Direct conversion of syngas to DME as a green fuel in a high pressure microreactor: Influence of slurry solid content on characteristics and reactivity of washcoated CuO–ZnO–Al2O3/HZSM-5 nanocatalyst

Microchannels of a stainless steel microreactor were successfully washcoated with slurry of Cu–ZnO–Al₂O₃/HZSM-5 (CZAZ) nanocatalyst with different concentrations (10, 20 and 30 wt.%). The properties of nanocatalyst and the washcoated microchannels were investigated by XRD, FESEM, N₂ physisorption, FTIR, EDX-Dot mapping and EDX-Line mapping analysis. The best adherence was observed for 20 wt.% catalyst which has a uniform coating, almost no cracks and homogenous dispersion of copper and zinc. Trend of weight gain during 10 soaks in catalyst slurry was very slow for 10 wt.% but faster for 20 and 30 wt.%. Low amount of weight gain was observed for the last soaks of catalyst slurry in the case of 30 wt.% washcoating. The performance of microreactor with different slurry concentrations were evaluated in direct synthesis of DME at 200–300 °C, 60–150 cm³/min and 40 bar. Regardless of slurry concentration, the microreactor exhibited a better reactivity in comparison to fixed-bed reactor performance. Among three different slurry concentrations, 20 wt.% catalyst slurry revealed the best reactivity in direct DME synthesis. The reduction in reactor performance at higher flow rates was significant in the fixed-bed reactor while microreactor, particularly 20 wt.% washcoated channels, revealed less drastic reduction.     

低温电化学合成氨催化剂研究进展

传统的高温高压Haber-Bosch法合成氨工艺消耗大量化石能源,并排放大量的温室气体。在常温常压下通过电化学方法将氮还原成氨是一种潜在策略。电化学固氮领域的主要研究方向之一是通过开发有效的氮还原催化剂来提高电流效率和氨产率。基于对50多篇文献的分析,本文综述了近20年来电化学合成氨催化剂的研究进展,通过对低温下电化学合成氨的金属基和非金属基不同催化剂以及催化效率进行总结和比较,关注具有高法拉第效率和高氨产率的几种金基催化剂,以及电解质性质、掺杂改性对于开发高效的过渡金属基、非金属基催化剂的重要性,对比分析了这3类催化剂的优缺点以及发展潜力。     

柴油机颗粒物-氮氧化物减排系统贵金属催化剂研究进展

汽车排放的氮氧化物(NO_x)和碳烟颗粒物(PM)会对环境和人类健康造成严重的危害,但是现有的技术仅能对NO_x或PM的排放实现单独净化。与其他尾气净化技术相比,柴油机颗粒物-氮氧化物减排系统(DPNR)兼具NO_x和PM净化效果,成为下一代NO_x和PM协同净化的首选催化系统。本文综述了DPNR催化反应机理以及系统中NO_x和PM系统净化用的贵金属催化剂的研究进展;总结了Pt基催化剂在不同条件下同时消除NO_x和PM的催化活性,系统地讨论了Ba、K、Mn等元素掺杂对Pt基催化剂的影响。同时归纳比较Ag基、Ru基与Pt基催化剂在PM氧化和NO_x消除方面的区别,为研究开发同时消除NO_x和PM的高效催化剂提供参考。     

铂族金属单原子催化剂的制备、表征技术研究进展

单原子催化不仅将多相催化领域研究从纳米尺度深入到了原子尺度,有助于从原子层次研究和认识非均相催化反应过程,也使得进一步提高活性铂族金属原子利用率、降低催化剂成本成为可能。基于国内外多年来在单原子催化领域取得的研究成果,介绍了铂族金属单原子催化剂的制备方法与表征技术,总结归纳了不同制备方法的参数控制关键、适用范围,以及不同表征数据分析、存在的问题与挑战。在不同表征技术融合创新的基础上,对于铂族金属单原子催化剂的可控制备技术尽早实现工业化应用提出了展望。     

A Review on Metal-support Interaction in Automotive Catalysts

TWC-equipped exhausts are widely used in gasoline-fueled vehicles to meet stringent emission regulations. The main components in TWCs are precious metals such as palladium (Pd), platinum (Pt), and rhodium (Rh) as the active component, and inorganic oxides such as γ-alumina (Al 2 O 3 ), ceria (CeO 2 ), zirconia (ZrO 2 ) and ceria-zirconia (CeO 2-ZrO 2 ) are used as the support. Interaction of precious metals and support plays an important role in the thermal stability and catalytic performance of TWCs. The support can improve the dispersion of precious metals and suppress the sintering of precious metals at high temperature. In the same, precious metals can also enhance the redox performance and oxygen storage capacity of support. This paper reviews the reaction phenomenon and mechanism of precious metals (Pt, Pd, Rh) and supports such as Al 2 O 3 , CeO 2-based composite oxides.     

Improved methane oxidation activity of P-doped γ-Al2O3 supported palladium catalysts by tailoring the oxygen mobility and electronic properties

Micro-mesoporous P-doped γ-Al₂O₃ with cluster morphology was obtained via an efficient ultrasound-assisted sol-gel process and taken as carrier to construct palladium catalysts for methane oxidation. It was revealed that the structure and properties of catalysts were significantly influenced by the phosphorus precursors with diverse valence and acidity. Dissimilar reducibility of surface hydroxyl and oxygen species is observed in the catalysts derived from different phosphorus sources, indicating the difference in the oxygen mobility and the capacity of the catalysts to convert intermediate CO. The behavior of charge-transfer transition and d-d transition, the transfer ability of electrons from palladium particles into the antibonding 2π* orbitals of CO, together with the surface acidity and electronic density of palladium species was likewise tailored, which demonstrated the metal-support interaction could be tuned, making palladium species behave with diverse status and electronic structures. The optimized properties cooperatively provided an enhancement in catalytic performance of P-containing catalysts.     

Structure and oxygen storage capacity of Pd/Pr/CeOe-ZrO2 catalyst： effects of impregnated praseodymia

Praseodymium （Pr） was impregnated to CeO2-ZrO2 solid solution by an impregnation method. The as-obtained Pr modi- fied CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts. The structure and reducibility of the fresh and hydrother- really aged catalysts were characterized by X-ray diffraction （XRD）, Raman, X-ray photoelectron spectroscopy （XPS）, CO chemi- sorption and H2 temperature-programmed reduction （H2-TPR）. The oxygen storage capacity （OSC） was evaluated with CO serving as probe gas. Effects of impregnated Pr on the structure and oxygen storage capacity of catalysts were investigated. The results showed that the aged Pr-impregnated samples had much higher OSC and better reducibility than the unmodified ones. The scheme of structural evolutions of the catalysts with and without Pr was also established. Partial of the impregnated Pr diffused into the bulk of CeO2-ZrO2 during ageing, which inhibited the sintering, and increased the amount of oxygen vacancies in CeO2-ZrO2 support. Furthermore, those impregnated Pr species which covered on the surface of the support obstructed the strong metal-support interaction between Pd and Ce so as to reduce the encapsulation of Pd as well as the back spill-over of the oxygen during the catalytic process.     

Pd含量对催化剂加氢脱氧性能的影响

采用浸渍法制备了系列不同Pd含量的催化剂,通过XRD、H_2-TPR、BET等分析表征技术和以油酸甲酯为模型化合物的加氢反应体系,考察了Pd含量对催化剂催化加氢脱氧性能和催化加氢饱和性能的影响。结果表明,适量的Pd有助于提高Pd在载体上的分散度,减小其与载体的相互作用强度,从而可提高催化剂的加氢脱氧性能和加氢饱和性能,也可使油酸甲脂的加氢脱氧方式越容易按加氢脱羧或脱羰的方式进行;2%Pd/γ-Al_2O_3催化剂的催化加氢脱氧转化率和加氢饱和转化率均为100%,且加氢脱氧方式完全按加氢脱羧或脱羰方式进行。     

热老化对Pd/Al_2O_3选择性催化NH_3反应性能的影响(英文)

研究了在三效催化反应过程中热老化对Pd/Al_2O_3选择性催化NH_3反应性能的影响。在稀/富循环流中进行稳态实验,采用X射线衍射(XRD)、BET比表面积、X射线光电子能谱(XPS)、拉曼光谱(Raman)和透射电镜(TEM)对催化剂的物理化学性质进行表征。结果表明,高温热老化导致活性金属钯的分散度降低、颗粒尺寸增大、Pd~(2+)活性物种的相对比例下降,这些微结构变化促使催化剂的三效活性降低、氨选择性增加。热老化诱导催化剂表面活性钯颗粒明显增大,较大的钯颗粒有助于NO解离生成活性氮物种,进而与氢反应生成NH_3。