96-14-0Relevant academic research and scientific papers
Mercaptosilane-assisted synthesis of highly dispersed and stable Pt nanoparticles on HL zeolites for enhancing hydroisomerization of n-hexane
Liu, Cun,Liu, Haiou,Wang, Jinshan,Zhang, Xiongfu,Zhu, Peng
, p. 3482 - 3492 (2022/02/21)
The synergistic effect between metal and acid sites has been considered to be of great importance to n-alkane hydroisomerization catalyzed by bifunctional catalysts. Herein, we report a facile mercaptosilane-assisted in situ synthesis approach to achieve stable and highly dispersed small Pt nanoparticles supported on HL zeolite catalysts (Pt/HL-SH) for n-hexane hydroisomerization. In comparison with the catalysts (Pt/HL-C) synthesized by a traditional ion-exchange method, the Pt/HL-SH catalysts show both high activity and excellent catalytic stability and also no obvious sintering of Pt nanoparticles is observed during the reaction due to the fact that the Pt/HL-SH catalysts possess both higher dispersion of Pt particles within the HL nanocrystals and more mesopores produced by mercaptosilane. Moreover, the regeneration stability of n-hexane hydroisomerization over Pt/HL-SH catalysts was also examined by five continuous cycles, demonstrating excellent regeneration properties. Thus, the mercaptosilane-assisted in situ synthesis approach is a promising way to prepare bifunctional catalysts for enhancing their catalytic performance in n-alkane hydroisomerization.
Visible-Light-Enhanced Cobalt-Catalyzed Hydrogenation: Switchable Catalysis Enabled by Divergence between Thermal and Photochemical Pathways
Mendelsohn, Lauren N.,MacNeil, Connor S.,Tian, Lei,Park, Yoonsu,Scholes, Gregory D.,Chirik, Paul J.
, p. 1351 - 1360 (2021/02/01)
The catalytic hydrogenation activity of the readily prepared, coordinatively saturated cobalt(I) precatalyst, (R,R)-(iPrDuPhos)Co(CO)2H ((R,R)-iPrDuPhos = (+)-1,2-bis[(2R,5R)-2,5-diisopropylphospholano]benzene), is described. While efficient turnover was observed with a range of alkenes upon heating to 100 °C, the catalytic performance of the cobalt catalyst was markedly enhanced upon irradiation with blue light at 35 °C. This improved reactivity enabled hydrogenation of terminal, di-, and trisubstituted alkenes, alkynes, and carbonyl compounds. A combination of deuterium labeling studies, hydrogenation of alkenes containing radical clocks, and experiments probing relative rates supports a hydrogen atom transfer pathway under thermal conditions that is enabled by a relatively weak cobalt-hydrogen bond of 54 kcal/mol. In contrast, data for the photocatalytic reactions support light-induced dissociation of a carbonyl ligand followed by a coordination-insertion sequence where the product is released by combination of a cobalt alkyl intermediate with the starting hydride, (R,R)-(iPrDuPhos)Co(CO)2H. These results demonstrate the versatility of catalysis with Earth-abundant metals as pathways involving open-versus closed-shell intermediates can be switched by the energy source.
Boosting homogeneous chemoselective hydrogenation of olefins mediated by a bis(silylenyl)terphenyl-nickel(0) pre-catalyst
Lücke, Marcel-Philip,Yao, Shenglai,Driess, Matthias
, p. 2909 - 2915 (2021/03/14)
The isolable chelating bis(N-heterocyclic silylenyl)-substituted terphenyl ligand [SiII(Terp)SiII] as well as its bis(phosphine) analogue [PIII(Terp)PIII] have been synthesised and fully characterised. Their reaction with Ni(cod)2(cod = cycloocta-1,5-diene) affords the corresponding 16 VE nickel(0) complexes with an intramolecularη2-arene coordination of Ni, [E(Terp)E]Ni(η2-arene) (E = PIII, SiII; arene = phenylene spacer). Due to a strong cooperativity of the Si and Ni sites in H2activation and H atom transfer, [SiII(Terp)SiII]Ni(η2-arene) mediates very effectively and chemoselectively the homogeneously catalysed hydrogenation of olefins bearing functional groups at 1 bar H2pressure and room temperature; in contrast, the bis(phosphine) analogous complex shows only poor activity. Catalytic and stoichiometric experiments revealed the important role of the η2-coordination of the Ni(0) site by the intramolecular phenylene with respect to the hydrogenation activity of [SiII(Terp)SiII]Ni(η2-arene). The mechanism has been established by kinetic measurements, including kinetic isotope effect (KIE) and Hammet-plot correlation. With this system, the currently highest performance of a homogeneous nickel-based hydrogenation catalyst of olefins (TON = 9800, TOF = 6800 h?1) could be realised.
Cationic strontium hydride complexes supported by an NNNN-type macrocycle
Carpentier, Ambre,Englert, Ulli,H?llerhage, Thomas,Maron, Laurent,Okuda, Jun,Spaniol, Thomas P.
supporting information, p. 6316 - 6319 (2021/07/02)
A trinuclear strontium hydride [(Me4TACD)3Sr3(μ2-H)4(thf)][B(C6H3-3,5-Me2)4]2 (Me4TACD = 1,4,7,10-tetramethyltetraazacyclododecane) and a mixed calcium strontium hydride [(Me4TACD)2CaSr(μ-H)2(thf)][B(C6H3-3,5-Me2)4]2 were isolated by hydrogenolysis of cationic benzyl precursors. A solution of [(Me4TACD)2CaSr(μ-H)2(thf)][B(C6H3-3,5-Me2)4]2 shows hydride ligand exchange between calcium and strontium centers and higher affinity of the hydride ligand toward calcium.
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.
Physicochemical and Catalytic Properties of Ni,H/ZSM-5 and Ni,H/ZSM-5–Binder Catalysts Prepared in the Absence and in the Presence of Binder
Grzechowiak, J. R.,Jaroszewska, K.,Masalska, A.
, p. 851 - 861 (2020/02/21)
Physicochemical and catalytic properties of H/ZSM-5 and Ni,H/ZSM-5 along with Ni,H/ZSM-5–Al2O3 (1 : 1) systems were examined. The systems with a binder were prepared by two different methods of mixing zeolite with aluminum hydroxide. The samples were characterized by N2 sorption (at 77 K), X-ray diffraction, 27Al magic-angle spinning (MAS) NMR spectroscopy, temperature-programmed desorption of ammonia and adsorption of pyridine. Preparation of the zeolite catalyst with aluminium hydroxide was made by two methods: (1) mixing of powders and (2) combining appropriate pastes. Regardless of the method used for mixing there was no blocking of zeolite channels by aluminum oxide. The method of mixing zeolite with aluminium hydroxide powders promotes migration of aluminum from aluminum hydroxide/oxide to the zeolite framework. The results of n-hexane conversion showed that with Ni,H/ZSM-5 a slightly lower conversion than with H/ZSM-5 catalyst was observed that can be explained by a reduced yield of cracking products. Ni,H/ZSM-5–Al2O3 (1 : 1) catalytic systems were insignificantly less efficient in n-hexane transformation than alumina free samples but at the same time they were less selective towards hydrocarbons with boiling temperatures higher than this of n-hexane, precursors of carbonaceous deposits.
Well-dispersed nickel nanoparticles on the external and internal surfaces of SBA-15 for hydrocracking of pyrolyzed α-cellulose
Trisunaryanti, Wega,Suarsih, Endah,Triyono,Falah, Iip Izul
, p. 1230 - 1237 (2019/01/23)
Catalysts comprising nickel supported on SBA-15 were prepared by wet impregnation and co-impregnation methods. Wet impregnation was performed by directly dispersing an Ni(NO3)2·6H2O aqueous solution into SBA-15, whereas in co-impregnation, ethylene glycol (EG) was added to nickel nitrate aqueous solution prior to dispersion into SBA-15. After drying and calcination, NiO/SBA-15w and NiO/SBA-15c were produced. Later, after the reduction process, Ni/SBA-15w and Ni/SBA-15c were obtained. The prepared catalysts were evaluated for the hydrocracking of pyrolyzed α-cellulose. The TEM images revealed that the catalysts prepared by wet impregnation showed inhomogeneous distribution of nickel loading, whereas catalysts prepared by co-impregnation using EG exhibited homogeneous distribution and formed no nickel aggregates. During hydrocracking of pyrolyzed α-cellulose, Ni/SBA-15c with total acidity, nickel loading, particle size, and specific surface area of 7.27 m mol g?1, 5.20 wt%, 3.17 nm, and 310.0 m2 g?1, respectively, exhibited the best catalytic performance compared to other prepared catalysts with 67.35 wt% conversion of liquid product with maximum selectivity in producing 13.09 wt% of 3-methyl-pentane. Moreover, Ni/SBA-15w with total acidity, nickel loading, particle size, and specific surface area of 10.87 m mol g?1, 8.15 wt%, 7.01 nm, and 628.0 m2 g?1, respectively, produced 69.89 wt% liquid product without hydrocarbons. Study of selectivity towards the formation of liquid hydrocarbons was carried out via double step hydrocracking using Ni/SBA-15w, and 18.55 wt% of n-hexane was produced in the liquid product.
Tailoring the structure and acid site accessibility of mordenite zeolite for hydroisomerisation of n-hexane
Pastvova, Jana,Pilar, Radim,Moravkova, Jaroslava,Kaucky, Dalibor,Rathousky, Jiri,Sklenak, Stepan,Sazama, Petr
, p. 159 - 172 (2018/06/14)
Mordenite zeolites with diffusion-restricted access to the acid sites located in mono-dimensional 12-ring channels and 8-ring side pockets have found broad applications as catalysts for hydroisomerisation of linear C5 and C6 alkanes and other highly relevant acid-catalysed processes. The accessibility of the porous structure of mordenite (MOR) zeolite is traditionally enhanced by dealumination, but this is invariably connected with a dramatic reduction in the aluminium content and corresponding concentration of the acid sites in the zeolites. Here we describe the preparation of MOR zeolite with high micropore volume, three-dimensional supermicropores (d ～ 7.5 ?) and good acid site accessibility by concurrent extraction of Si and Al using postsynthesis fluorination-alkaline-acid treatment. The concurrent extraction of Si and Al enables formation of more developed supermicroporous structure and preservation of the molecular Si/Al. The procedure yields MOR with a crystalline structure in which the Si/Al ratio and the micropore volume can be tailored (Si/Al from ～ 6, VMI up to 0.25 cm3.g?1) by the chemical conditions of the treatment. The Al-rich 3D supermicroporous structure with accessible Br?nsted and Lewis active sites provides strongly enhanced activity, selectivity and long-term catalytic stability in the transformation of n-hexane into the corresponding branched isomers.
Isomerisation of n-hexane over bifunctional Pt-heteropoly acid catalyst: Enhancing effect of gold
Alazman, Abdulrahman,Belic, Domagoj,Kozhevnikova, Elena F.,Kozhevnikov, Ivan V.
, p. 80 - 89 (2017/11/27)
Isomerisation of n-hexane was studied in the presence of acid and bifunctional metal-acid catalysts based on Keggin-type heteropoly acids (HPA), in particular focusing on Cs2.5H0.5PW12O40 (CsPW) and Pt/CsPW as the catalysts, using a fixed-bed microreactor under differential conditions (n-hexane conversion ≤ 10%) at 180–220 °C, ambient pressure and a ratio of n-hexane and H2 partial pressures of 0.06–0.24. The turnover rate of HPA-catalysed isomerisation was found to correlate with the acid strength of HPA (initial enthalpy of ammonia adsorption). Bifunctional Pt-HPA catalysts were more efficient than monofunctional HPA catalysts. In the isomerisation over Pt/CsPW bifunctional catalyst, n-hexane dehydrogenation step was found to equilibrate at a molar ratio of Pt and H+ surface sites Pts/H+ ≥ 0.8, corresponding to a Pt loading ≥6%. Bimetallic PtAu/CsPW catalyst showed higher activity in n-hexane isomerisation than Pt/CsPW, although the Au alone without Pt was inert. In the presence of Au, the turnover rate at Pt sites increased more than twofold. The effect of Au is attributed to PtAu alloying. Scanning transmission electron microscopy–energy dispersive X-ray spectroscopy (STEM-EDX) and X-ray diffraction (XRD) analyses of PtAu/CsPW indicated the presence of bimetallic PtAu nanoparticles with a wide range of Pt/Au atomic ratios.
