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131.
Hydrogenation of aromatics under mild conditions on transition metal complexes in zeolites. A cooperative effect of molecular sieves 总被引:1,自引:0,他引:1
The hydrogenation of aromatics, i.e. benzene, toluene, -methylstyrene, anisole, and ethyl benzoate, can be carried out under a very low (1/12000) catalyst to substrate ratio, and mild reaction conditions (80°C, 6 atm of H2O), on Rh and Ni organometallic complexes anchored on USY zeolites. A strong cooperative effect between the faujasite surface and the transition metal surface complex is thought to be responsible for the simultaneous enhancement of concentrations of arene and H2 in the neighborhood of the catalytic centers, and for the observed electronic effects. 相似文献
132.
Fluorescence yield near-edge spectroscopy (FYNES) above the carbon K edge and temperature programmed reaction spectroscopy (TPRS) have been used as the methods for characterizing the reactivity and structure of adsorbed aniline and aniline derived species on the Ni(100) and Ni(111) surfaces over an extended range of temperatures and hydrogen pressures. The Ni(100) surface shows appreciably higher hydrogenolysis activity towards adsorbed aniline than the Ni(111) surface. Hydrogenolysis of aniline on the Ni(100) surface results in benzene formation at 470 K, both in reactive hydrogen atmospheres and in vacuum. External hydrogen significantly enhances the hydrogenolysis activity for aniline on the Ni(100) surface. Based on spectroscopic evidence, we believe that the dominant aniline hydrogenolysis reaction is preceded by partial hydrogenation of the aromatic ring of aniline in the presence of 0.001 Torr of external hydrogen on the (100) surface. In contrast, very little adsorbed aniline undergoes hydrogen induced C-N bond activation on the Ni(111) surface for hydrogen pressures as high as 10–7 Torr below 500 K. Thermal dehydrogenation of aniline dominates with increasing temperature on the Ni(111) surface, resulting in the formation of a previously observed polymeric layer which is stable up to 820 K. Aniline is adsorbed at a smaller angle relative to the Ni(111) surface than the Ni(100) surface at temperatures below the hydrogenolysis temperature. We believe that the proximity and strong -interaction between the aromatic ring of the aniline and the surface is one major factor which controls the competition between dehydrogenation and hydrogen addition. In this case the result is a substantial enhancement of aniline dehydrogenation relative to hydrogenation on the Ni(111) surface. 相似文献
133.
Qin Yang Bingqing Ge Pei Yuan Shuting Luo Hongwei Zhang Zhengyu Zhao Jiujun Zhang Shidong Wang Xiaojun Bao Xiangdong Yao 《Advanced functional materials》2023,33(25):2214588
Electrocatalytic hydrogenation (ECH) is a burgeoning strategy for the sustainable utilization of hydrogen. However, how to effectively suppress the competitive hydrogen evolution reaction (HER) is a big challenge to ECH catalysis. In this study, amine (NH2 R)-coordinated Pd nanoparticles loaded on carbon felt (Pd@CF) as a catalyst is successfully synthesized by a one-step solvothermal reduction method using oleylamine as the reducing agent. An exceptional ECH reactivity on benzaldehyde is achieved on the optimal Pd@CF catalyst in terms of a high conversion (89.7%) and selectivity toward benzyl alcohol (89.8%) at −0.4 V in 60 min. Notably, the Faradaic efficiency for producing benzyl alcohol is up to 90.2%, much higher than that catalyzed by Pd@CF-without N-group (41.1%) and thecommercial Pd/C (20.9%). The excellent ECH performance of Pd@CF can be attributed to the enriched electrons on Pd surface resulted from the introduction of NH2 R groups, which strengthens both the adsorption of benzaldehyde and the adsorbed hydrogen (Hads) on Pd, preventing the combination of Hads to form H2, that is, inhibiting the HER. This study gives a new insight into design principles of highly efficient electrocatalysts for the hydrogenation of unsaturated aldehydes molecules. 相似文献
134.
Zhenzhen Li Yutie Gong Aihua Xu Jiayu Zhao Qiong Li Lijie Dong Chuanxi Xiong Ming Jiang 《Advanced functional materials》2023,33(40):2301009
Thermo-responsive dielectric materials are in urgent demand owing to the rapid development of smart electronic/electrical systems. Although different types and structures of thermally responsive dielectric materials have been continuously reported, their dielectric response behaviors all originate from thermodynamic phase transitions. Herein, it is demonstrated that structural relaxation in poly(vinylidene fluoride) (PVDF), a non-thermodynamic phase transition, can induce a significant thermal dielectric pulse at room temperature. The dielectric pulse strength of up to 6.3 × 105 at 20 Hz, with a dielectric pulsing temperature of 24 °C, is achieved from polyethylene glycol (PEG)-PVDF coaxial nanofibrous films (PVDF@PEG), fabricated via a continuous blow spinning method. Moreover, the films exhibit excellent flexibility, adjustable strength and toughness, switchable hydrophilicity/hydrophobicity, and effective thermal management capability. The relaxation-induced dielectric pulsing effect, outstanding multifunctionality, and simple preparation combine to promote further scalability and prospects of PVDF@PEG. In particular, the work contributes to the discovery of the relaxation-induced dielectric response mechanism, which provides a new strategy for the generation of thermo-responsive dielectric materials. 相似文献
135.
用直接合成法制备了不同铝硅物质的量比Al-SBA-15(β)(β=n(Al)/n(Si)=0,0.02,0.03,0.05)介孔分子筛,并采用浸渍法制备了金属负载量m=35%的CZZ/Al-SBA-15(β)负载型介孔催化剂,考察了Al/Si比对负载催化剂结构和性能的影响。采用N_2吸附-脱附、X射线衍射(XRD)、H_2程序升温还原(H_2-TPR)、CO_2吸附(CO_2-TPD)、NH3吸附(NH3-TPD)和透射电子显微镜(TEM)等手段对样品进行了表征,在固定床反应器上评价了其CO_2加氢合成甲醇的催化性能。实验结果表明,CZZ/Al-SBA-15(β)具有介孔结构,Al的引入不但增加了载体表面酸性位点,同时还提高了催化剂表面铜分散度(DCu%)和铜比表面积(SCu)以及促进了Cu~+-O-Zn活性位的形成,从而大大提高了催化剂的活性。其中CZZ/Al-SBA-15(0.03)催化剂的甲醇选择性达到26%,与不掺铝的CZZ/Al-SBA-15(0)催化剂相比,甲醇选择性提高了11%,但随着掺Al量的继续增加,酸性太强,CO_2吸附能力下降,活性反而降低。 相似文献
136.
研究了有机杂质甲醛、甲醇以及其它低级醇对丁炔二醇催化氢化的影响 ;并根据实验数据计算出氢化反应的动力学参数 ,为放大实验及工业设计提供参考数据。 相似文献
137.
The first measurement of a turnover rate with respect to surface intermediate concentration in a high pressure heterogeneous catalytic reaction is reported. By using infrared-visible sum frequency generation to study the hydrogenation of ethylene on Pt(111), it was found that the surface concentration of -bonded ethylene, the key reaction intermediate, represented approximately 4% of a monolayer. Thus the absolute turnover rate per surface adsorbed ethylene molecule is 25 times faster than the rate measured per platinum atom. To explain these results, we propose a model of weakly adsorbed ethylene intermediates reacting on atop sites. 相似文献
138.
The BINAP-Ru(II) catalyst (2,2-bis(diphenylphosphino)-1,1-binaphthyl)chloro(p-cymene)rutheniun chloride is found to be highly active and enantioselective for homogeneous asymmetric hydrogenation of o-chloroacetophenone to optically pureo-chloro-(1-phenyl)ethanol. In contrast to results of Noyori and coworkers, no organic and inorganic bases are required to obtain high activities and enantioselectivities 相似文献
139.
Aromatic Hydrogenation Catalysis: A Review 总被引:14,自引:0,他引:14
High aromatic content in diesel fuel has been recognized both to lower the fuel quality and to contribute significantly to the formation of undesired emissions in exhaust gases [1, 2]. Because of the health hazards associated with these emissions, environmental regulations governing the composition of diesel fuels are being tightened in both Europe and the United States, leading to limitations on aromatics [3, 4]. 相似文献
140.
继续进行炼油企业结构调整 加快我国加氢工艺技术发展 总被引:1,自引:1,他引:1
指出近年来我国炼油企业结构调整已初见成效,加氢工艺技术获得了较快发展,预测21世纪初将是加氢工艺大展宏图的时代,应充分利用石油资源加快我国加氢工艺技术发展;并介绍了重点研究开发和推广应用的各项加氢技术。 相似文献