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.
Nanostructured Fe-N-C materials represent a new type of "platinum-like" non-noble-metal catalyst for various electrochemical reactions and organic transformations. However, no consensus has been reached on the active sites of the Fe-N-C catalysts because of their heterogeneity in particle size and composition. In this contribution, we have successfully prepared atomically dispersed Fe-N-C catalyst, which exhibited high activity and excellent reusability for the selective oxidation of the C-H bond. A wide scope of substrates, including aromatic, heterocyclic, and aliphatic alkanes, were smoothly oxidized at room temperature, and the selectivity of corresponding products reached as high as 99%. By using sub-ångström-resolution HAADF-STEM in combination with XPS, XAS, ESR, and Mössbauer spectroscopy, we have provided solid evidence that Fe is exclusively dispersed as single atoms via forming FeN (x = 4-6) and that the relative concentration of each FeN species is critically dependent on the pyrolysis temperature. Among them, the medium-spin FeN affords the highest turnover frequency (6455 h), which is at least 1 order of magnitude more active than the high-spin and low-spin FeN structures and 3 times more active than the FeN structure, although its relative concentration in the catalysts is much lower than that of the FeN structures.
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.
The ever-increasing amount of anthropogenic carbon dioxide (CO2) emissions has resulted in great environmental impacts, the heterogeneous catalysis of CO2 hydrogenation to methanol is of great significance.
The electrochemical oxygen reduction reaction in acidic media offers an attractive route for direct hydrogen peroxide (H 2 O 2 ) generation and on-site applications. Unfortunately there is still a lack of cost-effective electrocatalysts with high catalytic performance. Here, we theoretically designed and experimentally demonstrated that a cobalt single-atom catalyst (Co SAC) anchored in nitrogendoped graphene, with optimized adsorption energy of the *OOH intermediate, exhibited a high H 2 O 2 production rate, which even slightly outperformed the state-of-the-art noble-metal-based electrocatalysts. The kinetic current of H 2 O 2 production over Co SAC could reach 1 mA=cm 2 disk at 0.6 V versus reversible hydrogen electrode in 0.1 M HClO 4 with H 2 O 2 faraday efficiency > 90%, and these performance measures could be sustained for 10 h without decay. Further kinetic analysis and operando X-ray absorption study combined with density functional theory (DFT) calculation demonstrated that the nitrogen-coordinated single Co atom was the active site and the reaction was rate-limited by the first electron transfer step.
The single-atom Co–N–C catalyst with the structure of CoN4C8-1-2O2 shows excellent performance for the chemoselective hydrogenation of nitroarenes to produce azo compounds under mild reaction conditions.
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