MnOx/carbon nanotube/reduced graphene oxide nanohybrids as high-performance supercapacitor electrodes

Nanohybrids consisting of both carbon and pseudocapacitive metal oxides are promising as high-performance electrodes to meet the key energy and power requirements of supercapacitors. However, the development of high-performance nanohybrids with controllable size, density, composition and morphology remains a formidable challenge. Here, we present a simple and robust approach to integrating manganese oxide (MnOx) nanoparticles onto flexible graphite paper using an ultrathin carbon nanotube/reduced graphene oxide (CNT/RGO) supporting layer. Supercapacitor electrodes employing the MnOx/CNT/RGO nanohybrids without any conductive additives or binders yield a specific capacitance of 1070 F g−1 at 10 mV s−1, which is among the highest values reported for a range of hybrid structures and is close to the theoretical capacity of MnOx. Moreover, atmospheric-pressure plasmas are used to functionalize the CNT/RGO supporting layer to improve the adhesion of MnOx nanoparticles, which results in theimproved cycling stability of the nanohybrid electrodes. These results provide information for the utilization of nanohybrids and plasma-related effects to synergistically enhance the performance of supercapacitors and may create new opportunities in areas such as catalysts, photosynthesis and electrochemical sensors

Oxidative dehydrogenation of ethane to ethylene over LiCl/MnOx/PC catalysts

The catalytic stability of LiCl/MnOx/PC catalyst have been investigated, the deactivation mechanism was discussed. The experimental results show that ethane conversion decreases and ethylene selectivity keeps about 90% as reaction time increases. The main deactivation reasons of LiCl/MnOx/PC catalyst for oxidative dehydrogenation of ethane (ODHE) to ethylene are the transition of active species Mn2O3 to MnO species and the loss of arrive component Cl in catalyst. instead of ethane with FCC tailed-gas, the stability of LiCl/MnOx/PC catalyst has been largely improved.

Oxidative destruction of chlorobenzene and o-dichlorobenzene on a highly active catalyst: MnOx/TiO2-Al2O3

A highly active catalyst, MnOx/TiO2-Al2O3, was prepared by impregnating MnOx species on TiO2-modified Al2O3. The TiO2 species in TiO2-Al2O3 support is in a monolayer dispersion, and the MnOx species is again highly dispersed on TiO2-Al2O3 Support. The total oxidation of chlorobenzene and o-dichlorobenzene on MnOx/TiO2-Al2O3 catalyst can be achieved at 300 degreesC and 250 degreesC respectively, at the space velocity of 8000 h(-1). The activity of MnOx/TiO2-Al2O3 catalyst (Mn loading 11.2 wt%) is gradually increased in the first 10-20 h and then keeps stable at least for the measured 52 h at 16,000 h(-1). Furthermore, no chlorinated organic byproducts are detected in the effluent during the oxidative destruction of chlorobenzene and o-dichlorobenzene. It is proposed that the partially chlorinated and highly dispersed manganese oxide on a monolayer TiO2-modified Al2O3 is responsible for the high and stable activity for the total oxidation of chlorinated aromatics. (C) 2001 Academic Press.

One-step synthesis of 2-pentanone from ethanol over K-Pd/MnOx-ZrO2-ZnO catalyst

A highly active and selective K-Pd/MnOx-ZrO2-ZnO catalyst for the one-step synthesis of 2-pentanone from ethanol is described. The possible reaction pathways for ethanol reaction over K-Pd/MnOx-ZrO2-ZnO catalyst were investigated by means of TPSR, CO2- and NH3-TPD techniques. The reactions were performed in a fixed bed continuous flow reactor. Complete conversion with high selectivity for 2-pentanone, was observed under 370 similar to 390degreesC, 2 similar to 4 MPa, GHSV = 8000 similar to 10,000 h(-1) and LHSV < 1.25 h(-1) conditions. Ethanol reactions over K-Pd/MnOx-ZrO2-ZnO catalyst showed that the catalyst could catalyze dehydrogenation. aldol. dehydration and hydrogenation reactions. Both acidic and basic properties are found on the surface of K-Pd/MnOx-ZrO2-ZnO catalyst, whose multifunctionality with the combination of basic, acid and metal sites may be responsible for the efficiency of the K-PdMnOx-ZrO2-ZnO catalyst. (C) 2004 Elsevier B.V. All rights reserved.

Enhanced oxidation activity from modified ceria: MnOx-ceria, CrOx-ceria and Mg doped VOx-ceria

Ceria is an important component of catalysts for oxidation reactions that proceed through the Mars-van Krevelen mechanism, promoting activity. A paradigm example of this is the VOx–CeO2 system for oxidative dehydrogenation reactions, where vanadium oxide species are supported on ceria and a special synergy between them is behind the enhanced activity: reduction of the catalyst is promoted by ceria undergoing reduction. This leads to favourable oxygen vacancy formation and hydrogen adsorption energies—useful descriptors for the oxidation activity of VOx–CeO2 catalysts. In this paper, we examine if this promoting effect on ceria-based catalysts holds for other metal oxide modifiers and we investigate MnOn– and CrOn–CeO2(111) (n = 0 − 4) as examples. We show, combining density functional theory calculations and statistical thermodynamics that similarly to the vanadia modifier, the stable species in each case is MnO2– and CrO2–CeO2. Both show favourable energetics for oxygen vacancy formation and hydrogen adsorption, indicating that VO2–CeO2 is not the only system of this type that can have an enhanced activity for oxidation reactions. However, the mechanism involved in each case is different: CrO2–CeO2 shows similar properties to VO2–CeO2 with ceria reduction upon oxygen removal stabilising the 5+ oxidation state of Cr. In contrast, with MnO2–CeO2, Mn is preferentially reduced. Finally, a model system of VO2–Mg:CeO2 is explored that shows a synergy between VO2 modification and Mg doping. These results shed light on the factors involved in active oxidation catalysts based on supported metal oxides on ceria that should be taken into consideration in a rational design of such catalysts.

Electrochemical deposition of manganese oxide-phosphate-reduced graphene oxide composite and electrocatalysis of the oxygen evolution reaction

A composite of manganese oxide and reduced graphene oxide (rGO) is prepared in a single step electrochemical reduction process in a phosphate buffer solution for studying as an electrocatalyst for the oxygen evolution reaction (OER). The novel composite catalyst, namely, MnOx-Pi-rGO, is electrodeposited from a suspension of graphene oxide (GO) in a neutral phosphate buffer solution containing KMnO4. The manganese oxide incorporates phosphate ions and deposits on the rGO sheet, which in turn is formed on the substrate electrode by electrochemical reduction of GO in the suspension. The OER is studied with the MnOx-Pi-rGO catalyst in a neutral phosphate electrolyte by linear sweep voltammetry. The results indicate a positive influence of rGO in the catalyst. By varying the ratio of KMnO4 and GO in the deposition medium and performing linear sweep voltammetry for the OER, the optimum composition of the deposition medium is obtained as 20 mM KMnO4 + 6.5% GO in 0.1 M phosphate buffer solution of pH 7. Under identical conditions, the MnOx-Pi-rGO catalyst exhibits 6.2 mA cm(-2) OER current against 2.9 mA cm(-2) by MnOx-Pi catalyst at 2.05 V in neutral phosphate solution. The Tafel slopes measured for OER at MnOx-Pi and MnOx-Pi-rGO are similar in magnitude at about 0.180 V decade(-1). The high Tafel slopes are attributed to partial dissolution of the catalyst during oxygen evolution. The O-2 evolved at the catalyst is measured by the water displacement method and the positive role of rGO on catalytic activity of MnOx-Pi is demonstrated.

Ce-基催化剂上CH_4低温催化燃烧的研究

Ce-基催化剂在汽车尾气净化，工业废气处理，烃类重整，烃类选择加氢等方面均有广泛的应用。近几十年来关于如何制备高活性、高稳定性的非贵金属复合氧化物催化剂一直是催化研究的重要课题之一。Ce-基催化剂主要都是通过其它金属氧化物M掺杂到CeO_2中形成Ce_(1-x)M_xO（M为掺杂物）固溶体。本文选用CeO_2作为主要研究对象，用柠檬酸法有目的的引入化学特性、离子半径不同的另一组分，用x值表示各元素间的化学计量比，优化催化剂的组成、结构，来调节所合成固溶体氧化物的物理化学性质。分别以碱土金属Ca、稀土金属La以及过渡金属Ni和Mn为掺杂物制备出含其它不同离子的Ce-基催化剂；将具有较高活性的Ni_(0.7)Ce_(0.3)O负载在ZrO_2上，以CH_4燃烧为模型反应，考察催化剂活性和氧化还原性的关系。1．Ce-Ca-La-O体系单独Ca或La分别加入到CeO_2中后催化剂的活性比单独的CeO_2的活性要高出很多，完全转化温度要下降近100℃，而且它们的H_2-TPR实验也证实了其氧化还原能力有很大的提高。将Ca和La同时引入到CeO_2的复合氧化物Ce-La-Ca-O材料，其活性比无La的Ce-Ca-O的活性没有明显的提高，而且反而要比Ce-La-O的活性低，且其HZ一TPR实验也显示出和复合氧化物Ce-Ca-O的轮廓一样。2．Ce-Ni-Mn-O体系对NiO、MnO_x、CeO_2三种金属氧化物，在优化两种金属氧化物最佳配比（组成）后，在复合氧化物中掺杂第三种金属氧化物以考察第三种金属对其甲烷燃烧活性的影响。（l）CeO_2-MnO_x体系中，在Ce_(0.8)Mn_(0.2)O掺杂NiO后，发现当Ni的摩尔量为-10％时，活性提高幅度的很大，完全燃烧的温度下降了近50℃，可在550℃将CH_4完全氧化到CO_2。（2）CeO_2-NiO体系中，Ce_(0.3)Ni_(0.7)O可在530℃将CH_4完全氧化到CO_2。向其中掺杂Mn后，复合氧化物的活性反而下降，要在550oC才能将CH4完全氧化到C02。这可能是阴离子缺陷减少所致。（3）NIO一Mnox体系中，Nio，IMn090掺杂Ce后，催化活性有大幅度提高，特别是Nio．ICeyMno90（0．3三y生0．8）中催化剂的活性更高，可在530oC体系中，其中y＝0．5时更突出。3．Ni-Ce-O／ZrOZ体系（1）Ni1-x一Cex一O体系中，独立的CeOZ相促进了NIO的还原和表面积增加。（2）少量的CeOZ的掺杂明显改善了NIO对cH4完全氧化反应的活性。继续增加Ce的量催化活性弱有增加，然后下降。在Ce的掺杂量为30％时，即Nio7Ceo3O，催化活性最佳，此时甲烷完全转化的温度为530oC。（3）催化剂Ni07Ceo3O具有很好的稳定性，900oC下焙烧，还能在540oC将CH4完全氧化到COZ。（4）催化剂Pd／Ni07Ceo30的催化活性与Pd／A12O3的活性相当。（5）催化剂Ni07Ce03O负载在不同的载体上，发现ZrOZ作载体效果最佳，其次为5102，这可能是ZrOZ、5102对NIO、CeOZ相对惰性有关；而MgO、A1203虽表面积较大，但作为载体效果却不好，可能其易与NIO、CeOZ发生反应有关。（6）Nio7Ceo3O负载在ZrOZ上，提高了表面积同时促进了Nio7Ceo3O还原性，以负载量为50％时活性最好。结构分析发现有两个新相生成，Ni4Zro和CeZO3。（7）通过对比发现Nio7Ceo3O（50％）／ZrOZ体系高活性除了ZrOZ作为载体提高表面积外，Zr02和Ce在这里还起到助催化剂的作用。4．还探讨了Pr掺杂到CeO2，以及YSZ作为载体负载过渡金属氧化物在甲烷催化燃烧反应种的作用。

Oxidative dehydrogenation of ethane and propane over Mn-based catalysts

The catalytic performances of Mn-based catalysts have been investigated for the oxidative dehydrogenation of both ethane (ODE) and propane (ODP). The results show that a LiCl/MnOx/PC (Portland cement) catalyst has an excellent catalytic performance for oxidative dehydrogenation of both ethane and propane to ethylene and propylene, more than 60% alkanes conversion and more than 80% olefins selectivity could be achieved at 650 degrees C. In addition, the results indicate that Mn-based catalysts belong to p-type semiconductors, the electrical conductivity of which is the main factor in influencing the olefins selectivity. Lithium, chlorine and PC in the LiCl/MnOx/PC catalyst are all necessary components to keep the excellent catalytic performance at a low temperature.