Platinum-based heterogeneous catalysts are critical to many important commercial chemical processes, but their efficiency is extremely low on a per metal atom basis, because only the surface active-site atoms are used. Catalysts with single-atom dispersions are thus highly desirable to maximize atom efficiency, but making them is challenging. Here we report the synthesis of a single-atom catalyst that consists of only isolated single Pt atoms anchored to the surfaces of iron oxide nanocrystallites. This single-atom catalyst has extremely high atom efficiency and shows excellent stability and high activity for both CO oxidation and preferential oxidation of CO in H2. Density functional theory calculations show that the high catalytic activity correlates with the partially vacant 5d orbitals of the positively charged, high-valent Pt atoms, which help to reduce both the CO adsorption energy and the activation barriers for CO oxidation.
Supported metal nanostructures are the most widely used type of heterogeneous catalyst in industrial processes. The size of metal particles is a key factor in determining the performance of such catalysts. In particular, because low-coordinated metal atoms often function as the catalytically active sites, the specific activity per metal atom usually increases with decreasing size of the metal particles. However, the surface free energy of metals increases significantly with decreasing particle size, promoting aggregation of small clusters. Using an appropriate support material that strongly interacts with the metal species prevents this aggregation, creating stable, finely dispersed metal clusters with a high catalytic activity, an approach industry has used for a long time. Nevertheless, practical supported metal catalysts are inhomogeneous and usually consist of a mixture of sizes from nanoparticles to subnanometer clusters. Such heterogeneity not only reduces the metal atom efficiency but also frequently leads to undesired side reactions. It also makes it extremely difficult, if not impossible, to uniquely identify and control the active sites of interest.The ultimate small-size limit for metal particles is the single-atom catalyst (SAC), which contains isolated metal atoms singly dispersed on supports. SACs maximize the efficiency of metal atom use, which is particularly important for supported noble metal catalysts. Moreover, with well-defined and uniform single-atom dispersion, SACs offer great potential for achieving high activity and selectivity.In this Account, we highlight recent advances in preparation, characterization, and catalytic performance of SACs, with a focus on single atoms anchored to metal oxides, metal surfaces, and graphene. We discuss experimental and theoretical studies for a variety of reactions, including oxidation, water gas shift, and hydrogenation. We describe advances in understanding the spatial arrangements and electronic properties of single atoms, as well as their interactions with the support. Single metal atoms on support surfaces provide a unique opportunity to tune active sites and optimize the activity, selectivity, and stability of heterogeneous catalysts, offering the potential for applications in a variety of industrial chemical reactions.
A cost-effective catalyst should have a high dispersion of the active atoms, together with a controllable surface structure for the optimization of activity, selectivity, or both. We fabricated nanocages by depositing a few atomic layers of platinum (Pt) as conformal shells on palladium (Pd) nanocrystals with well-defined facets and then etching away the Pd templates. Density functional theory calculations suggest that the etching is initiated via a mechanism that involves the formation of vacancies through the removal of Pd atoms incorporated into the outermost layer during the deposition of Pt. With the use of Pd nanoscale cubes and octahedra as templates, we obtained Pt cubic and octahedral nanocages enclosed by {100} and {111} facets, respectively, which exhibited distinctive catalytic activities toward oxygen reduction.
The recent explosive growth in research on catalysis by supported single metal atoms proves the scientific interest in this new frontier of heterogeneous catalysis. A supported single-atom catalyst (SAC) contains only isolated individual atoms dispersed on, and/or coordinated with, the surface atoms of an appropriate support. SACs not only maximize the atom efficiency of expensive metals but also provide an alternative strategy to tune the activity and selectivity of a catalytic reaction. When single metal atoms are strongly anchored onto high-surface-area supports, SACs offer a great potential to significantly transform the field of heterogeneous catalysis, which has been critical to enabling many important technologies. In this Perspective, I discuss the most recent advances in preparing, characterizing, and catalytically testing SACs with a focus on correlating the structural perspective of the anchored single metal atoms to the observed catalytic performances. The grand challenge to successfully developing practical SACs is to find appropriate approaches to strongly anchor the single metal atoms and to keep them stable and functional during the desired catalytic reactions. I will highlight the recent advances to overcome this barrier to develop SACs for a variety of important catalytic transformations of molecules.
The catalytic hydrogenation of nitroarenes is an environmentally benign technology for the production of anilines, which are key intermediates for manufacturing agrochemicals, pharmaceuticals and dyes. Most of the precious metal catalysts, however, suffer from low chemoselectivity when one or more reducible groups are present in a nitroarene molecule. Herein we report FeO x -supported platinum single-atom and pseudo-single-atom structures as highly active, chemoselective and reusable catalysts for hydrogenation of a variety of substituted nitroarenes. For hydrogenation of 3-nitrostyrene, the catalyst yields a TOF of B1,500 h À 1 , 20-fold higher than the best result reported in literature, and a selectivity to 3-aminostyrene close to 99%, the best ever achieved over platinum group metals. The superior performance can be attributed to the presence of positively charged platinum centres and the absence of Pt-Pt metallic bonding, both of which favour the preferential adsorption of nitro groups.
High specific activity and cost effectiveness of single-atom catalysts hold practical value for water gas shift (WGS) reaction toward hydrogen energy. We reported the preparation and characterization of Ir single atoms supported on FeO(x) (Ir1/FeO(x)) catalysts, the activity of which is 1 order of magnitude higher than its cluster or nanoparticle counterparts and is even higher than those of the most active Au- or Pt-based catalysts. Extensive studies reveal that the single atoms accounted for ∼70% of the total activity of catalysts containing single atoms, subnano clusters, and nanoparticles, thus serving as the most important active sites. The Ir single atoms seem to greatly enhance the reducibility of the FeO(x) support and generation of oxygen vacancies, leading to the excellent performance of the Ir1/FeO(x) single-atom catalyst. The results have broad implications on designing supported metal catalysts with better performance and lower cost.
Earth-abundant Ni single atoms on commercial carbon black were synthesized in large quantities via an economic and scalable protocol, with record-high selectivity and activity toward CO production. Scaling up the electrodes into a 10 3 10-cm 2 modular cell achieves a high overall current over 8 A while maintaining a nearly exclusive CO evolution.
We report a robust synthesis of Ag@Au core-shell nanocubes by directly depositing Au atoms on the surfaces of Ag nanocubes as conformal, ultrathin shells. Our success relies on the introduction of a strong reducing agent to compete with and thereby block the galvanic replacement between Ag and HAuCl4. An ultrathin Au shell of 0.6 nm thick was able to protect the Ag in the core in an oxidative environment. Significantly, the core-shell nanocubes exhibited surface plasmonic properties essentially identical to those of the original Ag nanocubes, while the SERS activity showed a 5.4-fold further enhancement owing to an improvement in chemical enhancement. The combination of excellent SERS activity and chemical stability may enable a variety of new applications.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.