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Accounts of Chemical Research Dec 2022The sustainable synthesis of fuels and chemicals is key to attaining a carbon-neutral economy. This can be achieved by mimicking the light-harvesting and catalytic...
The sustainable synthesis of fuels and chemicals is key to attaining a carbon-neutral economy. This can be achieved by mimicking the light-harvesting and catalytic processes occurring in plants. Solar fuel production is commonly performed via established approaches, including photovoltaic-electrochemical (PV-EC), photoelectrochemical (PEC), and photocatalytic (PC) systems. A recent shift saw these systems evolve into integrated, compact panels, which suit practical applications through their simplicity, scalability, and ease of operation. This advance has resulted in a suite of apparently similar technologies, including the so-called artificial leaves and PC sheets. In this Account, we compare these different thin film technologies based on their micro- and nanostructure (i.e., layered vs particulate), operation principle (products occurring on the same or different sides of the panel), and product/reaction scope (overall water splitting and CO reduction, or organics, biomass, and waste conversion).For this purpose, we give an overview of developments established over the past few years in our laboratory. Two light absorbers are generally required to overcome the thermodynamic challenges of coupling water oxidation to proton or CO reduction with good efficiency. Hence, tandem artificial leaves combine a lead halide perovskite photocathode with a BiVO photoanode to generate syngas (a mixture of H and CO), whereas PC sheets involve metal-ion-doped SrTiO and BiVO particles for selective formate synthesis from CO and water. On the other hand, only a single light absorber is needed for coupling H evolution to organics oxidation in the thermodynamically less demanding photoreforming process. This can be performed by immobilized carbon nitride (CN) in the case of PC sheets or by a single perovskite light absorber in the case of PEC reforming leaves. Such systems can be integrated with a range of inorganic, molecular, and biological catalysts, including metal alloys, molecular cobalt complexes, enzymes, and bacteria, with low overpotentials and high catalytic activities toward selective product formation.This wide reaction scope introduces new challenges toward quantifying and comparing the performance of different systems. To this end, we propose new metrics to evaluate the performance of solar fuel panels based on the areal product rates and commercial product value. We further explore the key opportunities and challenges facing the commercialization of thin film technologies for solar fuels research, including performance losses over larger areas and catalyst/device recyclability. Finally, we identify emerging applications beyond fuels, where such light-driven panels can make a difference, including the waste management, chemical synthesis, and pharmaceutical industries. In the long term, these aspects may facilitate a transition toward a light-driven circular economy.
Topics: Solar Energy; Carbon Dioxide; Titanium; Water
PubMed: 36395337
DOI: 10.1021/acs.accounts.2c00477 -
Sensors (Basel, Switzerland) Jun 2022During recent decades, metal oxide semiconductors (MOS) have sparked more attention in various applications and industries due to their excellent sensing... (Review)
Review
During recent decades, metal oxide semiconductors (MOS) have sparked more attention in various applications and industries due to their excellent sensing characteristics, thermal stability, abundance, and ease of synthesis. They are reliable and accurate for measuring and monitoring environmentally important toxic gases, such as NO, NO, NO, HS, CO, NH, CH, SO, and CO. Compared to other sensing technologies, MOS sensors are lightweight, relatively inexpensive, robust, and have high material sensitivity with fast response times. Green nanotechnology is a developing branch of nanotechnology and aims to decrease the negative effects of the production and application of nanomaterials. For this purpose, organic solvents and chemical reagents are not used to prepare metal nanoparticles. On the contrary, the synthesis of metal or metal oxide nanoparticles is done by microorganisms, either from plant extracts or fungi, yeast, algae, and bacteria. Thus, this review aims at illustrating the possible green synthesis of different metal oxides such as ZnO, TiO, CeO, SnO, InO, CuO, NiO, WO and FeO, as well as metallic nanoparticles doping.
Topics: Gases; Metal Nanoparticles; Nanotechnology; Oxides; Semiconductors
PubMed: 35808164
DOI: 10.3390/s22134669 -
Yakugaku Zasshi : Journal of the... 2023Organic nitroxyl radicals represented by 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) are known to be compounds that catalyze alcohol oxidation reactions. These... (Review)
Review
Organic nitroxyl radicals represented by 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) are known to be compounds that catalyze alcohol oxidation reactions. These catalytic reactions can be applied to a wide range of compounds with hydroxy and amino groups. It is also possible to selectively oxidize primary alcohols by designing the skeleton around the nitroxyl radical moiety for use in organic synthesis. Reactions can also be carried out by electrochemical methods, and the electrical current measured during the reaction can be used to quantify the substrates. Therefore, the combination of reactions catalyzed by nitroxyl radicals and electrochemical techniques is expected to be applied as a new analytical method. However, since the reaction does not proceed rapidly in neutral aqueous solutions, it has mostly been applied in basic aqueous solutions or organic solvents, and there have been no reports on sensor applications under physiological conditions. Herein, we have developed a novel catalyst, nortropine N-oxyl (NNO), which is highly active even in neutral aqueous solutions, and have found that it can be used for the analysis of biological components and drugs under physiological conditions. The combination of this method with enzymatic reactions made it possible to specifically detect certain compounds. In this review, we describe a novel analytical method that combines these nitroxyl radicals with electrochemical methods.
Topics: Oxidation-Reduction; Nitrogen Oxides; Catalysis; Water; Free Radicals
PubMed: 36724933
DOI: 10.1248/yakushi.22-00143 -
International Journal of Environmental... Mar 2023The emission of harmful gases has seriously exceeded relative standards with the rapid development of modern industry, which has shown various negative impacts on human... (Review)
Review
The emission of harmful gases has seriously exceeded relative standards with the rapid development of modern industry, which has shown various negative impacts on human health and the natural environment. Recently, metal-organic frameworks (MOFs)-based materials have been widely used as chemiresistive gas sensing materials for the sensitive detection and monitoring of harmful gases such as NO, HS, and many volatile organic compounds (VOCs). In particular, the derivatives of MOFs, which are usually semiconducting metal oxides and oxide-carbon composites, hold great potential to prompt the surface reactions with analytes and thus output amplified resistance changing signals of the chemiresistors, due to their high specific surface areas, versatile structural tunability, diversified surface architectures, as well as their superior selectivity. In this review, we introduce the recent progress in applying sophisticated MOFs-derived materials for chemiresistive gas sensors, with specific emphasis placed on the synthesis and structural regulation of the MOF derivatives, and the promoted surface reaction mechanisms between MOF derivatives and gas analytes. Furthermore, the practical application of MOF derivatives for chemiresistive sensing of NO, HS, and typical VOCs (e.g., acetone and ethanol) has been discussed in detail.
Topics: Humans; Metal-Organic Frameworks; Acetone; Environment; Ethanol; Gases; Oxides; Volatile Organic Compounds
PubMed: 36901399
DOI: 10.3390/ijerph20054388 -
Biosensors May 2023Wide-ranging research efforts have been directed to prioritize scientific and technological inventions for healthcare monitoring. In recent years, the effective... (Review)
Review
Wide-ranging research efforts have been directed to prioritize scientific and technological inventions for healthcare monitoring. In recent years, the effective utilization of functional nanomaterials in various electroanalytical measurements realized a rapid, sensitive, and selective detection and monitoring of a wide range of biomarkers in body fluids. Owing to good biocompatibility, high organic capturing ability, strong electrocatalytic activity, and high robustness, transition metal oxide-derived nanocomposites have led to enhancements in sensing performances. The aim of the present review is to describe key advancements of transition metal oxide nanomaterials and nanocomposites-based electrochemical sensors, along with current challenges and prospects towards the development of a highly durable and reliable detection of biomarkers. Moreover, the preparation of nanomaterials, electrode fabrication, sensing mechanism, electrode-bio interface, and performance of metal oxides nanomaterials and nanocomposite-based sensor platforms will be described.
Topics: Electrochemical Techniques; Nanocomposites; Oxides; Transition Elements; Biomarkers
PubMed: 37232903
DOI: 10.3390/bios13050542 -
Molecules (Basel, Switzerland) Oct 2022These days, explorations have focused on designing two-dimensional (2D) nanomaterials with useful (photo)catalytic and environmental applications. Among them,... (Review)
Review
These days, explorations have focused on designing two-dimensional (2D) nanomaterials with useful (photo)catalytic and environmental applications. Among them, MXene-based composites have garnered great attention owing to their unique optical, mechanical, thermal, chemical, and electronic properties. Various MXene-based photocatalysts have been inventively constructed for a variety of photocatalytic applications ranging from pollutant degradation to hydrogen evolution. They can be applied as co-catalysts in combination with assorted common photocatalysts such as metal sulfide, metal oxides, metal-organic frameworks, graphene, and graphitic carbon nitride to enhance the function of photocatalytic removal of organic/pharmaceutical pollutants, nitrogen fixation, photocatalytic hydrogen evolution, and carbon dioxide conversion, among others. High electrical conductivity, robust photothermal effects, large surface area, hydrophilicity, and abundant surface functional groups of MXenes render them as attractive candidates for photocatalytic removal of pollutants as well as improvement of photocatalytic performance of semiconductor catalysts. Herein, the most recent developments in photocatalytic degradation of organic and pharmaceutical pollutants using MXene-based composites are deliberated, with a focus on important challenges and future perspectives; techniques for fabrication of these photocatalysts are also covered.
Topics: Graphite; Environmental Pollutants; Metal-Organic Frameworks; Carbon Dioxide; Oxides; Hydrogen; Pharmaceutical Preparations; Sulfides
PubMed: 36296531
DOI: 10.3390/molecules27206939 -
Toxicology and Applied Pharmacology Jul 2022Workers in the oil and gas extraction industry are at risk of inhaling volatile organic compounds. Epidemiological studies suggest oil vapor inhalation may affect...
Workers in the oil and gas extraction industry are at risk of inhaling volatile organic compounds. Epidemiological studies suggest oil vapor inhalation may affect cardiovascular health. Thus, in this hazard identification study we investigated the effects of inhalation of crude oil vapor (COV) on cardiovascular function. Male rats were exposed to air or COV (300 ppm) for 6 h (acute), or 6 h/day × 4 d/wk. × 4 wk. (sub-chronic). The effects of COV inhalation were assessed 1, 28, and 90 d post-exposure. Acute exposure to COV resulted in reductions in mean arterial and diastolic blood pressures 1 and 28 d after exposure, changes in nitrate-nitrite and HO levels, and in the expression of transcripts and proteins that regulate inflammation, vascular remodeling, and the synthesis of nitric oxide (NO) in the heart and kidneys. The sub-chronic exposure resulted in a reduced sensitivity to α-adrenoreceptor-mediated vasoconstriction in vitro 28 d post-exposure, and a reduction in oxidative stress in the heart. Sub-chronic COV exposure led to alterations in the expression of NO synthases and anti-oxidant enzymes, which regulate inflammation and oxidative stress in the heart and kidneys. There seems to be a balance between changes in the expression of transcripts associated with the generation of reactive oxygen species (ROS) and antioxidant enzymes. The ability of antioxidant enzymes to reduce or inhibit the effects of ROS may allow the cardiovascular system to adapt to acute COV exposures. However, sub-chronic exposures may result in longer-lasting negative health consequences on the cardiovascular system.
Topics: Animals; Antioxidants; Cardiovascular System; Gases; Hydrogen Peroxide; Inflammation; Inhalation Exposure; Male; Oxidative Stress; Petroleum; Rats; Reactive Oxygen Species
PubMed: 35598716
DOI: 10.1016/j.taap.2022.116071 -
Veterinary Medicine and Science May 2023Manganese (Mn) is an important trace element for laying hen's nutrition, which is required in small amounts in the diet. Its deficiency results in lowered production...
BACKGROUND
Manganese (Mn) is an important trace element for laying hen's nutrition, which is required in small amounts in the diet. Its deficiency results in lowered production performance and eggshell quality.
OBJECTIVES
This experiment was conducted to investigate the influence of different sources and levels of Mn on egg production performance and eggshell quality in aged laying hens.
METHODS
A total of 720, 83-week-old Hy-Line W-36 laying hens were fed a non-Mn supplemented basal diet for 4-week (to ime Mn-exhaustion of body) and then were allocated to a completely randomized design with 10 treatments, six replicates and 12 birds each. Concentration of Mn in the non-Mn supplemented basal diet was 10.34 mg/kg (treatment 1), the added doses of dietary Mn were included 30, 60, and 90 mg/kg of three different sources (Mn-oxide, Mn-sulphate, and Mn-organic) for treatments 2-10, respectively. The experiment lasted for 12 week.
RESULTS
Dietary supplementation with either organic or inorganic Mn sources significantly enhanced egg production (EP), egg mass (EM), feed conversion ratio (FCR), and relative eggshell weight (RESW) compared with the non-Mn supplemented diet. However, the experimental diets did not influence feed intake (FI), egg weight, and other eggshell quality traits. Based on the broken line regression models, the performance traits were optimized at 30-40 mg/kg Mn concentration when supplemented by Mn-sulphate or Mn-organic. Although, it was 80-90 mg/kg when supplemented by Mn-oxide. The relative bio-efficacy of inorganic Mn sources include Mn-oxide and Mn-sulphate in compare with Mn-organic were estimated 45% and 87% (for EP trait), 30% and 94% (for EM trait), 36% and 99% (for FCR trait), and 37% and 78% (for RESW trait), respectively.
CONCLUSIONS
In the aged laying hens, Mn requirement is higher than the NRC's recommendation. Sulphate and organic sources of Mn are more effective than Mn-oxide.
Topics: Animals; Female; Manganese; Chickens; Egg Shell; Animal Feed; Dietary Supplements; Oxides; Sulfates
PubMed: 36920852
DOI: 10.1002/vms3.1116 -
Molecules (Basel, Switzerland) May 2023Over the years, Ru(bpy)(py)(O)([RuO]) has garnered considerable interest owing to its extensive use as a polypyridine mono-oxygen complex. However, as the active-site...
Over the years, Ru(bpy)(py)(O)([RuO]) has garnered considerable interest owing to its extensive use as a polypyridine mono-oxygen complex. However, as the active-site Ru=O bond changes during the oxidation process, [RuO] can be used to simulate the reactions of various high-priced metallic oxides. In order to elucidate the hydrogen element transfer process between the Ruthenium-oxo-polypyridyl complex and organic hydride donor, the current study reports on the synthesis of [RuO], a polypyridine mono-oxygen complex, in addition to and (organic hydride compounds) and derivative: . Through H-NMR analysis and thermodynamics- and kinetics-based assessments, we collected data on [RuO] and two organic hydride donors and their corresponding intermediates and established a thermodynamic platform. It was confirmed that a one-step hydride transfer reaction between [RuO] and these organic hydride donors occurs, and here, the advantages and nature of the new mechanism approach are revealed. Accordingly, these findings can considerably contribute to the better application of the compound in theoretical research and organic synthesis.
Topics: Ruthenium; Organometallic Compounds; Oxidation-Reduction; Oxides; Hydrogen
PubMed: 37298875
DOI: 10.3390/molecules28114401 -
Sensors (Basel, Switzerland) Apr 2022Metal oxide nanowires have become popular materials in gas sensing, and more generally in the field of electronic and optoelectronic devices. This is thanks to their... (Review)
Review
Metal oxide nanowires have become popular materials in gas sensing, and more generally in the field of electronic and optoelectronic devices. This is thanks to their unique structural and morphological features, namely their single-crystalline structure, their nano-sized diameter and their highly anisotropic shape, i.e., a large length-to-diameter aspect ratio. About twenty years have passed since the first publication proposing their suitability for gas sensors, and a rapidly increasing number of papers addressing the understanding and the exploitation of these materials in chemosensing have been published. Considering the remarkable progress achieved so far, the present paper aims at reviewing these results, emphasizing the comparison with state-of-the-art nanoparticle-based materials. The goal is to highlight, wherever possible, how results may be related to the particular features of one or the other morphology, what is effectively unique to nanowires and what can be obtained by both. Transduction, receptor and utility-factor functions, doping, and the addition of inorganic and organic coatings will be discussed on the basis of the structural and morphological features that have stimulated this field of research since its early stage.
Topics: Anisotropy; Nanoparticles; Nanowires; Oxides
PubMed: 35591040
DOI: 10.3390/s22093351