ChemCatChem
·
2017
·Vol. 10
·期 6
·1376-1384
·
IF 4.803
Zhaoxia Zheng,Zhicheng Luo,Chen Zhao
Graphical Taking the cross : Morphologically cross-shaped HZSM-5 loaded Ru nanoparticles demonstrate high activity (rate: 7.8 g g −1 h −1 ) in the selective hydrogenolysis of guaiacol to benzene in water with a nearly quantitative yield accompanied with high durability. Hydrogenolysis of C−O bonds is an important tool for synthesis of valuable fuels and chemicals from biomass. In this contribution, we report that morphologically cross-shaped HZSM-5-loaded Ru nanoparticles have demonstrated high activity in the selective hydrogenolysis of guaiacol to benzene in water with 97 % yield and a rate of 7.8 g g −1 h −1 accompanied with high durability. N 2 sorption analysis showed that Ru/HZSM-5 (cross-shaped) had a large mesoporous surface area and pore volume for loading small and uniform Ru nanoparticles, as confirmed by TEM images. The stronger interaction of Ru and cross-shaped HZSM-5 was simultaneously confirmed by a higher hydrogen reduction temperature of RuO 2 on calcined Ru/HZSM-5, a blueshift of Ru δ+ -(CO) n , Ru δ+ -(CO), and Ru 0 -(CO) species in the IR spectra of adsorbed CO, and a higher Ru 3d 5/2 binding energy in X-ray photoelectron spectroscopy measurements. The reaction constant in guaiacol hydrogenolysis to phenol over cross-shaped Ru/HZSM-5 (0.051 min −1 ) was 3–4 times higher than that on spherical and cuboid Ru/HZSM-5 (0.012–0.029 min −1 ) at identical conditions, attributed to the remarkable hydrogenolysis catalytic capability of Ru nanoparticles on cross-shaped HZSM-5. In addition, adsorption of guaiacol and hydrogen was more substantial on cross-shaped Ru/HZSM-5, as evidenced by of IR and mass spectroscopy, respectively. The higher adsorption of guaiacol is attributed to the abundant Lewis acid sites on cross-shaped Ru/HZSM-5, as the Al−OH enriched Lewis acid sites favor the adsorption of oxygen-containing guaiacol. The higher rate constant in the primary step, together with the adsorbed high concentrated reactant and hydrogen (with nearly first-order reaction kinetics) on cross-shaped Ru/HZSM-5, facilitates the overall tandem reaction, leading to an excellent hydrogenolysis catalyst working at hydrothermal conditions for biomass conversion.
研究领域:
催化化学
·
能源化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Russian Journal of Physical Chemistry A
·
2024
·Vol. 98
·期 10
·2219-2232
·
IF 0.7
Guiling Wu,Zhao Wenli,Yang Xinyue,Niu Xiaopo,Guo Zhen,Liu Danni,Wang Qingfa
Abstract Producing high-density fuel of alkylated decalins from hydrodeoxygenation (HDO) of naphthalene derivatives is an environmentally friendly but still challenging method. Herein, a bifunctional Ru/HZSM-5 catalyst was fabricated by acid treatment (citric acid, oxalic acid, nitric acid) to effectively synthesize the alkylated decalins via HDO of naphthalene derivative. Acid treatment adjusted the acidic site distribution of Ru/HZSM-5. Nitric acid treatment (NA) resulted in more abundance of weak acidic sites which was beneficial for the dehydration process in HDO, and the lowest ratio of BAS/LAS to promote the hydrogenation of alkylated octalins, the rate-determining step of HDO. NA-treated Ru/HZSM-5 showed the highest HDO activity with the highest selectivity of 1,2-dimethyldecalin (74%). Besides, it also presents good HDO activity of naphthalene derivatives to produce high-density hydrocarbons. Therefore, Ru/HZ5-NA is a promising catalyst for the production of alkylated decalins and other high-value biofuels and chemicals.
研究领域:
催化化学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
ENERGY & FUELS
·
2024
·
IF 5.2
Jia-yuan Tian,Jun Hu,Feng Lin,Yu-long Ma,Yong-gang Sun,Ying-bo Zhu,Jin-peng Wei,Yi-ting Lei,Jing-jing Wu
The catalytic selective hydrodeoxygenation of guaiacol to value-added cyclohexane is one of the sustainable biomass utilization pathways for which the Ru/HZSM-5 support catalyst has been considered as promising. However, the effect of the catalyst morphology on the catalytic properties must be further investigated. Four Ru catalysts with different support morphologies, two-dimensional nanosheets (Ru/HZSM-5-P), brick-shaped (Ru/HZSM-5-G), cross-shaped (Ru/HZSM-5-J), and irregular particles (Ru/HZSM-5-D), were prepared by the impregnation method to investigate the effects of catalyst morphology and acidity on the conversion efficiency of lignin-derived guaiacol to cyclohexane. The catalytic activity data showed that Ru/HZSM-5-P exhibited the best catalytic performance among the four catalysts with a conversion rate of 99.9% for guaiacol and a yield of 99.9% for cyclohexane. The characterization results showed significant differences among the four catalysts in terms of accessibility (thickness and pore volume), acidity, metal particle size, and reduction temperature. The Ru/HZSM-5-P catalyst with a two-dimensional nanosheet structure showed the best accessibility, smaller metal particle size, reasonable metal–support interaction, and appropriate B/L. The relatively strong acid centers facilitate the activation of C–C and C–O bonds. Besides, the reduced Ru species on the Ru/ZSM-5 catalyst exhibited high H2 adsorption activity, which was beneficial for the adsorption of guaiacol. This indicates that the difference in catalyst morphology could greatly affect its catalytic activity, thereby altering the conversion rate of reactants and selectivity of the products.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
Frontiers of Chemical Science and Engineering
·
2022
·Vol. 16
·期 10
·1505-1513
·
IF 4.803
Abuduwayiti Reyila,Ma Feng-Yun,Fan Xing
Four supported catalysts, nickel and ruthenium on a HZSM-5 support, were prepared by equal volume impregnation and in-situ decomposition of carbonyl nickel. The properties of catalysts were investigated by catalytic hydro-conversion of 2,2′-dinaphthyl ether as the model compound and extraction residue of Naomaohu lignite as the sample under an initial H 2 pressure of 5 MPa and temperature at 150 °C. According to the catalytic hydro-conversion results of the model compound, Ni—Ru/HZSM-5 exhibited the best catalytic performance. It not only activated H 2 into H⋯H, but also further heterolytically split H⋯H into immobile H − attached on the acidic centers of Ni—Ru/HZSM-5 and relatively mobile H + . Catalytic hydro-conversion of the extraction residue from Naomaohu lignite was further examined over the optimized catalyst, Ni—Ru/HZSM-5. Detailed molecular compositions of products from the extraction residue with and without hydrogenation were characterized by Fourier transform infrared spectroscopy and gas chromatography/mass spectrometry. The analytical results showed that the oxygen-containing functional groups in products of hydrogenated extraction residue were obviously reduced after the catalytic treatment. The relative content of oxygenates in the product with catalytic treatment was 18.57% lower than that in the product without catalytic treatment.
研究领域:
化学工程
·
材料科学
✓ 已验证
DOI
高影响因子
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