6765-39-5Relevant academic research and scientific papers
Heterogeneous Non-noble Catalyst for Highly Selective Production of Linear α-Olefins from Fatty Acids: A Discovery of NiFe/C
Zhang, Zihao,Lin, Wenwen,Li, Yafei,Okejiri, Francis,Lu, Yubing,Liu, Jixing,Chen, Hao,Lu, Xiuyang,Fu, Jie
, p. 4922 - 4928 (2020)
Catalytic deoxygenation of even-numbered fatty acids into odd-chain linear α-olefins (LAOs) has emerged as a complementary strategy to oligomerization of ethylene, which only affords even-chain LAOs. Although enzymes and homogeneous catalysts have shown promising potential for this application, industrial production of LAOs through these catalytic systems is still very difficult to accomplish to date. A recent breakthrough involves the use of an expensive noble-metal catalyst, Pd/C, through a phosphine ligands-assisted method for LAOs production from fatty acid conversion. This study presents a unique, cost-friendly, non-noble bimetallic NiFe/C catalyst for highly selective LAOs production from fatty acids through decarbonylative dehydration. In the presence of acetic anhydride and phosphine ligand, a remarkable improvement in the yield of 1-heptadecene from the conversion of stearic acid was found over the supported bimetallic catalyst (NiFe/C) as compared to corresponding monometallic counterparts (Ni/C and Fe/C). Through optimization of the reaction conditions, a 70.1 % heptadecene yield with selectivity to 1-heptadecene as high as 92.8 % could be achieved over the bimetallic catalyst at just 190 °C. This unique bimetallic NiFe/C catalyst is composed of NiFe alloy in the material bulk phase and a surface mixture of NiFe alloy and oxidized NiFeδ+ species, which offer a synergized contribution towards decarbonylative dehydration of stearic acid for 1-heptadecene production.
Highly selective production of linear 1-heptadecene from stearic acid over a partially reduced MoO: X catalyst
Chen, Hao,Chen, Kequan,Fu, Jie,Li, Yafei,Liu, Jixing,Liu, Miaomiao,Lu, Xiuyang,Okejiri, Francis,Ouyang, Pingkai,Zhang, Zihao
, p. 4456 - 4459 (2020)
Here, a MoOx-T based catalyst was developed by a simple reduction of MoO3 precursors at different temperatures. Interestingly, a partially reduced MoOx-600 catalyst obtained by reducing the MoO3 precursor at 600 °C shows the co-existence of a mixture of different valence states (0, +4, ～+6) of Mo, and as a result, provides a superior catalytic activity.
Rate constants for reactions of alkyl radicals with water and methanol complexes of triethylborane
Jin, Jing,Newcomb, Martin
, p. 5098 - 5103 (2007)
(Chemical Equation Presented) Reactions of secondary alkyl radicals with triethylborane and several of its complexes were studied. The H-atom transfer reactions from Et3B-OH2 and Et3B-OD2 were suppressed by addition of pyridine to the reaction mixture. Rate constants for reactions of secondary alkyl radicals with triethylborane and its complexes with water, deuterium oxide, methanol, and THF at ambient temperature were determined by radical clock methods. Cyclization of the 1-undecyl-5-hexenyl radical and ring opening of the 1-cyclobutyldodecyl radical were evaluated as clock reactions. The cyclobutylcarbinyl radical ring opening had the appropriate velocity for relatively precise determinations of the ratios of rate constants for H-atom transfer trapping and rearrangement, and these ratios combined with an estimated rate constant for the cyclobutylcarbinyl radical ring opening gave absolute values for the rate constants for the H-atom transfer reactions. For example, the triethylborane-water complex reacts with a secondary alkyl radical in benzene at 20°C with a rate constant of 2 × 104 M -1 s-1. Variable temperature studies with the Et 3B-CH3OH complex in toluene indicate that the hydrogen atom transfer reaction has unusually high entropic demand, which results in substantially more efficient hydrogen atom transfer trapping reactions in competition with radical ring opening and cyclization reactions at reduced temperatures.
Synthesis and characterization of a supported Pd complex on carbon nanofibers for the selective decarbonylation of stearic acid to 1-heptadecene: The importance of subnanometric Pd dispersion
Bitter, Harry,Fuertes, Sara,Henao, Wilson,Ochoa, Elba,Pinilla, Jose Luis,Scott, Elinor,Suelves, Isabel,Torres, Daniel,Van Haasterecht, Tomas
, p. 2970 - 2985 (2020/06/17)
Production of linear α-olefins from renewable sources is gaining increasing attention because it allows the transition from the current petrochemical synthesis route to a more sustainable scenario. In this work, we describe the synthesis and characterization of an innovative catalyst based on a di-μ-chloro-bis[palladium(ii) anthranilate] complex highly dispersed by incipient wetness impregnation over acyl chlorinated carbon nanofibers. The subnanometric dispersion of the metal complex allowed higher catalytic efficiency for the selective decarbonylation of stearic acid to 1-heptadecene as compared to the reference homogenous catalyst. The best catalytic performance (90 mol% selectivity, 71 mol% conversion, and TON = 484) was achieved under mild reaction conditions (atmospheric pressure, 140 °C) with a Pd loading in solution of 0.14 mol%. The post-mortem catalyst characterization and the recyclability tests evidenced the high stability of the catalyst. The highly dispersed catalyst developed in this work provides new opportunities in the rational design of more efficient catalytic systems for the sustainable transformation of fatty acids.
A Method for preparing alpha-olefins from Biomass-derived fat and oil
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Paragraph 0191-0202; 0218-0222, (2020/09/22)
The present invention relates to a method for preparing alpha-olefins from biomass-derived fats and oils. According to the preparation method, all of the various saturated or unsaturated fatty acids in the biomass-derived fats and oils can be prepared into alpha-olefins, and a conventional problem that the saturated fatty acids do not participate in a reaction or a mixture is generated due to polyunsaturated fatty acids can be solved. Thus, the present invention can be advantageously used to prepare alpha-olefins from biomass.
Alkene synthesis by photocatalytic chemoenzymatically compatible dehydrodecarboxylation of carboxylic acids and biomass
Nguyen, Vu T.,Nguyen, Viet D.,Haug, Graham C.,Dang, Hang T.,Jin, Shengfei,Li, Zhiliang,Flores-Hansen, Carsten,Benavides, Brenda S.,Arman, Hadi D.,Larionov, Oleg V.
, p. 9485 - 9498 (2019/10/11)
Direct conversion of renewable biomass and bioderived chemicals to valuable synthetic intermediates for organic synthesis and materials science applications by means of mild and chemoselective catalytic methods has largely remained elusive. Development of artificial catalytic systems that are compatible with enzymatic reactions provides a synergistic solution to this enduring challenge by leveraging previously unachievable reactivity and selectivity modes. We report herein a dual catalytic dehydrodecarboxylation reaction that is enabled by a crossover of the photoinduced acridine-catalyzed O-H hydrogen atom transfer (HAT) and cobaloxime-catalyzed C-H-HAT processes. The reaction produces a variety of alkenes from readily available carboxylic acids. The reaction can be embedded in a scalable triple-catalytic cooperative chemoenzymatic lipase-acridine-cobaloxime process that allows for direct conversion of plant oils and biomass to long-chain terminal alkenes, precursors to bioderived polymers.
The Effect of the Active Component Content on the Catalytic Activity of Nickel Sulfide Catalysts in Olefin Synthesis from Stearic Acid
Katsman,Danyushevsky, V. Ya.,Karpov,Kuznetsov,Shishilov,Berenblyum
, p. 622 - 628 (2019/06/24)
Abstract: The effect of active component content on the catalytic activity of supported sulfide catalysts in the synthesis of C17 olefins from stearic acid has been studied. It has been shown that an increase in the nickel content leads to a decrease in the catalyst activity; in addition, there is a negative correlation between the activity and the fraction of large particles on the support surface. The highest heptadecene selectivity (50–60%) is observed for alumina-supported catalysts owing to the higher degree of dispersion of the active component.
An Engineered Self-Sufficient Biocatalyst Enables Scalable Production of Linear α-Olefins from Carboxylic Acids
Lu, Chen,Shen, Fenglin,Wang, Shuaibo,Wang, Yuyang,Liu, Juan,Bai, Wen-Ju,Wang, Xiqing
, p. 5794 - 5798 (2018/06/01)
Fusing the decarboxylase OleTJE and the reductase domain of P450BM3 creates a self-sufficient protein, OleT-BM3R, which is able to efficiently catalyze oxidative decarboxylation of carboxylic acids into linear α-olefins (LAOs) under mild aqueous conditions using O2 as the oxidant and NADPH as the electron donor. The compatible electron transfer system installed in the fusion protein not only eliminates the need for auxiliary redox partners, but also results in boosted decarboxylation reactivity and broad substrate scope. Coupled with the phosphite dehydrogenase-based NADPH regeneration system, this enzymatic reaction proceeds with improved product titers of up to 2.51 g L-1 and volumetric productivities of up to 209.2 mg L-1 h-1 at low catalyst loadings (～0.02 mol%). With its stability and scalability, this self-sufficient biocatalyst offers a nature-friendly approach to deliver LAOs.
Amines as effective ligands in iridium-catalyzed decarbonylative dehydration of biosourced substrates
Ternel, Jérémy,Léger, Bastien,Monflier, Eric,Hapiot, Frédéric
, p. 3948 - 3953 (2018/08/16)
Linear α-olefins (LAOs) and linear internal olefins (LIOs) are essential intermediates in the synthesis of surfactants, lubricants, and polymers. Concurrently with petroleum-based industrial processes, the production of LAOs and LIOs from renewable feedstocks has gained increasing interest in recent years. Organometallic catalysts have been developed designedly, especially Pd, Fe and Ir catalysts. However, such catalysts are mostly stabilized by phosphanes, ligands sometimes difficult to handle especially on large scales. Alternatives to phosphanes would thus be highly desirable. In the present study, we demonstrate that Ir catalysts coordinated by amines are suitable to decarbonylate a wide range of biosourced substrates under mild conditions. The resulting LAOs and LIOs are obtained with good conversion provided that the nature and the quantity of the amines are controlled accurately. The LAO/LIO selectivity can also be tuned by a judicious choice of experimental conditions. Interestingly, the Ir-based catalytic system is applicable to the decarbonylative dehydration of saturated, unsaturated and polyunsaturated fatty acids.
Revealing the Influence of Silver in Ni–Ag Catalysts on the Selectivity of Higher Olefin Synthesis from Stearic Acid
Danyushevsky, V. Ya.,Murzin, V. Yu.,Kuznetsov,Shamsiev,Katsman,Khramov,Zubavichus,Berenblyum
, p. 57 - 65 (2018/03/06)
Results on the conversion of stearic acid to olefins over Ni–Ag/γ-Al2O3 catalysts are presented. XANES and EXAFS experiments in situ and DFT calculations were applied to reveal the structure of active sites therein. It is shown that the introduction of Ag to Ni catalysts leads to an increase in the olefin yield. After a reduction in hydrogen (350°C, 3 h) alumina-supported nanoparticles of nickel sulfides and metallic Ag are formed. The role of metal hydrides formed during the reaction is extensively discussed.
