Unraveling the molecular and growth mechanism of colloidal black In2O3-x.

Black metal oxides with varying concentrations of O-vacancies display enhanced optical and catalytic properties. However, direct solution syntheses of this class of materials have been limited despite being highly advantageous given the different synthetic handles that can be leveraged towards control of the targeted material. Herein, we present an alternate colloidal synthesis of black In2O3-x nanoparticles from the simple reaction between In(acac)3 and oleyl alcohol. Growth studies by PXRD, TEM, and STEM-EDS coupled to mechanistic insights from 1H, 13C NMR revealed the particles form via two paths, one of which involves In0. We also show that variations in the synthesis atmosphere, ligand environment, and indium precursor can inhibit formation of the black In2O3-x. The optical spectrum for the black nanoparticles displayed a significant redshift when compared to pristine In2O3, consistent with the presence of O-vacancies. Raman spectra and surface analysis also supported the presence of surface oxygen vacancies in the as-synthesized black In2O3-x.

Halide-driven polymorph selectivity in the synthesis of MnX (X = S, Se) nanoparticles.

Devising synthetic strategies to control crystal structure is of great importance as materials properties are governed by structure. MnS is a great model system as it has three known stable polymorphs. Herein, we show the selective synthesis of colloidal wurtzite- and rock-salt-type MnS under identical reactions conditions changing only the manganese halide precursor. Mixtures of Mn halides or halide surrogate (e.g., NH4Cl) also enabled polymorph control. Powder X-ray diffraction aliquot studies of the reactions revealed the crystal structure at the onset of nucleation and that of the final product is the same, unlike the Ostwald ripening transformation observed in other systems. The halide-driven selectivity was also observed in the synthesis of manganese selenide nanoparticles. In this system, variation of the Mn halide precursor allowed access to the wurtzite- and rock salt-type polymorphs of MnSe, as well as the pyrite-MnSe2 phase. Based on this work, the mixing of metal salts might be a simple and effective strategy towards polymorph control and access materials with new crystal structures.

Incorporation of Metal Phosphide Domains into Colloidal Hybrid Nanoparticles.

Colloidal hybrid nanoparticles have generated considerable attention in the inorganic nanomaterials community. The combination of different materials within a single nanoparticle can lead to synergistic properties that can enable new properties, new applications, and the discovery of new phenomena. As such, methodologies for the synthesis of hybrid nanoparticles that integrate metal-metal, metal chalcogenide, metal oxide, and oxide-chalcogenide domains have been extensively reported in the literature. However, colloidal hybrid nanoparticles containing metal phosphide domains are rare, despite being attractive systems for their potentially unique catalytic, photocatalytic, and optoelectronic properties. In this Forum Article, we report a study of the synthesis of colloidal hybrid nanoparticles that couple the metal phosphides Ni2P and CoxPy with Au, Ag, PbS, and CdS using heterogeneous seeded-growth reactions. We also investigate the transformation of Au-Ni heterodimers to Au-Ni2P, where phosphidation of preformed metal-metal hybrid nanoparticles offers an alternative route to metal phosphide systems. We also study sequential cation-exchange reactions to target specific metal phosphide hybrids, i.e., the transformation of Ni2P-PbS into Ni2P-Ag2S and then Ni2P-CdS. Throughout all of these pathways, the accompanying discussion emphasizes the synthetic rationale, as well as the challenges in synthesis and characterization that are unique to these systems. In particular, the observation of oxide shells that surround the phosphide domains has implications for the potential photocatalytic applications of these hybrid nanoparticles.

Interlaced crystals having a perfect Bravais lattice and complex chemical order revealed by real-space crystallography.

The search for optimal thermoelectric materials aims for structures in which the crystalline order is disrupted to lower the thermal conductivity without degradation of the electron conductivity. Here we report the synthesis and characterisation of ternary nanoparticles (two cations and one anion) that exhibit a new form of crystalline order: an uninterrupted, perfect, global Bravais lattice, in which the two cations exhibit a wide array of distinct ordering patterns within the cation sublattice, forming interlaced domains and phases. Partitioning into domains and phases is not unique; the corresponding boundaries have no structural defects or strain and entail no energy cost. We call this form of crystalline order 'interlaced crystals' and present the example of hexagonal CuInS2. Interlacing is possible in multi-cation tetrahedrally bonded compound with an average of two electrons per bond. Interlacing has minimal effect on electronic properties, but should strongly reduce phonon transport, making interlaced crystals attractive for thermoelectric applications.

Electron transfer kinetics in water splitting dye-sensitized solar cells based on core-shell oxide electrodes.

Photoelectrochemical water splitting occurs in a dye-sensitized solar cell when a [Ru(bpy)3]2+-based dye covalently links a porous TiO2 anode film to IrO2 x nH2O nanoparticles. The quantum yield for oxygen evolution is low because of rapid back electron transfer between TiO2 and the oxidized dye, which occurs on a timescale of hundreds of microseconds, When iodide is added as an electron donor, the photocurrent increases, confirming that the initial charge injection efficiency is high. When the porous TiO2 film is coated with a 1-2 nm thick layer of ZrO2 or Nb2O5, both the charge injection rate and back electron transfer rate decrease. The efficiency of the cell increases and then decreases with increasing film thickness, consistent with the trends in charge injection and recombination rates. The current efficiency for oxygen evolution, measured electrochemically in a generator-collector geometry, is close to 100%. The factors that lead to polarization of the photoanode and possible ways to re-design the system for higher efficiency are discussed.

Anodic deposition of colloidal iridium oxide thin films from hexahydroxyiridate(IV) solutions.

A facile, in-situ deposition route to stable iridium oxide (IrO(x)·nH(2)O) nanoparticle thin films from [Ir(OH)(6)](2-) solutions is reported. The [Ir(OH)(6)](2-) solution, made by alkaline hydrolysis of [IrCl(6)](2-), is colorless and stable near neutral pH, and forms blue IrO(x)·nH(2)O nanoparticle suspensions once it is adjusted to acidic or basic conditions. IrO(x)·nH(2)O nanoparticle thin films are grown anodically on glassy carbon, fluorine-doped tin oxide, and gold electrodes by electrolyzing [Ir(OH)(6)](2-) solutions at +1.0-1.3 V versus Ag/AgCl. The thickness of the IrO(x)·nH(2)O films can be controlled by varying the concentration of [Ir(OH)(6)](2-) , the deposition potential, and/or the deposition time. These thin films are stable between pH 1 and 13 and have the lowest overpotential (η) for the oxygen evolution reaction (OER) of any yet reported. Near neutral pH, the Tafel slope for the OER at a IrO(x)·nH(2)O film/Au rotating disk electrode was 37-39 mV per decade. The exchange current density for the OER was 4-8 × 10(-10) A cm(-2) at a 4 mC cm(-2) coverage of electroactive Ir.

Template electrodeposition of single-phase p- and n-type copper indium diselenide (CuInSe2) nanowire arrays.

CuInSe(2) nanowire arrays were fabricated by electrodeposition from aqueous solutions of copper sulfate, indium sulfate, selenium dioxide, and citric acid, using anodic alumina membranes as templates. X-ray diffraction patterns showed that the wires were single phase (chalcopyrite structure) but polycrystalline, and a band gap of ∼1 eV was obtained from optical measurements. TEM and SEM confirmed that the grain size in nanowires annealed at 400 °C was in the range of 40 nm. The composition of the nanowires was uniform along the length of the wires and could be tuned by varying the electrodeposition potential. Analysis by ICP-MS showed that naowires grown at -700 mV were slightly Cu-rich, whereas those grown at -750 mV were slightly In-rich. Mott-Schottky plots were employed to determine the doping type and flat band potential, verifying that the Cu- and In-rich wires were p- and n-type, respectively. Single-wire electrical transport measurements were also performed and showed that both types of wires had resistivities in the range 10(-1)-10(-3) Ω·cm, consistent with carrier concentrations in the range 10(18)-10(20) cm(-3).

Photoassisted overall water splitting in a visible light-absorbing dye-sensitized photoelectrochemical cell.

Iridium oxide nanoparticles stabilized by a heteroleptic ruthenium tris(bipyridyl) dye were used as sensitizers in photoelectrochemical cells consisting of a nanocrystalline anatase anode and a Pt cathode. The dye coordinated the IrO(2) x nH(2)O nanoparticles through a malonate group and the porous TiO(2) electrode through phosphonate groups. Under visible illumination (lambda > 410 nm) in pH 5.75 aqueous buffer, oxygen was generated at anode potentials positive of -325 mV vs Ag/AgCl and hydrogen was generated at the cathode. The internal quantum yield for photocurrent generation was ca. 0.9%. Steady-state luminescence and time-resolved flash photolysis/transient absorbance experiments were done to measure the rates of forward and back electron transfer. The low quantum yield for overall water splitting in this system can be attributed to slow electron transfer (approximately 2.2 ms) from IrO(2) x nH(2)O to the oxidized dye. Forward electron transfer does not compete effectively with the back electron transfer reaction from TiO(2) to the oxidized dye, which occurred on a time scale of 0.37 ms.