Steam reforming and dehydrogenation of methanol: Difference in the catalytic functions of copper and group VIII metals

Takezawa, Nobutsune; Iwasa, Nobuhiro

doi:10.1016/s0920-5861(96)00195-2

Cited by 393 publications

(325 citation statements)

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“…Assuming the reactive species being the dominant OH(ads) at 3-fold hollow sites (with a larger coordination of Zn atoms; as calculated in [17]) and  2 formaldehyde in tbt configuration, a mechanism already qualitatively suggested by Takezawa and Iwasa [47] and Takahashi et al [48] for a Cu/SiO 2 catalyst could possibly proceed via a dioxomethylene species originating from the addition of surface hydroxyls to adsorbed formaldehyde. Dioxomethylene, also the intermediate of the reverse methanol synthesis reaction, is then supposed to dehydrogenate to a formate group.…”

Section: Surface Chemistry On Pdzn During Msrmentioning

confidence: 76%

Steam reforming of methanol on PdZn near-surface alloys on Pd(1 1 1) and Pd foil studied by in-situ XPS, LEIS and PM-IRAS

Rameshan

Weilach

Stadlmayr

et al. 2010

Journal of Catalysis

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The CO2-selectivity in methanol steam reforming was investigated for a "multilayer" PdZn 1:1 surface alloy (thickness of ~1.3 nm) and for a subsurface-Zn diluted "monolayer" PdZn surface alloy, both exhibiting a 1:1 composition in the surface layer. Despite having almost the same surface layer stoichiometry, these two types of near-surface alloys exhibit different corrugations and electronic structures. The CO2-selective multilayer alloy features a lowered density of states close to the Fermi edge and surface ensembles of PdZn exhibiting a "Zn-up/Pd-down" corrugation, acting as bifunctional active sites both for reversible water activation as ZnOH and for reaction of methanol (via formaldehyde + ZnOH) toward CO2. The thermochemical stability limit of the multilayer alloy at around 573 K was determined in-situ at elevated pressures of water, methanol and CO, applying in-situ XPS, PM-IRAS spectroscopy, LEIS and AES. Above 573 K, the coordination of the surface 1:1 PdZn layer with subsurfaceZn gradually decreased by bulk diffusion of Zn "escaping" from the second and deeper layers, resulting in a transition from the CO2-selective PdZn "multilayer" state to the unselective "monolayer" state, which only catalyses methanol dehydrogenation to CO.

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Section: Surface Chemistry On Pdzn During Msrmentioning

confidence: 76%

Steam reforming of methanol on PdZn near-surface alloys on Pd(1 1 1) and Pd foil studied by in-situ XPS, LEIS and PM-IRAS

Rameshan

Weilach

Stadlmayr

et al. 2010

Journal of Catalysis

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“…A presença dos gases CH 4 , CO e CO 2 foi observada, mas suas concentrações não foram relevantes. Como grande parte do etanol foi convertida a eteno, a seletividade para hidrogênio também foi muito baixa (13% em média).…”

Section: Testes Catalíticosunclassified

“…A produção de hidrogênio através da reforma a vapor de hidrocarbonetos e álcoois 2 pode favorecer o uso deste gás como uma alternativa aos atuais combustíveis de origem fóssil, além de remover a dificuldade de estocagem e distribuição. A reforma a vapor do metanol tem sido amplamente estudada já há algum tempo 3,4 , enquanto que os estudos a respeito da reforma a vapor de etanol têm aumentado nos últimos anos [5][6][7] . O uso do etanol, obtido no Brasil, através da cana-de-açúcar, matéria-prima renovável, apresenta vantagens do ponto de vista ambiental, pois, não contribui com o aumento da concentração de CO 2 na atmosfera, tendo em vista que todo o CO 2 produzido ao longo do processo de geração de hidrogênio é, posteriormente, consumido na renovação da safra.…”

Section: Introductionunclassified

Produção de hidrogênio a partir da reforma a vapor de etanol utilizando catalisadores Cu/Ni/gama-Al2o3

et al. 2007

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catalysts were prepared by an impregnation method with 2.5 or 5% wt of copper and 5 or 15% wt of nickel and applied in ethanol steam reforming. The catalysts were characterized by atomic absorption spectrophotometry, X-ray diffraction, temperature programmed reduction with hydrogen and nitrogen adsorption. The samples showed low crystallinity, with the presence of CuO and NiO, both as crystallites and in dispersed phase, as well as of NiO-Al 2 O 3 . The catalytic tests carried out at 400 o C, with a 3:1 water/ethanol molar ratio, indicated the 5Cu/5Ni/Al 2 O 3 catalyst as the most active for hydrogen production, with a hydrogen yield of 77% and ethanol conversion of 98%.Keywords: copper-nickel catalysts; ethanol steam reforming; hydrogen. INTRODUÇÃOOs combustíveis fósseis, como petróleo e carvão, além de submeterem os países à instabilidade de preços e gerarem resíduos que comprometem as condições ambientais, um dia estarão esgotados. Deste modo, torna-se atrativa a busca de rotas alternativas para geração de energia. Entre estas, destaca-se o uso de biomassa vegetal para produção de álcool e biodiesel. Estes podem ser usados diretamente em motores à combustão ou no caso do álcool, como fonte de hidrogênio para células a combustível, gerando energia elétrica 1 . A produção de hidrogênio através da reforma a vapor de hidrocarbonetos e álcoois 2 pode favorecer o uso deste gás como uma alternativa aos atuais combustíveis de origem fóssil, além de remover a dificuldade de estocagem e distribuição. A reforma a vapor do metanol tem sido amplamente estudada já há algum tempo 3,4 , enquanto que os estudos a respeito da reforma a vapor de etanol têm aumentado nos últimos anos [5][6][7] . O uso do etanol, obtido no Brasil, através da cana-de-açúcar, matéria-prima renovável, apresenta vantagens do ponto de vista ambiental, pois, não contribui com o aumento da concentração de CO 2 na atmosfera, tendo em vista que todo o CO 2 produzido ao longo do processo de geração de hidrogênio é, posteriormente, consumido na renovação da safra.Os catalisadores de cobre e níquel suportados em alumina têm mostrado atividade e seletividade apropriadas para a produção de hidrogênio através da reforma a vapor do etanol 6,[8][9][10] . Muitos pesquisadores têm sugerido que catalisadores contendo cobre favorecem a desidrogenação de etanol a acetaldeído [11][12][13] , enquanto que os que contêm níquel favorecem a quebra da ligação carbono-carbono para formação de metano, monóxido de carbono e hidrogênio 7 . Assim, em função de possíveis interações entre cobre e níquel, que podem influenciar a atividade catalítica, este trabalho teve por objetivo o estudo da preparação e caracterização de catalisadores de níquel e cobre sobre alumina em diferentes teores e ordem de adição dos metais, bem como a avaliação catalítica dos mesmos na reação de reforma a vapor de etanol. PARTE EXPERIMENTAL Preparação dos catalisadores

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“…As unsupported pure Pd exhibits only a poor selectivity 22 , the observed high activity and selectivity for CO 2 formation was ascribed to the formation of distinct PdZn, PdIn and PdGa alloys upon reductive activation at elevated temperatures 18 . Best characterized is the Pd/ZnO system, where alloy formation has been studied and confirmed by X-ray diffraction (XRD) 18,23 , temperature-programmed reduction (TPR) 18,23 and X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) [24][25][26] .…”

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confidence: 99%

Growth and structural stability of well-ordered PdZn alloy nanoparticles

Penner

Jenewein

Gabasch

et al. 2006

Journal of Catalysis

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Despite many recent attempts to unravel the structure of novel PdZn alloys, promising catalysts in methanol steam reforming, a detailed study on the formation of Pd-Zn alloy particles and of their structural and thermal stability is still missing. We take advantage of the unique properties of epitaxially grown Pd particles embedded in layers of amorphous ZnO and mechanically stabilized by SiO 2 , and present an electron microscopy study of the preparation of well-ordered PdZn alloy nanoparticles at surprisingly low reduction temperatures. They are formed by topotactic growth on the surface of the Pd nanoparticles and are structurally and thermally stable in a broad temperature regime (473 -873 K). At and above 873K, partial decomposition of PdZn and beginning interaction with the SiO 2 support has been observed. Keywords:Thin film model catalyst, hydrogen reduction, alloy formation, electron microscopy, selected area electron diffraction ManuscriptMuch recent effort has been invested in the development of suitable catalysts for methanol steam reforming 1-15 as this is one of the most promising processes for hydrogen production with a high hydrogen-to-carbon ratio 16 . Cu/ZnO catalysts have been commercially used to produce hydrogen with high selectivity and activity 2-6 , but they suffer from deactivation at reaction temperatures above 573 K 17 . Recently, novel Pd/ZnO systems 3-15 (as well as Pd/Ga 2 O 3 and Pd/In 2 O 3 18,19 ) have attracted more attention because of their enhanced long-term and thermal stability 20,21 . As unsupported pure Pd exhibits only a poor selectivity 22 , the observed high activity and selectivity for CO 2 formation was ascribed to the formation of distinct PdZn, PdIn and PdGa alloys upon reductive activation at elevated temperatures 18 . Best characterized is the Pd/ZnO system, where alloy formation has been studied and confirmed by X-ray diffraction (XRD) 18,23 , temperature-programmed reduction (TPR) 18,23 and X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) [24][25][26] . Iwasa et al. 23 observed PdZn alloy formation upon reduction at very low T (≥ 473 K). Density functional studies revealed the close relationship between the electronic structure of PdZn and Cu-based catalysts giving rise to a similar catalytic performance in methanol steam reforming 27,28 . Comparatively few studies have been carried out on the structural characterization of the PdZn alloys by electron microscopy, and these were limited to overview imaging of powder catalysts in the as-prepared state and after hydrogen reduction, thereby mainly supporting XRD measurements 29,30 . The Pd-Zn system is known to form several stable bulk alloy phases 31 . The most important and thermally most stable is the PdZn (β1) phase, which crystallizes in a tetragonal (AuCu-type) L1 0 structure 32 . A key point for understanding the catalytic pecularities of the above-mentioned Pd-Zn alloy particles is also to determine their surface composition. Recent experiments in our laboratory 33 show that a well-orde...

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Steam reforming and dehydrogenation of methanol: Difference in the catalytic functions of copper and group VIII metals

Cited by 393 publications

References 54 publications

Steam reforming of methanol on PdZn near-surface alloys on Pd(1 1 1) and Pd foil studied by in-situ XPS, LEIS and PM-IRAS

Steam reforming of methanol on PdZn near-surface alloys on Pd(1 1 1) and Pd foil studied by in-situ XPS, LEIS and PM-IRAS

Produção de hidrogênio a partir da reforma a vapor de etanol utilizando catalisadores Cu/Ni/gama-Al2o3

Growth and structural stability of well-ordered PdZn alloy nanoparticles

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