d–p Orbital hybridization in RhSn catalyst boosts hydrogen oxidation reaction under alkaline electrolyte

Su, Lixin; Zhao, Yuanmeng; Jin, Yiming; Fan, Xinran; Liu, Zeyu; Luo, Wei

doi:10.1039/d2ta05828f

Cited by 11 publications

(5 citation statements)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the optimized catalyst, the involved Ni/NiO and Ir–O species provide an oxygenophilic surface for the catalyst, thereby enhancing the binding of OH species and ultimately increasing the concentration of OH ad species on the surface. 37–39 Simultaneously, the electron transfer from Ni/NiO to Ir mitigates the HBE on Ir sites from an excessively strong level to a moderate level, thus facilitating the desorption process of H ad . The simultaneous binding of H ad and OH ad thereby accelerates the crucial Volmer step (H ad -M + OH − ↔ H 2 O + e − + M*) to a certain extent, consequently augmenting the catalytic activity.…”

Section: Resultsmentioning

confidence: 99%

A trinary support of Ni/NiO/C to immobilize Ir nanoclusters for alkaline hydrogen oxidation

Kang,

Peng,

Wei

et al. 2024

Dalton Trans.

View full text Add to dashboard Cite

show abstract

Section: Resultsmentioning

confidence: 99%

A trinary support of Ni/NiO/C to immobilize Ir nanoclusters for alkaline hydrogen oxidation

Kang,

Peng,

Wei

et al. 2024

Dalton Trans.

View full text Add to dashboard Cite

show abstract

“…As demonstrated in Figure i, for the high-resolution Ru 3p XPS spectra, contrast with Ru/C (462.94 eV), the binding energies of Ru 0 in Sn-Ru/C (491.63 eV) and Ga-Ru/C (462.47 eV) are much lower, suggesting the electron transfer from Sn or Ga to Ru, resulting in a decreased Ru valance state in Sn-Ru/C and Ga-Ru/C. In addition, the Sn 3d spectrum (Figure S5) in Sn-Ru/C displays three peaks at 482.0, 484.3, and 486.4 eV, which can be attributed to Ru 3p, Sn 3d 5/2 of metallic Sn, and oxidative Sn, respectively. , Moreover, as shown in Figure S6, Ga in Ga-Ru/C is also in the form of metallic Ga (1117.20 eV) and partial oxidation states. , The partial oxidation states might be due to the inevitable surface oxidation by exposure to air. Moreover, to further understand the electronic effect, Mulliken charges and electron density difference were obtained on Sn-Ru, Ga-Ru, and Ru.…”

Section: Resultsmentioning

confidence: 99%

Boosting Hydrogen Oxidation Kinetics by Promoting Interfacial Water Adsorption on d-p Hybridized Ru Catalysts

Liang

et al. 2023

ACS Catal.

Self Cite

View full text Add to dashboard Cite

The search for highly efficient and cost-effective electrocatalysts for hydrogen oxidation reaction (HOR) under alkaline electrolytes is essential for the commercial application of anion exchange membrane fuel cells. However, the kinetics of HOR in an alkaline media is much slower than that in an acidic electrolyte, which usually results in orders of magnitude decrease in the catalytic performance. Herein, we report the synthesis of d-p orbital hybridized Ru catalysts through Sn/Ga doping. Density functional theory (DFT) calculations and experimental results including H 2 -temperature programmed desorption (H 2 -TPD) and in situ Raman spectra unveil that the electronic structure modification of Ru derived from the unconventional d-p hybridization could lead to the promoted interfacial water adsorption ability and optimized hydrogen adsorption free energy during the alkaline HOR process. As expected, the d-p hybridized Ru catalyst shows much decreased formation energy of water, which contributes to the changed potential-determining step (PDS) and remarkable HOR activity with the mass activity up to 1790 mA mg Ru −1 . This work not only illustrates the key role of interfacial water adsorption ability but also provides a strategy for rationally designing advanced electrocatalysts for alkaline HOR.

show abstract

“…For real operative fuel cells, CO tolerance of the anode HOR catalysts is another critical concern in the presence of trace CO impurities in industrial H 2 supply. − According to the CO stripping curves recorded in 0.1 M KOH solutions (Figure S8), the peak position of Pt 2 –Rh NSs exhibits a 60 mV negative shift compared to commercial Pt/C, implying a much weaker CO surface binding. Figure a shows the polarization curves of the CO oxidation reaction (COOR) on Pt 2 –Rh NSs, a/c-Rh NSs, and Pt/C, where the Pt 2 –Rh NSs exhibit the lowest onset potential.…”

Section: Resultsmentioning

confidence: 99%

Host–Guest Ensemble Effect on Dual-Pt atom-on-Rh Nanosheets Enables High-Efficiency and Anti-CO Alkaline Hydrogen Oxidation

et al. 2023

View full text Add to dashboard Cite

Explicit atomic coordinations of binary metal atoms on low-dimensional host–guest-type bimetallic nanomaterials can arouse unique ensemble effects and significantly improve the catalysis performances, but they confront a formidable challenge in chemical synthesis. Here, we draw on a thermoinduced secondary crystallization process of preprepared amorphous/crystalline hybrid ultrathin Rh nanosheets (NSs) to capture Pt atoms into the two-dimensional (2D) Rh lattice, by which precisely controlled Pt atomic dispersions from a single atom to dual atoms and to clustered atoms can be facilely elected and embedded into the ultrathin Rh hosts. Among them, the dual-Pt atom-on-Rh (denoted as Pt2–Rh) NSs exhibit an extremely high activity and an excellent CO tolerance for the alkaline hydrogen oxidation reaction (HOR), achieving a 18.5 times higher mass activity at 50 mV overpotential than that of commercial Pt/C. Theoretical studies indicate that the host–guest ensemble effect aroused by the specific pairwise Pt2-on-Rh coordination feature can moderately enhance both the surface *H and *OH bindings, which synergistically lower the free energy of the rate-determining Volmer step and thus promote the combination of neighboring *H and *OH to form H2O. Enhanced *H adsorption can also prevent the main available sites from being occupied by hydroxyl groups in alkaline conditions. The free energy diagram and anti-CO experiments coherently indicate that the oxidation of *CO by neighboring *OH to form *COOH is kinetically more favorable to proceed on the Pt2–Rh NSs, effectively preventing the catalysts from being poisoned. This work sheds light on the ensemble effect of host–guest heteroatom coordinations for designing high-efficiency alkaline HOR catalysts.

show abstract

d–p Orbital hybridization in RhSn catalyst boosts hydrogen oxidation reaction under alkaline electrolyte

Abstract: Exploiting new strategy to design hydrogen oxidation reaction (HOR) catalysts with high-performance under alkaline electrolyte is highly desirable for the development of alkaline exchange membrane fuel cell (AEMFC). Herein, we...

Cited by 11 publications

References 53 publications

A trinary support of Ni/NiO/C to immobilize Ir nanoclusters for alkaline hydrogen oxidation

A trinary support of Ni/NiO/C to immobilize Ir nanoclusters for alkaline hydrogen oxidation

Boosting Hydrogen Oxidation Kinetics by Promoting Interfacial Water Adsorption on d-p Hybridized Ru Catalysts

Host–Guest Ensemble Effect on Dual-Pt atom-on-Rh Nanosheets Enables High-Efficiency and Anti-CO Alkaline Hydrogen Oxidation

Contact Info

Product

Resources

About