96-37-7Relevant academic research and scientific papers
Niobium-containing lindqvist isopolyanions [NbxW6-xO19](2+x)- used as precursors for hydrodesulfurization catalysts with isomerization properties
Bouadjadja-Rohan, Karolina,Lancelot, Christine,Fournier, Michel,Bonduelle-Skrzypczak, Audrey,Hugon, Antoine,Mentré, Olivier,Lamonier, Carole
, p. 2067 - 2075 (2015)
Lindqvist isopolyanions [NbxW6-xO19](2+x)- (x = 0-4 and 6) were prepared and their spectroscopic and thermal properties were determined by Raman and IR spectroscopy as well as TGA/DSC. The structure of the [NbW5O19]3- anion obtained as single crystal was determined. Ni-promoted alumina-supported hydrodesulfurization (HDS) catalysts were prepared from the best soluble NbW polyoxometalates. In the calcined catalysts, better dispersion of the metallic species is observed when using NbW isopolyanions instead of the conventional ammonium metatungstate. The presence of niobium was expected to introduce acidity leading to isomerization property in classical NiW HDS catalysts. In HDS reaction conditions (under hydrogen pressure and sulfided environment) the cyclohexane isomerization into methylcyclopentane activity of niobium-based catalysts was found up to 5 times superior to that of conventional NiW catalyst, showing the beneficial effect of niobium for this reaction. [NbxW6-xO19](2+x)- Lindqvist type isopolyanions were synthesized and characterized to prepared NbWNi-based alumina-supported hydrodesulfurization catalysts. Nb-containing catalysts showed improved CC6 isomerization properties under HDS conditions (H2 pressure and H2S presence) compared to those of a reference NiW catalyst related to the acid properties induced by niobium.
Fabricating nickel phyllosilicate-like nanosheets to prepare a defect-rich catalyst for the one-pot conversion of lignin into hydrocarbons under mild conditions
Cao, Meifang,Chen, Bo,He, Chengzhi,Ouyang, Xinping,Qian, Yong,Qiu, Xueqing
supporting information, p. 846 - 857 (2022/02/09)
The one-pot conversion of lignin biomass into high-grade hydrocarbon biofuels via catalytic hydrodeoxygenation (HDO) holds significant promise for renewable energy. A great challenge for this route involves developing efficient non-noble metal catalysts to obtain a high yield of hydrocarbons under relatively mild conditions. Herein, a high-performance catalyst has been prepared via the in situ reduction of Ni phyllosilicate-like nanosheets (Ni-PS) synthesized by a reduction-oxidation strategy at room temperature. The Ni-PS precursors are partly converted into Ni0 nanoparticles by in situ reduction and the rest remain as supports. The Si-containing supports are found to have strong interactions with the nickel species, hindering the aggregation of Ni0 particles and minimizing the Ni0 particle size. The catalyst contains abundant surface defects, weak Lewis acid sites and highly dispersed Ni0 particles. The catalyst exhibits excellent catalytic activity towards the depolymerization and HDO of the lignin model compound, 2-phenylethyl phenyl ether (PPE), and the enzymatic hydrolysis of lignin under mild conditions, with 98.3% cycloalkane yield for the HDO of PPE under 3 MPa H2 pressure at 160 °C and 40.4% hydrocarbon yield for that of lignin under 3 MPa H2 pressure at 240 °C, and its catalytic activity can compete with reported noble metal catalysts.
Highly Selective Hydrodeoxygenation of Lignin to Naphthenes over Three-Dimensional Flower-like Ni2P Derived from Hydrotalcite
Chen, Guanyi,Diao, Xinyong,Ji, Na,Jia, Zhichao,Li, Changzhi,Li, Xinxin,Liu, Caixia,Liu, Qingling,Lu, Xuebin,Ma, Longlong,Song, Chunfeng,Wang, Shurong,Zhao, Yujun
, p. 1338 - 1356 (2022/02/07)
A strategy for low-temperature synthesis of hydrotalcite-based nickel phosphide catalysts (Ni2P-Al2O3) with flower-like porous structures was proposed. The in situ reduction of red phosphorus at 500 °C enables Ni2P catalysts with small particle size and abundant active and acidic sites, which facilitate the activation of substrates and H2. In the hydrodeoxygenation of guaiacol, a 100% conversion and 94.5% yield of cyclohexane were obtained over the Ni2P-Al2O3 catalyst under 5 MPa H2 at 250 °C for 3 h. Other lignin-derived phenolic compounds could also afford the corresponding alkanes with yields higher than 85%. Moreover, Ni2P-Al2O3 exhibited high hydrodeoxygenation activity in the deconstruction of more complex wood structures, including lignin oil and real lignin. Among the two different types of Ni sites of Ni(1) and Ni(2) in Ni2P, density functional theory (DFT) calculations showed that the Ni(2) site, highly exposed on the Ni2P-Al2O3 surface, possesses a stronger ability to break C-OH bonds during the hydrodeoxygenation of guaiacol in comparison with the Ni(1) site.
Improved Hydrodeoxygenation of Phenol to Cyclohexane on NiFe Alloy Catalysts Derived from Phyllosilicates
Han, Qiao,Wang, Hui,Rehman, Mooeez Ur,Shang, Xin,Chen, Haijun,Ji, Na,Tong, Xinli,Shi, Hui,Zhao, Yujun
supporting information, p. 5069 - 5076 (2021/12/14)
A phyllosilicate-derived NiFe/SiO2 catalyst (NiFe/SiO2?AE) was successfully prepared by the ammonia evaporation method and applied in the hydrodeoxygenation of phenol to cyclohexane. Another two catalysts were also prepared for a comparison by impregnation (NiFe/SiO2?IM) and deposition-precipitation (NiFe/SiO2?DP) methods, respectively. It was found that Ni?Fe alloy, the active sites for the hydrogenolysis of C?O bond, can be obtained by the reduction of NiFe2O4 (IM) or phyllosilicate (DP and AE) by H2. The AE strategy can generate more phyllosilicate structure, which improves the dispersion of both Ni?Fe alloy and metallic Ni sites and allows the formation of more interface between these two kinds of sites as well. Therefore, the NiFe/SiO2?AE exhibits a significantly high catalytic performance in the HDO of phenol to cyclohexane. Moreover, the turnover frequency of Ni?Fe alloy sites over NiFe/SiO2?AE catalysts is much higher than those of other two catalysts. It is suggested that the enhanced synergy between the two kinds of active sites in the adsorption of C?O groups and hydrogen molecules ensures the superior intrinsic activity in HDO process.
Influence of Nitrate and Phosphate on Silica Fibrous Beta Zeolite Framework for Enhanced Cyclic and Noncyclic Alkane Isomerization
Hitam, Che Ku Nor Liana Che Ku,Izan, Siti Maryam,Jalil, Aishah Abdul,Nabgan, Walid
, p. 1723 - 1735 (2020/02/28)
Phosphate and nitrate were loaded on silica BEA (P/HSi?BEA and N/HSi?BEA), which is fibrously protonated by the impregnation method for n-hexane and cyclohexane isomerization. The characterization analysis specified the removal of tetrahedral aluminum atoms in the framework, which was triggered by the existence of phosphate and nitrate groups in the catalyst. The exchanged role of Si(OH)Al to P-OH as active acidic sites in the P/HSi?BEA catalyst reduced its acidic strength, which was confirmed by the FTIR results. Lewis acidic sites of P/HSi?BEA performance are a significant part in the generation of high protonic acid sites, as proven by the in situ ESR study. However, FTIR evacuation and 27Al NMR revealed that the reduction in the amount of extraframework Al (EFAl) is due to its interaction with the nitrate group on the outside of the catalyst surface. The N/HSi?BEA catalyst exhibited high acidic strength because of the existence of more Si(OH)Al, which was initiated during the nitrate-incorporation process. Of significance is that the catalytic performance of n-hexane isomerization in the presence of hydrogen reached 50.3% product isomer yield at 250 °C, which might be ascribed to the presence of P-OH active sites that are responsible for accepting electrons, forming active protonic acid sites. NO3-EFAl interaction induced the formation of Br?nsted acid sites, and higher mesopore volume favors the production of cyclohexane isomers up to 48.4% at 250 °C. This fundamental study exhibits that significant interactions given by such phosphate and nitrate groups with the unique silica fibrous BEA support could enhance isomerization, which contributes to the high quality of fuel.
Highly Active Superbulky Alkaline Earth Metal Amide Catalysts for Hydrogenation of Challenging Alkenes and Aromatic Rings
Eyselein, Jonathan,F?rber, Christian,Grams, Samuel,Harder, Sjoerd,Knüpfer, Christian,Langer, Jens,Martin, Johannes,Thum, Katharina,Wiesinger, Michael
supporting information, p. 9102 - 9112 (2020/03/30)
Two series of bulky alkaline earth (Ae) metal amide complexes have been prepared: Ae[N(TRIP)2]2 (1-Ae) and Ae[N(TRIP)(DIPP)]2 (2-Ae) (Ae=Mg, Ca, Sr, Ba; TRIP=SiiPr3, DIPP=2,6-diisopropylphenyl). While monomeric 1-Ca was already known, the new complexes have been structurally characterized. Monomers 1-Ae are highly linear while the monomers 2-Ae are slightly bent. The bulkier amide complexes 1-Ae are by far the most active catalysts in alkene hydrogenation with activities increasing from Mg to Ba. Catalyst 1-Ba can reduce internal alkenes like cyclohexene or 3-hexene and highly challenging substrates like 1-Me-cyclohexene or tetraphenylethylene. It is also active in arene hydrogenation reducing anthracene and naphthalene (even when substituted with an alkyl) as well as biphenyl. Benzene could be reduced to cyclohexane but full conversion was not reached. The first step in catalytic hydrogenation is formation of an (amide)AeH species, which can form larger aggregates. Increasing the bulk of the amide ligand decreases aggregate size but it is unclear what the true catalyst(s) is (are). DFT calculations suggest that amide bulk also has a noticeable influence on the thermodynamics for formation of the (amide)AeH species. Complex 1-Ba is currently the most powerful Ae metal hydrogenation catalyst. Due to tremendously increased activities in comparison to those of previously reported catalysts, the substrate scope in hydrogenation catalysis could be extended to challenging multi-substituted unactivated alkenes and even to arenes among which benzene.
Phospholane-Based Ligands for Chromium-Catalyzed Ethylene Tri- And Tetramerization
Boelter, Scott D.,Davies, Dan R.,Klosin, Jerzy,Margl, Peter,Milbrandt, Kara A.,Mort, Darrek,Rosen, Mari S.,Vanchura, Britt A.,Wilson, David R.,Wiltzius, Molly
supporting information, (2020/02/27)
Chromium complexes with bis(phospholane) ligands were synthesized and evaluated for ethylene tetramerization in a high-throughput reactor. Three ligand parameters - the phospholane substituent, the ligand backbone, and the type of phosphine (cyclic vs acyclic) - were investigated. The size of the phospholane substituent was found to impact the selectivity of the resulting catalysts, with smaller substituents leading to the production of larger proportions of 1-octene. Changing the ligand backbone from 1,2-phenylene to ethylene did not impact catalysis, but the use of acyclic phosphines in place of the cyclic phospholanes had a detrimental effect on catalytic activity. Selected phospholane-chromium complexes were evaluated in a 300 mL Parr reactor at 70 °C and 700 psi of ethylene pressure, and the ethylene oligomerization performance was consistent with that observed in the smaller, high-throughput reactor. MeDuPhos-CrCl3(THF) (MeDuPhos = 1,2-bis(2,5-dimethylphospholano)benzene; THF = tetrahydrofuran) gave activity and selectivity for 1-octene (54.8 wt %) similar to the state-of-the-art i-PrPNP-CrCl3(THF) (64.0 wt %) (PNP = bis(diphenylphosphino)amine), while EtDuPhos-CrCl3(THF) (EtDuPhos = 1,2-bis(2,5-diethylphospholano)benzene) exhibited even higher activity, with catalyst selectivity shifted toward 1-hexene production (90 wt %). These results are surprising, given the prevalence of the aryl phosphine motif in ligands used in ethylene oligomerization catalysts and the inferior performance of previously reported catalysts with alkyl phosphine-containing ligands.
Ethylene Tetramerisation: A Structure-Selectivity Correlation
Makume, Boitumelo F.,Holzapfel, Cedric W.,Maumela, Munaka C.,Willemse, J. Alexander,van den Berg, Jan A.
, p. 2308 - 2315 (2020/11/03)
The effect of ethylene tetramerisation ligand structures on 1-octene selectivity is well studied. However, by-product formation is less understood. In this work, a range of PNP ligand structures are correlated with the full product selectivity and with catalyst activity. As steric bulk on the N-substituent increases, the product selectivity shifts from >10 % to 3% of both C6 cyclics and C16+ by-products. 1-Octene peaks at ca. 70%. Thereafter, only 1-hexene increases. Similar selectivity changes were observed for ortho-Ph-substituted PNP ligands. The C10-14 selectivity was less affected by the ligand structure. The ligand effect on the changes in selectivity is explained mechanistically. Lastly, an increase in ligand steric bulk was found to improve catalyst activity and reduce polymer formation by an order of magnitude. It is proposed that steric bulk promotes formation of cationic catalytic species which are responsible for selective ethylene oligomerisation.
Effects of steam on toluene hydrogenation over a Ni catalyst
Atsumi, Ryosuke,Kobayashi, Keisuke,Xieli, Cui,Nanba, Tetsuya,Matsumoto, Hideyuki,Matsuda, Keigo,Tsujimura, Taku
, (2019/12/23)
The catalytic toluene hydrogenation over Ni/SiO2 was carried out using H2 or a H2/H2O mixture. The toluene conversion and MCH selectivity were evaluated under partial steam pressures 0?10 kPa, at H2/t
Two-step catalytic conversion of lignocellulose to alkanes
Sun, Zhuohua,Buwalda, Daniel,Barta, Katalin
, p. 23727 - 23734 (2019/08/12)
Direct conversion of lignocellulose to alkanes is challenged by the complex and recalcitrant nature of the starting material. Generally, alkanes are obtained from one of the main lignocellulose constituents (cellulose, hemicellulose or lignin) after their separation, and platform chemicals derived therein. Here we describe a two-step methodology, which uses unprocessed lignocellulose directly, targeting a mixture of alkanes. The first step involves the near-complete conversion of lignocellulose to alcohols, using a copper doped porous metal oxide (Cu-PMO) catalyst in supercritical methanol. The second step comprises a novel solvent exchange procedure and the exhaustive hydrodeoxygenation (HDO) of the complex mixture of aliphatic alcohols, obtained upon depolymerization, to C2-C10 alkanes by either HZSM-5 or Nafion at 180 °C in conjunction with Pd/C in dodecane. This describes an unprecedented two-step process from lignocellulose to hydrocarbons, with an overall carbon yield of 50%.
