Nanoarchitectonics Design Strategy of Metal-Organic Framework and Bio-Metal-Organic Framework Composites for Advanced Wastewater Treatment through Adsorption.

Freshwater depletion is an alarm for finding an eco-friendly solution to treat wastewater for drinking and domestic applications. Though several methods like chlorination, filtration, and coagulation-sedimentation are conventionally employed for water treatment, these methods need to be improved as they are not environmentally friendly, rely on chemicals, and are ineffective for all kinds of pollutants. These problems can be addressed by employing an alternative solution that is effective for efficient water treatment and favors commercial aspects. Metal organic frameworks (MOFs), an emerging porous material, possess high stability, pore size tunability, greater surface area, and active sites. These MOFs can be tailored; thus, they can be customized according to the target pollutant. Hence, MOFs can be employed as adsorbents that effectively target different pollutants. Bio-MOFs are a kind of MOFs that are incorporated with biomolecules, which also possess properties of MOFs and are used as a nontoxic adsorbent. In this review, we elaborate on the interaction between MOFs and target pollutants, the role of linkers in the adsorption of contaminants, tailoring strategy that can be employed on MOFs and Bio-MOFs to target specific pollutants, and we also highlight the effect of environmental matrices on adsorption of pollutants by MOFs.

Metal-organic frameworks (MOFs) for energy production and gaseous fuel and electrochemical energy storage applications.

The increasing energy demands in society and industrial sectors have inspired the search for alternative energy sources that are renewable and sustainable, also driving the development of clean energy storage and delivery systems. Various solid-state materials (e.g., oxides, sulphides, polymer and conductive nanomaterials, activated carbon and their composites) have been developed for energy production (water splitting-H2 production), gaseous fuel (H2 and CH4) storage and electrochemical energy storage (batteries and supercapacitors) applications. Nevertheless, the low surface area, pore volume and conductivity, and poor physical and chemical stability of the reported materials have resulted in higher requirements and challenges in the development of energy production and energy storage technologies. Thus, to overcome these issues, the development of metal-organic frameworks (MOFs) has attracted significant attention. MOFs are a class of porous materials with extremely high porosity and surface area, structural diversity, multifunctionality, and chemical and structural stability, and thus they can be used in a wide range of applications. In the present review, we precisely discuss the interesting properties of MOFs and the various methodologies for their synthesis, and also the future dependence on the valorization of solid waste for the recovery of metals and organic ligands for the synthesis of new classes of MOFs. Subsequently, the utilization of these interesting characteristics for energy production (water splitting), storage of gaseous fuels (H2 and CH4), and electrochemical storage (batteries and supercapacitors) applications are described. However, although MOFs are efficient materials with versatile uses, they still have many challenges, limiting their practical applications. Therefore, finally, we highlight the challenges associated with MOFs and show the way forward in overcoming them for the development of these highly porous materials with large-scale practical utility.

On the physics of dispersive electron transport characteristics in SnO2 nanoparticle-based dye sensitized solar cells.

The present study elucidates dispersive electron transport mediated by surface states in tin oxide (SnO2) nanoparticle-based dye sensitized solar cells (DSSCs). Transmission electron microscopic studies on SnO2 show a distribution of ∼10 nm particles exhibiting (111) crystal planes with inter-planar spacing of 0.28 nm. The dispersive transport, experienced by photo-generated charge carriers in the bulk of SnO2, is observed to be imposed by trapping and de-trapping processes via SnO2 surface states present close to the band edge. The DSSC exhibits 50% difference in performance observed between the forward (4%) and reverse (6%) scans due to the dispersive transport characteristics of the charge carriers in the bulk of the SnO2. The photo-generated charge carriers are captured and released by the SnO2 surface states that are close to the conduction band-edge resulting in a very significant variation; this is confirmed by the hysteresis observed in the forward and reverse scan current-voltage measurements under AM1.5 illumination. The hysteresis behavior assures that the charge carriers are accumulated in the bulk of electron acceptor due to the trapping, and released by de-trapping mediated by surface states observed during the forward and reverse scan measurements.

MoS2 actuators: reversible mechanical responses of MoS2-polymer nanocomposites to photons.

New molybdenum disulfide (MoS2)-based polymer composites and their reversible mechanical responses to light are presented, suggesting MoS2 as an excellent candidate for energy conversion. Homogeneous mixtures of MoS2/polydimethylsiloxane (PDMS) nanocomposites (0.1-5 wt.%) were prepared and their near infrared (NIR) mechanical responses studied with increasing pre-strains. NIR triggering resulted in an extraordinary change in stress levels of the actuators by ~490 times. Actuation responses of MoS2 polymer composites depended on applied pre-strains. At lower levels of pre-strains (3-9%) the actuators showed reversible expansion while at high levels (15-50%), the actuators exhibited reversible contraction. An opto-mechanical conversion (η)∼0.5-3 MPa W(-1) was calculated. The ratio of maximum stress due to photo-actuation (σmax) at 50% strain to the minimum stress due to photo-actuation (σmin) at 3% strain was found to be ∼315-322% for MoS2 actuators (for 0.1 to 5 wt.% additive), greater than single layer graphene (∼188%) and multi-wall nanotube (∼172%) photo-mechanical actuators. Unlike other photomechanical actuators, the MoS2 actuators exhibited strong light-matter interactions and an unambiguous increase in amplitude of photomechanical response with increasing strains. A power law dependence of σmax/σmin on strains with a scaling exponent of ß = 0.87-1.32 was observed, suggesting that the origin of photomechanical response is intertwined dynamically with the molecular mechanisms at play in MoS2 actuators.

Tailoring Interfacial Physicochemical Properties in Cu2O-TiO2@rGO Heterojunction: Insights from EXAFS and Electron Trap Distribution Analysis.

In this study, a solution-based synthesis technique was utilized to produce Cu2O nanoparticles (NPs) on TiO2 nanofibers (TNF), which were then subsequently coated with reduced graphene oxide (rGO) nanosheets. In the absence of any cocatalyst, CTNF@rGO-3% composite displayed an ideal photocatalytic H2 evolution rate of 96 µmol g-1 h-1 under visible light irradiation, this was 10 times higher than that of pure TNF. At 420 nm, the apparent quantum efficiency of this composite reached a maximum of 7.18%. Kelvin probe force microscopy demonstrated the formation of an interfacial electric field that was oriented from CTNF to rGO and served as the driving force for interfacial electron transfer. The successful establishment of an intimate interface between CTNF@rGO facilitated the efficient transfer of charges and suppressed the rate of recombination of photogenerated electron-hole pairs, leading to a substantial enhancement in photocatalytic performance. X-ray photoelectron spectroscopy, photoluminescence spectra, and electrochemical characterization provide further confirmation that formation of a heterojunction between CTNF@rGO leads to an extension in the lifetimes of the photogenerated charge carriers. The experimental evidence suggests that a p-n heterojunction is the mechanism responsible for the significant photocatalytic activity observed in the CTNF@rGO composite during H2 evolution.

Recent development of organic-inorganic hybrid photocatalysts for biomass conversion into hydrogen production.

Over the last few years, photocatalysis using solar radiation has been explored extensively to investigate the possibilities of producing fuels. The production and systematic usage of solar fuels can reduce the use of fossil-based fuels, which are currently the primary source for the energy. It is time for us to exploit renewable sources for our energy needs to progress towards a low-carbon society. This can be achieved by utilizing green hydrogen as the future energy source. Solar light-assisted hydrogen evolution through photocatalytic water splitting is one of the most advanced approaches, but it is a non-spontaneous chemical process and restricted by a kinetically demanding oxidation evolution reaction. Sunlight is one of the essential sources for the photoreforming (PR) of biomass waste into solar fuels, or/and lucrative fine chemicals. Hydrogen production through photoreforming of biomass can be considered energy neutral as it requires only low energy to overcome the activation barrier and an alternate method for the water splitting reaction. Towards the perspective of sustainability and zero emission norms, hydrogen production from biomass-derived feedstocks is an affordable and efficient process. Widely used photocatalyst materials, such as metal oxides, sulphides and polymeric semiconductors, still possess challenges in terms of their performance and stability. Recently, a new class of materials has emerged as organic-inorganic hybrid (OIH) photocatalysts, which have the benefits of both components, with peculiar properties and outstanding energy conversion capability. This work examines the most recent progress in the photoreforming of biomass and its derivatives using OIHs as excellent catalysts for hydrogen evolution. The fundamental aspects of the PR mechanism and different methods of hydrogen production from biomass are discussed. Additionally, an interaction between both composite materials at the atomic level has been discussed in detail in the recent literature. Finally, the opportunities and future perspective for the synthesis and development of OIH catalysts are discussed briefly with regards to biomass photo-reforming.

Assessing the role of plasma-engineered acceptor-like intra- and inter-grain boundaries of heterogeneous WS2-WO3 nanosheets for photocurrent characteristics.

High-temperature annealing in tungsten disulfide resulted in heterogeneous WS2-WO3 in which intra- (within WS2 and WO3) and inter- (between WS2 and WO3) grain boundaries were observed, which were highly critical for charge transport and recombination. The heterogeneous WS2-WO3 phase was evidenced by observing the coexistence of d-spacing values of 0.26 nm (WS2) and 0.37 nm (WO3) in transmission electron microscopic (TEM) studies. Further systematic high-resolution TEM studies elucidated that intra-grain boundaries separated crystallites within WS2 and WO3, while inter-grain boundaries separated WS2 from WO3. As WS2 and WO3 are both n-type, these defects are acceptor-like in the grain boundaries and they actively participate in the capture (trapping) process, which impedes charge transport characteristics in the heterogeneous WS2-WO3 films. Plasma treatment in the heterogeneous WS2-WO3 film, for 60 minutes using argon, energetically modulated the defects in the intra/inter-grain boundaries, as evidenced from detailed comparative photocurrent characteristics obtained individually in (i) pristine WS2, (ii) heterogeneous WS2-WO3 and (iii) Ar plasma-treated heterogeneous WS2-WO3 films under blue and green lasers, along with AM1.5 (1 sun) illumination. Detrimental roles (trapping/de-trapping and scattering) of grain boundary states on photoelectrons were seen to be significantly suppressed under the influence of plasma.

Plasma driven nano-morphological changes and photovoltaic performance in dye sensitized 2D-layered dual oxy-sulfide phase WS2 films.

The present work examined dye sensitized 2D layered tungsten disulfide (WS2) as a photo-anode in solar cells with no use of nanocrystalline metal oxides as electron acceptors such as titanium dioxide. It is observed that coating WS2 directly onto a fluorine doped tin oxide (FTO) transparent conductor, annealed at 530 °C, resulted in a mixed oxy-sulfide dual phase as confirmed by transmission electron microscopy and X-ray diffraction studies. Further studies on the surface morphology of the dual phase WS2-WO3 film showed a random distribution of platelets which further shaped into precisely regulated hexagonal platelets upon plasma treatment. High resolution transmission electron microscopic studies elucidated two different phases, WS2 and WO3, with d-spacing values of 0.26 nm and 0.37 nm, respectively. A well-defined grain boundary was also observed which separated the oxy-sulfide phase in the sample. The dual WS2-WO3 phase films showed optical absorption in the wavelength range of 350 nm-800 nm with a systematic increase in plasma exposure duration. Photovoltaic devices fabricated using the WS2-WO3 mixed phase photo-anodes resulted in 0.61% efficiency (η) which further was observed to be sensitive to the plasma exposure as it was observed that the 20 minute plasma treated sample increased the η value to 0.67%. Plasma treatment on the dual-phase samples orients and modifies the shapes of the platelets with a significant change in the surface which eventually influences the charge transport in resulting photovoltaic devices and thus the variation with respect to exposure duration.

Effects of gas-phase and wet-chemical surface treatments on substrates induced vertical, valley-hill & micro-granular growth morphologies of close space sublimated CdTe films.

We implemented gas-phase (argon plasma) and wet-chemical (HNO3) surface treatments on close space sublimated (CSS) Cadmium Telluride (CdTe) thin films exhibiting morphologies of (i) vertically aligned walls on copper (Cu) and stainless steel (SS) substrates, (ii) valley-hills on aluminum (Al) substrates and (iii) micro-granules on nickel (Ni). As all the growth conditions (temperature, pressure, duration and source/substrate distance) were exactly the same in the CSS process to coat CdTe films, it is asserted that the various microstructures were raised only on Cu, Al, Ni and SS substrates. Plasma and HNO3 surface treatments on metal substrates did not affect the CdTe morphologies in terms of specific structures but it was observed that structural, optical and electrical charge transport characteristics were highly tunable by the two surface treatments. Thus, substrate driven morphological evaluation followed by surface treatments was enabled. The present study demonstrated various microstructures of CdTe films on metallic thin foil substrates to attempt the establishment of flexible opto-electronics based on CdTe.

Two-dimensional layered semiconductor/graphene heterostructures for solar photovoltaic applications.

Schottky barriers formed by graphene (monolayer, bilayer, and multilayer) on 2D layered semiconductor tungsten disulfide (WS2) nanosheets are explored for solar energy harvesting. The characteristics of the graphene-WS2 Schottky junction vary significantly with the number of graphene layers on WS2, resulting in differences in solar cell performance. Compared with monolayer or stacked bilayer graphene, multilayer graphene helps in achieving improved solar cell performance due to superior electrical conductivity. The all-layered-material Schottky barrier solar cell employing WS2 as a photoactive semiconductor exhibits efficient photon absorption in the visible spectral range, yielding 3.3% photoelectric conversion efficiency with multilayer graphene as the Schottky contact. Carrier transport at the graphene/WS2 interface and the interfacial recombination process in the Schottky barrier solar cells are examined.

Extraordinary photoresponse in two-dimensional In(2)Se(3) nanosheets.

We demonstrate extraordinary photoconductive behavior in two-dimensional (2D) crystalline indium selenide (In2Se3) nanosheets. Photocurrent measurements reveal that semiconducting In2Se3 nanosheets have an extremely high response to visible light, exhibiting a photoresponsivity of 3.95 × 10(2) A·W(-1) at 300 nm with an external quantum efficiency greater than 1.63 × 10(5) % at 5 V bias. The key figures-of-merit exceed that of graphene and other 2D material-based photodetectors reported to date. In addition, the photodetector has a fast response time of 1.8 × 10(-2) s and a specific detectivity of 2.26 × 10(12) Jones. The photoconductive response of α-In2Se3 nanosheets extends into ultraviolet, visible, and near-infrared spectral regions. The high photocurrent response is attributed to the direct band gap (EG = 1.3 eV) of In2Se3 combined with a large surface-area-to-volume ratio and a self-terminated/native-oxide-free surface, which help to reduce carrier recombination while keeping fast response, allowing for real-time detection under very low-light conditions.

2D layered insulator hexagonal boron nitride enabled surface passivation in dye sensitized solar cells.

A two-dimensional layered insulator, hexagonal boron nitride (h-BN), is demonstrated as a new class of surface passivation materials in dye-sensitized solar cells (DSSCs) to reduce interfacial carrier recombination. We observe ~57% enhancement in the photo-conversion efficiency of the DSSC utilizing h-BN coated semiconductor TiO2 as compared with the device without surface passivation. The h-BN coated TiO2 is characterized by Raman spectroscopy to confirm the presence of highly crystalline, mixed monolayer/few-layer h-BN nanoflakes on the surface of TiO2. The passivation helps to minimize electron-hole recombination at the TiO2/dye/electrolyte interfaces. The DSSC with h-BN passivation exhibits significantly lower dark saturation current in the low forward bias region and higher saturation in the high forward bias region, respectively, suggesting that the interface quality is largely improved without impeding carrier transport at the material interface. The experimental results reveal that the emerging 2D layered insulator could be used for effective surface passivation in solar cell applications attributed to desirable material features such as high crystallinity and self-terminated/dangling-bond-free atomic planes as compared with high-k thin-film dielectrics.

Layered semiconductor molybdenum disulfide nanomembrane based Schottky-barrier solar cells.

We demonstrate Schottky-barrier solar cells employing a stack of layer-structured semiconductor molybdenum disulfide (MoS(2)) nanomembranes, synthesized by the chemical-vapor-deposition method, as the critical photoactive layer. An MoS(2) nanomembrane forms a Schottky-barrier with a metal contact by the layer-transfer process onto an indium tin oxide (ITO) coated glass substrate. Two vibrational modes in MoS(2) nanomembranes, E(1)(2g) (in-plane) and A(1g) (perpendicular-to-plane), were verified by Raman spectroscopy. With a simple stacked structure of ITO-MoS(2)-Au, the fabricated solar cell demonstrates a photo-conversion efficiency of 0.7% for ~110 nm MoS(2) and 1.8% for ~220 nm MoS(2). The improvement is attributed to a substantial increase in photonic absorption. The MoS(2) nanomembrane exhibits efficient photo-absorption in the spectral region of 350-950 nm, as confirmed by the external quantum efficiency. A sizable increase in MoS(2) thickness results in only minor change in Mott-Schottky behavior, indicating that defect density is insensitive to nanomembrane thickness attributed to the dangling-bond-free layered structure.