ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2024
·
IF 10.8
Handan Zhang,Liping Li,Xinhui Liu,Linshuai Duan,Xin Zhang,Lu Dong,Xiqin Liu,Pengcheng Li,Bohan Li,Mengzhu Xue,Guohui Xia
Humin, endowed with abundant redox functional groups, can be reduced anaerobically under dark. When reduced humin encounters O2, the possibility of ·OH formation arises. However, the exploration of ·OH generation mediated by humin has not been comprehensively conducted. The study found that O2 oxidized the reduced humin, generating 8.61 μmol/g of ·OH. After isolating humin using the methyl isobutyl ketone (MIBK) method, the lipid component was identified as the primary contributor to ·OH generation. Subsequent polar separation revealed that the lipid fraction extracted from the ethanol–water mixture with a volume ratio of 7:3 (LFEW7:3) played the most significant role in ·OH production. Further characterization confirmed that the simultaneous presence of aromatic C═C and C═O were the predominant features contributing to the ·OH generation. The ·OH generation experiments with humin-pyridine analogue compound demonstrated that polycyclic pyridine N (≥3 rings) played a significant role in promoting the ·OH generation. Most importantly, the study compared the ·OH production by humin and homologous humic acid, indicating that ·OH generated by humin was higher than that of humic acid. Overall, these affirmative findings manifested the overlooked role of humin in ·OH production and offered valuable insights into the mechanism of ·OH generation by humin in the dark.
研究领域:
环境科学
·
生物化学
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DOI
PubMed
高影响因子
ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY
·
2019
·
IF 4.527
Guangfei Liu,Jiaqi Zhu,Ruofei Jin,Jiti Zhou,Zhanming Gao,Jing Wang
As an important fraction of humic substances , humin has been found capable of stimulating bioreduction reactions. However, whether humin could promote abiotic reduction and the effects of coexisting soluble humic substance and insoluble mineral remained unsolved. In this study, a humin sample was isolated from a paddy soil . Cyclic voltammetry, electron paramagnetic resonance, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analyses of the humin indicated the existence of redox-active quinone moieties and other oxygen-containing groups. The humin could be reduced by sulfide and its presence stimulated the abiotic reduction of acid red 27 (AR27) and four other azo dyes by sulfide. In the presence of 100–1000 mg/L intact humin, the sulfide-mediated AR27 reduction efficiency in 7 d was enhanced from 56.3% to 92.5%. The stimulating behavior of intact humin was observed for 100–300 mg/L AR27 and increased with the increase of sulfide concentration (1.2–3.0 mM). Much higher stimulating effects were found with the presence of humin pre-reduced by sulfide. Moreover, for sulfide-mediated AR27 reduction, the coexistence of humin (500 mg/L) and humic acid (10–30 mg/L) or Wyoming sodium-montmorillonite (SWy-2, 1–4 g/L) led to better promotion activities than the presence of single component. And synergistic promotion of sulfide-mediated AR27 reduction was observed with coexisting humin and SWy-2 due to enhanced Fe(II) production. These findings extended our understanding of the influence of humin on reductive transformation of pollutants in the environment.
研究领域:
环境科学
·
土壤学
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产品关联
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2023
·
IF 8.4
Junyan Fu,Chang Chen,Richard Lee Smith Jr.,Xinhua Qi
Humins, which are intractable carbon byproducts formed during thermochemical conversion of carbohydrates, are considered to be undesirable because of their adverse effects on product yields, catalyst activity, stability, and recycling. Herein, we show that the alcohol-soluble fraction of humins can be used to directly synthesize ordered mesoporous carbons (OMCs) by the classical solvent evaporation-induced self-assembly (EISA) method without the use of aldehydes or metal ion cross-linkers. The key mechanistic feature of the self-assembly of alcohol (ethanol)-soluble humins is that ulmic acid-containing humins act to cross-link micelles according to condensation reactions occurring in humins formation. The prepared OMCs show well-defined two-dimensional (2D) hexagonal mesoporous structures having uniform pore sizes (3.5 to 4.8 nm), high surface areas (∼600 m2 g–1), and pore volumes (∼0.4 cm3 g–1). Using dyes as model pollutants, selective adsorption of OMCs for macromolecular organic pollutants was confirmed, thus the resulting OMC materials appear to have many technological applications. The method proposed for humins conversion to ordered materials may serve as a simple and green way to utilize undesirable and commonly generated humins in carbohydrate conversions, which should improve the sustainability of carbohydrate transformation schemes and broaden the scope of biomass-based or natural humic acid precursors.
研究领域:
材料科学
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化学工程
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环境科学
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DOI
高影响因子
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
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2016
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IF 3.652
Shurong Wang,Haizhou Lin,Yuan Zhao,Jingping Chen,Jinsong Zhou
Humin, a solid by-product formed during the acid-catalyzed conversion of carbohydrate to platform chemicals, can be further utilized by pyrolysis technology. In this study, two humins derived from glucose (humin-g) and xylose (humin-x) were characterized by elemental analysis, FTIR and 13 C NMR. Both humins were polymers rich in furan rings, and their carbon contents were more than 66%. Thermogravimetry and pyrolysis kinetic analyses based on Flynn-Wall-Ozawa and Friedman methods suggested that the activation energies for both humins increased as their conversion rates increased. At low conversion rates, the activation energy of humin-x was higher than that of humin-g, but this was reversed at high conversion rates. The results suggest that humin-g has better thermal stability following the removal of weak linkages at low temperature. Finally, Py-GC/MS was employed to study the product distribution from humin pyrolysis. The mechanisms for formation of typical products and the influence of temperature on product distribution are discussed.
研究领域:
化学工程
·
生物质能源
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DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
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2021
·Vol. 27
·期 49
·12659-12666
·
IF 5.236
Mingwei Ma,Na Liang,Pan Hou,Peng Zhang,Jingjie Cao,Hui Liu,Xingliang Xu,Huijuan Yue,Ge Tian,Shouhua Feng
Graphical The by-product (called humins) is accompanied by a one-pot catalytic conversion reaction of furfural (FAL) to isopropyl levulinate (PL), which is carbonized (Humins-700) and applied to a new experiment of electromagnetic wave absorption, showing superior electromagnetic wave absorption performance. The minimum reflection loss (RLmin) value is −47.3 dB at 13.0 GHz with a thickness of 2.0 mm. This provides inspiration that humins can be applied to electromagnetic wave absorption. Both one-pot catalytic conversion of furfural (FAL) to isopropyl levulinate (PL) and carbonization of by-product (humins) for electromagnetic wave absorption are discussed, which provides inspiration that humins can be applied to electromagnetic wave absorption. In the former, phosphotungstic acid (PW) is employed as a homogeneous catalyst to convert FAL to PL via a tandem reaction in one pot, with the formation of a vast amount of humins. With FAL and various intermediates as substrates, it was found that humins was a polymerization product of FAL, furfuryl alcohol (FOL) and furfuryl ester (FE) with furan rings. In addition, the in situ attenuated total reflection infrared (ATR-IR) spectra also provided a basis for the proposed reaction route. In the latter, with the humins as raw material, P species and WO 3 doped nano-porous carbon (Humins-700) platform formed after high-temperature annealing is used for electromagnetic wave absorption and manifests desirable absorption performance. The minimum reflection loss (RL min ) value is −47.3 dB at 13.0 GHz with a thickness of 2.0 mm and the effective absorption bandwidth reaches 4.5 GHz (11.2–5.7 GHz).
研究领域:
化学工程
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材料科学
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DOI
PubMed
高影响因子
GREEN CHEMISTRY
·
2022
·Vol. 24
·期 13
·5219-5227
·
IF 11.034
Lincai Peng,Chaonan Tao,Hui Yang,Junhua Zhang,Huai Liu
Catalytic upgradation of carbohydrates in concentrated feeds well conforms to the demands for the industrial deployment of bio-based fuels and chemicals, but the majority of existing explorations merely focused on the utilization of dilute feedstock. In this contribution, the degradation behavior of both dilute (20 g L−1) and concentrated glucose (200 g L−1) in an ethanol medium was comparatively investigated by acid catalysis. The increase of the glucose concentration from 20 to 200 g L−1 largely boosted the formation of water-soluble oligomers (WSO) instead of solid humins (SHU). The high initial glucose concentration favored the formation of glucose oligomers, and the high instantaneous concentration of EL and 5-hydroxymethylfurfural (HMF) also exacerbated the polymerization reactions, both of which are responsible for the formation of excessive WSO in a concentrated feed. Structural characterization revealed that substituted furans, 2,5-dioxo-6-hydroxyhexanal (DHH) and its analogue are the main fragments in WSO20, while WSO200 largely consisted of glucosyl units as well as furanic and aromatic fragments linked with aliphatic units, leading to the distinct structure of SHU from the two feed concentrations. This work provides insights into the effect of the feed concentration on product formation during acid-catalyzed ethanolysis of glucose, facilitating the development of optimal processes for valorizing concentrated sugars.
研究领域:
生物化学
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可再生资源工程
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2023
·
IF 8.4
Wenyan Zhang,Haoyu Zhang,Yirong Feng,Tingting Ma,Fengyang Liu,Shuangfei Zhao,Jiming Yang,Yuguang Li,Dong Ji,Weiwei Tang,Xiaowei Li,Zheng Fang,Wei He,Kai Guo
In this article, the photocatalytic polymerization of 5-hydroxymethylfurfural (HMF) was applied in the preparation of photo-generated humins (L-H) for the first time. The molecular weight and furan ring content of L-H would be increased by introducing HMF into low-molecular-weight humins (LMW-H) extracted from spoiled HMF under visible light. Compared with humins prepared by the thermal-acid method (A-H), the molecular weight of L-H was less than 800 g/mol; therefore, L-H exhibited great solubility in various solvents and high chemical reactivity for structure modification. Also, the structure units had great differences between L-H and A-H. A-H only consisted of 2,5-dioxo-6-hydroxyhexanal (DHH) and HMF, while L-H also included the 5-hydroxy-4-keto-pentenoic acid (HKPA) generated by reacting HMF with singlet-oxygen. Then, the furan-based polymers were obtained through the classic Diels–Alder (DA) reaction to realize resource utilization of L-H. HKPA units in L-H provided more reaction sites for DA reaction. Characterizations by nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectrum, microscopy, differential scanning calorimetry (DSC), and tensile properties proved that the polymer DA-L-H containing D–A bonds had self-healing properties, and the recovery efficiency could reach 92.8%. Through the utilization of biomass waste humins, the recycling of resources and sustainable economic development could be realized.
研究领域:
材料科学
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化学工程
·
可再生资源利用
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Junyan Fu,Chang Chen,Richard Lee Smith,Xinhua Qi
Supported metal nanoparticles (NPs) have many potential applications in environmental, energy and catalysis fields. Herein, a general strategy for embedding metallic element, multi-metal or metal alloy nanoparticles into ordered mesoporous carbons (OMCs) with one pot reaction is described that uses alcohol-soluble humins as carbon precursors, metal ions as metal NP precursors and nonionic surfactant (F127) in ethanol with evaporation induced self-assembly (EISA) soft-template method. The synthesis method for NP@OMC materials is applicable to single metals (Fe, Co, Ni, Zn, Ru, Mg, Ca, and Zr) or multiple metals and allows formation of mono-metal nanoparticle or alloy nanoparticle-embedded OMC materials with dense loadings of up to ca . 20 wt%. As proof-of-concept, the catalytic performance of Fe x Ni y @OMC for glucose hydrogenation at controlled stoichiometric ratios ( x : 0, 1, 3; y : 3, 1, 0) were shown to give sorbitol yields of 99.6% at 160 °C in 3 h reaction time. The Fe x Ni y @OMC materials outperformed reported Ru catalysts for glucose hydrogenation and their structure and dispersion in the OMC inhibited Ni agglomeration and leaching. The proposed general strategy, which uses alcohol-soluble humins carbon precursors, is broadly applicable to single or multiple metals and allows simple control of metal or metallic element NP composition, metal NP loading and NP dispersion in metal NP-embedded ordered mesoporous carbon materials.
研究领域:
材料科学
·
催化化学
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产品关联
DOI
高影响因子
BIOMASS & BIOENERGY
·
2025
·
IF 5.8
Shujie Wang,Hetao Zhang,Zhongping Shao,Li Liu
In comparison to the thriving lignocellulosic biomass, the research on humins derived from marine biomass has not been thoroughly investigated. By choosing glucosamine (GlcN) as a model, the transformation process from raw material to solution intermediates until humins solid was demonstrated for the first time. The key intermediates were successfully captured and identified to be pyrazine dimers, such as 1-[5-(2,3,4-Trihydroxybutyl)-2-pyrazinyl]-1,2,3,4-butanetetrol and 1-[5-(3,4-dihydroxy-1-buten-1-yl)-2-pyrazinyl]-1,2,3,4-butanetetrol, which are formed through ring-opening of GlcN. By means of HPLC-MS/MS, FT-IR, XPS, elemental analyses and SEM characterizations, three elementary reactions were revealed including etherification reaction of pyrazine dimers and HMF, aldol condensation of LA, and thermal oxidation. At early stage, pyrazine dimers are linked by etherification. HMF could be linked through etherification as well, with LA reacted with the CHO group of HMF by aldol condensation. At the later stage, the thermal oxidation deepens, resulting in the enhancement of C=O. Moreover, GlcN-derived humins were engineered into porous carbon materials with excellent CO 2 adsorption capacity up to 5.60 mmol/g, whereas the CO 2 uptake was well correlated with the volume of micropores below 0.82 nm.
研究领域:
生物质转化
·
材料科学
·
环境工程
·
化学合成
·
碳捕集
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产品关联
DOI
高影响因子
Toxics
·
2025
·Vol. 13
·期 8
·686
·
IF 4.1
Qi Wang,Aiguo Gu,Hongzhen Lian,Jie Zou
Understanding the differences in the adsorption behaviors of tetrabromobisphenol A (TBBPA) and tetrabromobisphenol S (TBBPS) on soils is critical for assessing their environmental mobility and risks. This study investigated the adsorption characteristics and patterns of TBBPA/S across various soil types. Adsorption kinetics analysis indicated that the adsorption of TBBPA/S on soils followed pseudo-secondary-order kinetics. Isotherm results revealed that the Langmuir model described TBBPA adsorption more accurately, while the Freundlich model was a better fit for TBBPS adsorption, suggesting distinct adsorption mechanisms due to their differing properties. Correlation analysis and principal component analysis (PCA) were performed to identify the key soil physicochemical properties influencing TBBPA/S adsorption. The results showed that TBBPA adsorption was inversely correlated with soil pH and positively correlated with clay content. In contrast, TBBPS adsorption displayed negative correlations with soil pH and sand content, and positive correlations with amorphous iron, amorphous aluminum, and free iron content. Further analysis of different treated soil fractions demonstrated that soil organic matter dominated the adsorption of TBBPA/S, with humic acid playing a more significant role than humin. The adsorption behavior characteristics of TBBPA/S on different soils provide fundamental data for understanding their environmental fate in soil systems.
研究领域:
环境科学
·
土壤化学
·
污染物吸附
·
环境风险评估
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产品关联
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Hui Yang,Chaonan Tao,Lincai Peng,Junhua Zhang,Liang He,Huai Liu
It remains a challenging task for the efficient conversion of carbohydrates to value-added chemicals at concentrated feedstock solution. In this contribution, the acid-catalyzed processing of high-concentration C5/C6 sugars (180 g/L) in the ethylene glycol (EG) solvent system was investigated, and prominent discrepancy was noticed between C5 and C6 sugars. A large amount of liquefied products was achieved in the concentrated C6 sugars EG solution, whereas the main products in the case of C5 sugars were found to be solid humins. The reaction mechanism studies revealed that EG can shelter fructose and reaction intermediates (5-hydroxymethylfurfural and levulinic acid) from the cross-polymerization and self-etherification reactions, thereby reducing the generation of solid humins during the fructose liquidation process. However, in the case of xylose, the copolymerization between EG and furfural (FF) generates a solid resin, thus rendering a high solid product yield. Moreover, the produced FF–EG resin was found to be a polymer with high molecular weight formed by connecting the furan ring and the alkyl structure through an ether bond. This finding provides insights into the acid-catalyzed conversion of concentrated C5/C6 sugars in EG, facilitating rationally designed processes for the valorization of concentrated carbohydrates.
研究领域:
化学工程
·
生物化学
·
催化
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产品关联
DOI
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2022
·
IF 11.357
Ruixia Han,Zhe Wang,Jitao Lv,Zhe Zhu,Guang-Hui Yu,Gang Li,Yong-Guan Zhu
Microbially mediated iron redox processes are of great significance in the biogeochemical cycles of elements, which are often coupled with soil organic matter (SOM) in the environment. Although the influences of SOM fractions on individual reduction or oxidation processes have been studied extensively, a comprehensive understanding is still lacking. Here, using ferrihydrite, Shewanella oneidensis MR-1, and operationally defined SOM components including fulvic acid (FA), humic acid (HA), and humin (HM) extracted from black soil and peat, we explored the SOM-mediated microbial iron reduction and hydroxyl radical (•OH) production processes. The results showed that the addition of SOM inhibited the transformation of ferrihydrite to highly crystalline iron oxides. Although FA and HA increased Fe(II) production over four times on average due to complexation and their high electron exchange capacities, HA inhibited 30–43% of the •OH yield, while FA had no significant influence on it. Superoxide (O2•–) was the predominant intermediate in •OH production in the FA-containing system, while one- and two-electron transfer processes were concurrent in HA- and HM-containing systems. These findings provide deep insights into the multiple mechanisms of SOM in regulating microbially mediated iron redox processes and •OH production.
研究领域:
环境科学
·
微生物学
·
地球化学
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DOI
高影响因子
危险品化学品经营许可证（带存储）