Enzymatic biosensing by covalent conjugation of enzymes to 3D-networks of graphene nanosheets on arrays of vertically aligned gold nanorods: Application to voltammetric glucose sensing.

The authors demonstrate efficient direct electron transfer from the enzyme glucose oxidase to vertically aligned gold nanorods with a diameter of ~160 nm and a length of ~2 µm that are covalently linkage to a 3-dimensional network of reduced graphene oxide nanosheets. The assembly can be prepared by a 2-step electrochemical procedure. This hybrid structure holds the enzyme in a favorable position while retaining its functionality that ultimately provides enhanced performance for enzymatic sensing of glucose without utilizing mediators. The nanorod assembly was applied to the voltammetric detection of glucose. Figures of merit include an electrochemical sensitivity of 12 µA·mM-1·cm-2 (obtained from cathodic peak current at a voltage of -0.45 V vs. Ag/AgCl), a 3 µM detection limit (at signal/noise = 3), and a wide linear range (0.01-7 mM). The hybrid nanostructure has a heterogeneous electron transfer rate constant (ks) of 2.9 s-1. The high electrochemical activity is attributed to the synergistic effect of a large active surface and an enhanced electron transfer efficiency due to covalent amide linkage. Graphical Abstract Schematic of the procedure utilized for the fabrication of an electrochemical biosensor based on gold nanorods (AuNRs) modified with a reduced graphene oxide (rGO)/glucose oxidase (GOx) conjugate. The enzyme electrode was employed to the determination of glucose by differential pulse voltammetry.

Surface passivation of lead sulfide nanocrystals with low electron affinity metals: photoluminescence and photovoltaic performance.

During the last decade, solution-processed colloidal quantum dots (CQDs) have attracted significant attention for low-cost fabrication of optoelectronic devices. In this study, lead sulfide (PbS) CQDs were synthesized via the hot injection method and the effect of doping elements with low electron affinity, including cadmium, calcium and zinc, on the passivation of trap states was investigated. A red-shift in the luminescence emission was observed by doping through passivation of lead dangling bonds. Time-resolved photoluminescence measurements showed that the lifetime of charged carriers was significantly enhanced by cadmium doping (∼80%) which is quite noticeable compared with calcium- and zinc-doped nanocrystals. External quantum efficiency measurements on thin solid films (∼300 nm) prepared by spin coating supported improved lifetime of carriers through passivation of mid-gap trap states. In order to show the potential application of the doping process, bulk heterojunction CQD solar cells were fabricated. It was found that the power conversion efficiency (PCE) was improved up to ∼40%; the highest improvement was observed with the Cd treatment. Finally, density functional theory (DFT) and electrochemical impedance spectroscopy (EIS) were employed to study the effect of doping on the density of states. The results showed that doping with low electron affinity metals effectively reduced the deep trap states of PbS QDs.

Hybrid zinc oxide/graphene electrodes for depleted heterojunction colloidal quantum-dot solar cells.

Recently, hybrid nanocomposites consisting of graphene/nanomaterial heterostructures have emerged as promising candidates for the fabrication of optoelectronic devices. In this work, we have employed a facile and in situ solution-based process to prepare zinc oxide/graphene quantum dots (ZnO/G QDs) in a hybrid structure. The prepared hybrid dots are composed of a ZnO core, with an average size of 5 nm, warped with graphene nanosheets. Spectroscopic studies show that the graphene shell quenches the photoluminescence intensity of the ZnO nanocrystals by about 72%, primarily due to charge transfer reactions and static quenching. A red shift in the absorption peak is also observed. Raman spectroscopy determines G-band splitting of the graphene shell into two separated sub-bands (G(+), G(-)) caused by the strain induced symmetry breaking. It is shown that the hybrid ZnO/G QDs can be used as a counter-electrode for heterojunction colloidal quantum-dot solar cells for efficient charge-carrier collection, as evidenced by the external quantum efficiency measurement. Under the solar simulated spectrum (AM 1.5G), we report enhanced power conversion efficiency (35%) with higher short current circuit (80%) for lead sulfide-based solar cells as compared to devices prepared by pristine ZnO nanocrystals.

Chemical processing of three-dimensional graphene networks on transparent conducting electrodes for depleted-heterojunction quantum dot solar cells.

We present a novel chemical procedure to prepare three-dimensional graphene networks (3DGNs) as a transparent conductive film to enhance the photovoltaic performance of PbS quantum-dot (QD) solar cells. It is shown that 3DGN electrodes enhance electron extraction, yielding a 30% improvement in performance compared with the conventional device.