Preferential oxidation of carbon monoxide over Pt, Au monometallic catalyst, and Pt–Au bimetallic catalyst supported on ceria in hydrogen-rich reformate

The objective of this paper was to study a preferential oxidation (PROX) of carbon monoxide over monometallic catalysts including Pt, Au and Pt–Au bimetallic catalyst supported on ceria in hydrogen-rich reformate. Single step sol–gel method (SSG) and impregnation on sol–gel method (ISG) were chosen for the preparation of the catalysts. The characteristics of these catalysts were investigated by X-ray diffractometer (XRD), Brunauer–Emmet–Teller (BET) method, transmission electron microscope (TEM), scanning electron microscope (SEM) and temperature-programmed reduction (TPR). The XRD patterns of the catalysts showed only the peaks of ceria crystallite and no metal peak appeared. From TEM images, the active components were seen to be dispersed throughout the ceria support. The TPR patterns of PtAu/CeO₂ catalyst prepared by SSG showed the reduction peaks were within a low temperature range and therefore, the catalysts prepared by SSG exhibited excellent catalytic activity for preferential oxidation of CO. Bimetallic Pt–Au catalyst improved the activity (90% conversion and 50% selectivity at 90 °C) because of the formation of a new phase. When the metal content of (1:1) PtAu/CeO₂ catalyst prepared by SSG was increased, the CO conversion did not change much while the selectivity decreased in the low temperature range (50–90 °C). The CO conversion increased with increasing W/F ratio. The presence of CO₂ and H₂O had a negative effect on CO conversion and selectivity due to blocking of carbonate and water on active sites.     

Highly dispersed MgO-supported model Pd-Mo catalysts prepared from bimetallic clusters: Chemisorption and selective catalytic reduction of NO

Model supported palladium and palladium-molybdenum catalysts prepared from organometallic precursors and previously characterized by a variety of chemical and physical methods were examined by IR spectroscopy of NO chemisorption and tested for their activities as catalysts in the competitive NO + CO + O₂ reaction. The IR results reveal distinctive behavior of the catalyst made from a bimetallic precursor, and the activity results show that this catalyst is more selective for NO reduction than the other catalysts, but its stability is vulnerable to the reaction conditions. The high selectivity is attributed to Pd-Mo interactions, which are inferred to be stronger in the catalyst prepared from a bimetallic precursor than in catalysts prepared from monometallic precursors.     

Stability of Pt-Co bimetallic particles: effect of the support induced morphology on reactivity in CO hydrogenation

The structure and the stability of bimetallic particles are controlled by their interaction with surface oxide species on support or by support geometry. Location and size of the bimetallic particles estimated by XRD and XPS, depends on the environment and treatment. Thus, the Pt-Co bimetallic particles entrapped in NaY zeolite cages become unstable upon mild oxidation by O₂ and/or reaction with surface protons causing the Co²⁺ ions formed to migrate irreversibly from the supercages into the sodalite cages as determined by TPR and TPD. Differences in the selectivity pattern observed for the CO hydrogenation over alumina and NaY zeolite supported Pt-Co catalysts, can be interpreted by the interaction between bimetallic particles with surface cobalt oxide species and the zeolite cage wall, respectively.On leave from Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, PR China.     

The nucleation, growth, and stability of oxide-supported metal clusters

The optimization of oxide-supported metal clusters as heterogeneous catalysts requires a detailed understanding of the metal cluster–oxide interface. Model catalysts, prepared by deposition of a catalytically active metal onto a thin film oxide support, closely mimic real-world catalysts, yet are amenable to study using surface sensitive techniques. Surface science methods applied to model catalysts, combined with the use of in situ high-pressure reaction studies, have provided a wealth of information about cluster structure and reactivity. STM capabilities for imaging individual particles under reaction temperatures and pressures offer a new approach for studying supported cluster catalysts on a particle-by-particle basis. This article describes recent work in our laboratories using variable temperature STM to investigate the role of the support and its defects in the nucleation and stabilization of metal clusters.     

Nucleation and growth of Pd clusters in mordenite

The nucleation and growth of Pd clusters in mordenite were investigated using in situ extended X-ray absorption fine structure (EXAFS) spectroscopy and Fourier transform infrared (FTIR) spectroscopy of absorbed CO. Calcination of [Pd(NH₃)₄]²⁺-exchanged mordenite at 350°C in O₂ results in decomposition of the amine complex and formation of square-planar Pd²⁺ oxo species within the mordenite pores. Reduction of these species at 150°C in H₂ yields Pd clusters with an average nuclearity of 3. On an average two 2.22 Å Pd-O bonds are associated with each Pd₃ cluster; we infer that this interaction serves to anchor the clusters within the pores. After reduction at 150°C, the FTIR spectrum of irreversibly adsorbed CO is indicative of a mixture of Pd⁺, Pd^δ+, and Pd⁰ carbonyl species. Reduction at 350°C produces larger intrazeolitic Pd clusters (average nuclearity of 6) that exhibit only a weak interaction with the mordenite, as evidenced by their facile aggregation in the presence of CO at 30°C. Reduction at 450°C yields large 20 Å Pd clusters that we infer are located on external mordenite surfaces or locally disrupt the intracrystalline structure.     

CO hydrogenation towards higher alcohols catalysed on SiO2-grafted and zeolite-entrapped Ru,Co and RuCo bimetallic clusters: Their EXAFS and FTIR characterization and catalytic performances

Some Ru and Co carbonyl clusters in zeolite pores such as Ru₃(CO)₁₂/NaY, [HRu₆(CO)₁₈]^–/NaY, [Ru₆(CO)₁₈]^2–/NaX, Co₄(CO)₁₂/NaY and Co₆(CO)₁₆/NaY were prepared by the ship-in-bottle technique, and characterized by FTIR and EXAFS. The RuCo bimetallic carbonyl cluster was prepared by reductive carbonylation of the oxidized RuCo/NaY, which provides the proposed assignment to [HRUCo₃(CO)₁₂]/NaY. The tailored Ru, RuCo and Co catalysts were prepared by H₂ reduction from the precursors, e.g. Ru, RuCo bimetallic and Co carbonyl clusters impregnated on SiO₂ and entrapped in NaY and NaX zeolites. The RuCo bimetallic carbonyl cluster-derived catalysts showed substantially higher activities and selectivities for oxygenates such as C₁–C₅ alcohols in CO hydrogenation (CO/H₂ = 0.33-1.0, 5 bar, 519–543 K). By contrast, hydrocarbons such as methane were preferentially obtained on the catalysts prepared from Ru₆, Ru₃ and Co₄ carbonyl clusters and provided lower CO conversion and poor selectivities for oxygenates. The RuCo bimetals are proposed to be associated with the selective formation of higher alcohols in CO hydrogenation.     

Facile synthesis of hierarchical flower-like Ag/Cu2O and Au/Cu2O nanostructures and enhanced catalytic performance in electrochemical reduction of CO2

Novel, hierarchical, flower-like Ag/Cu₂O and Au/Cu₂O nanostructures were successfully fabricated and applied as efficient electrocatalysts for the electrochemical reduction of CO₂. Cu₂O nanospheres with a uniform size of ~180 nm were initially synthesized. Thereafter, Cu₂O was used as a sacrificial template to prepare a series of Ag/Cu₂O composites through galvanic replacement. By varying the Ag/Cu atomic ratio, Ag_0.125/Cu₂O, having a hierarchical, flower-like nanostructure with intersecting Ag nanoflakes encompassing an inner Cu₂O sphere, was prepared. The as-prepared Ag_x/Cu₂O samples presented higher Faradaic efficiencies (FE) for CO and relatively suppressed H₂ evolution than the parent Cu₂O nanospheres due to the combination of Ag with Cu₂O in the former. Notably, the highest CO evolution rate was achieved with Ag_0.125/Cu₂O due to the larger electroactive surface area furnished by the hierarchical structure. The same hierarchical flower-like structure was also obtained for the Au_0.6/Cu₂O composite, where the FE_CO (10%) was even higher than that of Ag_0.125/Cu₂O. Importantly, the results reveal that Ag_0.125/Cu₂O and Au_0.6/Cu₂O both exhibit remarkably improved stability relative to Cu₂O. This study presents a facile method of developing hierarchical metal-oxide composites as efficient and stable electrocatalysts for the electrochemical reduction of CO₂.     

Role of tungsten in supported Pt-W reforming catalysts Part II. Influence of the tungsten loading and metal-support interactions effect

Support Pt-W catalysts are studied for 3-methylhexane reforming. The increase in tungsten loading and the use of SiO₂ support instead of Al₂O₃ in Pt-W catalysts leads to the decrease in total activity and aromatization selectivity. X-ray Photoelectron Spectroscopy (XPS) has been applied to bimetallic Pt-W/Al₂O₃ and SiO₂ catalysts with different Pt/W ratios to try to explain the catalytic results. Observations lead to the conclusion that tungsten species are strongly anchored on the support in Pt-W/Al₂O₃ catalysts at low tungsten concentration. In this case, tungsten species are not reducible (oxidation state +VI) and not accessible catalytically; tungsten is hindered by small Pt particles. At large tungsten loadings, beyond the theoretical monolayer capacity of the support, a fraction of tungsten species migrates to the surface and becomes reducible. This fraction of tungsten-reducible species and large platinum particles are accessible on the surface, but another fraction of tungsten species strongly anchored on the support remains not accessible and not reducible. A model is proposed.     

Sol derived gold–palladium bimetallic nanoparticles on TiO2: structure and catalytic activity in CO oxidation

Bimetallic AuPd catalysts were prepared by deposition of bimetallic aqueous sols formed in different ways: (i) co-reduction of the precursor Au and Pd ions by Na-citrate/tannic acid mixture, (ii) reduction of Au(III) ions onto preformed Pd sol, and (iii) reduction of Pd(II) ions onto a preformed Au sol. The Au/TiO₂ and Pd/TiO₂ samples as references were prepared from their respective sols. The structure of the samples was characterized by XRF, XRD, XPS, TEM and CO chemisorption both in the as-prepared state and after calcination and reduction. The catalytic activities of the calcined/reduced catalysts in the CO oxidation were compared. The presence of bimetallic crystalline phases was evidenced in all three samples both in the as prepared and calcined/reduced states, however, various extents of Pd surface enrichment were determined. The catalytic activity of the bimetallic samples regardless of the preparation method, is about the same as that of the mixture of the monometallic samples. No significant synergism is suggested in the present bimetallic samples.     

γ‐Alumina supported Cu‐Ni bimetallic catalysts: Characterization and selective hydrogenation of 1,3‐butadiene

Addition of a second metal often improves the selectivity of a supported catalyst for the hydrogenation of 1,3‐butadiene. Catalysts containing 15 wt% Ni and varying amounts of Cu were prepared and characterized by TPR, XRD and XPS. The Cu‐Ni interaction affects the reduction behavior of the catalysts. TPR result shows that the synergetic effect of copper and nickel modifies the capability of metal to combine with hydrogen in bulk phase. The Ni 2p spectra in XPS shows significant shifts toward lower binding energies with increasing copper loading. From XRD results it is represented that aggregation of nickel occurs more easily due to the copper addition. The adding of copper on Ni/Al₂O₃ makes the conversion rate decreased and increases the selectivity to 1‐butene.     

Structure and catalytic properties of Cu-Ni bimetallic catalysts for hydrogenation

The dependence of catalytic activity and selectivity of Cu-Ni bimetallic catalysts for oil hydrogenation on CuNi ratios have been investigated while they were reduced at low temperature (230 °C). Two maxima occurred at Cu₂Ni₁ and Cu₁Ni₃ in the activity-CuNi curve. Cu riched catalysts have higher selectivity than Ni riched ones, and may cause dehydrogenation and isomerization of linoleate at the beginning of the reaction. The structures of the catalysts reduced at different temperatures have been studied by means of XRD, XPS, EXAFS and FMR et al. The structure of the catalysts reduced at 230 °C can be described as an aggregate of Cu particles inlaid with Ni atoms and unreduced NiO, and the easily reduced Cu always segregates on the surface, while homogeneous solid solution particles can be formed in the case 400 °C being used as reduction temperature.     

Structure and promotion of bimetallic catalysts: Activity and selectivity

Activity and selectivity of carbon monoxide hydrogenation can be effectively controlled by using bimetallic catalysts. There are two effects which should be taken into consideration: (1) influencing the mode of CO chemisorption: dissociative vs associative, or (2) affecting the amount and type of surface hydrogen: weakly vs strongly bound to the surface.Associative CO chemisorption is controlled by two factors: either by the formation of an alloy phase as is for PtFe or PdFe where rehybridization of the Pd d-orbital results in a decreased back donation, or by an effect of a charged particles such as Fe³⁺ or RE ions which operates via a charge polarization. In highly dispersed state, e.g. inside a zeolite cage, similar effect is operative. In both cases oxygenates formation is a significant reaction pathway.The mode of hydrogen chemisorption also affects the selectivity of the reaction. When the activated form of hydrogen is in large proportion, all the processes which require hydrogen are suppressed, consequently olefin formation is the main route of reaction.The factors influencing both hydrogen and CO chemisorption will be considered. Here the paper will be focused on the effect of alloying, metal dispersion and shape selective environment.Prepared for presentation at American Institute of Chemical Engineering, 1990 Spring National Meeting, March 18–22, 1990, The Peabody, Orlando Fl-Fischer-Tropsch Synthesis V: Effect of Local Coordination Environment Around the Active Metal.     

Mixed protein-templated luminescent metal clusters (Au and Pt) for H2O2 sensing

A simple and cost-effective method to synthesize the luminescent noble metal clusters (Au and Pt) in chicken egg white aqueous solution at room temperature is reported. The red-emitting Au cluster is used as fluorescent probe for sensitive detection of H₂O₂.     

The hydrogenation of acetylene on supported bimetallic Pt-Ir and Pt-Re catalysts

Hydrogenation of acetylene has been studied with a series of Pt-Re and Pt-Ir catalysts. The results supplied some information concerning the importance of the potential electronic structure (ligand) effect of alloying and on the effect of selfpoisoning.     

Osmium ligand deficient clusters as catalysts for liquid phase hydrocarbon transformations

Reduction of OsO₄ by molecular hydrogen in alkane (cycloalkane) or benzene media at 20–150 °C yields small osmium clusters of the Os₁C_0.34-0.48H_0-0.6 composition with a specific surface area of 34–46 m²/g. The systems obtained are shown to be ligand deficient osmium clusters (LDC) of 7–16 Å in diameter, stabilized by a small amount of carbonaceous ligands with Os-Os = 2.68-1.70 Å and Os-C = 2.11-2.19 Å. The characteristics of these chemically prepared Os-LDC are similar to those of Ni- and Co-LDC, prepared by a vapour phase synthesis. The novel Os-LDC effectively catalyze hydrogenolysis of alkanes and cycloalkanes at 100–150 ° C and initial H₂ pressure of 5 MPa, hydrogenation of cyclopentadiene and arenes at 20 ° C, multiple H/D exchange between CH₄ and D₂ at 100–120 ° C and methanation of CO₂ at 150–180 ° C.     

Penetration of Deposited Ag and Cu Overlayers Through Alkanethiol Self-Assembled Monolayers on Gold

The purpose of our research is to study the reactions, interactions, or penetration between vacuum deposited metals (M) and the organic functional end groups (OFGs) of self-assembled monolayers (SAMs) on Au films under controlled conditions. Metal/SAM/Au systems are models for understanding bonding at M/organic interfaces and the concomitant adhesion between the different materials. In broad terms, the M/OFGs form interacting interfaces (e.g., Cr/COOH or Cu/COOH) in which the deposit resides on top of the OFGs or weakly interacting interfaces through which the overlayer penetrates and resides at the SAM/gold interface. We present a review of XPS results from weakly interacting systems (Cu/CH₂OH, CU/CN, Ag/CH₃, Ag/COOH) and discuss in more depth the time-temperature dependence of the disappearance of the metal from the M/SAM interface following deposition using ISS on the Ag/CH₃ and Ag/COOH systems. XPS and ISS were used to characterize five alkanethiols terminated with CH₃, COOH(C—11 and C—16 chain lengths), CN and CH₂OH before and after depositing up to 1.0 nm Ag or Cu at ca. 10^-7 torr. XPS spectra indicate that no strong interaction occurs between the deposited Ag and the COOH organic functional group, although a stronger interaction is evident on a C—16 COOH, and a unidentate is formed for Cu on the CH₂OH. An interaction between Cu and CN is evident, and penetration into the SAM occurs to a greater extent than for Cu on CH₂OH. The Ag interaction with CH₃ is weak. ISS compositional depth profiles for Ag on COOH and CH₃, taken from 113 to 293 K, indicate that Ag remains on the surface of the C—11 COOH for up to 1 h after deposition, whereas Ag penetrates CH₃ in less than 5 min at 295 K. The time for Ag to penetrate into a C-16 COOH is several times longer than for the C—11 COOH and depends on the SAM temperature.     

Influence of the Electronic Structure of the Metal at the Polymer/Metal Interface: A Tentative Interpretation on the Basis of Lewis Acid-Base Reactions

In the present paper, we examine the link between theoretical qualitative predictions made on the grounds of the Lewis acid-base concept and the actual interface built between polyamide-6,6 (PA-6,6) and copper, and PA-6,6 and platinum. By using a combination of very-surface-sensitive photoemission spectroscopies and model polymers, it becomes possible to obtain important information about the chemical nature of the polymer/metal interface. Our experiments show a complete dissociative chemisorption of the polymer on Pt, while PA-6,6 retains its chemical integrity on copper.     

Effect of interparticle interaction on the low temperature oxidation of CO over size-selected Au nanocatalysts supported on ultrathin TiC films

This work aims to get insight into the influence of interparticle interactions on catalysis. The low temperature CO oxidation is used as a model reaction. A strong dependence of the catalytic activity and stability of gold nanoparticles uniformly dispersed on polycrystalline TiC films was observed as a function of the interparticle distance. Two samples with similar height distributions (∼2 nm), but with different average interparticle distances (∼30 and ∼80 nm), were synthesized using diblock copolymer encapsulation. Their chemical reactivity was investigated by temperature programmed desorption (TPD), and reactive coarsening and subsequent deactivation was observed for the sample with the smallest interparticle distance. The system with the largest average interparticle distance showed higher stability towards agglomeration and longer lifetime.     

Reducibility and CO hydrogenation over Pt and Pt-Co bimetallic catalysts encaged in NaY-zeolite

Temperature programmed techniques (TPR, TPD) and X-ray diffraction (XRD) have been used to study ion migration and location as well as reducibility of platinum and cobalt ions encapsulated in Pt/NaY, Co/NaY and Pt-Co/NaY zeolites prepared by ion exchange. The temperature required to reduce Co²⁺ in NaY was significantly lowered by the presence of Pt and dependent upon the relative locations of Pt and Co ions in zeolite cages. The exact location was controlled by the calcination condition and the metal contents. For bimetallic catalyst with low Pt content (0.5 wt% Pt and 0.9 wt% Co), the TPR results indicated that reduction of Co²⁺ ions in the vicinity of Pt shifted toward lower temperature, while that of Co²⁺ staying alone was not affected. With high Pt loading (4.5 wt% Pt, 0.7 and 2.6 wt% Co), however, most of the Co²⁺ ions were reduced by means of Pt at temperature below 723 K after calcination at 573 K. The temperature for Pt reduction in bimetallic catalysts was somewhat higher than Pt/NaY and increased with Co atomic fraction, indicating that mixed oxide, PtCo _x O _y , might be formed during calcination. After reduction in hydrogen at 723 K, highly dispersed metal particles were formed. These fine particles were most probably confined inside zeolite cages as indicated by the absence of XRD peak for all samples after calcination and reduction. Surface composition of the bimetallic particles may be different for catalysts with similar Pt content but different Co loading. Accordingly, H/Pt ratios of 1.0 and 0.72 for catalysts with low and high Co content, respectively, were shown by hydrogen chemisorption. It was further supported by the increase in TPD peak intensity with Co loading in the high temperature range, which was related to the reoxidation of Co in bimetallic particles by surface hydroxyl groups. Preliminary results on CO hydrogenation demonstrated that activity and methanol selectivity were higher on Pt-Co bimetallic catalysts than either over monometallic Pt or Co catalyst, which was consistent with the Pt enhanced Co reduction and formation of Pt-Co bimetallic particles.     

Synthesis, characterization, and crystal structures of two new polyoxomolybdate wheel clusters

Two new polyoxomolybdates Na₅(NH₄)₁₆[Mo₅₇Mn₆(NO)₆O₁₇₄ (OH)₃(H₂O)₂₄] · 44H₂O (1) and (NH₄)₂₁[Mo₅₇Cu₆(NO)₆O₁₆₈(OH)₃(H₂O)₂₄] · 53H₂O (2) were synthesized in aqueous solution and characterized by elemental analysis, IR, TG analysis and single-crystal X-ray diffraction. They represent interesting examples of integrating and embedding magnetic 3d metal ions into the diamagnetic polyoxomolybdate host structure.