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• Bi-modified MoVNbTeO catalysts possess enhanced tolerance toward severe reaction conditions during ODE process. • Incorporated bismuth influences on Te mobility within 6-membered channels of M1 structure. • The improved stability and activity of MoVNbTeO catalysts relates to enhanced Te surface concentration. This work presents the investigation of Bi-modified MoVNbTeO catalysts for oxidative dehydrogenation of ethane (ODE) using the combination of NAP-XPS, in situ XRD and XANES/EXAFS techniques. It was found that introduction of Bi improves the tolerance of catalysts toward severe reaction conditions (high temperature and/or enhanced ethane/oxygen ratio) resulting in a significant decrease in the degree of deactivation. In accordance with NAP-XPS data, the surface/subsurface Te concentration was maintained for Bi-containing MoVNbTeO catalysts even after treatment with a reducing reaction mixture (C 2 H 6 /O 2 >3) at temperatures up to 460 °C. In the case of the unmodified catalyst, such treatment resulted in the surface/subsurface depletion of Te due to the reduction into the Te° state followed by its sublimation into the gas phase. The incorporation of Bi within extended six-membered channels of the M1 structure was suggested based on XANES/EXAFS data. Such incorporation probably influences the mobility of Te within channels, resulting in the limitation of Te diffusion from the particle bulk to the surface. The improved tolerance of catalytically active M1 phase toward severe reaction conditions was confirmed by in situ XRD data during heating in a mixture of 8 wt % C 2 H 6 /He. [ABSTRACT FROM AUTHOR]

From macro- to nano-engineering of a promising CeO 2 -ZrO 2 -doped NiO-Al 2 O 3 /Ni-foam catalyst has been demonstrated for the oxidative dehydrogenation of ethane to ethylene (ODE), through facial wet chemical etching of a Ni-foam followed post modification with CeO 2 and ZrO 2 . The NiO-Al 2 O 3 /Ni-foam (denoted as NANF) achieved a high ethane conversion of 25.2% but with a very low ethylene selectivity of 43.1% at 450 °C. ZrO 2 -doping of the NANF led to a remarkable improvement in the ethylene selectivity but serious deterioration of activity while the CeO 2 -doping showed an opposite effect. Co-doping of the NANF using optimal amount of CeO 2 and ZrO 2 markedly promoted not only the activity but also the selectivity to ethylene. For example, over the 1CeO 2 -5ZrO 2 -NANF (CeO 2 :1 wt%, ZrO 2 :5 wt%) catalyst, a high ethane conversion of 40.3% was obtained with a 60.6% ethylene selectivity for a feed gas of C 2 H 6 /O 2 /N 2 = 1/1/8 at 500 °C and a gas hourly space velocity of 18,000 cm 3 g −1 h −1 , corresponding to a high ethylene productivity of 510 g Ethylene kg cat −1 h −1 . In nature, co-doping with CeO 2 and ZrO 2 synergistically tamed the NiO for selective H-abstraction of the ethane molecules other than over oxidation of them. [ABSTRACT FROM AUTHOR]

X-ray Photoelectron Spectroscopy (XPS) has been used to investigate titania-supported vanadyl phosphates (VOPO4) with respect to thermal treatments and catalytic runs in the oxidative dehydrogenation (ODH) of ethane. The surface characterization of monolayer (9.6 wt.%) and sub-monolayer (6.5 wt.%) VOPO4 samples has been performed after calcination in air and after catalytic tests at different temperature (T=450 and 550 °C). Vanadyl phosphates are well dispersed on the TiO2 surface. The oxidation state, surface distribution and evolution of vanadium and titanium species have been analysed by the V 2p3/2 and Ti 2p3/2 peak-fitting procedures. The interaction with the support allows the formation of different vanadium species, V5+ phosphate, V5+ and V4+ oxide species, whose relative fraction depends both on the nature of the support and on the samples treatments. The amount of tetravalent vanadium species in the samples progressively increases as effect of the temperature. Surface modifications of the titania support are evidenced by XPS after impregnation, calcination and catalytic tests. [Copyright &y& Elsevier]

Combinatorial methodologies are emerging as powerful tools in heterogeneous catalysis. Previously, we have established a strong correlation between catalysts prepared as thin films for high-throughput primary screening to those prepared in bulk for secondary screening in a multi-channel fixed bed (MCFB) microreactor for the ethane oxidative dehydrogenation process [Proc. Natl. Acad. Sci. U.S.A. 96 (1999) 11077]. Numerous catalysts with improved performance over literature compositions were also reported. With this high-throughput technology, tens of thousands of new compositions have been synthesized and tested. In this paper, we describe in detail the discovery of a new class of catalysts with extraordinary performance improvements. These catalysts contain Ni, Nb, and Ta or Co mixed oxides. The respective ternary systems were first screened in a thin film form (∼200 μg catalyst loading). Then they were scaled up to 50 mg level and screened in an MCFB microreactor. The optimal compositions were Ni0.62Ta0.10Nb0.28Ox and Ni0.62Ta0.20Nb0.18Ox. They convert 20.5% of ethane with 86.2% selectivity to ethylene and 20.0% of ethane with 86.1% selectivity to ethylene at 300 °C, respectively, as compared to 3.3% conversion of ethane with 82.9% selectivity to ethylene for the state-of-the-art catalyst Mo0.72V0.26Nb0.02Ox under identical testing conditions. One of these compositions, Ni0.62Ta0.10Nb0.28Ox, was further scaled up to 5 g and tested in a conventional bench scale reactor. The performance improvement is consistent with measurements made on the MCFB microreactor. [Copyright &y& Elsevier]

[Display omitted] • Al 2 O 3 -Supported NiO improve the catalytic performance of bulk NiO in ethane ODH. • NiO-support interaction determine selectivity to ethylene. • NiO-support interaction determine the reducibility of catalysts. • High selectivity related also with a higher number of nickel and oxygen. vacancies. Nickel oxides supported on γ-alumina (Ni-loading from 5 to 30 wt% NiO) have been synthesized and tested in the oxidative dehydrogenation (ODH) of ethane in order to determine the importance of the NiO-support interaction. The best performance was achieved by the catalyst with 15 wt% NiO; higher NiO-loadings lead to the formation of unselective bulk-like NiO and lower Ni-loadings present high proportion of free alumina surface sites. The presence of oxalic acid and/or niobium in the synthesis gel resulted in the formation of NiO particles with similar size, but higher crystallinity and reducibility than the standard 15 wt% NiO catalyst. The obtained results have revealed that, in addition to NiO crystal size, the nickel oxide-support interaction determines the catalytic performance of these catalysts. [ABSTRACT FROM AUTHOR]