BIOMASS & BIOENERGY
·
2026
·
IF 7
Ge-liang Xie,Yu Luo,Kai-cheng Xia,Sheng-ren Li,Lujiang Xu,Zhen Fang
Aromatic amines, particularly aniline derivatives, serve as pivotal intermediates in the manufacture of dyes, pharmaceuticals, and polymers. However, their conventional synthesis remains heavily reliant on fossil feedstocks and frequently employs toxic reagents. The valorization of lignin presents a promising, renewable pathway to these valuable compounds, yet the reactivity of lignin-derived phenols varies markedly depending on their functional group substituents. Herein, a pronounced "promotion-inhibition dichotomy" is reported. Alkyl substituents substantially enhance reactivity-achieving a 44.3 mol% yield of aromatic amines from 4-propylphenol, representing a 34.7% increase over phenol. Conversely, methoxy groups exert a strong inhibitory effect in limiting the yield of aromatic amines from 4-propylguaiacol to only 11.0 mol%. Furthermore, Mo-Ga/HZSM-5 catalyst employed under NH 3 -H 2 atmosphere effectively doubled the yield of aromatic amines to 25.9 mol%. A sequential hydrodeoxygenation-amination strategy is further devised, boosting the yield to 34.1 mol%. Notably, by integrating this two-step strategy with a lignin-first biorefining approach, a 16.6 mol% of aromatic amines (based on lignin) could be achieved from birch. This study elucidates key reactivity principles in lignin valorization and demonstrates an integrated strategy that advances the sustainable production of aromatic amines from renewable biomass.
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CHEMICAL ENGINEERING SCIENCE
·
2026
·
IF 4.3
Ling Chen,Xiangyu Ma,Tingting Wang,Qingliang Li,Ruru Qian,Mengting Cui,Haizhu Yu,Manzhou Zhu
The atomic precision of metal nanoclusters reveals their size-dependent physicochemical properties and highlights the challenges in achieving controllable synthesis at the single-atom level. Herein, we report a series of silver clusters adopting an atom-by-atom evolution pattern, including Ag 13 (SR 1 ) 12 (DPPP) 3 , Ag 14 (SR 1 ) 12 (DPPF) 3 , and Ag 15 (SR 1 ) 12 (DPPB) 3 (Ag 13 -Ag 15 , HSR 1 and DPPP/DPPF/DPPB denote 3,5-bis(trifluoromethyl)thiophenol, and 1,3-bis(diphenylphosphino)propane/ferrocene/butane). Each of these three clusters comprises a shell structure with three groups of Ag 2 (SR 1 ) 4 (DPPX) (X=P/F/B) blocks, while the metallic core corresponds to singly, linearly, and triangularly capped distorted octahedral Ag 6 structures. So far, Ag 13 represents the first 1e metal cluster. The kinetic monitoring and the molecular dynamic (MD) simulations demonstrate the nucleation driven by ligand flexibility. The structural peculiarities of the nanoclusters (which are loaded on activated carbon) govern their divergent catalytic behaviors in epoxide carboxylation reactions. The DPPF stabilized Ag 14 cluster exhibits high activity (98 % yield in 20 h at 75°C, and well maintained after 5 cycles), outperforming Ag 13 (56 %) and Ag 15 (65 %) under otherwise identical conditions. The DFT results show that CO 2 could be significantly stabilized by parallel benzene rings around AgS 2 in Ag 14 , forming π-CO 2 -π structures. This study establishes a dual structure–activity relationship: ligand flexibility regulates the nucleation process during synthesis, whereas the resultant surface defects induced by rigid ligands determine catalytic performance.
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JOURNAL OF CATALYSIS
·
2026
·
IF 6.5
Wanyi Li,Wenbiao Zhang,He Li,Yi Tang,Yahong Zhang
Molybdenum disulfide (MoS 2 ) holds promise in catalysis due to its edge-confined activity, but its structural rigidity and strong in-plane Mo-S bonding limit the exposure of active sites. Herein, we propose a high-curvature support-induced method using ultrasmall ZSM-5 subcrystals (Z-5-SC) to tailor the formation of NiMoS 2 on them. The high curvature and abundant external silanol groups of Z-5-SC induce tensile strain and strong interfacial anchoring, generating short and curved NiMoS 2 slabs with enhanced sulfur vacancies and Ni-Mo-S phase formation. Compared to nanocrystalline zeolite supports, the NiMoS 2 /Z-5-SC exhibits 7.3-fold higher hydrodesulfurization (HDS) activity toward 4,6-dimethyldibenzothiophene ( k HDS = 0.624 h −1 ), rapid hydrodenitrogenation (HDN) response with minimized HDS suppression in simultaneous HDS and HDN reactions, and excellent cycling stability over 15 cycles. This work presents an effective curvature-engineering strategy to enhance the catalytic potential of MoS 2 , offering new insights into the design of engineered two-dimensional materials for hydrotreating and beyond.
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ACS Omega
·
2026
·
IF 4.3
Bingjie Chen,Zhenrun Wu,Qingbo Zhu,Hong Wang,Shuai Yuan,Arlan Z. Abilmagzhanov,Svetlana A. Tungatarova,Xingcai Lu,Zhandong Wang
C7–C10 aromatics are indispensable components of aviation fuels to meet the swelling need for sealing rings in aero engines. Aromatics with a short and single substituent have weak low-temperature reactivity, yet this may be enhanced under a fuel blend environment. In this work, we investigated low-temperature oxidation chemistry of n-propylbenzene, a representative C9 aromatic in a blend with n-heptane, in a jet-stirred reactor. Time-of-flight molecular beam mass spectrometry using synchrotron vacuum ultraviolet radiation as a photon ionization source was used for product analysis and species identification. Thirty-six species were identified by comparison of measured photoionization efficiency curves and calculated species ionization energies, and six of them are key reaction intermediates of n-propylbenzene oxidation. Kinetic model simulations captured the measured mole fractions of reactants, main products, and intermediates with some discrepancies. Furthermore, many oxygenated aromatics are missing in the model, reflecting insufficient understanding of n-propylbenzene low-temperature chemistry. Low-temperature oxidation pathways were proposed based on molecular structures of reaction intermediates. This work explored low-temperature oxidation of n-propylbenzene under a fuel blend environment, which might be useful to unravel the low-temperature chemistry of C7–C10 aromatics in practical jet fuels.
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高影响因子
CHEMISTRY OF MATERIALS
·
2023
·
IF 8.6
Meijun Wan,Yunchao Zheng,Xuemei Dai,Honglin Yang,Jingqiu Zhou,Jing Ou,Yaxin Yang,Meifang Liao,Zhining Xia,Lujun Wang
Covalent organic framework (COF) as a kind of crystalline porous material possesses intriguing advantages, including low density, large surface area, permanent porosity, and excellent chemical stability. This novel material has shown great potential in the development of chromatographic stationary-phase materials. In this work, a room-temperature solvothermal method was utilized to yield a uniformly spherical COF-modified silica named Sil-COF. Then, the thiol-ene click chemistry was further used to modify thiolated β-cyclodextrin on the spherical Sil-COF composite for chiral separation called Sil-COF-CD. A series of characterization methods were performed to identify the successful construction of COF-modified stationary-phase materials. Then, three types of nonpolar substances realized baseline separation on the Sil-COF column. In addition, 2-phenylpropionic acid and 1-phenyl-1-propanol were selected as model enantiomers to identify the chiral recognition capability of the Sil-COF-CD column. Sil-COF and commercial β-CD columns were compared to further confirm the superiority of the prepared chiral column. In addition, both COF-modified columns possessed good repeatability. The results open a new avenue to apply spherical chiral COF for the preparation of the HPLC stationary phase.
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ANALYTICAL LETTERS
·
2022
·
IF 2.267
Yu Huang,Yi Wu,Wenhui Li,Xiaohui Yan,Dapeng Wu
Highly spherical porous silica particles (PSPs) with a controlled pore size were prepared by ultrasonic spray drying and were used as a packing material for high-performance liquid chromatography (HPLC). By using organic additives added to the silica sol as porogens instead of low-melting salts, choosing the size of the colloidal SiO2 particles, and varying the type and the ratio of additives, the pore size of the PSPs was finely tuned from 2.9 to 34.4 nm. Subsequently, PSPs having pore sizes of 7.4, 13.5, and 29.0 nm were modified by chlorodimethyloctadecylsilane (PSPs-C18), and HPLC columns packed with the different PSPs-C18 were evaluated systematically using aromatic compounds and alkylbenzene derivatives as probes. A plate number of 81,000/m and the relative standard deviation of less than 1% in the retention time were obtained for pentylbenzene over 100 injection and HPLC separation cycles for the 7.4-PSPs-C18 column. Five proteins were also separated within 25 min using the 29.0-PSPs-C18 column.
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JOURNAL OF CHROMATOGRAPHY A
·
2022
·
IF 4.601
Changjun Hu,Zhentao Li,Zhuang Hu,Qiaoyan Li,Yuanyuan Fu,Zilin Chen
Crown ethers are macrocyclic polyether compounds containing multiple -oxo-methylene-structural units, which are often used for recognition of metal ions and ammonium ions. Inspired by the molecular design of rotaxanes, a novel covalent organic nanospheres material (CON ADBC-Tp) constructed by 4,4′-diaminodibenzo-18-crown-6 (ADBC) and 2,4,6-triformylphloroglucinol (Tp) was rationally designed as stationary phase for the separation of compounds containing imidazole structure. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR) were carried out to confirm the morphology and composition of ADBC-Tp and ADBC-Tp modified capillary column. Thanks to the introduction of crown ether building ligands, the prepared capillary column exhibited excellent separation selectivity towards protonated imidazole structure, with benzimidazole and its 2-substituted derivatives as modal analytes. Moreover, separation of fungicides, nucleobases, short peptides and sulfanilamides were achieved on ADBC-Tp@capillary. The multifunctional ADBC-Tp@capillary with satisfactory reproducibility and stability gives great promise for separation science.
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高影响因子
ANALYST
·
2021
·Vol. 146
·期 21
·6643-6649
·
IF 4.616
Qiaoyan Li,Zhentao Li,Yuanyuan Fu,Igor Clarot,Ariane Boudier,Zilin Chen
Covalent organic frameworks (COFs) are a class of porous materials with high surface area, high porosity, good stability and tunable structure that have been widely used in the separation area. In this work, we have proposed the in situ synthesis of a novel COF composed of 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl)trianiline (Tz) and 1,4-dihydroxyterephthalaldehyde (Da) onto the capillary inner surface for electrochromatographic separation. Fourier transform infrared (FT-IR) spectroscopy, elemental analysis (EA) and scanning electron microscopy (SEM) have facilitated the characterization of the prepared capillary columns. The COF (TzDa) modified OT-CEC column exhibited satisfactory separation selectivity towards neutral compounds (such as chlorobenzenes and alkylbenzenes), acidic and basic compounds (such as phenols and anilines), food additives (vanillin and its analogues) and small biomolecules (such as amino acids and polypeptides). Furthermore, the TzDa modified capillary was quite stable and reproducible. The relative standard deviations for retention times of the test analytes (alkylbenzenes) were as follows: for intra-day (n = 3) runs (≤1.74%), inter-day (n = 3) runs (≤2.25%) and between columns (n = 3) (≤4.83%). This new type of COF-based stationary phase has tremendous potential in separation science.
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高影响因子
CHIRALITY
·
2021
·Vol. 33
·期 10
·710-721
·
IF 2.437
Hui Bai,Lei Chen
Simultaneous separation of the enantiomer and impurities is a huge challenge for the quality control of the chiral drug. In this work, mixed-mode chiral ligand exchange stationary phases (CSPs) modified by octyl and sulfhydryl ligands were prepared by vapor deposition and click chemistry methods. Qualitative and quantitative determination of the prepared CSPs were achieved by Fourier transform infrared spectroscopy, solid-state 13 C CP/MAS NMR, and elemental analysis. The chiral resolution of CSPs was investigated through a comprehensively chromatographic evaluation of various racemates. Besides, the thermodynamic experiment was carried out to elucidate the contribution of hydrophobic ligand to the improvement of chiral recognition and selectivity. Atenolol and its degradation products were analyzed on the synthesized CSPs and compared with the commercial chiral column. A good separation of atenolol enantiomers from its acid and alkaline degradation impurities was simultaneously achieved on the C 8 /L-Hypro CSP. This new CSP is expected to have more applications in the quality control of other chiral drugs.
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FUEL
·
2021
·
IF 6.609
Mingxing Zhao,Jun Hu,Shiliang Wu,Liu Yang,Xue An,Peng Yuan,Ping Lu
Cyclohexanols, promising oxygenated fuel additives and value-added chemicals, can be obtained by hydrodeoxygenation (HDO) of lignin-derived phenolics. Here, an N-doped bimetallic RuCoN x /NC catalyst was facilely prepared for HDO by direct pyrolysis of chitin impregnated with precursors of Ru and Co. Characterization of RuCoN x /NC with N 2 sorption, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and NH 3 temperature-programmed desorption (NH 3 -TPD) reveal that the metallic particles of electron-deficient Ru species and electron-enriched Co species were uniformly anchored on the micro-mesoporous N-doped carbon matrix with high dispersion and nano-scale size. The abundant accessible active sites and continuous spillover of H from Ru to Co make RuCoN x /NC an excellent HDO catalyst. 4-Propylguaiacol, a typical phenolic compound from lignin degradation, was hydrodeoxygenated into 92% 4-propylcyclohexanol over RuCoN x /NC at 210 ℃. With temperature increasing, propylcyclohexane became the major product, possessing 95% selectivity at 280 °C after 6 h. Reusability tests show that RuCoN x /NC can be recycled four times without the loss of conversion and initial selectivity. HDO of other phenolic compounds confirms the general applicability of RuCoN x /NC.
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JOURNAL OF CHROMATOGRAPHY A
·
2021
·
IF 4.759
Tao Bao,Sicen Wang,Nan Zhang,Juan Zhang
Inspired by the outstanding functions of 3-aminopropyltriethoxysilane (APTES), which can be used for functionalization of both covalent organic frameworks (COFs) and substrate surfaces, herein, a proof-of-concept demonstration was carried out by one-step synthesis and immobilization of COF-1 in capillary. COF-1 was grown on the inner wall of capillary using APTES, which played a triple role of catalyst, stabilizer, and connecting arm during the process. The immobilization of COF-1 on silicon surface was confirmed by scanning electron microscopy. Moreover, COF-1 modified capillary (COF-1@capillary) column exhibited excellent performance in the electrochromatographic separation of amino acids . High resolution and separation efficiency (225,378 plates/m for 4-methylbiphenyl) were successfully achieved. Separation of methylbenzene , styrene , ethylbenzene , chlorobenzene , 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, 4-methylbiphenyl, naphthalene , and 4-vinylbipheny in the electro-driven mode confirmed the successful growth of COF-1 on the inner wall of capillary. The developed facile method for the immobilization of COF-1 may pave the way for further application prospects of boron-based COFs.
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JOURNAL OF CHROMATOGRAPHY A
·
2021
·
IF 4.759
Yunchao Zheng,Meijun Wan,Jingqiu Zhou,Qiurong Luo,Die Gao,Qifeng Fu,Jing Zeng,Fengjiao Zu,Lujun Wang
Covalent organic frameworks (COFs) have showed expected potential in chromatographic separation due to unique structure and excellent performance. Nowadays, COF materials applied as chromatographic stationary phases is still in its infancy. Here, we modified COF materials on silica using benzene-1,4,5-tetracarboxylic dianhydride (PMDA) and 1,3,5-tris-(4-aminophenyl)triazine (TAPT) monomers by one-pot synthetic method for performing mixed-mode function, named as SiO 2 @COF. Five characterization methods including thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Fourier transform infrared spectrometry (FT-IR), elemental analysis (EA) and powder X-ray diffraction (XRD) verified the morphology, structure characteristics and physicochemical properties of the materials. SiO 2 @COF for performing the separation of polar and nonpolar analytes on high performance liquid chromatography (HPLC) achieved the desired results. Retention mechanisms of the constructed SiO 2 @COF were researched via observing the effects of mobile phase with retention times. Results exhibited that the prepared stationary phase can provide various interaction modes, including hydrophobic, hydrophilic, hydrogen bonding and π-π interactions. In conclusion, the prepared SiO 2 @COF stationary phase can execute mixed-mode separation abilities and show potential for complex samples analysis.
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