JOURNAL OF CATALYSIS
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2022
·
IF 8.047
Beilei Cui,Hua Wang,Jinyu Han,Qingfeng Ge,Xinli Zhu
The relatively cheap and abundant Ni as a catalyst for hydrodeoxygenation (HDO) of biomass lignin-derived phenolics at 350 °C and atmospheric pressure suffers from unfavorable C-C hydrogenolysis toward CH 4 with a lower direct deoxygenation (DDO) activity. Herein, we demonstrate that the activity and selectively of Ni for HDO of m-cresol can be modified through the differences of strong metal-support interaction (SMSI) on anatase and rutile TiO 2 . Characterizations showed that the presence of SMSI depended strongly on the crystal phase of TiO 2 . The SMSI dominates on Ni/a-TiO 2 after reduction at 350 °C, resulting in Ni particles partially covered by a TiO x overlayer, and this overlayer became sufficiently thick at 650 °C, causing a significant reduction of CO chemisorption. Although the catalyst became selective for DDO to toluene, the overall HDO activity was significantly reduced because of excessive SMSI. In contrast, the Ni/r-TiO 2 catalyst reduced at 350 °C exhibited little SMSI and was active for C-C hydrogenolysis like a bare Ni catalyst. Increasing reduction temperature to 650 °C, the Ni/r-TiO 2 catalyst showed moderate SMSI and became selective to toluene through DDO while completely inhibited CH 4 formation. The toluene and total aromatics yields were 84.8 and 92.2%, respectively, at full conversion. More importantly, the turnover frequency for DDO (2.43 min −1 ) on the Ni/r-TiO 2 catalyst reduced at 650 °C was ∼40 and ∼14 times higher than that of Ni on rutile and anatase, respectively, reduced at 350 °C. This study provides an example of “Goldilocks principle” in catalysis, i.e., the best performing catalyst offers a balanced SMSI!
研究领域:
催化
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化学工程
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材料科学
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DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Junqian Wang,Yi Wang,Yuqi Wang,Xinyi Li,Caichao Wu,Tianyu Zhang,Bin Tian,Lili Qian,Yang Guo,Le Wu,Lan Zheng,Yanan Li,Xin Ding
Currently, traditional hydrodeoxygenation (HDO) catalysts have various shortcomings such as low activity levels and vulnerability to deactivation. Therefore, a series of MXene-supported Ni-M (M = Pd, Pt, Ru) bimetallic catalysts were designed and prepared. The above catalysts were also comprehensively characterized using XRD, BET, H 2 -TPR, NH 3 -TPD, XPS, SEM and TEM methods. Moreover, due to the largest particular specific surface area, moderate amount of acid sites and the strongest three-electron transfer channels between support and active metals of Ni-Pd/MXene catalyst, it exhibited the superior catalytic performance to achieve 100 % guaiacol conversion and 35.15 % highest overall yields of HDO products (Y HDO ) under the optimal reaction conditions (at 340 °C for 8 h, utilizing in-situ hydrogen source: formic acid). Furthermore, a detailed discussion on the main reaction pathways and mechanism of guaiacol HDO catalyzed by Ni-Pd/MXene was provided, an unique bimetallic synergistic “relay catalytic” theory has been proposed. Kinetic studies revealed that phenol, one of the main HDO products, is primarily generated via guaiacol demethoxylation, while catechol dehydroxylation to phenol acts as the rate-determining step. This work introduces a new strategy for the development of HDO catalysts.
研究领域:
化学工程
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催化科学
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能源材料
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DOI
高影响因子
CATALYSIS LETTERS
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2025
·Vol. 155
·期 9
·1-12
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IF 2.4
Peng Zhou-Xin,Wu Yu-chen,Xiao Shi-Yun,Zhou Hua-Lan,Wang Sheng-Kang,Wang Xue-Song
Low-cost nickel catalyst (Ni@C/C) derived from a metal organic framework (MOF) was synthetized for the hydrodeoxygenation (HDO) of biomass-derived vanillin. Unlike expensive noble-metal catalysts, Ni@C/C achieves full conversion of vanillin to 2-methoxy-4-methylphenol (MMP)—a key biofuel precursor—under mild conditions (180 °C, 2 MPa H₂). Ni@C/C exhibited excellent catalytic activity for the HDO of vanillin in isopropanol. Moreover, the main product of vanillyl alcohol (VA) under N 2 was 4-(isopropoxymethyl)-2-methoxyphenol (iPMP). The possible mechanism of vanillin by using Ni@C/C catalyst was that Vanillin was hydrogenated to generate VA, and VA was hydrogenated on Ni@C/C to generate MMP by two HDO paths: (1) VA was directly HDO to generate MMP; (2) VA was hydrogenated with isopropanol to generate iPMP by dehydration, then iPMP was hydrogenated to produce MMP. The Ni-based catalyst is relatively cheap and the preparation method is facile, green, and easy to scale up, thus achieving a low-cost transformation of biomass to bio-oils and chemicals. Graphical
研究领域:
催化化学
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生物质转化
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绿色化学
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能源材料
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有机合成
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
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IF 20.2
Jiang Li,Zhidong An,Yue Kong,Le Zhang,Jinqi Yang,Xiaojing Wang,Jiatian Wang,Delong Duan,Qi Zhang,Ran Long,Dionisios G. Vlachos,Zhenxing Li
The conversion of polyethylene terephthalate (PET) plastic into low-boiling monomers like para -xylene (PX) that can be purified easier with lower energy consumption represents a promising strategy for circular economy that seamlessly integrating into current prevailing high-quality PET production chain. Herein, a selective bimetallic RuFe catalyst was successfully fabricated for hydrodeoxygenation (HDO) of dimethyl terephthalate (DMT) (a model compound of PET) and PET plastics to PX with yield as high as 88.9 % and 82.6 %, respectively, comparable to state-of-the-art examples. H 2 -TPR and EXAFS combined with benchmark test over model catalysts confirmed that small Ru clusters and Ru-N x coordination are responsible for the high aromatics selectivity, on which vertical adsorption of carbonyl group (C O) is preferred. This study not only shows a promising PX-based PET recycling route, the highly selective C–O bond cleavage on Ru catalyst and corresponding structure-selectivity relationship also guide the catalyst design for other value-added biomass-based HDO reactions.
研究领域:
化学工程
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材料科学
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催化
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环境科学
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产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
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2023
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IF 7.5
Xin Zhang,Jingyun Jiang,Hao Li
Hydrodeoxygenation (HDO) of bio-oils obtained by rapid pyrolysis of biomass into high value-added chemicals generally required harsh conditions. Herein, three kinds of mixed-phase ZrO 2 supports (denoted as ZSX, X = 2–4) with different crystal structure proportions were prepared by one-pot hydrothermal synthesis method, and their performance on the properties of Pd/ZrO 2 catalysts were investigated for vanillin HDO. Pd/ZS3 exhibited excellent efficiency in HDO of vanillin, a typical model compound of lignin, achieving approximately 100% yield of 2-methoxy-4-methylphenol (MMP) in presence of n-butanol as solvent and polymethyl hydrogen siloxane (PMHS) as hydrogen donor under mild conditions (35 °C, 1 h). It was due to catalytic synergy of exposed metal active sites, oxygen vacancies (O v ) and acid sites to occur electron transfer and enhance interaction between Pd and ZrO 2 . By tuning the crystal structure of ZrO 2 support, the influence of O v and acid sites of Pd/ZrO 2 over vanillin HDO performance was investigated, Pd/ZS2 with abundant O v and Pd/ZS4 with substantial acid sites promoted hydrogenation and hydrogenolysis , respectively, Pd/ZS3 possessed preferable conversion and selectivity as having the properties of both at once. Additionally, reaction pathway was also proposed in which vanillin was converted to MMP by combining intermediate of 4-hydroxy-methyl-2-methoxyphenol (HMP) with active hydrogen species while removing water. This developed catalysts with different crystalline highlighted an enormous promise for HDO of bio-oils into green fuel under mild conditions.
研究领域:
催化
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化学工程
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绿色化学
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材料科学
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DOI
高影响因子
RENEWABLE ENERGY
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2022
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IF 8.634
Riyang Shu,Hao Jiang,Long Xie,Xiaozhou Liu,Tao Yin,Zhipeng Tian,Chao Wang,Ying Chen
Hydrodeoxygenation (HDO) is an effective technology for the conversion of bio-oil to high quality liquid fuels, in which an active and stable catalyst is crucial to gain a high reaction efficiency. In this work, a novel bifunctional catalyst of different Ru-based biochar catalyst coupled with silicotungstic acid (HSiW) was proposed to conduct the HDO of lignin-derived phenolic compounds under mild reaction condition. Ru/C-bamboo catalyst exhibited a better HDO performance than other Ru-based biochar catalysts and commercial Ru/C catalyst. Catalyst characterizations showed that Ru/C-bamboo catalyst possessed a rich mesoporous structure of 0.06 cm 3 /g mesopore volume and 0.07 cm 3 /g micropore volume, with a large specific surface area of 209 m 2 / g. A high metal dispersion and a good hydrogen adsorption ability were achieved in Ru/C-bamboo catalyst. And Guaiacol can be completely converted to cyclohexane with 87.7% selectivity at the temperature of 140 °C. Other typical phenolic compounds were also transformed into corresponding cycloalkanes with high yields above 90% in most cases. Besides, the lignin-oil also had a great improvement on the stability and the heat value after upgradation, with an increase of hydrocarbon content from 9.7% to 31.9%. This result indicated the potential of the bifunctional catalyst in the field of lignin-oil valorization.
研究领域:
催化
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化学工程
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可再生能源
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生物化学
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产品关联
DOI
高影响因子
FUEL
·
2018
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IF 4.908
Fei Wang,Junming Xu,Jianchun Jiang,Peng Liu,Fanglin Li,Jun Ye,Minghao Zhou
Catalysts were prepared and utilized in the hydrotreatment of vegetable oil and FAME to produce diesel-like hydrocarbons. Mo 2 C/AC catalyst displayed the higher catalytic activity with 100.00% conversion and 21.01% cracking ratio, compared to MoO/Al 2 O 3 (85.64%, 25.79%), MoS 2 /Al 2 O 3 (83.46%, 11.88%), Mo/Al 2 O 3 (67.99%, 33.19%), NiP/Al 2 O 3 (48.72%, 3.49%), Ni/Al 2 O 3 (18.12%, 0.00%), and MoO/AC (56.05%, 18.55%). The reaction condition was also optimized, and the bio-diesel achieved 100.00% conversion, 9.67% cracking ratio and 0.73 HDO/DC ratio over Mo 2 C/AC under the optimal condition. The conversion over Mo 2 C/AC dropped from 100.00% to 87.08% and 71.06% with cycles. The results of XRD , XPS and N 2 adsorption–desorption demonstrated that the coke deposited on the surface of catalyst and the formation of MoO 2 and MoO 3 led to the deactivation. After regeneration, the catalyst recovered and achieved 99.36% conversion.
研究领域:
化学工程
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催化
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可再生能源
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生物燃料
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产品关联
DOI
高影响因子
ACS Catalysis
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2022
·
IF 13.7
Ping He,Qisong Yi,Huawei Geng,Yuanchao Shao,Meng Liu,Zhijie Wu,Wenhao Luo,Yuanshuai Liu,Valentin Valtchev
Liquid-phase hydrodeoxygenation (HDO), catalyzed by metal or metal-acid sites, provides an effective catalytic strategy to remove oxygen-containing functionalities of lignin-derived phenolic compounds on the route to fuels and chemicals. Developing the catalyst with high activity and stability is crucial for such a chemical process but still remains a significant challenge. In this contribution, highly dispersed subnanometric Ru metal clusters (<1.5 nm) encapsulated in the cavities of MWW zeolites, including HMCM-22 and its siliceous analog ITQ-1, have been developed for the HDO of guaiacol, an important lignin-derived phenolic monomer, in an apolar liquid phase under mild conditions (160 °C, 3 MPa H2). We validate the effective encapsulation of Ru metal clusters in ITQ-1 and HMCM-22 zeolite cavities via complementary characterization methods. The detailed reaction pathways of the HDO of guaiacol are depicted by using guaiacol, phenol, and anisole as reactants. The subnanometric Ru metal clusters confined in MWW zeolite thin layers (20–30 nm in thickness) show remarkable enhancement in HDO activity compared to the large metal particles. The close proximity between Ru metal clusters and Brønsted acid sites (BAS) confined in zeolite constraints delivers a synergistic effect, leading to an additional enhancement in catalytic activity as well as product selectivity. The super stability of the ultrafine Ru metal clusters against sintering and leaching after successive catalytic runs is achieved. The well-defined mono- or bifunctional Ru-containing MWW zeolite catalysts enable the fundamental understanding of HDO of lignin-derived phenolic compounds in the apolar liquid phase and also provide a prototype for the design of superior catalysts for other energy-related transformations.
研究领域:
催化
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化学工程
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材料科学
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能源
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产品关联
DOI
高影响因子
CARBON
·
2025
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IF 11.6
Jing-jing Wu,Jia-yuan Tian,Feng Lin,Yu-long Ma,Yong-gang Sun
The catalytic conversion of lignin-derived monomer guaiacol to cyclohexanol is pivotal for the development of emerging biofuels. However, designing highly selective hydrodeoxygenation (HDO) catalysts for this process remains challenging. In this study, a Mott-Schottky catalyst comprising nitrogen-doped carbon-encapsulated cobalt NPs (Co@NC) was prepared by pyrolyzing the ZIF-67 precursor, and its catalytic mechanism in the conversion of guaiacol was elucidated. A series of characterizations revealed that nitrogen atom doping induced electron migration from the cobalt core to the carbon layer, thereby precisely regulating the electron density distribution of both the carbon shell and cobalt active sites. Activity experiments combined with density functional theory (DFT) calculations indicated that the reconstructed electronic structure optimized the adsorption capacity for guaiacol and hydrogen, Enabling complete substrate conversion and efficient cyclohexanol production under mild conditions. Compared with traditional catalysts such as nitrogen-doped carbon-supported cobalt (Co/NC) and carbon-encapsulated cobalt (Co@C) catalysts, the excellent performance of Co@NC underscores the critical regulatory role of the electron migration effect in enhancing selective HDO activity. This work provides a novel design strategy focused on electronic structure for optimization the high-value conversion of lignin-derived compounds.
研究领域:
催化化学
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材料科学
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化学工程
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物理化学
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可再生能源
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2019
·Vol. 21
·期 10
·2709-2719
·
IF 9.405
Hao Tang,Ning Li,Guangyi Li,Aiqin Wang,Yu Cong,Guoliang Xu,Xiaodong Wang,Tao Zhang
For the first time, gasoline and jet fuel range C7–C8 cycloalkanes and aromatics were selectively synthesized by the alcoholysis of poly(ethylene terephthalate) (PET) waste, followed by solvent-free hydrogenation and hydrodeoxygenation (HDO). It was found that methanol is highly reactive for the alcoholysis of PET waste. In the absence of any catalyst, a high yield of dimethyl terephthalate (97.3%) was achieved under mild conditions (473 K, 3.5 h). Dimethyl terephthalate exists as a solid and can be automatically separated from methanol with a decrease in temperature. Subsequently, dimethyl terephthalate was liquefied to dimethyl cyclohexane-1,4-dicarboxylate by hydrogenation over noble metal catalysts. Among the investigated catalysts, Pt/C exhibited the highest activity. Finally, the dimethyl cyclohexane-1,4-dicarboxylate as obtained was further hydrodeoxygenated to C7–C8 cycloalkanes and aromatics that can be used as gasoline or additives to improve the densities (or volumetric heat value) and sealabilities of current bio-jet fuels. Bimetallic Ru–Cu/SiO2 was found to be a promising HDO catalyst. According to the characterization results, the excellent HDO performance of Ru–Cu/SiO2 can be explained by the formation of smaller Ru–Cu alloy particles during the catalyst preparation. In real applications, dimethyl cyclohexane-1,4-dicarboxylate can also be simultaneously hydrodeoxygenated with biomass derived oxygenates to produce jet fuel with a suitable content of cycloalkanes and aromatics.
研究领域:
化学工程
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材料科学
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环境科学
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能源
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产品关联
DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE
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2018
·Vol. 54
·期 4
·2940-2959
·
IF 2.993
Xiang Mei,Wu Dongfang
Hierarchically structured ETS-10-supported highly dispersed Co (Co/HMETS-10) is a promising catalyst to selectively catalyse hydrodeoxygenation (HDO) of lignin-derived phenolic compounds. It is shown that almost 100% guaiacol conversion and 96.9% cyclohexane yield are achieved under mild conditions. Co/HMETS-10 exhibits much higher activity and superior reusability due to the advantageous effects of its unique framework, hierarchical structure, Lewis acid sites and Co species. The hierarchically porous structure benefits mass transfer and facilitates the combination of the reacting substrate and acid, metal sites. The characteristic shape selectivity of ETS-10 structure and moderate amount of Lewis acid lead to the high HDO selectivity. In addition, compared with Ni and Fe, Co is more inclined to function in hydrogenolysis of C aryl –OMe bond, thereby improving the catalytic performance. Further HDO experiments indicate the excellent catalytic performance and extensive applicability in selectively deep deoxygenation of various lignin model compounds for production of cycloalkanes.
研究领域:
催化
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化学工程
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材料科学
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可持续化学
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DOI
高影响因子
ACS Applied Energy Materials
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2021
·
IF 6.024
Xiangchen Kong,Chao Liu,Baolong Wang,Weicong Xu,Yuyang Fan,Ming Li,Rui Xiao
A complex copper acid catalyst (SA-Cu/CuMgAlOx) was developed with boosted catalytic activity for the hydrodeoxygenation (HDO) of lignin-derived phenolics. Remarkably, the yields of total monomers and cyclohexanes from the HDO of lignin pyrolysis bio-oil were significantly improved after the catalyst modification with salicylic acid, which increased by 17 and 40%, respectively, at 300 °C for 8 h. The catalyst characterizations revealed that acidic oxygen-containing functional groups (−OH and −COOH) were introduced onto the catalyst surface without corrosion to the metallic framework. The acidic groups contributed to the formation of surface Brønsted acid sites, which participated in the hydrogenolysis and dehydroxylation reactions of the phenolics in bio-oil. The catalyst was deactivated after four cycles of bio-oil HDO and could be recovered after the removal of carbon deposits and the reactivation of Cu species. The results offered appealing opportunities for tailoring more efficient copper-containing catalysts for the HDO of lignin-based phenolics.
研究领域:
化学工程
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催化
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可再生能源
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生物化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）