NEW JOURNAL OF CHEMISTRY
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2025
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IF 2.5
Ruiping Wei,Mingzhu Yao,Ziqi Wang,Huijun Liu,Rongying Xia,Lei Yang,Guanghui Ma,Lijing Gao,Xiaomei Pan,Guomin Xiao
The properties of support have significant effects on the catalytic performance of supported catalysts. The present study involves the synthesis of a series of Mo-modified NbOPO4 supports, which were subsequently utilized for the preparation of supported NiCu bimetallic catalysts via a hydrothermal method. All catalysts were evaluated in the HDO of oleic acid to long-chain alkanes without carbon loss, an essential procedure for contemporary industrial applications. The effects of acidity and porosity on the dispersity and valence states of the metal components were systematically investigated via BET, XRD, SEM, XPS, NH3-TPD, and H2-TPR. Catalytic performance of the materials for HDO of oleic acid was assessed and it revealed that NiCu supported on Mo-modified NbOPO4 exhibited significantly enhanced selectivity for C18 compared to those supported on NbOPO4 (53.10% VS 84.16%) under the mild reaction condition of 250 °C reaction temperature, 3 MPa initial H2 pressure and 7 h reaction time. The resluts demonstrated the significant potential of Mo-modified NbOPO4 as a support for NiCu bimetallic catalysts, enabling efficient conversion of oleic acid into C18 and highlighted the crucial role of support modification in enhancing catalytic performance.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
FUEL
·
2025
·
IF 7.5
Xuan Liu,Hao Xu,Hao Li
The conventional Hydrogenation deoxygenation (HDO) process is accompanied by harsh reaction conditions (high temperature, high hydrogen pressure, and long reaction time), leading to problems such as easy catalyst deactivation and poor product selectivity. Therefore, the design of hydrodeoxygenation catalysts that can achieve controllable reaction paths, directional product selectivity and high reaction efficiency under mild conditions has become the key to the problem. Phenolic resin (RF) formed by resorcinol–formaldehyde condensation reaction was introduced as a carbothermal reducing agent to prepare oxygen defect-rich Pd/Nb 2 O 5 -T-RF catalysts. The concentration of oxygen defects on the catalyst surface was changed by adjusting the calcination temperature, which affected the electronic properties and acid properties of the catalyst surface interface and promoted the C-O bond breaking. At 25 ℃ and 80 min, Pd/Nb 2 O 5 -700-RF obtained 100 % Vanillin (VAN) conversion and 98.0 % 2-methoxy-4-methylphenol (MMP) selectivity, and the catalytic performance was significantly better than that of the catalysts without RF treatment as well as other calcination temperatures. Characterization and experimental results showed that the electron-deficient oxygen defect facilitated the adsorption and activation of vanillin and vanillyl alcohol, while promoting the hydrogen spillover on the catalyst surface and improving the HDO catalytic performance. In addition, the method is universal for reducible transition metal oxides and can be further extended to different metal oxide catalysts and applied to other fields.
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DOI
高影响因子
JOURNAL OF CATALYSIS
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2023
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IF 7.3
Hao Xu,Hao Li
Constructing heterogeneous catalysts with high efficiency and stability to achieve biomass HDO under comparatively mild conditions is an arduous challenge. Crystal phase of metal oxides supports could affect the geometric and electronic properties, causing the variation of catalytic performance. Herein, a series of Pd/Nb 2 O 5 catalysts of pseudohexagonal crystal phase (Nb 2 O 5 -TT), orthorhombic phase (Nb 2 O 5 -T) and monoclinic phase (Nb 2 O 5 -H) are prepared through regulating the annealing temperature. Impressively, Pd/Nb 2 O 5 -T catalyst showed amazing catalytic performance of 100% conversion and 98.9% selectivity of 2-methoxy-4-methylphenol (MMP) at room temperature (25℃) within 30 min, superior than Pd/Nb 2 O 5 -TT, Pd/Nb 2 O 5 -H and other Pd-based catalysts that had been reported. Besides, the Pd/Nb 2 O 5 -T perform robust stability and maintain its high activity after ten times recovery experiment. This catalytic system is also suitable for different kinds of aldehydes compounds at room temperature, exhibiting the high activity and selectivity towards deoxygenated products. Based on the characterizations and experimental validations, it has confirmed that the strong metal-support interaction (SMSI) effect generates via electron transfer between Pd species and Nb 2 O 5 -T support, where in situ reduction of PdO occurred during the reaction, generating active interfacial Pd-O-Nb sites and accelerating the breaking of C-O bonds. The insights of this work provide a guiding direction for the future design of highly selective heterogeneous catalysts by crystal phase modulation engineering.
研究领域:
催化化学
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材料科学
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能源化学
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产品关联
DOI
高影响因子
Journal of Energy Chemistry
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2016
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IF 2.322
Qi Wang,Neeraj Gupta,Guodong Wen,Sharifah Bee Abd Hamid,Dang Sheng Su
Vanillyl alcohol, which is made up of an aromatic ring , an alcoholic hydroxyl group, a phenolic hydroxyl group and a methoxy group, was selected as the model molecule of lignin. Various carbon materials supported Pd catalysts were chosen to catalyze the HDO of vanillyl alcohol. The catalysts were characterized via TEM, TPD, XRD, XPS and CO-chemisorption. It was found that different carbon materials could obviously influence the particle sizes, dispersion and distribution of Pd or PdO particles. Palladium and carbon can synergistically catalyze the room-temperature HDO of vanillyl alcohol even at room temperature, and the carboxyl group was found to be the effective active acid site during the reaction. Possible reaction mechanism was also proposed. The existence of the effective active acid sites on the carbon supports could obviously lower the reaction temperature without decreasing the selectivity, as a result, making the production of renewable fuels by HDO much more economically feasible, which is of much importance.
研究领域:
化学工程
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可再生能源
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产品关联
DOI
高影响因子
Sustainable Energy & Fuels
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2022
·Vol. 6
·期 18
·4183-4196
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IF 6.813
Shuai Wang,Yanxiu Liu,Mei Zhang,Feng Li,Yanguang Chen,Hua Song
Aqueous-phase hydrodeoxygenation (HDO) of biomass-derived phenolic compounds is considered as one of the most promising ways to convert biomass into fuels and value-added chemicals. The aim of this study is to develop highly active and water-resistant catalysts with a low price. For this purpose, with cheap transition Ni as the active phase, supported Ni@C/MxOy(x) and Ni@C/Al2O3(5)-glucose catalysts (MxOy stands for ZrO2, CeO2, TiO2 or Al2O3 and x represents Ni loading) were prepared from Ni-MOF-74/MxOy (x). The prepared catalysts were characterized by TG, H2-TPR, XRD, BET, HRTEM, XPS and NH3-TPD. The effect of the support, Ni loading and glucose incorporation on the HDO performance of phenol was investigated. The results showed that the Ni@C/Al2O3(5) catalyst with Al2O3 as the support and a low Ni loading of 5% exhibited the best HDO activity. The superior performance with such a low Ni loading greatly reduced the cost of the catalysts. Furthermore, the total yield of the deoxygenated product over Ni@C/Al2O3(5) was increased by 22.3% after the incorporation of glucose when the molar ratio of phenol/water was 1 : 1.25. In addition, the fixed-bed reactor experiment revealed that the HDO performance of Ni@C/Al2O3(5)-glucose almost remained stable during 48 h on-stream operation, indicating its excellent stability.
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
高影响因子
GREEN CHEMISTRY
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2020
·Vol. 22
·期 13
·4341-4349
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IF 9.48
Yuxue Xiao,Qingwei Meng,Xiaoli Pan,Chao Zhang,Zaihui Fu,Changzhi Li
para-Xylene (PX) is a basic building block of polyethylene terephthalate, which is currently produced from petroleum resources. Developing a renewable route to PX is highly desirable to address both economic and environmental concerns. Several attempts used noble metal catalysts, e.g. Pd/Al2O3, to synthesize PX from biomass-derived 4-methyl-3-cyclohexene-1-carboxaldehyde (4-MCHCA), but suffered from a severe decarbonylation reaction, resulting in toluene as the main product. In this paper, we report an FeOx modification strategy to suppress the decarbonylation reaction on a Pd/Al2O3 catalyst, leading to a drastic shift in selectivity towards PX with a yield up to 81% via a cascade dehydroaromatization–hydrodeoxygenation (DHA–HDO) pathway. Characterization and control experiments revealed that the electron density of Pd sites decreased in an FeOx-modified Pd/Al2O3 catalyst compared to Pd/Al2O3, thus tuning the preferential adsorption mode of the substrate from η2-(C,O), the key transition state of the decarbonylation reaction, to the η1-(O) mode that favors the hydrodeoxygenation process. Notably, this designed catalyst is highly stable and is readily applicable in the selective synthesis of a broad range of desired aromatic chemicals via the same DHA–HDO pathway from cyclohex-3-enecarbaldehyde derivatives. Overall, this work develops a controllable catalyst modification strategy that tailors an efficient catalyst for petroleum-independent bio-PX synthesis.
研究领域:
催化化学
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可再生资源化学
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环境科学
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产品关联
DOI
高影响因子
ACS Catalysis
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2022
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IF 13.7
Hui Wang,Wenru Zhao,Mooeez Ur Rehman,Wei Liu,Yuxi Xu,Huijiang Huang,Shengping Wang,Yujun Zhao,Donghai Mei,Xinbin Ma
In the utilization of renewable resources derived from biomass, hydrodeoxygenation (HDO) is one of the most critical steps in the bio-oil upgrading process. Herein, a series of copper phyllosilicate nanotube (CuPSNT) catalysts were successfully prepared and applied in the chemosynthesis of cyclohexane via the phenol HDO reaction. Against the presumption that mono-metal copper was not active for the complete hydrogenation of aromatic compounds, a cyclohexane yield of 97.8% at the total conversion of phenol was achieved at 230 °C on the CuPSNT catalysts with a Cu/Si ratio of 1:1. The kinetic analysis suggested that further conversion of cyclohexanol to cyclohexane is the rate-determining step in the phenol HDO. Cu0 accounts for the hydrogenation, while Cu+ is responsible for the adsorption of phenol and cyclohexanol and in charge of further cyclohexanol dehydration. This conclusion is further confirmed by density functional theory calculations. This work demonstrates that the synergy between Cu0 and Cu+ species of CuPSNT catalysts plays a critical role in the HDO process of phenol, and mono-metal Cu can accomplish both the saturation of aromatic rings and the removal of oxygen groups.
研究领域:
催化化学
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可再生资源利用
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2023
·
IF 7.4
Puxiang Yan,Haiyong Wang,Yuhe Liao,Chenguang Wang
Upgrading biomass to renewable diesel and jet fuels is essential to achieve carbon neutrality. Herein, diesel and jet fuels range alkanes were produced by HAA of 2-methylfuran and furfural over solid acid SO 4 2- /TiO 2 and subsequent HDO over Pd/NbOPO 4 . A series of SO 4 2- /TiO 2 catalysts were synthesized by wetness impregnation to produce C15 fuel precursors. S/Ti-450 with a calcination temperature of 450 °C exhibited the highest activity, affording 97.9 % yield of C15 fuel precursor. Sufficient Brønsted acid sites and moderate Brønsted acid strength are responsible for the super catalytic performance of S/Ti-450. Stability studies demonstrated that S/Ti-450 could be regenerated. Furthermore, the application of S/Ti-450 in the HAA reaction was extended to other carbonyl compounds (e.g., butanal, cyclohexanone and acetone) and high yields of desired fuel precursors were obtained. Finally, C15 fuel precursor was further converted to long-chain alkanes via HDO over Pd/NbOPO 4 , yielding 85.0 % diesel and jet fuels range alkanes.
研究领域:
化学工程
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可再生能源
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2022
·
IF 8.035
Xiaoxian Li,Min Lin,Rui Li,Qiang Lu,Mingde Yang,Yulong Wu
In this work, methods employing ethanol for dispersion as well as precursor combination by rotary evaporation were combined to produce Ni-based ZSM-22 catalysts. The catalytic activity in palmitic acid deoxygenation over Ni/Z22@E was enhanced compared with that of the wet-impregnated method. The conversion of palmitic acid reached 98.9 %, in which C16/C15 alkane was as high as 4.07. The Ni species on the surface of catalysts showed strong stability so that not susceptible to inactivation by coking or leaching. In addition, the mechanism and kinetics of the palmitic acid deoxygenation reaction were analyzed. The results showed that the ethanol dehydration reaction was the most difficult to occur, and the high C 16 alkanes selectivity can be attributed to the low activation energy of the hydrodeoxygenation (HDO) pathway. Both experimental and kinetics calculation results suggested that there may be a mechanistic change in the fatty acid deoxygenation reaction at around 240 °C that resulted in a large increase in the hydrodecarboxylation (HDX) pathway. Based on this, selected adjustments of the products were proposed for fatty alcohols below 220 °C, C 16 alkanes between 260 and 280 °C, and C 15 alkanes above 280 °C.
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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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Qunfeng Chen,Daobin Tang,Qi Zhang,Zhiyuan Tang,Longlong Ma,Xinghua Zhang
Electron-metal support interactions (EMSI), which can tailor the microenvironment through electron transfer and coordination structure design, are an effective strategy to augment the intrinsic catalytic activity of catalysts. However, it remains challenging to establish the interfacial structure and interfacial electron configuration of catalysts to precisely regulate and enhance EMSI. In this work, the spatially defective sites and specific electronic states of Pd-UiO-66 were modified by in-situ constructing a W-O-Zr interface to strengthen the EMSI between Pd nanoparticles (Pd NPs) and UiO-66 support via implanting W into the defective Pd-UiO-66, realizing the effective hydrodeoxygenation (HDO) of vanillin (VAN) at room temperature (RT). The as-prepared catalyst Pd-UiO-66–0.24 W achieved > 99 % conversion of VAN and > 99 % yield of 2-methoxy-4-methylphenol (MMP) within 12 h, which surpassed the previous reports. The DFT analysis revealed that the narrow band-gap energy between Pd-UiO-66–0.24 W and H 2 molecule, along with the σ or π coordination adsorption between p and d orbitals of the implanted W and O in C=O, facilitated the activation of the H 2 molecules and reactant molecules. In addition, the constructed electron-deficient W-O-Zr interfacial sites provided more acidic sites that favor the cleavage of C-O bonds, promoting the HDO process of VAN. This work provides important insights into the modulation of EMSI, structural defects and acidic sites of metal–organic frameworks (MOFs)-based catalysts for efficient HDO of lignin-derived oxygenated compounds.
研究领域:
催化化学
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材料科学
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理论计算化学
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产品关联
DOI
高影响因子
JOURNAL OF THE ENERGY INSTITUTE
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2019
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IF 3.774
Biqin Lin,Rongxuan Li,Riyang Shu,Chao Wang,Zhengqiu Yuan,Yong Liu,Ying Chen
Hydrodeoxygenation (HDO) is an indispensable and important reaction in the fuel production process. Generally, the catalysts for HDO contain metal or acidic active sites, and the co-existence of them can significantly promote the HDO performance. While the subtle interaction between metal and acidic active sites is still not very clear. Herein, a series of Ru-based catalysts with different supports were prepared by photochemical method to obtain both of the high Ru dispersion and the moderate acidity. Among the catalysts with various supports, Ru/TiO 2 –Al 2 O 3 showed the most efficient performance in the HDO process of phenolic compounds. Guaiacol was converted into cyclohexane with above 90% selectivity at 240 °C. Other typical phenolic compounds, including phenol, anisole, p -cresol, 1,2-dimethoxybenzene, benzofuran , eugenol and dibenzyl ether, were all transformed into the corresponding cycloalkanes with yield close to 100%. The synergistic effect between highly dispersed Ru and moderate acid site played the key role for the enhanced production of hydrocarbon fuels. Moreover, this catalytic system was also effective on the raw bio-oil upgradation for producing high yield of hydrocarbons and alkylphenols, which has the potential to be used as biofuels.
研究领域:
催化
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化学工程
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能源
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2023
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IF 8.4
Xiangchen Kong,Chao Liu,Yuyang Fan,Ming Li,Rui Xiao
The conversion of crude lignin bio-oil to jet fuels is a highly desirable target for biorefineries, especially in light of the global energy crisis. The key to achieving this goal is the realistic tuning of catalyst efficiency and selectivity for expected products. Herein, a copper catalyst with enhanced activity for hydrodeoxygenation (HDO) of crude lignin bio-oil to jet fuel precursors was developed in this work. The copper catalyst, a copper-doped porous metal oxide, was modified with a series of moderate organic acids to graft the acidic O-groups as potential Brønsted acid sites for HDO reactions. The copper catalyst modified with propanoic acid exhibited exceptional catalytic performance for the upgrading of lignin pyrolysis bio-oil, giving yields of jet fuel precursor range cycloalkanes and cycloalcohols of 10.04 and 14.20 C%, which were improved by 88.0 and 42.7% compared with those from the blank. Meanwhile, the corresponding hydrogenation and deoxygenation degrees of the products reached 91.5 and 65.9%, respectively, which were improved by 17.3 and 31.8%. Likewise, the overall double bond equivalence and aromaticity index of the products given by the modified copper catalyst were as low as 2.8 and 0.1, which were substantially reduced by 18.0 and 50%, correlating to higher HDO efficiency. The abundant Brønsted acid sites with proper strength and the affluent pore structures of the propanoic acid-modified copper catalyst mainly contributed to its outstanding catalytic activity. The findings suggest promising avenues for increasing the efficiency of heterogeneous catalysts in the HDO of lignin-based bio-oil to alternative fuels.
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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生物炼制
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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）