Against the backdrop of global energy transition, methyl propyl carbonate (MPC) has become a key solvent for high-safety lithium-ion battery electrolytes. To solve the problems of poor thermal stability and low conversion efficiency of traditional catalysts in the transesterification of dimethyl carbonate (DMC) and n-propyl alcohol (NPA) to MPC, a temperature-resistant anion exchange resin catalyst (TR-AER-p(V-D-7)-PhO-) was developed, and a reactive distillation (RD) process was proposed. The catalyst exhibited excellent thermal stability, with 91.99% of its strong-base group capacity retained after aging at 95 degrees C for 100 h. Under the optimized reaction conditions, NPA conversion, MPC yield, and selectivity reached 60.33%, 52.17%, and 86.47%, respectively. A pseudo-homogeneous kinetic model was established, and the kinetic parameters were obtained. Besides, a 25theoretical-stage RD column was designed, achieving nearly complete NPA conversion (similar to 100%), 91.05% MPC yield, and 91.45% selectivity. The experimental results agreed well with the simulation. This work provides a green and efficient technical route for MPC production via the synergistic optimization of catalyst structure and process sustainability.

Extraction oxidation desulfurization technology represents a crucial complementary approach to hydrodesulfurization with its effectiveness fundamentally dependent on the performance of the oxidation desulfurization catalyst. A dual-active-site catalyst, based on phosphotungstic acid (HPW) supported on defect-engineered UiO-66, was developed for extraction oxidative desulfurization of diesel. The defect UiO-66 support was fabricated via a grinding method, and glycine (Gly) was subsequently introduced as a molecular bridge to achieve uniform and stable immobilization of HPW within the metal-organic framework. The obtained catalyst was employed in an ODS process of model diesel (n-octane with 1000 ppmS DBT) at room temperature, where H2O2 served as the oxidant and acetonitrile as the extractant. The results revealed that the Zr active sites in UiO-66 can effectively decompose H2O2 into reactive oxygen radicals at room temperature; subsequently such oxygen radicals combine with the W active site in HPW to form highly oxidizing tungsten peroxide species. By optimization of Zr/W ratios, this synergistic effect endowed the UiO-GlyPW composite with exceptional catalytic performance, enabling complete desulfurization of a model oil containing 1000 ppm sulfur within 10 min at room temperature under the conditions of an O/S molar ratio of 5, a catalyst dosage of 3.0 wt %, and an oil-to-extractant ratio of 1.This work provides fundamental insights into the rational design of dual-active-site catalysts for efficient ODS processes under ambient conditions.

Efficient removal of mercury (Hg(II)) from aqueous media remains a critical challenge for environmental protection and public health. Herein, we reported a novel aerogel absorbent, GO@TA@Cys-20, synthesized by thiolgroup grafting onto the framework of a GO@TA composite. The absorbent exhibits an ultrahigh Hg(II) adsorption capacity of (696.9 mg/g), excellent selectivity, and a broad working pH range (1-12). The adsorption isotherm and kinetics analyses reveal that the process follows the Freundlich model and pseudo-second-order kinetics, respectively, indicating a multilayer chemisorption mechanism. Thermodynamic parameters indicate the adsorption is a spontaneous process. The combination of experimental characterizations and density functional theory (DFT) calculations identifies thiol groups as the primary active sites for Hg(II) capture, forming strong coordination bonds. Moreover, a layered porous structure with interconnected bridges is conducive to the improvement of the adsorption capacity of GO@TA@Cys-20. These findings highlight GO@TA@Cys-20 as a promising and durable adsorbent for mercury remediation in contaminated water systems.

ABSTRACT Mercury remediation requires adsorbents with strong affinity, selectivity, and chemical stability. Here, Pd‐catalyzed Buchwald–Hartwig amination of nitroarenes (BH–NO 2 ) was extended to polycondensation, producing a nitrogen‐rich, three‐dimensional crosslinked poly(aniline)‐like network (PN‐PTA). PN‐PTA achieved a distribution coefficient of 2.1 × 10 8 mL g −1 and >99.9% Hg 2+ removal within 10 min. It maintained effective adsorption across pH 1–12, resisted competing ions and harsh chemical conditions, and enabled fixed‐bed purification to sub‐ppb levels. Spectroscopic analyses and DFT calculations indicate that N–Hg coordination provides the primary binding interaction, while the confined polymer environment further stabilizes Hg 2+ . PN‐PTA retained 89.3% removal efficiency after 25 adsorption–desorption cycles. These results demonstrate BH–NO 2 polycondensation as a useful route to nitrogen‐rich polymer networks for Hg 2+ removal from complex water matrices.

Conventional bromide cocatalysts such as tetrabutylammonium bromide (TBAB) are effective for the cycloaddition of CO2 with epoxides, but their industrial application is limited by difficult separation and poor recyclability. Herein, an ionic metal-organic framework (IMOF) catalyst, [D][Br]@sUiO-66-NH2, was prepared by immobilizing 1-H-1,4-diazabicyclo[2.2.2]octane bromide ([D][Br]) on sUiO-66-NH2 through postsynthetic modification. XRD, FT-IR, XPS, SEM, N2 physisorption, and TG analyses (TGA) confirmed the successful incorporation of [D][Br] while preserving the framework structure and porosity of the support. Under solvent- and cocatalyst-free conditions, the catalyst achieved quantitative conversion of styrene oxide (SO) with 80.55% selectivity to styrene carbonate (SC) at 110 °C and 1.0 MPa CO2 after 12 h using 6.0 wt % catalyst. The catalyst also exhibited good reusability, with the GC yield of SC decreasing only slightly from 80.55% to 79.38% after 8 cycles. These results demonstrate that MOF-based immobilization of DABCO-derived bromide species is an effective strategy for developing recyclable heterogeneous catalysts for CO2 cycloaddition.

Base-facilitated transesterification reactions hold a central position in the chemical industry, as they serve as crucial strategies for producing numerous chemicals, particularly for manufacturing ethyl methyl carbonate (EMC) electrolyte of lithium batteries from ethanol (EtOH) and dimethyl carbonate (DMC). However, reported catalysts face challenges including catalyst deactivation and environmental pollution. To tackle these challenges, we report functionalized quaternary ammonium ionic liquids with fine-tuned electronegativity and alkalinity via anion design and electron-withdrawing/donating substituents on the quaternary ammonium. NB222Im achieves the fastest and highest catalytic performance to date; at an ultra-mild reaction time of 5 min and 58 degrees C, its EMC yield reaches 55.61% with 91.57% product selectivity. We successfully correlate electrostatic attraction/electron delocalization ability of anions with the catalytic performance, visualizing the effective production of ethoxy group from EtOH, the selective cleavage of methoxy group from DMC, and their directional combination to form EMC by the nitrogen atoms in imidazole anions. Moreover, compared with the uncatalyzed system, DFT calculations on the proposed reaction mechanism demonstrate that NB222Im can lower the reaction energy barrier for the conversion of DMC to EMC. This barrier is also lower than that of the EMC-to-DEC pathway, thus endowing this ionic liquid with high selectivity toward EMC formation. This work offers a viable strategy to overcome conventional catalyst drawbacks and new insights for efficient EMC synthesis catalyst design, and promotes electrode material development.

In practical wastewater treatment, microporous polymers and polyphenolic materials often suffer from limited adsorption performance for heavy metal ions, primarily due to the restricted pore structure of the former and the poor chemical stability of the latter. Herein, a novel EA@CMPA composite is developed via in-situ confinement of ellagic acid (EA) within Conjugated Microporous Poly(aniline) (CMPA) for efficient Hg(II) removal. EA is anchored within CMPA through dual interactions: (i) hydrogen-bonding and (ii) protonation. This design endows the composite with hierarchically structured mesoporous diffusion channels and abundant active adsorption sites, thereby enabling EA@CMPA to enhancement of the adsorption kinetics and capacity. The resulted EA@CMPA(200) has high Hg(II) adsorption rate h of 640 mg g-1 min-1 and adsorption capacity of 1024 mg g-1. Notably, EA@CMPA maintains a regeneration efficiency over 81.5% after 7 cycles of intensive reuse, demonstrating that the water-soluble ellagic acid is efficiently confined within the pore channels. It also exhibits excellent anti-interference ability and selectivity in actual Hg-containing wastewater, with Hg(II) removal rate of 95.41% and selectivity approaching 100%. The adsorption behavior and mechanism are characterized by FT-IR, XPS, and DFT calculations, revealing that the synergistic interactions between C=O and-NH-sites drive superior Hg(II) capture. This study highlights the potential of EA@CMPA as a high-performance adsorbent for mercury remediation.

The development of highly active catalysts is crucial for oxidative desulfurization (ODS) to meet the growing demand for sulfur-free fuels. In this study, a defect-rich composite catalyst UiO-DAlaPW was successfully synthesized via mechanochemical grinding, wherein phosphotungstic acid (HPW) was encapsulated within a defectengineered UiO-66 framework, utilizing D-alanine (DAla) as a bridging molecule. The synthesized catalyst, UiODAlaPW, significantly enhances the utilization efficiency of hydrogen peroxide (H2O2). In the model oil ODS system, the material exhibited exceptional catalytic performance: achieving deep desulfurization at room temperature within merely 5 min under conditions of extremely low acetonitrile cosolvent usage and a low oxidant/ sulfur (O/S) ratio, accompanied by remarkably high H2O2 utilization efficiency. Moreover, the catalyst maintained high desulfurization efficiency even in the absence of acetonitrile. Characterization by XRD, FT-IR, TGA, and XPS confirmed the successful encapsulation of HPW within the UiO-66 framework. Mechanistic studies revealed a significant synergistic effect between UiO-66 and HPW. The effective cooperation of the two active sites, namely Zr in UiO-66 and PW, significantly enhances the catalytic performance, contributing to superior oxidative desulfurization activity.

Ethyl methyl carbonate (EMC) is the most widely used solvent in lithium-ion battery electrolytes. However, its synthesis via transesterification of dimethyl carbonate (DMC) with diethyl carbonate (DEC) is limited by a high energy barrier. In this work, acid-base bifunctional catalysts [TEA][Im]@M-ZIF-8 (M = Fe, Zr, Ti) were constructed by loading the basic ionic liquid tetraethylammonium imidazolate ([TEA][Im]) into the ZIF-8 framework and introducing Lewis acidic metal centers. The materials were synthesized rapidly at room temperature, with ZIF-8 nucleation completing within 20 s and further shortened to 10 s upon Fe doping. Among them, [TEA][Im]@Fe-ZIF-8 exhibited optimal performance, affording an EMC yield of 70.06% after response surface optimization, and retaining 97.9% activity after six cycles. Characterization confirmed that Fe was uniformly dispersed in the ZIF-8 framework via Fe-N coordination, generating an acid-base bifunctional surface. Combined DFT calculations and in situ FTIR analysis revealed the synergistic catalytic pathway and mechanism between the Fe center and the imidazolate basic site, unambiguously identifying TS3 as the rate-determining step.

The production of high-purity propylene glycol monomethyl ether acetate (PMA) through the transesterification of propylene glycol monomethyl ether (PM) and methyl acetate (MeOAc) is traditionally catalyzed by sodium methoxide. However, the practical application of this method is significantly hindered by the inherent limitations of sodium methoxide, such as its high sensitivity to moisture and propensity for solid precipitation, which impede its effective use in continuous processes. This work proposed a continuous catalytic distillation (CD) process utilizing Amberlyst 15 cation exchange resin as the catalyst. A comprehensive series of reaction kinetic and CD experiments were conducted to evaluate the performance of the proposed process. The results demonstrate that under the optimal operating conditions, namely an ester-to-ether molar ratio of 6:1, a reflux ratio of 5:1, a total feed rate of 0.92 g. min-1, and an evaporation rate of 266.47 m3.m-2.h-1, the conversion rate of PM achieves 99.95%, and the PMA yield is 97.31%. Based on these findings, a process flowsheet for a continuous CD process tailored for the production of electronic-grade PMA is presented. This design incorporates light and heavy removal steps to ensure the production of PMA with a purity of 99.99%. Additionally, the process utilizes pressure swing distillation to recover MeOAc, thereby enhancing the overall efficiency and sustainability of the production process. The proposed continuous CD process offers a highly efficient, cost-effective, and environmentally sustainable solution for the production of electronic-grade PMA. (c) 2025 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

AbstractDimethyl carbonate (DMC) is an important chemical raw material extensively used in organic synthesis, lithium‐ion battery electrolytes, etc. The primary method for industrial synthesis of DMC involves transesterification between ethylene carbonate and MeOH but faces issues with difficult catalyst separation and low catalytic activity. Based on the synergistic catalytic activity of cation and anion, this study develops poly(ionic liquid)s of [NXPIL][PHO] and [N3PIL][Y] with varying alkaline sites and alkalinity levels. This is accomplished by constructing functional polymer monomers containing free radical polymerization sites and nitrogen‐containing alkaline groups, and by polymerizing them with suitable cross‐linking monomers in a specific ratio before exchanging the resulting polymers with different anions. Results show that doping with nitrogen‐containing alkaline groups leads to enhanced basic functional sites while appropriate anions provide intensified alkalinity levels. The [N3PIL][PHO] obtained exhibits superior catalytic activity in transesterification synthesis of DMC, with a yield of 91.43% and selectivity of 99.96% at a reaction time of 2 h. The study also investigates the impact of poly(ionic liquid) cationic structure and anion types, as well as their interactions, on catalytic performance. The findings reveal that the catalytic activity of poly(ionic liquid) is restricted by the interactions between cation and anion. Based on these findings, a possible reaction mechanism was proposed, providing theoretical support for the high‐efficiency production of DMC.

The concentration of complexed Cr( iii ) in industrial-grade tris(2-carboxyethyl) isocyanurate can be reduced to meet semiconductor-grade standards through an adsorption–recrystallization process using electron-rich sulfonated polymers.

The heavy-metal contamination of aquatic environments presents imminent threat. Herein, we report a class of dual-heteroatomic conjugated microporous poly(aniline)s showing high-affinity separation performance toward heavy metals. The prepared keto-CMPA shows monolayer adsorption capacity for Hg (II) as high as 980 mg g(-1) according to the Langmuir model, and ultra-rapid kinetic with h reaching 30.41 mg g(-1) that could be described by the pseudo-second-order model. It maintains excellent stability across six reuses under harsh conditions, and furthermore demonstrates ultradeep separation efficiency that could adsorb almost all of heavy metals to ppb level with low usage. For further industrialization, a competent adsorption device was developed to remove heavy metals down to 1 ppb with a remarkable breakthrough over 20,000 BV. Characterizations and DFT calculation showed that the triangular synergistic region formed by the N-O-sites in the singular CMPA structure provided a feasible binding energy to enable the above impressive performance.

Developing an efficient and sustainable method for producing ethyl methyl carbonate (EMC), a key electrolyte component in lithium-ion batteries, is essential to meet the growing industrial demand and comply with green chemistry principles. Conventional homogeneous processes suffer from excessive sodium-based solid waste and energy-intensive separations, creating an urgent need for a greener alternative. Inspired by the respiratory function of biological lungs, we have rationally designed a novel series of structured flexible ionic polymer catalysts. By introducing polar substrate-sensitive flexible adsorption networks and hydrogen bond-induced selective molecular adsorption active sites, these catalysts enable selective molecular adsorption and activation targeting towards ethanol, making them highly effective and selective with excellent durability. In a mild fixed-bed continuous reaction at 248 K, the EMC yield reaches 67% with a selectivity of over 94%; under reactive distillation conditions, the ethanol conversion exceeds 99.5% with EMC selectivity remaining above 95%. They also demonstrate exceptional operational stability for >3500 h, outperforming all base-triggered transesterification catalysts such as MOF-808. Compared with conventional sodium methoxide, more importantly, our heterogeneous catalysts eliminate 475 t a(-1) of solid waste and reduce separation energy consumption and operating costs by 20%, further quantitatively addressing the mandate of Green Chemistry. This study not only establishes a high-efficiency catalytic pathway for EMC production but also provides a generalizable strategy for designing adaptive catalysts aligned with sustainable chemical manufacturing.

Ethyl methyl carbonate (EMC) serves as a vital raw material in the production of electrolytes for lithium-ion batteries. In recent years, there has been increasing focus on the development of economically efficient methods to prepare EMC through the transesterification occurring between dimethyl carbonate (DMC) and diethyl carbonate (DEC). Nevertheless, the acidic or alkaline catalysts commonly used at present are not suitable for this system. Herein, the acid-base double active site catalyst, known as [DBU+][IM−]@UiO-66, is designed and prepared to enable its application in the synthesis of EMC. The synthesis of [DBU+][IM−]@UiO-66 involves the incorporation of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and imidazole (IM) molecules within the porous framework of UiO-66. The integration of these components creates an active catalyst with acid sites provided by the defect of UiO-66 and base sites derived from [DBU+][IM−] ionic liquid. The porous structure of UiO-66 offers an extensive surface area, ensuring sufficient exposure of the active sites for catalytic reactions. This catalyst combines the mutually reinforcing effects of acid and base sites, enhancing its catalytic performance and selectivity in the desired reaction. In the targeted synthesis of EMC, the [DBU+][IM−]@UiO-66 catalyst demonstrates remarkable efficiency. An EMC yield of 62% and an EMC selectivity of 99.5% were achieved, which demonstrated the effectiveness of the reaction system. The acid sites facilitate the activation of the reactants, while the base sites contribute to the formation of intermediate species. This dual functionality enhances the reaction kinetics and promotes the desired conversion of starting materials into EMC.

The semiconductor industry's rapid evolution necessitates ultra-high-purity N-methyl pyrrolidone (NMP) as an essential electronic-grade solvent. The development of an efficient coordination material to reduce trace metal ions, particularly Na and K metal ions, to below 1 ppb in NMP solution is a significant challenge. To address this, a novel coordination material, St-DVB-g-ACE, has been developed for the removal of Na and K metal ions from NMP. The material was synthesized by grafting 4 '-aminobenzo-15-crown-5-ether onto a strong acid gel resin. The resulting St-DVB-g-ACE-3 exhibited excellent coordination performance for Na and K metal ions, with maximum Langmuir adsorption capacities reaching 20,000 mu g/g and 33,333 mu g/g, respectively. Of particular interest was the ability of St-DVB-g-ACE-3 to reduce all trace metal ions in industrial-grade NMP to below 1 ppb within a fixed bed column, achieving the stringent requirements for electronic-grade NMP at the G3 level. Additionally, the absorbent enhances the purity of NMP from 99.82 % to 99.84 %, indicating that the material is not dissolved and can exist stably in NMP. Its excellent recyclability and reproducibility make it highly practical for industrial use. Density functional theory (DFT) simulation, complemented by spectral analyses, revealed the interaction force and thermodynamic properties between Na and K metal ions and crown ether ring, and illustrated the interaction between anionic sulfonic group (- SO3- ) and metal ions. The prepared resin-grafted crown ether adsorbents are highly effective in the thorough removal of trace metal ions from NMP solution, offering a novel and effective method for the production of electronic-grade NMP.

Designing efficient adsorbents for the deep removal of refractory dibenzothiophene (DBT) from fuel oil is vital for addressing environmental issues such as acid rain. Herein, zinc gluconate and urea-derived porous carbons SF-ZnNC-T (T represents the carbonization temperature) were synthesized without solvents. Through a temperature-controlled process of "melting the zinc gluconate and urea mixture, forming H-bonded polymers, and carbonizing the polymers," the optimal carbon, SF-ZnNC-900, was obtained with a large surface area (2280 m2 g-1), highly dispersed Zn sites, and hierarchical pore structures. Consequently, SF-ZnNC-900 demonstrated significantly higher DBT adsorption capacity of 43.2 mg S g1, compared to just 4.3 mg S g-1 for the precursor. It also demonstrated good reusability, fast adsorption rate, and the ability for ultra-deep desulfurization. The superior DBT adsorption performance resulted from the evaporation of residual zinc species, which generated abundant mesopores that facilitated DBT transformation, as well as the formation of Zn-Nx sites that strengthened the host-guest interaction (DE--1.466 eV). The solvent-free synthesized highly dispersed Zn-doped carbon shows great potential for producing sulfur-free fuel oil and for designing metal-loaded carbon adsorbents. (c) 2024 Institute of Process Engineering, Chinese Academy of Sciences. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co., Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Ethyl methyl carbonate (EMC) is the most extensively used solvent in lithium-ion battery electrolytes. In recent years, the technology for producing EMC through the highly atom-economical transesterification of dimethyl carbonate and diethyl carbonate has garnered widespread attention. However, the commonly used sodium alkoxide basic catalysts exhibit poor catalytic activity due to their insolubility in this nonpolar reaction system. To address this, basic ionic liquids were confined and supported on a lipophilic carrier (UiO-66-NDC) by controlling the lipophilicity, ionic liquid loading, and pore structure through substituent groups on UiO-66-NDC. This led to the development of a catalyst with superior catalytic performance, [DBU+][IM-]@UiO-66-NDC(50). At 108.7 °C, a catalyst dosage of 9.7 wt %, and a 1.4:1 DMC:DEC ratio for 4 h, the yield of EMC reached 62.5%, achieving high catalytic activity for the transesterification synthesis of EMC. Furthermore, the study explored the lipophilicity variations during the modification of [DBU+][IM-]@UiO-66-NDC(X) with naphthyl groups, revealing the mechanism behind the formation of lipophilicity. Finally, using the prepared [DBU+][IM-]@UiO-66-NDC(50) catalytic material, the reaction kinetics for the transesterification synthesis of EMC from dimethyl carbonate and diethyl carbonate was investigated, providing support for the development of lithium-ion battery energy storage technology.

Tar residue produced in the phosgenation process is one of the important hazardous wastes in the toluene diisocyanate (TDI) industry. The efficient degradation and utilization of TDI tar residue have become a tough challenge for TDI enterprises worldwide. Traditional landfill and incinerator processes do not properly use the organic resources in tar residue, and they also pose a danger of soil and air contamination. This study explores aminolysis using polyamines as a highly efficient alternative to TDI tar residue valorization. Aminolysis offers high degradation rates and TDA yields without requiring added catalysts or solvents, presenting a potentially atom-economical process. Using diethylenetriamine (DETA), a TDA yield of approximately 60% alongside the value-added coproduct 1-(2-aminoethyl)-2-imidazolidone (AEI) was achieved under optimized conditions. Density functional theory (DFT) calculations and experimental results support a three-step mechanism involving a sequential amine attack on urea linkages, followed by cyclization. This work demonstrates the potential of aminolysis as a cleaner and effective route for the chemical recycling of TDI tar residue.