Tuning of catalytic CO oxidation by changing composition of Rh-Pt bimetallic nanoparticles

Recent breakthroughs in synthesis in nanoscience have achieved control of size and composition of nanoparticles that are relevant for catalyst design. Here, we show that the catalytic activity of CO oxidation by Rh/Pt bimetallic nanoparticles can be changed by varying the composition at a constant size (9+/-1 nm). Two-dimensional Rh/Pt bimetallic nanoparticle arrays were formed on a silicon surface via the Langmuir-Blodgett technique. Composition analysis with X-ray photoelectron spectroscopy agrees with the reaction stoichiometry of Rh/(Pt+Rh). CO oxidation rates that exhibit a 20-fold increase from pure Pt to pure Rh show a nonlinear increase with surface composition of the bimetallic nanoparticles that is consistent with the surface segregation of Pt. The results demonstrate the possibility of controlling catalytic activity in metal nanoparticle-oxide systems via tuning the composition of nanoparticles with potential applications for nanoscale design of industrial catalysts.     

Hydrodechlorination of chlorobenzene over polymer-stabilized palladium-platinum bimetallic colloidal nanocatalysts

Poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized Pd, Pt, Pd-Pt nanocatalysts were prepared and characterized by transmission electron microscopy (TEM). Hydrogenation of chlorobenzene was carried out over these colloidal nanocatalysts under ambient conditions. The catalytic properties for the hydrogenation of chlorobenzene depended on the composition of the bimetallic nanocatalysts. The conversion of chlorobenzene over PVP-Pd (83.64%) was higher than that of PVP-Pt (66.67%), which indicated that the activity of Pd was higher than that of Pt. In 10 hrs. the conversions of all the bimetallic nanocatalysts were higher than that of PVP-Pt (66.67%) monometallic nanocatalysts, and the maximum conversion of chlorobenzene (95.34%) was achieved using PVP-Pd/Pt = 1/1 catalytic system, which was much higher than that of the physical mixture of monometallic nanocatalysts (PVP-Pd and PVP-Pt) at the same Pd/Pt ratio as the PVP-Pd/Pt bimetallic nanocatalysts used. The selectivity to benzene and cyclohexane of the bimetallic nanocatalysts (with < or = 40 mol% Pt) was similar to that of PVP-Pd monometallic nanocatalysts, and nearly approximately 100% selectivity to benzene could be obtained, the selectivity to cyclohexane increased slowly with increasing of platinum content in bimetallic nanocatalysts.     

Effect of pretreatment conditions on particle size of bimetallic pt-au catalysts supported on ZnO/Al2O3 and its activity for toluene oxidation

Bimetallic Pt-Au catalysts supported on ZnO/Al2O3 were prepared by incipient wetness impregnation (IW-IMP) method with different pretreatment conditions such as flow velocity, calcination temperature, and heating rate under H2 during the calcination procedure, and characterized by X-ray diffraction (XRD), CO chemisorption, and scanning transmission electron microscopy (STEM) equipped energy dispersive spectroscopy (EDS). Furthermore, catalytic activity for complete oxidation of toluene was measured using a flow reactor under atmospheric pressure. Finally, relationship between the particle sizes with pretreatment conditions and catalytic activity for toluene on the bimetallic Pt-Au catalysts was discussed. In these results, nanosized bimetallic Pt-Au particles on ZnO/Al2O3 could be prepared by IW-IMP method. Relationship between the Pt and Au particle size and activity for toluene oxidation was clearly observed.     

原位表面掺杂增强PtNiCoRh纳米晶对C1燃料电氧化的催化性能

异质原子掺杂的铂基纳米晶在多相催化领域具有广阔的应用前景,然而基于原位表面掺杂策略来优化表面原子构型仍颇具挑战.本研究通过原位表面掺杂的化学方法制备出多枝状PtNiCoRh四元金属纳米晶.抗坏血酸和铑离子的配位作用实现了铑离子的延迟还原,从而可控地将铑原子锚定在催化剂表面层.电催化研究表明原位表面掺杂的Pt₆₇Ni₁₆Co₁₆Rh₁纳米晶针对甲醇、甲醛和甲酸电氧化都具有优异的催化活性、稳定性及抗CO中毒特性.原位电化学红外光谱结果表明抗腐蚀性强的铑原子的表面掺杂能有效调控催化剂表面Pt位点,其中CO中毒中间体以更容易氧化消除的桥位态吸附在Rh–Pt异质位点.本研究提出的原位表面掺杂策略将有助于设计高原子利用率的高效多相催化剂.     

Deposition of metal nanoparticles on carbon nanotubes via hexane modified water-in-CO2 microemulsion at room temperature

Carbon nanotube-supported metallic nanoparticles (Pd, Rh, and bimetallic Pd-Rh) with diameters in the range 2-10 nm can be synthesized by hydrogen reduction of metal ions dissolved in the water core of a CO2 microemulsion in liquid CO2 at room temperature. The microemulsion is stabilized by sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and dissolved in liquid CO2 with the aid of hexane as a modifier. The metal nanoparticles synthesized in the microemulsion can be deposited on surfaces of multi-walled carbon nanotubes (MWCNTs) by stirring in the liquid CO2 phase. This simple method produces uniformly distributed metal nanoparticles on surfaces of the MWCNTs with high yields. The carbon nanotube-supported Pd/Rh bimetallic nanoparticles exhibit high catalytic activities for hydrogenation of aromatic compounds and can be reused without losing catalytic activity.     

A comprehensive study on the effect of Ru addition to Pt electrodes for direct ethanol fuel cell

The electro-oxidation of ethanol was studied over nanosized Pt and different compositions of PtRu catalysts synthesized by the borohydride reduction method. Physicochemical characterizations of the catalyst material were made by X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with EDX analysis and transmission electron microscopy (TEM). XRD patterns showed that Ru induces a contraction of the Pt lattice. EDX provided the composition of binary catalysts while TEM images indicated uniform distribution of discrete nanoparticle of the catalysts with narrow range. The electro-catalytic activities of the materials towards ethanol oxidation were investigated through electrochemical techniques, viz. cyclic voltammetry (CV), potentiodynamic polarization, chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) at room temperature. The onset potential of ethanol electro-oxidation is lowered on bimetallic PtRu catalysts compared to that on Pt alone. Of the investigated catalyst compositions the one with the highest electrocatalytic activity was found to be Pt₈₂Ru₁₈. This enhancement towards ethanol oxidation is explained on the basis of a structural effect and modified bi-functional mechanism.     

Structural and electronic studies of supported Pt and Au epitaxial clusters on tungsten oxide surface

In the present paper we investigated the growth and electronic properties of Pt or Au clusters and formation of Pt-Au bimetallic clusters prepared “in-situ” on tungsten oxide surface by physical deposition under vacuum. The epitaxial tungsten oxide thin films were prepared by oxidation of W(110) single-crystal surface using a RF oxygen plasma source followed by thermal annealing. The chemical state of the system, the interaction between deposit and substrate and formation of Pt-Al alloy were investigated by photoelectron spectroscopy excited by synchrotron radiation (SRPES) and K;α X-ray source (XPS). We found that in contrary to Au clusters the Pt ones strongly interacts with the substrate. Deposition of both Pt and Au on the surface at the substrate temperature of 300 °C gave rise to the formation of bimetallic core-shell clusters. The detail structure of the bimetallic system depends on the order of deposited metals. These findings can explain some properties of Pt/WOx and Au/WOx as well as Pt-Au/WOx bimetallic catalysts and gas sensors.     

Fast and facile preparation of reduced graphene oxide supported Pt–Co electrocatalyst for methanol oxidation

In this study, we report a scalable, fast, and facile method for preparation of reduced graphene oxide (RGO) sheets supported Pt–Co electrocatalyst for methanol oxidation. Mixed reducing agents were used and the activity of the catalysts was studied. It was found that the presence of RGO leads to higher activity, which might be due to the increasing of electrochemically accessible surface areas and easier charge–transfer at the interfaces. Co can greatly enhance the electrocatalytic activity and moderate the poisoning of Pt catalyst. Under same Pt loading mass and experimental conditions, the RGO-Pt-Co catalyst shows the highest electro catalytic activity and improved resistance to carbon monoxide poisoning among the prepared catalysts.     

Enthalpies of Formation of Noble Metal Binary Alloys Bearing Rh or Ir

The modified embedded atom method proposed by authors has been applied to calculating the enthalpies of formation of random alloys and the ordered intermetallic compounds for noble metal binary systems bearing Rh or Ir. The present results are in good agreement with those of Miedema theory, available experiments and the first-principles quantum mechanics calculations. The present results indicate that Cu-Rh, Cu-Ir, Ag-Rh, Ag-Ir, Au-Rh, Au-Ir, Pd-Rh and Pd-Ir systems are repulsive, however, Ni-Rh, Ni-Ir, Pt-Ir, Pt-Rh and Rh-Ir systems form solid solutions and Ni-Rh, Ni-Ir and Pt-Rh show ordering tendency.     

Synthesis and characteristics of Ag/Pt bimetallic nanocomposites by arc-discharge solution plasma processing

Arc discharge in solution, generated by applying a high voltage of unipolar pulsed dc to electrodes of Ag and Pt, was used as a method to form Ag/Pt bimetallic nanocomposites via electrode erosion by the effects of the electric arc at the cathode (Ag rod) and the sputtering at the anode (Pt rod). Ag/Pt bimetallic nanocomposites were formed as colloidal particles dispersed in solution via the reduction of hydrogen radicals generated during discharge without the addition of chemical precursor or reducing agent. At a discharge time of 30?s, the fine bimetallic nanoparticles with a mean particle size of approximately 5?nm were observed by transmission electron microscopy (TEM). With increasing discharge time, the bimetallic nanoparticle size tended to increase by forming an agglomeration. The presence of the relatively small amount of Pt dispersed in the Ag matrix could be observed by the analytical mapping mode of energy-dispersive x-ray spectroscopy and high-resolution TEM. This demonstrated that the synthesized particle was in the form of a nanocomposite. No contamination of other chemical substances was detected by x-ray photoelectron spectroscopy. Hence, solution plasma could be a clean and simple process to effectively synthesize Ag/Pt bimetallic nanocomposites and it is expected to be widely applicable in the preparation of several types of nanoparticle.     

Catalytic properties of Pt cluster-decorated CeO2 nanostructures

Uniform clusters of Pt have been deposited on the surface of capping-agent-free CeO₂ nanooctahedra and nanorods using electron beam (e-beam) evaporation. The coverage of the Pt nanocluster layer can be controlled by adjusting the e-beam evaporation time. The resulting e-beam evaporated Pt nanocluster layers on the CeO₂ surfaces have a clean surface and clean interface between Pt and CeO₂. Different growth behaviors of Pt on the two types of CeO₂ nanocrystals were observed, with epitaxial growth of Pt on CeO₂ nanooctahedra and random growth of Pt on CeO₂ nanorods. The structures of the Pt clusters on the two different types of CeO₂ nanocrystals have been studied and compared by using them as catalysts for model reactions. The results of hydrogenation reactions clearly showed the clean and similar chemical surface of the Pt clusters in both catalysts. The support-dependent activity of these catalysts was demonstrated by CO oxidation. The Pt/CeO₂ nanorods showed much higher activity compared with Pt/CeO₂ nanooctahedra because of the higher concentration of oxygen vacancies in the CeO₂ nanorods. The structure-dependent selectivity of dehydrogenation reactions indicates that the structures of the Pt on CeO₂ nanorods and nanooctahedra are different. Thes differences arise because the metal deposition behaviors are modulated by the strong metal-metal oxide interactions.     

一种新型催化剂制备氢化丁腈橡胶的研究

用自制的Rh-Ru双金属单配体催化剂（BMSC）对丁腈橡胶（NBR）进行加氢，制得氢化丁腈橡胶（HNBR），其加氢度达98％以上，产物无凝胶。这种新型催化剂具有与RhCl(PPh3)3相当的高活性和高选择性，且价格较廉。研究了催化剂浓度、第二配体L2用量、H2压力、反应时间、NBR胶液浓度等不同反应参数及分段升温等加氢工艺对NBR加氢反应的影响规律。并获得工业上易于实施、成本较低、加氢度达98％以上的工艺条件。     

Chemical fluid deposition of monometallic and bimetallic nanoparticles on ordered mesoporous silica as hydrogenation catalysts

A simple and green method of depositing monometallic (Ru, Rh, Pd) and bimetallic nanoparticles (Ru-Rh, Ru-Pd and Rh-Pd) on an ordered mesoporous silica support (MCM-41) in supercritical carbon dioxide (scCO2) is described. Metal acetylacetonates were used in the experiments as CO2-soluble metal precursors. Suitable temperature and pressure conditions for synthesizing each kind of nanoparticles were applied in this study. The characterizations of these nanocomposites were performed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDS). The nanoparticles had average sizes varying from 2 nm to 8 nm. The Ru nanoparticles were clearly shown to be inside the mesopores of MCM-41 from the TEM image. These nanocomposites used as catalysts for hydrogenation was demonstrated. The efficiency of the scCO2 prepared Ru/MCM-41 catalyst was nearly 8 times than that of a Ru/MCM-41 catalyst prepared by conventional impregnation method.     

Size‐Controlled Synthesis of Sub‐10 nm PtNi3 Alloy Nanoparticles and their Unusual Volcano‐Shaped Size Effect on ORR Electrocatalysis

Dealloyed Pt bimetallic core–shell catalysts derived from low‐Pt bimetallic alloy nanoparticles (e.g, PtNi₃) have recently shown unprecedented activity and stability on the cathodic oxygen reduction reaction (ORR) under realistic fuel cell conditions and become today's catalyst of choice for commercialization of automobile fuel cells. A critical step toward this breakthrough is to control their particle size below a critical value (≈10 nm) to suppress nanoporosity formation and hence reduce significant base metal (e.g., Ni) leaching under the corrosive ORR condition. Fine size control of the sub‐10 nm PtNi₃ nanoparticles and understanding their size dependent ORR electrocatalysis are crucial to further improve their ORR activity and stability yet still remain unexplored. A robust synthetic approach is presented here for size‐controlled PtNi₃ nanoparticles between 3 and 10 nm while keeping a constant particle composition and their size‐selected growth mechanism is studied comprehensively. This enables us to address their size‐dependent ORR activities and stabilities for the first time. Contrary to the previously established monotonic increase of ORR specific activity and stability with increasing particle size on Pt and Pt‐rich bimetallic nanoparticles, the Pt‐poor PtNi₃ nanoparticles exhibit an unusual “volcano‐shaped” size dependence, showing the highest ORR activity and stability at the particle sizes between 6 and 8 nm due to their highest Ni retention during long‐term catalyst aging. The results of this study provide important practical guidelines for the size selection of the low Pt bimetallic ORR electrocatalysts with further improved durably high activity.     

Glycerol valorization by base-free oxidation with air using platinum–nickel nanoparticles supported on activated carbon as catalyst prepared by a simple microwave polyol method

Biodiesel is one of the most common biofuels, and its production yields a large amount of glycerol as a by-product. It is necessary to develop new technologies for the use of this by-product, adding value to the biodiesel production chain. In this work we investigated glycerol oxidation under mild reaction conditions (air as oxidizing agent and base-free medium) promoted by suitable catalysts. We prepared mono- and bimetallic catalysts of platinum, copper and nickel in the form of nanoparticles by conventional heating and by an alternative method using microwave heating. The nanoparticles were dispersed in activated carbon and tested in glycerol oxidation aiming its valorization into molecules with high added value. Copper and nickel monometallic materials were not active in glycerol oxidation. Platinum monometallic and platinum–copper and platinum–nickel bimetallic materials showed catalytic activity, with platinum–nickel prepared by microwave heating being the most active material in reactions tested. This catalyst presented glycerol conversion of approximately 20% with a turnover number of 9465 in a reaction time of 6 h and 58% of selectivity to glyceric acid, the main product obtained. The best performance of platinum–nickel prepared by microwave heating catalyst was attributed to the probable formation of a metallic alloy between Pt and Ni, as evidenced by the decrease in the lattice parameter for PtNi bimetallic nanoparticles. The results showed that it was possible to obtain an active catalyst in glycerol oxidation reaction under mild conditions via a simple methodology using microwave heating, which demands 94% less time in comparison with conventional heating.     

A stepwise-designed Rh-Au-Si nanocomposite that surpasses Pt/C hydrogen evolution activity at high overpotentials

Hydrogen evolution by electrocatalysis is an attractive method of supplying clean energy.However,it is challenging to find cheap and efficient alternatives to rare and expensive platinum based catalysts.Pt provides the best hydrogen evolution performance,because it optimally balances the free energies of adsorption and desorption.Appropriate control of these quantities is essential for producing an efficient electrocatalyst.We demonstrate,based on first principles calculations,a stepwise designed Rh-Au-Si ternary catalyst,in which adsorption (the Volmer reaction) and desorption (the Heyrovsky reaction) take place on Rh and Si surfaces,respectively.The intermediate Au surface plays a vital role by promoting hydrogen diffusion from the Rh to the Si surface.Theoretical predictions have been explored extensively and verified by experimental observations.The optimized catalyst (Rh-Au-SiNW-2) has a composition of 2.2∶28.5∶69.3 (Rh∶Au∶Si mass ratio) and exhibits a Tafel slope of 24.0 mV·dec-1.Its electrocatalytic activity surpasses that of a commercial 40 wt.％ Pt/C catalyst at overpotentials above 0.19 V by exhibiting a current density of greater than 108 mA·cm-2.At 0.3 V overpotential,the turnover frequency of Rh-Au-SiNW-2 is 10.8 times greater than that of 40 wt.％ Pt/C.These properties may open new directions in the stepwise design of highly efficient catalysts for the hydrogen evolution reaction (HER).     

Generalized Rapid Synthesis of Supported Nanocluster Catalyst for Mild Hydrogenation of Phenol toward KA Oil

Homogeneous and nanometric metal clusters with unique electronic structures are promising for catalysis, however, common synthesis techniques for metal clusters suffer from large size and even metal nanocrystals attributing to their high surface energy and unsaturated configurations. Herein, a generalized rapid annealing strategy for synthesizing a series of supported metal clusters as superior catalysts is developed. Remarkably, TiO₂ supported platinum nanoclusters (Pt NC/TiO₂) exhibits the excellent catalytic activity to realize phenol hydrogenation under mild conditions. The complete phenol conversion rate and 100% selectivity toward KA oil are achieved in aqueous solution at room temperature and normal pressure. Semi-continuous scale up production of KA oil is successfully performed under mild conditions. Such excellent performance mainly originates from the partial reconstruction of Pt NC/TiO₂ in aqueous phenol solution. Considering that the phenol can be produced from lignin, this study underpins a facile, sustainable, and economical route to synthesize nylon from biomass.     

Pt/Cr and Pt/Ni catalysts for oxygen reduction reaction: to alloy or not to alloy?

Bimetallic systems such as Pt-based alloys or non-alloys have exhibited interesting catalytic properties but pose a major challenge of not knowing a priori how the electronic and chemical properties will be modified relative to the parent metals. In this work, we present the origin of the changes in the reactivity of Pt/Cr and Pt/Ni catalysts, which have been of wide interest in fuel cell research. Using spin-polarized density functional theory calculations, we have shown that the modification of Pt surface reactivity in Pt/Ni is purely of geometric origin (strain). We have also found that the Pt-Ni bonding is very weak, which explains the observed instability of Pt-Ni catalysts under electrochemical measurements. On the other hand, Pt/Cr systems are governed by strong ligand effect (metal-metal interaction), which explains the experimentally observed reactivity dependence on the relative composition of the alloying components. The general characteristics of the potential energy curves for O2 dissociative adsorption on the bimetallic systems and the pure Pt clarify why the d-band center still works for Pt/Cr despite the strong Pt-Cr bonding and high spin polarization of Pt d-states. On the basis of the above clarifications, viable Pt-Cr and Pt-Ni structures, which involve nano-sized alloys and non-alloy bulk catalyst, which may strike higher than the currently observed oxidation reduction reaction activity are proposed.     

Dendrimer templated synthesis of one nanometer Rh and Pt particles supported on mesoporous silica: catalytic activity for ethylene and pyrrole hydrogenation

Monodisperse rhodium (Rh) and platinum (Pt) nanoparticles as small as approximately 1 nm were synthesized within a fourth generation polyaminoamide (PAMAM) dendrimer, a hyperbranched polymer, in aqueous solution and immobilized by depositing onto a high-surface-area SBA-15 mesoporous support. X-ray photoelectron spectroscopy indicated that the as-synthesized Rh and Pt nanoparticles were mostly oxidized. Catalytic activity of the SBA-15 supported Rh and Pt nanoparticles was studied with ethylene hydrogenation at 273 and 293 K in 10 torr of ethylene and 100 torr of H 2 after reduction (76 torr of H 2 mixed with 690 torr of He) at different temperatures. Catalysts were active without removing the dendrimer capping but reached their highest activity after hydrogen reduction at a moderate temperature (423 K). When treated at a higher temperature (473, 573, and 673 K) in hydrogen, catalytic activity decreased. By using the same treatment that led to maximum ethylene hydrogenation activity, catalytic activity was also evaluated for pyrrole hydrogenation.     

Catalytic reduction of U(VI) with hydrazine on palladium catalysts in acid solutions

The stability of finely dispersed palladium supported on silica gel with respect to various acids was studied. It was shown that palladium catalysts can be used in moderately acidic media under reducing conditions. In nitric acid solutions within a wide range of experimental conditions, the palladium catalysts do not initiate reduction of U(VI) with hydrazine. The catalytic properties of palladium catalysts differing in the size of nanocrystallites of the active metal were examined in the reduction of U(VI) with hydrazine in sulfuric acid solutions. The specific activity of Pd/SiO₂ catalysts is determined solely by the size of metal nanocrystals and is independent of the metal content on the support. The negative size effect is observed, i.e., the surface Pd atoms located on large crystallites exhibit higher catalytic activity. The results obtained were interpreted on the basis of the concepts of the energy nonuniformity of the surface atoms and of the mechanism of U(VI) catalytic reduction with hydrazine in the sulfuric acid solutions.