Hydrocarbon Extraction with Ionic Liquids.

Separation and reaction processes are key components employed in the modern chemical industry, and the former accounts for the majority of the energy consumption therein. In particular, hydrocarbon separation and purification processes, such as aromatics extraction, desulfurization, and denitrification, are challenging in petroleum refinement, an industrial cornerstone that provides raw materials for products used in human activities. The major technical shortcomings in solvent extraction are volatile solvent loss, product entrainment leading to secondary pollution, low separation efficiency, and high regeneration energy consumption due to the use of traditional organic solvents with high boiling points as extraction agents. Ionic liquids (ILs), a class of designable functional solvents or materials, have been widely used in chemical separation processes to replace conventional organic solvents after nearly 30 years of rapid development. Herein, we provide a systematic and comprehensive review of the state-of-the-art progress in ILs in the field of extractive hydrocarbon separation (i.e., aromatics extraction, desulfurization, and denitrification) including (i) molecular thermodynamic models of IL systems that enable rapid large-scale screening of IL candidates and phase equilibrium prediction of extraction processes; (ii) structure-property relationships between anionic and cationic structures of ILs and their separation performance (i.e., selectivity and distribution coefficients); (iii) IL-related extractive separation mechanisms (e.g., the magnitude, strength, and sites of intermolecular interactions depending on the separation system and IL structure); and (iv) process simulation and design of IL-related extraction at the industrial scale based on validated thermodynamic models. In short, this Review provides an easy-to-read exhaustive reference on IL-related extractive separation of hydrocarbon mixtures from the multiscale perspective of molecules, thermodynamics, and processes. It also extends to progress in IL analogs, deep eutectic solvents (DESs) in this research area, and discusses the current challenges faced by ILs in related separation fields as well as future directions and opportunities.

Molecular insights into dicationic versus monocationic ionic liquids as a high hydrophobic alternative for the separation of phenol from waters.

The hydrophobic nature of an extractant is particularly critical in the treatment of wastewater. Considering that dicationic ionic liquids (DILs) are likely to be more hydrophobic, a comparative study of the separation of phenol from waters using [NTf2]- based monocationic ionic liquids (MILs) and DILs is carried out both from experimental and theoretical analysis perspectives. Experimental results revealed that DILs exhibited superior extraction ability compared to MILs, with extraction efficiencies of 93.7% and 97.4% using [BMIM][NTf2] and [C6(MIM)2][NTf2]2 as extractants, respectively. The microscopic examination through theoretical calculations elucidated the higher hydrophobicity and extraction efficiency of DILs over MILs. The results indicated that the DIL showed stronger hydrophobicity than the MIL because the hydrogen bond strength between the DIL and water was lower than that of the MIL. Although the hydrogen bond strength between the DIL and phenol was lower than that of the MIL, the stronger van der Waals forces existed between DIL and phenol, so DIL was more efficient in extracting phenol. In addition, the experimental parameters were optimized to provide basic data for application, such as mass ratio of ILs to water, extraction time and temperature, pH, and initial phenol content. Finally, the DILs were recovered using rotary evaporation apparatus, and the results demonstrated that DILs had good recovery and reuse performance. In brief, this work could provide an effective method for the treatment of phenol-containing wastewater. And the revelation of molecular mechanism is expected to positively impact the design of high-performance task-specific ILs.

Environmental Sustainability of π-Electron Donor-Based Deep Eutectic Solvents for Toluene Absorption: A Life-Cycle Perspective.

The novel π-electron donor-based deep eutectic solvents (DESs) have been shown to be a promising type of absorbent with excellent performance on toluene absorption. However, their greenness or sustainability is still unclear. Thus, to bridge the gap and give a comprehensive evaluation for their industrialization potential, the life cycle assessment (LCA) was used to evaluate the potential environmental impacts incurred from their production and usage for absorbing toluene. The environmental profiles are also compared with that of popular choline chloride (ChCl) based DES, common organic solvent triethylene glycol (TEG) and ionic liquid ([EMIM][Tf2 N]). The results indicate that among the involved hydrogen bond acceptors (HBAs), TEBAC generally imparts lower environmental impacts than other HBAs but has higher impacts than ChCl. Although TEBAC-PhOH is not the most environmentally friendly absorbent during the production stage, its outstanding absorption performance minimizes the environmental impact when absorbing the same mass of toluene. Furthermore, the environmental impacts of the toluene absorption process using TEBAC-PhOH is significantly lower than that of [EMIM][Tf2 N], slightly lower than TEG. Therefore, considering both absorption performance and environmental impacts, TEBAC-PhOH can be used as a promising "green and sustainable" toluene absorbent to traditional absorbents and ionic liquids.

Energy Applications of Ionic Liquids: Recent Developments and Future Prospects.

Ionic liquids (ILs) consisting entirely of ions exhibit many fascinating and tunable properties, making them promising functional materials for a large number of energy-related applications. For example, ILs have been employed as electrolytes for electrochemical energy storage and conversion, as heat transfer fluids and phase-change materials for thermal energy transfer and storage, as solvents and/or catalysts for CO2 capture, CO2 conversion, biomass treatment and biofuel extraction, and as high-energy propellants for aerospace applications. This paper provides an extensive overview on the various energy applications of ILs and offers some thinking and viewpoints on the current challenges and emerging opportunities in each area. The basic fundamentals (structures and properties) of ILs are first introduced. Then, motivations and successful applications of ILs in the energy field are concisely outlined. Later, a detailed review of recent representative works in each area is provided. For each application, the role of ILs and their associated benefits are elaborated. Research trends and insights into the selection of ILs to achieve improved performance are analyzed as well. Challenges and future opportunities are pointed out before the paper is concluded.

Mechanistic insight into the effect of active site motif structures on direct oxidation of methane to methanol over Cu-ZSM-5.

Direct oxidation of methane to methanol (DMTM), a highly challenging reaction in C1 chemistry, has attracted lots of attention. Herein, we investigate the continuous H2O-mediated N2O-DMTM over a series of Cu-ZSM-5-n zeolites prepared by a solid-state ion-exchange method. Excellent CH3OH productivity (194.8 µmol gcat-1 h-1) and selectivity (67.1%) can be achieved over Cu-ZSM-5-0.3%, which surpasses most recently reported zeolite catalysts. The effect of the active site motif structure on the reaction was systematically investigated by the combined experimental and theoretical studies. It has been revealed that both the monomeric [Cu]+ and binuclear [Cu]+-[Cu]+ sites function to produce CH3OH, following the radical rebound mechanism, wherein the latter one plays a dominant role due to the synergistic effect of neighboring [Cu]+ that can efficiently reduce the N2O dissociation barrier to generate active oxygen for CH4 oxidation. Microkinetic modeling results further show that the dicopper site possesses a much higher net reaction rate (1.23 × 105 s-1) than the monomeric Cu site (0.962 s-1); moreover, H2O can shift the rate determining step from the CH3OH desorption step to the N2O dissociation step over the dicopper site, thereby efficiently favoring CH3OH production and resisting carbon deposition. Generally, the study in the present work would substantially favor other highly efficient catalyst designs.

Influences and mechanisms of pyrolytic conditions on recycling BTX products from passenger car waste tires.

Pyrolysis is an effective method for waste tire disposal. However, it has rarely been used to recycle specific highly valuable components (such as benzene, toluene, and xylene (BTX)) from tire rubbers, owing to complicated pyrolytic reactions. This study investigated the pyrolysis process of passenger-car-waste-tires (PCWT) with the help of TG-DTG and Py-GC/MS. Based on response surface methodology (RSM), the effect of pyrolytic parameters on the yields of pyrolytic oil and BTX is evaluated. Furthermore, the BTX generation mechanisms are discussed from the perspective of aliphatic and aromatic hydrocarbon transformations. Additionally, pyrolytic conditions including temperature, rubber particle size, pressure, and gas flow rate were systemically investigated and the optimum pyrolytic condition for yield of BTX (26.5 g per 100 g tire rubber) was obtained [765 K, 0.7 mm, 0.52 MPa and 2.5 mL (g min)-1]. Therein, yield of benzene, toluene and xylene were 1.07, 5.03 and 20.40 g per 100 g tire rubber, respectively. During PCWT pyrolysis, BTX is primarily obtained via the Diels-Alder reactions of small-chain alkenes and transformations of limonene and aromatics. This study elucidates the BTX generation mechanisms during PCWT pyrolysis and clarifies the effects of varying pyrolytic conditions on BTX generation.

Mesoscale study of crystal-plane effects of Ni catalysts on CO2 hydrogenation.

Crystal-plane effects have pivotal roles in the design of catalysts. In this study, a branched Ni (Ni-BN) catalyst was mainly exposed at the Ni(322) surface and was synthesized in the presence of H2. A Ni nanoparticle (Ni-NP) catalyst was mainly exposed at Ni(111) and Ni(100) surfaces and was synthesized without H2. The Ni-BN catalyst showed higher CO2 conversion and methane selectivity than the Ni-NP catalyst. DRIFTS revealed that, unlike the formate route for methanation over the Ni-BN catalyst, the main methanation pathway over the Ni-NP catalyst was the CO2 direct dissociation route, which revealed that the diversity of reaction mechanisms of CO2 methanation on different crystal planes led to the disparity in catalyst activity. DFT calculation of the CO2 hydrogenation reaction over various surfaces showed that the energy barriers on Ni(110) and Ni(322) surfaces were lower than those of Ni(111) and Ni(100) surfaces, which was also related to different pathways of the reaction mechanism. Microkinetic analysis showed the reaction rates on Ni(110) and Ni(322) surfaces were higher than those of other surfaces, and CH4 was the main product on all calculated surfaces, whereas the yields of CO on Ni(111) and Ni(100) surfaces were higher. Kinetic Monte Carlo simulations revealed that the Ni(322) surface with stepped sites was responsible for CH4 generation, and that simulated methane selectivity was consistent with experimental results. The crystal-plane effects of the two morphologies of Ni nanocrystals explained why the reaction activity of the Ni-BN catalyst was greater than that of the Ni-NP catalyst.

Collaborative Purification of Tert-Butanol and N2O over Fe/Co-Zeolite Catalysts.

N2O is a greenhouse gas and a candidate oxidant. Volatile organic pollutants (VOCs) have caused great harm to the atmospheric ecological environment. Developing the technique utilizing N2O as the oxidant to oxidize VOCs to realize the collaborative purification has significant importance and practical value for N2O emission control and VOC abatement. Therefore, the study of N2O catalytic oxidation of tert-butanol based on zeolite catalysts was carried out. A series of molecular sieves, including FER, MOR, ZSM-5, Y, and BEA, were selected as the catalyst objects, and the 1.5% wt Fe and Co were, respectively, loaded on the zeolite catalysts via the impregnation method. It was found that the catalytic performance of BEA was the best among the molecular sieves. Comparing the catalytic performance of Fe-BEA under different load gradients (0.25~2%), it was found that 1.5% Fe-BEA possessed the best catalytic activity. A series of characterization methods showed that Fe3+ content in 1.5% Fe-BEA was the highest, and more active sites formed to promote the catalytic reaction. The α-O in the reaction eventually oxidized tert-butanol to CO2 over the active site. The Co mainly existed in the form of Co2+ cations over Co-BEA samples; the 2% Co-BEA possessing higher amounts of Co2+ exhibited the highest activity among the prepared Co-BEA samples.

Deep insights into the viscosity of deep eutectic solvents by an XGBoost-based model plus SHapley Additive exPlanation.

Deep eutectic solvents (DESs) are emerging as novel green solvents for the processes of mass transport and heat transfer, in which the viscosity of DESs is important for their industrial applications. However, for DESs, the measurement of viscosity is time-consuming, and there are many factors influencing the viscosity, which impedes their wider application. This study aims to develop a data-driven model which could accurately and rapidly predict the viscosity of diverse DESs at different temperatures, and furthermore boost the design and screening of novel DESs. In this work, we collected 107 DESs with 994 experimental values of viscosity from published works. Given the significant effect of water on viscosity, the water content of each collected DES was labeled. The Morgan fingerprint was first employed as a feature to describe the chemical environment of DESs. And four machine learning algorithms were used to train models: support vector regression (SVR), random forest (RF), neural network (NN), and extreme gradient boosting (XGBoost), and XGBoost showed the best predictive performance. In combination with the powerful interpretation method SHapley Additive exPlanation (SHAP), we further revealed the positive or negative effect of features on viscosity. Overall, this work provides a machine learning model which could predict viscosity precisely and facilitate the design and application of DESs.

Synergistic Effect of Sr-O Divacancy and Exposing Facets in SrTiO3 Micro/Nano Particle: Accelerating Exciton Formation and Splitting, Highly Efficient Co2+ Photooxidation.

As a typical perovskite-type crystal, polyhedral strontium titanate (SrTiO3 ) has shown anisotropic charge transport behavior in recent studies, however, the carrier transportation and transition of which has not been explained very clearly. This work present the existence of Sr and O divacancies in the novel rhombicuboctahedron SrTiO3 micro/nano particles (Sr1- x TiO3- x /TiO2- x ) with exposing (100), (110) and (111) facets and the diameter of 300-700 nm synthesized via hydrothermal synthesis, and also summarizes the dissociation mechanism of self-trapped excitons (STEs) caused by the divacancy and facet effect. In addition, most importantly, the metastable STEs with ultra-low binding energy (Eb  < 3 meV) under illumination are discovered. Combining the model of S-scheme heterojunction, a conversion mechanism of photoinduced carriers is proposed. The photocatalytic reaction of Co2+ is used as the probe reaction, and the unique Sr1- x TiO3- x /TiO2- x possesses a high photooxidation efficiency of Co2+ , by which 70.3% of Co2+ is oxidized to Co3+ (CoOOH) in 5 min. This finding may provide a guideline for an optimal design of the photocatalytic materials for the recovery and extraction of metal ions based on SrTiO3 .

strong synergistic effect of the (110) and (100) facets of the SrTiO3 perovskite micro/nanocrystal: decreasing the binding energy of exciton and superb photooxidation capability for Co2.

Crystal facet regulation is an effective method for preparing SrTiO3 or other perovskite semiconductor materials with high photochemical catalysis performance. In general, the edge-truncated cube of SrTiO3 micro-nano particles has been widely reported because of the multiple crystal facets exposed at the same time. However, the effect of the (110) facet and the interaction between the (100) and (110) facets on the properties of photo-induced carriers is still not very clear. In this article, we have designed and prepared two edge-truncated cube SrTiO3-a small and large area proportion of the (110) facet, respectively. In addition to the morphological and structural characterization, high-resolution XPS and femtosecond multiphoton transient absorption (fs-TA) spectroscopy were used to detect the atomic vacancy and were applied to confirm the state of carrier transition. The results showed that the larger (110) facet led to two influences-more Sr vacancies and more self-trapping excitons (STEs) with an ultra-low binding energy (Eb = 2.13 meV), about 1.17 meV lower than that of the sample with the smaller (110) facet. In particular, the larger (110) facet also caused a much higher photooxidation performance for Co2+ to Co3+. This study not only enriches the arsenal of SrTiO3 materials but also sheds new insights into the understanding of the synergistic effect essence of the (100) and (110) facets, which could promote the development of new perovskite photocatalytic materials, particularly in the recovery of heavy metals.

Reviewing and screening ionic liquids and deep eutectic solvents for effective CO2 capture.

CO2 capture is essential for both mitigating CO2 emissions and purifying/conditioning gases for fuel and chemical production. To further improve the process performance with low environmental impacts, different strategies have been proposed, where developing liquid green absorbent for capturing CO2 is one of the effective options. Ionic liquids (IL)/deep eutectic solvents (DES) have recently emerged as green absorbents with unique properties, especially DESs also benefit from facile synthesis, low toxicity, and high biodegradability. To promote their development, this work summarized the recent research progress on ILs/DESs developed for CO2 capture from the aspects of those physical- and chemical-based, and COSMO-RS was combined to predict the properties that are unavailable from published articles in order to evaluate their performance based on the key properties for different IL/DES-based technologies. Finally, top 10 ILs/DESs were listed based on the corresponding criteria. The shared information will provide insight into screening and further developing IL/DES-based technologies for CO2 capture.

Effective absorption of dichloromethane using deep eutectic solvents.

Chlorinated volatile organic compounds (VOCs), of which dichloromethane (DCM) has become one of the main components because of its extensive use and strong volatility, are recognized as extremely hazardous and refractory pollutants in the atmosphere. The efficient treatment of DCM is of great significance to the protection of environment and human health. In this work, the strategy of DCM capture with deep eutectic solvents (DESs) with different hydrogen bond acceptors (HBAs) and hydrogen bond donors (HBDs) was proposed and systematically investigated. The experimental results show that tetrabutylphosphonium chloride: levulinic acid ([P4444][Cl]-LEV) presents the most excellent DCM absorption capacity among all DESs studied and considerable capacity in [P4444][Cl]-LEV (1:2) with 899 mg DCM/g DES (5.58 mol DCM/mol DES) at 30 °C and DCM partial pressure of 0.3 bar can be achieved. The microscopic absorption mechanism is explored by 1HNMR and FT-IR spectra as well as quantum chemistry calculations, indicating that the absorption is a physical process. The interaction energy analysis suggests that the greater the interaction energy between DES and DCM, the greater the saturated absorption capacity of DCM. The hydrogen bond (HB) contributes most to the weak interaction between DCM and HBA/HBD, and both HBA and HBD play an important role in the absorption of DCM.

Study of passenger-car-waste-tire pyrolysis: Behavior and mechanism under kinetical regime.

The pyrolysis of passenger-car-waste-tires (PCWT) has recently attracted widespread attention because it is a highly effective disposal method. However, a comprehensive understanding of real tire pyrolytic processes is limited owing to the complicated PCWT pyrolysis reaction system, particularly regarding the reaction mechanism. This study investigated the PCWT pyrolytic processes using a thermogravimetric analyzer coupled with mass spectrometry and analyzed all the pyrolytic products using pyrolysis-gas chromatography coupled with mass spectrometry. The composition and distribution of the PCWT pyrolytic products were investigated under a kinetic regime to eliminate other influences on the intrinsic reaction. The pyrolytic products mainly consisted of chain and cyclic alkenes, and monocylic aromatics. Importantly, an integral pyrolytic mechanism network for the PCWT was established based on the pyrolysis of single rubbers (natural, styrene butadiene, and butadiene rubbers). The reaction routes for the main products were determined according to the mechanism. Moreover, a kinetic study of the PCWT pyrolysis revealed the activation energy for this complicated reaction system.

H2 O-Built Proton Transfer Bridge Enhances Continuous Methane Oxidation to Methanol over Cu-BEA Zeolite.

Direct oxidation of methane to methanol (DMTM) is a big challenge in C1 chemistry. We present a continuous N2 O-DMTM investigation by simultaneously introducing 10 vol % H2 O into the reaction system over Cu-BEA zeolites. Combining a D2 O isotopic tracer technique and ab initio molecular dynamics (AIMD) simulation, we for the first time demonstrate that the H2 O molecules can participate in the reaction through a proton transfer route, wherein the H2 O molecules can build a high-speed proton transfer bridge between the generated moieties of CH3 - and OH- over the evolved mono(µ-oxo) dicopper ([Cu-O-Cu]2+ ) active site, thereby pronouncedly boosting the CH3 OH selectivity (3.1→71.6 %), productivity (16.8→242.9 µmol gcat -1 h-1 ) and long-term reaction stability (10→70 h) relative to the scenario of absence of H2 O. Unravelling the proton transfer of H2 O over the dicopper [Cu-O-Cu]2+ site would substantially contribute to highly efficient catalyst designs for the continuous DMTM.

Highly efficient capture of odorous sulfur-based VOCs by ionic liquids.

This study proposes the capture of dimethyl sulfide (DMS) and dimethyl disulfide (DMDS) from waste gas using an ionic liquid (IL), namely, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf2N]), and examines the process from a molecular level to the laboratory scale, which is then scaled up to the industrial level. The binding energy and weak interactions between DMS/DMDS and the anion/cation in [EMIM][Tf2N] were investigated using quantum chemistry calculations to identify the capture mechanism at the molecular scale. A thermodynamic model (UNIFAC-Lei) was established by the vapor-liquid equilibrium data of the [EMIM][Tf2N] + DMS/DMDS systems measured at the laboratory scale. The equilibrium and continuous absorption experiments were performed, and the results demonstrated that [EMIM][Tf2N] exhibits a highly efficient capture performance at atmospheric conditions, particularly, absorption capacities (AC) for DMS and DMDS are 189.72 and 212.94 mg g-1, respectively, and partial coefficients (PC) as more reasonable evaluation metrics for those are 0.509 × 10-4 and 6.977 × 10-4 mol kg-1 Pa-1, respectively, at the 100 % breakthrough. Finally, a mathematical model of the strict equilibrium stage was established for process simulations, and the absorption process was conceptually designed at the industrial scale, which could provide a decision-making basis for chemical engineers and designers.

Mechanistic insight into H2-mediated Ni surface diffusion and deposition to form branched Ni nanocrystals: a theoretical study.

Present work systematically investigates the kinetic role played by H2 molecules during Ni surface diffusion and deposition to generate branched Ni nanostructures by employing Density Functional Theory (DFT) calculations and ab initio molecule dynamic (AIMD) simulations, respectively. The Ni surface diffusion results unravel that in comparison to the scenarios of Ni(110) and Ni(100), both the subsurface and surface H hinder the Ni surface diffusion over Ni(111) especially under the surface H coverage of 1.5 ML displaying the lowest Ds values, which greatly favors the trapping of the adatom Ni and subsequent overgrowth along the 111 direction. The Ni deposition simulations by AIMD further suggest that both the H2 molecule (in solution) and surface dissociatively adsorbed atomic H can promote Ni depositions onto Ni(111) and Ni(110) facets in a liquid solution. Moreover, a cooperation effect between H2 molecules and surface atomic H can be clearly observed, which greatly favors Ni depositions. Additionally, in addition to working as the solvent, the liquid C2H5OH can also interact with the Ni(111) surface to produce the surface atomic H, which then favored the Ni deposition. Finally, the Ni deposition rate predicted using the deposition constant (Ddep) was found to be much higher than its surface diffusion rate predicted using Ds for Ni(111) and Ni(110), which quantitatively verified the overgrowth along the 111 and 110 directions to produce the branched Ni nanostructures.