Application of metal-organic frameworks and their derivates for thermal-catalytic C1 molecules conversion.

One-carbon (C1) catalysis refers to the conversion of compounds with a single carbon atom, especially carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4), into clean fuels and valuable chemicals via catalytic strategy is crucial for sustainable and green development. Among various catalytic strategies, thermal-driven process seems to be one of the most promising pathways for C1 catalysis due to the high efficiency and practical application prospect. Notably, the rational design of thermal-driven C1 catalysts plays a vital role in boosting the targeted products synthesis of C1 catalysis, which relies heavily on the choice of ideal active site support, catalyst fabrication precursor, and catalytic reaction field. As a novel crystalline porous material, metal-organic frameworks (MOFs) has made significant progress in the design and synthesis of various functional nanomaterials. However, the application of MOFs in C1 catalysis faces numerous challenges, such as thermal stability, mechanical strength, yield of MOFs, and so on. To overcome these limitations and harness the advantages of MOFs in thermal-driven C1 catalysis, researchers have developed various catalyst/carrier preparation strategies. In this review, we provide a concise overview of the recent advancements in the conversion of CO, CO2, and CH4 into clean fuels and valuable chemicals via thermal-catalytic strategy using MOFs-based catalysts. Furthermore, we discuss the main challenges and opportunities associated with MOFs-based catalysts for thermal-driven C1 catalysis in the future.

The pivotal role of bromine in FeMnKBr/YNa catalyst for CO2 hydrogenation to light olefins.

Light olefins are key intermediates in the synthesis of petrochemicals, and the conversion of stabilized carbon dioxide to light olefins using catalysts containing halogenated elements such as chlorine is a major challenge. Building on previous reports emphasizing the toxic effects of halogen elements on catalysts, we present the synthesis of FeMnKBr/YNa catalysts. This involved the synthesis of the catalyst by melt permeation using Br-containing potassium salts, other metal nitrates and YNa zeolites. The catalyst performed well in converting syngas (H2/CO2 = 3) to light olefins with a selectivity of 56.2%, CO2 conversion of 34.4%, and CO selectivity of 13.6%. Adding Br aids in reducing the Fe phase, boosts catalyst carburization, and produces more iron carbide species. It also moderately deposits carbon on the active center's surface, enhancing active phase dispersion. Br's electronegativity mitigates the influence of K, reducing catalyst's carbon-carbon coupling ability, leading to more low-carbon olefins generation.

A facile method for separating fine water droplets dispersed in oil through a pre-wetted mesh membrane.

To achieve the successful separation of emulsions containing fine dispersed droplets and low volume fractions, a membrane with pore sizes comparable to or smaller than the droplet size is typically required. Although this approach is effective, its utilization is limited to the separation of emulsions with relatively large droplets. To overcome this limitation, a secondary membrane can be formed on the primary membrane to reduce pore size, but this can also be time-consuming and costly. Therefore, a facile and effective method is still required to be developed for separating emulsions with fine droplets. We introduce a pre-wetted mesh membrane with a pore size significantly larger than droplets, easily fabricated by wetting a hydrophilic stainless-steel mesh with water. Applying this membrane to emulsion separation via gravity-driven flow confirms a high efficiency greater than 98%, even with droplets approximately 10 times smaller than the pore size.

Mechanism insight into the N-C polar bond and Pd-Co heterojunction for improved hydrogen evolution activity.

Constructing platinum-like materials with excellent catalytic activity and low cost has great significance for hydrogen evolution reaction (HER) during electrolysis of water. Herein, palladium nanoparticles (NPs) deposition on the surface of Co NPs using nitrogen-doped carbon (NC) as substrate, denoted as N-ZIFC/CoPd-30, are manufactured and served as HER electrocatalysts. Characterization results and density functional theory calculations validate that Pd-Co heterojunctions with NC acting as "electron donators" promote the Pd species transiting to the electron-rich state based on an efficient electron transfer mechanism, namely the N-C polar bonds induced strong metal-support interaction effect. The electron-rich Pd sites are beneficial to HER. Satisfactorily, N-ZIFC/CoPd-30 have only low overpotentials of 16, 162, and 13 mV@-10 mA cm-2 with the small Tafel slopes of 98 mV/decade, 126 mV/decade, and 72 mV/decade in pH of 13, 7, and 0, respectively. The success in fabricating N-ZIFC/CoPd opens a promising path to constructing other platinum-like electrocatalysts with high HER activity.

Oxygen vacancy enhanced photocatalytic activity of Cu2O/TiO2 heterojunction.

In this study, a method was developed to create oxygen vacancies in Cu2O/TiO2 heterojunctions. By varying the amounts of ethylenediaminetetraacetic acid (EDTA), sodium citrate, and copper acetate, Cu2O/TiO2 with different Cu ratios were synthesized. Tests on CO2 photocatalytic reduction revealed that Cu2O/TiO2's performance is influenced by Cu content. The ideal Cu mass fraction in Cu2O/TiO2, determined by inductively coupled plasma (ICP), is between 0.075% and 0.55%, with the highest CO yield being 10.22 µmol g-1 h-1, significantly surpassing pure TiO2. High-resolution transmission electron microscopy and electron paramagnetic resonance studies showed optimal oxygen vacancy in the most effective heterojunction. Density functional theory (DFT) calculations indicated a 0.088 eV lower energy barrier for ∗CO2 to ∗COOH conversion in Cu2O/TiO2 with oxygen vacancy compared to TiO2, suggesting that oxygen vacancies enhance photocatalytic activity.

1,3-diene-based AIEgens: Stereoselective synthesis and applications.

In recent years, significant advancements have been made in the synthesis and application of 1,3-dienes. This specific structural motif has garnered significant attention from researchers in materials science and biology due to its unique aggregation-induced emission (AIE) properties and extensive conjugation systems. The luminescent characteristics of these compounds are notably influenced by the geometry of the two double bonds. Therefore, it is essential to consolidate stereoselective synthetic strategies for 1,3-dienes. This comprehensive review seeks to elucidate the diverse techniques employed to attain stereo-control in the synthesis of 1,3-diene-based AIE luminogens (AIEgens). Particular emphasis is placed on comprehending the determinants of stereoselectivity and exploring the array of substrates amenable to these methods. Furthermore, the review underscores the AIE properties exhibited by these compounds and their extensive utility in organic light-emitting diodes (OLEDs), stimuli-responsive materials, sensors, bioimaging, and photodynamic therapy (PDT).

Electro-, thermo-, and photocatalysis of versatile nanocomposites toward tandem process.

Tandem reactions involve multi-step processes conducted in one pot, offering a cost-effective, environmentally friendly, and efficient approach to chemical transformations with high atom economy. The catalytic systems employed in tandem reactions are crucial for achieving desirable activity, selectivity, and stability. Researchers worldwide have extensively explored catalytic processes driven by various energy fields, such as electrocatalysis, thermocatalysis, and photocatalysis, aiming to facilitate multiple reactions and bond transformations. Continuous advancements have been made in reaction conditions, catalyst design, and preparation methods. This review provides a comprehensive overview of recent progress in tandem reactions, specifically focusing on electro-, thermo-, and photocatalysis, and categorizes them into catalysts, reactors, and fields based on their applications. Furthermore, the review highlights the significance of rational design in nanomaterial catalysts and the integration of multiple energy sources, emphasizing their potential to enhance selectivity, performance, and the development of combined catalysis.

Boosting CO2 electrocatalysis through electrical double layer regulations.

Interfacial investigation for fine-tuning microenvironment has recently emerged as a promising method to optimize the electrochemical CO2 reduction system. The electrical double layer located at the electrode-electrolyte interface presents a particularly significant impact on electrochemical reactions. However, its effect on the activity and selectivity of CO2 electrocatalysis remains poorly understood. Here, we utilized two-dimensional mica flakes, a material with a high dielectric constant, to modify the electrical double layer of Ag nanoparticles. This modification resulted in a significant enhancement of current densities for CO2 reduction and an impressive Faradaic efficiency of 98% for CO production. Our mechanistic investigations suggest that the enhancement of the electrical double layer capacitance through mica modification enriched local CO2 concentration near the reaction interface, thus facilitating CO2 electroreduction.

Steerable mass transport in a photoresponsive system for advanced anticounterfeiting.

Numerous anticounterfeiting platforms using photoresponsive materials have been designed to improve information security, enabling applications in anticounterfeiting technology. However, fabricating sophisticated micro/nanostructures using bidirectional mass transport to achieve advanced anticounterfeiting remains challenging. Here, we propose one strategy to achieve steerable mass transport in a photoresponsive system with the assistance of solvent vapor at room temperature. Upon optimizing the host-guest ratio and the width of photoisomerized areas, wettability gradient is acquired just photo-patterning once, then bidirectional mass transport is realized due to the competition of mass transport induced by surface energy gradient of the material itself and flow of the solvent on the film surface with wettability gradient. Taking advantage of the interaction between solvent and film surface with wettability gradient, this bidirectional polymer flow has been successfully applied in multi-mode anticounterfeiting. This work paves a promising avenue toward high-level information storage in soft materials, demonstrating the potential applications in anticounterfeiting.

An opportunity for acerola pulp (Malpighia emarginata DC) valorization evaluating its performance during the block cryoconcentration by physicochemical, bioactive compounds, HPLC-ESI-MS/MS, and multi-elemental profile analysis.

The present study evaluated the effect of cryoconcentration of pulp blocks of acerola (Malpighia emarginata DC). The study evaluated cryoconcentration in three stages. The cryoconcentrated samples, the ice fractions, and the initial pulp were evaluated for physicochemical composition, bioactive composition, and multielement profile. The cryoconcentrated sample obtained in the third stage of cryoconcentration showed the best results for the concentration factor, process efficiency, total soluble solids content, red color intensity, and increasing of the macro and micronutrients: Cu, Ca, S, Sr, K, Mn, Na, P, Mg, Fe. All stages presented good performance in the total soluble solids content, increase in the titratable acidity of the concentrates, and progressive increase in the intensity of the red color. Generally, higher levels of total phenolic and antioxidant activity were found for the 2nd and 3rd concentrates. The phenolic activity showed an increase of 166.90% in the 3rd stage concentrate compared to fresh pulp, and the antioxidant activity was 112.10% by the ABTS method and 131.60% by the DPPH method, both in the 3rd stage concentrate. The major individual polyphenols were Ferulic acid, Protocatechuic acid, and Taxifolin, with significant increases in the concentration of the compounds in the 2nd and 3rd stage concentrates. In addition, the contents of potentially toxic metals were below detection limits. During the cryoconcentration process, there was a decrease in the values ​​of vitamin C content, moisture content, density, and elements Cu, Sr, and Zn.

Designing highly efficient oxygen evolution reaction electrocatalyst of high-entropy oxides FeCoNiZrOx: Theory and experiment.

The correlations between the experimental methods and catalytic activities are urgent to be defined for the design of highly efficient catalysts. In this work, a new oxygen evolution reaction electrocatalyst of high-entropy oxide (HEO) FeCoNiZrOx was designed and analyzed by experimental and theoretical methods. On account of the shortened coordinate bond along with the increased annealing temperature, the atomic/electronic structures of active site were adjusted quantitatively with the aid of the pre-designed correlator of d electron density, which contributed to adjust the catalytic activity of HEO specimens. The prepared HEO specimen exhibited the low overpotentials of 245 mV at 10 mA cm-2 and 288 mV at 100 mA cm-2 with small Tafel slope of 35.66 mV dec-1, fast charge transfer rate, and stable electrocatalytic activity. This strategy would be adopted to improve the catalytic activity of HEO by adjusting the d electron density of transition metal ions with suitable preparation method.

Boosting electrocatalytic performance via electronic structure regulation for acidic oxygen evolution.

High-purity hydrogen produced by water electrolysis has become a sustainable energy carrier. Due to the corrosive environments and strong oxidizing working conditions, the main challenge faced by acidic water oxidation is the decrease in the activity and stability of anodic electrocatalysts. To address this issue, efficient strategies have been developed to design electrocatalysts toward acidic OER with excellent intrinsic performance. Electronic structure modification achieved through defect engineering, doping, alloying, atomic arrangement, surface reconstruction, and constructing metal-support interactions provides an effective means to boost OER. Based on introducing OER mechanism commonly present in acidic environments, this review comprehensively summarizes the effective strategies for regulating the electronic structure to boost the activity and stability of catalytic materials. Finally, several promising research directions are discussed to inspire the design and synthesis of high-performance acidic OER electrocatalysts.

Determination of the Concentration of Heavy Metals in Artisanal Cheeses Produced in the Mexican States of Tabasco and Chiapas.

Cheese consumption provides humans with minerals, proteins, carbohydrates, and vitamins. In Mexico, several cheese varieties are produced, each with its texture, scent, and flavor. The artisanal cheeses made in the states of Tabasco and Chiapas-including, among others, the varieties named crema (cream), doble crema (double cream), oaxaca, panela, fresco, bola, poro, cotija, and asadero-have a high demand in the domestic and foreign markets. The intensification of anthropic activity in these states causes an increased emission to the environment of contaminants like heavy metals, which could reach human foodstuffs through the food chains. In particular, heavy metal contents in cheeses consumed daily by these states' local populations might represent a public health risk. Because of that, our objectives in this work were to determine the concentrations of lead, cadmium, nickel, copper, zinc, and iron in artisanal cheeses produced in the states of Tabasco and Chiapas and to determine the values of the hazard quotient (HQ), total hazard quotient (THQ), and cancer risk total (CRT) for adult and young men and women. The results of our analyses of cheese samples from the states of Tabasco and Chiapas showed that the average concentrations (mg kg-1) of cadmium (0.0023 ± 0.002, 0.0023 ± 0.002 mg kg-1, respectively, for each state), lead (0.0047 ± 0.00, 0.0051 ± 0.002), nickel (0.0039 ± 0.0046, 0.0031 ± 0.0039), copper (0.0199 ± 0.021, 0.0202 ± 0.022), zinc (0.1611 ± 0.18, 0.194 ± 0.21), and iron (61.84 ± 4.23, 65.76 ± 6.61 mg kg-1), the first three values lower than the limits established by the FAO/WHO and Codex Alimentarius. The value of THQ that we obtained was less than one, and that of CRT was within the limits established by the US-EPA, which means that the consumption of artisanal cheeses from Tabasco and Chiapas by humans does not imply a risk of disease or cancer.

Impact and repercussions of the Ostwald-de Izaguirre theory for adsorption from liquid mixtures: A 100-year perspective.

The theory developed in 1922 by Wolfgang Ostwald and Ramón de Izaguirre for adsorption from solution is revisited one hundred years later, with a main focus on its impact and repercussions. A concise historical account is initiated with an examination of the circumstances under which that work was generated. After providing some biographic data about the authors' backgrounds at the time they developed it, a concise description of the so-called Ostwald-de Izaguirre theory is presented. This is followed by an assessment of its impact as a whole in the first decades after it was produced. Starting from about 1960, interest was focused on two separate outcomes from the theory: (i) the first classification of adsorption isotherms ever proposed, and (ii) an equation (Ostwald-de Izaguirre equation) that describes adsorption by solids of binary mixtures of miscible liquids and allows separating the contributions from both components of the solution. Although still in occasional use today, the isotherm classification made by Ostwald and de Izaguirre is of almost exclusively historical interest, having been displaced by Giles' classification. Unlike this, the Ostwald-de Izaguirre equation is still used and, since it derives from a simple mass balance, there is general agreement that no assumptions were made that limit its use. Thus, it seems that there is nothing to prevent the applicability of this equation in the future.

The concerted proton-electron transfer mechanism of proton migration in the electrochemical interface.

The proton migration in the electrochemical interface is a fundamental electrochemical processes in proton involved reactions. We find fractional electron transfer, which is inversely proportional to the distance between the proton and electrode, during the proton migration under constant potential. The electrical energy carried by the transferred charge facilitates the proton to overcome the chemical barrier in the migration pathway, which is accounting for more than half electrical energy in the proton involved reactions. Consequently, less charge transfer and energy exchange take place in the reduction process. Therefore, the proton migration in the electrochemical interface is an essential component of the electrochemical reaction in terms of electron transfer and energy conversation, and are worthy of more attention in the rational design and optimization of electrochemical systems.

Construction of High Accuracy Machine Learning Interatomic Potential for Surface/Interface of Nanomaterials-A Review.

The inherent discontinuity and unique dimensional attributes of nanomaterial surfaces and interfaces bestow them with various exceptional properties. These properties, however, also introduce difficulties for both experimental and computational studies. The advent of machine learning interatomic potential (MLIP) addresses some of the limitations associated with empirical force fields, presenting a valuable avenue for accurate simulations of these surfaces/interfaces of nanomaterials. Central to this approach is the idea of capturing the relationship between system configuration and potential energy, leveraging the proficiency of machine learning (ML) to precisely approximate high-dimensional functions. This review offers an in-depth examination of MLIP principles and their execution and elaborates on their applications in the realm of nanomaterial surface and interface systems. The prevailing challenges faced by this potent methodology are also discussed.

Understanding oxygen evolution mechanisms by tracking charge flow at the atomic level.

Current classifications of oxygen evolution catalysts are based on energy levels of the clean catalysts. It is generally asserted that a LOM-catalyst can only follow LOM chemistry in each electron transfer step and that there can be no mixing between AEM and LOM steps without an external trigger. We use ab initio theory to track the charge flow of the water-on-catalyst system and show that the position of water orbitals is pivotal in determining whether an electron transfer step is water dominated oxidation (WDO), lattice-oxygen dominated oxidation (LoDO), or metal dominated oxidation (MDO). Microscopic photo-catalytic pathways of TiO2 (110), a material whose lattice oxygen bands lie above the metal bands, show that viable OER pathways follow either all AEM steps or mixed AEM-LOM steps. The results provide a correct description of redox chemistries at the atomic level and advance our understanding of how water-splitting catalysts produce desorbed oxygen.