Efficient Reaction Research Articles

Raman Monitoring of the Electro-Optical Synergy-Induced Enhancements in Carbon-Bromine Bond Cleavage, Reaction Rate, and Product Selectivity of p-Bromothiophenol.

Electro-optical synergy has recently been targeted to improve the separation of hot carriers and thereby further improve the efficiency of plasmon-mediated chemical reactions (PMCRs). However, the electro-optical synergy in PMCRs needs to be more deeply understood, and its contribution to bond dissociation and product selectivity needs to be clarified. Herein, the electro-optical synergy in plasmon-mediated reduction of p-bromothiophenol (PBTP) was studied on a plasmonic nanostructured silver electrode using in situ Raman spectroscopy and theoretical calculations. It was found that the electro-optical synergy-induced enhancements in the cleavage of carbon-bromine bonds, reaction rate, and product selectivity (4,4'-biphenyl dithiol vs thiophenol) were largely affected by the applied bias, laser wavelength, and laser power. The theoretical simulation further clarified that the strong electro-optical synergy is attributed to the matching of energy band diagrams of the plasmonic silver with those of the adsorbed PBTP molecules. A deep understanding of the electro-optical synergy in PBTP reduction and the clarification of the mechanism will be highly beneficial for the development of other highly efficient PMCRs.

High-Yield Synthesis of Hierarchical SAPO-34 by Recrystallization Method for Efficient Methanol-to-Olefin Reactions.

Prolonging the lifetime of SAPO-34 catalysts and enhancing their olefin selectivity in methanol-to-olefin (MTO) reactions are critical yet challenging objectives. Here, a series of hierarchical SAPO-34 catalysts were synthesized using a straightforward recrystallization method. The incorporation of triethylamine into the recrystallization mother liquor facilitated the formation of mesopores, achieving a high solid yield of up to 90%. Notably, the addition of phosphoric acid and ammonium polyvinyl phosphate alcohol during the recrystallization process significantly enhanced the crystallinity and regularity of the hierarchical SAPO-34 crystals, consequently increasing the mesopore size. Due to the substantially improved mass transfer efficiency and moderated acidity, the SP34-0.14P-0.06R catalysts exhibited a prolonged operational life of 344 min and80.3%selectivity ofethylene and propylene at aWHSV of 2h-1. This performance markedly surpasses that of the parent SP34 catalyst, which demonstrated a lifetime of 136 min and a selectivity of 78.0%. Remarkably, the SP34-0.14P-0.06R maintained a lifetime of 166 minutes even at a high WHSV of 10h-1, which is more than 5-fold greater than that of the original microporous SP34. This research offers valuable insights into the design and development of hierarchically porous zeolites with high yields, enhancing the efficiency of MTO reactions and other applications.

Plasmon-Mediated Organic Photoelectrochemistry Applied to Amination Reactions.

Organic electrochemistry is currently experiencing an era of renaissance, which is closely related to the possibility of carrying out organic transformations under mild conditions, with high selectivity, high yields, and without the use of toxic solvents. Combination of organic electrochemistry with alternative approaches, such as photo-chemistry was found to have great potential due to induced synergy effects. In this work, we propose for the first time utilization of plasmon triggering of enhanced and regio-controlled organic chemical transformation performed in photoelectrochemical regime. The advantages of the proposed route is demonstrated in the model amination reaction with formation of C-N bond between pyrazole and substituted benzene derivatives. Amination was performed in photo-electrochemical mode on the surface of plasmon active Au@Pt electrode with attention focused on the impact of plasmon triggering on the reaction efficiency and regio-selectivity. The ability to enhance the reaction rate significantly and to tune products regio-selectivity is demonstrated. We also performed density functional theory calculations to inquire about the reaction mechanism and potentially explain the plasmon contribution to electrochemical reaction rate and regioselectivity.

Schottky Junction Enhanced Photosynthesis of Hydrogen Peroxide by Ultrathin Porous Carbon Nitride Supported Ni Nanoparticles.

Artificial photosynthesis for high-value hydrogen peroxide (H2O2) through a two-electron reduction reaction is a green and sustainable strategy. However, the development of highly active H2O2 photocatalysts is impeded by severe carrier recombination, ineffective active sites, and low surface reaction efficiency. We developed a dual optimization strategy to load dense Ni nanoparticles onto ultrathin porous graphitic carbon nitride (Ni-UPGCN). In the absence and presence of sacrificial agents, Ni-UPGCN achieved H2O2 production rates of 169 and 4116 μmol g-1 h-1 with AQY (apparent quantum efficiency) at 420 nm of 3.14% and 17.71%. Forming a Schottky junction, the surface-modified Ni nanoparticles broaden the light absorption boundary and facilitate charge separation, which act as active sites, promoting O2 adsorption and reducing the formation energy of *OOH (reaction intermediate). This results in a substantial improvement in both H2O2 generation activity and selectivity. The Schottky junction of dual modulation strategy provides novel insights into the advancement of highly effective photocatalytic agents for the photosynthesis of H2O2.

Slow freeze‐thaw cycles enhanced hybridization of kilobase DNA with long complementary sticky ends

The creation of large information molecules may have played an essential role in the origins of life. In this study, we conducted slow freeze‐thaw (F/T) experiments to test the possibility of enhanced hybridization between the complementary sticky ends attached to kilobase‐sized DNA fragments at sub‐nanomolar concentrations. DNA fragments of 2‐ and 3‐kilobase pairs (kbp) with 50‐base complementary sticky ends that can form 5 kbp‐sized hybridization products were mixed. While simple incubation provided little hybridization product, significantly effective hybridization was observed after freezing and thawing at a controlled time rate (<0.3 K min⁻¹), even with small DNA concentrations (<1 nM). Furthermore, slow thawing had a more effect on hybridization than slow freezing. The reaction efficiency was reduced by rapid thawing instead of slow thawing, suggesting that the eutectic phase concentration played an important role in hybridization. A slow F/T cycle was effective even for the hybridization reaction between two 10 kbp DNA fragments, which yielded a 20 kbp product at sub‐nanomolar concentrations. Repeating the slow F/T cycle significantly improved the reaction efficiency. The possible role of the F/T cycles in early Earth environments is discussed here.

Utilizing banana peel in conjunction with TiO2 photocatalyst for the efficient decolorization of malachite green

Porous materials are frequently integrated into TiO2 photocatalysts due to their enhanced surface area and reaction efficiency. This study aimed to enhance the efficiency of wastewater treatment by developing a TiO2 combined with banana peel (BP) through the sol-gel method. The TiO2/BP composite was extensively analyzed using a range of methods, such as X-ray diffraction (XRD), field emission transmission electron microscopy (FESEM), energy dispersive X-ray (EDX) analysis, diffuse reflectance spectroscopy (DRS UV–vis), photoluminescence spectra (PL), and Brunauer–Emmett–Teller (BET) analysis. Subsequent evaluation of the photoactivity of the TiO2/BP composite compared to bare TiO2 particles revealed a noteworthy enhancement in decolorizing malachite green (MG) dye under visible light. Furthermore, recyclability testing further demonstrated consistent performance for up to four cycles, highlighting the potential application of this porous material-based photocatalytic composite in wastewater treatment.

Accumulation of Long-Lived Photogenerated Holes at Indium Single Atom Catalysts via Two Coordinate Nitrogen Vacancy Defect Engineering for Enhanced Photocatalytic Oxidation.

Visible light-driven photocatalytic oxidation by photogenerated holes has immense potential for environmental remediation applications. While the electron-mediated photoreduction reactions are often at the spotlight, active holes possess a remarkable oxidation capacity that can degrade recalcitrant organic pollutants, resulting in non-toxic byproducts. However, the random charge transfer and rapid recombination of electron-hole pairs hinder the accumulation of long-lived holes at the reaction center. Herein, we report a novel method employing defect-engineered indium (In) single atom photocatalysts, dispersed in carbon nitride foam (In-Nv-CNF), to overcome these challenges and make further advances in photocatalysis. This Nv (nitrogen vacancy) defect-engineered strategy produces a remarkable extension in the lifetime of photogenerated holes and an increase in the concentration of photogenerated holes in In-Nv-CNF. Consequently, the optimized In-Nv-CNF demonstrates a remarkable 50-fold increase in photo-oxidative degradation rate compared to pristine CN, effectively breaking down two widely used antibiotics (tetracycline and ciprofloxacin) under visible light. The contaminated water treated by In-Nv-CNF has proven to be completely non-toxic based on the growth of E. coli before and after treatment. Structural-performance correlations between Nv defect engineering and long-lived hole accumulation in In-Nv-CNF are established and validated through experimental and theoretical agreement. This work has the potential to elevate the efficiency of overall photocatalytic reactions from a hole-centric standpoint. This article is protected by copyright. All rights reserved.

Recognition of 8-Oxo-2′-deoxyguanosine in DNA Using the Triphosphate of 2′-Deoxycytidine Connecting the 1,3-Diazaphenoxazine Unit, dCdapTP

DNA is constantly damaged by various external and internal factors. In particular, oxidative damage occurs in a steady state, and 8-oxo-2′-deoxyguanosine (oxodG) is known as the main oxidative damage. OxodG is a strong genotoxic nucleoside and is thought to be involved in the pathogenesis of cancer and neurological diseases. However, a breakthrough method to detect the position of oxodG in DNA has not yet been developed. Therefore, we attempted to develop a novel method to detect oxodG in DNA using artificial nucleosides. Recently, we have succeeded in the recognition of oxodG in DNA by a single nucleotide elongation reaction using nucleoside derivatives based on a purine skeleton with a 1,3-diazaphenoxazine unit. In this study, we developed a new nucleoside derivative with a pyrimidine skeleton in order to further improve the recognition ability and enzymatic reaction efficiency. We, therefore, designed and synthesized 2′-deoxycytidine-1,3-diazaphenoxazine (Cdap) and its triphosphate derivatives. The results showed that it was incorporated into the primer strand relative to the dG template because of its cytidine skeleton, but it was more effective at the complementary position of the oxodG template. These results indicate that the new nucleoside derivative can be considered as one of the new candidates for the detection of oxodG in DNA.

Recombinase polymerase amplification: method’s characteristics and applications in diagnostics of infectious diseases

Isothermal amplification techniques have been actively developed in recent years and are gradually introduced into the range of methods for infectious disease diagnostics. One of the fastest isothermal methods is recombinase polymerase amplification (RPA). This review contains information about the principle of RPA, the role of individual reaction components and primer design considerations. It provides information on characteristics of various methods of RPA results detection, effects of inhibitors, temperature and agitation on the efficiency of reaction. Approaches to quantitative and multiplex RPA are described, as well as some variants of portable devices designed to identify infectious agents. The conclusion summarizes advantages and disadvantages of RPA in comparison with other amplification methods.

High-Entropy Lanthanide-Organic Framework as an Efficient Heterogeneous Catalyst for Cycloaddition of CO2 with Epoxides and Knoevenagel Condensation.

Multimetallic synergistic effects have the potential to improve CO2 cycloesterification and Knoevenagel reaction processes, outperforming monometallic MOFs. The results demonstrate superior performance in these processes. To investigate this, we created and characterized a selection of single-component Ln(III)-MOFs (Ln = Eu, Tb, Gd, Dy, Ho) and high-entropy lanthanide-organic framework (HE-LnMOF) using solvent-thermal conditions. The experiments revealed that HE-LnMOF exhibited heightened catalytic efficiency in CO2 cycloesterification and Knoevenagel reactions compared to single-component Ln(III) MOFs. Moreover, the HE-LnMOF displayed significant stability, maintaining their structural integrity after five cycles while sustaining elevated conversion and selectivity rates. The feasible mechanisms of catalytic reactions were also discussed. HE-LnMOF possess multiple unsaturated metal centers, acting as Lewis acid sites, with oxygen atoms connecting the metal, and hydroxyl groups on the ligand serving as base sites. This study introduces a novel method for synthesizing HE-LnMOF and presents a fresh application of HE-LnMOF for converting CO2.

Regulating Interfacial Microenvironment in Aqueous Electrolyte via a N2 Filtering Membrane for Efficient Electrochemical Ammonia Synthesis.

Electrochemical synthesis of ammonia (NH3) in aqueous electrolyte has long been suffered from poor nitrogen (N2) supply owing to its low solubility and sluggish diffusion kinetics. Therefore, creating a N2 rich microenvironment around catalyst surface may potentially improve the efficiency of nitrogen reduction reaction (NRR). Herein, a delicately designed N2 filtering membrane consisted of polydimethylsiloxane is covered on catalyst surface via superspreading. Because this membrane let the dissolved N2 molecules be accessible to the catalyst but block excess water, the designed N2 rich microenvironment over catalyst leads to an optimized Faradaic efficiency of 39.4% and an NH3 yield rate of 109.2µgh-1mg-1, which is superior to those of the most report metal-based catalysts for electrochemical NRR. This study offers alternative strategy for enhancing NRR performance.

Water-Ice Microstructures and Hydration States of Acridinium Iodide Studied by Phosphorescence Spectroscopy.

Ice has been suggested to have played a significant role in the origin of life partly owing to its ability to concentrate organic molecules and promote reaction efficiency. However, the techniques for studying organic molecules in ice are absorption-based, which limits the sensitivity of measurements. Here we introduce an emission-based method to study organic molecules in water ice: the phosphorescence displays high sensitivity depending on the hydration state of an organic salt probe, acridinium iodide (ADI). The designed ADI aqueous system exhibits phosphorescence that can be severely perturbed when the temperature is higher than 110 K at a concentration of the order of 10-5 M, indicating changes in hydration for ADI. Using the ADI phosphorescent probe, it is found that the microstructures of water ice, i.e., crystalline vs. glassy, can be strongly dictated by a trace amount (as low as 10-5 M) of water-soluble organic molecules. Consistent with cryoSEM images and temperature-dependent Raman spectral data, the ADI is dehydrated in more crystalline ice and hydrated in more glassy ice. The current investigation serves as a starting point for using more sensitive spectroscopic techniques for studying water-organics interactions at a much lower concentration and wider temperature range.

Water‐Ice Microstructures and Hydration States of Acridinium Iodide Studied by Phosphorescence Spectroscopy

AbstractIce has been suggested to have played a significant role in the origin of life partly owing to its ability to concentrate organic molecules and promote reaction efficiency. However, the techniques for studying organic molecules in ice are absorption‐based, which limits the sensitivity of measurements. Here we introduce an emission‐based method to study organic molecules in water ice: the phosphorescence displays high sensitivity depending on the hydration state of an organic salt probe, acridinium iodide (ADI). The designed ADI aqueous system exhibits phosphorescence that can be severely perturbed when the temperature is higher than 110 K at a concentration of the order of 10−5 M, indicating changes in hydration for ADI. Using the ADI phosphorescent probe, it is found that the microstructures of water ice, i.e., crystalline vs. glassy, can be strongly dictated by a trace amount (as low as 10−5 M) of water‐soluble organic molecules. Consistent with cryoSEM images and temperature‐dependent Raman spectral data, the ADI is dehydrated in more crystalline ice and hydrated in more glassy ice. The current investigation serves as a starting point for using more sensitive spectroscopic techniques for studying water‐organics interactions at a much lower concentration and wider temperature range.

One-step hydrothermal synthesis of nanowire-like W/Mo-Ni3S2/NF electrocatalysts for highly efficient hydrogen evolution reactions

The design of nanostructures and the adjustment of components are very important to improve the performance of hydrogen evolution electrocatalysts. In this paper, Ni, W and Mo trimetallic catalysts are studied from the aspects of morphology, structure and electronic transfer, and a better combination of hydrogen reaction efficiency is obtained. The W/Mo co-doped nickel sulfide electrocatalyst was synthesized on Ni foam by one-step hydrothermal method. As anticipated, the individual incorporation of either tungsten (W) or molybdenum (Mo) into the electrocatalyst did not yield satisfactory enhancements in hydrogen evolution reaction (HER) performance. However, when both W and Mo were co-doped onto the electrocatalyst, a significant improvement in catalyst material performance was observed. Hence, the coexistence of W and Mo is the key to improve HER electrocatalytic activity. In 1 M KOH solution, the W/Mo-Ni3S2/NF electrocatalyst exhibited exceptional HER activity with an overpotential of only 136 mV at a current density of 10 mA·cm−2 and demonstrated excellent cycle stability exceeding 20 hours. In this paper, the strategy of bimental co-doping composite is adopted to adjust the structure of nickel sulfide, which provides reference value for the design of reasonable and efficient HER electrocatalyst.

Constructing an Open-Structured J-Type ZnIn2S4/In(OH)3 Heterojunction for Photocatalytical Hydrogen Generation.

Constructing heterojunctions to separate photogenerated carriers is an effective strategy for improving the efficiency of photocatalytic reactions. A J-type heterojunction is a recently reported efficient anisotropic heterojunction. Herein, taking anisotropic ZnIn2S4 (ZIS) nanosheets as an example of a type-II heterojunction, we report for the first time the concept of open and closed structures (O and C structure) of J-type heterojunctions. A simple ammonia-post-treatment method was employed to prepare the O- and C-structured J-type ZnIn2S4/In(OH)3 (ZIS/IOH) heterojunctions. The O-structured J-type ZIS/IOH (OJ-ZIS/IOH) heterojunction exhibits a high hydrogen production activity, reaching 400 μmol·h-1, 2.67 times higher than that of pristine ZIS. However, the activity of the C-structured heterojunction (CJ-ZIS/IOH) is close to that of pristine ZIS. The findings emphasize the importance of the cooperation of photogenerated carrier separation and transport in J-type heterojunctions, providing insights into developing efficient heterojunction photocatalysts.

Enhancement of Catalytic Efficiency of Enzymatic Redox Reactions by Composing Horseradish Peroxidase-Modified Electrode with Ionic Liquids

We have kinetically estimated the enzymatic redox reaction at the horseradish peroxidase (HRP)-modified electrode combined with ionic liquids by adding N-(2-methoxythethyl)-N-methylpyrrolidinium bis(trifluoromethane sulfonyl)imide (MEMPTFSI) to HRP/carbon paste (CP)/Ketjenblack EC600JC (EC). The fluctuation of the steady-state reduction current of HRP at the HRP/CP-modified electrode progressively increased as the applied potential was lowered. The enzymatic redox reaction with hydrogen peroxide as a substrate at the HRP/CP/EC/MEMPTFSI-modified electrode and the HRP/CP-modified electrode could be correlated by the Michaelis–Menten equation. The Michaelis constant of the enzymatic redox reaction at the HRP/CP/EC/MEMPTFSI-modified electrode was the same as that at the HRP/CP-modified electrode. On the other hand, the turnover number of the enzymatic redox reaction at the HRP/CP/EC/MEMPTFSI-modified electrode was six times larger than that at the HRP/CP-modified electrode. Consequently, the specificity constant of the enzymatic redox reaction at the HRP/CP/EC/MEMPTFSI-modified electrode was much higher than that at the HRP/CP-modified electrode.

Facet Dependence of the Oxygen Evolution Reaction on Co3O4, CoFe2O4, and Fe3O4 Epitaxial Film Electrocatalysts.

The main obstacle for the electrocatalytic production of "green hydrogen" is finding suitable electrocatalysts which operate highly efficiently over extended periods of time. The topic of this study is the oxygen evolution reaction (OER), one of the half-reactions of water splitting. It is complex and has intricate kinetics, which impairs the reaction efficiency. Transition metal oxides have shown potential as electrocatalysts for this reaction, but much remains unknown about the atomic scale processes. We have investigated structure-composition-reactivity correlations for Co3O4, CoFe2O4, and Fe3O4 epitaxial thin-film electrocatalysts exposing either the (001) or (111) surface facets. We found that for Co3O4, the (001) facet is more reactive, while for the other oxides, the (111) facet is more active. A Tafel-like evaluation reveals systematically smaller "Tafel" slopes for the (001) facets. Furthermore, the slopes are smaller for the iron-containing films. Additionally, we found that the oxyhydroxide skin layer which forms under OER reaction conditions is thicker on the cobalt oxides than on the other oxides, which we attribute to either a different density of surface defects or to iron hindering the growth of the skin layers. All studied skin layers were thinner than 1 nm.

Study on the impact of methanol steam reforming reactor channel structure on hydrogen production performance

The design and operation of embedded reactors involve chemical reaction efficiency issues, with the main consideration being heat and mass transfer characteristics. The contact area of the porous catalytic coating with methanol is affected by the reactor structure, to improve the hydrogen yield and reveal the mechanism of the channel structure on the hydrogen production performance, the hydrogen production performance of circle-triangle, circle-square, square-circle, square-square, and triangle-circle channels was investigated. The reasons for the differences in methanol conversion, hydrogen, and carbon monoxide selectivity were analyzed from the perspective of heat and mass transfer using a three-rate reaction mechanism. The results showed that the circle-triangle channel performed outstandingly in the hydrogen production from methanol steam reforming with 98.61 % methanol conversion, 88.74 % hydrogen selectivity, and 29.06 % CO selectivity. The shapes and sizes of the different channel structures affect the fluid flow pattern and velocity distribution, which in turn affect the mass transfer efficiency and lead to differences in hydrogen production performance. The circle-triangle channel exhibits superior heat transfer and material transport performance, which can improve the hydrogen production efficiency of methanol steam reforming and help provide an important reference for the embedded reactor design.

Analytical and experimental evaluation of LaNi5-xMx, where M = Fe, Mn, and Al hydrides for hydrogen compression applications

Metal Hydride Hydrogen Compressors (MHHC) will play a vital role in the hydrogen economy in the coming times. Developing a more efficient and optimized MHHC requires revisiting the existing materials and selecting the best-suited material. The current work compares LaNi5-xMx, where M = Fe, Mn, and Al hydrides, through a thermodynamic evaluation of the compressor's performance. The operating conditions have been chosen as 20 to 40 °C for absorption and 80 to 140 °C for desorption to provide a baseline for comparing the materials. The performance parameters include thermal efficiency, pressure ratio, and throughput (i.e. mass of hydrogen delivered per 100 g of hydride (wt.%)). The Pressure Concentration Isotherms (PCIs) are taken from the published literature, and the equilibrium pressures at the desired temperature conditions are calculated from the van't Hoff equation. LaNi4.8Al0.2 gives good performance throughout the studied temperature and pressure range. The throughput of LaNi4.8Al0.2 drops from 1.4 wt.% to around 1 wt.% at high absorption temperatures. A separate experimental study of LaNi4.8Al0.2 is documented where it is used in a prototype of MHHC, and its performance parameters are compared with the thermodynamic analysis. The reaction kinetics, throughput, pressure ratio, and efficiency are reported. A pressure ratio of 4.2 is achieved with an efficiency of 5.2 % at 3 bar supply pressure, and absorption and desorption temperatures of 30 and 140 °C, respectively.

Two 2D Metal-Organic Frameworks Based on Purine Carboxylic Acid Ligands for Photocatalytic Oxidation of Sulfides and CO2 Chemical Fixation.

Two two-dimensional (2D) layered metal-organic frameworks (MOFs), namely, {[Yb(L)(H2O)2NO3]·2H2O}n (Yb-MOF) and [Er(L)(H2O)3Cl]n (Er-MOF) (H2L = 5-((6H-purin-6-yl)amino)isophthalic acid), were constructed by a solvothermal method and characterized. The catalytic performance study showed that the Yb-MOF could efficiently catalyze the oxidation of sulfides to sulfoxides under 15 W light-emitting diode (LED) blue light irradiation. Electron paramagnetic resonance spectroscopy and free-radical trapping experiments demonstrated that the photocatalytic reaction process involved •O2-, and the corresponding mechanism was proposed. Moreover, Er-MOF exhibited good catalytic efficiency and excellent substrate tolerance in the cycloaddition reaction of CO2, and the reaction conditions were mild. After 5 cycles, the catalytic activities of two MOFs did not significantly decrease, and the framework structures remained unchanged. Therefore, the Yb-MOF and Er-MOF were considered efficient and stable heterogeneous catalysts.