Single Atoms of Pt-Group Metals Stabilized by N-Doped Carbon Nanofibers for Efficient Hydrogen Production from Formic Acid

Bulushev, Dmitri A.; Zacharska, Monika; Lisitsyn, A.S.; Podyacheva, O. Yu.; Hage, Fredrik S.; Ramasse, Quentin M.; Bangert, U.; Bulusheva, L. G.

doi:10.1021/acscatal.6b00476

Cited by 275 publications

(210 citation statements)

References 46 publications

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“…This suggests the importance of the support selection when striving to prepare stable atom catalysts. It has been reported in the literature that doping the graphene lattice with N can enhance the Pt–C support interaction energy, resulting in highly stable Pt catalysts444546. This enhanced binding energy from the incorporation of N-dopants in the graphene lattice has been attributed to creating preferred nucleation sites for metals and metal oxides47.…”

Section: Discussionmentioning

confidence: 99%

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

et al. 2016

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Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance. S ecuring renewable and reliable sources of clean energy is one of the world's foremost challenges. Addressing this challenge is not only critical for the global economy but will also aid in the mitigation of environmental and health hazards caused by fossil fuels 1 . Hydrogen is the cleanest fuel available and is believed to be one of the most promising energy sources of the twenty-first century 2,3 . However, the majority of the hydrogen produced today is derived from steam-reformed methane, which is sourced from fossil reserves and produces a substantial amount of CO 2 (ref. 4). The production of hydrogen from water electrolysis is a promising alternative to the current CO 2 -emitting fossil fuel-based energy systems 5,6 .Platinum (Pt)-based catalysts are generally considered to be the most effective electrocatalysts for the hydrogen evolution reaction (HER) 5,7 . Unfortunately, Pt is expensive and scarce, limiting the commercial potential for such catalysts. The development of active, stable and inexpensive electrocatalysts for water splitting is a key step in the realization of a hydrogen economy, which is based on the use of molecular hydrogen for energy storage.Significant effort has been devoted to the search of non-preciousmetal-based HER catalysts, including sulfide-based materials 8-11 , and C 3 N 4 (refs 12-14). Although these candidate materials show promising activities for the HER, the activities of these catalysts in their present form are insufficient for industrial applications 15 .To overcome the challenges associated with the Pt HER catalysts and to drive the cost of H 2 production from water electrolysis down, it is very important to markedly decrease the Pt loading and increase the Pt utilization efficiency. Currently, supported Pt nanoparticles (NPs) are typically used to promote Pt activity towards the HER. Unfortunately, the geometry of the NPs limit the majority of the Pt atoms to the particle core, deeming them ineffect...

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Section: Discussionmentioning

confidence: 99%

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

et al. 2016

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“…The easy decomposition of formic acid is favored by the proximity of a formed adsorbed hydrogen atom and a hydrogen atom of the carboxyl fragment, which are directed toward each other. This is an ideal configuration for the formation of hydrogen and CO 2 molecules [72].…”

Section: Predicting the Effect Of Heteroatom-mediated Smsi On The Catmentioning

confidence: 99%

Understanding Heteroatom-Mediated Metal–Support Interactions in Functionalized Carbons: A Perspective Review

2018

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Featured Application: Surface engineering for catalysis and energy.Abstract: Carbon-based materials show unique chemicophysical properties, and they have been successfully used in many catalytic processes, including the production of chemicals and energy. The introduction of heteroatoms (N, B, P, S) alters the electronic properties, often increasing the reactivity of the surface of nanocarbons. The functional groups on the carbons have been reported to be effective for anchoring metal nanoparticles. Although the interaction between functional groups and metal has been studied by various characterization techniques, theoretical models, and catalytic results, the role and nature of heteroatoms is still an object of discussion. The aim of this review is to elucidate the metal-heteroatoms interaction, providing an overview of the main experimental and theoretical outcomes about heteroatom-mediated metal-support interactions. Selected studies showing the effect of heteroatom-metal interaction in the liquid-phase alcohol oxidation will be also presented.

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“…7,12 The adsorption and catalytic properties of Cu are very much different from the properties of Pt-group metals.…”

Section: Introductionmentioning

confidence: 99%

Copper on carbon materials: stabilization by nitrogen doping

et al. 2017

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The applicability of Cu/C catalysts is limited by sintering of Cu leading to deactivation in catalytic reactions.We show that the problem of sintering could be resolved by N-doping of the carbon support. Cu nanocatalysts with 1 at% of metal were synthesized by Cu acetate decomposition on N-free and Ndoped (5.7 at% N) mesoporous carbon supports as well as on thermally expanded graphite oxide.Catalytic properties of these samples were compared in hydrogen production from formic acid decomposition. The N-doping leads to a strong interaction of the Cu species with the support providing stabilization of Cu in the form of clusters of less than 5 nm in size and single Cu atoms, which were observed in a significant ratio by atomic resolution HAADF/STEM even after testing the catalyst under harsh conditions of the reaction at 600 K. The mean size of the obtained Cu clusters was by a factor of 7 smaller than that of the particles in the N-free catalyst. The N-doped Cu catalyst possessed good stability in the formic acid decomposition at 478 K for at least 7 h on-stream and a significantly higher catalytic activity than the N-free Cu catalysts. The nature of the strongly interacting Cu species was studied by XPS, XRD and other methods as well as by DFT calculations. The presence of single Cu atoms in the N-doped catalysts should be attributed to their strong coordination by pyridinic nitrogen atoms at the edge of the graphene sheets of the support. We believe that the N-doping of the carbon support will allow expanding the use of Cu/C materials for different applications avoiding sintering and deactivation.

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Single Atoms of Pt-Group Metals Stabilized by N-Doped Carbon Nanofibers for Efficient Hydrogen Production from Formic Acid

Cited by 275 publications

References 46 publications

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

Understanding Heteroatom-Mediated Metal–Support Interactions in Functionalized Carbons: A Perspective Review

Copper on carbon materials: stabilization by nitrogen doping

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