Catalysts
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2022
·Vol. 12
·期 4
·371
·
IF 4.501
Minghao Zhou,Fei Ge,Jing Li,Haihong Xia,Junli Liu,Jianchun Jiang,Changzhou Chen,Jun Zhao,Xiaohui Yang
Lignin is an attractive renewable source of aromatics with a low effective hydrogen to carbon ratio (H/Ceff). The catalytic hydrodeoxygenation (HDO) of lignin-derived model compounds is a key strategy for lignin upgrading. In this work, the HDO of guaiacol, a typical lignin-derived compound, was carried out over metal–organic framework (MOF)-derived Ni-based catalysts. A monometallic Ni-MOF catalyst and different ratios of bimetallic NiMo-MOF catalysts were synthesized by a hydrothermal process, followed by a carbonization process. Among these catalysts, Ni3Mo1@C exhibited an excellent catalytic performance, affording a guaiacol conversion of 98.8% and a cyclohexanol selectivity of 66.8% at 240 °C and 2 MPa H2for 4 h. The addition of Mo decreased the particle size of the spherical structure and improved the dispersion of metal particles. The synergistic effect between Ni and Mo was confirmed by various means, including ICP, XRD, SEM, TEM, and NH3-TPD analyses. In addition, the effect of the reaction temperature, time, and H2pressure during the HDO process is discussed in detail.Keywords:guaiacol;hydrodeoxygenation;Ni-based bimetallic catalysts;MOF
研究领域:
化学工程
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催化科学
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DOI
高影响因子
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
·
2023
·
IF 6
Dayi Guo,Bo Cai,Rui Kang,Shuai Wang,Junfeng Feng,Hui Pan
Hydrodeoxygenation is one of the key steps to upgrade of biomass derived bio-oil into valuable biofuels and chemicals. Developing of highly reactive and cost-effective catalysts for bio-oil hydrodeoxygenation is highly desired. Layered Ni x Co y Al z catalyst was prepared using layered double hydroxide (LDH) as the precursors. The optimized Ni 1 Co 3 Al 2 -600 catalyst exhibits excellent catalytic performance for guaiacol hydrodeoxygenation. Guaiacol could completely converted with 90.0% of cyclohexanol selectivity under relatively mild reaction conditions. The XRD and HRTEM characterizations of the as prepared catalysts confirmed the formation of Ni-Co alloy and the XPS analysis revealed the strong interaction between Al species with both Ni and Co in catalyst Ni 1 Co 3 Al 2 -600, which should contribute to its high catalytic activity for guaiacol hydrodeoxygenation. Catalyst Ni 1 Co 3 Al 2 -600 also demonstrated excellent versatility for the hydrodeoxygenation reactions of guaiacyl and syringyl compounds as well as high stability. The results from this work could provide a new approach for the constructing of effective catalysts from non-noble metal LDHs.
研究领域:
能源化学
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催化化学
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DOI
高影响因子
RSC Advances
·
2017
·Vol. 7
·期 25
·15272-15277
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IF 3.108
Yunhua Li,Juan Fu,Binghui Chen
Ni2P supported catalysts have extensively been studied for various hydrodeoxygenation (HDO) reactions. However, the main products are cyclohexane or cyclohexanol for lignin-derived compounds HDO over these catalysts. In this study, we investigate the catalytic conversion of anisole, phenol and guaiacol to benzene over Ni2P/SiO2 by probing the reaction conditions. The results show that a lower reaction temperature and higher H2 pressure favour the hydrogenation of these model chemicals to cyclohexane, whereas a higher reaction temperature and lower H2 pressure aid the generation of benzene. The cyclohexane and benzene yields are 89.8% and 96.0% at 1.5 MPa and 573 K and 0.5 MPa and 673 K, respectively. By eliminating the influence of internal and external diffusion, the low intrinsic activation energy of 58.2 kJ mol−1 is obtained, which explains the high catalytic activity. In addition, although guaiacol HDO has a low conversion due to the space steric effect of its substituents, it presents a similar reaction pathway to obtain anisole and phenol, which is dependent on reaction conditions. The long-run evaluation experiment shows that the activity and selectivity of anisole HDO to benzene changes slightly for 36 h.
研究领域:
化学工程
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催化科学
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DOI
高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
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2017
·
IF 2.323
Xiaobang Liu,Bao Gao,Yaotai Jiang,Ning Ai,Dongshun Deng
In this work, the solubility data of CO2 in three kinds of guaiacol-based deep eutectic solvents (DESs) at 293.15, 303.15, 313.15, and 323.15 K and pressures below 600.0 kPa were determined. The DESs were prepared from guaiacol and quaternary ammonium salts (QASs, including choline chloride, acetylcholine chloride, and diethylamine hydrochloride) with a molar ratio of guaiacol to QAS of 3:1, 4:1, and 5:1. Henry’s law was used to correlate the solubility data, and the thermodynamic properties, such as standard Gibbs free energy, standard enthalpy, and standard entropy of these systems were derived. The solubility of CO2 increased with increasing molar ratio of guaiacol to QAS in each kind of DES. The dissolution enthalpies were negative at all conditions. The dissolution capacities of present DESs for CO2 were further compared with those of other DESs and several common ionic liquids.
研究领域:
化学工程
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环境化学
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热力学
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绿色溶剂
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碳捕集与封存
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DOI
高影响因子
FUEL
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2026
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IF 7.8
Jian Wang,Yu Zhao,Tianhua Yang,Xinyong Diao,Yao Tong,Shuang Cui,Bingshuo Li,Rundong Li
Guaiacol, an important lignin-derived compound, presents a central challenge in the efficient upgrading of biomass into sustainable biofuels. Conventional conversion processes are often limited by dependence on corrosive acids, noble metals, or external hydrogen sources, leading to increased costs and safety concerns. In this study, we developed a hydrothermal conversion method that enables guaiacol to catechol transformation without the need for external hydrogen or inorganic acids. This was accomplished using transition-metal-based n Ni– y MoO x /Nb 2 O 5 catalysts capable of cleaving C–O bonds. The results showed that the Ni/MoO x ratio was critical in governing the formation of the NiMoO 4 spinel phase while inducing a strong metal–support interaction (SMSI) that directly affected the surface acidity and oxygen vacancy concentration. Using the 5Ni-5MoO x /Nb 2 O 5 catalyst (Ni/Mo = 1:1) at 300 °C for 2 h, 26.15% guaiacol conversion was achieved, with catechol selectivity 12.9-fold higher than in the noncatalytic system. This superior performance originated from a synergistic effect between the moderate acid strength and the high concentration of defective oxygen vacancies, which collectively drove the selective cleavage of the O–CH 3 bond. The produced catechol serves as a pivotal platform intermediate for synthesizing renewable fuel additives and advanced biofuel components. This study presents a sustainable catalyst design strategy for converting lignin resources into valuable biofuel precursors.
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DOI
高影响因子
Catalysts
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2024
·Vol. 14
·期 11
·827
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IF 3.8
Yumeng Song,Ping Chen,Hui Lou,Xiaoming Zheng,Xiangen Song
In this work, the highly efficient hydrogenation of guaiacol catalyzed by ruthenium supported on Al2O3-TiO2(Ru/Al2Ti1) at very mild conditions was carried out. At temperatures as low as 25 °C and 2 MPa H2, about 60% of guaiacol could be converted to 2-methoxycyclohexanol (MCH) with a selectivity as high as 94% on the Ru/Al2Ti1catalyst with an appropriate hydrogen pressure. At temperatures above 50 °C, almost all of the guaiacol could be converted with the catalyst of Ru/Al2Ti1, mainly into hydrogenated products such as MCH. The surprisingly efficient hydrogenation of guaiacol at low temperatures was most likely due to the ability of Ru particles loaded on the specific complex metal oxide carriers, particularly the reduction of the edge effect of Ru, to activate phenyl and hydrogen and reduce the competition of the dimethoxy process. These findings about the high activity of the Ru/Al2Ti1catalyst at nearly room temperature may be helpful to upgrading the industrial process of the pyrolysis bio-oils.
研究领域:
催化化学
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可再生能源
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工业化学
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
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2012
·Vol. 14
·期 10
·2799-2806
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IF 6.32
CaiFei Wang,JiaQin Sun,XiangDong Liu,Atsushi Sudo,Takeshi Endo
Two fully bio-based benzoxazine monomers, 3-furfuryl-8-methoxy-3,4-dihydro-2H-1,3-benzoxazine (Bzf) and 3-octadecyl-8-methoxy-3,4-dihydro-2H-1,3-benzoxazine (Bzs), have been successfully synthesized via a solventless method. Their structures have been confirmed by FTIR spectroscopy, NMR spectroscopy, and elemental analysis. Copolymerization of the monomers has been investigated by differential scanning calorimetry (DSC) measurements. The results reveal that they undergo homogeneous copolymerization when the Bzf–Bzs molar ratio exceeds 1 : 2. The furan moiety of Bzf was found to have beneficial effects on the copolymerization, including an accelerating effect on the curing process, improvement of the cross-linking density, and enhancement of the thermal properties of the copolymerized resins. Based on the mechanism of ring-opening polymerization of benzoxazines, these effects may be attributed to the electrophilic aromatic substitution of the furan ring structure. These findings have significant implications for the design of new fully bio-based polybenzoxazines with desirable properties.
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DOI
高影响因子
ACS Omega
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2020
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IF 2.87
Hong Hai Wang,Zhi Ling Liu,Yu Cong Song,Hao Li
Hydrodeoxygenation (HDO) is one of the effective methods to upgrade biomass pyrolysis oil, but the development of a low-cost, high-performance HDO catalyst still faces enormous challenges. In this work, a facile and eco-friendly approach is developed to synthesize the Ni2P@hierarchical HZSM-5 catalyst. Structure and acidity of the catalyst can be controlled by simply adjusting the proportions of ammonia solution and the silicon to aluminum ratio, which are closely related to the performance of the catalyst. Experimental results reveal that the Ni2P@hierarchical HZSM-5 catalyst with Si/Al = 85 under NH3·H2O/Ni = 14 exhibits the highest activity of 98% guaiacol conversion, along with a 78.8% yield of cyclohexane (reaction conditions: 300 °C, 3 MPa H2). In addition, the guaiacol reaction network is provided.
研究领域:
催化化学
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能源化学
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产品关联
DOI
PubMed
高影响因子
ACS Catalysis
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2016
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IF 9.307
Jingbo Mao,Jinxia Zhou,Zhi Xia,Zhiguang Wang,Zhanwei Xu,Wenjuan Xu,Peifang Yan,Kairui Liu,Xinwen Guo,Z. Conrad Zhang
Gold nanoparticles on a number of supporting materials, including anatase TiO2 (TiO2-A, in 40 nm and 45 μm), rutile TiO2 (TiO2-R), ZrO2, Al2O3, SiO2 , and activated carbon, were evaluated for hydrodeoxygenation of guaiacol in 6.5 MPa initial H2 pressure at 300 °C. The presence of gold nanoparticles on the supports did not show distinguishable performance compared to that of the supports alone in the conversion level and in the product distribution, except for that on a TiO2-A-40 nm. The lack of marked catalytic activity on supports other than TiO2-A-40 nm suggests that Au nanoparticles are not catalytically active on these supports. Most strikingly, the gold nanoparticles on the least-active TiO2-A-40 nm support stood out as the best catalyst exhibiting high activity with excellent stability and remarkable selectivity to phenolics from guaiacol hydrodeoxygenation. The conversion of guaiacol (∼43.1%) over gold on the TiO2-A-40 nm was about 33 times that (1.3%) over the TiO2-A-40 nm alone. The selectivity of phenolics was 87.1%. The products are mainly phenolic compounds with no aromatics and saturated hydrocarbons such as cyclohexane. The gold particle size ranging from 2.7 to 41 nm and water content were found to significantly affect the Au/TiO2-A-40 nm catalyst activity but not the product selectivity. The reaction rates of 0.26 and 0.91 (min–1 g-cat–1 cm3) were determined for guaiacol hydrogenation and catechol hydrogenation, respectively. Bimolecular methylation was established as the dominant mechanism for methyl group transfer among the phenolics. Two major pathways of guaiacol hydrogenation to phenolics over the 0.4Au-19 nm/TiO2-A-40 nm are proposed: (1) direct hydrogenation of guaiacol to form phenol and methanol, (2) hydrodehydroxylation of catechol intermediate from the transmethylation between guaiacol and phenol.
研究领域:
化学工程
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催化科学
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产品关联
DOI
高影响因子
PEST MANAGEMENT SCIENCE
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2022
·Vol. 78
·期 11
·4557-4568
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IF 4.462
Delong Wang,Min Li,Chunxia Yuan,Yali Fang,Zhijia Zhang
BACKGROUND The natural 1,8-dihydroxynaphthalene (DHN) melanin biosynthesis inhibitors (MBIs) are one of the promising approaches to the integrated management of plant diseases but have received scarce attention until now. Herein, to explore the natural DHN MBIs used in the control of northern corn leaf blight (NCLB), a library of 53 essential oil compounds was used to screen the MBIs against Exserohilum turcicum , the causal pathogen of NCLB, using tricyclazole as a reference compound. RESULTS The results of morphological change in the colony, thermogravimetric analysis, ultraviolet–visible spectroscopy, and transmission electron microscopy confirmed that guaiacol could effectively inhibit the melanin production at 50 μg/mL under in vitro conditions. The in vitro bioassay results indicated that this inhibition effect was concentration-dependent and the minimum inhibition concentration of guaiacol was 50 μg/mL. The in vivo experimental results demonstrated that guaiacol significantly inhibited appressorium formation and penetration on corn leaf sheaths at the concentration of 500 μg/mL. The pot experiment results revealed that there were no differences between guaiacol (500 μg/mL) and tricyclazole (100 μg/mL) in control efficacy. The enzymatic assay suggested that guaiacol might exert the activity through inhibiting DHN polymerization to form melanins, which was distinct from tricyclazole. CONCLUSIONS Taken together, this study screened out guaiacol as a natural MBI from 53 essential oil compounds and verified its effectiveness in the control of NCLB at 500 μg/mL. Above all, this research opened an avenue for exploring natural DHN MBIs in the integrated management of plant diseases. © 2022 Society of Chemical Industry.
研究领域:
植物病理学
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农学
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植物化学
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DOI
PubMed
高影响因子
JOURNAL OF RARE EARTHS
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2022
·
IF 4.632
Feng Lin,Yudan Zhong,Yulong Ma,Yonggang Sun,Xiuqin Men,Yingbo Zhu
Hydrodeoxygenation (HDO) of renewable lignin-derived biomass in aqueous-phase to produce high value-added products is of great significance. However, developing new catalysts with high activity and excellent stability in an aqueous phase faces considerable challenges. Rare earth doping can effectively regulate the water exchange rate constant (WERC) value of the catalyst and play an important role in promoting the hydrolysis of ether bonds. Therefore, in this paper the bimetallic supported catalyst Ni–La 2 O 3 /H-ZSM-5 doped with rare earth metal La 2 O 3 was prepared, and used to catalyze the conversion of the lignin model compound guaiacol to cyclohexanol in the aqueous phase. The conversion of guaiacol catalyzed by 10Ni–3La 2 O 3 /H-ZSM-5 reaches 100%, and the selectivity of the product cyclohexanol is 85%. A series of characterizations illustrate that the doping of La 2 O 3 causes the electron transfer between La 2 O 3 –Ni and changes the distribution of Ni, and a strong metal carrier interaction occurs between the bimetallic Ni–La 2 O 3 and H-ZSM-5. This can effectively promote the hydrolysis of the C–O ether bond in guaiacol and significantly improve the activity of the catalyst. The possible catalytic reaction mechanism of Ni–La 2 O 3 /H-ZSM-5 catalytic conversion of guaiacol was proposed.
研究领域:
催化化学
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生物质转化
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能源化学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
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2025
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IF 4.8
Xin Han,Shanguang Xu,Fan Zhang,Ruiying Chai,Shanguo Du,Xiuling Jiao,Dairong Chen,Jie Zhang
Bimetallic catalysts composed of a primary hydrogenation metal with an oxyphilic metal often exhibit superior catalytic performance compared to their single-metal counterparts. This study elucidates the bimetallic synergy of cobalt-modified MgO-supported Pt catalysts for promoting the selective hydrodeoxygenation of guaiacol to cyclohexanol. The incorporation of Co significantly enhanced both the activity and cyclohexanol selectivity of the Pt/MgO catalyst, with performance following a volcanic trend relative to Co content. The optimal catalyst, Pt-15Co/MgO, exhibited remarkable performance, achieving 98 % guaiacol conversion and 96 % cyclohexanol selectivity at 180 °C and 1 MPa H 2 pressure. The addition of Co effectively suppressed the growth of Pt particles and improved Pt dispersion. Moreover, Co modification could induce the electron transfer from Co to Pt and promote the reduction of Pt species, leading to the formation of more active Pt 0 sites beneficial for hydrogen activation. The presence of oxyphilic Co also could promote the adsorption of the guaiacol molecules and enhance hydrogen spillover. Pt and Co exhibited a distinct synergistic effect in the hydrodeoxygenation process: Co sites primarily promoted C–O bond cleavage, while Pt sites facilitated hydrogen activation. This complementary cooperation altered the reaction pathway, lowered the activation energy, and thereby improved the catalytic performance. These findings offer a rational strategy for designing highly efficient bimetallic catalysts and provide theoretical guidance for the catalytic conversion of lignin-derived oxygenates.
研究领域:
催化化学
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可再生能源
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生物质转化
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多相催化
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木质素高值化
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）