Search

[Display omitted] • A novel type of PILs has been fabricated. • PILs integrate the permanent pores of porous solids with the exceptional properties of ILs. • PILs possess high activity and selectivity for the DBT oxidation. • IL moiety serves as an extractant to enrich DBT and creates an electrostatic solvent effect. • UiO-66 moiety serves as a catalysis to handily catalyze the ODS reaction. Developing a highly efficient strategy for the stabilization of the solid-liquid interface is a persistent pursuit for researchers. Herein, porous ionic liquids based on UiO-66 (Zr) porous materials were synthesized and applied to the selective desulfurization catalysis, which integrates the permanent pores of porous solids with the exceptional properties of ionic liquids. Results show that porous ionic liquids possess high activity and selectivity for dibenzothiophene. Experimental analysis and density functional theory calculations revealed that the ionic liquids moiety served as an extractant to enrich dibenzothiophene into the porous ionic liquids phase through the π···π and C H···π interactions. Additionally, the electrostatic solvent effect in the porous ionic liquids contributes to the stabilization solid-liquid interface, which was favorable for UiO-66 moiety to catalytically activate hydrogen peroxide (H 2 O 2) to generate ·OH radicals, and subsequently oxidized dibenzothiophene to the corresponding sulfone. It is hoped that the development of porous ionic liquids could pave a new route to the stabilization of the solid-liquid interface for catalytic oxidation. [ABSTRACT FROM AUTHOR]

The electrocatalytic CO2 reduction (ECR) to produce valuable fuel is a promising process for addressing atmospheric CO2 emissions and energy shortages. In this study, Cl‐anion doped cadmium sulfide structures were directly fabricated on a nickel foam surface (Cl/CdS‐NF) using an in situ hydrothermal method. The Cl‐anion doping could significantly improve ECR activity for CO production in ionic liquid and acetonitrile mixed solution, compared to pristine CdS. The highest Faradaic efficiency of CO is 98.1 % on a Cl/CdS‐NF‐2 cathode with an excellent current density of 137.0 mA cm−2 at −2.25 V versus ferrocene/ferrocenium (Fc/Fc+, all potentials are versus Fc/Fc+ in this study). In particular, CO Faradaic efficiencies remained above 80 % in a wide potential range of −2.05 V to −2.45 V and a maximum partial current density (192.6 mA cm−2) was achieved at −2.35 V. The Cl/CdS‐NF‐2, with appropriate Cl anions, displayed abundant active sites and a suitable electronic structure, resulting in outstanding ECR activity. Density functional theory calculations further demonstrated that Cl/CdS is beneficial for increasing the adsorption capacities of *COOH and *H, which can enhance the activity of the ECR toward CO and suppress the hydrogen evolution reaction. [ABSTRACT FROM AUTHOR]

This study employed the DFT method to calculate the catalytic activity of various organic functional groups during phenol production on seaweed biochar. It also used machine learning to analyze the correlation between electronic structure parameters of different sites and their catalytic activity. Finally, it summarized the essential characteristics of the most active site. [Display omitted] • Establishing cluster models of algal biochar catalyst and its catalytic mechanisms for lignin upgrading using a DFT method. • Decision trees, random forests, gradient boosting, and extreme gradient boosting were used to establish prediction models. • The random forest method performs best in revealing catalyst reactivity. • Fukui function is an effective descriptor for evaluating the reaction activity of adsorption sites. With the continuous development of the industrialization process, the reserves of primary energy sources such as petroleum have sharply decreased. The development of efficient and economical catalysts is of great significance in promoting the rapid pyrolysis of biomass to produce high-quality liquid fuels and chemicals. In this study, density functional theory (DFT) and machine learning (ML) were used to explore the catalytic reaction mechanism of guaiacol pyrolysis over seaweed biochar catalyst. Models of algae biochar catalysts with oxygen-containing or nitrogen-containing functional groups were established, and the surface transformation mechanism of guaiacol over the biochar catalyst was calculated using DFT. Furthermore, four machine learning methods (decision tree (DT), random forest (RF), gradient boosting (GB), and extreme gradient boosting (XGBoost)) were used to establish a mathematical model based on catalyst characteristics for predicting key intermediate adsorption energy during catalysis reaction. The fitting results and performance analysis of each prediction model show that the RF method-trained model has the highest accuracy. Fukui function (f-) was proved as an effective descriptor to evaluate the reactivity of adsorbed sites. This study provides a pathway to developing more efficient biochar catalysts, which could lead to more sustainable and environmentally friendly energy solutions. [ABSTRACT FROM AUTHOR]

[Display omitted] • UiO-66-BAPILs were designed and fabricated for oxidative desulfurization. • The permanent cavity in UiO-66-BAPILs was validated by gas uptake experiments and molecular size simulations. • UiO-66-BAPILs exhibited higher catalytic activity than the two components. • The mechanism was in detail studied by experiments and theoretical calculations. Porous ionic liquids have been highlighted with special interest for their desirable catalytic activity and extraction properties. Herein, bifunctional porous ionic liquids (denoted UiO-66-BAPILs) were synthesized by dispersing UiO-66 into a pyridinium-based Brønsted acidic ionic liquid ([BSPy][CF 3 SO 3 ]) for oxidative desulfurization. The permanent cavity of UiO-66 moiety in UiO-66-BAPILs was validated as well-preserved by the SO 2 uptake experiments and molecular size simulations. Under the optimum reaction conditions, the sulfur removal could reach up to 99.5% with hydrogen peroxide as the oxidant. Additionally, bifunctional UiO-66-BAPILs were deemed as both extractants and catalysts during the reaction. A possible mechanism has been proposed that UiO-66-BAPILs extract the aromatic sulfur compounds via π···π interactions and C-H···π interactions and meanwhile oxidize them with peroxysulfonic acids and •OH radicals. These findings will open up new avenues to facilitate the catalytic oxidation performance by constructing bifunctional Brønsted acidic porous ionic liquids. [ABSTRACT FROM AUTHOR]

Lignin is a vital organic constituent of plant biomass and it can be transformed into value-added chemicals through chemical processes. This study employs the Density Functional Theory (DFT) to investigate the mechanistic effects of various oxidants on the depolymerization of sodium lignosulfonate model compounds into vanillin. Under alkaline conditions, OH- ions participation in the hydrolysis of β-O-4 bonds has been predicted. The dehydration of dihydroconiferyl alcohol to form eugenol, with an energy barrier of 69.0 kcal/mol was identified as the major rate-determining step in the oxidation reaction. In the absence of an oxidant, the energy barrier for the oxidation of eugenol to vanillin was 77.8 kcal/mol. However, when using nitrobenzene or H 2 O 2 as oxidants, the energy barrier has significantly decreased to 12.6 kcal/mol and 21.4 kcal/mol, respectively. The effects of temperature and pressure on the rate-determining step of the reaction were analyzed using Statistical Product and Service Solutions (SPSS) software. These results have demonstrated that the energy barrier for the hydrolysis reaction's rate-determining step is positively correlated with temperature but negatively correlated with pressure. These theoretical findings would potentially help in designing the experiments and aid in enhancing the selectivity and yield of vanillin. [Display omitted] • OH- ions promote the breaking of β-O-4 bonds. • Using oxidants like nitrobenzene or H 2 O 2 reduces energy barrier. • Nitrobenzene oxidizes isoeugenol to vanillin with lower energy barrier. [ABSTRACT FROM AUTHOR]

[Display omitted] • Graphdiyne-like boron nitride nanosheets were transformed into SAAs. • SAAs exhibit an enhanced adsorption capacity. • The CO 2 adsorption mechanism was evaluated in detail. • Charge transfer is the main factor in CO 2 adsorption. Developing an efficient adsorbent with optimal absorption capacity for carbon dioxide (CO 2) has always been a significant issue. Recently, single-atom adsorbents (SAAs) have been highlighted with special interest as a promising material with a wide range of applications. Nevertheless, comprehending the intricate mechanisms of gas adsorption on SAAs remains an enormous challenge. Herein, we have systematically evaluated the adsorption mechanisms over the transition metals (Fe, Co, Ni, Cu, and Zn) embedded onto the graphdiyne-like boron nitride monolayer using density functional theory calculations. Results show that SAAs exhibit a promoted capacity compared to the pristine graphdiyne-like boron nitride monolayer, mainly ascribed to the electron donation and back-donation mechanism between metal and CO 2. Further, BNene/Fe is favorable for CO 2 adsorption with the strongest interaction energy (−20.7 kcal mol−1). We hope this work will facilitate the design of SAAs in the field of gas adsorption. [ABSTRACT FROM AUTHOR]