Evaporation-Induced Self-Assembly of Metal Oxide Inverse Opals: From Synthesis to Applications

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

Silica-Coated Gold Nanorod Supraparticles: A Tunable Platform for Surface Enhanced Raman Spectroscopy

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

Estimation of Temperature Homogeneity in MEMS-Based Heating Nanochips via Quantitative HAADF-STEM Tomography

Sample holders for transmission electron microscopy (TEM) based on micro-electro-mechanical systems (MEMS) have recently become popular for investigating the behavior of nanomaterials under in situ or environmental conditions. The accuracy and reproducibility of these in situ holders are essential to ensure the reliability of experimental results. In addition, the uniformity of an applied temperature trigger across the MEMS chip is a crucial parameter. In this work, it is measured the temperature homogeneity of MEMS-based heating sample supports by locally analyzing the dynamics of heat-induced alloying of Au@Ag nanoparticles located in different regions of the support through quantitative fast high-angle annular dark-field scanning TEM tomography. These results demonstrate the superior temperature homogeneity of a microheater design based on a heating element shaped as a circular spiral with a width decreasing outwards compared to a double spiral-shaped designed microheater. The proposed approach to measure the local temperature homogeneity based on the thermal properties of bimetallic nanoparticles will support the future development of MEMS-based heating supports with improved thermal properties and in situ studies where high precision in the temperature at a certain position is required

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

Nanoparticle proximity controls selectivity in benzaldehyde hydrogenation

Disentangling the effects of nanoparticle proximity and size on thermal catalytic performance is challenging with traditional synthetic methods. Here we adapt a modular raspberry-colloid-templating approach to tune the average interparticle distance of PdAu alloy nanoparticles, while preserving all other physicochemical characteristics, including nanoparticle size. By controlling the metal loading and placement of pre-formed nanoparticles within a 3D macroporous SiO2 support and using the hydrogenation of benzaldehyde to benzyl alcohol and toluene as the probe reaction, we report that increasing the interparticle distance (from 12 to 21 nm) substantially enhances selectivity towards benzyl alcohol (from 54% to 99%) without compromising catalytic performance. Combining electron tomography, kinetic evaluation and simulations, we show that interparticle distance modulates the local benzyl alcohol concentration profile between active sites, consequently affecting benzyl alcohol readsorption, which promotes hydrogenolysis to toluene. Our results illustrate the relevance of proximity effects as a mesoscale tool to control the adsorption of intermediates and, hence, catalytic performance. (Figure presented.)

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

Influence of carbon support surface modification on the performance of nickel catalysts in carbon dioxide hydrogenation

The interaction between metal nanoparticles and a support is of key importance in catalysis. In this study, we demonstrate that the introduction of oxygen- or nitrogen-containing surface groups on a graphite nanoplatelet support influences the performance of nickel supported catalysts during CO2 hydrogenation. By careful design of the synthesis conditions, the Ni nanoparticle size of the fresh catalysts was not affected by the type of support surface groups. A combination of H2 chemisorption and high resolution TEM demonstrates that the available metal surface depends on the interaction with the carbon support. The amination treatment to introduce nitrogen-containing groups results in the weakest interaction between the Ni and the support, showing the highest initial Ni weight-based activity, although at the expense of nanoparticle stability. Hence initial enhancement in activity is not always optimal for long term catalysis. The use of carbon with a higher density of oxygen functional groups that are stable above 350 °C, is beneficial for preventing deactivation due to particle growth. Furthermore, small amounts of contaminants can have a substantial influence on the CH4 selectivity at low conversions

Influence of carbon support surface modification on the performance of nickel catalysts in carbon dioxide hydrogenation

The interaction between metal nanoparticles and a support is of key importance in catalysis. In this study, we demonstrate that the introduction of oxygen- or nitrogen-containing support surface groups on a graphite nanoplatelet support influence the performance of nickel supported catalysts during CO2 hydrogenation. By careful design of the synthesis conditions, the Ni nanoparticle size of the fresh catalysts was not affected by the type of support surface groups. A combination of H2 chemisorption and high resolution TEM demonstrates that the available metal surface depends on the interaction with the carbon support. The amination treatment results in the weakest interaction between the Ni and the support, showing the highest initial Ni weight-based activity, although at the expense of nanoparticle stability. Hence initial enhancement in activity is not always optimal for long term catalysis. The use of carbon with a higher density of oxygen functional groups that are stable above 350 °C, is beneficial for preventing deactivation due to particle growth. Furthermore, small amounts of contaminants can have a substantial influence on the CH4 selectivity at low conversions

Identifying the Optimal Pd Ensemble Size in Dilute PdAu Alloy Nanomaterials for Benzaldehyde Hydrogenation

Unraveling metal nuclearity effects is central for active site identification and the development of high-performance heterogeneous catalysts. Herein, a platform of nanostructured palladium (Pd) in gold (Au) dilute alloy nanoparticles supported on raspberry-colloid-templated (RCT) silica was employed to systematically assess the impact of the Pd ensemble size for the low-nuclearity regime in the Au surface layer, from single atoms to clusters, on the catalytic performance in the liquid-phase hydrogenation of benzaldehyde to benzyl alcohol. Combining catalyst evaluation, detailed characterization, and mechanistic studies based on density functional theory, we show that Pd single atoms in the Au surface plane (corresponding to samples with 4 atom % Pd in Au) are virtually inactive in this reaction and benzyl alcohol production is optimal over small Pd clusters (corresponding to samples with 10-12 atom % Pd in Au) due to superior benzaldehyde adsorption and transition state stabilization for the C-H bond formation step. For larger Pd ensembles (samples with ≥10 atom % Pd in Au), C-O bond hydrogenolysis occurs, promoting toluene formation and decreasing the selectivity toward benzyl alcohol, in line with a relatively lowered C-O bond cleavage barrier. Nevertheless, the nanostructured bimetallic Pd13Au87/SiO2-RCT catalyst still outperforms monometallic Pd counterparts in terms of selectivity for benzyl alcohol over toluene at comparable conversion and rate. Furthermore, the stability is improved compared to pure Pd nanoparticles due to inhibited particle agglomeration in the RCT silica matrix

Particle Size Effects of Carbon Supported Nickel Nanoparticles for High Pressure CO2 Methanation

Supported nickel nanoparticles are promising catalysts for the methanation of CO2. The role of nickel particle size on activity and selectivity in this reaction is a matter of debate. We present a study of metal particle size effects on catalytic stability, activity and selectivity, using nickel on graphitic carbon catalysts. Increasing the Ni particle size from 4 to 8 nm led to a higher catalytic activity, both per gram of nickel and normalized surface area. However, the apparent activation energy remained the same (∼105 kJ mol−1). Comparing experiments at atmospheric to 30 bar pressure demonstrates the importance of testing under industrially relevant pressures; the highest selectivity is obtained at high CO2 conversions and pressures. Finally, the selectivity was particle size-dependent. The largest particles were not only most active but also most selective to methane. With this work we contribute to the ongoing debate about Ni particle size effects in CO2 methanation