ACS Sustainable Chemistry & Engineering
·
2022
·
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
·
生物质转化
·
材料科学
✓ 已验证
DOI
高影响因子
RENEWABLE ENERGY
·
2022
·
IF 8.634
Siteng Rong,Hongzi Tan,Zhaobin Pang,Zhiyuan Zong,Rongrong Zhao,Zhihe Li,Zhe-Ning Chen,Ning-Ning Zhang,Weiming Yi,Hongyou Cui
Lignin could be depolymerized into large amount of phenolic compounds via fast pyrolysis . The upgrade of phenolic compounds via hydrodeoxygenation (HDO) involves multiple reaction pathways. It is challenging to selectively remove the oxygen-containing groups while keeping the aromatic rings intact. In this work, hierarchical Nb 2 O 5 (H–Nb 2 O 5 ) microspheres with abundant oxygen vacancies were synthesized to anchor the Pd clusters, which is featured with strong metal-support interaction via the electron transfer between Pd species and Nb species. For phenol HDO reaction, the oxygen vacancies were prone to interact with the phenolic hydroxy groups, resulting in phenol molecule adsorbed in a “nonplanar” manner, greatly weakening the C Ar -O bonds and averting the ring hydrogenation. Besides, the activated hydrogen atoms on Pd clusters could migrate to the vicinity of oxygen vacancies via spillover, promoting the cleavage of C Ar -O bond to obtain benzene. Current work provides a deep insight into the synergetic catalytic mechanism of Pd/H–Nb 2 O 5 catalyst for phenol HDO reaction, and also sheds light on the design and synthesis of high-efficient catalysts in other heterogeneous catalysis fields.
研究领域:
催化化学
·
材料科学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Bowen Luo,Rongxuan Li,Riyang Shu,Chao Wang,Jingtao Zhang,Ying Chen
Simple and efficient catalytic routes have been explored to upgrade the raw lignin oil. Though homogeneous catalysis is easy to operate and possesses a high reaction rate, it also suffers from the difficulty of product separation. In this work, we used H3BO3 as a novel homogeneous catalyst coupled with Ru/C to overcome the separation problem and carry out the hydrodeoxygenation (HDO) of phenolic compounds and raw lignin oil. H3BO3 showed an outstanding performance over the liquid organic and mineral acids, with a good catalyst recyclability. Phenolic model compounds including monomers and dimers can be efficiently converted into cycloalkanes with yields close to 100%. Moreover, the raw lignin oil also had a good HDO result by using this bifunctional catalyst (H3BO3 and Ru/C). The content of hydrocarbons increased from 7.9% to 93.1% at 260 °C, which promoted the upgraded lignin oil capable to be used as fuel directly.
研究领域:
化学工程
·
可再生能源
✓ 已验证
DOI
高影响因子
BIOMASS & BIOENERGY
·
2022
·
IF 5.774
Yanlin Xu,Zhuoyi Liu,Bin Liu,Bin Dong,Yichuan Li,Yanpeng Li,Hailing Guo,Yongming Chai,Chenguang Liu
Pulping black liquor is a serious source of water pollution worldwide, which is very difficult to subsequently treat. Lignin is the main component of the black liquor and is the only natural aromatic recyclable resource, which is burnt as waste in the Kraft pulping industry. Designing an efficient lignin conversion catalyst that suitable for the strong alkaline environment of black liquor harbors tremendous carbon-neutral potential but still remains a scientific and technological challenge. In this work, the strong alkaline environment of black liquor was simulated, and low-cost pretreated Ni/AC catalysts were adopted to the hydrodeoxygenation (HDO) of a lignin model (guaiacol), and a breakthrough was achieved in the efficient transformation of lignin compound into hydrocarbons. By multitechniques, (e.g., FT-IR, XPS , Boehm titration, HRTEM), the relevance between introducing functional acid groups and the surface properties of catalysts was revealed. It is found that the increased acidic groups are responsible for the enhanced C (sp2) -O cleavage reactions, while improving the dispersion of Ni NPs and thus enhance the HDO efficiency. It is worth noting that better selectivity of benzene and lower hydrogen consumption are achieved on Ni/NOAC during the HDO process. Furthermore, the reaction routes of guaiacol on catalysts with different functional acid groups were proposed. This work provides guidance for efficient utilization of lignin in waste black liquor, and is of great significance to the development of sustainable carbon-neutral biorefinery and environmental protection.
研究领域:
化学工程
·
环境科学
·
生物能源
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Shiyu Wu,Xincheng Cao,Peng Liu,Jiaping Zhao,Jianchun Jiang,Junming Xu
The selective hydrogenation of natural oils to produce fatty alcohols is a key process for synthesizing liquid alkanes and high-value chemicals. However, the development of catalysts capable of enhancing hydrodeoxygenation (HDO) selectivity while suppressing carbon–carbon (C–C) bond cleavage to minimize carbon loss remains a significant challenge. In this study, a FeReOx/CeO2 catalyst was developed, which was characterized by high selectivity to octadecanol (93.8%, 210 °C) and liquid alkanes from stearic acid under mild conditions. Notably, the FeReOx/CeO2 catalyst exhibited a higher hydrodeoxygenation selectivity in the production of liquid alkanes than decarboxylation (DCO) (C18: 84.2% vs C17: 15.8% at 240 °C). Detailed characterization of the FeReOx/CeO2 catalyst revealed that excellent catalytic activity originated from the synergistic interaction between Fe and ReOx. The introduction of ReOx not only enhanced the adsorption of stearic acid but also improved the dispersion of metallic Fe. The weak acidity of metallic Fe could inhibit the cleavage of the C–C bond to a certain extent to obtain alkane products with high hydrodeoxygenation selectivity. Furthermore, the catalyst exhibited strong stability without significant deactivation after five cycles.
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
ChemSusChem
·
2020
·Vol. 13
·期 17
·4409-4419
·
IF 7.962
Xinxin Li,Bo Zhang,Xiaoli Pan,Jianwei Ji,Yujing Ren,Hua Wang,Na Ji,Qiying Liu,Changzhi Li
Graphical Oh! Sweet naphthene : Ir-ReO x /SiO 2 is employed for the one-pot conversion of lignin feedstocks and typical lignin model compounds into naphthenes. The excellent activity of Ir-ReO x /SiO 2 is attributed to the synergistic effect between Ir and ReO x species based on characterization of the catalysts and control experiments. The direct transformation of lignin into fuels and chemicals remains a huge challenge because of the recalcitrant and complicated structure of lignin. In this study, rhenium oxide-modified iridium supported on SiO 2 (Ir-ReO x /SiO 2 ) is employed for the one-pot conversion of various lignin model compounds and lignin feedstocks into naphthenes. Up to 100 % yield of cyclohexane from model compounds and 44.3 % yield of naphthenes from lignin feedstocks are achieved. 2 D HSQC NMR spectroscopy before and after the reaction confirms the activity of Ir-ReO x /SiO 2 in the cleavage of the C−O bonds and hydrodeoxygenation of the depolymerized products. H 2 temperature-programmed reduction, temperature-programmed desorption of NH 3 , IR spectroscopy of pyridine adsorption, X-ray photoelectron spectroscopy, X-ray absorption fine structure analysis, and control experiments reveal that a synergistic effect between Ir and ReO x in Ir-ReO x /SiO 2 plays a crucial role in the high performance; ReO x is mainly responsible for the cleavage of C−O bonds, whereas Ir is responsible for hydrodeoxygenation and saturation of the benzene rings. This methodology opens up an energy-efficient route for the direct conversion of lignin into valuable naphthenes.
研究领域:
化学工程
·
催化科学
✓ 已验证
DOI
高影响因子
FUEL
·
2022
·
IF 8.035
Mingxing Zhao,Jun Hu,Ping Lu,Shiliang Wu,Chao Liu,Yahui Sun
Efficient hydrodeoxygenation of lignin-derived bio-oils to cycloalkanes was achieved over bifunctional RuCoW x /NC catalyst prepared by in situ pyrolysis method. The performance of RuCoW x /NC was investigated in HDO of 4-propylguaiacol, considering the influences of catalysts, initial H 2 pressure, and reaction temperature. Catalyst screening reveals that RuCoW 0.03 /NC afforded the highest propylcyclohexane yield of 71.3% from 4-propylguaiacol at 220 ℃. At 240 ℃, the yield of propylcyclohexane increased to 95.2 %. The heavy fraction of rice husk bio-oil, primarily composed of lignin-derived phenolic compounds, could be upgraded to 98.3% hydrocarbons at 280 ℃ over RuCoW 0.03 /NC. The synergistic interaction between highly dispersed Co and Ru metal sites and WO x acidic sites is responsible for the excellent HDO activity of RuCoW 0.03 /NC. Besides, RuCoW 0.03 /NC exhibited high stability after four cycles.
研究领域:
化学工程
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2022
·Vol. 46
·期 47
·22672-22685
·
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
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS TODAY
·
2015
·
IF 3.893
Jing Xing,Liang Song,Cong Zhang,Mingdong Zhou,Li Yue,Xuebing Li
Upgrading of lignin derived bio-oil is a very promising way to relieve humankind's dependence on traditional fossil fuels. Eugenol, a model compound for lignin monomers with a methoxyl group and a hydroxyl group, was hydrodeoxygenated in aqueous phase with Pd/C as hydrogenation catalyst and ZSM-5 zeolite as hydrolysis and dehydration catalysts. The bulky lignin monomers had difficulty in accessing the acid sites of the micropores of ZSM-5 zeolite, thus we introduced mesopores via alkaline treatment under various conditions. Alkali-treated ZSM-5 zeolites showed higher conversion and hydrocarbon selectivity compared to the parent ZSM-5 zeolite. When ZSM-5 zeolite was treated at 338 K, the conversion and the hydrocarbon selectivity increased by 21% and 24%, respectively. In addition, much more weak acid sites of ZSM-5 zeolites after alkaline treatment also promoted the hydrolysis and dehydration process.
研究领域:
化学工程
·
能源科学
✓ 已验证
DOI
高影响因子
Frontiers of Chemical Science and Engineering
·
2024
·Vol. 18
·期 5
·1-10
·
IF 4.3
Li Kaile,Yu Shijie,Li Qinghai,Zhang Yanguo,Zhou Hui
Lignin, an abundant aromatic polymer in nature, has received significant attention for its potential in the production of bio-oils and chemicals owing to increased resource availability and environmental issues. The hydrodeoxygenation of guaiacol, a lignin-derived monomer, can produce cyclohexanol, a nylon precursor, in a carbon-negative and environmentally friendly manner. This study explored the porous properties and the effects of activation methods on the Ru-based catalyst supported by environmentally friendly and cost-effective hydrochar. Highly selective cleavage of C aryl -O bonds was achieved under mild conditions (160 °C, 0.2 MPa H 2 , and 4 h), and alkali activation further improved the catalytic activity. Various characterization methods revealed that hydrothermal treatment and alkali activation relatively contributed to the excellent performance of the catalysts and influenced their porous structure and Ru dispersion. X-ray photoelectron spectroscopy results revealed an increased formation of metallic ruthenium, indicating the effective regulation of interaction between active sites and supports. This synergistic approach used in this study, involving the valorization of cellulose-derived hydrochar and the selective production of nylon precursors from lignin-derived guaiacol, indicated the comprehensive and sustainable utilization of biomass resources.
研究领域:
化学工程
·
环境科学
✓ 已验证
DOI
高影响因子
FUEL
·
2021
·
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
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
RENEWABLE ENERGY
·
2022
·
IF 8.634
Wei Lv,Xiaohong Hu,Yuting Zhu,Ying Xu,Shijun Liu,Peili Chen,Chenguang Wang,Longlong Ma
Herein, the catalysts of ruthenium and molybdenum oxide nanoparticles supported on activated carbon (AC) were synthesized by precursor stepwise impregnation and employed for the hydrodeoxygenation (HDO) of lignin oil. The XRD, TEM, XPS and NH 3 -TPD-MS result of RuMoO x /AC catalysts confirm that the method of loading molybdenum precursor before ruthenium precursor is advantageous for the MoO x and Ru nanoparticles high dispersion and the reduction of MoO x species enhance the amount of acidity of catalyst. Meanwhile, the reduction temperature of RuMoO x /AC-1-T catalysts could effectively regulate the MoO x species that determine the activity and product distribution of HDO. The conversion of aromatic monomers/dimers were up to 96% with high selectivity of hydrocarbon over RuMoO x /AC-1-350 catalyst at 160 °C and 30 bar H 2 . Which is attributed to the MoO 3 and Ru species possess the excellent activity of benzene ring deep hydrogenation, ether bond breaking and acid dehydration. The RuMoO x /AC-1-350 catalyst effectively converted lignin oil (from the depolymerization of cornstalk hydrolysis residue) into hydrocarbons (56.9 wt%) and cyclohexanol/ethers (18.7 wt%) under 280 °C and 3 bar H 2 . The durability of the RuMoO x /AC-1-350 catalyst for HDO of lignin oil was also investigated and showed that the RuMoO x /AC-1-350 catalyst had good stability, regenerability and repeatability.
研究领域:
催化化学
·
能源化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）