David Kingston

Low-temperature approach to highly emissive copper indium sulfide colloidal nanocrystals and their bioimaging applications.

We report our newly developed low-temperature synthesis of colloidal photoluminescent (PL) CuInS2 nanocrystals (NCs) and their in vitro and in vivo imaging applications. With diphenylphosphine sulphide (SDPP) as a S precursor made from elemental S and diphenylphosphine, this is a noninjection based approach in 1-dodecanethiol (DDT) with excellent synthetic reproducibility and large-scale capability. For a typical synthesis with copper iodide (CuI) as a Cu source and indium acetate (In(OAc)3) as an In source, the growth temperature was as low as 160 °C and the feed molar ratios were 1Cu-to-1In-to-4S. Amazingly, the resulting CuInS2 NCs in toluene exhibit quantum yield (QY) of ~23% with photoemission peaking at ~760 nm and full width at half maximum (FWHM) of ~140 nm. With a mean size of ~3.4 nm (measured from the vertices to the bases of the pyramids), they are pyramidal in shape with a crystal structure of tetragonal chalcopyrite. In situ (31)P NMR (monitored from 30 °C to 100 °C) and in situ absorption at 80 °C suggested that the Cu precursor should be less reactive toward SDPP than the In precursor. For our in vitro and in vivo imaging applications, CuInS2/ZnS core-shell QDs were synthesized; afterwards, dihydrolipoic acid (DHLA) or 11-mercaptoundecanoic acid (MUA) were used for ligand exchange and then bio-conjugation was performed. Two single-domain antibodies (sdAbs) were used. One was 2A3 for in vitro imaging of BxPC3 pancreatic cancer cells. The other was EG2 for in vivo imaging of a Glioblastoma U87MG brain tumour model. The bioimaging data illustrate that the CuInS2 NCs from our SDPP-based low-temperature noninjection approach are good quality.

Low-temperature approach to high-yield and reproducible syntheses of high-quality small-sized PbSe colloidal nanocrystals for photovoltaic applications.

Small-sized PbSe nanocrystals (NCs) were synthesized at low temperature such as 50-80 °C with high reaction yield (up to 100%), high quality, and high synthetic reproducibility, via a noninjection-based one-pot approach. These small-sized PbSe NCs with their first excitonic absorption in wavelength shorter than 1200 nm (corresponding to size < ∼3.7 nm) were developed for photovoltaic applications requiring a large quantity of materials. These colloidal PbSe NCs, also called quantum dots, are high-quality, in terms of narrow size distribution with a typical standard deviation of ∼7-9%, excellent optical properties with high quantum yield of ∼50-90% and small full width at half-maximum of ∼130-150 nm of their band-gap photoemission peaks, and high storage stability. Our synthetic design aimed at promotion of the formation of PbSe monomers for fast and sizable nucleation with the presence of a large number of nuclei at low temperature. For formation of the PbSe monomer, our low-temperature approach suggests the existence of two pathways of Pb-Se (route a) and Pb-P (route b) complexes. Either pathway may dominate, depending on the method used and its experimental conditions. Experimentally, a reducing/nucleation agent, diphenylphosphine, was added to enhance route b. The present study addresses two challenging issues in the NC community, the monomer formation mechanism and the reproducible syntheses of small-sized NCs with high yield and high quality and large-scale capability, bringing insight to the fundamental understanding of optimization of the NC yield and quality via control of the precursor complex reactivity and thus nucleation/growth. Such advances in colloidal science should, in turn, promote the development of next-generation low-cost and high-efficiency solar cells. Schottky-type solar cells using our PbSe NCs as the active material have achieved the highest power conversion efficiency of 2.82%, in comparison with the same type of solar cells using other PbSe NCs, under Air Mass 1.5 global (AM 1.5G) irradiation of 100 mW/cm(2).

Low-temperature noninjection approach to homogeneously-alloyed PbSe(x)S(1-x) colloidal nanocrystals for photovoltaic applications.

Homogeneously alloyed PbSe(x)S(1-x) nanocrystals (NCs) with their excitonic absorption peaks in wavelength shorter than 1200 nm were developed for photovoltaic (PV) applications. Schottky-type solar cells fabricated with our PbSe₀.₃S₀.₇ NCs as their active materials reached a high power conversion efficiency (PCE) of 3.44%, with an open circuit voltage (V(oc)) of 0.49 V, short circuit photocurrent (J(sc)) of 13.09 mA/cm², and fill factor (FF) of 0.54 under Air Mass 1.5 global (AM 1.5G) irradiation of 100 mW/cm². The syntheses of the small-sized colloidal PbSe(x)S(1-x) NCs were carried out at low temperature (60 °C) with long growth periods (such as 45 min) via a one-pot noninjection-based approach in 1-octadecene (ODE), featuring high reaction yield, high product quality, and high synthetic reproducibility. This low-temperature approach employed Pb(oleate)₂ as a Pb precursor and air-stable low-cost thioacetamide (TAA) as a S source instead of air-sensitive high-cost bis(trimethylsilyl)sulfide ((TMS)₂S), with n-tributylphosphine selenide (TBPSe) as a Se precursor instead of n-trioctylphosphine selenide (TOPSe). The reactivity difference of TOPSe made from commercial TOP 90% and TBPSe made from commercial TBP 97% and TBP 99% was addressed with in situ observation of the temporal evolution of NC absorption and with ³¹P nuclear magnetic resonance (NMR). Furthermore, the addition of a strong reducing/nucleation agent diphenylphosphine (DPP) promoted the reactivity of the Pb precursor through the formation of a Pb-P complex, which is much more reactive than Pb(oleate)₂. Thus, the reactivity of TBPSe was increased more than that of TAA. The larger the DPP-to-Pb feed molar ratio, the more the Pb-P complex, the higher the Se amount in the resulting homogeneously alloyed PbSe(x)S(1-x) NCs. Therefore, the use of DPP allowed reactivity match of the Se and S precursors and led to sizable nucleation at low temperature so that long growth periods became feasible. The present study brings insight into the formation mechanism of monomers, nucleation/growth of colloidal composition-tunable NCs, and materials design and synthesis for next-generation low-cost and high-efficiency solar cells.

Green synthesis of tunable Cu(In1−xGax)Se2 nanoparticles using non-organic solvents

A green synthesis route of Cu(In1−xGax)Se2 nanoparticles with variable Ga content is described in this report for the first time. Only water and a minimum amount of energy input are used. Heating appropriate amounts of Cu, In, Ga and Se dispersed in an aqueous solution containing mercapto-acetic acid in a microwave oven gives rise to small and uniform nanoparticles. These new materials have been characterized to confirm composition, geometrical and structural properties. Transmission electron microcopy (TEM) confirmed size distribution around 4 nm. XRD confirmed the chalcopyrite structure with an average crystallite size of 3 nm. Atomic concentration and oxidation states of the different elements have been investigated using X-ray photoelectron spectroscopy (XPS). UV-visible absorption characterization confirmed the tunable optical properties of these materials. The proposed synthesis is scalable for commercial production with minimal environmental impact.

Ultraviolet ZnSe1–xSx Gradient-Alloyed Nanocrystals via a Noninjection Approach

Highly emissive ultraviolet ZnSeS nanocrystals (NCs), with a core-shell-like structure, were designed and synthesized via a one-step noninjection approach in 1-octadecene (ODE). These ultraviolet ZnSeS NCs exhibit bright bandgap emission with high color purity and little trap emission. With full width at half-maximum (fwhm) of ∼21 nm only, photoluminescent (PL) quantum yield (QY) of ∼60% was estimated for one ensemble dispersed in toluene exhibiting bandgap absorption peaking at ∼380 nm and bandgap emission at ∼389 nm. These alloyed ZnSeS NCs present a cubic crystal structure consisting of a Se-rich core and a S-rich shell. Such a gradiently alloyed structure was suggested by our investigation on the temporal evolution of optical properties of the growing ZnSeS NCs monitored from 80 to 300 °C, together with structural and compositional characterization performed with XRD, XPS, EDX, and TEM. This newly developed one-step noninjection approach was achieved with zinc oleate (Zn(OA)(2)), diphenylphosphine selenide (SeDPP), and diphenylphosphine sulfide (SDPP) as Zn, Se, and S precursors, respectively. ZnSe monomers mainly participated in nucleation at ∼120 °C, while both ZnSe and ZnS monomers contributed to NC formation in later growth stages (∼160 °C and higher). (31)P NMR study demonstrates that SeDPP is more reactive than SDPP toward Zn(OA)(2), and also supports such a model proposed on the combination of ZnSe and ZnS monomers leading to nucleation/growth of ZnSeS alloyed NCs. The present study offers conceptual methodology to various highly photoluminescent alloyed NCs with high quality, high particle yield, and high synthetic reproducibility.

Adsorption of Pentane Insoluble Organic Matter from Oilsands Bitumen onto Clay Surfaces

Abstract The effectiveness of commercial oilsands separation processes relies on the water wettability of the solids. Consequently, the interaction between the mineral and organic matter types present in oilsands is of interest. In this work, we report results related to the adsorption of a pentane insoluble fraction from bitumen on kaolinite and illite, the major clay types present in oilsands. We determined adsorption from toluene solution by illite and kaolinite and use a combination of spectroscopic techniques to probe the organic coated clay surfaces to different depths. The results are compared with similar data for equivalent natural fractions from oilsands.

Colloidal Clay Gelation: Relevance to Current Oil Sands Operations

Abstract Ultrafines are predominantly delaminated colloidal clays with dimensions <0.3 μm that exist naturally in oil sands and are released during conditioning of surface-mined ores. Critical concentrations of these ultrafines and the cations present in process water are capable of forming flocculated structures with a very high water holding capacity. During primary separation of bitumen these ultrafines are detrimental to recovery as a result of increased slurry viscosity as well as through slime coating of released bitumen. Disposition into tailings ponds eventually produces mature fine tailings (MFT) as a result of thixotropic gel formation that entraps coarser solids. The ultrafines concentration of ~3 wt% observed in MFT coincides with the critical gelation concentration determined for suspensions of ultrafines in salt solutions with cationic concentrations representative of that in pond water. This observation accounts for 100% of the water holding capacity of MFT and also explains why virtually no water is released once an MFT gel state has been formed. Here, we review earlier research in this area and identify the harmful effects of ultrafines in some current problematic ores.

The Comparison of Bitumens from Oil Sands with Different Recovery Profiles

Abstract It has been proposed that, regardless of origin, the recovery of bitumen from oil sands is related to its viscosity. Asphaltene and resin contents are known to affect the viscosity of bitumen. In this article we compare the composition of solvent-extracted bitumens from several Athabasca oil sands with very different recovery profiles. After careful removal of any associated mineral matter by ultra-centrifugation, each bitumen sample was separated into saturate, aromatic, resin, and asphaltene (SARA) fractions by an enhanced SARA technique. The individual components were then characterized by several complementary analytical techniques, including carbon, nitrogen, nitrogen, sulfur, size exclusion chromatography molecular weight (MWn) plus proton and 13C nuclear magnetic resonance spectroscopy. Based on this comparison, we see no correlation between the recovery of bitumen and its composition.