Sustainable Energy & Fuels
·
2018
·Vol. 2
·期 8
·1837-1843
·
IF 0
Zihao Zhang,Zhe Chen,Hao Chen,Xin Gou,Kequan Chen,Xiuyang Lu,Pingkai Ouyang,Jie Fu
In this study, the deoxygenation of stearic acid over a series of Ni-based catalysts in the absence of hydrogen and solvents was investigated. Ni/Al2O3, Ni/TiO2, Ni/ZrO2, and Ni/AC (activated carbon) were synthesized using the wetness impregnation method, and Ni/AC showed the best activity for deoxygenation. X-ray diffraction, transmission electron microscopy, H2 temperature-programmed reduction, and N2 adsorption–desorption analyses revealed that Ni had an average particle size of about 9.6 nm with good crystallinity, the largest surface area and strong Ni–carrier interactions in Ni/AC. These properties of Ni/AC contributed to its good deoxygenation activity. Ni/AC produced hydrocarbons (71.4% yield) such as heptadecane, heptadecene, aromatics, and cracking paraffins under optimized reaction conditions. Furthermore, it was found that the deoxygenation of stearic acid over Ni/AC in the absence of hydrogen and solvent proceeds mainly via decarbonylation.
研究领域:
化学工程
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催化
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材料科学
✓ 已验证
产品关联
DOI
Catalysts
·
2020
·Vol. 10
·期 11
·1304
·
IF 3.52
Qiang Yuan,Jifeng Pang,Wenguang Yu,Mingyuan Zheng
A high-performance Pt catalyst supported on SBA-15 was developed for furfural decarbonylation. Compared to Pt catalysts loaded on microporous DeAl-Hbeta zeolite and hierarchical micro-mesoporous MFI nanosheet (NS) materials, the 1%Pt/SBA-15 catalyst afforded notably higher activity, furan selectivity and stability owing to the negligible acid sites and proper mesopores on the SBA-15 support. Among a set of 1%Pt/SBA-15 catalysts bearing Pt nanoparticles (NPs) with sizes of 2.4–4.3 nm, the catalyst with 3.7 nm Pt NPs afforded the highest furan selectivity. Over the optimal catalyst, 88.6% furan selectivity and ca. 90% furfural conversion were obtained at 573 K and a high weight hourly space velocity (WHSV) of 16.5 h−1. Moreover, the reaction temperatures at 440–573 K and the ratios of H2to furfural at 0.79–9.44 did not affect the reaction selectivity notably, showing that the reaction over 1%Pt/SBA-15 can be conducted over a wide range of conditions. The catalyst was stable under the harsh reaction conditions and lasted for 90 h without significant deactivation, demonstrating the superior property of SBA-15 as a catalyst support for furfural decarbonylation.Keywords:decarbonylation;furfural;furan;platinum;SBA-15
研究领域:
催化化学
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能源化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2022
·
IF 4.198
Tianhao Xu,Xingyu Zhou,Xiong Xiao,Yan Yuan,Long Liu,Tianzeng Huang,Chunya Li,Zhi Tang,Tieqiao Chen
A nickel-catalyzed decarbonylative thioetherification of carboxylic acids with thiols was developed. Under the reaction conditions, benzoic acids, cinnamic acids, and benzyl carboxylic acids coupled with various thiols including both aromatic and aliphatic ones produce the corresponding thioethers in up to 99% yields. Moreover, this reaction was applicable to the modification of bioactive molecules such as 3-methylflavone-8-carboxylic acid, probenecid, and flufenamic acid, and the synthesis of acaricide chlorbenside. These results well demonstrated the potential synthetic value of this new reaction in organic synthesis.
研究领域:
有机化学
·
合成化学
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2024
·
IF 3.8
Zhenya Zhang,Chao Chen,Zihao Zhang,Bolong Li,Jianghao Wang,Jie Fu
The decarbonylation of fatty acids presents a promising method for synthesizing sustainable long-chain olefins. However, the development of catalysts that combine satisfactory efficiency and selectivity for fatty acid decarbonylation still encounters challenges. In this study, we developed an N-doped carbon-supported PtCo bimetallic catalyst for fatty acid decarbonylation. Employing stearic acid as a substrate, we achieved a combined heptadecene selectivity of 64.4% and a total hydrocarbon selectivity of 95.7% alongside a stearic acid conversion rate of 83.1%. The superior performance of the PtCo3Nx@NC catalyst can be attributed to the formation and influence of the Pt–CoNx interface, characterized by unique electronic and geometric properties that underlie bimetallic synergy. This research introduces new avenues for the decarbonylation of fatty acids, offering an environmentally friendly approach to producing long-chain olefins from biomass.
研究领域:
催化化学
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可再生资源化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2023
·
IF 3.6
Qi Dang,Jiani Chen,Tianbao Li,Long Liu,Tianzeng Huang,Chunya Li,Tieqiao Chen
A palladium-catalyzed decarbonylative annulation of 2-arylbenzoic acids with internal alkynes via C(sp2)–H activation has been developed. A series of phenanthrenes were produced in moderate to good yield with good functional group tolerance. The mechanism study indicated that the C(sp2)–H activation should be the rate-determining step during the reaction.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
PubMed
高影响因子
GREEN CHEMISTRY
·
2020
·Vol. 22
·期 13
·4341-4349
·
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
✓ 已验证
产品关联
DOI
高影响因子
Green Chemical Engineering
·
2025
·
IF 7.6
Jiankun Yu,Weixiao Sun,Kuan Huang,Jin Xu,Fuzeyu Zhong,Xiaohu Ge,Wenyao Chen,Gang Qian,Yueqiang Cao,Jianrong Zeng,Jianbo Ma,Xinggui Zhou,Xuezhi Duan,Jing Zhang,Lilong Jiang
Due to escalating carbon emissions, increasing attention is being focused on the synthesis of biomass-derived liquid fuels with a low CO 2 footprint. Currently, the dominant biobased liquid fuel in the diesel range is green diesel, produced via deoxygenation of non-edible natural/waste oils and their free fatty acid components into engine-compatible diesel-range alkanes. Industrially, sulfided NiMo or CoMo catalysts are typically used, leading to total hydrocarbon yields of 70-80 wt%. However, their inevitable sulfur leaching often contaminates the products and requires the addition of sulfur-containing agents. Here, we developed a highly selective sulfur-free Ni-Cu alloy catalyst by disentangling the electronic and size effects, to enable green diesel synthesis through the decarbonylation of palmitic acid—the most common fatty acid in these feedstocks. An unprecedented decarbonylation product (pentadecane) yield of 98% (on a molar basis) was achieved using a Ni-Cu alloy catalyst with a Ni/Cu ratio of 1:1 under mild reaction conditions (2 MPa H 2 , 250 °C). Minimal metal sintering or leaching was observed after multiple reuses. Kinetic studies show that incorporating Cu into Ni markedly reduces both the apparent activation energy and the reaction order for the conversion of palmitic acid. These results, combined with catalyst characterization, reveal that introducing Cu into Ni not only facilitates the adsorption and activation of the carboxylic hydroxyl group to promote the reductive deoxygenation of palmitic acid into aldehyde/alcohol intermediates—the slow step in decarbonylation—but also weakens the adsorption of C–C bonds on Ni by enhancing its electron density.
研究领域:
能源化学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
·
2022
·
IF 8.129
Hao Zhu,Fei Wang,Jianchun Jiang,Zeng Zhang,Yuchan Du,Junfeng Feng,Xiaoxiang Jiang
In order to deal with the deficiency of active sites in Ni catalyst, Ni Fe nanosheet (Ni-Fe/Al 2 O 3 -NS) catalyst was synthesized by using Ni-Fe-Al LDH as the precursor. The catalyst was further utilized in the lipid hydrotreatment for green diesel production. With a lamellar structure and large Ni loading (more than 60%), the Ni-Fe/Al 2 O 3 -NS catalyst possessed abundant Ni sties with high dispersion, large surface area, and strong acidity. Moreover, in Ni-Fe/Al 2 O 3 -NS the highly active Ni 3 Fe phase was formed, which promoted the decarbonylation route in hydrotreatment. The Ni-Fe/Al 2 O 3 -NS catalyst achieved 98.7% conversion with 98.1% alkane yield in oleic acid hydrotreatment under very mild conditions (220 °C, 2 MPa of hydrogen pressure, 3 h). The catalytic performance of Ni-Fe/Al 2 O 3 -NS was much higher than traditional Ni-Fe/Al 2 O 3 and other catalysts reported in current related studies.
研究领域:
催化化学
·
能源材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2024
·
IF 7.1
Zhenya Zhang,Bolong Li,Jianghao Wang,Jing Li,Jie Fu
The quest for economical and efficient heterogeneous catalysts for the synthesis of long-chain α-olefins from biomass-derived fatty acids is of utmost significance. Regrettably, the generation of olefins by the dehydrative decarbonylation of fatty acids without the inclusion of additives is seldom documented. This scarcity is mostly attributed to the occurrence of competing decarboxylation and cracking processes. In this study, bimetallic CoZn@NC catalysts were prepared by decomposing ZIFs (CoZn) via a semisacrificial template-assisted strategy. The resulting CoZn@NC-900 catalysts are highly efficient and outperform Pt/C in stearic acid decarbonylation. In a batch reactor, these catalysts demonstrate 85.8% stearic acid conversion with up to 52.4% combined alkene yield at 350 °C for 1 h. The binding of N and Co forms the active decarbonylation sites, while Zn promotes the formation of Co subnanoparticles through spatial segregation effects, effectively reducing the acidity of the catalyst and thus ultimately inhibiting C–C cracking. Moreover, the CoZn@NC catalysts showed good stability, and the catalytic decarbonylation activity was maintained after several consecutive uses. This work presents a cost-effective strategy for the efficient catalytic decarbonylation of carboxylic acids with the inhibition of C–C cracking and shows promise for enabling the production of high-value olefins from biomass sources.
研究领域:
催化化学
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可再生资源化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2015
·Vol. 17
·期 5
·2888-2895
·
IF 8.02
Jian-hua Guo,Guang-yue Xu,Fei Shen,Yao Fu,Ying Zhang,Qing-xiang Guo
The long-chain alkanes obtained from the hydrodeoxygenation of plant oils are ideal substitutes for diesel. In this work, a new efficient catalytic system was established for the conversion of plant oil to long-chain alkanes under mild conditions with a bi-functional Ru/La(OH)3 catalyst. The hydrodeoxygenation of stearic acid was performed in an autoclave with Ru-based catalysts with different supports (HZSM-5, ZSM-5, SiO2–Al2O3, SiO2, ZrO2, Mg(OH)2, La(OH)3, and La2O3). Among these catalysts, Ru supported on basic La(OH)3 showed a remarkable catalytic performance for the reaction. Over 98% of long-chain alkanes were obtained with 100% conversion of stearic acid at 200 °C and 4 MPa H2. When crude Jatropha oil was hydrogenated, about 80.7 wt% of long chain alkanes were obtained under the optimized conditions (200 °C, 4 MPa H2, 8 h). The high efficiency of the Ru/La(OH)3 catalyst could be due to a co-effect of the high hydrogenation activity of Ru and the basic La(OH)3 support which can attract the acidic raw material. Additionally, the Ru/La(OH)3 catalyst was recycled four times and maintained a good activity and stability. The reaction pathway was also explored by using stearic acid as a model compound. Hydrogenation–decarbonylation could be the main pathway to produce n-heptadecane, which has one carbon atom less than stearic acid.
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
✓ 已验证
产品关联
DOI
高影响因子
Green Energy & Environment
·
2023
·
IF 13.3
Lin Yuan,Yancheng Hu,Guangyi Li,Fengan Han,Aiqin Wang,Yu Cong,Tao Zhang,Feng Wang,Ning Li
The production of industrial chemicals with renewable biomass feedstock holds potential to aid the world in pursuing a carbon-neutral society. Trimellitic and trimesic acids are important commodity chemicals in industry that are prepared by the oxidation of petroleum-derived trimethylbenzene. To reduce the dependence on the limited oil source, we develop a potential sustainable alternative towards trimellitic and trimesic acids using biomass-based 2-methyl-2,4-pentandiol (MPD), acrylate and crotonaldehyde as starting materials. The process for trimellitic acid includes dehydration/D-A reaction of MPD and acrylate, flow aromatization over Pd/C catalyst, hydrolysis and catalytic aerobic oxidation (60% overall yield). The challenging regioselectivity issue of D-A reaction is tackled by a matched combination of temperature and deep eutectic solvent ChCl/HCO 2 H. Crotonaldehyde can also participate in the reaction, followed by Pd/C-catalyzed decarbonylation/dehydrogenation and oxidation to provide trimesic acid in 54% overall yield. Life cycle assessment implies that compared to conventional fossil process, our biomass-based routes present a potential in reducing carbon emissions.
研究领域:
生物化学
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绿色化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Frontiers of Chemical Science and Engineering
·
2022
·Vol. 17
·期 2
·139-155
·
IF 4.803
Shi Haonan,Gu Xiaoyu,Shi Yinteng,Wang Dandan,Shu Sihao,Wang Zhongze,Chen Jixiang
Porous carbon-encapsulated Ni and Ni–Sn intermetallic compound catalysts were prepared by the one-pot extended Stöber method followed by carbonization and tested for in-situ hydrothermal deoxygenation of methyl palmitate with methanol as the hydrogen donor. During the catalyst preparation, Sn doping reduces the size of carbon spheres, and the formation of Ni–Sn intermetallic compounds restrain the graphitization, contributing to larger pore volume and pore diameter. Consequently, a more facile mass transfer occurs in carbon-encapsulated Ni-Sn intermetallic compound catalysts than in carbon-encapsulated Ni catalysts. During the in-situ hydrothermal deoxygenation, the synergism between Ni and Sn favors palmitic acid hydrogenation to a highly reactive hexadecanal that easily either decarbonylate to n -pentadecane or is hydrogenated to hexadecanol. At high reaction temperature, hexadecanol undergoes dehydrogenation-decarbonylation, generating n -pentadecane. Also, the C-C bond hydrolysis and methanation are suppressed on Ni-Sn intermetallic compounds, favorable for increasing the carbon yield and reducing the H 2 consumption. The n -pentadecane and n -hexadecane yields reached 88.1% and 92.8% on carbon-encapsulated Ni 3 Sn 2 intermetallic compound at 330 °C. After washing and H 2 reduction, the carbon-encapsulated Ni 3 Sn 2 intermetallic compound remains stable during three recycling cycles. This is ascribed to the carbon confinement that effectively suppresses the sintering and loss of metal particles under harsh hydrothermal conditions.
研究领域:
催化
·
化学工程
·
材料科学
·
能量转换
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有机化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）