Bimetallic catalysts: Requirements for stabilizing PVP removal depend on the surface composition

H. Ziaei-Azad, N. Semagina
Applied Catalysis A: General 482, 327-335
Publication year: 2014


  • Effect of PVP removal on catalysis by bimetallic nanoparticles was studied.
  • Pd–Ir catalysts stabilized by PVP were tested after calcination treatments.
  • Ring opening activity of catalysts with Ir-rich surface does not require clean surface.
  • Pd-rich catalysts must be cleaned before the catalysis.


Alloy and core–shell bimetallic Pd–Ir nanoparticles stabilized by polyvinylpyrrolidone (PVP) and deposited on alumina were subjected to PVP removal via thermal treatments. Less than 25% of the PVP was removed at 200 °C calcination/375 °C reduction, while the 400 °C calcination eliminated over 95% of PVP. The treated samples were tested in the gas-phase ring opening of indane at 350 °C. The cleaning was paramount for the bimetallic catalysts with Pd-rich surfaces that only exhibited activity after 400 °C calcination, while the catalysts with Ir-rich surfaces were similarly active irrespective of the presence or absence of the PVP residuals. For the CO chemisorption, complete cleaning was required for all catalysts. The study is supported by CO-DRIFTS, CO-TPD, indane-TPD, carbon analysis, TEM, CO chemisorption and catalytic measurements, and shows that the necessity to remove PVP depends on the nature of metals in bimetallic catalysts and their surface arrangements. © 2014 Elsevier, reprinted with permission.

Suppression of addition reactions during thermal cracking using hydrogen and sulfided iron catalyst

F.K. Habib, C. Diner, J.M. Stryker, N. Semagina, M.R. Gray
Energy & Fuels 27 (11), 6637-6645
Publication year: 2013

Due to the complexity of the vacuum residue fraction of petroleum and bitumen, a model compound was used to probe cracking and addition reactions in the liquid phase. Hydrogenation reactions were conducted in a batch microreactor at 430 °C, 13.9 MPa H2 for 30 min using a solution of 1,3,6,8-tetrahexylpyrene (THP) in tetralin. Sulfided iron was prepared on α-alumina, γ-alumina, and glass beads as support materials. The hypothesis of this study was that addition reactions can be suppressed under hydrogenation conditions by using iron sulfide as a low-activity catalyst in the presence of hydrogen gas and a hydrogen donor solvent, by saturating olefin intermediates. The products were analyzed by high performance liquid chromatography, gas chromatography, matrix-assisted laser desorption ionization mass spectrometry, and proton nuclear magnetic resonance spectroscopy to investigate conversion and product distribution for different catalysts and without added catalyst. The results show that sulfided iron can give significant suppression of addition reactions, decreasing from 63 mol % for the noncatalytic reaction to 13 mol % under catalytic conditions, and shifting the selectivity toward cracking, without competitive hydrogenation of the aromatics. The catalysts were characterized by measuring bulk and surface composition, and by scanning electron microscopy before and after the reaction. The data show that catalyst does not have an impact on conversion; therefore, the data do not support the claim that free radicals are efficiently hydrogenated. The results confirm the presence of iron sulfide on the catalyst surface and a change in its crystalline structure from pyrite to pyrrhotite during reaction. This study shows the value of using a low-cost iron catalyst, as compared to the commercial nickel-based catalysts, as an additive to reduce the amount of coke formation in thermal cracking processes conducted in the presence of hydrogen. © American Chemical Society, reprinted with permission.

Size-and structure-controlled mono-and bimetallic Ir–Pd nanoparticles in selective ring opening of indan

H. Ziaei-Azad, C.X. Yin, J. Shen, Y. Hu, D. Karpuzov, N. Semagina
Journal of Catalysis 300, 113-124
Publication year: 2013


  •  Size- and structure-controlled Pd/Ir mono- and bimetallic particles were synthesised.
  •  Two contiguous surface Ir atoms form an active site in indan ring opening (RO).
  •  Pd serves as an inert surface diluting or Ir dispersing agent.
  •  Pd(core)Ir(shell) gives 19% higher selective RO yield than industrial PtIr catalyst.


Nearly monodispersed 1.6 nm Ir, 2.3 nm Pd nanoparticles, 2.7 nm Pd(core)–Ir(shell) and 2.2 nm Pd–Ir alloys with mixed surface atoms were synthesised in the presence of polyvinylpyrrolidone (PVP) and studied in the atmospheric ring opening of indan. The nanoparticles and supported catalysts were characterised by UV–vis spectroscopy, TGA, TEM, EDX, TPR, XPS, ISS and XANES. The nanoparticle size and structure control allowed insights into the bimetallic catalyst functioning. As soon as two contiguous surface Ir atoms exist on the nanoparticle surface, they display the same catalytic properties, most likely through the dicarbene ring-opening mechanism. Palladium serves only as a dispersing agent in Pd(core)–Ir(shell) structures providing 100% Ir dispersion, or as an inert surface diluting metal in Pd–Ir formulations with mixed nanoparticle surface. The Pd–Ir core–shell structure allows maximum selective ring-opening yield, which is 19% higher than that for the industrial Pt–Ir catalyst. © 2013 Elsevier, reprinted with permission.

PVP-stabilized mono-and bimetallic Ru nanoparticles for selective ring opening

J. Shen, X. Yin, D. Karpuzov, N. Semagina
Catalysis Science & Technology 3 (1), 208-221
Publication year: 2013

Selective ring opening of naphthenic molecules in oil upgrading should result in no loss in molecular weight. Benzocyclopentane (indan) ring opening was studied under hydrogen atmospheric pressure at 609 K over poly-(vinylpyrrolidone)-stabilized Ru, Ir and Pd monometallic and Ru–Ir and Ru–Pd bimetallic nanocatalysts prepared by simultaneous reductions. The particle size (mostly within 2 nm) and their monodispersity were confirmed by transmission electron microscopy, while X-ray photoelectron spectroscopy indicated the bimetallics’ alloy structure. Pd catalysts displayed the lowest activity in the ring opening; Ru showed the highest formation of undesired o-xylene and lights. Monometallic Ir displayed the highest activity and selectivity toward 2-ethyltolueneand n-propylbenzene. In bimetallic structures, higher Ir content led to improved catalytic performance. Next to the monometallic Ir catalyst, the newly developed Ru1Ir4/γ-Al2O3 catalyst (with 1 : 4 molar ratio of Ru to Ir) displayed superior single cleavage selectivity as well as lower cracking activity compared to industrial Pt–Ir catalysts at a comparable indan conversion. The study can pave the way in the development of Pt-free Ru-containing catalystswith narrow size distributions for selective ring opening, especially taking into consideration a possibility of their higher S-resistance as compared to the Pt catalysts. © 2013 The Royal Society of Chemistry, reproduced with permission.

Iridium-and platinum-free ring opening of indan

J. Shen, N. Semagina
ACS Catalysis 4 (1), 268-279
Publication year: 2013

A 3- and 2-fold increase in selectivities toward 2-ethyltoluene and n-propylbenzene, respectively, in indan ring opening (RO) was achieved by introducing palladium to the ruthenium catalyst. The product selectivities for the Ru–Pd system with the 4:1 molar ratio were the same as those for monometallic iridium, known for its outstanding single cleavage selectivity; the lights formation was suppressed as compared with the monometallic platinum catalyst. A further increase in the Pd amount did not result in the selectivity improvement and brought down the activity to the low level of Pd. The bimetallic catalysts were synthesized in the presence of poly-(vinylpyrrolidone). The bimetallic systems revealed sintering resistance up to 400 °C, as compared with their monoforms. The indan RO activity was maximized after precalcination at 200 °C. The suggested nanoparticles’ bimetallicity was consistent with the results of CO-TPD, CO–DRIFTS, thermal stability tests, and a chemical probe reaction (olefin hydrogenation, in which only Pd is active). The Pd–Ru system is envisioned as a viable alternative to monometallic Ir for RO.  © 2014 American Chemical Society, reprinted with permission.

Electrochemical behavior of tungsten carbide-based materials as candidate anodes for solid oxide fuel cells

A. Torabi, T.H. Etsell, N. Semagina, P. Sarkar
Electrochimica Acta 67, 172-180
Publication year: 2012

Tungsten carbide-based electrodes under mixed hydrogen–methane and methane fuels have been investigated as potential anode materials for solid oxide fuel cell (SOFC) application. Firstly, it was shown that hydrogen is not a suitable fuel for the carbide-based materials. A conventional WC–YSZ composite and a carbide infiltrated porous YSZ support were then studied. Ac impedance spectroscopy revealed that the ohmic resistance and the charge-transfer polarization of these cells were reasonably low. The chemical reaction polarization, however, was relatively large, particularly under methane fuel. The carbide-based electrodes were then modified by incorporation of ceria and/or ruthenium. Not only did the co-existence of CeO2 and Ru synergically enhance the cell performance, more importantly it also greatly improved the stability of the polarized cell. Although bulk phase analysis confirmed the presence of a minor amount of tungsten oxide, surface analysis showed that the oxide phase remained superficial. It was then proposed that surface oxidation of the carbide phase was essentially a part of the fuel oxidation process and, as long as the rate of carbide oxidation and that of oxide recarburization remained comparable, the cell performance was stable.  © 2012 Elsevier, reprinted with permission.

Structured catalysts via multiple stage thermal oxidation synthesis of FeCrAl alloy sintered microfibers

J.E. Samad, J.A. Nychka, N.V. Semagina
Chemical Engineering Journal 168 (1), 470-476
Publication year: 2011

A structured catalyst support was developed based on FeCrAl alloy sintered microfibers (SMF) via multiple stage thermal oxidation in air for 1 h at 930 °C, 1 h at 960 °C and 2 h at 990 °C. The procedure resulted in the formation of a forest of predominantly α-alumina whiskers (200 nm in height and 100 nm apart). Palladium deposition and reduction yielded 0.5 wt.% Pd/SMF with 20 nm nanoparticle size. The catalyst was tested in three-phase hydrogenation of 2-methyl-3-buten-2-ol, and due to its pore structure allowed eliminating internal mass transfer limitations. The developed support can be beneficial to catalytic reactions suffering from mass transfer limitations and catalyst deactivation via pore mouth blocking. As compared to other methods of structured catalyst preparation, the thermal oxidation procedure is simple, fast and environmentally benign, and eliminates problems associated with poor adhesion of traditional washcoated layers of powdered catalysts or supports.  © 2011 Elsevier, reprinted with permission.

Size- and shape- controlled Pd nanoparticles in a fluorometric Tsuji-Trost reaction

Y. Yang, L.D. Unsworth, N. Semagina
Journal of Catalysis 281 (1), 137-146
Publication year: 2011

Pd nanoparticles catalyze Tsuji–Trost reaction for Pd fluorometric detection in the presence of PPhvia atomic dissolution:


  • Pd nanoparticles catalyze Tsuji–Trost reaction used for Pd fluorometric detection.
  • Nanoparticle activity is correlated with the number of defect surface atoms.
  • The reaction occurs via atomic dissolution and Ostwald ripening.
  • The highest rate is concomitant with the formation of largest nanoparticles.
  • Optimum PPh3 concentration exists for the fastest reaction.


Palladium nanospheres of 2.4 and 3.8 nm diameter and nanocubes of 18 nm rib length were used to catalyze a fluorometric Tsuji–Trost reaction for the transformation of a phenyl allyl ether to a fluorescent phenol in the presence of triphenylphosphine, which was pivotal to the catalytic activity. Turnover frequencies calculated per defect atoms were found similar for all nanoparticles, indicating that these atoms are the active sites. However, kinetic studies combined with Pd leaching and transmission electron microscopy analyses in the presence of various reaction components showed Pd leaching via oxidative addition of a reactant, followed by nanoparticle growth depending on the PPh3 concentration. The formation of largest particles was found for the fastest reaction with PPh3/Pd molar ratio of 4, in the range from 0 to 9. This study shows the validity of the atomic dissolution mechanism in the reaction of interest. © 2011 Elsevier, reproduced with permission.

Kinetics of catalytic steam gasification of bitumen coke

A. Karimi, N. Semagina, M.R. Gray
Fuel 90 (3), 1285-1291
Publication year: 2011

The catalytic steam gasification of coke from Athabasca bitumen was investigated by thermogravimetric analysis using K2CO3 and Na2CO3 as catalysts, both of which reduced the activation energy of the reaction considerably to 1.2 × 105 J mol−1 and 1.3 × 105 J mol−1, respectively, down from 2.1 × 105 J mol−1 for the uncatalyzed reaction. The reaction rates varied with the partial pressure of steam between 60 kPa and 85 kPa consistent with a Langmuir–Hinshelwood model, but a first order equation was also sufficient given the low partial pressures. The initial rate of gasification of the coke particles correlated linearly with the estimated external surface area of the particles, as expected from a surface reaction involving a non-porous solid. The initial reaction rate increased with increasing the catalyst loading up to 2.4 (mol potassium)/kg. A portion of the catalyst penetrated into the coke, as confirmed by secondary ion mass spectroscopy analysis, where it could not promote the reaction with steam. This result was consistent with a small increase observed in the reaction rate at low catalyst loading. The shrinking core model was successful in predicting the rates at higher conversions from the initial rate data, despite increases in BET surface area with conversion. © 2011 Elsevier, reprinted with permission.

Nanoparticle shape effect study as an efficient tool to reveal the structure sensitivity of olefinic alcohol hydrogenation

R. Ma, N. Semagina
The Journal of Physical Chemistry C 114 (36), 15417-15423
Publication year: 2010

Monodisperse Pd nanocubes of 20 nm rib length and Pd nanospheres of 3.0 nm diameter were synthesized in the presence of cetyltrimethylammonium bromide and used to investigate the structure sensitivity of three-phase 2-methyl-3-buten-2-ol hydrogenation. Turnover frequencies per all surface atoms were found as 2.58 s−1 for the cubes and 3.86 s−1 for the spheres at 313 K, indicating that (100) atoms of the cubes comprising ∼98% of all surface atoms have lower activity than other surface atoms of the spheres, composed of atoms on (111), (100) terraces, edges, and vertices. Apparent activation energies of 23 kJ/mol for the cubes and 17 kJ/mol for the spheres in the verified kinetic regime confirmed the reaction structure sensitivity. Assuming that only (100) and (111) atoms are active on the sphere surface, a hypothetical most active Pd nanostructure was predicted as a tetrahedron allowing twice higher activity per Pd loading as compared to a spherical particle. © 2010 American Chemical Society, reprinted with permission.

Recent advances in the liquid‐phase synthesis of metal nanostructures with controlled shape and size for catalysis

N. Semagina, L. Kiwi‐Minsker
Catalysis Reviews 51 (2), 147-217
Publication year: 2009

Recent advances in the liquid‐phase synthesis of metal nanostructures of different sizes and shapes are reviewed regarding their catalytic properties. The controlled synthesis of nanostructures is based on the colloid chemistry techniques in the solution, which use organic nanoreactors and a variety of stabilizers. Their catalytic activity and selectivity depend on the particle’s shape and size, as shown for Suzuki and Heck coupling, hydrogenations, hydrogenolysis, oxidations, and electron‐transfer reactions. The knowledge of a reaction’s structure‐sensitivity relationship is important for the rational catalyst design in view of process intensification. Nanostructures can be used per se and in supported form to meet the requirements of an eventual process. © 2009 Taylor & Francis.

Palladium nanohexagons and nanospheres in selective alkyne hydrogenation

N. Semagina, L. Kiwi-Minsker
Catalysis Letters 127 (3-4), 334-338
Publication year: 2009

Palladium nanohexagons were prepared using a seed-mediated method. Their catalytic performance in 2-methyl-3-butyn-2-ol hydrogenation was compared to the one of monodispersed Pd nanospheres. Quantitative correlations between initial turnover frequencies (TOFs) and nanoparticle surface compositions showed independence of TOFs calculated per atoms on Pd(111) facets on particle size and shape. © 2009 Springer, reproduced with permission.

Kinetics of the solvent-free hydrogenation of 2-methyl-3-butyn-2-ol over a structured Pd-based catalyst

M. Crespo-Quesada, M. Grasemann, N. Semagina, A. Renken, L. Kiwi-Minsker
Catalysis Today 147 (3), 247-254
Publication year: 2009

The solvent-free selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE) was studied over a Pd/ZnO structured catalyst and compared to its behavior in water-assisted conditions. The catalytic behavior was correlated with the surface properties of the catalysts which were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The catalyst showed high selectivity and stability with the performance being superior to that of the industrial Lindlar catalyst (50%). The addition of a sulphur-containing modifier in the reaction mixture was found to affect the activity and to hinder the over-hydrogenation reaction. The MBE yield of ∼97% was attained at MBY conversion >99%. The reuse of the catalyst showed that it deactivated by a 38% and that its selectivity slightly increased (∼0.5%) over 10 runs. The reaction kinetics was modeled using a Langmuir–Hinshelwood mechanism considering competitive adsorption for the organic species and dissociative adsorption for hydrogen. The kinetic experiments were planned and the results analyzed following a design of experiments (DOE) methodology. This approach led not only to a robust model that predicts the reaction rate in a wide range of reaction conditions but also to the determination of its kinetic parameters.  © 2009 Elsevier, reprinted with permission.

Three-phase catalytic hydrogenation of a functionalized alkyne: mass transfer and kinetic studies with in situ hydrogen monitoring

A. Bruehwiler, N. Semagina, M. Grasemann, A. Renken, L. Kiwi-Minsker, A. Saaler, H. Lehmann, W. Bonrath, F. Roessler
Industrial & Engineering Chemistry Research 47 (18), 6862-6869
Publication year: 2008

Systematic studies of mass transfer interactions with intrinsic reaction kinetics were performed for the three-phase selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE) over a modified Pd/CaCO3 catalyst under solvent free conditions. Hydrogen concentration in the liquid phase (CH2,b) was monitored in situ during the catalytic reaction by means of the “Fugatron” analyzer. Reactions were carried out in an autoclave at different stirring rates at two concentrations of hydrogen (5 and 13 mol·m−3). For stirring speeds higher than 1500 rpm no influence of gas−liquid mass transfer was observed. Hydrogen liquid−solid (L-S) mass transfer was found to be negligible, whereas the MBY mass L-S transfer becomes important at high MBY conversions at high hydrogen concentration. Low stirrer speed caused the reaction rate and MBE selectivity to decrease. No internal mass transfer limitations were observed, and conditions for the kinetic regime were found. The kinetics modeled followed the Langmuir−Hinshelwood mechanism and was consistent with the experimental data. © 2008 American Chemical Society, reprinted with permission.

Monodispersed Pd nanoparticles for acetylene selective hydrogenation: particle size and support effects

M. Ruta, N. Semagina, L. Kiwi-Minsker
The Journal of Physical Chemistry C 112 (35), 13635-13641
Publication year: 2008

Monodispersed Pd nanoparticles (8, 11, and 13 nm in diameter) as confirmed by high resolution transmission electron microscopy were prepared via the reverse microemulsion method and deposited on structured supports consisting of carbon nanofibers (CNF) grown on sintered metal fibers (SMF). The CNF/SMF supports were subjected to oxidative treatments to introduce O-functional groups on the CNF surface. These groups were characterized by temperature-programmed decomposition (TPD) and X-ray photoelectron spectroscopy. The catalysts were used to study (a) the effect of Pd size and (b) the effect of the support nature on the selective acetylene hydrogenation. Antipathetic size dependence of TOF disappeared at particle size bigger than 11 nm. Initial selectivity to ethylene was found size-independent. The deactivation due to coke deposition was faster for smaller particles. The structure-sensitivity relations for the catalysts investigated are discussed in terms of “geometric” and “electronic nature” of the size effect and rationalized regarding Pd−Cx phase formation which is size-dependent. Supports with increased acidity diminished the formation of coke and changed the byproduct distribution toward ethane.  © 2008 American Chemical Society, reprinted with permission.