ACS Sustainable Chemistry & Engineering
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2022
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IF 9.224
Ruixue Liu,Xinli Li,Zhendi Jia,Yiyun Wang,Yanli Peng,Congming Tang,Zhi Chen,Lin Dong
The hydrodeoxygenation of lactic acid (LA) to propionic acid (PA) is of great significance for the conversion of biomass to valuable products; however, it remains a great challenge because of the trade-off between LA conversion and PA selectivity. Here, we prepared ultrathin MoS2 nanosheets containing rich sulfur vacancies by lithium exfoliation. With the increase of the lithium exfoliation time, sulfur vacancy in MoS2 is accordingly increased and LA adsorption and activation on sulfur vacancy is enhanced. Increasing sulfur vacancy lowered the valence band simultaneously and enhanced the dissociation of the H2 molecule. Density functional theory (DFT) calculations showed that the sulfur vacancy efficiently adsorbed α-C–OH of the LA molecule, weakened the C–O bond, and achieved selective conversion of LA to PA. At 215 °C, 92.4% of LA conversion and 95.8% PA selectivity were achieved over the sulfur vacancy-rich MoS2 nanosheets, which broke the activity–selectivity trade-off on hydrodeoxygenation of LA, and notably surpassed those of previously reported catalysts. More importantly, the activity of the catalyst remained almost unchanged after 8 cycles of reaction.
研究领域:
催化化学
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生物质转化
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材料科学
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DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
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2022
·Vol. 46
·期 47
·22672-22685
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IF 3.925
Jing Wang,Mei Zhang,Feng Li,Huan Wang,Yanguang Chen,Hua Song
To deeply understand the role of P in hydrodeoxygenation (HDO), SiO2-supported Ni and Ni–P catalysts with different P/Ni ratios (x) were prepared. The as-prepared samples were characterized by various characterization methods. The HDO activity and product distribution over the Ni/SiO2 and N–P/SiO2-x were compared and the effects of x on the structure, acidity, formation mechanism of active phases and HDO performance were studied taking m-cresol HDO as a model reaction. The results showed that the introduction of P promotes the formation of smaller active sites and contributes to the creation of weak and medium strength acid sites through the formation of P–OH groups and Niδ+ in Ni2P. HDO over the Ni/SiO2 catalyst occurs mainly via the hydrogenation (HYD) route with 3-methyl-cyclohexanol (3-MCHnol) as the main product. However, for Ni–P/SiO2-x catalysts, methyl-cyclohexane (MCH) selectivity increases first and then decreases with the increase of x, reaching a maximum of 95% at x = 1. The acidity generated by the introduction of P contributes to increased MCH selectivity, while the dehydration of 3-MCHnol to MCH occurs mainly on acid sites. However, the excessively high P content (x ≥ 2.0) leads to a significant increase of MB (toluene) selectivity, which is associated with the increase in Ni(I) sites. About 100% m-cresol conversion was achieved with Ni–P/SiO2-1.0 when the m-cresol (g)/catalyst (g) ratio was 3, with MCH (99.4%) as the major product, showing great promise for deep HDO catalysis.
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
FUEL
·
2021
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IF 6.609
Jinlei Chen,Dechao Wang,Fenqiang Luo,Xinyu Yang,Xingyong Li,Shuirong Li,Yueyuan Ye,Duo Wang,Zhifeng Zheng
Production of valuable chemicals and fuels from waste animal fat and vegetable oils can serve as alternatives to fossil energy. In this study, the selective production of alkanes and higher fatty alcohol via hydrodeoxygenation (HDO) of palmitic acid over red mud-supported nickel catalysts (Ni/RM) was reported. Meanwhile, the study has investigated the effect of Ni loading, reaction temperature, hydrogen pressure on the HDO of palmitic acid, analyzed the reusability of Ni/RM and explored the possible reaction mechanism. The results show that palmitic acid is completely converted over 7%Ni/RM. The selectivity of fatty alcohol and alkanes are 92.54% (260 °C) and 100% (300 °C), respectively. Ni/RM has shown the highest catalytic performance as compared to commercial Ni/SiO 2 and Ni/γ-Al 2 O 3 catalysts. The 7%Ni/RM also demonstrates stable catalytic performance after multiple times of reuse. Moreover, hexadecanol plays an important role in hydrodeoxygenation, decarbonylation, and decarboxylation routes.
研究领域:
化学工程
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能源科学
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产品关联
DOI
高影响因子
ACS Catalysis
·
2022
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IF 13.7
Yue Zhang,Lin Li,Fei Liu,Haifeng Qi,Leilei Zhang,Weixiang Guan,Yuefeng Liu,Aiqin Wang,Tao Zhang
The selective reduction of primary amides to the corresponding amines is a key reaction in both pharmaceutical chemistry and the polymer industry; yet, it requires a stoichiometric amount of expensive and environmentally unfriendly hydride reagents. Hydrodeoxygenation (HDO), on the other hand, is a highly desired environmentally benign alternative; yet, it presents significant challenges in activity and selectivity control. In this work, we have developed a bifunctional 2Ru1W/SiO2 catalyst, which afforded 93.6% conversion and 83.7% selectivity of the primary amine after reaction for 12 h for the HDO of cyclohexanecarboxamide at 433 K, and the initial reaction rate reached 48.2 h–1, 1 order of magnitude higher than other catalysts reported earlier. The catalyst also presented excellent reusability and substrate diversity. The performances of various Ru–W/SiO2 catalysts critically depend on the synergy between W and Ru, with the best performance accessible at the W/Ru atomic ratio of 0.27. Characterizations and reaction kinetics have revealed that Ru promoted the reduction of W6+ to W5+ via hydrogen spillover, and the resultant low-coordinated W5+ is responsible for the selective activation of the C═O bond of the amide, leading to almost zero reaction order with respect to the amide and much lower apparent activation energy over the 2Ru1W/SiO2 bimetallic catalysts in contrast to the first order and higher activation energy over Ru/SiO2. Nevertheless, W/Ru ratios higher than 0.27 resulted in larger WOx domains and lower valence states of W, which adsorbed the amide substrate so strongly that the catalyst surface was poisoned, leading to a dramatic decrease in both activity and selectivity. The catalyst strategy as well as the mechanism understanding presented in this work will provide insights into the bifunctional catalyst design used for other demanding chemical transformations.
研究领域:
催化化学
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材料科学
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环境化学
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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
Xiangze Du,Xiaomei Lei,Linyuan Zhou,Yong Peng,Yan Zeng,Huiru Yang,Dan Li,Changwei Hu,Hermenegildo Garcia
In the context of the preparation of liquid fuels derived from biomass with zero CO2 footprint, fatty acids appear as suitable feedstocks. However, reduction of carboxylic acid groups usually requires harsh reaction conditions and the development of efficient solid catalysts. Herein, bimetallic Ni–Mo nitrides have been obtained by a procedure not involving nitridation of the corresponding oxide, but reductive decomposition of the tris(ethylenediamine)nickel molybdate at temperatures between 550 and 700 °C. Successful formation of the Ni3Mo3N nitride is confirmed by X-ray diffraction. Ni3Mo3N samples are found to be efficient catalysts for the hydrodeoxygenation of palmitic acid to C15/C16 alkanes with a combined selectivity over 90 and 100% palmitic acid conversion and higher activity than analogous Ni–Mo nitrides obtained by NH3 nitridation of NiMoO4. Ni3Mo3N is found recyclable with only a slight decay in the catalytic activity upon consecutive reuses attributable to the neutralization of acid sites. The present results show an opportunity that bimetallic nitrides offer as robust advanced solid catalysts for reactions of biomass conversion requiring harsh conditions.
研究领域:
化学工程
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催化材料
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可再生资源转化
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DOI
高影响因子
ChemistrySelect
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2025
·Vol. 10
·期 20
·e01019
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IF 2
Siqi Wang,Yazhou Wang,Yonggang Ji,Zhenye Li,Yueli Dai
Graphical This study investigated the reactivity of nickel phosphide, copper phosphide, and cobalt phosphide catalysts in the hydrodeoxygenation of furfural to 2-methylfuran. Appropriate acidic and adsorbent configurations were employed to facilitate the production of 2-methylfuran. Among the catalysts tested, the copper phosphide catalyst exhibited the highest selectivity for 2-methylfuran. A series of transition metal (Ni, Cu, and Co) phosphides were prepared by temperature programmed reduction method. The effect of the metal species and the initial P/Cu molar ratios on the catalytic activity of furfural hydrodeoxygenation was investigated, and the reaction conditions were optimized. Complete conversion of furfural was achieved under conditions of 220 °C and 15 bar for 4 h over Ni 2 P, CoP, or Cu 3 P catalysts. Notably, a selectivity of 95% of 2-methylfuran was attained when the Cu 3 P-3 was employed as a catalyst. The experimental results showed that a suitable P/Cu molar ratio could promote the conversion of the intermediate furfuryl alcohol to 2-methylfuran while avoiding the generation of overhydrogenation products. Under the optimal reaction conditions, the Cu 3 P-3 catalyst could be used for four times with only a slight decrease in catalytic performance.
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
JOURNAL OF ALLOYS AND COMPOUNDS
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2024
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IF 5.8
Xue Wu,Hui Li,Wenlin Xu,Ge Fei,Minghao Zhou,Xin Zhao
Lignin accounted for the second largest amount in biomass, and was regarded as an important carbon source and important renewable source for value-added chemicals. Herein, a series of lignin-derived carbon-based heterogeneous catalyst was synthesized through a simple hydrothermal method , using Co-MOFs as template. Lignin was introduced as a carbon material into MOF catalysts. Through some characterizations, it has been proven that lignin has been successfully introduced into MOF materials and significantly improved the catalyst performance. Then, lignin-MOF derived catalysts (Co/C-EL-X) were successfully introduced into the catalytic hydrodeoxygenation of lignin-derived phenols . The addition of enzymatic hydrolysis lignin (EL) in catalysts, calcination temperature and some other factors were investigated in detail, considering the catalytic performance during the HDO of vanillin and other typical lignin-derived phenols. Co/C-EL-0.5(500) exhibited the best catalytic performance for the conversion of different kinds of lignin-derived phenols to either 2-methoxy-4-methylphenol (MMP) or cyclohexanol . Under the optimal conditions of 240 °C, 0 MPa N 2 , and 2 h, the conversion rate of vanillin reached 100 %, and the yield of 4-methyl-2-methoxyphenol (MMP) was up to 92 %. Furthermore, vanillin could also be converted into 4-methylcyclohexanol (MCYL) by changing the initial nitrogen pressure. Also, Co/C-EL-0.5 (500) exhibited high activity for the conversion of other lignin-derived phenols into cyclohexanol (COL). This work provided a novel strategy for the catalytic valorization of lignin sources.
研究领域:
化学工程
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可再生资源利用
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产品关联
DOI
高影响因子
RENEWABLE ENERGY
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2024
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IF 9
Daxin Jiang,Min Lin,Yuhao Yan,Lulu Zhan,Rui Li,Yulong Wu
Catalytic hydrodeoxygenation (HDO) is an effective way to produce high–value products from lignin-derived phenolic compounds. In this work, three different morphologies of Ni/CeO 2 catalysts (amorphous, cubic, and rod-shaped) have been prepared through the conventional wet impregnation method. They can be used for the HDO of guaiacol to prepare cyclohexanol, an important chemical raw material. The influence of different morphologies of CeO 2 on catalytic activity was explored. The research results indicate that Ni/CeO 2 –r catalysts with rod-shaped structures exhibit excellent catalytic properties. As a result, a 100 % conversion rate and 96.9 % cyclohexanol yield were achieved on the Ni/CeO 2 –r catalyst at 240 °C. The catalytic performance of the three catalysts follows this order: Ni/CeO 2 –r (rod-shaped) > Ni/CeO 2 –c (cubic) > Ni/CeO 2 –p (amorphous). The results of Raman and XPS indicate significant differences in the surface oxygen vacancy in catalysts with different morphologies. The Ni/CeO 2 –r catalyst has the highest oxygen vacancy concentration and defect. In addition, Ni/CeO 2 –r also has the largest specific surface area (S BET ) and the highest nickel dispersion, and forms more Ni 0 because of the strong interaction of Ni species and CeO 2 support. Therefore, Ni/CeO 2 –r exhibits the most excellent catalytic performance for the hydrogenation of guaiacol than the other two catalysts. Moreover, the cycling activity test was also investigated over the Ni/CeO 2 –r catalyst. After five cycles, the conversion rate of guaiacol and the yield of cyclohexanol hardly decrease. This work provides vital ideas for the development of higher-activity, higher-stability, and low-cost catalysts for the conversion of lignin-derived phenolic compounds in the future.
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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2021
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IF 9.676
Shanshuai Chen,Weichen Wang,Xue Li,Puxiang Yan,Wanying Han,Tian Sheng,Tiansheng Deng,Wanbin Zhu,Hongliang Wang
Catalytic hydrodeoxygenation (HDO) of biomass-derived oxy-compounds to advanced hydrocarbon fuels usually requires bifunctional catalysts containing metals and acidic sites. The appropriate tuning of metal and/or acidic active sites at interfaces of bifunctional catalysts can significantly improve catalyst activity and product selectivity. Here, 4-trifuoromethyl salicylic acid (TFMSA), as a hydrothermal stable organic acid, was employed to tailor the bifunctional interface of Ru/γ-Al 2 O 3 to enhance the catalytic performance on converting lignin-derived phenols to jet fuel range cycloalkanes. More than 80% phenol was converted into cyclohexane at 230 °C for 1 h over Ru/γ-Al 2 O 3 modified by TFMSA, which was about three times higher than that over unmodified Ru/γ-Al 2 O 3 . X-ray diffraction (XRD), Transmission electron microscope (TEM), H 2 chemisorption, and energy dispersive X-ray spectroscopy (EDS) elemental mapping results indicated that Ru nanoparticles and TFMSA were well distributed on γ-Al 2 O 3 , and a nanoscale intimacy between Ru and TFMSA was reached. Meanwhile, Fourier transform infrared spectroscopy after pyridine adsorption (Py-FT-IR) analysis proved that Brønsted acidic sites on the catalytic interfaces of TFMSA modified Ru/γ-Al 2 O 3 had been improved. Moreover, the kinetic and density functional theory (DFT) results suggested that the synergistic effects of adjacent Ru nanoparticles and acidic sites were crutial for promoting the rate-limiting conversion step of phenol HDO to cyclohexane.
研究领域:
催化化学
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能源科学
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材料科学
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产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2018
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IF 6.14
Guohua Zhu,Kui Wu,Liang Tan,Weiyan Wang,Yanping Huang,Diyu Liu,Yunquan Yang
Magnetic colloidal sol was first prepared and added in the mixed solution of Ni(NO3)2 and Al(NO3)3. After the constant-pH coprecipitation and calcination, magnetic NiO–Al2O3@Fe3O4 mixed oxides were formed and used as supports for Pt-based catalysts. The activities of these magnetic Pt/NiO–Al2O3@Fe3O4 catalysts were tested in the hydrodeoxygenation (HDO) of phenols such as 4-ethylphenol, 4-methylphenol, and guaiacol. These exhibited high HDO activity, and aromatic hydrocarbons were produced through a coupling process of hydrodeoxygenation and dehydrogenation. The addition of Fe enhanced both the conversion and aromatic hydrocarbons selectivity, which was attributed to the electron transfer between metallic Pt and Fe. For example, after the liquid phase HDO of 4-ethylphenol at 300 °C and 2.0 MPa for 1.5 h, 97.9% conversion and 18.3% toluene selectivity were obtained. When the reaction time was prolonged to 8 h, ethylbenzene selectivity increased to 88.0%. Moreover, these Pt/NiO–Al2O3@Fe3O4 catalysts were easily recycled from the liquid reaction mixture by employing an external magnet, but the dehydrogenation stability needs to be further improved.
研究领域:
化学工程
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催化材料科学
✓ 已验证
DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
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2024
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IF 5.6
Xialin Ji,Mengqing Zhou,Yongzhi Xiong,Changzhou Chen,Jianchun Jiang
Utilization of biomass derived raw material to create advanced and high value carbon biochar have attracted tremendous attention, the exploration and functionalization of novel biomass derived raw material have presented serious challenges to contemporary chemical industry. Therefore, a new renewable biomass-derived hollow carbon sphere derived from eco-friendly and environmental-friendly puffball loaded different active sites was designed to generate Co 8 M 2 /BC catalysts. The novel biomass puffball derived catalysts exhibited an excellent catalytic efficiency in hydrodeoxygenation of biomass derived phenols to obtain value-added chemicals and fuels. In this work, Vanillin (VAN) was used as a model substrate to estimate the catalytic efficiency of as-prepared Co 8 M 2 /BC catalysts. The results showed that the Co 8 Mo 2 /BC catalyst exhibited excellent catalytic activity for the VAN hydrodeoxygenation reaction to achieve achieved 99.24% conversion of VAN and 92.79% yield of 2-methoxy-4-methylphenol (MMP) under the optimal reaction conditions (240°C, 4 h, 1 MPa H 2 and 15 mL isopropanol). The uniquely shaped hollow sphere carbon, large specific surface area and synergistic catalytic effect of the Co-Mo alloy was the key reasons for the perfect hydrodeoxygenation ability. H 2 temperature program reduction (H 2 -TPR) illustrated the strong interaction between biochar and active sites and the NH 3 temperature programmed desorption (NH 3 -TPD) demonstrated a suitable amount of acid sites was responsible for high catalytic hydrodeoxygenation performance. In addition, the possible reaction mechanization of VAN hydrodeoxygenation was also proposed in the end of the study. This work provided new sights in preparation of advanced biomass derived biochar catalysts for catalytic hydrodeoxygenation of biomass derived phenols to produce high value chemicals and fuels.
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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产品关联
DOI
高影响因子
CATALYSIS LETTERS
·
2020
·Vol. 151
·期 2
·338-343
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IF 2.482
Shi Hexian,Zhang Linfeng,Wu Yudong,Yu Rui,Peng Yang,Wang Yantao,Li Teng,Yang Weiran
Abstract Glucose and its derivatives are valuable and sustainable carbon sources that can be converted into varieties of value-added chemicals. In this study, d -glucaric acid was selectively converted to 3-iodoadipic acid (3-IAA) by hydrodeoxygenation in HI-Rh/C-H 2 system. During this process, HI was a reducing reagent, which can be regenerated in situ by metal catalyzed hydrogenation. The reaction pathway was proposed based on the intermediates identification. Under the optimal conditions, 67.2% yield of 3-IAA was obtained at 130 ℃ for 4 h. As a platform molecule, 3-IAA can be further converted to varieties of building block efficiently, such as adipic acid (AA) and 3-hydroxyadipic acid (3-HAA). Graphic Abstract
研究领域:
化学工程
·
可再生资源转化
✓ 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）