Light alloying element-regulated noble metal catalysts for energy-related applications

Chen, Hui; Zhang, Bo; Liang, Xiao; Zou, Xiaoxin

doi:10.1016/s1872-2067(21)63899-8

Cited by 33 publications

(22 citation statements)

References 201 publications

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“…Introducing light elements (e.g., B, C, N in the p-block group) into the metal lattice is an important method to improve the catalytic activity of transition metals. [64][65][66] However, due to the small size, low content and disordered distribution of these light atoms, it is often difficult to reveal their alloying effects on catalytic performances. The Pd-B alloy represents one of the most typical light element-doped metal catalytic systems, and has been widely studied in many catalytic reactions such as selective hydrogenation reactions of alkynes, formic acid (HCOOH) and hydrous hydrazine (H 2 NNH 2 ÁH 2 O) decompositions.…”

Section: P-block-element Doped Metal Catalystsmentioning

confidence: 99%

d–sp orbital hybridization: a strategy for activity improvement of transition metal catalysts

Chen

Wang

et al. 2022

Chem. Commun.

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Section: P-block-element Doped Metal Catalystsmentioning

confidence: 99%

d–sp orbital hybridization: a strategy for activity improvement of transition metal catalysts

Chen

Wang

et al. 2022

Chem. Commun.

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“…It is not clear that to what extent B-doping may affect the Pt lattice and the electronic structure of surface Pt sites and thereby resulting in the activity and durability of a Pt–B catalyst . The first report on the synthesis and application of B-doped PGMs in energy electrocatalysis is on a Pd–B/C catalyst for the formic acid oxidation reaction by this group in 2009 and has triggered a series of relevant research works. − Despite that Pd–B/C was later found to exhibit an improved ORR activity relative to Pd/C, , in general, Pd-based catalysts (including Pd–B/C) are far inferior to Pt-based catalysts in terms of overall ORR performance, in particular, durability in acidic media, and are thus not competent in PEMFC’s application. Given the similar lattice structure of Pt and Pd, it is of great interest to explore the prospect of developing the B-doped Pt catalyst (Pt–B/C) with a more effective ORR performance than the Pt/C benchmark catalyst in PEMFCs.…”

Section: Introductionmentioning

confidence: 99%

Interstitial B-Doping in Pt Lattice to Upgrade Oxygen Electroreduction Performance

et al. 2022

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The dissolution of M in currently popular Pt–M alloy catalysts (M = Co, Ni, and Fe) during the oxygen reduction reaction (ORR) may deter their wide application in proton exchange membrane fuel cells (PEMFCs). In this work, interstitial B-doping in the Pt lattice is instead used to design a durable and active ORR catalyst, by taking advantage of its unique regulation of the electronic structure of surface Pt sites. 3 nm Pt–B nanoparticles on carbon black (Pt–B/C) are obtained using dimethylamine borane (DMAB) as a reductant and the B source in a mixed H2O–ethylene glycol precursor solution. The formation of the B-doped Pt catalyst is verified by inductively coupled plasma-atomic emission spectrometry, X-ray diffractometry, and spherical aberration-corrected scanning transmission electron microscopy. Both half-cell and single-cell tests indicate that the as-synthesized Pt–B/C catalyst outperforms the commercial Pt/C(com) in terms of activity and durability. In particular, the Pt–B/C-based PEMFC exhibits an initial maximum power density 1.24 times as high as the Pt/C(com)-based one under otherwise same conditions, with a 15% decay for the former versus a 45% decay for the latter after 30 000 cycles of the accelerated degradation test (ADT). Comparative DFT calculations on B-doped and undoped Pt(111) surfaces reveal that the lowered Pt d-band center and the strong interaction of Pt–B bonding weaken the binding of OH and O species to surface Pt sites and lessen oxidative disruption of surface Pt atoms. This interstitial metalloid doping in conjunction with the simple and scalable synthesis protocol enables the Pt–B/C to be a competitive ORR catalyst for the PEMFCs.

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“…[18] Alloy with light elements to form the interstitial Pd-H, [19,20] Pd-C, [21] Pd-O, [22,23] Pd-B, [24,25] Pd-P, [26,27] Pd-S [28] and Pd-N [29] compounds have been proved to be a powerful strategy to optimize the electrocatalytic performance. [30,31] The doping light elements can reform the performance of conventional Pd-based catalysts in the following ways [32] : i) The light elements (e.g., H, C, and B) can evenly infiltrate into the metal lattice in consequence of their smaller atomic size resulting in the lattice expansion of Pd; ii) There would occur a significant electron transfer between doping light atoms and adjacent Pd atoms on the basis of the different electronegativities; iii) The orbital hybrid mode in Pd-nonmetal alloys is s, p-d orbital hybridization between light elements and Pd atoms, distinct from the d-d orbital hybridization in conventional Pd-based catalysts, which can change the charge distribution of Pd atoms and ameliorate the adsorption free energy of catalytic sites. Among the Pd-nonmetal alloys, the Pd hydrides are the most widely investigated catalysts due to the extremely high affinity of Pd with H atoms.…”

Section: Research Articlementioning

confidence: 99%

Ethanol‐Induced Hydrogen Insertion in Ultrafine IrPdH Boosts pH‐Universal Hydrogen Evolution

Wang

Jiang

Lin

et al. 2022

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Engineering Pt‐free catalysts for hydrogen evolution reaction (HER) with high activity and stability is of great significance in electrochemical hydrogen production. Herein, in situ chemical H intercalation into ultrafine Pd to activate this otherwise HER‐inferior material to form the ultrafine IrPdH hydride as an efficient and stable HER electrocatalyst is proposed. The formation of PdIrH depends on a new hydrogenation strategy via using ethanol as the hydrogen resource. It is demonstrated that H atoms in IrPdH originate from the OH and CH2 of ethanol, which fills the gap of ethanol as the hydrogen source for the preparation of Pd hydride. Thanks to the incorporation of H/Ir atoms and ultrafine structure, the IrPdH exhibits superior HER activity and stability in the whole pH range. The IrPdH delivers very low overpotentials of 14, 25 and 60 mV at a current density of 10 mA cm–2 respectively in 0.5 m H2SO4, 1 m KOH, and 1 m PBS electrolytes, which are much better than those of commercial Pt/C and most reported noble metal electrocatalysts. Theoretical calculations confirm that interstitial hydrogen availably refines the electronic density of Pd and Ir sites, which optimizes the adsorption of *H and leads to the significant enhancement of HER performance.

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Light alloying element-regulated noble metal catalysts for energy-related applications

Cited by 33 publications

References 201 publications

d–sp orbital hybridization: a strategy for activity improvement of transition metal catalysts

d–sp orbital hybridization: a strategy for activity improvement of transition metal catalysts

Interstitial B-Doping in Pt Lattice to Upgrade Oxygen Electroreduction Performance

Ethanol‐Induced Hydrogen Insertion in Ultrafine IrPdH Boosts pH‐Universal Hydrogen Evolution

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