NO reduction, CO and hydrocarbon oxidation over combustion synthesized Ag/CeO2 catalyst

The combustion technique produces ionically dispersed Ag on a nano-crystalline CeO2 surface. The catalysts thus produced were characterized by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. Catalytic properties towards NO reduction, CO and hydrocarbon oxidation have been investigated using the temperature programmed reaction technique in a packed bed tubular reactor. These results are compared with alpha-Al2O3 supported finely divided Ag metal particles synthesized by the same method. Both oxidation and reduction reactions over Ag/CeO2 have been observed to occur at lower temperatures compared to Ag/Al2O3. The rate and turnover frequency of the NO+CO reaction over 1% Ag/CeO2 are 56.3 mu mol g(-1) s(-1) and 0.97 s(-1) at 225 degrees C respectively. Activation energy (E-a) values are 71 and 67 kJ mol(-1) for CO+O-2 and NO+CO reactions, respectively, over 1% Ag/CeO2 catalyst.

Formation of Ce1-xPdxO2-delta solid solution in combustion-synthesized Pd/CeO2 catalyst: XRD, XPS, and EXAFS investigation

Pd/CeO2 (1 at. %) prepared by the solution-combustion method shows a higher catalytic activity for CO oxidation and NO reduction than Pd metal, PdO, and Pd dispersed over CeO2 by the conventional method. To understand the higher catalytic properties, the structure of 1 at. % Pd/CeO2 catalyst material has been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. The diffraction lines corresponding to Pd or PdO are not observed in the high-resolution XRD pattern of 1 at. % Pd/CeO2. The structure of 1 at. % Pd/CeO2 could be refined for the composition of Ce0.99Pd0.01O1.90 in the fluorite structure with 5% oxide ion vacancy. Pd(3d) peaks in the XPS in I at. % Pd/CeO2 are shifted by 3 eV indicating that Pd is in a highly ionic +2 state. EXAFS studies show the average coordination number of 3 around Pd2+ ion in the first shell of 1 at. % Pd/CeO2 at a distance of 2.02 Angstrom, instead of 4 as in PdO. The second shell at 2.72 Angstrom is due to Pd-Pd correlation which is larger than 2.69 Angstrom in PdO. The third shell at 3.31 Angstrom having 7 coordination is absent either in Pd metal or PdO, which can be attributed to -Pd2+-Ce4+- correlation. Thus, 1 at. % Pd/CeO2 forms the Ce1-xPdxO2-delta type of solid solution having -Pd2+-O-2-Ce4+- kinds of linkages.

Recent advances in auto exhaust catalysis

In last 30 years innovative research in the area of auto exhaust catalysis is being developed and CeO2 has been found to play a major role in this area due to its unique redox properties. In this review, auto exhaust emission and its impact on earth’s environment, global concern and recent advances in science and technology in automotive exhaust catalysis have been documented. A new preparative method of dispersing metal ions by solution combustion technique over CeO2 and TiO2 resulting mainly Ce1−xMxO2−δ, Ti1−xMxO2−δ and Ce1−x−yTixMyO2−δ (M = Pd, Rh and Pt) catalysts, structure of these materials, their catalytic properties towards auto exhaust catalysis, structure–property relation and mechanism of catalytic reactions are accounted here. In these materials, metal ions are incorporated into substrate matrix to a certain limit in the solid solution form and we have established a new direction in heterogeneous catalysis by turning to the concept of dispersed metal ions as catalytically active sites from the conventionally nurtured idea of metal particles as active centers for catalysis.

Nanocatalysis and Prospects of Green Chemistry

Designing and developing ideal catalyst paves the way to green chemistry. The fields of catalysis and nanoscience have been inextricably linked to each other for a long time. Thanks to the recent advances in characterization techniques, the old technology has been revisited with a new scope. The last decade has witnessed a flood of research activity in the field of nanocatalysis, with most of the studies focusing on the effect of size on catalytic properties. This led to the development of much greener catalysts with higher activity, selectivity and greater ease of separation from the reaction medium. This Minireview describes the emerging trends in the field of nanocatalysis with implications towards green chemistry and sustainability.

The dual role of borohydride depending on reaction temperature: synthesis of iridium and iridium oxide

Temperature dependent reaction products are observed when borohydride is present in aqueous solutions containing Ir3+. At temperatures of 40 degrees C and above, metallic iridium is formed while under ambient conditions of 25 degrees C, borohydride results in an alkaline environment that helps in hydrolyzing the precursor to form IrO2. The Ir foams and IrO2 are subsequently used to study their catalytic properties.

Noble metal ion substituted CeO2 catalysts: Electronic interaction between noble metal ions and CeO2 lattice

In last 40 years, CeO2 has been found to play a major role in the area of auto exhaust catalysis due to its unique redox properties. Catalytic activity is enhanced when CeO2 is added to the noble metals supported Al2O3 catalysts. Reason for increase in catalytic activity is due to higher dispersion of noble metals in the form of ions in CeO2. This has led to the idea of substitution of noble metal ions in CeO2 lattice acting as adsorption sites instead of nanocrystalline noble metal particles on CeO2. In this article, a brief review of synthesis, structure and catalytic properties of noble metal ions dispersed on CeO2 resulting in noble metal ionic catalysts (NMIC) like Ce1-xMxO2-delta, Ce1-x-yTixMyO2-delta, Ce1-x-yZrxMyO2-delta, Ce1-x-ySnxMyO2-delta and Ce1-x-yFexMyO2-delta (M = Pt, Pd, Rh and Ru) are presented. Substitution of Ti, Zr, Sn and Fe in CeO2 increases oxygen storage capacities (OSC) due to structural distortion, whereas dispersion of noble metal ions in Ti, Zr, Sn and Fe substituted CeO2 supports increase both OSC and catalytic activities. Electronic interaction between noble metal ions and CeO2 in NMICs responsible for higher OSC and higher catalytic activities is discussed. (C) 2015 Published by Elsevier B.V.

Magnetic Cross-Linked Enzyme Aggregates (mCLEAs) of Candida antarctica Lipase: An Efficient and Stable Biocatalyst for Biodiesel Synthesis

Enzyme-catalyzed production of biodiesel is the object of extensive research due to the global shortage of fossil fuels and increased environmental concerns. Herein we report the preparation and main characteristics of a novel biocatalyst consisting of Cross-Linked Enzyme Aggregates (CLEAs) of Candida antarctica lipase B (CALB) which are covalently bound to magnetic nanoparticles, and tackle its use for the synthesis of biodiesel from non-edible vegetable and waste frying oils. For this purpose, insolubilized CALB was covalently cross-linked to magnetic nanoparticles of magnetite which the surface was functionalized with –NH2 groups. The resulting biocatalyst combines the relevant catalytic properties of CLEAs (as great stability and feasibility for their reutilization) and the magnetic character, and thus the final product (mCLEAs) are superparamagnetic particles of a robust catalyst which is more stable than the free enzyme, easily recoverable from the reaction medium and reusable for new catalytic cycles. We have studied the main properties of this biocatalyst and we have assessed its utility to catalyze transesterification reactions to obtain biodiesel from non-edible vegetable oils including unrefined soybean, jatropha and cameline, as well as waste frying oil. Using 1% mCLEAs (w/w of oil) conversions near 80% were routinely obtained at 30°C after 24 h of reaction, this value rising to 92% after 72 h. Moreover, the magnetic biocatalyst can be easily recovered from the reaction mixture and reused for at least ten consecutive cycles of 24 h without apparent loss of activity. The obtained results suggest that mCLEAs prepared from CALB can become a powerful biocatalyst for application at industrial scale with better performance than those currently available.

Characterization of cobalt based TPP-bipy coordination polymer

Comunicación a congreso: Póster presentado en The 4th EuCheMS Chemistry Congress (4ECC), Prague, Czech Republic, August 26–30, 2012

Crystal structure and characterization of a new μ-oxo bridged iron porphyrin

Comunicacion a congreso: Póster presentado en VIII Reunión Científica de Bioinorgánica – Bioburgos 2013 (Burgos, 7 al 10 de julio de 2013)

Vanadyl arsenates as catalysts for selective oxidation of organic sulfides and alkenes

artículo científico (postprint)

Catalisadores à base de Mg/La e de Al/La para a produção de biodiesel a partir de óleos refinados e ácidos

A crescente preocupação com a preservação do meio ambiente aliada às perspectivas de esgotamento das fontes de energia obtidas dos combustíveis fósseis tem impulsionado a indústria a desenvolver combustíveis alternativos a partir de recursos renováveis e processos ambientalmente não agressivos. O biodiesel, uma mistura de ésteres de ácidos graxos obtida pela transesterificação catalítica de óleos vegetais com álcoois de cadeia curta (metanol ou etanol) é um combustível alternativo importante, pelo fato das suas propriedades (índice de cetano, conteúdo energético e viscosidade) serem similares às do diesel obtido a partir do petróleo. No presente trabalho, a transesterificação do óleo de soja com metanol para a produção de biodiesel foi estudada em presença de catalisadores sólidos à base de Mg/La e Al/La com propriedades ácido-básicas. Catalisadores de Mg/La com uma relação molar Mg/La igual a 9:1 foram preparados por coprecipitação utilizando três métodos que se diferenciavam quanto ao tipo de agente precipitante e a temperatura de calcinação. O catalisador preparado com (NH4)2CO3/NH4OH como agente precipitante e calcinado a 450 C apresentou as melhores características físico-químicas e catalíticas. Catalisadores à base de Mg/La e Al/La com diferentes composições químicas foram sintetizados nas condições de preparo selecionadas. O comportamento catalítico destes materiais foi investigado frente à reação de transesterificação do óleo de soja com metanol. O catalisador de Al/La com uma relação molar Al/La igual a 9:1 mostrou o melhor desempenho catalítico (rendimento em ésteres metílicos igual a 84 % a 180 C) e pode ser reutilizado por pelo menos três ciclos de reação. Também foram realizados testes catalíticos na presença do óleo de soja com 10 % de ácido oleico verificando-se que os catalisadores utilizados possuem sítios capazes de catalisar as reações de transesterificação e esterificação

Facile route to fabricate large-scale silver microtubes

Large-scale uniform Ag microtubes with high length diameter ratios have been first successfully synthesized by a facile approach, using low-cost super fine glass fibers as templates. The samples were characterized by SEM and XRD. The investigations showed that calcining or adding of PEG-1000 and alcohol could greatly improve the mechanical strength of the sample. Especially the products exhibited favorable catalytic properties during the degradation of Rhodamine B by NaBH4. (c) 2007 Elsevier B.V. All rights reserved.

新型固体酸催化剂的设计制备及其性能研究

酸催化剂可以用来催化烃类裂解、重整、异构、烯烃水和、烷基化和酯化等重要化学反应，在石油炼制和石油化工领域有极其广泛的应用。与传统液体酸相比，新型固体酸催化剂具有容易与反应物和产物分离、易再生、不腐蚀反应器、环境污染少等优点，因此研究开发环境友好的新型固体酸催化剂成为国际上催化领域研究的热点。本论文研究新型固体酸催化剂的酸强度和延长催化剂使用寿命的方法，具有很高的工业实用价值和理论意义。 研究了固体酸催化剂在正己烷异构化和异丁醇脱水这两个反应的催化活性，结果显示：1）复合超强酸催化剂，2）Hβ及其负载催化剂，3）负载杂多酸，4）ZrO2·Bi2O3、ZrO2·CaO四类催化剂酸强度较高且强度大小为:1＞2≈3＞4。氢溢流的引入提高了Pt-SO42-/ ZrO2催化剂在反应中的催化活性,一定程度上弥补了酸强度的不足，也使一些原本没活性的催化剂有了一定的活性，如MOO3催化剂。 研究了异丁烷在12wt%V2O5/γ-Al2O3催化剂上脱氢制异丁烯的反应和异丁烯在50wt%HSiW/SiO2、Amberlyst-15和Amberlyst-35树脂催化剂上的迭代反应，均获得了较好的催化活性。 首次将催化剂表面的疏油性应用在酸催化领域，在硅胶负载的钨硅酸中掺杂不同含量聚四氟乙烯制备出具有一定疏油性的催化剂，用异丁烯迭代反应作为探针反应着重研究了催化剂表面的适当疏油性对催化剂的寿命和产物选择性的影响。结果显示催化剂表面的疏油性不仅提高了C8 =的选择性并且有效延长催化剂寿命。这主要是由于催化剂表面具有适当的疏油性，反应的中间产物C8=易于从具有疏油性的表面脱附，减少了C8=继续在催化剂表面进行连续反应生成C12=和C16=的机会，因此提高了C8=的选择性。这可能促进了更高的产物选择性，低的积炭量和较长的催化剂使用寿命。 研究了催化剂表面的疏水疏油性在醋酸与正丁醇的酯化反应中的应用。结果显示，当酯化反应产物为液相时，催化剂表面的疏水疏油性非常有利于产物从催化剂表面脱附，能有效提高正丁醇的转化率。 关键词：酸强度，钨硅酸，聚四氟乙烯，疏油性，寿命