Mechanistic insights on Bi-potentiodynamic control towards atomistic synthesis of electrocatalysts for hydrogen evolution reaction.

Herein, electrochemically assisted dissolution-deposition (EADD) is utilized over a three-electrode assembly to prepare an electrocatalyst for hydrogen evolution reaction (HER). Cyclic voltammetry is performed to yield atomistic loading of platinum (Pt) over SnS2 nanostructures via Pt dissolution from the counter electrode (CE). Astonishingly, the working electrode (WE) swept at 50 mV/s is found to compel Pt CE to experience 1000-3000 mV/s. The effect of different potential scan rates at the WE have provided insight into the change in Pt dissolution and its deposition behaviour over SnS2 in three electrode assembly. However, uncontrolled overpotentials at CE in a three-electrode assembly made Pt dissolution-deposition behavior complex. Here, for the first time, we have demonstrated bi-potentiodynamic control for dissolution deposition of Pt in four-electrode assembly over Nickel (Ni) foam. The dual cyclic voltammetry is applied to achieve better control and efficiency of the EADD process, engendering it as a pragmatically versatile and scalable synthesis technique.

Polygonal gold nanocrystal induced efficient phase transition in 2D-MoS2for enhancing photo-electrocatalytic hydrogen generation.

Plasmonic nanocrystals (NCs) assisted phase transition of two-dimensional molybdenum disulfide (2D-MoS2) unlashes numerous opportunities in the fields of energy harvesting via electrocatalysis and photoelectrocatalysis by enhancing electronic conductivity, increasing catalytic active sites, lowering Gibbs free energy for hydrogen adsorption and desorption, etc. Here, we report the synthesis of faceted gold pentagonal bi-pyramidal (Au-PBP) nanocrystals (NC) for efficient plasmon-induced phase transition (from 2 H to 1 T phase) in chemical vapor deposited 2D-MoS2. The as-developed Au-PBP NC with the increased number of corners and edges showed an enhanced multi-modal plasmonic effect under light irradiations. The overpotential of hydrogen evolution reaction (HER) was reduced by 61 mV, whereas the Tafel slope decreased by 23.7 mV/dec on photoexcitation of the Au-PBP@MoS2hybrid catalyst. The enhanced performance can be attributed to the light-induced 2H to 1 T phase transition of 2D-MoS2, increased active sites, reduced Gibbs free energy, efficient charge separation, change in surface potential, and improved electrical conductivity of 2D-MoS2film. From density functional theory (DFT) calculations, we obtain a significant change in the electronic properties of 2D-MoS2(i.e. work function, surface chemical potential, and the density of states), which was primarily due to the plasmonic interactions and exchange-interactions between the Au-PBP nanocrystals and monolayer 2D-MoS2, thereby enhancing the phase transition and improving the surface properties. This work would lay out finding assorted routes to explore more complex nanocrystals-based multipolar plasmonic NC to escalate the HER activity of 2D-MoS2and other 2D transition metal dichalcogenides.

CuO Nanoparticles Decorated ZnO Nanorods Based Extended-Gate Field-Effect-Transistor (EGFET) for Enzyme-Free Glucose Sensing Application.

In this work, CuO nanoparticles (NPs) decorated zinc oxide nanorods (ZnO NRs) on fluorine-doped tin oxide (FTO) substrate has been used as a working electrode. This working electrode has been used as an extended gate for field-effect transistor. The main objective is to use the EGFET (extended gate field effect transistor) as a glucose sensor. The proposed glucose sensor has good sensitivity of 6.643 mV/mM with a wide range of linearity (1mM-8mM) which covers the glucose level of human blood ranging from 4.4 mM to 6.6 mM. This novel concept of the glucose sensing using CuO NPs decorated ZnO nanorods based EGFET may be explored for sensing other saccharides such as mannose, fructose, and sucrose. This vertically grown ZnO nanorods decorated with CuO NPs based electrode gives reliable selectivity, good repeatability, and more stability. The performance of proposed sensor is also compared with commercially available glucose sensors. The sensitivity performance of the glucose sensor also confirms the capability to detect the glucose level from human blood and serum.

Author Correction: Au nanoparticles modified CuO nanowire electrode based non-enzymatic glucose detection with improved linearity.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Synergistic effect of CdSe quantum dots (QDs) and PC61BM on ambient-air processed ZnO QDs/PCDTBT: PC61BM:CdSe QDs/MoO3 based ternary organic solar cells.

This paper reports the synergistic effect of colloidal CdSe quantum dots (QDs) and PC61BM on the performance of ITO/ZnO QDs/PCDTBT:PC61BM:CdSe QDs/MoO3/Ag based ternary organic solar cells (OSCs). The MoO3 and ZnO QDs (∼2.87 nm) layers work as the transparent hole transport layer (HTL) and electron transport layer (ETL), respectively. The CdSe QDs (∼4.58 nm) are blended with PC61BM:PCDTBT binary solution to improve the optical properties and charge transportation. Significant photoluminescence (PL) quenching is observed when part of the PC61BM is replaced by CdSe QDs with equivalent weight in the PCDTBT. The proposed ternary OSC gives an open-circuit voltage of 854 mV, a short circuit current density of 14 mA cm-2, fill factor of 42% and power conversion efficiency (PCE) of 5.02%. The PCE of the ternary OSC is increased by more than 38% compared to the binary OSC. This significant improvement in the performance parameters is attributed to the enhanced absorption and higher transportation of photo-generated charge carriers, as well as the increased charge dissociation due to the synergistic effect of CdSe QDs and PC61BM. The external quantum efficiency is also enhanced significantly in the ternary OSC due to the better conversion of solar energy into electrical energy.

Au nanoparticles modified CuO nanowireelectrode based non-enzymatic glucose detection with improved linearity.

This paper explores gold nanoparticle (GNP) modified copper oxide nanowires(CuO NWs)based electrode grown on copper foil for non-enzymatic glucose detection in a wide linear ranging up to 31.06 mM, and 44.36 mM at 0.5 M NaOH and 1 M NaOH concentrations. The proposed electrode can be used to detect a very low glucose concentration of 0.3 µM with a high linearity range of 44.36mM and sensitivity of 1591.44 µA mM-1 cm-2. The electrode is fabricated by first synthesizing Cu (OH)2 NWs on a copper foil by chemical etching method and then heat treatment is performed to convert Cu (OH)2 NWs into CuO NWs. The GNPs are deposited on CuO NWs to enhance the effective surface-to-volume ratio of the electrode with improved catalytic activity. The surface morphology has been investigated by XRD, XPS, FE-SEM and HR-TEM analysis. The proposed sensor is expected to detect low-level of glucose in urine, and saliva. At the same time, it can also be used to measure extremely high sugar levels (i.e. hyperglycemia) of ~ 806.5454 mg/dl. The proposed sensor is also capable of detecting glucose after multiple bending of the GNP modified CuO NWs electrode. The proposed device is also used to detect the blood sugar level in human being and it is found that this sensor's result is highly accurate and reliable.

Superficial fabrication of gold nanoparticles modified CuO nanowires electrode for non-enzymatic glucose detection.

This paper describes a low-cost facile method to construct gold (Au) nanoparticles (NPs) modified copper oxide (CuO) nanowires (NWs) electrode on copper foil for the detection of glucose. Copper foil has been converted to aligned CuO NWs arrays by sequential formation of Cu(OH)2 followed by heat treatment induced phase transformation to CuO. Au NPs are deposited on CuO NWs via simple reductive solution chemistry to impart high surface to volume ratio and enhanced catalytic activity of the resulting electrode. Structure, microstructure and morphology of Cu, Cu(OH)2 NWs, CuO NWs, and Au NPs modified CuO NWs are investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The homogeneous distribution of Au NPs (average diameter ∼12 nm) on CuO NWs (average diameter 100 nm and aspect ratio ∼20) is confirmed by high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM) and elemental mapping. This CuO based glucose detection method gives the highest sensitivity along with the maximum linearity range. This non-enzymatic glucose sensor based on Au modified CuO NWs electrode gives broad linearity range from 0.5 µM to 5.9 mM. The sensor exhibits sensitivity of 4398.8 µA mM-1 cm-2, lower detection limit of 0.5 µM, and very fast response time of ∼5 s. Properties of the proposed glucose sensor are also investigated in human blood and it is found that the sensor is highly accurate and reliable. In addition, higher sensitivity and lower detection limit confirm that this device is suitable for invasive detection in saliva and urine.

Defect mediated magnetic transitions in Fe and Mn doped MoS2.

We report single-phase syntheses of undoped 2H-MoS2 as well as Mn and Fe doped MoS2 by a facile hydrothermal route. The formation of the 2H-MoS2 phase was confirmed by XRD and was corroborated with Raman spectra. The morphology of the doped and undoped MoS2 nanostructures comprised sheets, as revealed by TEM and STEM images. The fine granular structure was observed by high resolution TEM micrographs. The STEM-EDS results show dopant concentrations of ∼1 atom% corresponding to Mn and Fe in doped MoS2. The undoped MoS2 revealed diamagnetic behavior at room temperature and paramagnetic behavior in the range (100 to 300 K). The Mn-MoS2 sample displayed ferromagnetism below 20 K with a coercive field of ∼50 Oe. Such a sample may be utilized for magnetic switching purposes at low temperatures. The onset of the antiferromagnetic interaction was observed below 145 K in Fe-MoS2 samples. They have been understood in terms of long-range magnetic interactions amongst the dipole moments mediated via surface defects as well as the interaction between the dipoles and the surface charges. The findings are corroborated with the help of EPR studies.

Growth morphology and special diffraction characteristics of multifaceted gold nanoparticles.

This paper deals with morphology of synthesized nano gold particles through seed based growth. Various types of morphologies have been observed. They primarily relate to decahedral and truncated tetrahedral shapes. Their relative abundance is dependent on temporal evolution of nanoparticles. These shapes are understood to have evolved from a seed having symmetry that is a supergroup of the point groups possessed by these nanoparticles. The usual pentagonal twinned morphologies observed under High Resolution Transmission Electron Microscopy have displayed two distinct types of interfaces. They have been attributed to cubic and icosahedral three-fold orientations. Such a discussion is lacking in literature. The five triangular faces of decahedral particles are essentially rotational twins resulting out of a common five-fold axis. Two special diffraction features for truncated tetrahedral particles have been observed. They refer to (i) triangular streaks around Braggs spots conforming to three fold symmetry of these particles and (ii) by observation of forbidden reflections of the type 1/3{422} and 2/3{422} along 〈422〉 directions. Latter has been understood in terms of intrinsic fault whereas former arises owing to shape transform of nanoparticles. The presence of faults has helped rationalize decrease of lattice parameter vis-à-vis that of standard FCC gold. The variation of intensities of these forbidden reflections seems to be arising out of density of such intrinsic faults in nano gold particles in addition to dynamical effects.

Engineered Solution-Liquid-Solid Growth of a "Treelike" 1D/1D TiO2 Nanotube-CdSe Nanowire Heterostructure: Photoelectrochemical Conversion of Broad Spectrum of Solar Energy.

This work presents a hitherto unreported approach to assemble a 1D oxide-1D chalcogenide heterostructured photoactive film. As a representative system, bismuth (Bi) catalyzed 1D CdSe nanowires are directly grown on anodized 1D TiO2 nanotube (T_NT). A combination of the reductive successive-ionic-layer-adsorption-reaction (R-SILAR) and the solution-liquid-solid (S-L-S) approach is implemented to fabricate this heterostructured assembly, reported in this 1D/1D form for the first time. XRD, SEM, HRTEM, and elemental mapping are performed to systematically characterize the deposition of bismuth on T_NT and the growth of CdSe nanowires leading to the evolution of the 1D/1D heterostructure. The resulting "treelike" photoactive architecture demonstrates UV-visible light-driven electron-hole pair generation. The photoelectrochemical results highlight: (i) the formation of a stable n-n heterojunction between TiO2 nanotube and CdSe nanowire, (ii) an excellent correlation between the absorbance vis-à-vis light conversion efficiency (IPCE), and (iii) a photocurrent density of 3.84 mA/cm2. This proof-of-concept features the viability of the approach for designing such complex 1D/1D oxide-chalcogenide heterostructures that can be of interest to photovoltaics, photocatalysis, environmental remediation, and sensing.

Different shades of cholesterol: Gold nanoparticles supported on MoS2 nanoribbons for enhanced colorimetric sensing of free cholesterol.

In the present study, we manifest that traditionally used gold nanoparticles when supported on molybdenum disulfide nanoribbons matrix (MoS2 NRs-Au NPs) show synergistically enhanced intrinsic peroxidase like catalytic activity and can catalyze the oxidation of 3,3',5,5' tetramethyl benzidine by H2O2 to produce a highly sensitive blue shade product depending on level of free cholesterol, when tested on complex system of human serum. Further the system attests appreciable kinetics, owing to Km value as low as 0.015 mM and better loading capacity (Vmax=6.7×10(-6) M s(-1)). Additionally, the proposed system is stable for weeks with ability to perform appreciably in wide pH (3-6) and temperature range (25-60 °C). Utilizing this potential, the present work proposes a cholesterol detection color wheel which is used along with cost effective cholesterol detection strips fabricated out of proposed MoS2 NRs-Au NPs system for quick and reliable detection of free cholesterol using unaided eye.

A unique architecture based on 1 D semiconductor, reduced graphene oxide, and chalcogenide with multifunctional properties.

A unique heterostructured optoelectronic material (HOM), consisting of a reduced graphene oxide (RGO) layer with spatially distributed CdS, suspended by zinc oxide (ZnO) nanorods, is presented. The key features of this HOM are the assembly of the components in a manner so as to realize an effective integration between the constituents and the ability to modify the electronic properties of the RGO. For the first time, the location of RGO (as a suspended layer) along with the tuning of its charge-transport properties (n-/p-type) and its influence on the photo(electro)chemical processes has been examined systematically by using this ZnO/RGO/CdS HOM as a case study. The n-type RGO interlayer facilitates >100 % increase in the photocurrent density and 25 % increase in the photodegradation of a dye, compared to ZnO/CdS, thus demonstrating its multifunctionality. At 3.2 mA cm(-2) , this HOM architecture helps to achieve the highest photocurrent density utilizing ZnO, RGO, and CdS as building blocks in any form. The work is significant for the following reasons: i) other one dimensional (1D) oxides/chalcogenides or 1D oxides/dyes may be designed with similar architectures; ii) HOMs with tunable optical absorbance and charge-transport properties could be realized; iii) related application areas (e.g., sensing or solar fuel generation) should be greatly benefited.

TiO2 nanotube (T_NT) surface treatment revisited: Implications of ZnO, TiCl4, and H2O2 treatment on the photoelectrochemical properties of T_NT and T_NT-CdSe.

The surface treatment of an anodized TiO(2) nanotube (T_NT) is very desirable for enhancing its photoelectrochemical properties and often is a prerequisite to deposition of any overlying layer for photoactivity efficiency improvement. This study provides a comparative analysis of the effects of such surface treatments and the mechanistic insights behind the observed improvements in the performance of the treated T_NTs. T_NT surface treatment using three approaches, viz., TiCl(4), Zn(NH(3))(4)(2+), and H(2)O(2) is examined. TiCl(4) and Zn(NH(3))(4)(2+) treatment results in the formation of discontinuous islands of the respective oxides with 5-10 nm and 15-20 nm diameter particles. TiCl(4) treatment demonstrates an increase of 7.4% in photovoltage and is the most effective of the three approaches. Zn(NH(3))(4)(2+) treatment also results in an ~2% increase in photovoltage. However, a surface treatment of T_NT using H(2)O(2) results only in a favourable shift in flatband potential (80 mV). The T_NTs are rendered ineffective as H(2)O(2) treatment causes the destabilization of the T_NT at the base. Finally, the activity of an overlying chalcogenide layer is improved with the TiCl(4) and Zn(NH(3))(4)(2+) treatment (and not with H(2)O(2)) as evident from the photoelectrochemical responses: (J(T_NT-TiO(2)-CdSe) > J(T_NT-ZnO-CdSe) > J(T_NT-CdSe) > J(T_NT-H(2)O(2)-CdSe)).

1D CdS/PbS heterostructured nanowire synthesis using cation exchange.

Heterostructured CdS nanowires with PbS deposits forming p-n junctions have been synthesized by successive cation exchange. The method developed herein opens up the possibility of preparing a spatially distributed heterojunction-based multifunctional electrode. The (photo)electrochemical activity of the material may be chemically tuned by changing the size and density of the p type PbS nanoparticles.