Atomically precise structures of Pt2(S-Adam)4(PPh3)2 complexes and catalytic application in propane dehydrogenation

Lin, Xin; Zhang, Junying; Tang, Jie; Yang, Yang; Liu, Chao; Huang, Jiahui

doi:10.1039/d1nr07286b

Cited by 5 publications

(6 citation statements)

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Briefly, Pt precursors were prepared firstly via the coordination of K 2 PtCl 4 with the corresponding ligands (1-adamantanethiol and triphenylphosphine) in the presence of phase transfer agent (tetra-n-octylammonium bromide) and NaBH 4 . 43 Subsequently, the resulting metal precursors were loaded on OCNTs (denoted as Pt/CNT) and then annealed at different temperatures of 400, 600, and 800 °C in argon. The asprepared catalysts were denoted as Pt/CNT-400, Pt/CNT-600, and Pt/CNT-800, with the actual Pt loadings of 4.4, 4.7, and 4.6 wt %, as determined by inductively coupled plasma optical emission spectrometer (ICP-OES).…”

Section: Preparation and Characterization Of Catalystsmentioning

confidence: 99%

Distance-Dependent Charge Redistribution Boosts Hydrogen Evolution in Hybrid Catalysts

Lin,

Li,

et al. 2024

ACS Catal.

Self Cite

View full text Add to dashboard Cite

The hybrid catalysts have demonstrated decent catalytic performance for hydrogen evolution reaction (HER), but the specific roles and interactions of different species contributing to the activity remain ambiguous. Here we synthesized Pt hybrid catalysts through the ligand preprotected pyrolysis method, which has demonstrated its universality for preparing Ir and Ru hybrid catalysts due to the unique constraining and pulling effects exerted by ligands. The hybrid catalysts demonstrated higher activity than single-component catalysts, such as Pt single atoms or Pt nanoparticles. Particularly, the Pt/CNT-600 hybrid catalyst displayed good HER activity with a low overpotential of 15 mV at −10 mA cm −2 , and its mass activity was 8 times than that of Pt/ C-20%. In hybrid catalysts, the synergistic effect via charge redistribution in the Pt 1 and Pt n sites afforded the optimal Pt−H binding energy for fast HER kinetics. More importantly, it presented an intense dependence of charge distribution on the distance between Pt 1 and Pt n sites, and the volcanic curve indicated the optimal distance of approximately 0.43 nm for the synergistic effect. Consequently, we proposed that the Pt n -mPt 1 active units offered the dominant contribution to catalytic activity, resulting from the collective synergistic effect between Pt n and every adjacent Pt 1 site. This study not only presents a universal method for synthesizing hybrid catalysts but also offers fresh insights into their rational design and activity enhancement by manipulating the intersite distance and interaction effect.

show abstract

Section: Preparation and Characterization Of Catalystsmentioning

confidence: 99%

Distance-Dependent Charge Redistribution Boosts Hydrogen Evolution in Hybrid Catalysts

Lin,

Li,

et al. 2024

ACS Catal.

Self Cite

View full text Add to dashboard Cite

show abstract

“…In the study of catalyst selection, the ability to activate CH bonds is a point that should not be neglected in the selection of catalysts. For the well‐known Cr‐based catalysts [17–21] and Pt‐based catalysts [22–30], for example, each of them has a different way of activating CH bonds, and their ability to activate CH bonds is of course also different. Pt‐based catalysts activate propane CH bonds mainly through adsorption and electron transfer processes.…”

Section: Introductionmentioning

confidence: 99%

Theoretical research on Pd cluster catalysts for the direct dehydrogenation of propane to propylene

Wang,

Kang

2024

Int J of Quantum Chemistry

View full text Add to dashboard Cite

In this article, the feasibility of catalytic dehydrogenation of propane by Pd clusters (Pd7, Pd6C, Pd6Si, Pd6Ge, and Pd6Sn) was investigated by using density functional theory (DFT). It was found that Pd6Sn has the strongest electron mobility and the ability to activate CH bonds, and the highest adsorption barrier (−75.16 kcal/mol) with propylene. The first pathway of the Pd6Sn‐catalyzed primary reaction has the lowest decisive step barrier (16.65 kcal/mol), and the second pathway of the secondary reaction has the highest decisive step barrier (62.25 kcal/mol). It was demonstrated that both the catalyst's electron‐leaping ability and the ability to activate CH bonds were the key factors affecting the activity, and the adsorption strength of the catalyst to the product was the main factor affecting the selectivity. It was shown that Pd cluster‐catalyzed PDH is theoretically feasible and Pd6Sn is likely to be a potential cluster catalyst for propane dehydrogenation.

show abstract

“…16 After ligands that provide S and P coordinating atoms to Pt were introduced, the atomic Pt species exhibit a mixed oxidation state of positively charged Pt 2+ and metallic Pt 0 , showing better catalytic performance than Pt in the positively charged Pt 2+ state, with a propane conversion of about 18.3% and propylene selectivity of 93% at 550 °C in PDH. 21 Chen et al also suggested that fully exposed Pt 3 clusters on defect-rich graphene show a unique atomic arrangement where two Pt atoms are connected to the C/O atoms on the support and likely carry a positive charge, while the third Pt atom, bonded solely to other Pt atoms, may be metallic in character. Their experiments showed a high conversion (35.4%) and alkene selectivity (99.0%) for nbutane dehydrogenation at 450 °C compared to single Pt atoms and typical Pt nanoparticles.…”

Section: Introductionmentioning

confidence: 99%

“…Atomically dispersed metal species on metal-oxide supports usually carry positive charges when coordinated to oxygen ions, but sometimes they can remain in a metallic zerovalent state. ,,− For instance, as the Pt loading decreases, a dramatic increase in the proportion of positively charged Pt δ+ species was observed on the subnanometer-sized metal clusters over γ-Al 2 O 3 . After ligands that provide S and P coordinating atoms to Pt were introduced, the atomic Pt species exhibit a mixed oxidation state of positively charged Pt 2+ and metallic Pt 0 , showing better catalytic performance than Pt in the positively charged Pt 2+ state, with a propane conversion of about 18.3% and propylene selectivity of 93% at 550 °C in PDH . Chen et al.…”

Section: Introductionmentioning

confidence: 99%

Identifying the Active Phase on Atomically Dispersed Catalysts for Propane Dehydrogenation: Positively Charged vs Metallic Transition Metals

Hu,

Lei,

Sui

et al. 2024

ACS Catal.

View full text Add to dashboard Cite

Atomically dispersed transition-metal catalysts have received increasing research interest in heterogeneous catalysis. However, the nature of the real active phase, specifically how the oxidation state of active species may affect the catalytic performance, remains elusive. In this work, ab initio molecular dynamics and large-scale molecular dynamics simulations based on neural network potentials have been employed to assess the structural stability of 52 single-and dual-atom catalysts with transition metals including Mn−Cu, Ru−Ag, and Os−Au embedded in the metal or oxygen vacancies on the defective TiO 2 surface. On the thermodynamically stable surfaces, microkinetic analysis combined with results from DFT calculations indicates the metal atoms stabilized in the Ti vacancies with a positive oxidation state generally promote propane dehydrogenation (PDH) with the assistance of adjacent O sites, whereas those in the O vacancies exhibiting metallic properties act as a sole active site for C−H bond activation. The scaling relations established show that the adsorption energies of H and H&H can be used as two simple but effective PDH activity descriptors across both positively charged and metallic metal-doped surfaces. The calculated TOF under the realistic experimental conditions reaches a maximum at a slightly negative oxidation state, implying the Pt and Ir in the metallic state would dominate the kinetics of PDH. Moreover, a high selectivity toward propylene may be attained because the scaling relation between the activation energies for the C−H bond breaking in propane and propylene is broken in the absence of multiple metallic metal−metal sites on the atomically dispersed catalysts. An understanding of this structure−activity relationship is of vital importance for the rational design and optimization of heterogeneous catalysts for light alkane dehydrogenation.

show abstract

Atomically precise structures of Pt₂(S-Adam)₄(PPh₃)₂ complexes and catalytic application in propane dehydrogenation

Abstract: As the bridge between single metal atoms and metal nanoclusters, atomically precise metal complexes are of great significance for the controlled synthesis and catalytic applications at the atomic level. Herein,...

Cited by 5 publications

References 65 publications

Distance-Dependent Charge Redistribution Boosts Hydrogen Evolution in Hybrid Catalysts

Distance-Dependent Charge Redistribution Boosts Hydrogen Evolution in Hybrid Catalysts

Theoretical research on Pd cluster catalysts for the direct dehydrogenation of propane to propylene

Identifying the Active Phase on Atomically Dispersed Catalysts for Propane Dehydrogenation: Positively Charged vs Metallic Transition Metals

Contact Info

Product

Resources

About