ZrO_2对CuO-ZnO-ZrO_2催化剂低压合成甲醇的促进作用

我们曾报道CO_2/H_2在CuO-ZnO及CuO-ZnO-ZrO_2催化剂上低压合成甲醇的反应,指出CuO-ZnO-ZrO_2对CO_2/H_2制甲醇具有较高的活性和选择性。本文通过TPD-MS测试研究了第3组分ZrO_2的加入对CO_2/H_2在CuO-ZnO-ZrO_2催化剂上低压合成甲醇的促进作用。 1 实验部分 催化剂的评价在恒压流动反应系统内进行。用色谱仪分析产物(Porapak Q柱,4 mm×3m,柱温120℃,CO、CO_2、CH_3OH、H_2O的保留时间分别为0.55、0.84、4.72、6.6 min),热     

La2O3对Ni/γ-Al2O3甲烷化催化剂的助催化作用

我国将稀土作为助剂引入镍基甲烷化催化剂,大大提高了催化剂的活性和热稳定性,并已投入工业应用［1－3］．稀土对不同镍催化剂反应性能及其作用机理的研究已有一些报导［3－7］．谢有畅等观察到镍负载在经单层La2O3改性的γ－Al2O3表面,其晶粒要比没有La2O3时小得多．Rotgerink等认为添加La后反应速率的增加不只是由于几何效应,而是La对甲烷化本身有促进作用,单位镍表面的活性是随La含量不同而改变的,活性增加的同时表观活化能也增加［5］．作为助剂的La2O3在氢还原和反应过程中的变化及其作用的研究和讨论较少,目前一般认为添…     

NO2在Ag/Pt(110)双金属表面上的吸附和分解

利用俄歇电子能谱(AES)和程序升温脱附谱(TDS)研究了NO₂在Ag/Pt(110)双金属表面的吸附和分解.室温下NO₂ 在Ag/Pt(110)双金属表面发生解离吸附, 生成NO(ads)和O(ads)表面吸附物种. 在升温过程中NO(ads)物种发生脱附或者进一步分解. 500 K时NO₂在Ag/Pt(110)双金属表面发生解离吸附生成O(ads)表面吸附物种. Pt 向Ag传递电子, 从而削弱Pt－O键的强度, 降低O(ads)从Pt 表面的并合脱附温度. 发现能够形成具有稳定组成的Ag/Pt(110)合金结构, 其表现出与Pt(110)-(1×2)相似的解离吸附NO₂能力, 但与O(ads)的结合明显弱于Pt(110)-(1×2). 该AgPt(110)合金结构是可能的低温催化直接分解氮氧化物活性结构.     

Optimal promotion planning—depth and frequency—for a two-stage supply chain under Markov switching demand

In considering the retailer–supplier supply chain, this paper analyzes how a retailer reasonably decides both the depth and frequency of the price discount promotion including or excluding a supplier’s inventory decision. Assuming that the promotion frequency used by the retailer is probabilistic, we model a promotion-inventory decision under an AR(1) demand with a Markov switching promotion regime. After obtaining the optimal promotion plan, our analysis also considers the behavior of the optimal promotion decision; the retailer’s price format selection, either an Every-Day-Low-Price policy (EDLP) or a Promotion policy (HiLo); and the impact of information sharing of promotion status on the system’s performance. Our results suggest that a retailer tends to overpromote if inventory cost is excluded in its promotion decision, that increasing the market share is a preferable action for both the retailer and the supplier, that total margin and price-elasticity play an important role in selecting the price format, and that the profitability for a supplier of sharing promotion information depends on the transition probabilities of the Markov switching regime.     

A stochastic manpower planning model under varying class sizes

Solution related to different types of manpower planning problems arising in different industries and organizations are very much helpful for proper planning and implementation of different objectives. Previously those type of problems are mostly solved under the deterministic set up. Gradually several scientists have developed different types of stochastic models appropriate for solving such types of problems. The present study is an attempt to develop a stochastic manpower planning model under the set up where the classes are of varying sizes and promotion occurs only on the basis of seniority. The work of second author was supported by a research fellowship from Council of Scientific and Industrial Research (Sanction No. 9/28(611)/2003-EMR-I), India.     

Revealing the unexpected promotion effect of EuOx on Pt/CeO2 catalysts for catalytic combustion of toluene

Pt/Eu₂O₃-CeO₂ materials with different Eu concentrations were prepared and applied to toluene destruction, and the remarkable promotion impact of EuO_x on Pt/CeO₂ can be observed. The characterization results reveal that the presence of EuO_x significantly enhances the redox property, lattice O concentration, and Ce³⁺ ratio of the Pt/CeO₂ material, which facilitates the dispersion and activity of Pt active sites and thus accelerates the decomposition process of toluene. Among all catalysts, a sample with an Eu content of 2.5 at.% (Pt/EC-2.5) possesses the best catalytic activity with 0.09 vol% of toluene completely destructed at 200 °C under a relatively high GHSV of 50000 h^?1. The possible reaction pathway and mechanism of toluene combustion over Pt/Eu₂O₃-CeO₂ samples are presented according to in-situ DRIFTS, which confirms that the toluene oxidation process obeys the Mars-van Krevelen mechanism with aldehydes and ketones as primary organic intermediates.     

Tuning the CO2 Hydrogenation Selectivity of Rhodium Single-Atom Catalysts on Zirconium Dioxide with Alkali Ions

Tuning the coordination environments of metal single atoms (M₁) in single-atom catalysts has shown large impacts on catalytic activity and stability but often barely on selectivity in thermocatalysis. Here, we report that simultaneously regulating both Rh₁ atoms and ZrO₂ support with alkali ions (e.g., Na) enables efficient switching of the reaction products from nearly 100 % CH₄ to above 99 % CO in CO₂ hydrogenation in a wide temperature range (240–440 °C) along with a record high activity of 9.4 mol_CO g_Rh⁻¹ h⁻¹ at 300 °C and long-term stability. In situ spectroscopic characterization and theoretical calculations unveil that alkali ions on ZrO₂ change the surface intermediate from formate to carboxy species during CO₂ activation, thus leading to exclusive CO formation. Meanwhile, alkali ions also reinforce the electronic Rh₁-support interactions, endowing the Rh₁ atoms more electron deficient, which improves the stability against sintering and inhibits deep hydrogenation of CO to CH₄.     

Promotion Effects of Nickel Catalysts of Dry Reforming with Methane

The promotion effects of nickel catalyst of dry reforming with methane were extensively investigated by means of XRD, SEM, EDX, N₂‐adsorption and H₂‐adsorption. XRD characterization indicated that good dispersion of nickel oxide and MgO promoter is achieved over γ‐Al₂O₃ support. Addition of MgO promoter effectively retards the formation of NiAl₂O₄ phase. SEM and EDX analysis exhibited that the addition of rare‐earth metal oxide CeO₂ effectively promotes the Ni metal dispersion on the surface of the catalysts despite of undesirable self‐dispersion of CeO₂ promoter. Furthermore, the nickel component is gradually dispersed on the surface of the support following the exposure to reaction gas mixture for a period of time. The addition of MgO inhibited the self‐dispersion and promotion effect of CeO₂ on Ni dispersion on the catalysts. H₂ chemisorption revealed that the addition of the alkaline oxide MgO promoter significantly prohibits the metal dispersion on the catalyst. Inappropriate promoter addition can result in sharp decrease of the metal dispersion, N₂‐adsorption indicated that oxide promoter was mostly concentrated on the outer layer of the alumina support while the nickel metal was generally dispersed in the support pores. Addition of promoters contributed to more reduction in mesopore volume.     

CO Hydrogenation over Re-Co Bimetallic Catalysts Supported over SiO2, Al2O3 and NaY Zeolite

The promotion of rhenium on the reduction of Co²⁺ ions in cobalt based samples prepared by various methods, such as, sol/gel technique, incipient wetness impregnationof Al₂O₃ and NaY, has been investigated in the CO hydrogenation. Among the samples the reducibility of the sol/gel, Re-Co/Al₂O₃ and Re-Co/NaY(IM) were the highest compared to Re-Co/NaY (IE) [8]. In addition to facilitating reduction of Co²⁺ ions, the rhenium increased the rate of reaction and the formation ofC₅₊ hydrocarbons at 10 bar pressures. The samples pretreated in various manner, revealed an about five fold increase in activity and an increase in the chain length in the NaYsupported sample while the activity and selectivity changed in various way in the sol/gel prepared samples. Simultaneously, rhenium increased the amount of olefins of low carbon numbers.In the mechanism the rhenium provides an action preventing fast deactivation of cobalt.     

Efficient promotion strategies in hierarchical organizations

The Peter principle has recently been investigated by means of an agent-based simulation, and its validity has been numerically corroborated. It has been confirmed that, within certain conditions, it can really influence in a negative way the efficiency of a pyramidal organization adopting meritocratic promotions. It was also found that, in order to bypass these effects, alternative promotion strategies should be adopted, as for example a random selection choice. In this paper, within the same line of research, we study promotion strategies in a more realistic hierarchical and modular organization, and we show the robustness of our previous results, extending their validity to a more general context. We also discuss why the adoption of these strategies could be useful for real organizations.