Ligand-protected metal nanoclusters controlled by atomic accuracy (i. e. atomically precise metal NCs) have recently attracted considerable attention as active sites in heterogeneous catalysts. Using these atomically precise metal NCs, it becomes possible to create novel heterogeneous catalysts based on a size-specific electronic/geometrical structure of metal NCs and understand the mechanism of the catalytic reaction easily. However, to create high-performance heterogeneous catalysts using atomically precise metal NCs, it is often necessary to remove the ligands from the metal NCs. This review summarizes previous studies on the creation of heterogeneous catalysts using atomically precise metal NCs while focusing on the calcination as a ligand-elimination method. Through this summary, we intend to share state-of-art techniques and knowledge on (1) experimental conditions suitable for creating high-performance heterogeneous catalysts (e.g., support type, metal NC type, ligand type, and calcination temperature), (2) the mechanism of calcination, and (3) the mechanism of catalytic reaction over the created heterogeneous catalyst. We also discuss (4) issues that should be addressed in the future toward the creation of high-performance heterogeneous catalysts using atomically precise metal NCs. The knowledge and issues described in this review are expected to lead to clear design guidelines for the creation of novel heterogeneous catalysts.

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Toward the creation of high-performance heterogeneous catalysts by controlled ligand desorption from atomically precise metal nanoclusters

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.

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

Operando characterization of working catalysts, requiring per definitionem the simultaneous measurement of catalytic performance, is crucial to identify the relevant catalyst structure, composition and adsorbed species. Frequently applied operando techniques are discussed, including X-ray absorption spectroscopy, near ambient pressure X-ray photoelectron spectroscopy and infrared spectroscopy. In contrast to these area-averaging spectroscopies, operando surface microscopy by photoemission electron microscopy delivers spatially-resolved data, directly visualizing catalyst heterogeneity. For thorough interpretation, the experimental results should be complemented by density functional theory. The operando approach enables to identify changes of cluster/nanoparticle structure and composition during ongoing catalytic reactions and reveal how molecules interact with surfaces and interfaces. The case studies cover the length-scales from clusters via nanoparticles to meso-scale aggregates, and demonstrate the benefits of specific operando methods. Restructuring, ligand/atom mobility, and surface composition alterations during the reaction may have pronounced effects on activity and selectivity. The nanoscale metal/oxide interface steers catalytic performance via a long ranging effect. Combining operando spectroscopy with switching gas feeds or concentration-modulation provides further mechanistic insights. The obtained fundamental understanding is a prerequisite for improving catalytic performance and for rational design.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/smll.202004289

Operando Surface Spectroscopy and Microscopy during Catalytic Reactions: From Clusters via Nanoparticles to Meso-Scale Aggregates

https://pubs.acs.org/doi/pdf/10.1021/acs.jpcc.1c01096

The Journal of Physical Chemistry C Virtual Special Issue on Metal Clusters, Nanoparticles, and the Physical Chemistry of Catalysis

The catalytic properties of nanoparticles depend on their size, shape and surface/defect structure, with the entire catalyst performance being governed by the corresponding distributions. Herein, we present two routes of mono- and bimetallic nanoparticle synthesis that enable control of the structural parameters, i.e., wet-chemical synthesis and laser ablation in liquid-phase. The latter is particularly suited to create defect-rich nanoparticles. Impregnation routes were applied to prepare Ni and NiCu nanoparticles, whereas nano- and femtosecond laser ablation in liquid-phase were employed to prepare Ni and NiAu nanoparticles. The effects of the Ni:Cu ratio in impregnation and of laser fluence and liquid-medium on laser ablation are discussed. The atomic structure and (surface) composition of the nanoparticles were characterized by electron microscopic (BF-TEM, DF-TEM, HRTEM) and spectroscopic/diffraction techniques (EDX, SAED, XPS, IR), complemented by theory (DFT). The chemically synthesized bimetallic NiCu nanoparticles initially had Cu-rich surfaces, which changed to Ni-rich upon reaction. For laser ablation, depending on conditions (fluence, type of liquid), highly defective, ordered, or core/shell-like nanoparticles were produced. The case studies highlight the specific benefits of each preparation method for catalyst synthesis and discuss the potential of nanoparticles produced by pulsed laser ablation for catalytic applications.

Chemical and Laser Ablation Synthesis of Monometallic and Bimetallic Ni-Based Nanoparticles

Doping gold nanoclusters with palladium has been reported to increase their catalytic activity and stability. PdAu24 nanoclusters, with the Pd dopant atom located at the center of the Au cluster core, were supported on titania and applied in catalytic CO oxidation, showing significantly higher activity than supported monometallic Au25 nanoclusters. After pretreatment, operando DRIFTS spectroscopy detected CO adsorbed on Pd during CO oxidation, indicating migration of the Pd dopant atom from the Au cluster core to the cluster surface. Increasing the number of Pd dopant atoms in the Au structure led to incorporation of Pd mostly in the S-(M-S) n protecting staples, as evidenced by in situ XAFS. A combination of oxidative and reductive thermal pretreatment resulted in the formation of isolated Pd surface sites within the Au surface. The combined analysis of in situ XAFS, operando DRIFTS, and ex situ XPS thus revealed the structural evolution of bimetallic PdAu nanoclusters, yielding a Pd single-site catalyst of 2.7 nm average particle size with improved CO oxidation activity.

Dynamics of Pd Dopant Atoms inside Au Nanoclusters during Catalytic CO Oxidation.

Pd nanoparticles (1 wt %; mean size ∼4 nm) were supported on ∼2 μm sized, but few nanometers thick, graphene nanoplatelets (GNPs) and compared to 1 wt % Pd on activated carbon or γ-alumina. Catalyst morphology, specific surface area, and Pd particle size were characterized by SEM, BET, and TEM, respectively. H2-TPD indicated that GNPs intercalated hydrogen, which may provide additional H2 supply to the Pd nanoparticles during C2H4 hydrogenation. Whereas the two types of Pd/GNPs (NaOH vs calcinated) catalysts were less active than Pd/C and Pd/Al2O3 below 40 °C, at 55 °C they were about 3-4 times more active. As for example Pd/GNPs (NaOH) and Pd/Al2O3 exhibited not too different mean Pd particle size (3.7 vs 2.5 nm, respectively), the higher activity is attributed to the additional hydrogen supply likely by the metal/support interface, as suggested by the varying C2H4 and H2 orders on the different supports. Operando XANES measurements during C2H4 hydrogenation revealed the presence of Pd hydride. The Pd hydride was more stable for Pd/GNPs (NaOH) than for Pd/C, once more pointing to a better hydrogen supply by graphene nanoplatelets.

Klaus Dobrezberger

Papers

Dynamics of Pd Dopant Atoms inside Au Nanoclusters during Catalytic CO Oxidation.

Hydrogenation on Palladium Nanoparticles Supported by Graphene Nanoplatelets