Journal of Environmental Chemical Engineering
·
2025
·Vol. 13
·期 6
·119794
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IF 7.2
Peng Zuo,Xianping Chu,Fanfan Liu,Xu Cai,Ruichen Li,Yanbo Sun,Zhouqin Xu,Zhiwei Zhang,Yun Shen,Jinyun Liu,Yefeng Liu
In this study, a novel strategy was developed to synthesize a defect-rich, highly dispersed N, P co-doped molybdenum-based catalyst (MoO 3 /NCG-P) by anchoring phosphomolybdic acid (PMA) clusters onto dopamine (PDA)-modified graphene oxide (GO), followed by thermal treatment. The self-polymerized PDA layer not only served as a nitrogen-rich carbon precursor but also provided abundant anchoring sites for PMA immobilization, while PMA simultaneously acted as both the Mo and P sources. Upon pyrolysis, PMA was in situ decomposed into ultrafine molybdenum trioxide (MoO 3 ) nanoparticles enriched with vacancy defects, and uniformly dispersed on N, P co-doped porous graphene sheets (NCG-P) derived from GO@PDA. This process simultaneously generated strong interfacial coupling and a high density of defect sites, facilitated electron transfer between MoO 3 and the N, P co-doped carbon matrix, endowed the catalyst with enhanced structural stability and excellent surface accessibility. Benefiting from these structural and electronic advantages, in the oxidative desulfurization (ODS) of dibenzothiophene (DBT) using H 2 O 2 as the oxidant, MoO 3 /NCG-P achieved complete removal of 4000 ppm DBT within 20 min at 60 °C, using only 0.03 g of catalyst and a H 2 O 2 /S molar ratio of 2. Furthermore, the catalyst demonstrated excellent reusability, with no significant loss of activity observed over ten consecutive cycles. Mechanistic investigations based on free radical scavenging experiments and in situ electron paramagnetic resonance analysis confirmed that the ODS process predominantly follows a hydroxyl radical-mediated oxidation pathway. These findings offer valuable insights for the design of efficient, stable, and scalable molybdenum-based catalysts for practical ODS applications.
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CHEMICAL ENGINEERING JOURNAL
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2026
·
IF 12.5
Chenhua Shu,Jun Yang,Jiayi Zhang,Helin Fan,Xingyu Dai,Dan Luo,Shuo Mi,Tonghua Sun
To solve the problem of the deep eutectic solvents synthesized with small volume hydrogen bond acceptors and hydrogen bond donors entering the cavity of pore generator and occupying their pore structure, supramolecular deep eutectic solvent (SDES) was firstly introduced to construct porous deep eutectic solvent (PDES). Thereby, a PDES was synthesized by using ZIF − 8 encapsulating peroxophosphotungstate (PPT) as pore generator and SDES composed of methyl-β-cyclodextrin (M − β − CD) and levulinic acid (LA) as steric hindrance solvents. The characterization results indicated that PPT was encapsulated successfully within ZIF − 8 to prepare [PPT@ZIF − 8]. [PPT@ZIF − 8] and [M − β − CD/LA] remain structure stable after forming PDES and [M − β − CD/LA] do not fill the cavity of [PPT@ZIF − 8]. The PDES [PPT@ZIF − 8][M − β − CD/LA] was applied for oil desulfurization and the desulfurization rate of dibenzothiophene in model oils could reach 100% within 2.5 h using H 2 O 2 as oxidant. The desulfurization by [PPT@ZIF − 8][M − β − CD/LA] combined the extractive desulfurization with [M − β − CD/LA] as extractant and the oxidative desulfurization with [PPT@ZIF − 8] as catalyst. Furthermore, [PPT@ZIF − 8][M − β − CD/LA] has excellent regeneration performance. This work will provide a new route to construct PDESs and will promote the industrial application of porous liquids.
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CHEMICAL ENGINEERING SCIENCE
·
2026
·
IF 5.1
Mengying Lin,Hanyue Lou,Zhaoyang Qi,Jie Chen,Changshen Ye,Ting Qiu
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 defect-engineered UiO-66 framework, utilizing D-alanine (DAla) as a bridging molecule. The synthesized catalyst, UiO-DAlaPW, significantly enhances the utilization efficiency of hydrogen peroxide (H 2 O 2 ). 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 H 2 O 2 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.
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Journal of the Taiwan Institute of Chemical Engineers
·
2026
·
IF 6.9
Zijie Luo,Huicong Zhang,Fashe Li,Hua Wang
Background In recent years, most countries have imposed stricter standards on the sulfur content in fuel oils. Thiophene compounds, predominantly benzothiophene (BT) and dibenzothiophene (DBT), are difficult to remove from biodiesel derived from waste cooking oil. Adsorption desulfurization using activated carbon is regarded as a potential solution. But the removal efficiency of common activated carbon for thiophene could not meet the requirement. Therefore, it is important to develop a carbon material that is highly efficient and selective. Methods This study used tobacco stalks as carbon precursors and zeolite as a templating agent to prepare biomass-based zeolite templated carbon (Bio-ZTC). Subsequently, HNO 3 was used to modify its pore size and surface functional groups, resulting in a material (Bio-ZTC-M) with abundant hierarchical pore structures and surface functional groups. The adsorption performance and mechanism of Bio-ZTC-M for BT in biodiesel were investigated through characterization techniques, adsorption kinetics and molecular dynamics analyses. Significant findings Under the optimal conditions, the removal efficiency of Bio-ZTC-M for BT in biodiesel reaches 68.07 % within 30 s at 20°C. In the process of BT adsorption by Bio-ZTC-M, both physical adsorption (π-π interactions and dipole-dipole interactions) and chemical adsorption (Lewis acid-base interactions) coexist. Furthermore, increasing the proportion of ultramicropores (0.65-1 nm) and mesopores in carbon materials is beneficial to the adsorption of BT.
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Journal of Environmental Chemical Engineering
·
2026
·
IF 7.2
Ning Gao,Yike Yao,Yunbo Wang,Mengjie Fan,Xiaoqian Peng,Yingwen Chen
In high-viscosity, metal salt-based deep eutectic solvents (DESs), strong hydrogen-bonding interactions frequently hinder mass transfer, limit ROS formation, and reduce synergistic catalytic activity. To address these challenges, a low-viscosity DES incorporating Brønsted-Lewis acidic sites was synthesized from FeCl₃·6H₂O and propionic acid. In this configuration, solid PMS acts as a slow-release oxidant, thereby preserving the DES’s functional integrity and sustaining its catalytic efficiency. Characterization and oxidative desulfurization evaluation revealed alternating Fe ion redox states within the DES, along with a dual cyclic reaction pathway involving the regeneration of Cl⁻ and Cl radicals. The electron-transfer activity of Cl radicals not only generates multiple reactive oxygen species (·ClO and ·O 2 ⁻) but also modulates the nucleophilic and electrophilic reactivity of organosulfur compounds. Under mild conditions at 40 °C, the catalytic system achieves over 99.7% desulfurization of model oil containing up to 1500 mg kg -1 sulfur within 20 minutes, while demonstrating excellent recyclability over seven consecutive cycles. DFT analyses indicate that radical oxidation serves as the dominant pathway for thiophene sulfone formation, with perpropionic acid playing an auxiliary role by extending the lifetime of reactive oxygen species and enhancing the oxidation process. Overall, the controlled release of solid PMS reduces impurity effects on the DES, while radicals and reactive oxygen species promote S-O bond formation and the removal of organosulfur compounds from the oil phase.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2023
·
IF 4.2
Shao-Qi Zhi,Jun-Yuan Zhang,Song-Hai Wu,Wen-Shuang Zhu,Yu-Dong Shan,Yong Liu,Xu Han
Turning aromatic sulfur impurities to value-added polymers is a promising technology for fuel desulfurization. In this study, Cu(I,II)@g-C3N4 plates prepared via facile calcination show high reactivity in catalytic oxidation of benzothiophene (BT) by persulfate in a mixture of MeCN/H2O (v/v = 50/50). Quenching experiments rule out the primary contributions of SO4•–, •OH, and O2•– to BT oxidation and confirm the presence of carbon-centered radicals during the desulfurization process. XPS and Raman analyses reveal that Cu(I) and graphitic-N are reactive sites for persulfate activation, accompanied with moderate activation of the peroxo group in persulfate via the nonradical pathway. Solid characterizations indicate the formation of polybenzothiophene S,S-dioxide during the oxidation process, which further reveals that the moderately activated persulfate abstracts H from BT to form a BT radical cation, followed by subsequent polymerization of BT radical cations to a BT tetramer, and then the BT tetramer is further oxidized to a BT S,S-dioxide tetramer. The high electrochemical stability and pseudo-capacitive properties of the obtained polymers also imply their high potential to be used for capacitors. This work provides new insight on turning aromatic sulfur impurities in fuels to “treasures”.
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APPLIED CATALYSIS A-GENERAL
·
2023
·
IF 5.5
Huifang Liu,Chengpeng Liu,Ni Zhen,Jing Dong,Yingnan Chi,Changwen Hu
Recently, Pickering emulsions provide a green and efficient solution for interfacial catalysis. However, in an emulsion system the separation of products and the recycle of catalysts rely on time- and energy-consuming centrifugation and filtration. Herein, a straightforward emulsion assisted assembly strategy has been developed to fabricate amphiphilic polyoxoniobates (PONbs), [C n H 2n+1 N(CH 3 ) 3 ] 6 KHNb 6 O 19 /SiO 2 (C n -Nb 6 /SiO 2 ; n = 14, 16, and 18). The honeycomb-like C 16 -Nb 6 /SiO 2 composite not only can form stable Pickering emulsion in the n-octane/water system but also can effectively catalyze oxidative desulfurization under mild conditions. Notably, after the reaction, the oil phase and the emulsion phase were automatically separated: the clean oil was collected by decantation, while the recycled emulsion was directly used for the next run. Moreover, C 16 -Nb 6 /SiO 2 is highly robust and can be consecutively used for up to eleven cycles with negligible loss of its catalytic activity.
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MATERIALS CHEMISTRY AND PHYSICS
·
2023
·
IF 4.6
Xiao Teng,Bo Zhang,Luxia Yin,Wanyi Tao,Zhang Wen,Zekai Zhang,Wensheng Ning
A series of PdO/CeO 2 /SiO 2 -z aerogel composites with different molar ratio of Si/Ce were facilely fabricated via sol-gel method combined with atmospheric drying technology, where a major of Ce 3+ species could be oxidized to Ce 4+ species by adding hydrogen peroxide. They were used to remove thiophenics from model fuels and aromatics, compared with PdO/SiO 2 and CeO 2 /SiO 2 aerogel composites. Adding Ce and Pd led to an appearance of weak Lewis acid centers on the surface of adsorbents. Compared with PdO/SiO 2 and CeO 2 /SiO 2 , the adsorption capacity of PdO/CeO 2 /SiO 2 -z significantly increased, in which PdO/CeO 2 /SiO 2 -100 performed best and the adsorption capacity for thiophene was 15.0 mg-S/g ads , which was about the sum of PdO/SiO 2 -636 and CeO 2 /SiO 2 -100. The case was attributed to π-complexation of Pd 2+ and S-M (Pd, Ce, acted as Lewis acid centers) bond (σ) with thiophenics, where the adsorption process was dominated by S–Ce bond. Combined with the same chemical state of Pd and Ce in single metal and bimetal adsorbents verified by XPS , it can be deduced that no synergistic interaction between Pd and Ce species was formed in the adsorption process. PdO/CeO 2 /SiO 2 -100 exhibited a higher resistance for competitive adsorption of aromatics and a good solvent washing regeneration performance. The adsorption process of PdO/CeO 2 /SiO 2 -100 for thiophene was well fitted by Langmuir isothermal and pseudo-secound-order model and were spontaneous and endothermic. The solvents (n-heptane, benzene and p-xylene) have no obvious effect on the adsorption thermodynamics and kinetics of PdO/CeO 2 /SiO 2 -100.
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Catalysts
·
2023
·Vol. 13
·期 4
·747
·
IF 3.9
Yan Gao,Yu Chen,Cuiying Wang,Aiping Yin,Hailong Li,Jianshe Zhao
In this work, the highly active polyoxometalate (PW2Mo2) with Venturello structure and its corresponding catalyst were applied in catalytic desulfurization for the first time. PW2Mo2as an active component was effectively encapsulated in hollow periodic mesoporous organosilica (HPMOS) to form the nanoreactor PW2Mo2@HPMOS, where the central cavity and mesoporous shell facilitate mass transfer and both provide a stable place to react with organic sulfides. Desulfurization test results show that the hollow nanoreactor PW2Mo2@HPMOS can almost remove four sulfides simultaneously from diesel in 2 h under mild conditions. Besides, the nanocatalyst PW2Mo2@HPMOS can be reused and recycled for at least seven consecutive tests without any noticeable loss in performance. With the rapid development of the economy, the massive use of sulfur-containing fuel has a huge impact on the global climate. After combustion of sulfur-containing fuel, the realized SOXis an important inducement of the formation of acid rain, and the realized sulfur particle is also a major source of haze. Therefore, removing sulfur compounds from fuel is an important issue that needs to be solved immediately.Keywords:polyoxometalates;hollow periodic mesoporous organosilica;nanoreactor;desulfurization;chemical process
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CHEMICAL ENGINEERING SCIENCE
·
2023
·
IF 4.7
Xinrong Ke,Ping Lu,Jinling Cai,Jiayuan Wang,Changshen Ye,Chen Yang,Ting Qiu
The removal of aromatic sulfur-containing species by adsorption method in liquid hydrocarbon fuels (LHFs) are concerned in worldwide, but it is still a challenge due to intricacy-designed adsorbents, resulting in high cost of preparation and poor stability. Herein, an easy-prepared adsorbent, Zn-NC-T (T represents the carbonization temperature, T = 600, 800 and 1000 °C), which derived from the carbonization of low-cost ZnCl 2 -chitosan polymers, is reported. The optimal Zn-NC-800 exhibits dibenzothiophene (DBT) uptakes of 43.3 mg S/g, which is superior to many reported desulfurization adsorbents, including metal–organic frameworks, zeolites and metal-loaded porous carbons. It also keeps satisfactory reusability with adsorption capacity loss of 5.3 mg S/g after 5 cycles because of the high-efficiency removal of adsorbates under high temperature regeneration. Moreover, the Zn-NC-800 shows great potential for sulfur-free LHFs production in the industry by breakthrough experiment for adsorbing low-concentration DBT (100 ppm w S) with ca. 0 ppm w S content in outlet LHFs. And the mechanism investigation on the adsorption isotherms and kinetics indicates that the adsorption process of DBT is controlled by chemisorption. Furthermore, DFT calculations suggest that the Zn, N-co-doped carbons show stronger adsorption strength (e.g., DBT, −1.79 eV) than the sole N-doped carbons (−0.93 eV), indicating the main contribution of Zn, N-cooperated adsorptive sites. The reported Zn-NC-T equips with advantages of low-cost raw materials, high adsorption capacity and good reusability, making it promising candidate for production of sulfur-free LHFs.
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MICROPOROUS AND MESOPOROUS MATERIALS
·
2022
·
IF 5.876
Erjian Huang,Yueyang Xu,Yachun Ren,Peng Zhang,Yongping Zeng
Faujasite (FAU)-type zeolites are promising adsorbents for the removal of sulfides from fuels, but their micropores are not capable to accommodate the large-sized thiophenic compounds. FAU zeolites (NaX and NaY with the low and high Si:Al ratios, respectively) with hierarchical micro/mesoporous structures were synthesized by sequential acid-base treatment to enhance the adsorption capacity and reduce the limitations of diffusion for the sulfides. To further to improve the desulfurization performance, the hierarchical structure of FAU zeolites containing Cu + were prepared by ion-exchange and methanol vapor-induced reduction methods at a relatively low temperature (473 K). For the large-sized benzothiophene , both the HP-Cu(I)Y and HP-Cu(I)X zeolites with mesopores have a very high adsorption capacity, reaching 51.8 mg S/g and 56.1 mg S/g, respectively. In addition, the results show that HP-Cu(I)X has a higher adsorption capacity than that of some other FAU-type adsorbents reported.
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Journal of Cleaner Production
·
2023
·
IF 11.1
Yulin Zhang,Guozhao Ji,Fahim Ullah,Aimin Li
The properties of tire pyrolysis oil are similar to diesel oil, but the high sulfur content in the pyrolysis oil limits its use in diesel engines . In this work, taking the boiling point range of traditional diesel oil as the cutting temperature, a fraction in the temperature range of 190–350 °C was obtained by distillation of tire pyrolysis oil (TPO 190–350 °C ). The sulfides in TPO 190–350 °C are mainly benzothiophene derivatives. And a simple and effective POM-based catalyst ([C 16 H 33 N(CH 3 ) 3 ] 3 PW 4 O 24 ) has been used in the oxidation desulfurization process for the removal of sulfur compounds from the oil. The catalyst played the role of transferring reactive oxygen species atoms on H 2 O 2 to sulfur compounds . The benzothiophene , dibenzothiophene , and 4,6-dimethyl-dibenzothiophene (500 ppm S) in model oil could be converted to the corresponding sulfone within 1 h at 40 °C. Even if the sulfur content was increased to 2000 ppm, the catalyst exhibited well catalytic performance under the same conditions. The catalyst could be recycled and reused with no loss of desulfurization efficiency. Distillation could effectively reduce the presence of olefins in the oil leading to reduce oxidation performance during the oxidation desulfurization process (ODS). In the subsequent desulfurization experiments of TPO 190–350 °C , a high desulfurization efficiency (91.28%) was achieved for TPO 190–350 °C , with initial sulfur contents of 11033 ppm declining to 961 ppm.
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危险品化学品经营许可证（带存储）