Styrene Hydroformylation with In Situ Hydrogen: Regioselectivity Control by Coupling with the Low-Temperature Water–Gas Shift Reaction

The hydroformylation of olefins is one of the most important homogeneously catalyzed industrial reactions for aldehyde synthesis. Various ligands can be used to obtain the desired linear aldehydes in the hydroformylation of aliphatic olefins. However, in the hydroformylation of aromatic substrates, branched aldehydes are formed preferentially with common ligands. In this study, a novel approach to selectively obtain linear aldehydes in the hydroformylation of styrene and its derivatives was developed by coupling with a water–gas shift reaction on a Rh single-atom catalyst without the use of ligands. Detailed studies revealed that the hydrogen generated in situ from the water–gas shift is critical for the highly regioselective formation of linear products. The coupling of a traditional homogeneous catalytic process with a heterogeneous catalytic reaction to tune product selectivity may provide a new avenue for the heterogenization of homogenous catalytic processes.     

Styrene Hydroformylation with In Situ Hydrogen: Regioselectivity Control by Coupling with the Low‐Temperature Water–Gas Shift Reaction

The hydroformylation of olefins is one of the most important homogeneously catalyzed industrial reactions for aldehyde synthesis. Various ligands can be used to obtain the desired linear aldehydes in the hydroformylation of aliphatic olefins. However, in the hydroformylation of aromatic substrates, branched aldehydes are formed preferentially with common ligands. In this study, a novel approach to selectively obtain linear aldehydes in the hydroformylation of styrene and its derivatives was developed by coupling with a water–gas shift reaction on a Rh single‐atom catalyst without the use of ligands. Detailed studies revealed that the hydrogen generated in situ from the water–gas shift is critical for the highly regioselective formation of linear products. The coupling of a traditional homogeneous catalytic process with a heterogeneous catalytic reaction to tune product selectivity may provide a new avenue for the heterogenization of homogenous catalytic processes.     

Native silica nanoparticle catalyzed anti-Markovnikov addition of thiols to inactivated alkenes and alkynes: a new route to linear and vinyl thioethers

A new route for the synthesis of linear and vinyl thioethers has been demonstrated using bare silica nanoparticle as catalyst at room temperature under solvent-free conditions. The catalyst can be reused up to six times without loss of catalytic activity.     

A simplified catalytic system for direct catalytic asymmetric aldol reaction of thioamides; application to an enantioselective synthesis of atorvastatin

A new catalytic system was developed for the direct catalytic asymmetric aldol reaction of thioamides. The new lithium-free Cu catalyst (second-generation catalyst) exhibited enhanced catalytic efficiency over the previously developed catalyst comprising [Cu(CH₃CN)₄]PF₆/Ph-BPE/LiOAr (first-generation catalyst), which required a tedious catalyst preparation process. In the reaction with the second-generation catalyst, the intermediate Cu-aldolate functioned as a Brønsted base to generate thioamide enolate, efficiently driving the catalytic cycle. The present aldol methodology culminated in a concise asymmetric synthesis of atorvastatin (Lipitor^®: atorvastatin calcium), a widely prescribed HMG-CoA reductase inhibitor for lowering low-density lipoprotein cholesterol.     

The adequacy of the observed kinetic order in catalyst and the differential selectivity patterns to the hypothesis of the cooperative mechanism of catalysis of the Suzuki—Miyaura reaction

The generally accepted mechanism of the Suzuki—Miyaura reaction suggests a sequential activation of the substrate (aryl halide) and the reagent (arylboronic acid) by a palladium catalyst with the formation of unsymmetric biaryl as a result of a single turnover of the catalytic cycle, i.e., it is linear from the kinetic point of view. At the same time, the use of an unconventional kinetic approach based on the analysis of the differential selectivity of the reaction, rather than the regularities of catalytic activity, indicates the inadequacy of the linear mechanism, that is consistent with the hypothesis of a nonlinear (the so-called cooperative) mechanism of catalysis, in which the product is formed as a result of the substrate and reagent activation by two different palladium-containing intermediates in two parallel catalytic cycles. The experimentally observed low kinetic orders of the Suzuki—Miyaura reaction with respect to the concentration of the palladium catalyst precursor under the ligand-free conditions of catalysis are also consistent with the cooperative mechanism and can be due to the changes in the relative amount of the catalyst in two parallel catalytic cycles and/or to the process of catalyst deactivation.

     

Direct synthesis of polyamides via catalytic dehydrogenation of diols and diamines

We report a direct synthesis of polyamides via catalytic dehydrogenation of diols and diamines. A PNN pincer ruthenium complex, the Milstein catalyst, was used for this reaction and polyamides with number average molecular weight from ～10 to 30 kDa could be obtained from a wide variety of diols and diamines bearing aliphatic or aromatic, linear or cyclic spacers. Because of the high catalytic selectivity of primary amine over secondary amine, polyamines could be conveniently incorporated into linear polyamides without tedious protection/deprotection steps. Compared with conventional condensation method, this catalytic system avoids the requirement of stoichiometric preactivation or in situ activation reagents and provides a much cleaner process with high atomic economy.     

Heterogeneous organocatalysis at work: functionalization of hollow periodic mesoporous organosilica spheres with MacMillan catalyst

We report a new method for the synthesis of hollow-structured phenylene-bridged periodic mesoporous organosilica (PMO) spheres with a uniform particle size of 100-200 nm using α-Fe(2)O(3) as a hard template. Based on this method, the hollow-structured phenylene PMO could be easily functionalized with MacMillan catalyst (H-PhPMO-Mac) by a co-condensation process and a "click chemistry" post-modification. The synthesized H-PhPMO-Mac catalyst has been found to exhibit high catalytic activity (98% yield, 81% enantiomeric excess (ee) for endo and 81% ee for exo) in asymmetric Diels-Alder reactions with water as solvent. The catalyst could be reused for at least seven runs without a significant loss of catalytic activity. Our results have also indicated that hollow-structured PMO spheres exhibit higher catalytic efficiency than solid (non-hollow) PMO spheres, and that catalysts prepared by the co-condensation process and "click chemistry" post-modification exhibit higher catalytic efficiency than those prepared by a grafting method.     

Neutral nickel oligo- and polymerization catalysts: the importance of alkyl phosphine intermediates in chain termination

An unconventional chain termination reaction has been explored for the SHOP (Shell higher olefin process)-type, anilinotropone, and salicylaldiminato nickel-based oligo- and polymerization catalysts by using density functional theory (DFT). Starting from the tetracoordinate alkyl phosphine complex, the termination reaction was found to involve a rearrangement of the alkyl chain to form a pentacoordinate β-agostic complex, β-hydride elimination, and olefinic chain dissociation and to compete with propagation at sufficiently high phosphine concentration and/or basicity. It provides the first complete and convincing mechanistic rationale for the decreasing chain lengths observed upon increasing phosphine concentration and basicity. The unconventional reaction was found to be a major termination pathway for the SHOP-type catalyst and is very unlikely to lead to branching and olefin isomerization, which is critical for explaining why the SHOP catalyst, in contrast to the anilinotropone and salicylaldiminato catalysts, tends to lead to the oligomerization of ethylene to form linear α-olefins. Based on our results we have proposed a new and extended catalytic cycle for the SHOP-type ethylene oligomerization catalyst. Finally, the importance of the new termination reaction for the SHOP-type catalyst suggests that this reaction may also operate with other ethylene oligomerization nickel catalysts. This prediction was confirmed for a pyrazolonatophosphine catalyst, for which the new termination route was found to be even more facile, which explains the short oligomers produced by this catalyst.     

镧掺杂硫酸钛的酸性及催化缩酮活性

以La2O3为镧源,硫酸钛掺杂镧后经高温焙烧制得一类稀土改性固体酸.用DTA,XRD表征催化剂结构,用吸附吡啶的FT-IR表征其表面酸性,由Hammett指示剂来测定酸强度,以正丁胺定量分析催化剂表面Bronsted酸和Lewis酸酸量;用环己酮与乙二醇缩酮化反应表征其酸催化性能.结果表明:催化剂表面同时存在B酸和L酸中心,且B/L酸量比与焙烧温度、镧的含量呈现较好的线性关系;在缩酮化反应中具有良好的催化活性,在300～600℃的实验范围内,催化活性随灼烧温度的升高而降低,随镧含量的增加而升高,兼有B酸和L酸的催化剂具有更好的催化活性.催化剂易回收和再生,反应后处理简单,无废酸排放,可重复使用多次,该固体酸是一种环境友好催化剂.     

硼、氮掺杂的二硫化钼用于氧还原电催化研究

对于碱性燃料电池的阴极反应,开发具有优异催化性能的新型催化剂至关重要.本工作采用一种简单的热解方法合成了硼、氮掺杂的二硫化钼(B,N-MoS2)材料并将其应用于氧还原(ORR)电催化分析.通过循环伏安法(CV)与线性扫描伏安法(LSV)等电化学分析方法,采用旋转盘电极(RDE)与旋转环盘电极(RRDE)等技术测试了该材...     

焦油催化裂化催化剂积炭失活的实验研究

对白云石、石灰石作用下生物质热解焦油催化裂化过程中的积炭失活问题进行了研究，考察了较长反应时间内催化剂积炭量和焦油转化率的变化情况。最长运行时间32 h，所得积炭质量分数为3%～15%，焦油转化率下降到70％左右。对不同来源焦油的生焦性、催化裂化反应条件等对积炭形成的影响作了考察，并从动力学角度对催化活性与积炭量之间的关系进行了分析，得到了单层积炭和多层积炭阶段线性和指数形式的关联式。     

Suppression of methane formation during Fisher-Tropsch synthesis using manganese-cobalt oxide supported on H-5A zeolite as a catalyst

In Fischer-Tropsch synthesis reaction, methane formation is one of the side reactions which must be suppressed in order to get better catalytic selectivity for light olefins. In the present study, we have modified cobalt based Fischer-Tropsch catalyst and developed a process to minimize methane production, consequently to produce maximum yield of light olefins. Manganese-cobalt oxide supported on H-5A zeolite catalyst was synthesized using modified H-5A zeolite, to increase its surface acid sites. Increased acidity of zeolite plays a major part in the suppression of methane formation during the Fischer-Tropsch reaction. The modified zeolite results in the electronic modification of catalyst surface by creating new active catalytic sites. The results are compared with other supported catalysts along with unmodified zeolite. Appreciable reduction in methane formation is achieved on modified zeolite supported catalyst in comparison with unsupported catalyst.     

An effective Pd-catalyzed hydroxycarbonylation of olefins with CO and HCOOH

A new protocol for Pd-catalyzed regioselective hydroxy-carbonylation of olefins with formic acid under low pressure of carbon monoxide has been developed. The same catalytic system provides good selectivity to 2-phenylpropionic acid in carbonylation of styrene and to linear acids in carbonylation of terminal alkenes. The reaction is highly susceptible to catalyst precursor and solvent nature.     

Synthesis of LPPE by gas-phase copolymerization of ethylene with 1-butene: A highly efficient chromium oxide supported catalyst

A modified chromium oxide supported catalyst has been developed and applied in industry for the manufacture of LPPE via the gas-phase (co)polymerization of ethylene. The catalyst contains surface chromium oxide in the oxidation number Cr²⁺, two modifiers (aluminum oxide and fluorine surface compounds), and silicon dioxide as a support. The activity of the new chromium oxide catalyst in the gas-phase copolymerization of ethylene with 1-butene is higher by a factor of 4–5 than that of the traditional commercial catalytic system based on the supported bis(triphenylsilylchromate) catalyst. An increased reactivity of 1-butene in its copolymerization with ethylene in the presence of the chromium oxide catalyst makes it possible to reduce the consumption of 1-butene in the synthesis of a linear medium-density PE (0.937–0.938 g/cm³). Gas pipes made of PE prepared with the new catalyst are characterized by improved resistance to crack propagation.     

New process of low-temperature methanol synthesis from CO/CO_2/H_2 based on dual-catalysis

A new process of low-temperature methanol synthesis from CO/CO2/H2 based on dual-catalysis has been developed. Some alcohols, especially 2-alcohol, were found to have high catalytic promoting effect on the synthesis of methanol from CO hydrogenation. At 443 K and 5 MPa, the synthesis of methanol could process high effectively, resulting from the synergic catalysis of Cu/ZnO solid catalyst and 2-alcohol solvent catalyst. The primary results showed that when 2-butanol was used as reaction solvent, the one-pass average yield and the selectivity of methanol, in 40 h continuous reaction at temperature as low as 443 K and 5 MPa, were high up to 46.51% and 98.94% respectively. The catalytic activity was stable and the reaction temperature was 80 K or so lower than that in current industry synthesis process. This new process hopefully will become a practical method for methanol synthesis at low temperature.     

Thermal deactivation mechanism and the effect of Nd addition on the deactivation of the Pt/SiO<Subscript>2</Subscript> catalyst for NO oxidation reaction

Pt-based catalysts cannot be used permanently for the diesel after-treatment system because the catalytic activity is decreased due to coarsening of Pt particles at high temperature of the exhaust gas. In this study, to prevent Pt-based catalyst from deactivation, Nd was added to the Pt/SiO₂ catalyst, and the effect of the Nd addition on the catalytic activity was investigated. The Pt/SiO₂ catalyst showed a high catalytic activity for the oxidation of NO but was severely deactivated after the fast thermal aging process. Pt crystallite size was increased and some Pt particles were buried in the SiO₂ pore during the fast thermal aging process, which led to the decrease of catalytic activity. Nd-added Pt/SiO₂ catalyst showed lower activity than Pt/SiO₂ catalyst, but Pt–Nd/SiO₂ catalyst maintained its catalytic activity after fast thermal aging process. It can be postulated that a stable Nd silicate, on which Pt particle is placed, protects SiO₂ pores from destruction and so the number of the catalytically active sites remains nearly unchanged. As a result the Pt–Nd/SiO₂ catalyst maintained its catalytic activity after fast thermal aging process.     

一种新型双亚胺吡啶铁系催化剂的乙烯低聚研究

线性α 烯烃广泛地应用于洗涤剂、增塑剂、润滑油等精细化学品的合成以及作为共单体制备线性低密度聚乙烯 (ＬＬＤＰＥ) .目前工业上主要是应用ＳＨＯＰ法[1] 、Ｃｈｅｖｒｏｎ工艺和Ａｍｏｃｏ工艺[2 ] 通过乙烯低聚制备 .近些年发展起来的新型高活性后过渡金属乙烯低聚催化剂能够高选择性地制备线性α 烯烃[3 ,4] .Ｂｒｏｏｋｈａｒｔ等[4] 的研究表明 ,对于双亚胺吡啶铁系乙烯聚合催化剂而言 ,配体上苯基的邻位取代基位阻减小可以实现乙烯低聚 ,并具有高活性、高选择性以及理想的低聚产物分布 .本文的工作是从配体的空间位阻效应对催化剂…     

New process of low-temperature methanol synthesis from CO/CO2/H2 based on dual-catalysis

A new process of low-temperature methanol synthesis from CO/CO₂/H₂ based on dual-catalysis has been developed. Some alcohols, especially 2-alcohol, were found to have high catalytic promoting effect on the synthesis of methanol from CO hydrogenation. At 443 K and 5 MPa, the synthesis of methanol could process high effectively, resulting from the synergic catalysis of Cu/ZnO solid catalyst and 2-alcohol solvent catalyst. The primary results showed that when 2-butanol was used as reaction solvent, the one-pass average yield and the selectivity of methanol, in 40 h continuous reaction at temperature as low as 443 K and 5 MPa, were high up to 46.51% and 98.94% respectively. The catalytic activity was stable and the reaction temperature was 80 K or so lower than that in current industry synthesis process. This new process hopefully will become a practical method for methanol synthesis at low temperature.     

Fe-P-O催化剂上甲烷氧化偶联反应强制振荡的研究

制备了可还原型甲烷氧化偶联反应催化剂ＦｅＰＯ,并在非稳态操作条件下,考察了浓度强制振荡操作对反应的强化作用,并对该体系催化剂进行了ＸＲＤ表征．结果表明,与稳态相比,非稳态下周期循环进料操作能够明显改善催化反应性能;催化剂在反应过程中有新的物相生成,并对甲烷活化产生较大的影响．     

氮化硼催化低碳烷烃氧化脱氢的活性起源探讨（英文）

页岩气的急速开采推动了以天然气替代石油的资源革命.除主组分甲烷外,天然气、页岩气中还包含大量乙烷、丙烷等低碳烷烃资源,将这些储量丰富的碳资源直接转化为烯烃等基础化学品有望革新以原油为基础的化学工业.现有烷烃催化脱氢制烯烃工艺中,直接脱氢过程吸热、热力学受限,且存在催化剂迅速失活的难题;而氧化脱氢是放热过程、无平衡限制,也无积碳等引发催化剂失活的问题,有利于提高反应效率、降低能耗,代表了更为高效和经济的新路线.但作为一个热力学爬坡过程,目前金属氧化物催化剂上烯烃产物很容易深度氧化到CO_2,选择性仍有待提高.非金属氮化硼能够有效活化低碳烷烃中的C-H键,促进烷烃氧化脱氢,并能够有效抑制深度氧化产物的生成,解决低碳烷烃临氧脱氢过程中产物易深度氧化的固有难题.本文综述了近期氮化硼在乙烷、丙烷、丁烷等低碳烷烃氧化脱氢制烯烃反应中的研究进展.以丙烷氧化脱氢为例,通过比较文献报道的几种氮化硼材料的氧化脱氢性能,发现羟基化氮化硼显示了最高的烯烃选择性和时空收率,以20.6%的丙烷转化率为基准,烯烃选择性超过90%,而时空收率可达6.8 golefin gcat~(-1) h~(-1).在此基础上,本文重点讨论了对于氮化硼材料催化活性起源的认识.主要实验事实和结论包括:氮化硼自身几乎没有氧化脱氢活性,而在烷烃氧化脱氢反应条件下存在活性诱导期;活性诱导期伴随着氮化硼边沿氧官能团化过程;氮化硼边沿B-O官能团没有脱氢活性,而B-OH官能团参与了氧化脱氢过程,辅助分子氧引发低碳烷烃脱氢反应;分子氧在羟基氮化硼边沿解离活化,反应过程中与边沿结构氧存在动态交换;氮化硼边沿羟基化定向合成过程可显著增强氧化脱氢反应活性.氮化硼作为一类新型烷烃氧化脱氢催化剂,目前正处于研究的初始阶段.因此,本文最后总结了一些关于氮化硼烷烃脱氢催化体系仍需深入研究的科学问题.