Arene ruthenium oxinato complexes: Synthesis, molecular structure and catalytic activity for the hydrogenation of carbon dioxide in aqueous solution

Two families of arene ruthenium oxinato complexes of the types [(η⁶-arene)Ru(η²-N,O-L)Cl] and [(η⁶-arene)Ru(η²-N,O-L)(OH₂)]⁺ have been synthesized from the dinuclear precursors [(η⁶-arene)RuCl₂]₂ (arene = para-cymeme or hexamethylbenzene) and the corresponding oxine LH (LH = 8-hydroxyquinoline, 5-chloro-8-hydroxyquinoline, 5,7-dichloro-8-hydroxyquinoline, 5-nitro-8-hydroxyquinoline, 5,7-dimethyl-8-hydroxyquinoline, 5,7-dichloro-2-methyl-8-hydroxyquinoline). The molecular structures of the neutral chloro complexes [(η⁶-C₆Me₆)Ru(η²-N,O-L)Cl] (LH = 8-hydroxyquinoline, 5,7-dichloro-2-methyl-8-hydroxyquinoline) and [(η⁶-MeC₆H₄Prⁱ)Ru(η²-N,O-L)Cl] (LH = 5,7-dichloro-2-methyl-8-hydroxyquinoline) as well as those of the cationic aqua derivatives [(η⁶-MeC₆H₄Prⁱ)Ru(η²-N,O-L)(OH₂)]⁺ (LH = 8-hydroxyquinoline, 5,7-dimethyl-8-hydroxyquinoline), isolated as the tetrafluoroborate salts, show in all cases a piano-stool arrangement with the arene ligand, the chelating oxinato ligand and the chloro or the aqua ligand surrounding the ruthenium center in a pseudo-tetrahedral fashion. The analogous reaction of [(η⁶-MeC₆H₄Prⁱ)RuCl₂]₂ with other N,O-chelating ligands such as 2-pyridinemethanol or tetrahydrofurfurylamine did not give the expected analogs but resulted in the formation of the complexes [(η⁶-MeC₆H₄Prⁱ)Ru(η²-NC₅H₄CH₂OH)Cl]⁺ and [(η⁶-MeC₆H₄Prⁱ)Ru(η¹-NHCH₂C₄H₃O)Cl₂]. The neutral and cationic complexes of the types [(η⁶-arene)Ru(η²-N,O-L)Cl] and [(η⁶-arene)Ru(η²-N,O-L)(OH₂)]⁺ have been found to catalyze the hydrogenation of carbon dioxide to give formate in alkaline aqueous solution with catalytic turnovers up to 400.     

Effect of acid-base properties on copper catalysts for hydrogenation of carbon dioxide

Acidic or basic components as co-catalysts were added to the Cu-based catalysts for hydrogenation of CO₂. Effects of acid-base properties on the catalytic activity and methanol selectivity are discussed.     

非负载型铁催化剂上二氧化碳加氢制低碳烯烃

研究了非负载型铁催化剂上CO₂加氢制低碳烯烃反应.结果显示,添加碱金属可显著提高铁催化剂上的CO₂转化率和烯烃选择性.在经K和Rb修饰的Fe催化剂上,CO₂转化率可达约40%,烯烃选择性达到50%以上,其中C₂~C₄烯烃收率超过10%.催化剂表征结果表明,碱金属促进了催化剂中碳化铁的生成,这可能是催化剂性能提高的一个关键原因.随着K含量由1 wt%增加至5 wt%,CO₂转化率及烯烃选择性均升高.但K含量过高时,催化剂活性降低.这可能是由于催化剂比表面积和CO₂化学吸附量降低所致.当K含量为5%~10%时,K-Fe催化剂上烯烃收率较高; 进一步添加适量的硼可进一步提高烯烃选择性,且CO₂转化率下降不大.     

Carbon dioxide hydrogenation: Efficient catalysis by an NHC-amidate Pd(II) complex

The utilization of carbon dioxide as a carbon source has long been a challenge in modern organic chemistry due to its low reactivity, yet high abundance. Herein we demonstrate the highly efficient hydrogenation of carbon dioxide into formic acid in the presence of an NHC-amidate Pd(II) complex. Excellent turnover number was observed when the catalyst was used under heterolytic conditions. This catalytic system provides a new and efficient carbon dioxide hydrogenation method.     

Role of single-site catalysts in the hydrogenation of thiophenes: from models systems to effective HDS catalysts

The hydrogenation of thiophenes, leading to cyclic thioethers, thiols or hydrocarbons and H₂S, can be achieved by single-site metal catalysts in both homogeneous and heterogeneous phase. An overview of the processes that have provided useful mechanistic information on hydrodesulfurization catalysis, is presented and commented.     

碱金属助剂对CoCu/TiO2催化剂上二氧化碳加氢合成长链烃的影响

大气中CO2浓度增加导致的温室效应以及化石燃料的匮乏正日益受到世界范围的关注. 由于CO2较强的惰性以及较高 C-C 偶联能垒, 迄今为止大部分研究都集中在CO2催化加氢制备各种 C1 化学品 (如 CH4, CH3OH, CO 等), 鲜有研究关注合成液态燃料 (C5+碳氢化合物). 目前,CO2加氢直接合成烃类主要通过CO2基费托合成反应 (CO2-FTS) 实现, 即先通过逆水煤气变换反应 (RWGS) 将CO2还原成 CO, 随后 CO 通过传统费托反应 (FTS) 加氢生成烃类化合物. 在两种工业化FTS 催化剂 (Fe 和 Co 基催化剂) 中, 钴基催化剂具有更高的反应活性和链增长能力, 以及较高的机械强度和稳定性. 然而,由于CO2的惰性, 造成催化剂表面物种的加氢程度更高, 使得甲烷更容易生成. 因而, 高反应活性、高选择性催化剂的开发是实现该过程的关键.本文采用沉积沉淀法制备了一系列双金属 CoCu/TiO2催化剂, 再通过初湿浸渍法对其进行碱金属助剂 (Li, Na, K, Rb和 Cs) 改性, 并用多种表征手段系统研究了碱金属助剂对催化剂物化性质及其催化CO2加氢制备长链烃反应的影响. 结果表明, 碱金属的加入对催化剂织构性质影响不大, 它们在催化剂表面发生富集, 且富集程度随碱金属原子序数的增加而降低. 另外, 碱金属的加入增强了CO2的吸附, 其中, Na 改性的 CoCu/TiO2催化剂的碱性最强; 同时还降低了 H2的脱附量,尤以 K, Rb 和 Cs 改性的催化剂为甚.在 250 oC, 5 MPa, 空速 3000 mL·gcat-1·h-1和 H2/CO2= 3 的反应条件下, 对不同碱金属助剂改性的催化剂进行评价. 结果表明, 不加助剂的 CoCu/TiO2催化剂上CO2转化率高达 23.1%, 但产物主要是 CH4, 此时CO2在 Co 活性中心上直接发生甲烷化反应; 碱金属助剂的引入显著抑制了 CH4的生成, 提高了长链烃的选择性, 但同时也降低了CO2转化率, 并且随着碱金属原子序数增大呈现先下降后上升的趋势, 表明合适的碱性强度可以更好地改性催化剂性能. 其中, Na 助剂改性的CoCu/TiO2催化剂的碱性最强, 且 H2的脱附量降低幅度较小, 因此, 该催化剂具有最高的 C5+烃类收率, 达到 5.4%; 同时CO2转化率为 18.4%, 烃类产物中 C5+烃类选择性为 42.1%. Na 助剂改性的 CoCu/TiO2催化剂还展现了良好的催化稳定性,反应 200 h 后,CO2转化率和 C5+选择性分别保持 18% 和 40%. 基于碱金属助剂对催化剂物化性质与反应性能的调变规律,可进一步指导CO2加氢直接合成长链碳催化剂的设计与合成.     

Pyridinium-functionalized metalloporphyrins as bifunctional catalysts for cycloaddition of epoxides and carbon dioxide

New pyridinium-functionalized metalloporphyrins MEtPpBr₄ (M = Zn²⁺, Co²⁺, Ni²⁺, Cu²⁺; EtPp = 5, 10, 15, 20-tetra(4-(3-(N-ethyl-4-pyridyl)pyrazolyl)phenyl)porphyrin) were synthesized as bifunctional catalysts for the cycloaddition reactions of epoxides and CO₂. The effects of catalyst loading, CO₂ pressure, reaction temperature and time on catalytic activity were investigated. ZnEtPpBr₄ ( 1 ) and CoEtPpBr₄ ( 2 ) exhibited efficient activities in the cycloaddition reactions of various epoxides with CO₂ as at 120 °C under 2 MPa of CO₂ pressure without solvent. Most of corresponding cyclic carbonates could be obtained in almost quantitative yields and > 99.9% selectivity with molar ratio of epoxide/catalyst 2222 after 8 hr of reaction.     

Comparison of the catalytic activity and sulfur resistance of Pd-W and Pd-complex supported catalysts

The catalytic activity and sulfur-resistance of palladium-tungsten and a palladium complex supported catalysts for selective hydrogenation of styrene to ethylbenzene are compared. The different behaviors are attributed to different active species.     

Heterogeneous catalysts for cyclic carbonate synthesis from carbon dioxide and epoxides

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Dehydrogenation of isobutane in the presence of carbon dioxide over supported vanadium oxide catalysts

Summary The dehydrogenation of isobutane to isobutene in the presence of carbon dioxide was carried out over supported vanadium oxide catalysts. The influence of the support on the catalytic performance was investigated. The isobutane conversion and isobutene selectivity in the presence of carbon dioxide were compared with the results obtained during the dehydrogenation reaction in the presence of helium (inert gas). The catalysts were characterized by temperature-programmed techniques (TPR, TPD-NH₃, TPD-CO₂).     

Polymer‐supported pyridinium catalysts for synthesis of cyclic carbonate by reaction of carbon dioxide and oxirane

Polymer‐supported pyridinium salts, prepared by quaternarization of crosslinked poly(4‐vinylpyridine) with alkyl halides, effectively catalyze the reaction of carbon dioxide (1 atm) and glycidyl phenyl ether (GPE) to afford the corresponding five‐membered cyclic carbonate (4‐phenoxymethyl‐1,3‐dioxolan‐2‐one). Poly(4‐vinylpyridine) quarternarized with alkyl bromides show high catalytic activities, and the reaction of carbon dioxide (1 atm) and GPE at 100 °C affords 4‐phenoxymethyl‐1,3‐dioxolan‐2‐one quantitatively in 6 h. The rate constant in the reaction of GPE and carbon dioxide in N‐methyl pyrrolidinone using poly(4‐vinylpyridine) quarternarized with n‐butyl bromide (k_obs = 102 min^?1) is almost comparable with those for homogeneous catalysts with good activities (e.g., LiI), and the rate of the reaction obeys the first‐order kinetics. A used catalyst may be recovered by centrifugation, and the recycled catalyst also promotes the reaction of GPE and carbon dioxide. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5673–5678, 2007     

Nickel catalysts supported on MgO with different specific surface area for carbon dioxide reforming of methane

In this paper, three kinds of MgO with different specific surface area were prepared, and their effects on the catalytic performance of nickel catalysts for the carbon dioxide reforming of methane were investigated. The results showed that MgO support with the higher specific surface area led to the higher dispersion of the active metal, which resulted in the higher initial activity. On the other hand, the specific surface area of MgO materials might not be the dominant factor for the basicity of support to chemisorb and activate CO₂, which was another important factor for the performance of catalysts. Herein, Ni/MgO(CA) catalyst with proper specific surface area and strong ability to activate CO₂ exhibited stable catalytic property and the carbon species deposited on the Ni/MgO(CA) catalyst after 10 h of reaction at 650 °C were mainly activated carbon species.     

Copolymerization of carbon dioxide and propylene oxide by several metallosalen‐based bifunctional catalysts

A series of new metallosalen‐based bifunctional catalysts with Co(III), Cr(III), Fe(III), Mn(III), and Ni(III) were synthesized for the first time, and a detailed study on the mechanism of the copolymerization of CO₂ and propylene oxide (PO) was performed. Meanwhile, the impact factors of the reaction conditions (metal cations, temperature, CO₂ pressure, and reaction time) on catalytic activity and selectivity were investigated. The results indicated that, with the increase of temperature, both the catalyst efficiency and the molecular weight of the copolymer decrease for all the five complexes. The salen‐Co(III) complex demonstrated higher activity under mild conditions: reaction temperature at 30 °C, copolymerization time of 24 hr, and 2 MPa of CO₂ pressure. The DSC curve indicated that the PPC by the salen‐Co(III) complex has the highest T_g of 46.19 °C. DTGA curves demonstrated that there were two thermal degradation peaks: the first is for the ester bond, and the second is for the C C bond.     

Pd/TiN nanocomposite catalysts for selective hydrogenation of phenol and its derivatives

Pd/TiN nanocomposite catalysts were fabricated for one-step selective hydrogenation of phenol to cyclohexanone successfully. High conversion of phenol (99%) and selectivity of cyclohexanone (98%) were obtained at 30℃ and 0.2 MPa H₂ for 12 h in the mixed solvents of H₂O and CH₂Cl₂. The Pd nanoparticles were stable in the reaction, and no aggregation was detected after four successive runs. The catalytic activity and selectivity depended on slightly the Pd particle sizes. The generality of the catalysts for this reaction was demonstrated by the selective hydrogenation of phenol derivatives, which showed that the catalyst was selective for the formation of cyclohexanone.     

Water-soluble (η-arene)ruthenium(II)-phosphine complexes and their catalytic activity in the hydrogenation of bicarbonate in aqueous solution

The reactions of [(η⁶-C₆H₆)RuCl₂]₂ and [(η⁶-p-cymene)RuCl₂]₂ with hydrogen in the presence of the water-soluble phosphines tppts (meta-trisulfonated triphenylphosphine) and pta (1,3,5-triaza-7-phosphaadamantane) afforded as the main species [(η⁶-C₆H₆)RuH(tppts)₂]⁺, [(η⁶-C₆H₆)RuH(pta)₂]⁺, [(η⁶-p-cymene)RuH(tppts)₂]⁺ and [(η⁶-p-cymene)RuH(pta)₂]⁺. This latter complex was also formed in the reaction of [(η⁶-p-cymene)RuCl₂(pta)] and hydrogen with a redistribution of pta. In addition, prolonged hydrogenation at elevated temperatures and in the presence of excess of pta led to the formation of the arene-free [RuH(pta)₄Cl], [RuH(pta)₄(H₂O)]⁺, [RuH₂(pta)₄] and [RuH(pta)₅]⁺ complexes. Ru-hydrides, such as [(η⁶-arene)RuH(L)₂]⁺, catalyzed the hydrogenation of bicarbonate to formate in aqueous solutions at p(H₂)=100 bar, T=50-70 °C.     

碳膜包覆的氧化铁纳米颗粒:一种高效的芳硝基化合物加氢催化剂

铁是地球上最丰富的元素之一,它在生命反应中起到至关重要的作用.目前,铁基催化剂广泛应用于合成氨、费托合成、NOx的选择性催化还原等.最近,铁因其含量丰富、价格低廉、无毒等优势而在多相催化方面引起了重点关注.最新研究发现,铁基催化剂在甲烷直接偶联制乙烯、氧还原以及芳硝基化合物的选择性加氢等领域具有突出表现,其中芳硝基化合物选择性加氢是一类具有重要应用前景的反应,这是因为苯胺(AN)是一种重要的精细化学品和有机中间体,广泛用于医药、染料、农药等行业,苯胺的年产量超过了400万吨,目前使用的催化剂主要有Raney Ni、负载镍、Ru/SnO2及少量铂碳、钯碳催化剂.但是,在Ni基催化剂上,硝基苯加氢主要经过间接缩合途径,同时会伴有氧化偶氮苯(AOB)、偶氮苯(AB)和氢化偶氮苯(HAB)等副产物生成,这些高沸点的副产物会带来一系列问题,如产物分离困难、产品纯度较低以及催化剂失活等.在这种情况下,为了加速苯胺生成,工业上一般采用过量的Raney Ni催化剂.贵金属(如Pt,Pd和Ru等)对催化芳硝基化合物加氢具有极高的活性,且苯胺的生成主要经过直接加氢途径.然而,由于成本过高,贵金属催化剂的大规模应用还存在一定的困难.本文采用简易的方法制备了一种铁基催化剂,在这个催化剂中氧化铁纳米颗粒被碳膜包覆并嵌入至平板碳中(Fe2O3@G-C).该催化剂由活性炭、苯胺及醋酸亚铁热解所得.通过扫描电镜(SEM)、拉曼光谱(Raman)及X射线衍射(XRD)分析,我们证实在原始碳颗粒上形成了新的碳膜.同时高倍透射电镜图也清楚地揭示了氧化铁纳米颗粒被碳膜包覆的结构.实验发现,Fe2O3@G-C-900催化剂(900oC热解所得)在芳硝基化合物选择性加氢反应中具有很高的活性.在2 MPa H2,70oC条件下反应2 h,硝基苯(NB)转化率达到95.4%,苯胺选择性达到99.1%,远远高于其他载体(活性炭、SiO2、Al2O3和MgO)负载的铁基催化剂.表征结果发现,Fe2O3@G-C-900催化剂的高活性可能与其具有较大的比表面积(573.7 m2/g)、孔体积(0.22 cm3/g,孔径小于2 nm)、高度分散的氧化铁纳米颗粒以及氧化铁纳米颗粒和其表面碳膜的协同作用密切相关.此外,催化剂中引入的氮原子不仅可以在包覆的碳膜上形成缺陷,也能进一步增强包覆在氧化铁纳米颗粒表面的碳膜的催化活性.通过对Fe2O3@G-C-900催化剂在硝基苯加氢反应中的循环使用活性的考察,发现该催化剂在循环使用5次后,仍具有良好的活性.更重要的是,在Fe2O3@G-C-900催化剂上硝基苯的加氢主要是直接途径,反应中没有高沸点AOB,AB和HAB等副产物生成.鉴于Fe2O3@G-C-900催化剂对NB加氢具有优异的活性,我们还进行了一系列含有不同取代基团的芳硝基化合物的加氢实验,发现对位取代的底物相对于间位及邻位的底物更容易发生加氢还原反应,这应归因于该催化剂的孔径较小(0.52 nm).这些研究方法可以扩展至其他金属催化剂的制备,以促进高效益和可持续的工业生产的发展.     

Alternating copolymerization of carbon dioxide and cyclohexene oxide catalyzed by silicon dioxide/Zn?CoIII double metal cyanide complex hybrid catalysts with a nanolamellar structure

Air‐stable hybrid catalysts of silicon dioxide/double metal cyanide complexes (Si‐DMCCs) based on Zn₃[Co(CN)₆]₂ (ZHCC) were prepared by an in situ sol–gel method. The Si‐DMCCs showed low crystallinity and a nanolamellar structure with a thickness of ～40–60 nm. In particular, a lamellar structure of regular hexagonal shape was observed for Si‐DMCCs with low SiO₂ content. These catalysts had very high catalytic activity for alternating copolymerization of cyclohexene oxide (CHO) and carbon dioxide. A turnover number of 11,444, turnover frequency of 3815 h^?1, and apparent efficiency of 7.5 kg polymer/g ZHCC (～24.0 kg polymer/g Zn) were achieved at 3.8 MPa and 100 °C. The poly(cyclohexenylene carbonate) (PCHC) polymers obtained were completely atactic with a molecular weight (M_n) of ～10 kg/mol and polydispersity of 2.0–3.0. The PCHCs had a structure of nearly alternating CHO and CO₂ units, with a molar fraction of carbonate units of 0.44–0.47. Preliminary investigations of the mechanism suggest that nucleophilic attack by neighboring oxygen atoms is involved in copolymerization initiation with Zn? Co^III DMCCs. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3128–3139, 2008     

Selective ethylene formation by pulse-mode electrochemical reduction of carbon dioxide using copper and copper-oxide electrodes

Although the electrochemical reduction of carbon dioxide (CO₂) with a copper electrode produces hydrocarbons, the activity toward the conversion of CO₂ is lost for several 10 min by the deposition of poisoning species on the electrode. To solve the poisoning species problem, the electrochemical reduction of CO₂ was carried out using a copper electrode with a pulse electrolysis mode with anodic as well as cathodic polarization. The anodic polarization intervals suppressed the deposition of poisoning species on the electrode, and the amount of two hydrocarbons, CH₄ and C₂H₄, barely decreased even after an hour. By choosing appropriate anodic potential and time duration, the selectivity for the C₂H₄ formation was greatly enhanced. The enhancement was found to be due to the copper oxide formed on the copper electrode. The selectivity was further improved when the electrochemical reduction was made with the copper-oxide electrode. The highest efficiency of about 28% is obtained at −3.15 V.     

超临界合成Pt修饰的TiO2用于光催化CO2还原制备太阳能燃料

考察了超临界条件下合成TiO2基光催化剂的性质,尤其是在超临界CO2下得到的分散在TiO2上Pt的特性,并与商品化TiO2性能进行了比较.另外,所得催化剂的光催化活性用CO2光还原制太阳能燃料进行了评价.结果表明,该催化剂可得到具有比商用TiO2更好或类似的性能(高比表面积、结晶度、表面羟基浓度,大的孔容、增强的可见光吸收、高的甲烷生成速率)而用于CO2还原制备燃料的反应中.这可归因于该催化剂超临界介质合成过程.     

Electrochemical reduction of carbon dioxide on copper in methanol with various potassium supporting electrolytes at low temperature

The electrochemical reduction of CO₂ at a Cu electrode was investigated in a methanol-based electrolyte using such potassium supporting salts as CH₃COOK, KBr, KI and KSCN at extremely low temperature (−30 °C). The main products obtained from CO₂ by the electrochemical reduction were methane, ethylene, ethane, carbon monoxide and formic acid. The maximum Faradaic efficiency of ethylene was 19.9% in KI/methanol-based catholyte at −3.0 V vs. Ag/AgCl saturated KCl. The best methane formation (27.0%) was obtained in CH₃COOK/methanol electrolyte at −3.0 V. In the system containing a potassium halide, the efficiency of hydrogen formation, being a competitive reaction against CO₂ reduction, was suppressed to less than 8.1%. The product selectivity of the electrochemical reduction of CO₂ in methanol was greatly affected by the anionic species. This research can contribute to the large-scale manufacturing of useful organic products from readily available and cheap raw materials: CO₂-saturated methanol from industrial absorbers (the Rectisol process). Received: 11 November 1998 / Accepted: 1 February 1999