Surfactant-free fabrication of porous PdSn alloy networks by self-assembly as superior freestanding electrocatalysts for formic acid oxidation

Qin, Qian; Xie, Jin; Dong, Qizhi; Yu, Gang; Chen, Hong

doi:10.1039/c9nj04931b

Cited by 16 publications

(17 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Although this feature deviates from our initial motivation, SnO x layers in conjunction with noble metals promote catalytic oxidation of small molecules, whereas SnO x alone shows negligible activity. ,− Particularly, PdSn-SnO 2 NPs are reported to have superior catalytic activity when compared to PdSn NPs, commercial Pd, and SnO 2 . , This catalytic enhancement on the oxidation of small alcohol molecules has been attributed to the affinity of SnO x for oxygenated-like species facilitates the conversion of CO ad to CO 2 . ,,, …”

Section: Results and Discussionmentioning

confidence: 67%

Phase-Controlled Synthesis of Pd–Sn Nanocrystal Catalysts of Defined Size and Shape

Bueno

Zhan

Wolfe

et al. 2021

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

Bimetallic Pd-based nanoparticles (NPs) are of interest as electrocatalysts for formic acid electrooxidation (FAEO) because of their higher initial catalytic activity and CO tolerance when compared to Pt. Intermetallic NPs (i-NPs) with specific geometric and electronic structures generally exhibit superior catalytic activity, selectivity, and durability when compared to their disordered (random alloy) counterparts; however, the colloidal synthesis of i-NPs remains a challenge. Here, a one-pot method was demonstrated as a facile route to obtain monodisperse Pd−Sn NPs with phase control, including intermetallic hexagonal Pd 3 Sn 2 (P6 3 /mmc), intermetallic orthorhombic Pd 2 Sn (Pnma), and alloy cubic Pd 3 Sn (FCC, Fm3m) as size-controlled NPs with quasi-spherical shapes. Initial metal precursor ratios and reaction temperature were critical parameters to achieving phase control. Also, slight modifications of synthetic conditions resulted in either Pd 2 Sn nanorhombohedra or nanorods with tunable aspect ratios. A systematic evaluation of the Pd−Sn NPs for FAEO showed that most presented higher specific activities when compared to commercial Pd/C, in which Pd 2 Sn quasi-spheres and nanorhombohedra showed the highest catalytic activity for FAEO. These results highlight the benefits of phase-controlled Pd-based nanocatalysts with defined nanocrystal size and shape, with use of trioctylphospine (TOP) and oleic acid (OA) central to shape and size control.

show abstract

Section: Results and Discussionmentioning

confidence: 67%

Phase-Controlled Synthesis of Pd–Sn Nanocrystal Catalysts of Defined Size and Shape

Bueno

Zhan

Wolfe

et al. 2021

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

show abstract

“…Most known Pd-M catalysts form alloys, which not only lead to a variation of the reaction mechanism, but also generally improve the stability. 36 …”

Section: Introductionmentioning

confidence: 99%

Enhanced Formic Acid Oxidation over SnO₂-decorated Pd Nanocubes

et al. 2020

View full text Add to dashboard Cite

The formic acid oxidation reaction (FAOR) is one of the key reactions that can be used at the anode of low-temperature liquid fuel cells. To allow the knowledge-driven development of improved catalysts, it is necessary to deeply understand the fundamental aspects of the FAOR, which can be ideally achieved by investigating highly active model catalysts. Here, we studied SnO 2 -decorated Pd nanocubes (NCs) exhibiting excellent electrocatalytic performance for formic acid oxidation in acidic medium with a SnO 2 promotion that boosts the catalytic activity by a factor of 5.8, compared to pure Pd NCs, exhibiting values of 2.46 A mg –1 Pd for SnO 2 @Pd NCs versus 0.42 A mg –1 Pd for the Pd NCs and a 100 mV lower peak potential. By using ex situ, quasi in situ, and operando spectroscopic and microscopic methods (namely, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption fine-structure spectroscopy), we identified that the initially well-defined SnO 2 -decorated Pd nanocubes maintain their structure and composition throughout FAOR. In situ Fourier-transformed infrared spectroscopy revealed a weaker CO adsorption site in the case of the SnO 2 -decorated Pd NCs, compared to the monometallic Pd NCs, enabling a bifunctional reaction mechanism. Therein, SnO 2 provides oxygen species to the Pd surface at low overpotentials, promoting the oxidation of the poisoning CO intermediate and, thus, improving the catalytic performance of Pd. Our SnO x -decorated Pd nanocubes allowed deeper insight into the mechanism of FAOR and hold promise for possible applications in direct formic acid fuel cells.

show abstract

“…What is more, the porous nanostructures not only can facilitate mass diffusion and transport but also hinder the dissolution and agglomeration of nanocatalysts. Hence, enormous efforts have been made to develop synthetic approaches to prepare Pd-based nanocatalysts with porous structures, including self-assembly [25], electrodeposition [26,27], hard template-engaged method [28,29], and so on. Despite these advances, those previously reported synthetic strategies are tedious and complex, dramatically impeding the large-scale practical applications of these nanomaterials in energy-related fields.…”

Section: Introductionmentioning

confidence: 99%

Cyanogel-Derived Synthesis of Porous PdFe Nanohydrangeas as Electrocatalysts for Oxygen Reduction Reaction

et al. 2021

View full text Add to dashboard Cite

It is important to develop cost-efficient electrocatalysts used in the oxygen reduction reaction (ORR) for widespread applications in fuel cells. Palladium (Pd) is a promising catalyst, due to its more abundant reserves and lower price than platinum (Pt), and doping an earth-abundant 3d-transition metal M into Pd to form Pd–M bimetallic alloys may not only further reduce the use of expensive Pd but also promote the electrocatalytic performance of ORR, owing to the synergistic effect between Pd and M. Here we report a cyanogel-derived synthesis of PdFe alloys with porous nanostructure via a simple coinstantaneous reduction reaction by using K2PdIICl4/K4FeII(CN)6 cyanogel as precursor. The synthesized PdFe alloys possess hydrangea-like morphology and porous nanostructure, which are beneficial to the electrochemical performance in ORR. The onset potential of the porous PdFe nanohydrangeas is determined to be 0.988 V, which is much more positive than that of commercial Pt/C catalyst (0.976 V) and Pd black catalyst (0.964 V). Resulting from the unique structural advantages and synergetic effect between bimetals, the synthesized PdFe nanohydrangeas with porous structure have outstanding electrocatalytic activity and stability for ORR, compared with the commercial Pd black and Pt/C.

show abstract

Surfactant-free fabrication of porous PdSn alloy networks by self-assembly as superior freestanding electrocatalysts for formic acid oxidation

Abstract: Porous PdSn networks synthesized by self-assembly at 60 °C for the first time with high electrocatalytic performance for formic acid oxidation.

Cited by 16 publications

References 66 publications

Phase-Controlled Synthesis of Pd–Sn Nanocrystal Catalysts of Defined Size and Shape

Phase-Controlled Synthesis of Pd–Sn Nanocrystal Catalysts of Defined Size and Shape

Enhanced Formic Acid Oxidation over SnO₂-decorated Pd Nanocubes

Cyanogel-Derived Synthesis of Porous PdFe Nanohydrangeas as Electrocatalysts for Oxygen Reduction Reaction

Contact Info

Product

Resources

About

Surfactant-free fabrication of porous PdSn alloy networks by self-assembly as superior freestanding electrocatalysts for formic acid oxidation

Abstract: Porous PdSn networks synthesized by self-assembly at 60 °C for the first time with high electrocatalytic performance for formic acid oxidation.

Cited by 16 publications

References 66 publications

Phase-Controlled Synthesis of Pd–Sn Nanocrystal Catalysts of Defined Size and Shape

Phase-Controlled Synthesis of Pd–Sn Nanocrystal Catalysts of Defined Size and Shape

Enhanced Formic Acid Oxidation over SnO2-decorated Pd Nanocubes

Cyanogel-Derived Synthesis of Porous PdFe Nanohydrangeas as Electrocatalysts for Oxygen Reduction Reaction

Contact Info

Product

Resources

About

Enhanced Formic Acid Oxidation over SnO₂-decorated Pd Nanocubes