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.

ConspectusInverse opals (IOs) are highly interconnected three-dimensional macroporous structures with applications in a variety of disciplines from optics to catalysis. For instance, when the pore size is on the scale of the wavelength of visible light, IOs exhibit structural color due to diffraction and interference of light rather than due to absorption by pigments, making these structures valuable as nonfading paints and colorants. When IO pores are in an ordered arrangement, the IO is a 3D photonic crystal, a structure with a plethora of interesting optical properties that can be used in a multitude of applications, from sensors to lasers. IOs also have interesting fluidic properties that arise from the re-entrant geometry of the pores, making them excellent candidates for colorimetric sensors based on fluid surface tension. Metal oxide IOs, in particular, can also be photo- and thermally catalytically active due to the catalytic activity of the background matrix material or of functional nanoparticles embedded within the structure.Evaporation-induced self-assembly of sacrificial particles has been developed as a scalable method for forming IOs. The pore size and shape, surface chemistry, matrix material, and the macroscopic shape of the IO, as well as the inclusion of functional components, can be designed through the choice of deposition conditions such as temperature and humidity, types and concentrations of components in the self-assembly mixture, and the postassembly processing. These parameters allow researchers to tune the optical, mechanical, and thermal transport properties of IOs for optimum functionality.In this Account, we focus on experimental and theoretical studies to understand the self-assembly process and properties of metal oxide IOs without (bare) and with (hybrid) plasmonic or catalytic metal nanoparticles incorporated. Several synthetic approaches are first presented, together with a discussion of the various forces involved in the assembly process. The visualization of the deposition front with time-lapse microscopy is then discussed together with analytical theory and numerical simulations to determine the conditions needed for the deposition of a continuous IO film. Subsequently, we present high-resolution scanning electron microscopy (SEM) of assembled colloids over large areas, which provides a detailed view of the evolution of the assembly process, showing that the organization of the colloids is initially dictated by the meniscus of the evaporating suspension on the substrate, but that gradually all grains rotate to occupy the thermodynamically most favorable orientation. High-resolution 3D transmission electron microscopy (TEM) is then presented together with analysis of the wetting of the templating colloids by the matrix precursor to provide a detailed picture of the embedding of metallic nanoparticles at the pore-matrix interface. Finally, the resulting properties and applications in optics, wetting, and catalysis are discussed, concluding with an outlook on the future of self-assembled metal-oxide-based IOs.

Plasmonic nanoparticle assemblies are promising functional materials for surface‐enhanced Raman spectroscopy (SERS). Gold nanorod (AuNR) assemblies are of particular interest due to the large, shape‐induced local field enhancement and the tunable surface plasmon resonance of the AuNRs. Designing the optimal assembly structure for SERS, however, is challenging and requires a delicate balance between the interparticle distance, porosity, and wetting of the assembly. Here, a new type of functional assemblies–called supraparticles–fabricated through the solvent‐evaporation driven assembly of silica‐coated gold nanorods into spherical ensembles, in which the plasmonic coupling and the mass transport is tuned through the thickness and porosity of the silica shells are introduced. Etching of the AuNRs allowed fine‐tuning of the plasmonic response to the laser excitation wavelength. Using a correlative SERS‐electron microscopy approach, it is shown that all supraparticles successfully amplified the Raman signal of the crystal violet probe molecules, and that the Raman signal strongly increased when decreasing the silica shell thickness from 35 to 3 nm, provided that the supraparticles have a sufficiently high porosity. The supraparticles introduced in this study present a novel class of materials for sensing, and open up a wide parameter space to optimize their performance.

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.