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101.
The electrochemical reduction of nitrate ion was studied by cyclic voltammetry on Pt(1 1 1) and [n(1 1 1) × (1 1 1)] stepped Pt surfaces, where n (=14, 10, 7, 6, 5, 4, 3, 2) is the number of terrace atoms, in 0.1 M HClO4 + 10 mM KNO3. The electrocatalytic nitrate reduction was found to hardly proceed on Pt(1 1 1) in the hydrogen adsorption region, while the electrocatalytic activity was improved with the increase in the step density. Inactivation was observed in the presence of adsorbed hydrogen or nitrate-derived reduced adsorbate, i.e. adsorbed NO, on (1 1 1) step sites. It was, therefore, concluded that the electrocatalytically active NO3− species does not adsorb on the (1 1 1) terraces but on the (1 1 1) monoatomic steps. The nitrate reduction current increased with the step density in a non-linear relationship. The overall current density at 0.21 V (RHE) corresponding to the peak potential of the main electrocatalytic nitrate reduction wave which was maximum at n = 2, abruptly increased with short terraces, i.e. n < 5, where the current wave of adsorbed hydrogen on the Pt stepped surface with comparatively narrow (1 1 1) terraces, denoted as Hnt, also appeared unmodified for n < 5 on voltammograms recorded in 0.1 M HClO4 in the absence of nitrate. 相似文献
102.
The work reported here represents initial attempts to develop a complete kinetic and mechanistic understanding of the reaction chemistry of H2S under coal liquefaction conditions, using both model systems and coal. Hydrogen sulphide was found to promote/catalyse the transfer of hydrogen from tetralin to 2-hydroxyquinoline (2-HOQ). The presence of H2S can increase the rate of hydrogen transfer from tetralin to 2-HOQ by a factor of 10 compared with the same reaction run in the absence of H2S. The energy of activation for hydrogen transfer was found to decrease by ≈5 kcal mol−1 in the presence of H2S. The presence of H2S was also found to promote loss of oxygen from 2-HOQ to form small amounts of quinoline. No evidence of CC or CN bond cleavage in 2-HOQ was noted under any of the reaction conditions studied. These results suggest that the presence of H2S reduces the temperatures necessary to promote effective hydrogen transfer from tetralin by 50–75 °C. Moreover, they imply that similar effects occur in H2S-promoted coal liquefaction. 相似文献
103.
Z. Vít 《Catalysis Letters》1992,13(1-2):131-136
Activity and selectivity of carbon supported Mo catalyst was tested in parallel hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene in the temperature range 260–350 °C at 2 MPa of hydrogen pressure and compared with that of commercial NiMo-alumina catalyst Shell 324. The main advantages of carbon supported Mo sulfide over commercial NiMo catalyst can be summarized as follows: the markedly higher HDN and better HDS activities normalized to moles of active metals, the lower content of piperidine in the reaction products and the distinctly better selectivity towards HDN reaction. 相似文献
104.
Hydrogen evolution during formaldehyde oxidation in alkaline solution has been monitored by Differential Electrochemical Mass Spectrometry on Au(111) and polycrystalline gold. The current efficiency for hydrogen evolution increases with higher concentration and is in the same range on both, polycrystalline Au and Au(111) electrode. The onset potentials and half-wave potentials are higher on Au(111). Reaction orders for the faradaic current on the bare gold electrodes have been determined as 0.21 for higher and 0.76 for lower concentrations. Reaction orders for hydrogen evolution during formaldehyde oxidation are 1.4 times higher in each case. Tafel slopes in the range of 140-160 mV are found. This signifies that the first reaction step involving the formation of adsorbed hydrogen is largely determining the overall reaction rate. In the presence of thallium adlayers hydrogen evolution from formaldehyde oxidation is largely suppressed. On the thallium modified polycrystalline Au, formaldehyde oxidation is shifted for 100 mV to higher potentials where Tl is partially desorbed and hydroxide is coadsorbed on the modified surface. On thallium modified Au(111), a similar process takes place, but in the same potential region as the onset of formaldehyde oxidation on the bare surface and therefore the formaldehyde oxidation is only slightly shifted. Tafel slopes are decreased to 80 mV/dec in the presence of thallium. In the presence of adsorbed thallium, the first reaction step is in equilibrium, the coverage with adsorbed hydrogen is smaller and its recombination to H2 is largely suppressed. 相似文献
105.
The effect of the hydride-forming intermetallic compound Zr2Fe on the aromatization of propane over high-silica zeolites of CVM type (Russian equivalent of ZSM-5) modified by Zn, Ga or Pt cations has been investigated. Aromatics yield and selectivity of aromatization are shown to increase essentially as a result of releasing hydrogen elimination by the intermetallic acceptor. The effect of hydrogen acceptor on propane conversion and product distribution appeared to be different depending on the composition of the catalyst used. Possible changes in the reaction mechanism in hydrogen removal conditions are discussed. 相似文献
106.
介绍了同心圆式反应器、板式反应器、壁反应器、微通道反应器在自热重整反应制氢中的特点。同心圆式反应器的传热是控制步骤,为强化传热而开发了空间形状不同和流体经过反应器不同腔体的先后顺序不同的反应器;板式反应器易于组装、拆卸和放大,而且热效率也比较高,是目前十分活跃的研究领域,重点在于操作参数和设计的优化及其高效壁载制氢催化剂的研制;壁反应器的反应表面和换热表面不分离,具有较高的热量耦合效果;微通道反应器具有优越的传热性能,但对加工和流体的性质有比较苛刻的要求。另外,不同燃料制氢机理的研究及其过程参数的稳态、瞬态模拟,为反应器的设计提供了理论依据。而制氢过程并行单元的研究为系统的集成奠定了基础。最后,指出开发板式壁反应器以及开展其在CO变换、净化方面的研究有较好的发展前景。 相似文献
107.
纳米尺寸硫化镍化学增感剂 总被引:4,自引:3,他引:4
本文发现了硫化镍纳米粒子对卤化银乳剂的化学增感作用,采用水不溶性的硫化镍纳米粒子作为化学增感剂,与水溶性的硫代硫酸钠增感剂相比,可以在乳剂灰雾增加不大的条件下明显提高乳剂的感光度和反差。 相似文献
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