Size sensitivity of supported Ru catalysts for ammonia synthesis: From nanoparticles to subnanometric clusters and atomic clusters

Li, Lingling; Jiang, Yafei; Zhang, Tianhua; Cai, Hualin; Zhou, Yanliang; Lin, Bingyu; Lin, Xingyi; Zheng, Ying; Zheng, Lirong; Wang, Xiuyun; Xu, Chaoqun; Au, Chak Tong; Jiang, Lilong; Li, Jun

doi:10.1016/j.chempr.2021.11.008

Cited by 97 publications

(71 citation statements)

References 60 publications

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“…Subnanometric metal clusters, with dimensions between metal SAs and NPs, have demonstrated unique electronic structures and thus extraordinary physical and chemical features distinctive from SAs and NPs 25 – 27 . So, one can expect that subnanometric clusters interact differently with reactants and intermediates, showing unusual selectivity and activity towards various catalytic reactions 28 . For example, Hutchings et al found that subnanometric Au clusters (~0.5 nm) were highly active for CO oxidation, whereas the activity of Au SAs and large Au NPs (>5 nm) was very low 29 .…”

Section: Introductionmentioning

confidence: 99%

Subnanometric Ru clusters with upshifted D band center improve performance for alkaline hydrogen evolution reaction

et al. 2022

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Subnanometric metal clusters usually have unique electronic structures and may display electrocatalytic performance distinctive from single atoms (SAs) and larger nanoparticles (NPs). However, the electrocatalytic performance of clusters, especially the size-activity relationship at the sub-nanoscale, is largely unexplored. Here, we synthesize a series of Ru nanocrystals from single atoms, subnanometric clusters to larger nanoparticles, aiming at investigating the size-dependent activity of hydrogen evolution in alkaline media. It is found that the d band center of Ru downshifts in a nearly linear relationship with the increase of diameter, and the subnanometric Ru clusters with d band center closer to Femi level display a stronger water dissociation ability and thus superior hydrogen evolution activity than SAs and larger nanoparticles. Benefiting from the high metal utilization and strong water dissociation ability, the Ru clusters manifest an ultrahigh turnover frequency of 43.3 s−1 at the overpotential of 100 mV, 36.1-fold larger than the commercial Pt/C.

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Section: Introductionmentioning

confidence: 99%

Subnanometric Ru clusters with upshifted D band center improve performance for alkaline hydrogen evolution reaction

et al. 2022

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“…In the present work, we choose the N 2 dissociation on the Ru 19 cluster as a model system to monitor the dynamic transformations of cluster structures during the reaction because it is hard to break the strong NN triple bond, making it a rate-determining step for NH 3 synthesis. 36,37 The diameter of the Ru 19 cluster is about ∼0.7 nm, which is close to the size that can be synthesized experimentally; 21 thus, it can serve as a good choice. Here, we directly compute the free energy profiles of the N 2 dissociation reaction at finite temperatures from AIMD simulation combined with the free energy calculation method.…”

Section: Introductionmentioning

confidence: 62%

“…It is still challenging to validate the phase transition catalysis of small clusters by experiment. Interestingly, a recent study reported by Jiang 21 has observed that Ru clusters at sub-nanometric levels with high reactivity at 400 °C occurred in the phase transition region; it might be related to phase transition catalysis. Therefore, according to the temperature dependence of the reaction entropy change, we can select a suitable temperature range for NH 3 synthesis in which the catalyst undergoes a solid–liquid phase transition.…”

Section: Resultsmentioning

confidence: 95%

“…Recently, sub-nanometer Ru clusters have been treated as active catalysts with better catalytic performances. 21 They can be rearranged under reaction conditions and expose more active sites, 22 suggesting that the structural dynamics of clusters can improve the catalytic activity of the NH 3 synthesis reaction. However, early theoretical studies on the NH 3 synthesis of Ru clusters employing DFT predetermine a stable or metastable configuration and search for the corresponding transition state of potential energy surfaces.…”

Section: Introductionmentioning

confidence: 99%

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Structural dynamics of Ru clusters during nitrogen dissociation in ammonia synthesis

Fan

Liu

Gong

et al. 2022

Phys. Chem. Chem. Phys.

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“…The ensemble size of noble metal atoms on the surface of the catalyst has a great influence on the reaction path and activity in many reactions [34–36,113–122] . For example, the electrocatalytic MOR mainly proceeds via a CO intermediate, which requires at least three contiguous Pt atoms on the catalyst surface [114] .…”

Section: The Roles Of the Ligand In Surface‐engineering Of Noble Meta...mentioning

confidence: 99%

Effects of Ligands on Synthesis and Surface‐Engineering of Noble Metal Nanocrystals for Electrocatalysis

Liu

Gao

2022

ChemElectroChem

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Noble metal nanocrystals are a family of important catalysts for a broad range of processes (especially electrocatalytic ones), which are usually obtained as a hybrid each containing a metallic core and a ligand shell. It is well recognized that the ligand plays a critical role in regulating the crystal growth into different shapes and maintaining the colloidal stability of the nanocrystals. Recently, more effects of the ligand were revealed in controlling both the synthesis and the surface property of noble metal nanocrystals, which could be maneuvered to achieve distinctive catalytic properties. In this review, we present a summary of the roles of the ligand based on typical results from the literature. The review begins with a discussion on the roles of the ligand in the controlled synthesis of noble metal nanocrystals, including the shape control, the reduction potential control for suppressing self-nucleation and galvanic replacement reaction, and the electroless plating effect for noble metal/non-noble metal co-reduction. The following section includes a discussion of the effects of the ligand on the surface property of noble metal nanocrystals, including the ensemble size engineering, the ligand-metal electron transfer, and the local microenvironment construction, toward designable electrocatalytic properties. At the end, we provide our perspectives on the future research of ligand engineering as an advanced technique for tailoring electrocatalytic properties of noble metal nanocrystals.

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Size sensitivity of supported Ru catalysts for ammonia synthesis: From nanoparticles to subnanometric clusters and atomic clusters

Cited by 97 publications

References 60 publications

Subnanometric Ru clusters with upshifted D band center improve performance for alkaline hydrogen evolution reaction

Subnanometric Ru clusters with upshifted D band center improve performance for alkaline hydrogen evolution reaction

Structural dynamics of Ru clusters during nitrogen dissociation in ammonia synthesis

Effects of Ligands on Synthesis and Surface‐Engineering of Noble Metal Nanocrystals for Electrocatalysis

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