Transition metal chalcogenides for next-generation energy storage.

Transition-metal chalcogenide nanostructures provide a unique material platform to engineer next-generation energy storage devices such as lithium-ion, sodium-ion, and potassium-ion batteries and flexible supercapacitors. The transition-metal chalcogenide nanocrystals and thin films have enhanced electroactive sites for redox reactions and hierarchical flexibility of structure and electronic properties in the multinary compositions. They also consist of more earth-abundant elements. These properties make them attractive and more viable new electrode materials for energy storage devices compared to the traditional materials. This review highlights the recent advances in chalcogenide-based electrodes for batteries and flexible supercapacitors. The viability and structure-property relation of these materials are explored. The use of various chalcogenide nanocrystals supported on carbonaceous substrates, two-dimensional transition metal chalcogenides, and novel MXene-based chalcogenide heterostructures as electrode materials to improve the electrochemical performance of lithium-ion batteries is discussed. The sodium-ion and potassium-ion batteries offer a more viable alternative to lithium-ion technology as they consist of readily available source materials. Application of various transition metal chalcogenides such as MoS2, MoSe2, VS2, and SnSx, composite materials, and heterojunction bimetallic nanosheets composed of multi-metals as electrodes to enhance the long-term cycling stability, rate capability, and structural strength to counteract the large volume expansion during the ion intercalation/deintercalation processes is highlighted. The promising performances of layered chalcogenides and various chalcogenide nanowire compositions as electrodes for flexible supercapacitors are also discussed in detail. The review also details the progress made in new chalcogenide nanostructures and layered mesostructures for energy storage applications.

Phytochemical Profiling, Biological Activities, and In Silico Molecular Docking Studies of Causonis trifolia (L.) Mabb. & J.Wen Shoot.

Causonis trifolia (L.) Mabb. & J.Wen, commonly known as "fox grape", is an ethnomedicinally important twining herb of the Vitaceae family, and it is used by ethnic communities for its wide range of therapeutic properties. Our research aims to investigate the chemical composition; antioxidant, anti-inflammatory, and antidiabetic activities; and mechanisms of interaction between the identified selective chemical compounds and the target proteins associated with antioxidant, anti-inflammatory, and antidiabetic effects of the optimised phenolic extract of Causonis trifolia (L.) Mabb. & J.Wen, shoot (PECTS) to endorse the plant as a potential drug candidate for a future bioprospecting programme. Here, we employed the response surface methodology (RSM) with a Box-Behnken design to enrich the methanolic extract of C. trifolia shoot with phenolic ingredients by optimising three key parameters: solvent concentration (% v/v, methanol:water), extraction temperature (°C), and extraction duration (hours). From the quantitative phytochemical estimation, it was evident that the PECTS contained good amounts of phenolics, flavonoids, tannins, and alkaloids. During the HPLC analysis, we identified a total of eight phenolic and flavonoid compounds (gallic acid, catechin hydrate, chlorogenic acid, caffeic acid, p-coumaric acid, sinapic acid, coumarin, and kaempferol) and quantified their respective contents from the PECTS. The GC-MS analysis of the PECTS highlighted the presence of 19 phytochemicals. In addition, the bioactivity study of the PECTS showed remarkable potentiality as antioxidant, anti-inflammatory, and antidiabetic agents. In silico molecular docking and computational molecular modelling were employed to investigate the anti-inflammatory, antioxidant, and antidiabetic properties of the putative bioactive compounds derived from the PECTS using the GC-MS technique to understand the drug-receptor interactions, including their binding pattern. Out of the 19 phytocompounds identified by the GC-MS analysis, one compound, ergosta-5,22-dien-3-ol, acetate, (3ß,22E), exhibited the best binding conformations with the target proteins involved in anti-inflammatory (e.g., Tnf-α and Cox-2), antioxidant (SOD), and antidiabetic (e.g., α-amylase and aldo reductase) activities. The nontoxic nature of this optimised extract was also evident during the in vitro cell toxicity assay against the Vero cell line and the in vivo acute toxicity study on BALB/c mice. We believe the results of the present study will pave the way for the invention of novel drugs efficacious for several ailments using the C. trifolia plant.

Colloidal Synthesis, Characterization, and Photoconductivity of Quasi-Layered CuCrS2 Nanosheets.

The current need to accelerate the adoption of photovoltaic (PV) systems has increased the need to explore new nanomaterials that can harvest and convert solar energy into electricity. Transition metal dichalcogenides (TMDCs) are good candidates because of their tunable physical and chemical properties. CuCrS2 has shown good electrical and thermoelectrical properties; however, its optical and photoconductivity properties remain unexplored. In this study, we synthesized CuCrS2 nanosheets with average dimensions of 43.6 ± 6.7 nm in length and 25.6 ± 4.1 nm in width using a heat-up synthesis approach and fabricated films by the spray-coating method to probe their photoresponse. This method yielded CuCrS2 nanosheets with an optical bandgap of ~1.21 eV. The fabricated film had an average thickness of ~570 nm, exhibiting a net current conversion efficiency of ~11.3%. These results demonstrate the potential use of CuCrS2 as an absorber layer in solar cells.

Correction: Solvent-driven azide-induced mononuclear discrete versus one-dimensional polymeric aromatic Möbius cadmium(II) complexes of an N6 tetradentate helical ligand.

Correction for 'Solvent-driven azide-induced mononuclear discrete versus one-dimensional polymeric aromatic Möbius cadmium(II) complexes of an N6 tetradentate helical ligand' by Farhad Akbari Afkhami et al., Dalton Trans., 2017, 46, 14888-14896, https://doi.org/10.1039/C7DT02952G.

Strain induced anisotropy in liquid phase epitaxy grown nickel ferrite on magnesium gallate substrates.

This work focuses on the nature of magnetic anisotropy in 2.5-16 micron thick films of nickel ferrite (NFO) grown by liquid phase epitaxy (LPE). The technique, ideal for rapid growth of epitaxial oxide films, was utilized for films on (100) and (110) substrates of magnesium gallate (MGO). The motivation was to investigate the dependence of the growth induced anisotropy field on film thickness since submicron films of NFO were reported to show a very high anisotropy. The films grown at 850-875 C and subsequently annealed at 1000 C were found to be epitaxial, with the out-of-plane lattice constant showing unanticipated decrease with increasing film thickness and the estimated in-plane lattice constant increasing with the film thickness. The uniaxial anisotropy field Hσ, estimated from X-ray diffraction data, ranged from 2.8-7.7 kOe with the films on (100) MGO having a higher Hσ value than for the films on (110) MGO. Ferromagnetic resonance (FMR) measurements for in-plane and out-of-plane static magnetic field were utilized to determine both the magnetocrystalline the anisotropy field H4 and the uniaxial anisotropy field Ha. Values of H4 range from -0.24 to -0.86 kOe. The uniaxial anisotropy field Ha was an order of magnitude smaller than Hσ and it decreased with increasing film thickness for NFO films on (100) MGO, but Ha increased with film thickness for films on (110) MGO substrates. These observations indicate that the origin of the induced anisotropy could be attributed to several factors including (i) strain due to mismatch in the film-substrate lattice constants, (ii) possible variations in the bond lengths and bond angles in NFO during the growth process, and (iii) the strain arising from mismatch in the thermal expansion coefficients of the film and the substrate due to the high growth and annealing temperatures involved in the LPE technique. The LPE films of NFO on MGO substrates studied in this work are of interest for use in high frequency devices.

Design, synthesis, in silico, and in vitro evaluation of 3-phenylpyrazole acetamide derivatives as antimycobacterial agents.

Mycobacterium tuberculosis (Mtb) is one of the most dangerous pathogens affecting immunocompetent and immunocompromised patients worldwide. Novel molecules, which are efficient and can reduce the duration of therapy against drug-resistant strains, are an urgent unmet need of the hour. In our current study, a series of new 2-(3-phenyl-1H-pyrazol-1-yl)acetamide and N'-benzylidene-2-(3-phenyl-1H-pyrazol-1-yl)acetohydrazide derivatives were designed, synthesized, and evaluated for their antimycobacterial potential. The biological evaluation revealed that 6b, 6m, 6l, 7a, and 7k exhibited selective and potent inhibitory activity against Mtb. Furthermore, compounds 6m and 7h were found to be nontoxic to Vero cells with CC50 of greater than 20 and 80 mg/ml, respectively, and exhibited promising selectivity indices (SI) of greater than 666 and 320, respectively. All derivatives exhibited excellent ADME (absorption, distribution, metabolism, and excretion) properties in silico. Also, all the derivatives were found compliant with Lipinski's rule of five, showing their druggability profile. Molecular docking insights of these derivatives have shown outstanding binding energies on the mycobacterial membrane protein large transporters. These results indicate that this scaffold may lead to a potential antimycobacterial drug candidate in the discovery of antitubercular agents.

Elastic distortion determining conduction in BiFeO3 phase boundaries.

It is now well-established that boundaries separating tetragonal-like (T) and rhombohedral-like (R) phases in BiFeO3 thin films can show enhanced electrical conductivity. However, the origin of this conductivity remains elusive. Here, we study mixed-phase BiFeO3 thin films, where local populations of T and R can be readily altered using stress and electric fields. We observe that phase boundary electrical conductivity in regions which have undergone stress-writing is significantly greater than in the virgin microstructure. We use high-end electron microscopy techniques to identify key differences between the R-T boundaries present in stress-written and as-grown microstructures, to gain a better understanding of the mechanism responsible for electrical conduction. We find that point defects (and associated mixed valence states) are present in both electrically conducting and non-conducting regions; crucially, in both cases, the spatial distribution of defects is relatively homogeneous: there is no evidence of phase boundary defect aggregation. Atomic resolution imaging reveals that the only significant difference between non-conducting and conducting boundaries is the elastic distortion evident - detailed analysis of localised crystallography shows that the strain accommodation across the R-T boundaries is much more extensive in stress-written than in as-grown microstructures; this has a substantial effect on the straightening of local bonds within regions seen to electrically conduct. This work therefore offers distinct evidence that the elastic distortion is more important than point defect accumulation in determining the phase boundary conduction properties in mixed-phase BiFeO3.

Multinary copper-based chalcogenide nanocrystal systems from the perspective of device applications.

Multinary chalcogenide semiconductor nanocrystals are a unique class of materials as they offer flexibility in composition, structure, and morphology for controlled band gap and optical properties. They offer a vast selection of materials for energy conversion, storage, and harvesting applications. Among the multinary chalcogenides, Cu-based compounds are the most attractive in terms of sustainability as many of them consist of earth-abundant elements. There has been immense progress in the field of Cu-based chalcogenides for device applications in the recent years. This paper reviews the state of the art synthetic strategies and application of multinary Cu-chalcogenide nanocrystals in photovoltaics, photocatalysis, light emitting diodes, supercapacitors, and luminescent solar concentrators. This includes the synthesis of ternary, quaternary, and quinary Cu-chalcogenide nanocrystals. The review also highlights some emerging experimental and computational characterization approaches for multinary Cu-chalcogenide semiconductor nanocrystals. It discusses the use of different multinary Cu-chalcogenide compounds, achievements in device performance, and the recent progress made with multinary Cu-chalcogenide nanocrystals in various energy conversion and energy storage devices. The review concludes with an outlook on some emerging and future device applications for multinary Cu-chalcogenides, such as scalable luminescent solar concentrators and wearable biomedical electronics.

Correction: Giant resistive switching in mixed phase BiFeO3via phase population control.

Correction for 'Giant resistive switching in mixed phase BiFeO3via phase population control' by David Edwards et al., Nanoscale, 2018, 10, 17629-17637.

Nanocrystals of CuMSnS4 (M = In or Ga) for solar energy conversion applications.

Quaternary MIMIIIMIVXVI4 (I-III-IV-VI4) chalcogenides obtained by cross-substitution of binary and ternary compounds remain relatively unexplored. We have for the first-time synthesized wurtzite and defect chalcopyrite phases of CuMSnS4 (M = In or Ga) in the form of nanocrystals. Optical measurements show that the CuMSnS4 (M = In or Ga) nanocrystals exhibit strong visible light absorption with band gap values between 1.15 and 1.4 eV, suitable for solar energy conversion applications.

Giant resistive switching in mixed phase BiFeO3via phase population control.

Highly-strained coherent interfaces, between rhombohedral-like (R) and tetragonal-like (T) phases in BiFeO3 thin films, often show enhanced electrical conductivity in comparison to non-interfacial regions. In principle, changing the population and distribution of these interfaces should therefore allow different resistance states to be created. However, doing this controllably has been challenging to date. Here, we show that local thin film phase microstructures (and hence R-T interface densities) can be changed in a thermodynamically predictable way (predictions made using atomistic simulations) by applying different combinations of mechanical stress and electric field. We use both pressure and electric field to reversibly generate metastable changes in microstructure that result in very large changes of resistance of up to 108%, comparable to those seen in Tunnelling Electro-Resistance (TER) devices.

Synthesis of Wurtzite Cu2ZnSnS4 Nanosheets with Exposed High-Energy (002) Facets for Fabrication of Efficient Pt-Free Solar Cell Counter Electrodes.

Two-dimensional (2D) semiconducting nanomaterials have generated much interest both because of fundamental scientific interest and technological applications arising from the unique properties in two dimensions. However, the colloidal synthesis of 2D quaternary chalcogenide nanomaterials remains a great challenge owing to the lack of intrinsic driving force for its anisotropic growth. 2D wurtzite Cu2ZnSnS4 nanosheets (CZTS-NS) with high-energy (002) facets have been obtained for the first time via a simple one-pot thermal decomposition method. The CZTS-NS exhibits superior photoelectrochemical activity as compared to zero-dimensional CZTS nanospheres and comparable performance to Pt counter electrode for dye sensitized solar cells. The improved catalytic activity can be attributed to additional reactive catalytic sites and higher catalytic reactivity in high-energy (002) facets of 2D CZTS-NS. This is in accordance with the density functional theory (DFT) calculations, which indicates that the (002) facets of wurtzite CZTS-NS possess higher surface energy and exhibits remarkable reducibility for I3- ions. The developed synthetic method and findings will be helpful for the design and synthesis of 2D semiconducting nanomaterials, especially eco-friendly copper chalcogenide nanocrystals for energy harvesting and photoelectric applications.

Solvent-driven azide-induced mononuclear discrete versus one-dimensional polymeric aromatic Möbius cadmium(ii) complexes of an N6 tetradentate helical ligand.

We report the synthesis and structural characterization of a heteroleptic mononuclear discrete complex [Cd(N3)2(L)(MeOH)]·MeOH (1·MeOH) and a one-dimensional coordination polymer of the composition [Cd3(N3)6(L)]n (2), fabricated from Cd(NO3)2·4H2O and the helical organic ligand benzilbis((pyridin-2-yl)methylidenehydrazone) (L) in the presence of two equivalents of NaN3. The formation of different structures is driven by the solvent. The former complex is formed in the presence of MeOH, while the latter complex is formed in EtOH. The CdII centre in 1·MeOH is trapped by the two pyridyl-imine units of the tetradentate ligand L, two azide ligands and one oxygen atom of one methanol ligand with the CdN6O coordination polyhedron yielding a square face monocapped trigonal prism. The asymmetric unit of 2 consists of three symmetrically independent atoms of CdII, six azide anions and one L. The polymeric structure of 2 is realized through chains of the Cd(N3)2 units which are decorated with Cd(N3)2L units. The CdII atoms from the backbone of the coordination polymer have a distorted octahedral coordination, while the remaining CdII atom forms a trigonal prism with two basal planes nearly parallel to each other. In both complexes, the 12π electron chelate ring of the CdL fragment is shown to be aromatic by establishing it as a Möbius object. Hirshfeld surface analysis of 1 in 1·MeOH and L in 2 showed that the structures of both species are highly dominated by HX (X = H, C and N) contacts, of which the latter two are highly favoured, as well as some contribution from highly enriched CC contacts is clearly observed.

Bulk Single Crystal-Like Structural and Magnetic Characteristics of Epitaxial Spinel Ferrite Thin Films with Elimination of Antiphase Boundaries.

Spinel ferrite NiFe2 O4 thin films have been grown on three isostructural substrates, MgAl2 O4 , MgGa2 O4 , and CoGa2 O4 using pulsed laser deposition. These substrates have lattice mismatches of 3.1%, 0.8%, and 0.2%, respectively, with NiFe2 O4 . As expected, the films grown on MgAl2 O4 substrate show the presence of the antiphase boundary defects. However, no antiphase boundaries (APBs) are observed for films grown on near-lattice-matched substrates MgGa2 O4 and CoGa2 O4 . This demonstrates that by using isostructural and lattice-matched substrates, the formation of APBs can be avoided in NiFe2 O4 thin films. Consequently, static and dynamic magnetic properties comparable with the bulk can be realized. Initial results indicate similar improvements in film quality and magnetic properties due to the elimination of APBs in other members of the spinel ferrite family, such as Fe3 O4 and CoFe2 O4 , which have similar crystallographic structure and lattice constants as NiFe2 O4 .

Pathways for Gold Nucleation and Growth over Protein Cages.

Proteins are widely utilized as templates in biomimetic synthesis of gold nanocrystals. However, the role of proteins in mediating the pathways for gold nucleation and growth is not well understood, in part because of the lack of spatial resolution in probing the complicated biomimetic mineralization process. Self-assembled protein cages, with larger size and symmetry, can facilitate in the visualization of both biological and inorganic components. We have utilized bacteriophage P22 protein cages of ∼60 nm diameter for investigating the nucleation and growth of gold nanocrystals. By adding a gold precursor into the solution with preexisting protein cages and a reducing agent, gold nuclei/prenucleation clusters form in solution, which then locate and attach to specific binding sites on protein cages and further grow to form gold nanocrystals. By contrast, addition of the reducing agent into the solution with incubated gold precursor and protein cages leads to the formation of gold nuclei/prenucleation clusters both in solution and on the surface of protein cages that then grow into gold nanocrystals. Because of the presence of cysteine (Cys) with strong gold-binding affinity, gold nanocrystals tend to bind at specific sites of Cys, irrespective of the binding sites of gold ions. Analyzing the results obtained using these alternate routes provide important insights into the pathways of protein-mediated biomimetic nucleation of gold that challenge the importance of incubation, which is widely utilized in the biotemplated synthesis of inorganic nanocrystals.

A Facile Electrochemical Reduction Method for Improving Photocatalytic Performance of α-Fe2O3 Photoanode for Solar Water Splitting.

Electrochemical reduction method is used for the first time to significantly improve the photo-electrochemical performance of α-Fe2O3 photoanode prepared on fluorine-doped tin oxide substrates by spin-coating aqueous solution of Fe(NO3)3 followed by thermal annealing in air. Photocurrent density of α-Fe2O3 thin film photoanode can be enhanced 25 times by partially reducing the oxide film to form more conductive Fe3O4 (magnetite). Fe3O4 helps facilitate efficient charge transport and collection from the top α-Fe2O3 layer upon light absorption and charge separation to yield enhanced photocurrent density. The optimal enhancement can be obtained for <50 nm films because of the short charge transport distance for the α-Fe2O3 layer. Thick α-Fe2O3 films require more charge and overpotential than thinner films to achieve limited enhancement because of the sluggish charge transport over a longer distance to oxidize water. Electrochemical reduction of α-Fe2O3 in unbuffered pH-neutral solution yields much higher but unstable photocurrent enhancement because of the increase in local pH value accompanied by proton reduction at a hematite surface.

A new family of wurtzite-phase Cu2ZnAS4-x and CuZn2AS4 (A = Al, Ga, In) nanocrystals for solar energy conversion applications.

A new family of quaternary semiconductors Cu2ZnAS4-x and CuZn2AS4 (A = Al, Ga, In) has been synthesized in the form of wurtzite phase nanocrystals for the first time. The nanocrystals can be converted to the stannite phase via thermal annealing under a N2 atmosphere. A direct band gap in the visible wavelength region combined with a high absorption cross-section makes these materials promising for solar energy conversion applications.

Synthesis of Hierarchical Nanoporous Microstructures via the Kirkendall Effect in Chemical Reduction Process.

A series of novel hierarchical nanoporous microstructures have been synthesized through one-step chemical reduction of micron size Cu2O and Co3O4 particles. By controlling the reduction time, non-porous Cu2O microcubes sequentially transform to nanoporous Cu/Cu2O/Cu dented cubic composites and hollow eightling-like Cu microparticles. The mechanism involved in the complex structural evolution is explained based on oxygen diffusion and Kirkendall effect. The nanoporous Cu/Cu2O/Cu dented cubic composites exhibit superior electrochemical performance as compared to solid Cu2O microcubes. The reduction of nonporous Co3O4 also exhibits a uniform sequential reduction process from nonporous Co3O4 to porous Co3O4/CoO composites, porous CoO, porous CoO/Co composites, and porous foam-like Co particles. Nanoscale channels originate from the particle surface and eventually develop inside the entire product, resulting in porous foam-like Co microparticles. The Kirkendall effect is believed to facilitate the formation of porous structures in both processes.

Longitudinal spin Seebeck effect contribution in transverse spin Seebeck effect experiments in Pt/YIG and Pt/NFO.

The spin Seebeck effect, the generation of a spin current by a temperature gradient, has attracted great attention, but the interplay over a millimetre range along a thin ferromagnetic film as well as unintended side effects which hinder an unambiguous detection have evoked controversial discussions. Here, we investigate the inverse spin Hall voltage of a 10 nm thin Pt strip deposited on the magnetic insulators Y3Fe5O12 and NiFe2O4 with a temperature gradient in the film plane. We show characteristics typical of the spin Seebeck effect, although we do not observe the most striking features of the transverse spin Seebeck effect. Instead, we attribute the observed voltages to the longitudinal spin Seebeck effect generated by a contact tip induced parasitic out-of-plane temperature gradient, which depends on material, diameter and temperature of the tip.

NanoCOT: Low-Cost Nanostructured Electrode Containing Carbon, Oxygen, and Titanium for Efficient Oxygen Evolution Reaction.

Developing high-efficiency, durable, and low-cost catalysts based on earth-abundant elements for the oxygen evolution reaction (OER) is essential for renewable energy conversion and energy storage devices. In this study, we report a highly active nanostructured electrode, NanoCOT, which contains carbon, oxygen, and titanium, for efficient OER in alkaline solution. The NanoCOT electrode is synthesized from carbon transformation of TiO2 in an atmosphere of methane, hydrogen, and nitrogen at a high temperature. The NanoCOT exhibits enhanced OER catalytic activity in alkaline solution, providing a current density of 1.33 mA/cm(2) at an overpotential of 0.42 V. This OER current density of a NanoCOT electrode is about 4 times higher than an oxidized Ir electrode and 15 times higher than a Pt electrode because of its nanostructured high surface area and favorable OER kinetics. The enhanced catalytic activity of NanoCOT is attributed to the presence of a continuous energy band of the titanium oxide electrode with predominantly reduced defect states of Ti (e.g., Ti(1+), Ti(2+), and Ti(3+)) formed by chemical reduction with hydrogen and carbon. The OER performance of NanoCOT can also be further enhanced by decreasing its overpotential by 150 mV at a current density of 1.0 mA/cm(2) after coating its surface electrophoretically with 2.0 nm IrOx nanoparticles.