Transition-metal-based Catalysts for Electrochemical Synthesis of Ammonia by Nitrogen Reduction Reaction: Advancing the Green Ammonia Economy.

Ammonia (NH3 ), a cornerstone in the chemical industry, has historically been pivotal for producing various valuable products, notably fertilizers. Its significance is further underscored in the modern energy landscape, where NH3 is seen as a promising medium for hydrogen storage and transportation. However, the conventional Haber-Bosch process, which accounts for approximately 170 million ton of NH3 produced globally each year, is energy-intensive and environmentally damaging. The electrochemical nitrogen reduction reaction (NRR) emerges as a sustainable alternative that operates in ambient conditions and uses renewable energy sources. Despite its potential, the NRR faces challenges, including the inherent stability of nitrogen and its competition with the hydrogen evolution reaction. Transition metals, especially ruthenium (Ru) and molybdenum (Mo), have demonstrated promise as catalysts, enhancing the efficiency of the NRR. Ru excels in catalytic activity, while Mo offers robustness. Strategies like heteroatom doping are being pursued to mitigate NRR challenges, especially the competing hydrogen evolution reaction. This review delves into the advancements of Ru and Mo-based catalysts for electrochemical ammonia synthesis, elucidating the NRR mechanisms, and championing the transition towards a greener ammonia economy. It also seeks to elucidate the core principles underpinning the NRR mechanism. This shift aims not only to address challenges inherent to traditional production methods but also to align with the overarching goals of global sustainability.

Facile deposition of FeNi/Ni hybrid nanoflower electrocatalysts for effective and sustained water oxidation.

Bimetallic iron-nickel (FeNi) compounds are widely studied materials for the oxygen evolution reaction (OER) owing to their high electrocatalytic performance and low cost. In this work, we produced thin films of the FeNi alloy on nickel foam (NF) by using an aerosol-assisted chemical deposition (AACVD) method and examined their OER catalytic activity. The hybrid FeNi/Ni catalysts obtained after 1 and 2 h of AACVD deposition show improved charge transfer and kinetics for the OER due to the strong interface between the FeNi alloy and Ni support. The FeNi/Ni-2h catalyst has higher catalytic activity than the FeNi/Ni-1h catalyst because of its nanoflower morphology that provides a large surface area and numerous active sites for the OER. Therefore, the FeNi/Ni-2h catalyst exhibits low overpotentials of 300 and 340 mV at 50 and 500 mA cm-2 respectively, and excellent stability over 100 h, and ∼0% loss after 5000 cycles in 1 M KOH electrolyte. Furthermore, this catalyst has a small Tafel slope, low charge transfer resistance and high current exchange density and thus surpasses the benchmark IrO2 catalyst. The easy, simple, and scalable AACVD method is an effective way to develop thin film electrocatalysts with high activity and stability.

Recent Advances in Processing and Applications of Heterobimetallic Oxide Thin Films by Aerosol-Assisted Chemical Vapor Deposition.

The fabrication of smart, efficient, and innovative devices critically needs highly refined thin-film nanomaterials; therefore, facile, scalable, and economical methods of thin films production are highly sought-after for the sustainable growth of the hi-tech industry. The chemical vapor deposition (CVD) technique is widely implemented at the industrial level due to its versatile features. However, common issues with a precursor, such as reduced volatility and thermal stability, restrict the use of CVD to produce novel and unique materials. A modified CVD approach, named aerosol-assisted CVD (AACVD), has been the center of attention due to its remarkable tendency to fabricate uniform, homogenous, and distinct nano-architecture thin films in an uncomplicated and straightforward manner. Above all, AACVD can utilize any custom-made or commercially available precursors, which can be transformed into a transparent solution in a common organic solvent; thus, a vast array of compounds can be used for the formation of nanomaterial thin films. This review article highlights the importance of AACVD in fabricating heterobimetallic oxide thin films and their potential in making energy production (e. g., photoelectrochemical water splitting), energy storage (e. g., supercapacitors), and environmental protection (e. g., electrochemical sensors) devices. A heterobimetallic oxide system involves two metallic species either in a composite, solid solution, or metal-doped metal oxides. Moreover, the AACVD tunable parameters, such as temperature, deposition time, and precursor, which drastically affect thin films microstructure and their performance in device applications, are also discussed. Lastly, the key challenges and issues of scaling up AACVD to the industrial level and processing for emerging functional materials are also highlighted.

Aerosol-Assisted Chemical Vapor Deposition Growth of NiMoO4 Nanoflowers on Nickel Foam as Effective Electrocatalysts toward Water Oxidation.

The fabrication of active and durable catalysts derived from transition metals is highly desired for the realization of efficient water oxidation reactions. This is particularly important to address the slow oxygen evolution reaction (OER) kinetics and hence can contribute to the conversion and storage of sustainable energy. In this study, the deposition of crystalline flowerlike 2D nanosheets of nickel molybdate (NiMoO4) directly on nickel foam (NF) through an aerosol-assisted chemical vapor deposition process is reported. The NiMoO4 nanosheets were developed on NF by altering the deposition time for 60 and 120 min at a fixed temperature of 480 °C. The structural determination by XRD and XPS analyses revealed a highly crystalline single phase NiMoO4. The micrographs of NiMoO4 show that the surface consisted of vertically aligned 2D nanosheets assembled into flowerlike structures. The nanosheets produced after 60 min deposition time on a network of NF is found to perform better for OER as compared to the one developed for 120 min. A reference current density of 10 mA cm-2 was achieved at an overpotential (η) of 320 mV, which was better as compared to that reported for the benchmark OER catalyst in 1.0 M KOH. Moreover, a small Tafel value (75 mV dec-1) and good OER stability for >15 h were also observed.

Rapid antibody diagnostics for SARS-CoV-2 adaptive immune response.

The emergence of a pandemic scale respiratory illness (COVID-19: coronavirus disease 2019) and the lack of the world's readiness to prevent its spread resulted in an unprecedented rise of biomedical diagnostic industries, as they took lead to provide efficient diagnostic solutions for COVID-19. However, these circumstances also led to numerous emergency use authorizations without appropriate evaluation that compromised standards, which could result in a larger than usual number of false-positive or false-negative results, leading to unwanted ambiguity in already confusing realities of the pandemic-hit closures of the world economy. This review is aimed at comparing the claimed or reported clinical sensitivity and clinical specificity of commercially available rapid antibody diagnostics with independently evaluated clinical performance results of the tests. Thereby, we not only present the types of modern antibody diagnostics and their working principles but summarize their experimental evaluations and observed clinical efficiencies to highlight the research, development, and commercialization issues with future challenges. Still, it must be emphasized that the serological or antibody tests do not serve the purpose of early diagnosis but are more suitable for epidemiology and screening populaces with an active immune response, recognizing convalescent plasma donors, and determining vaccine efficacy.

Design, Development and Evaluation of Thermal Properties of Polysulphone-CNT/GNP Nanocomposites.

Polysulphone (PSU) composites with carbon nanotubes (PSU-CNT) and graphene nanoplatelets (PSU-GNP) were developed through the solution casting process, using various weight load percentages of 1, 3, 5, and 10 wt% of CNT and GNP nanofillers. The microstructural and thermal properties of the PSU-based composites were compared. The microstructural characterisation of both composites (PSU-CNTs and PSU-GNPs) showed a strong matrix-filler interfacial interaction and uniform dispersion of CNTs and GNPs in the PSU matrix. The analysis demonstrated that both the thermal conductivity and effusivity improved with the increase in the weight percentage (wt%) of CNTs and GNPs because of the percolation effect. The polysulphone-based composite containing 10 wt% CNTs showed a remarkably high thermal conductivity value of 1.13 (W/m·K), which is 163% times higher than pure PSU. While the glass transition temperature (Tg) was shifted to a higher temperature, the thermal expansion was reduced in all the PSU-CNT and PSU-GNP composites. Interestingly, the CNTs allowed homogeneous distribution and a reasonably good interfacial network of interaction with the PSU matrix, leading to better microstructural characteristics and thermal properties than those of the PSU-GNP composites. The findings highlight the importance of controlling the nature, distribution, and content of fillers within the polymeric matrix.

Screen-Printed Graphene/Carbon Electrodes on Paper Substrates as Impedance Sensors for Detection of Coronavirus in Nasopharyngeal Fluid Samples.

Severe acute respiratory syndrome (SARS-CoV-2), the causative agent of the global pandemic, which has resulted in more than one million deaths with tens of millions reported cases, requires a fast, accurate, and portable testing mechanism operable in the field environment. Electrochemical sensors, based on paper substrates with portable electrochemical devices, can prove an excellent alternative in mitigating the economic and public health effects of the disease. Herein, we present an impedance biosensor for the detection of the SARS-CoV-2 spike protein utilizing the IgG anti-SARS-CoV-2 spike antibody. This label-free platform utilizing screen-printed electrodes works on the principle of redox reaction impedance of a probe and can detect antigen spikes directly in nasopharyngeal fluid as well as virus samples collected in the universal transport medium (UTM). High conductivity graphene/carbon ink is used for this purpose so as to have a small background impedance that leads to a wider dynamic range of detection. Antibody immobilization onto the electrode surface was conducted through a chemical entity or a biological entity to see their effect; where a biological immobilization can enhance the antibody loading and thereby the sensitivity. In both cases, we were able to have a very low limit of quantification (i.e., 0.25 fg/mL), however, the linear range was 3 orders of magnitude wider for the biological entity-based immobilization. The specificity of the sensor was also tested against high concentrations of H1N1 flu antigens with no appreciable response. The most optimized sensors are used to identify negative and positive COVID-19 samples with great accuracy and precision.

Aerosol-assisted nanostructuring of nickel/cobalt oxide thin films for viable electrochemical hydrazine sensing.

Herein, we report the fabrication of NiO-CoO films for the electrochemical detection of hydrazine. An electrochemical sensor was devised where aerosol assisted chemical vapor deposition (AACVD) was employed as a nifty method for synthesizing NiO-CoO films over FTO electrodes. NiO-CoO-nanoparticle (NP) and NiO-CoO-nanowall (NW) films were fabricated over FTO substrates. The electrocatalytic analysis was performed in a standard three-electrode electrochemical setup. NiO-CoO-NW/FTO showed enhanced electro-oxidation for hydrazine at all concentrations tested. XRD, XPS, EDX, and FE-SEM techniques were used to characterize the structural, morphological, and elemental properties of NiO-CoO films. The results showed improved sensitivity, a large dynamic range, and good long-term stability of NiO-CoO-NW films. The amperometric response was used to measure the detection limit, and it was as low as 0.01 µM, and the sensitivity is ∼33 µA µM-1 cm-2. Besides, the NiO-CoO-NW/FTO electrodes showed significant selectivity towards hydrazine upon testing cross-sensitivity to other common interfering molecules. This strategy of using NiO-CoO-NW/FTO electrodes prepared via AACVD has great potential for the direct determination of hydrazine in environmental sensing applications.

First theoretical framework of Z-shaped acceptor materials with fused-chrysene core for high performance organic solar cells.

Chrysene core containing fused ring acceptor materials have remarkable efficiency for high performance organic solar cells. Therefore, present study has been carried out with the aim to design chrysene based novel Z-shaped electron acceptor molecules (Z1-Z6) from famous Z-shaped photovoltaic material FCIC (R) for organic photovoltaic applications. End-capped engineering at two electron-accepting end groups 1,1-dicyanomethylene-3-indanone of FCIC is made with highly efficient end-capped acceptor moieties and impact of end-capped modifications on structure-property relationship, photovoltaic and electronic properties of newly designed molecules (Z1-Z6) has been studied in detail through DFT and TDDFT calculations. The efficiencies of the designed molecules are evaluated through energy gaps, exciton binding energy along with transition density matrix (TDM) analysis, reorganizational energy of electron and hole, absorption maxima and open circuit voltage of investigated molecules. The designed molecules exhibit red-shift and intense absorption in near-infrared region (683-749 nm) of UV-Vis-NIR absorption spectrum with narrowing of HOMO-LUMO energy gap from 2.31 eV in R to 1.95 in eV in Z5. Moreover, reduction in reorganization energy of electron from 0.0071 (R) to 0.0049 (Z5), and enhancement in open circuit voltage from 1.08 V in R to 1.20 V in Z5 are also observed. Twisted Z-shape of designed molecules prevents self-aggregation that facilitates miscibility of donor and acceptor. Low values of binding energy, excitation energy, and reorganizational energy (electron and hole) suggest that novel designed molecules offer high charge mobilities as compared to FCIC. Our findings indicate that these novel designed molecules can display better photovoltaic parameters and are suitable candidates if used in organic solar cells.

Synergistic effects in bimetallic Pd-CoO electrocatalytic thin films for oxygen evolution reaction.

Bimetallic catalysts due to the synergistic effects often outperform their single-component counterparts while exhibiting structure and composition-dependent enhancement in active sites, thereby having the potential to improve the current density and over-potential parameters in the water oxidation reaction. Herein, we demonstrate a simple and rapid, yet highly efficient method to fabricate Pd-CoO films of immaculate homogeneity as characterized using different imaging and spectroscopic techniques. The SEM images revealed that the films were composed of bimetallic spherical granules wherein both metals were uniformly distributed in an atomic ratio of ~ 1:1. The time-dependent investigations of the film fabrication behavior demonstrated that the films formed in shorter deposition times (1-2 h) display more porous character, allowing better access to the reaction centers. This character was transcribed into their enhanced electrocatalytic performance toward the oxygen evolution reaction (OER). Using this specific bimetallic formulation, we could attain a low over-potential of 274 mV for a current density of 10 mA cm-2, whereas the high current density value of > 200 mA cm-2 was achieved while still under 600 mV of over-potential. The cycling and current generation stability was also found to be sufficiently high, which can only be attributed to the facile electron transfer processes and a higher number of active sites available in homogeneous bimetallic films.

Facile and scalable fabrication of nanostructured nickel thin film electrodes for electrochemical detection of formaldehyde.

Fluorine doped tin oxide (FTO) substrates were deposited with thin metallic nickel films, having distinguishable surface morphologies, via a rapid, facile, and scalable approach i.e., aerosol assisted chemical vapor deposition (AACVD). The growth patterns of the nickel deposits were studied, showing a coalescing behavior as a function of the deposition time in a hierarchical fashion. These studies were followed by electrochemical measurements to design an efficient sensor for formaldehyde detection. The electrochemical responses were correlated with the surface characteristics of the films, whereas the optimized parameters were subjected to the evaluation of sensing performances. The developed sensor demonstrated a detection limit of 8.3 × 10-6 M and a sensitivity of 0.18 A M-1 within a linear range of 0-6.5 mM. Further, the sensor showed a response time of less than 5 s, selectivity against similar concentrations of methanol and formaldehyde, and recovery of ∼102% in a spiked fruit juice sample. Finally, the commercial viability of the fabrication procedure is tested using batch production analysis, and the high reproducibility of the data shows a promising future in mass production. It is envisaged that such low-cost fabrication procedures can be converted into many useful applications in the future.

Highly cytotoxic gold(i)-phosphane dithiocarbamate complexes trigger an ER stress-dependent immune response in ovarian cancer cells.

Ovarian cancer is a highly aggressive disease which is treated by surgery and platinum chemotherapy. However, a significant proportion of treated patients develop resistance to platinum treatment resulting in tumor relapse. Acquired platinum resistance has been recently correlated with activation of pro-survival endoplasmic reticulum (ER) stress responses. We hypothesized that Au complexes that induce severe ER stress might counteract pro-survival cellular attempts leading to the ER stress-mediated apoptosis and reduced platinum resistance. In this work, we prepared a series of highly cytotoxic AuI-dialkyldithiocarbamate complexes and investigated their anticancer potential in ovarian cancer cells. Complexes demonstrated surprisingly low stability in chloroform, resulting in the formation of an Au chain polymer, which also displayed excellent cytotoxicity. Lead complex 2 induced oxidative stress and ER stress-mediated p53-independent apoptosis associated with PARP cleavage and cell cycle arrest at G2/M phase. Importantly, 2 caused the surface exposure of calreticulin (CRT), which is the first step in the activation of cellular immunogenic response.

The Property Characterization of α-Sialon/Ni Composites Synthesized by Spark Plasma Sintering.

This study investigates the effect of micron-sized nickel particle additions on the microstructural, thermal, and mechanical property changes of α-sialon ceramic composites. The α-sialon/Ni composites were synthesized with an increasing amount of Ni (10-40 wt.%) using the spark plasma sintering technique and nanosized alpha precursors at a relatively low synthesis temperature of 1500 °C with a holding time of 30 min in each case. The density of the samples increased with the increase in Ni content of up to 15 wt.% and, with the further increase in Ni content, it became almost constant with a slight decrease. Furthermore, thermal conductivity and thermal expansion properties of Ni-sialon composites improved slightly with the inclusion of 10 wt.% Ni. The addition of Ni to α-sialon matrix resulted in a decrease in the hardness of the composites from HV10 21.6 to HV10 16.3, however the presence of Ni as a softer interfacial phase resulted in a substantial increase in the fracture toughness of these composites. Fracture toughness was found to increase by approximately 91% at 40 wt.% Ni addition.

Direct Deposition of Amorphous Cobalt-Vanadium Mixed Oxide Films for Electrocatalytic Water Oxidation.

Efficiency of water oxidation catalysts in terms of overpotential, current density, and voltage stability over time with facile methods of their fabrication remains a key challenge in developing competent mechanisms of storing energy in the form of green hydrogen fuels. In this work, a rapid one-step aerosol-assisted chemical vapor deposition (AACVD) method is employed to synthesize amorphous and highly active cobalt-vanadium mixed oxide catalysts (CoVOx) directly over fluorine-doped tin oxide (FTO) substrates. Morphological and structural characterizations made by field emission scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy techniques revealed the formation of pure-phase amorphous films with a gradual variation of topography as a function of deposition time. Of these films, the most active film (CoVOx-20) was obtained in 20 min deposition, showing a spongy networking of interwoven nanofibers with a homogeneous distribution of 3-4 nm pores, achieving an overpotential of 308 mV at 10 mA/cm2 current density. A much higher current density of 175 mA/cm2 could be achieved just at 380 mV of overpotential with Tafel slope as low as 62 mV/dec for this whole range while exhibiting long-term stability. Mass activity, electrochemical impedance spectroscopy data, and the estimation of electrochemically active surface area all endorsed this high catalytic performance of CoVOx-20, which is unprecedented for a low-cost, upscalable, and relatively less conductive substrate such as FTO used here. Our findings, thus, not only highlight the benefits of using AACVD in preparing two-dimensional amorphous catalysts but also prove the high efficiency of CoVOx materials thus obtained, as outlined in a plausible reaction mechanism.

Fabrication of CoTiO3-TiO2 composite films from a heterobimetallic single source precursor for electrochemical sensing of dopamine.

Cobalt titanate-titania composite oxide films have been grown on FTO-coated glass substrates using a single-source heterometallic complex [Co2Ti4(µ-O)6(TFA)8(THF)6]·THF () which was obtained in quantitative yield from the reaction of diacetatocobalt(ii) tetrahydrate, tetraisopropoxytitanium(iv), and trifluoroacetic acid from a tetrahydrofuran solution. Physicochemical investigations of complex have been carried out by melting point, FT-IR, thermogravimetric and single-crystal X-ray diffraction analyses. CoTiO3-TiO2 films composed of spherical objects of various sizes have been grown from by aerosol-assisted chemical vapor deposition at different temperatures of 500, 550 and 600 °C. Thin films characterized by XRD, Raman and X-ray photoelectron spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis have been explored for electrochemical detection of dopamine (DA). The cyclic voltammetry with the CoTiO3-TiO2 electrode showed a DA oxidation peak at +0.215 V while linear sweep voltammetry displayed a detection limit (LoD) of 0.083 µM and a linear concentration range of 20-300 µM for DA. Thus, the CoTiO3-TiO2 electrode is a potential candidate for the sensitive and selective detection of DA.

Core-Shell Vanadium Modified Titania@ß-In2S3 Hybrid Nanorod Arrays for Superior Interface Stability and Photochemical Activity.

Core-shell rutile TiO2@ß-In2S3 and modified V-TiO2@ß-In2S3 were synthesized to develop bilayer systems to uphold charge transport via an effective and stable interface. Morphological studies revealed that ß-In2S3 was deposited homogeneously on V-TiO2 as compared to unmodified TiO2 nanorod arrays. X-ray photoelectron spectroscopy (XPS) and electron energy loss spectrometry studies verified the presence of various oxidation states of vanadium in rutile TiO2 and the vanadium surface was utilized for broadening the charge collection centers in host substrate layer and hole quencher window. Subsequently, X-ray diffraction, high-resolution transmission electron microscopy, and Raman spectra confirmed the rutile phases of TiO2 and modified V-TiO2 along with the phases of crystalline ß-In2S3. XPS valence band study explored the interaction of valence band quazi Fermi levels of ß-In2S3 with the conduction band quazi Fermi levels of modified V-TiO2 for enhanced charge collection at the interface. Photoelectrochemical studies show that the photocurrent density of V-TiO2@ß-In2S3 is 1.42 mA/cm(2) (1.5AM illumination). Also, the frequency window for TiO2 was broadened by the vanadium modification in rutile TiO2 nanorod arrays, and the lifetime of the charge carrier and stability of the interface in V-TiO2@ß-In2S3 were enhanced compared to the unmodified TiO2@ß-In2S3. These findings highlight the significance of modifications in host substrates and interfaces, which have profound implications on interphase stability, photocatalysis and solar-fuel-based devices.

Development of molecular precursors for deposition of indium sulphide thin film electrodes for photoelectrochemical applications.

Symmetrical and unsymmetrical dithiocarbamato pyridine solvated and non-solvated complexes of indium(III) with the general formula [In(S2CNRR')3]·n(py) [where py = pyridine; R,R' = Cy, n = 2 (1); R,R' = (i)Pr, n = 1.5 (2); NRR' = Pip, n = 0.5 (3) and R = Bz, R' = Me, n = 0 (4)] have been synthesized. The compositions, structures and properties of these complexes have been studied by means of microanalysis, IR and (1)H-NMR spectroscopy, X-ray single crystal and thermogravimetric (TG/DTG) analyses. The applicability of these complexes as single source precursors (SSPs) for the deposition of ß-In2S3 thin films on fluorine-doped SnO2 (FTO) coated conducting glass substrates by aerosol-assisted chemical vapour deposition (AACVD) at temperatures of 300, 350 and 400 °C is studied. All films have been characterized by powder X-ray diffraction (PXRD) and energy dispersive X-ray analysis (EDX) for the detection of phase and stoichiometry of the deposit. Scanning electron microscopy (SEM) studies reveal that precursors (1)-(4), irrespective of different metal ligand design, generate comparable morphologies of ß-In2S3 thin films at different temperatures. Direct band gap energies of 2.2 eV have been estimated from the UV-vis spectroscopy for the ß-In2S3 films fabricated from precursors (1) and (4). The photoelectrochemical (PEC) properties of ß-In2S3 were confirmed by recording the current-voltage plots under light and dark conditions. The plots showed anodic photocurrent densities of 1.25 and 0.65 mA cm(-2) at 0.23 V vs. Ag/AgCl for the ß-In2S3 films made at 400 and 350 °C from the precursors (1) and (4), respectively. The photoelectrochemical performance indicates that the newly synthesised precursors are highly useful in fabricating ß-In2S3 electrodes for solar energy harvesting and optoelectronic application.

Bis(O-n-butyl dithio-carbonato-κS,S')bis-(pyridine-κN)manganese(II).

The structure of the title manganese complex, [Mn(C(5)H(9)OS(2))(2)(C(5)H(5)N)(2)] or [Mn(S(2)CO-n-Bu)(2)(C(5)H(5)N)(2)], consists of discrete monomeric entities with Mn(2+) ions located on centres of inversion. The metal atom is coordinated by a six-coordinate trans-N(2)S(4) donor set with the pyridyl N atoms located in the apical positions. The observed slight deviations from octa-hedral geometry are caused by the bite angle of the bidentate κ(2)-S(2)CO-n-Bu ligands [69.48 (1)°]. The O(CH(2))(3)(CH(3)) chains of the O-n-butyl dithio-carbonate units are disordered over two sets of sites with an occupancy ratio of 0.589 (2):0.411 (2).