INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Qian-Wen Lu,Qing He,Qing-Shuai Zhang,Da Sheng,Song-Hai Wu,Yong Liu,Xu Han
Although thermocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-formylfuran (DFF) by O2 is an important reaction, achieving a high yield of DFF is still challenging. In this study, a series of MoxCuy/NH2-SBA-15 are prepared, and Mo3Cu1/NH2-SBA-15 exhibits the desirable catalytic reactivity with a complete conversion of HMF and high selectivity of 94.4% toward DFF. XPS and EPR analyses indicate that the abundant oxygen vacancies (Ov) and Cu(I) are the reactive sites for O2 activation. Quenching experiments and various characterizations reveal that superoxo (≡Cu(II)/Ov-OO•) on the surface of catalyst, instead of •OH and O2•–, are the primary oxidizing species to abstract H from HMF to RCH2-O•, accompanied by the formation of ≡Cu(II)/Ov-OOH peroxo. Meanwhile, the doped Mo(V/VI) further activates ≡Cu(II)/Ov-OOH peroxo to form ≡Mo-(η2-O2) peroxo, which significantly promotes the oxidation selectivity of RCH2-O• toward DFF via the H-abstraction pathway. This study provides new insight on selective thermal-oxidation of biomass-derived compounds to high-value-added chemicals via regulating reactive oxidizing species on the surface of catalysts.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Shichao Peng,Hua Li,Wenjuan Liu,Junyi Yu,Zhaochao Xu,Mao Ye,Zhongmin Liu
Mass transfer of guest molecules is crucial for zeolite catalysis. Compared to intracrystalline diffusion, the surface barriers in zeolite catalysis have been less understood. Taking furfuryl alcohol oligomerization catalyzed by ZSM-5 zeolites as model reaction, here we present a single-crystal level study and gain insight into the surface barriers induced spatiotemporal evolution of oligomer products using structured illumination microscopy (SIM). It is shown that, as a result of the enhanced accessibility to zeolite crystals, promoting the surface permeability leads to the increase in catalytic reaction rate that is characterized as the generation rate of oligomer products.
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高影响因子
ACS Applied Energy Materials
·
2022
·
IF 6.959
Changfei Zou,Li Yang,Kaili Luo,Lei Liu,Xiyuan Tao,Lingguang Yi,Xianhu Liu,Zhigao Luo,Xianyou Wang
All-solid-state lithium metal batteries (ASSLMBs) with argyrodite-type Li6PS5Cl solid electrolyte (SE) show potential to replace current commercially available lithium-ion batteries by virtue of their potentially high energy density and safety. However, the interface incompatibility between sulfide solid electrolyte and lithium metal leads to an increase in interfacial resistance and the rapid growth of lithium dendrites, which greatly impede its commercial application. To alleviate the above problems, here a cell construction model has been put forward, in which composite polymer electrolytes (CPEs) with high ionic conductivity and good interface compatibility against lithium metal are employed as the interphase between Li6PS5Cl solid electrolyte and lithium metal. CPEs can prevent direct contact between lithium anode and Li6PS5Cl, and a soft CPE layer can solve the problem of high interfacial resistance caused by bad contact between the Li6PS5Cl solid electrolyte and the lithium metal anode. As a result, the symmetric cells Li/CPEs/Li6PS5Cl/CPEs/Li show stable polarization voltage over 140 h at a current density of 0.2 mA at 60 °C. Compared with the rapidly decaying capacity of the LiFePO4/Li6PS5Cl/Li cell, the initial discharge capacity of LiFePO4/Li6PS5Cl/CPEs/Li is 93.74 mAh/g, and after 15 cycles at 0.5 C, the capacity retention rate is still 75.1%. Therefore, the successful design of this cell structure based on the interface modification of Li6PS5Cl solid electrolyte provides good prospects for the commercial application of ASSLMBs.
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高影响因子
NEW JOURNAL OF CHEMISTRY
·
2013
·Vol. 38
·期 2
·845-851
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IF 2.966
Li-Li Tan,Yumo Zhang,Bao Li,Kai Wang,Sean Xiao-An Zhang,Yanchun Tao,Ying-Wei Yang
Highly selective binding of “solvent” molecules by 1,4-dimethoxypillar[5]arene (DMP[5]A) and their host–guest complexation in solution and the solid state have been investigated by multiple methods. Enthalpy changes and the size-fit effect play an important role in the high selectivity.
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高影响因子
ChemistrySelect
·
2023
·Vol. 8
·期 31
·e202300799
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IF 2.1
Lin-Jie He,Yao-Feng Wang,Peng-Xin Guan,Qing-Shan Niu,Hong-Ying Liu,Bao-Hua Xu
The vapor-phase nitrilation of dimethyl adipate (DMA) with ammonia (NH 3 ) is an environmentally benign route leading to adiponitrile (ADN) with great application value. In this study, the performance of HZSM-5 zeolites, widely used in industry as the solid acid catalysts, was investigated. It exhibits a strong correlation between the SiO 2 /Al 2 O 3 ratio (SAR) in HZSM-5 zeolites and the reactivity (both activity and selectivity). The influence of Al density closely related to the value of SAR on the reactivity of HZSM-5 was thus elucidated by mechanistic experiments. As a result, the introduction of Al element to the framework is beneficial to the activation of ester functionality, thus improving the activity, especially at a high liquid hourly space velocity (LHSV). However, a high Al density will lead to poor selectivity and deactivation due to too strong adsorption of esters and intermediates (e. g., amides). Herein, the balanced adsorption/desorption capability was reached on HZSM-5 with SAR as 631 (i. e., HZSM-5-631), which provides the best selectivity to nitriles (S ADN+MCP , 92.5 %) at a high single-pass conversion of DMA (C DMA , 98.0 %). Graphical The nitrilation of DMA over HZSM-5 with different SiO 2 /Al 2 O 3 was investigated, wherein HZSM-5 with SiO 2 /Al 2 O 3 of 631 exhibited excellent reactivity due to the balance of ester activation and amide intermediate desorption.
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高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2023
·Vol. 29
·期 60
·e202301827
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IF 4.3
Mengyan Zeng,Xin Chen,Jie Zhang
Hierarchical chiral structures have broad applications in optical devices, asymmetric catalysis, and biological systems. The delicate balance of various interactions are key to the self-assembly of chiral structures. Herein, a ternary co-assembly consisting of cationic pillar[5]arenes (P5As), anionic β- glucopyranoside ( β GlcD/ β GlcL), and Anderson-type polyoxometalates (POMs) were constructed. Through adjusting the stoichiometry of β GlcD, the assemblies were effectively controlled to form hierarchical nano-leaf assemblies with twisted nanoribbons in a homochiral direction. The co-assemblies exhibit strong Cotton effects, and successfully induced the chirality of Anderson-type POMs. More interestingly, by changing the central metal in Anderson-type POMs (XMo 6 O 24 3− (X=Cr, Al, and Ga)), even though the three clusters have the same numbers of charge and size, the hierarchical chirality of the related assemblies varied in the morphology of the assemblies and the Cotton effect in the CD spectra. Results in theoretical calculations and ITC titration indicates that the tiny difference in long-range electrostatic interaction would result in the anion recognition of POMs, modulated by β GlcD through host–guest inclusion and hydrogen bonding in the assembly process. Graphical β -Glucopyranoside, as a modulator, successfully induced the chirality of Anderson-type polyoxometalates and modulated the ternary co-assembly to form hierarchically chiral leaves. By substituting highly similar polyoxometalates, the accurate balance between short- and long-range interactions is demonstrated to be the key to the formation of chiral hierarchical microstructures.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2026
·
IF 9.1
Jiaxi Jin,Yuyang Xiao,Hao Lai,Ruixing Fu,Peilun Shen,Dianwen Liu,Xinyi Liang,Bo Peng
The efficient separation of chalcopyrite from sphalerite remains a significant challenge in flotation due to their similar surface properties. In this study, Trisodium 4-carboxy-5-mercapto-3-hydroxy-isothiazole (TCMHI) was introduced as a novel, eco-friendly, and selective organic depressant for sphalerite. Micro-flotation tests demonstrated that TCMHI (73 mg/L) could selectively depress sphalerite flotation (recovery <14%) at pH 7.0 while maintaining high chalcopyrite recovery (> 94%). Successful separation was achieved in artificially mixed mineral tests, yielding a concentrate with a Cu grade of 32.01% and a recovery of 96.65%. To validate its industrial applicability, bench-scale flotation tests were conducted on a real Cu Zn sulfide ore. The results showed that TCMHI achieved metallurgical performance comparable to the conventional depressant zinc sulfate (ZnSO 4 ), maintaining a copper recovery of 71.32% while effectively suppressing zinc recovery to 21.18% in the concentrate. Surface characterization techniques, including contact angle, zeta potential, and Atomic Force Microscopy (AFM), revealed that TCMHI preferentially adsorbs onto the sphalerite surface, forming a dense hydrophilic layer that hinders collector adsorption. X-ray Photoelectron Spectroscopy (XPS) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) analyses confirmed that TCMHI chemically adsorbs on sphalerite through the formation of stable Zn-TCMHI surface complexes. Density Functional Theory (DFT) calculations further elucidated the mechanism, showing that TCMHI forms a stable five-membered chelate ring with surface Zn atoms via its nitrogen and endocyclic sulfur atoms. Crucially, the adsorption energy of TCMHI on sphalerite (−209.76 kJ/mol) was found to be significantly more negative than that of the collector (−95.88 kJ/mol), explaining its superior depression performance. This work provides a promising reagent for the sustainable and efficient flotation separation of Cu Zn sulfide ores.
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ChemSusChem
·
2026
·Vol. 19
·期 3
·e202502450
·
IF 5.9
Mengmeng Jin,Yaolei Zhao,Weiting Li,Tiantian Xu,Jiazuo Wei,Jingjun Liu
2,5-Bis(hydroxymethyl)furan (BHMF) is a promising intermediate for the synthesis of pharmaceuticals and crown ethers, whereas achieving a high reaction rate in the hydrogenation of 5-hydroxymethylfurfural (5-HMF) to form BHMF remains challenge. In this work, a series of Cu/CeO 2 –x catalysts ( x denotes H, Air, Ar) were synthesized by calcination under different atmospheres (10% H 2 /Ar, Air, Ar) and evaluated for the 5-HMF hydrogenation to BHMF. Cu/CeO 2 –Ar exhibited a superior reaction rate of 26.8 mmol·g cat −1 ·h −1 and BHMF yield of 99.1% under the condition (180°C, 5 h, 1 MPa H 2 ), significantly outperforming Cu/CeO 2 –H and Cu/CeO 2 –Air. The characterizations reveal that the calcination in the oxygen-deficient argon atmosphere led to high Cu dispersion and minimized Cu particle size in the Cu/CeO 2 –Ar. These properties resulted in the abundant Cu + –O V –Ce 3+ sites and increased Cu 0 number. In situ Fourier transform infrared spectroscopy analysis elucidates the distinct roles of these active sites. Cu + sites are responsible for perpendicular adsorption of the 5-HMF carbonyl group, and Cu 0 sites drive efficient H 2 dissociation. In contrast, the O V –Ce 3+ sites do not adsorb 5-HMF and H 2 . The close synergy between numerous Cu 0 sites and abundant Cu + sites in the Cu/CeO 2 –Ar accelerates the process of 5-HMF hydrogenation to BHMF. Graphical The oxygen-deficient argon atmosphere led to high dispersion and small particle size of Cu in Cu/CeO 2 –Ar. These properties resulted in the abundant Cu + sites for the adsorption of CO from 5-HMF and the numerous Cu 0 sites to efficiently dissociate H 2 , synergistically boosting catalytic reaction rate to 26.8 mmol·g cat -1 ·h -1 .
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PubMed
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2026
·
IF 3.7
Biao Meng,Qing Xu,Xiaoling Liu,Qizhi Hu,Menglin Xie,Xiao Xu,Yu Zhou,Zhen Meng,Jun Wang
Catalytically converting 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) underpins renewable, bio -based plastics, yet designing metal-efficient catalysts remains challenging. Here, we combine alloy and support effects by anchoring AuPd alloy nanoparticles on 2D covalent organic frameworks (COFs). Rationalizing alloy composition and COF functionality yielded Au 67 Pd 33 /TTATP, which converted HMF → FDCA in water using atmospheric O 2 mild conditions, delivering >99% FDCA yield, stable reusability, a turnover number (TON) of ∼100 at HMF/metal = 100, increasing to 518 at 600 (86.4% yield). High performance stems from alloy-support synergy that (i) partitions function (Au: HMF dehydrogenation; Pd: O 2 activation) and (ii) matches adsorption-desorption (TTATP enriches HMF yet releases FDCA; alloy surfaces moderate HMF binding and avoid the strong FDCA adsorption of Pd alone), thereby enhancing metal atom efficiency. Graphical AuPd alloy nanoparticles were anchored on 2D covalent organic frameworks (COFs) to integrate alloy-support synergistic effects. The catalyst Au 67 Pd 33 /TTATP achieved >99% FDCA yield with the high metal utilization efficiency under mild conditions, owing to the synergy effect optimized reactant/product adsorption-desorption.
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PubMed
高影响因子
PROCESS SAFETY AND ENVIRONMENTAL PROTECTION
·
2026
·
IF 7.8
Cheng Zeng,Zhichao Tan,Youcai Zhao,Tao Zhou
The electrochemical hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) presents a sustainable strategy for biomass valorization, yet selectively upgrading HMF to BHMF with high conversion rate remains challenging. To address this issue, we introduced a computer-assisted framework integrating large language model (LLM), machine learning (ML) and Bayesian optimization to recommend optimal experimental conditions for the HMF-BHMF electrochemical system. We first utilized the multi-modal capacity of GPT-4o to automatically extract literature data via prompt engineering, forming a high-quality dataset comprising 248 experimental entries from 378 publications related to the HMF-BHMF conversion. This LLM-curated dataset was leveraged to train a deep neural network for predicting both conversion and selectivity in a multi-task learning setting. The trained model demonstrated strong predictive performance, achieving R² scores of 0.870 for conversion rate and 0.920 for selectivity. SHAP analysis revealed that electrochemical kinetics and electrode identity were the most influential factors governing conversion and selectivity respectively. Utilizing the machine learning model, Bayesian optimization identified optimized reaction conditions for balancing the trade-off between selectivity and conversion rate. Experimental validation of one such condition yielded 81.70% conversion and 52.08% selectivity, significantly outperforming experimental designs in literature. Our study offers a promising human–machine collaborative approach to accelerating experimental optimization, paving the way for more sustainable electrosynthetic pathways in biomass valorization.
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GREEN CHEMISTRY
·
2026
·
IF 9.2
Lin-Yu Jiao,Ze-Long Sun,Wen-Yu Luo,Ying-Ying Xu,Fei Wen,Yanfei Xu,Zhuo Li,Wei Zhao,Shanshan Liu,Mingyue Ding
Sustainable green energy has emerged as critically important topics, with catalytic valorization and utilization of biomass receiving considerable attentions in recent years. This study investigates the photocatalytic selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) using sonochemically synthesized g-C3N4/Bi2MoO6 heterostructured catalyst. A series of composites with varying mass ratios were fabricated, with the 1:1 (w/w) g-C3N4/Bi2MoO6 demonstrating the optimal catalytic performance. Systematic investigations were conducted to elucidate the effects of reaction conditions including irradiation wavelength, solvent polarity, reaction atmosphere, and substrate concentration on photocatalytic efficiency. The system achieved exceptional DFF selectivity of 90.8% with 92.2% HMF conversion under very mild conditions (air atmosphere and 10 W blue LED, 455 nm) with the generation of H2O2 as co-product, demonstrated the extremely high catalytic activity of the catalyst. The catalyst exhibited remarkable stability, as confirmed by recycling tests and post-reaction X-ray diffraction (XRD) characterization. Mechanistic studies through radical quenching experiments and electron paramagnetic resonance (EPR) spectroscopy identified superoxide radicals (·O2−) and photogenerated holes (h+) as the dominant reactive species, propose a dual-pathway oxidation mechanism. In this study, the S-scheme heterojunction charge transfer mechanism was comprehensively validated through systematic characterization and theoretical calculations, highlighting the pivotal role of S-scheme heterojunctions in selective oxidation reactions.
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高影响因子
ELECTROCHIMICA ACTA
·
2014
·
IF 4.086
Jianfeng Yu,Youqin Lu,Cunguang Yuan,Jinsheng Zhao,Min Wang,Renmin Liu
Indole-5-carboxylic acid monomer was electropolymerized on carbon modified glass carbon (GC) electrode, followed by the covalent bonding with pyridine-2,4-diamine by using 1-ethyl-(3-(dimethyl-amino-propyl)carbodiimide (EDAC), N-hydroxysulfosuccinimide sodium salt (NHS) catalyst, and then was complexed with copper ions to obtain the composite (CuINPD/C). The morphology and the chemical composition of the CuINPD/C catalyst were analyzed by scanning electron microscopy and X-ray photoelectron spectroscopy, respectively. Electrochemical measurements such as cyclic voltammetry, rotating disk electrode, rotating ring-disk electrode and electrochemical impedance spectroscopy were applied to obtain the mechanisms of the oxygen reduction reaction (ORR). All electrochemical measurements demonstrate that CuINPD/C is a good catalyst with excellent stability due to copper ions doping and carbon modification, which play a key role in increasing the current density and enhancing the charge transfer kinetics. Moreover, the average electron transfer number is about 3.1, indicating the ORR of CuINPD/C may takes a coexisting pathway involving both the two-electron and four-electron transfers.
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