above the Fermi level. This hot electron generation and energy upconversion process can be well-described by a photothermionic mechanism, where the presence of a bandgap in p-Cu 2- x Se facilitates the generation of energetic photothermal electrons. The lifetime of the transferred electrons in Cu 2- x Se-CdSe can reach ∼130 ps, which is nearly 100× longer than that of its metal-semiconductor counterpart. This result demonstrates a novel approach for harvesting the sub-bandgap near IR photons using plasmonic p-n junctions and the potential advantages of plasmonic semiconductors for hot carrier-based devices.

Strongly coupled, epitaxially fused colloidal nanocrystal (NC) solids are promising solution-processable semiconductors to realize optoelectronic devices with high carrier mobilities. Here, we demonstrate sequential, solid-state cation exchange reactions to transform epitaxially connected PbSe NC thin films into Cu 2 Se nanostructured thin-film intermediates and then successfully to achieve zinc-blende, CdSe NC solids with wide epitaxial necking along {100} facets. Transient photoconductivity measurements probe carrier transport at nanometer length scales and show a photoconductance of 0.28(1) cm 2 V -1 s -1 , the highest among CdSe NC solids reported. Atomic-layer deposition of a thin Al 2 O 3 layer infiltrates and protects the structure from fusing into a polycrystalline thin film during annealing and further improves the photoconductance to 1.71(5) cm 2 V -1 s -1 and the diffusion length to 760 nm. We fabricate field-effect transistors to study carrier transport at micron length scales and realize high electron mobilities of 35(3) cm 2 V -1 s -1 with on-off ratios of 10 6 after doping.

The metastable and thermodynamically favored phases of CuFeS 2 are shown to be alternatively synthesized during partial cation exchange of hexagonal Cu 2 S using various phosphorus-containing ligands. Transmission electron microscopy and energy dispersive spectroscopy mapping confirm the retention of the particle morphology and the approximate CuFeS 2 stoichiometry. Powder X-ray diffraction patterns and refinements indicate that the resulting phase mixtures of metastable wurtzite-like CuFeS 2 versus tetragonal chalcopyrite are correlated with the Tolman electronic parameter of the tertiary phosphorus-based ligand used during the cation exchange. Strong L-type donors lead to the chalcopyrite phase and weak donors to the wurtzite-like phase. To our knowledge, this is the first demonstration of phase control in nanoparticle synthesis using solely L-type donors.

Single-atom site catalysts (SACs) have aroused enormous attention and brought about new opportunities for many applications. Herein, we report a versatile strategy to rhodium (Rh) SAC by a facile cation exchange reaction. Remarkably, the Rh SAC modified CuO nanowire arrays on copper foam (Rh SAC-CuO NAs/CF) show unprecedented alkaline oxygen evolution reaction (OER) activity with a high current density of 84.5 mA cm -2 @1.5 V vs reversible hydrogen electrode (RHE), 9.7 times that of Ir/C/CF. More strikingly, when used as an anode and a cathode for overall water splitting, the Rh SAC-CuO NAs/CF can achieve 10 mA cm -2 at only 1.51 V. Density functional theory calculations reveal that the high OER and HER intrinsic catalytic activities result from moderate adsorption energy of intermediates on Rh SAC. Finally, we demonstrate the general synthesis of different single-atom noble-metal catalysts on CuO NAs (M SAC-CuO NAs/CF, where M = Ru, Ir, Os, and Au).

Aliovalent doping of CdSe nanocrystals (NCs) via cation exchange processes has resulted in interesting and novel observations for the optical and electronic properties of the NCs. However, despite over a decade of study, these observations have largely gone unexplained, partially due to an inability to precisely characterize the physical properties of the doped NCs. Here, electrostatic force microscopy was used to determine the static charge on individual, cation-doped CdSe NCs in order to investigate their net charge as a function of added cations. While the NC charge was relatively insensitive to the relative amount of doped cation per NC, there was a remarkable and unexpected correlation between the average NC charge and PL intensity, for all dopant cations introduced. We conclude that the changes in PL intensity, as tracked also by changes in NC charge, are likely a consequence of changes in the NC radiative rate caused by symmetry breaking of the electronic states of the nominally spherical NC due to the Coulombic potential introduced by ionized cations.

A series of Ag 1- x Cu x InS 2 nanocrystals (NCs) spanning from 0 ≤ x ≤ ∼1 was synthesized by partial cation exchange to identify copper's contributions to the electronic structure and spectroscopic properties of these NCs. Discrete midgap states appear above the valence band upon doping AgInS 2 NCs with Cu + (small x). Density functional theory calculations confirm that these midgap states are associated with the 3d valence orbitals of the Cu + impurities. With increasing x, these impurity d levels gradually evolve to become the valence-band edge of CuInS 2 NCs, but the highest-occupied orbital's description does not change significantly across the entire range of x. In contrast with this gradual evolution, Ag 1- x Cu x InS 2 NC photoluminescence shifts rapidly with initial additions of Cu + (small x) but then becomes independent of x beyond x > ∼0.20, all the way to CuInS 2 ( x = 1.00). Data analysis suggests small but detectable hole delocalization in the luminescent excited state of CuInS 2 NCs, estimated by Monte Carlo simulations to involve at most about four copper ions. These results provide unique insights into the luminescent excited states of these materials and they reinforce the description of CuInS 2 NCs as "heavily copper-doped NCs" in which photogenerated holes are rapidly localized in copper 3d-based orbitals.

Among the various reported post synthetic modifications of colloidal nanocrystals, cation exchange (CE) is one of the most promising and versatile approaches for the synthesis of nanostructures that cannot be directly synthesized from their constitutive precursors. Numerous studies have reported on the qualitative analysis of these reactions, but rigorous quantitative study of the thermodynamics of CE in colloidal nanoparticles is still lacking. We demonstrate using isothermal titration calorimetry (ITC), the thermodynamics of the CE between cadmium selenide (CdSe) nanocrystals and silver in solution can be quantified. We survey the influence of CdSe nanocrystal diameter, capping ligands and temperature on the thermodynamics of the exchange reaction. Results obtained from ITC provide a detailed description of overall thermodynamic parameters-equilibrium constant ( K eq ), enthalpy (Δ H), entropy (Δ S) and stoichiometry ( n)-of the exchange reaction. We compared the free energy change of reaction (Δ G) between CdSe and Ag + obtained directly from ITC for both CdSe bulk and nanoparticles with values calculated from previously reported methods. While the calculated value is closer to the experimentally obtained Δ G rxn for bulk particles, nanocrystals show an additional Gibbs free energy stabilization of ∼-14 kJ/mol Se. We discuss a thermochemical cycle elucidating the steps involved in the overall cation exchange process. This work demonstrates the application of ITC to probe the thermochemistry of nanoscale transformations under relevant solution conditions.

We have designed a facile synthetic strategy for the selective deposition of Au metal on all-inorganic CsPbBr 3 perovskite nanocrystals that includes the addition of PbBr 2 salt along with AuBr 3 salt. PbBr 2 is necessary because the addition of Au 3+ to solutions of CsPbBr 3 nanocrystals otherwise results in the exchange of Au 3+ ions from solution with Pb 2+ cations within the nanocrystal lattice to produce Cs 2 Au I Au III Br 6 nanocrystals with a tetragonal crystal structure and a band gap of about 1.6 eV, in addition to Au metal deposition. Including excess Pb 2+ ions in solution prevents the exchange reaction. Au metal deposits on the surface of the nanocrystals to produce the Au-CsPbBr 3 heterostructure nanoparticles with an Au particle diameter determined by the Au 3+ ion concentration. Fluorescence quenching caused by Au deposition monotonically increases with deposition size, but the fluorescence quantum yield (QY) is significantly greater than if any cation exchange has occurred. An optimized synthesis can produce Au-CsPbBr 3 nanoparticles with 70% QY and no evidence of cation exchange.

Postsynthetic chemical transformations of colloidal nanocrystals, such as ion-exchange reactions, provide an avenue to compositional fine-tuning or to otherwise inaccessible materials and morphologies. While cation-exchange is facile and commonplace, anion-exchange reactions have not received substantial deployment. Here we report fast, low-temperature, deliberately partial, or complete anion-exchange in highly luminescent semiconductor nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, I). By adjusting the halide ratios in the colloidal nanocrystal solution, the bright photoluminescence can be tuned over the entire visible spectral region (410-700 nm) while maintaining high quantum yields of 20-80% and narrow emission line widths of 10-40 nm (from blue to red). Furthermore, fast internanocrystal anion-exchange is demonstrated, leading to uniform CsPb(Cl/Br)3 or CsPb(Br/I)3 compositions simply by mixing CsPbCl3, CsPbBr3, and CsPbI3 nanocrystals in appropriate ratios.

Luminescence blinking is an inherent feature of optical emission from individual fluorescent molecules and quantum dots. There have been intense efforts, although not with complete resolution, toward the understanding of the mechanistic origin of blinking and also its mitigation in quantum dots. As an advance in our microscopic view of blinking, we show that the luminescence blinking of a quantum dot becomes unusually heavy in the temporal vicinity of a reactive transformation. This stage of heavy blinking is a result of defects/dopants formed within the quantum dot on its path to conversion. The evolution of blinking behavior along the reaction path allows us to measure the lifetime of the critical dopant-related intermediate in the reaction. This work establishes luminescence blinking as a single-nanocrystal level probe of catalytic, photocatalytic, and electrochemical events occurring in the solid-state or on semiconductor surfaces.

We demonstrate dual interface formation in nanocrystals (NCs) through cation exchange, creating epitaxial heterostructures within spherical NCs. The thickness of the inner-disk layer can be tuned to form two-dimensional (2D), single atomic layers (<1 nm). During the cation exchange reaction from copper sulfide to zinc sulfide (ZnS), we observe a solid-solid phase transformation of the copper sulfide phase in heterostructured NCs. As the cation exchange reaction is initiated, Cu ions replaced by Zn ions at the interfaces are accommodated in intrinsic Cu vacancy sites present in the initial roxbyite (Cu1.81S) phase of copper sulfide, inducing a full phase transition to djurleite (Cu1.94S)/low chalcocite (Cu2S), a more thermodynamically stable phase than roxbyite. As the reaction proceeds and reduces the size of the copper sulfide layer, the epitaxial strain at the interfaces between copper sulfide and ZnS increases and is maximized for a copper sulfide disk ∼ 5 nm thick. To minimize this strain energy, a second phase transformation occurs back to the roxbyite phase, which shares a similar sulfur sublattice to wurtzite ZnS. The observation of a solid-solid phase transformation in our unique heterostructured NCs provides a new pathway to control desired phases and an insight into the influence of cation exchange on nanoscale phase transitions in heterostructured materials.

Colloidal quantum dots (QDs) are promising candidates for the next generation of photovoltaic (PV) technologies. Much of the progress in QD PVs is based on using PbS QDs, partly because they are stable under ambient conditions. There is considerable interest in extending this work to PbSe QDs, which have shown an enhanced photocurrent due to multiple exciton generation (MEG). One problem complicating such device-based studies is a poor stability of PbSe QDs toward exposure to ambient air. Here we develop a direct cation exchange synthesis to produce PbSe QDs with a large range of sizes and with in situ chloride and cadmium passivation. The synthesized QDs have excellent air stability, maintaining their photoluminescence quantum yield under ambient conditions for more than 30 days. Using these QDs, we fabricate high-performance solar cells without any protection and demonstrate a power conversion efficiency exceeding 6%, which is a current record for PbSe QD solar cells.