Hydrophobic Microenvironment Modulation of Ru Nanoparticles in Metal-Organic Frameworks for Enhanced Electrocatalytic N2 Reduction.

The modulation of the chemical microenvironment surrounding metal nanoparticles (NPs) is an effective means to enhance the selectivity and activity of catalytic reactions. Herein, a post-synthetic modification strategy is developed to modulate the hydrophobic microenvironment of Ru nanoparticles encapsulated in a metal-organic framework (MOF), MIP-206, namely Ru@MIP-Fx (where x represents perfluoroalkyl chain lengths of 3, 5, 7, 11, and 15), in order to systematically explore the effect of the hydrophobic microenvironment on the electrocatalytic activity. The increase of perfluoroalkyl chain length can gradually enhance the hydrophobicity of the catalyst, which effectively suppresses the competitive hydrogen evolution reaction (HER). Moreover, the electrocatalytic production rate of ammonia and the corresponding Faraday efficiency display a volcano-like pattern with increasing hydrophobicity, with Ru@MIP-F7 showing the highest activity. Theoretical calculations and experiments jointly show that modification of perfluoroalkyl chains of different lengths on MIP-206 modulates the electronic state of Ru nanoparticles and reduces the rate-determining step for the formation of the key intermediate of N2H2 *, leading to superior electrocatalytic performance.

The recent advances in the approach of artificial intelligence (AI) towards drug discovery.

Artificial intelligence (AI) has recently emerged as a unique developmental influence that is playing an important role in the development of medicine. The AI medium is showing the potential in unprecedented advancements in truth and efficiency. The intersection of AI has the potential to revolutionize drug discovery. However, AI also has limitations and experts should be aware of these data access and ethical issues. The use of AI techniques for drug discovery applications has increased considerably over the past few years, including combinatorial QSAR and QSPR, virtual screening, and denovo drug design. The purpose of this survey is to give a general overview of drug discovery based on artificial intelligence, and associated applications. We also highlighted the gaps present in the traditional method for drug designing. In addition, potential strategies and approaches to overcome current challenges are discussed to address the constraints of AI within this field. We hope that this survey plays a comprehensive role in understanding the potential of AI in drug discovery.

Highly Selective Electroreduction of Nitrobenzene to Aniline by Co-Doped 1T-MoS2.

The selective electrocatalytic reduction of nitrobenzene (NB) to aniline demands a desirable cathodic catalyst to overcome the challenges of the competing hydrogen evolution reaction (HER), a higher overpotential, and a lower selectivity. Here, we deposit Co-doped 1T MoS2 on Ti mesh by the solvothermal method with different doping percentages of Co as x % Co-MoS2 (where x = 3, 5, 8, 10, and 12%). Because of the lowest overpotential, lower charge-transfer resistance, strong suppression of the competing HER, and higher electrochemical surface area, 8% Co-MoS2 achieves 94% selectivity of aniline with 54% faradaic efficiency. The reduction process follows first-order dynamics with a reaction coefficient of 0.5 h-1. Besides, 8% Co-MoS2 is highly stable and retains 81% selectivity even after 8 cycles. Mechanistic studies showed that the selective and exothermic adsorption of the nitro group at x % Co-MoS2 leads to a higher rate of NB reduction and higher selectivity of aniline. The aniline product is successfully removed from the solution by polymerization at FTO. This study signifies the impact of doping metal atoms in tuning the electronic arrangement of 1T-MoS2 for the facilitation of organic transformations.

Efficient Adsorption of Methylene Blue Using a Hierarchically Structured Metal-Organic Framework Derived from Layered Double Hydroxide.

The growing concerns about environmental pollution, particularly water pollution, are causing an increasing alarm in modern society. One promising approach to address this issue involves engineering existing materials to enhance their effectiveness. A one-step solvothermal reconstruction approach was used to build an eco-friendly two-dimensional (2D) AlNiZn-LDH/BDC MOF composite. The characterizations confirm the formation of a metal-organic framework (MOF) at the layered double hydroxide (LDH) surface. The resulting synthesized material, 2D AlNiZn-LDH/BDC MOF, demonstrated remarkable efficacy in decontaminating methylene blue (MB), a model cationic dye found in water systems. The removal performance of 2D AlNiZn-LDH/BDC MOF was significantly higher than that of pristine 2D AlNiZn-LDH. This improvement shows the potential to increase the adsorption capabilities of nanoporous LDH materials by incorporating organic ligands and integrating meso-/microporosity through MOF formation on their surfaces. Furthermore, their kinetic, isothermal, and thermodynamic studies elucidated the adsorption behavior of this composite material. The results of synthesized MOF showed excellent removal efficiency (92.27%) of 10 ppm of MB aqueous solution as compared to pristine LDH. Additionally, the as-synthesized adsorbent could be regenerated for six successive cycles. This method holds promise for the synthesis of novel and highly effective materials to combat water pollution, laying the groundwork for potential advancements in diverse applications.

Engineering Mn-Doped CdS Thin Films Through Chemical Bath Deposition for High-Performance Photoelectrochemical Water Splitting.

Doping conventional materials with a second element is an exciting strategy for enhancing catalytic performance via electronic structure modifications. Herein, Mn-doped CdS thin films were successfully synthesized with the aid of the chemical bath deposition (CBD) by varying the pH value (8, 10, and 12) and the surfactant amount (20, 40, 60 mg). Different morphologies like nano-cubes, nanoflakes, nano-worms, and nanosheets were obtained under different deposition conditions. The optimized Mn-doped CdS synthesized at pH=8 exhibited better photoelectrochemical (PEC) performance for oxygen evolution reaction (OER) than pure CdS films, with a maximum photocurrent density of 300 µA/cm2 at an external potential of 0.5 V, under sunlight illumination. The observed performance is attributed to the successful Mn doping, porosity, high surface area, and nanosphere morphology.

Recent Advances of Transition Metal Dichalcogenides-Based Materials for Energy Storage Devices, in View of Monovalent to Divalent Ions.

The fast growth of electrochemical energy storage (EES) systems necessitates using innovative, high-performance electrode materials. Among the various EES devices, rechargeable batteries (RBs) with potential features like high energy density and extensive lifetime are well suited to meet rapidly increasing energy demands. Layered transition metal dichalcogenides (TMDs), typical two dimensional (2D) nanomaterial, are considered auspicious materials for RBs because of their layered structures and large specific surface areas (SSA) that benefit quick ion transportation. This review summarizes and highlights recent advances in TMDs with improved performance for various RBs. Through novel engineering and functionalization used for high-performance RBs, we briefly discuss the properties, characterizations, and electrochemistry phenomena of TMDs. We summarised that engineering with multiple techniques, like nanocomposites used for TMDs receives special attention. In conclusion, the recent issues and promising upcoming research openings for developing TMDs-based electrodes for RBs are discussed.

2D MXenes Nanosheets for Advanced Energy Conversion and Storage Devices: Recent Advances and Future Prospects.

Since the initial MXenes were discovered in 2011, several MXene compositions constructed using combinations of various transition metals have been developed. MXenes are ideal candidates for different applications in energy conversion and storage, because of their unique and interesting characteristics, which included good electrical conductivity, hydrophilicity, and simplicity of large-scale synthesis. Herein, we study the current developments in two-dimensional (2D) MXene nanosheets for energy storage and conversion technologies. First, we discuss the introduction to energy storage and conversion devices. Later, we emphasized on 2D MXenes and some specific properties of MXenes. Subsequently, research advances in MXene-based electrode materials for energy storage such as supercapacitors and rechargeable batteries is summarized. We provide the relevant energy storage processes, common challenges, and potential approaches to an acceptable solution for 2D MXene-based energy storage. In addition, recent advances for MXenes used in energy conversion devices like solar cells, fuel cells and catalysis is also summarized. Finally, the future prospective of growing MXene-based energy conversion and storage are highlighted.

Synthesis of oxidized carboxymethyl cellulose-chitosan and its composite films with SiC and SiC@SiO2 nanoparticles for methylene blue dye adsorption.

The cationic methylene blue (MB) dye sequestration was studied by using oxidized carboxymethyl cellulose-chitosan (OCMC-CS) and its composite films with silicon carbide (OCMC-CS-SiC), and silica-coated SiC nanoparticles (OCMC-CS-SiC@SiO2). The resulting composite films were characterized through various analytical techniques, including Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Thermogravimetric analysis (TGA), Field emission scanning electron microscopy (FESEM), and energy-dispersive X-ray spectroscopy (EDS). The dye adsorption properties of the synthesized composite films were comprehensively investigated in batch experiments and the effect of parameters such as contact time, initial dye concentration, catalyst dosages, temperature, and pH were systematically evaluated. The results indicated that the film's adsorption efficiency was increased by increasing the contact time, catalyst amount, and temperature, and with a decreased initial concentration of dye solution. The adsorption efficiency was highest at neutral pH. The experimental results demonstrated that OCMC-CS films have high dye adsorption capabilities as compared to OCMC-CS-SiC, and OCMC-CS-SiC@SiO2. Additionally, the desorption investigation suggested that the adsorbents are successfully regenerated. Overall, this study contributes to the development of sustainable and effective adsorbent materials for dye removal applications. These films present a promising and environmentally friendly approach to mitigate dye pollution from aqueous systems.

Recent trends in wastewater treatment by using metal-organic frameworks (MOFs) and their composites: A critical view-point.

Respecting the basic need of clean and safe water on earth for every individual, it is necessary to take auspicious steps for waste-water treatment. Recently, metal-organic frameworks (MOFs) are considered as promising material because of their intrinsic features including the porosity and high surface area. Further, structural tunability of MOFs by following the principles of reticular chemistry, the MOFs can be functionalized for the high adsorption performance as well as adsorptive removal of target materials. However, there are still some major concerns associated with MOFs limiting their commercialization as promising adsorbents for waste-water treatment. The cost, toxicity and regenerability are the major issues to be addressed for MOFs to get insightful results. In this article, we have concise the current strategies to enhance the adsorption capacity of MOFs during the water-treatment for the removal of toxic dyes, pharmaceuticals, and heavy metals. Further, we have also discussed the role of metallic nodes, linkers and associated functional groups for effective removal of toxic water pollutants. In addition to conformist overview, we have critically analyzed the MOFs as adsorbents in terms of toxicity, cost and regenerability. These factors are utmost important to address before commercialization of MOFs as adsorbents for water-treatment. Finally, some future perspectives are discussed to give directions for potential research.

Novel and efficient Bi-doped CoTe nano-solar evaporators embedded on leno weave cotton gauze for efficient solar-driven desalination.

Solar-driven desalination is considered an alternative to the conventional desalination due to its nearly zero carbon footprint and ease of operating in remote areas. Water can be purified wherever sunlight is available, providing a viable solution to water shortage. Metal chalcogenide-based materials are revolutionary for solar evaporators due to their excellent photothermal conversion efficiency, facile synthesis methods, stability, and low cost. Herein we present a prototype Bi-doped CoTe nano-solar evaporator embedded on leno weave cotton gauze (Bi/CoTe@CG) using the sonication process. The nano-solar evaporator was synthesized using a simple hydrothermal approach to provide an opportunity to scale up. The as designed solar evaporator consisting of 5 % Bi/CoTe@CG showed an excellent water flux of 2.38 kg m-2 h-1 upon one sun radiation (1 kW m-2), considered among the highest literature-reported values. The introduced solar evaporator showed excellent solar efficiency of 96.7 %, good stability, and reusability for five cycles of one hour. The best doping ratio of Bi in CoTe was obtained as Bi0.5Co9.5Te with a contact angle of 11.9° in powder form. The hydrophilic nature of the designed solar-evaporator increased the water interaction with the embedded nano-solar evaporator, which helps the transfer of the heat to nearby water molecules, break their hydrogen bonding and increase the evaporation rate. The ion concentration, of the desalinated pure water collected using Bi/CoTe@CG, decreased by many orders of magnitude and it is far below the limit of WHO standards for Na+ and K+. Thus, a self-floating Bi-doped CoTe nano-solar evaporator deposited on cotton gauze (CG) is an excellent solar evaporator for seawater desalination. The proposed solar evaporator is another step towards introducing environmentally friendly desalination methods.

Anticancer Properties of Ru and Os Half-Sandwich Complexes of N,S Bidentate Schiff Base Ligands Derived from Phenylthiocarbamide.

The versatile coordinating nature of N,S bidentate ligands is of great importance in medicinal chemistry imparting stability and enhancing biological properties of the metal complexes. Phenylthiocarbamide-based N,S donor Schiff bases converted into RuII /OsII (cymene) complexes and characterized by spectroscopic techniques and elemental analysis. The hydrolytic stability of metal complexes to undergo metal-halide ligand exchange reaction was confirmed both by the DFT and NMR experimentation. The ONIOM (QM/MM) study confirmed the histone protein targeting nature of aqua/hydroxido complex 2 aH with an excellent binding energy of -103.19 kcal/mol. The antiproliferative activity against a panel of cancer cells A549, MCF-7, PC-3, and HepG2 revealed that ruthenium complexes 1 a-3 a were more cytotoxic than osmium complexes and their respective ligands 1-3 as well. Among these ruthenium cymene complex bearing sulfonamide moiety 2 a proved a strong cytotoxic agent and showed excellent correlation of cellular accumulation, lipophilicity, and drug-likeness to the anticancer activity. Moreover, the favorable physiochemical properties such as bioavailability and gastrointestinal absorption of ligand 2 also supported the development of Ru complex 2 a as an orally active anticancer metallodrug.

NiCo2O4 nano-needles as an efficient electro-catalyst for simultaneous water splitting and dye degradation.

Developing an efficient and non-precious bifunctional catalyst capable of performing water splitting and organic effluent degradation in wastewater is a great challenge. This article reports an efficient bifunctional nanocatalyst based on NiCo2O4, synthesized using a simple one-pot co-precipitation method. We optimized the synthesis conditions by varying the synthesis pH and sodium dodecyl sulfate (SDS) concentrations. The prepared catalyst exhibited excellent catalytic activity for the electrochemical oxygen evolution reaction (OER) and simultaneous methylene blue (MB) dye degradation. Among the catalysts, the catalyst synthesized using 1 g SDS as a surfactant at 100 °C provided the highest current density (658 mA cm-2), lower onset potential (1.34 V vs. RHE), lower overpotential (170 mV @ 10 mA cm-2), and smallest Tafel slope (90 mV dec-1) value. Furthermore, the OH˙ radicals produced during the OER electrochemically degraded the MB to 90% within 2 hours. The stability test conducted at 20 mA cm-2 showed almost negligible loss of the electrochemical response for OER, with 99% retention of the original response. These results strongly suggest that this catalyst is a promising candidate for addressing the challenges of wastewater treatment and energy generation.

Synergism of Co/Na in BiVO4 microstructures for visible-light driven degradation of toxic dyes in water.

In this work, we report a synergism of Co/Na in Co@Na-BiVO4 microstructures to boost the photocatalytic performance of bismuth vanadate (BiVO4) catalysts. A co-precipitation method has been employed to synthesize blossom-like BiVO4 microstructures with incorporation of Co and Na metals, followed by calcination at 350 °C. The structure and morphology of the as-prepared photocatalysts are characterized by XRD, Raman, FTIR, SEM, EDX, AFM, UV-vis/DRS and PL techniques. Dye degradation activities are evaluated by UV-vis spectroscopy, in which methylene blue, Congo red and rhodamine B dyes are chosen for comparative study. The activities of bare BiVO4, Co-BiVO4, Na-BiVO4, and Co@Na-BiVO4 are compared. To evaluate the ideal conditions, various factors that affect degradation efficiencies have been investigated. The results of this study show that the Co@Na-BiVO4 photocatalysts exhibit higher activity than bare BiVO4, Co-BiVO4 or Na-BiVO4. The higher efficiencies were attributed to the synergistic role of Co and Na contents. This synergism assists in better charge separation and more electron transportation to the active sites during the photoreaction.

A salt-baking 'recipe' of commercial nickel-molybdenum alloy foam for oxygen evolution catalysis in water splitting.

Ni-based metal foam holds promise as an electrochemical water-splitting catalyst, due to its low cost, acceptable catalytic activity and superior stability. However, its catalytic activity must be improved before it can be used as an energy-saving catalyst. Here, a traditional Chinese recipe, salt-baking, was employed to surface engineering of nickel-molybdenum alloy (NiMo) foam. During salt-baking, a thin layer of FeOOH nano-flowers was assembled on the NiMo foam surface then the resultant NiMo-Fe catalytic material was evaluated for its ability to support oxygen evolution reaction (OER) activity. The NiMo-Fe foam catalyst generated an electric current density of 100 mA cm-2 that required an overpotential of only 280 mV, thus demonstrating that its performance far exceeded that of the benchmark catalyst RuO2 (375 mV). When employed as both the anode and cathode for use in alkaline water electrolysis, the NiMo-Fe foam generated a current density (j) output that was 3.5 times greater than that of NiMo. Thus, our proposed salt-baking method is a promising simple and environmentally friendly approach for surface engineering of metal foam for designing catalysts.

Recent Advances in Transition Metal Tellurides (TMTs) and Phosphides (TMPs) for Hydrogen Evolution Electrocatalysis.

The hydrogen evolution reaction (HER) is a developing and promising technology to deliver clean energy using renewable sources. Presently, electrocatalytic water (H2O) splitting is one of the low-cost, affordable, and reliable industrial-scale effective hydrogen (H2) production methods. Nevertheless, the most active platinum (Pt) metal-based catalysts for the HER are subject to high cost and substandard stability. Therefore, a highly efficient, low-cost, and stable HER electrocatalyst is urgently desired to substitute Pt-based catalysts. Due to their low cost, outstanding stability, low overpotential, strong electronic interactions, excellent conductivity, more active sites, and abundance, transition metal tellurides (TMTs) and transition metal phosphides (TMPs) have emerged as promising electrocatalysts. This brief review focuses on the progress made over the past decade in the use of TMTs and TMPs for efficient green hydrogen production. Combining experimental and theoretical results, a detailed summary of their development is described. This review article aspires to provide the state-of-the-art guidelines and strategies for the design and development of new highly performing electrocatalysts for the upcoming energy conversion and storage electrochemical technologies.

Facile Synthesis of PdO.TiO2 Nanocomposite for Photoelectrochemical Oxygen Evolution Reaction.

The rapid depletion of fossil fuels and environmental pollution has motivated scientists to cultivate renewable and green energy sources. The hydrogen economy is an emerging replacement for fossil fuels, and photocatalytic water splitting is a suitable strategy to produce clean hydrogen fuel. Herein, the photocatalyst (PdO.TiO2) is introduced as an accelerated photoelectrochemical oxygen evolution reaction (OER). The catalyst showed significant improvement in the current density magnitude from 0.89 (dark) to 4.27 mA/cm2 (light) during OER at 0.5 V applied potential. The as-synthesized material exhibits a Tafel slope of 170 mVdec-1 and efficiency of 0.25% at 0.93 V. The overall outcomes associated with the photocatalytic activity of PdO.TiO2 demonstrated that the catalyst is highly efficient, thereby encouraging researchers to explore more related catalysts for promoting facile OER.

Electrocatalytic water oxidation on CuO-Cu2O modulated cobalt-manganese layered double hydroxide.

Layered double hydroxides (LDH) are potential electrocatalysts to address the sluggish oxygen evolution reaction (OER) of water splitting. In this work, copper oxide (CuO/Cu2O) nanoparticles are integrated with cobalt-manganese layered double hydroxide (CoMn-LDH) to enhance their performance towards OER. The catalyst is synthesized by growing CoMn-LDH nanosheets in the presence of CuO/Cu2O nanoparticles that were obtained by the calcination of the copper containing metal-organic framework (HKUST-1). The synthesized CoMn-LDH@CuO/Cu2O electrocatalyst shows excellent activity towards OER with an overpotential of 297 mV at a catalytic current density of 10 mA cm-2 and have a Tafel slope value of 89 mV dec-1. Moreover, a slight decrease in the performance parameters is observed until the 15 h of continuous operation. We propose that the conductive strength of CuO/Cu2O and its synergistic effect with the CoMn-LDH are responsible for the improved OER performance of the desired electrocatalyst.

Threshold concepts encountered by second year medical students in a Basic Health Science module; a qualitative study.

OBJECTIVE: To explore threshold concepts in a Basic Health Sciences module. METHODS: The qualitative study was conducted at the Islamabad Medical and Dental College, Islamabad, Pakistan, in March 2019, and comprised students and faculty members in the gastrointestinal tract module of spiral I of the integrated modular curriculum in Basic Health Sciences. Data on student experiences was collected using semi-structured interviews with open-ended questions. The data was coded and themes were identified by the researchers independently. A thematic matrix was produced, cross-referencing data relating to troublesome areas identified by the students against the threshold concept criteria. The identified themes were discussed among the researchers to reach consensus. Only the identified themes were taken as the expected threshold concepts in the gastrointestinal tract module. RESULTS: Of the 18 subjects, 14(77.8%) were students and 4(22.2%) were facilitators. There were 8 areas identified by the students as troublesome in the module; development of gastrointestinal tract, anatomical relations, electron transport chain, histology of gastrointestinal tract mucosa, peritoneal disposition, anal canal and ischioanal fossae, peristalsis, and absorption across gastrointestinal tract mucosa. Only development of gastrointestinal tract appeared to cross-match with all the criteria outlined for threshold concepts. The troublesome areas identified by the teachers were development of gastrointestinal tract, peritoneal disposition, anatomical relations, absorption across gastrointestinal tract and peristalsis. CONCLUSIONS: Development of gastrointestinal tract was found to be the threshold concept in the system-based integrated module of gastrointestinal tract. Most of the students found their previous knowledge inadequate in learning concepts of the module.

The Emergence of 2D MXenes Based Zn-Ion Batteries: Recent Development and Prospects.

Rechargeable zinc-ion batteries (ZIBs) with exceptional theoretical capacity have garnered significant interest in large-scale electrochemical energy storage devices due to their low cost, abundant material, inherent safety, high specific energy, and ecofriendly nature. Metal carbides/nitrides, known as MXenes, have emerged as a large family of 2D transition metal carbides or carbonitrides with excellent properties, e.g., high electrical conductivity, large surface functional groups (e.g., F, O, and OH), low energy barriers for the diffusion of electrolyte ions with wide interlayer spaces. After a decade of effort, significant development has been achieved in the synthesis, properties, and applications of MXenes. Thus, it has opened up various exciting opportunities to construct advanced MXene-based nanostructures for ZIBs with excellent specific energy and power. Herein, this review summarizes the advances across multiple synthesis routes, related properties, morphological and structural characteristics, and chemistries of MXenes for ZIBs. The recent development of MXene-based electrodes is introduced, and electrolytes for ZIBs are elucidated in detail. MXene-based rocking chair ZIBs, strategies to enhance the performance of MXene-based cathodes, suppress the dendrites in MXene-based anodes, and MXene-based flexible ZIBs are pointed out. A rational design and modification of the MXenes as well as the production of composites with metal oxides exhibits promise in solving issues and enhancing the electrochemical performance of ZIBs. Finally, the present challenges and future prospects for MXene-based ZIBs are discussed.

Identification of Catalytic Active Sites for Durable Proton Exchange Membrane Fuel Cell: Catalytic Degradation and Poisoning Perspectives.

Recent progress in synthetic strategies, analysis techniques, and computational modeling assist researchers to develop more active catalysts including metallic clusters to single-atom active sites (SACs). Metal coordinated N-doped carbons (M-N-C) are the most auspicious, with a large number of atomic sites, markedly performing for a series of electrochemical reactions. This perspective sums up the latest innovative and computational comprehension, while giving credit to earlier/pioneering work in carbonaceous assembly materials towards robust electrocatalytic activity for proton exchange membrane fuel cells via inclusive performance assessment of the oxygen reduction reaction (ORR). M-Nx -Cy are exclusively defined active sites for ORR, so there is a unique possibility to intellectually design the relatively new catalysts with much improved activity, selectivity, and durability. Moreover, some SACs structures provide better performance in fuel cells testing with long-term durability. The efforts to understand the connection in SACs based M-Nx -Cy moieties and how these relate to catalytic ORR performance are also conveyed. Owing to comprehensive practical application in the field, this study has covered very encouraging aspects to the current durability status of M-N-C based catalysts for fuel cells followed by degradation mechanisms such as macro-, microdegradation, catalytic poisoning, and future challenges.