Dilute Alloys Based on Au, Ag, or Cu for Efficient Catalysis: From Synthesis to Active Sites.

The development of new catalyst materials for energy-efficient chemical synthesis is critical as over 80% of industrial processes rely on catalysts, with many of the most energy-intensive processes specifically using heterogeneous catalysis. Catalytic performance is a complex interplay of phenomena involving temperature, pressure, gas composition, surface composition, and structure over multiple length and time scales. In response to this complexity, the integrated approach to heterogeneous dilute alloy catalysis reviewed here brings together materials synthesis, mechanistic surface chemistry, reaction kinetics, in situ and operando characterization, and theoretical calculations in a coordinated effort to develop design principles to predict and improve catalytic selectivity. Dilute alloy catalysts─in which isolated atoms or small ensembles of the minority metal on the host metal lead to enhanced reactivity while retaining selectivity─are particularly promising as selective catalysts. Several dilute alloy materials using Au, Ag, and Cu as the majority host element, including more recently introduced support-free nanoporous metals and oxide-supported nanoparticle "raspberry colloid templated (RCT)" materials, are reviewed for selective oxidation and hydrogenation reactions. Progress in understanding how such dilute alloy catalysts can be used to enhance selectivity of key synthetic reactions is reviewed, including quantitative scaling from model studies to catalytic conditions. The dynamic evolution of catalyst structure and composition studied in surface science and catalytic conditions and their relationship to catalytic function are also discussed, followed by advanced characterization and theoretical modeling that have been developed to determine the distribution of minority metal atoms at or near the surface. The integrated approach demonstrates the success of bridging the divide between fundamental knowledge and design of catalytic processes in complex catalytic systems, which can accelerate the development of new and efficient catalytic processes.

Unlocking synergy in bimetallic catalysts by core-shell design.

Extending the toolbox from mono- to bimetallic catalysts is key in realizing efficient chemical processes1. Traditionally, the performance of bimetallic catalysts featuring one active and one selective metal is optimized by varying the metal composition1-3, often resulting in a compromise between the catalytic properties of the two metals4-6. Here we show that by designing the atomic distribution of bimetallic Au-Pd nanocatalysts, we obtain a synergistic catalytic performance in the industrially relevant selective hydrogenation of butadiene. Our single-crystalline Au-core Pd-shell nanorods were up to 50 times more active than their alloyed and monometallic counterparts, while retaining high selectivity. We find a shell-thickness-dependent catalytic activity, indicating that not only the nature of the surface but also several subsurface layers play a crucial role in the catalytic performance, and rationalize this finding using density functional theory calculations. Our results open up an alternative avenue for the structural design of bimetallic catalysts.

Highly Ordered Inverse Opal Structures Synthesized from Shape-Controlled Nanocrystal Building Blocks.

Three-dimensional ordered porous materials known as inverse opal films (IOFs) were synthesized using nanocrystals with precisely defined morphologies. Comprehensive theoretical and experimental studies of the volume fraction ratio and electrostatic interactions between nanocrystals and polystyrene templating particles enabled the formation of highly ordered crack-free photonic structures. The synthetic strategy was first demonstrated using titanium dioxide (TiO2 ) nanocrystals of different shapes and then generalized to assemble nanocrystals of other functional materials, such as indium tin oxide and zinc-doped ferrite. Tunable photocatalytic activity of the TiO2 IOFs, modulated through the choice of the shape of TiO2 nanocrystals in conjunction with selecting desired macroscopic features of the IOF, was further explored. In particular, enhanced activity is observed for crack-free, highly ordered IOFs whose photonic properties can improve light absorption via the slow light effect. This study opens new opportunities in designing multi-length-scale porous nanoarchitectures having enhanced performance in a variety of applications.

Neural network assisted analysis of bimetallic nanocatalysts using X-ray absorption near edge structure spectroscopy.

X-ray absorption spectroscopy is a common method for probing the local structure of nanocatalysts. One portion of the X-ray absorption spectrum, the X-ray absorption near edge structure (XANES) is a useful alternative to the commonly used extended X-ray absorption fine structure (EXAFS) for probing three-dimensional geometry around each type of atomic species, especially in those cases when the EXAFS data quality is limited by harsh reaction conditions and low metal loading. A methodology for quantitative determination of bimetallic architectures from their XANES spectra is currently lacking. We have developed a method, based on the artificial neural network, trained on ab initio site-specific XANES calculations, that enables accurate and rapid reconstruction of the structural descriptors (partial coordination numbers) from the experimental XANES data. We demonstrate the utility of this method on the example of a series of PdAu bimetallic nanoalloys. By validating the neural network-yielded metal-metal coordination numbers based on the XANES analysis by previous EXAFS characterization, we obtained new results for in situ restructuring of dilute (2.6 at% Pd in Au) PdAu nanoparticles, driven by their gas and temperature treatments.

Dual role of CO in the stability of subnano Pt clusters at the Fe3O4(001) surface.

Interactions between catalytically active metal particles and reactant gases depend strongly on the particle size, particularly in the subnanometer regime where the addition of just one atom can induce substantial changes in stability, morphology, and reactivity. Here, time-lapse scanning tunneling microscopy (STM) and density functional theory (DFT)-based calculations are used to study how CO exposure affects the stability of Pt adatoms and subnano clusters at the Fe3O4(001) surface, a model CO oxidation catalyst. The results reveal that CO plays a dual role: first, it induces mobility among otherwise stable Pt adatoms through the formation of Pt carbonyls (Pt1-CO), leading to agglomeration into subnano clusters. Second, the presence of the CO stabilizes the smallest clusters against decay at room temperature, significantly modifying the growth kinetics. At elevated temperatures, CO desorption results in a partial redispersion and recovery of the Pt adatom phase.

Repulsive van der Waals forces enable Pickering emulsions with non-touching colloids.

Emulsions stabilized by solid particles, called Pickering emulsions, offer promising applications in drug delivery, cosmetics, food science and the manufacturing of porous materials. This potential stems from their high stability against coalescence and 'surfactant-free' nature. Generally, Pickering emulsions require that the solid particles are wetted by both phases and as a result, the adsorption free energy is often large with respect to the thermal energy (kBT). Here we provide the first experimental proof for an alternative scenario: non-touching (effectively non-wetting), charged, particles that are completely immersed in the oil phase through a balance of charge induced attractions and repulsions caused by van der Waals forces. These particles nonetheless stabilize the emulsion. The main advantage of this novel adsorption mechanism is that these particles can easily be detached from the interface simply by adding salt. This not only makes the finding fundamentally of interest, but also enables a triggered de-emulsification and particle recovery, which is useful in fields like enhanced oil recovery, heterogeneous catalysis, and emulsion polymerization.

Charging of poly(methyl methacrylate) (PMMA) colloids in cyclohexyl bromide: locking, size dependence, and particle mixtures.

We studied suspensions of sterically stabilized poly(methyl methacrylate) (PMMA) particles in the solvent cyclohexyl bromide (CHB; εr = 7.92). We performed microelectrophoresis measurements on suspensions containing a single particle species and on binary mixtures, using confocal microscopy to measure the velocity profiles of the particles. We measured the charge of so-called locked PMMA particles, for which the steric stabilizer, a comb-graft stabilizer of poly(12-hydroxystearic acid) (PHSA) grafted on a backbone of PMMA, was covalently bonded to the particle, and for unlocked particles, for which the stabilizer was adsorbed to the surface of the particle. We observed that locked particles had a significantly higher charge than unlocked particles. We found that the charge increase upon locking was due to chemical coupling of 2-(dimethylamino)ethanol to the PMMA particles, which was used as a catalyst for the locking reaction. For particles of different size we obtained the surface potential and charge from the electrophoretic mobility of the particles. For locked particles we found that the relatively high surface potential (∼ +5.1 kBT/e or +130 mV) was roughly constant for all particle diameters we investigated (1.2 µm < σ < 4.4 µm), and that the particle charge was proportional to the square of the diameter.

Direct Observation of Ni Nanoparticle Growth in Carbon-Supported Nickel under Carbon Dioxide Hydrogenation Atmosphere.

Understanding nanoparticle growth is crucial to increase the lifetime of supported metal catalysts. In this study, we employ in situ gas-phase transmission electron microscopy to visualize the movement and growth of ensembles of tens of nickel nanoparticles supported on carbon for CO2 hydrogenation at atmospheric pressure (H2:CO2 = 4:1) and relevant temperature (450 °C) in real time. We observe two modes of particle movement with an order of magnitude difference in velocity: fast, intermittent movement (vmax = 0.7 nm s-1) and slow, gradual movement (vaverage = 0.05 nm s-1). We visualize the two distinct particle growth mechanisms: diffusion and coalescence, and Ostwald ripening. The diffusion and coalescence mechanism dominates at small interparticle distances, whereas Ostwald ripening is driven by differences in particle size. Strikingly, we demonstrate an interplay between the two mechanisms, where first coalescence takes place, followed by fast Ostwald ripening due to the increased difference in particle size. Our direct visualization of the complex nanoparticle growth mechanisms highlights the relevance of studying nanoparticle growth in supported nanoparticle ensembles under reaction conditions and contributes to the fundamental understanding of the stability in supported metal catalysts.

Manganese Oxide as a Promoter for Copper Catalysts in CO2 and CO Hydrogenation.

In this work, we discuss the role of manganese oxide as a promoter in Cu catalysts supported on graphitic carbon during hydrogenation of CO2 and CO. MnOx is a selectivity modifier in an H2/CO2 feed and is a highly effective activity promoter in an H2/CO feed. Interestingly, the presence of MnOx suppresses the methanol formation from CO2 (TOF of 0.7 ⋅ 10-3 s-1 at 533 K and 40 bar) and enhances the low-temperature reverse water-gas shift reaction (TOF of 5.7 ⋅ 10-3 s-1) with a selectivity to CO of 87 %C. Using time-resolved XAS at high temperatures and pressures, we find significant absorption of CO2 to the MnO, which is reversed if CO2 is removed from the feed. This work reveals fundamental differences in the promoting effect of MnOx and ZnOx and contributes to a better understanding of the role of reducible oxide promoters in Cu-based hydrogenation catalysts.

Decoding reactive structures in dilute alloy catalysts.

Rational catalyst design is crucial toward achieving more energy-efficient and sustainable catalytic processes. Understanding and modeling catalytic reaction pathways and kinetics require atomic level knowledge of the active sites. These structures often change dynamically during reactions and are difficult to decipher. A prototypical example is the hydrogen-deuterium exchange reaction catalyzed by dilute Pd-in-Au alloy nanoparticles. From a combination of catalytic activity measurements, machine learning-enabled spectroscopic analysis, and first-principles based kinetic modeling, we demonstrate that the active species are surface Pd ensembles containing only a few (from 1 to 3) Pd atoms. These species simultaneously explain the observed X-ray spectra and equate the experimental and theoretical values of the apparent activation energy. Remarkably, we find that the catalytic activity can be tuned on demand by controlling the size of the Pd ensembles through catalyst pretreatment. Our data-driven multimodal approach enables decoding of reactive structures in complex and dynamic alloy catalysts.

Structural Control over Bimetallic Core-Shell Nanorods for Surface-Enhanced Raman Spectroscopy.

Bimetallic nanorods are important colloidal nanoparticles for optical applications, sensing, and light-enhanced catalysis due to their versatile plasmonic properties. However, tuning the plasmonic resonances is challenging as it requires a simultaneous control over the particle shape, shell thickness, and morphology. Here, we show that we have full control over these parameters by performing metal overgrowth on gold nanorods within a mesoporous silica shell, resulting in Au-Ag, Au-Pd, and Au-Pt core-shell nanorods with precisely tunable plasmonic properties. The metal shell thickness was regulated via the precursor concentration and reaction time in the metal overgrowth. Control over the shell morphology was achieved via a thermal annealing, enabling a transition from rough nonepitaxial to smooth epitaxial Pd shells while retaining the anisotropic rod shape. The core-shell synthesis was successfully scaled up from micro- to milligrams, by controlling the kinetics of the metal overgrowth via the pH. By carefully tuning the structure, we optimized the plasmonic properties of the bimetallic core-shell nanorods for surface-enhanced Raman spectroscopy. The Raman signal was the most strongly enhanced by the Au core-Ag shell nanorods, which we explain using finite-difference time-domain calculations.

3D Atomic-Scale Dynamics of Laser-Light-Induced Restructuring of Nanoparticles Unraveled by Electron Tomography.

Understanding light-matter interactions in nanomaterials is crucial for optoelectronic, photonic, and plasmonic applications. Specifically, metal nanoparticles (NPs) strongly interact with light and can undergo shape transformations, fragmentation and ablation upon (pulsed) laser excitation. Despite being vital for technological applications, experimental insight into the underlying atomistic processes is still lacking due to the complexity of such measurements. Herein, atomic resolution electron tomography is performed on the same mesoporous-silica-coated gold nanorod, before and after femtosecond laser irradiation, to assess the missing information. Combined with molecular dynamics (MD) simulations based on the experimentally determined 3D atomic-scale morphology, the complex atomistic rearrangements, causing shape deformations and defect generation, are unraveled. These rearrangements are simultaneously driven by surface diffusion, facet restructuring, and strain formation, and are influenced by subtleties in the atomic distribution at the surface.

Cobalt-Nickel Nanoparticles Supported on Reducible Oxides as Fischer-Tropsch Catalysts.

Efficient and more sustainable production of transportation fuels is key to fulfill the ever-increasing global demand. In order to achieve this, progress in the development of highly active and selective catalysts is fundamental. The combination of bimetallic nanoparticles and reactive support materials offers unique and complex interactions that can be exploited for improved catalyst performance. Here, we report on cobalt-nickel nanoparticles on reducible metal oxides as support material for enhanced performance in the Fischer-Tropsch synthesis. For this, different cobalt to nickel ratios (Ni/(Ni + Co): 0.0, 0.25, 0.50, 0.75, or 1.0 atom/atom) supported on reducible (TiO2 and Nb2O5) or nonreducible (α-Al2O3) oxides were studied. At 1 bar, Co-Ni nanoparticles supported on TiO2 and Nb2O5 showed stable catalytic performance, high activities and remarkably high selectivities for long-chain hydrocarbons (C5+, ∼80 wt %). In contrast, catalysts supported on α-Al2O3 independently of the metal composition showed lower activities, high methane production, and considerable deactivation throughout the experiment. At 20 bar, the combination of cobalt and nickel supported on reducible oxides allowed for 25-50% cobalt substitution by nickel with increased Fischer-Tropsch activity and without sacrificing much C5+ selectivity. STEM-EDX and IR of adsorbed CO pointed to a cobalt enrichment of the nanoparticle's surface and a weaker adsorption of CO in Co-Ni supported on TiO2 and Nb2O5 and not on α-Al2O3, modifying the rate-determining step and the catalytic performance. Overall, we show the strong effect and potential of reducible metal oxides as support materials for bimetallic nanoparticles for enhanced catalytic performance.

Quantitative 3D Characterization of Elemental Diffusion Dynamics in Individual Ag@Au Nanoparticles with Different Shapes.

Anisotropic bimetallic nanoparticles are promising candidates for plasmonic and catalytic applications. Their catalytic performance and plasmonic properties are closely linked to the distribution of the two metals, which can change during applications in which the particles are exposed to heat. Due to this fact, correlating the thermal stability of complex heterogeneous nanoparticles to their microstructural properties is of high interest for the practical applications of such materials. Here, we employ quantitative electron tomography in high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) mode to measure the 3D elemental diffusion dynamics in individual anisotropic Au-Ag nanoparticles upon heating in situ. This approach allows us to study the elemental redistribution in complex, asymmetric nanoparticles on a single particle level, which has been inaccessible to other techniques so far. In this work, we apply the proposed method to compare the alloying dynamics of Au-Ag nanoparticles with different shapes and compositions and find that the shape of the nanoparticle does not exhibit a significant effect on the alloying speed whereas the composition does. Finally, comparing the experimental results to diffusion simulations allows us to estimate the diffusion coefficients of the metals for individual nanoparticles.

Bridging the gap: 3D real-space characterization of colloidal assemblies via FIB-SEM tomography.

Insight in the structure of nanoparticle assemblies up to a single particle level is key to understand the collective properties of these assemblies, which critically depend on the individual particle positions and orientations. However, the characterization of large, micron sized assemblies containing small, 10-500 nanometer, sized colloids is highly challenging and cannot easily be done with the conventional light, electron or X-ray microscopy techniques. Here, we demonstrate that focused ion beam-scanning electron microscopy (FIB-SEM) tomography in combination with image processing enables quantitative real-space studies of ordered and disordered particle assemblies too large for conventional transmission electron tomography, containing particles too small for confocal microscopy. First, we demonstrate the high resolution structural analysis of spherical nanoparticle assemblies, containing small anisotropic gold nanoparticles. Herein, FIB-SEM tomography allows the characterization of assembly dimensions which are inaccessible to conventional transmission electron microscopy. Next, we show that FIB-SEM tomography is capable of characterizing much larger ordered and disordered assemblies containing silica colloids with a diameter close to the resolution limit of confocal microscopes. We determined both the position and the orientation of each individual (nano)particle in the assemblies by using recently developed particle tracking routines. Such high precision structural information is essential in the understanding and design of the collective properties of new nanoparticle based materials and processes.

In Situ Observation of Atomic Redistribution in Alloying Gold-Silver Nanorods.

The catalytic performance and optical properties of bimetallic nanoparticles critically depend on the atomic distribution of the two metals in the nanoparticles. However, at elevated temperatures, during light-induced heating, or during catalysis, atomic redistribution can occur. Measuring such metal redistribution in situ is challenging, and a single experimental technique does not suffice. Furthermore, the availability of a well-defined nanoparticle system has been an obstacle for a systematic investigation of the key factors governing the atomic redistribution. In this study, we follow metal redistribution in precisely tunable, single-crystalline Au-core, Ag-shell nanorods in situ, both at a single particle and an ensemble-averaged level, by combining in situ transmission electron spectroscopy with in situ extended X-ray absorption fine structure validated by ex situ measurements. We show that the kinetics of atomic redistribution in Au-Ag nanoparticles depend on the metal composition and particle volume, such that a higher Ag content or a larger particle size led to significantly slower metal redistribution. We developed a simple theoretical model based on Fick's first law that can correctly predict the composition- and size-dependent alloying behavior in Au-Ag nanoparticles, as observed experimentally.

Fully alloyed metal nanorods with highly tunable properties.

Alloyed metal nanorods offer a unique combination of enhanced plasmonic and photothermal properties with a wide variety in optical and catalytic properties as a function of the alloy composition. Here, we show that fully alloyed anisotropic nanoparticles can be obtained with complete retention of the particle shape via thermal treatment at surprisingly low temperatures. By coating Au-Ag, Au-Pd and Au-Pt core-shell nanorods with a protective mesoporous silica shell the transformation of the rods to a more stable spherical shape was successfully prevented during alloying. For the Au-Ag core-shell NRs the chemical stability was drastically increased after alloying, and from Mie-Gans and finite-difference time-domain (FDTD) calculations it followed that alloyed AuAg rods also exhibit much better plasmonic properties than their spherical counterparts. Finally, the generality of our method is demonstrated by alloying Au-Pd and Au-Pt core-shell NRs, whereby the AuPd and AuPt alloyed NRs showed a surprisingly high increase in thermal stability of several hundred degrees compared with monometallic silica coated Au NRs.