Bromide Ions Triggered Synthesis of Noble Metal–Based Intermetallic Nanocrystals

Wang, An‐Liang; Zhu, Lihua; Yun, Qinbai; Han, Sumei; Zeng, Li; Cao, Wenbin; Meng, Xiang‐Min; Xia, Jing; Lu, Qipeng

doi:10.1002/smll.202003782

Cited by 27 publications

(30 citation statements)

References 42 publications

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“…These activities are an order of magnitude higher than those of the commercial Pd/C. The mass activities achieved in this work all represent champion values compared with those of Pd-based catalysts reported to date (Table S5–S7), ,,,− highlighting the effectiveness of the unique strain-engineering strategy in achieving high performance of the catalysts in electrooxidation of a broad range of biomass-derived alcohols.…”

Section: Results and Discussionmentioning

confidence: 56%

“…Toward the oxidation of biomass-derived alcohols including ethanol, EG, and glycerol in an alkaline medium, the highly strained Au–Ag–Pd alloy nanowires outperformed the less strained counterparts, showing mass activities of up to 13.6, 18.2, and 11.1 A mg Pd –1 , respectively. These activity values are even higher than those of most Pd-based catalysts reported to date, ,,,− suggesting promising applicability of these catalysts in DAFC applications.…”

Section: Introductionmentioning

confidence: 76%

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Highly Strained Au–Ag–Pd Alloy Nanowires for Boosted Electrooxidation of Biomass-Derived Alcohols

Zhang

Liu

et al. 2021

Nano Lett.

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Although strain engineering is effective in boosting the activities of noble metal catalysts, it remains desirable to construct fully strained catalysts to push the activity to even higher levels. Herein, we report a novel route to strong lattice strains of a Pd-based catalyst by radial growth of a Pd-rich phase on Au–Ag alloy nanowires that are no thicker than 1.5 nm. It creates not only tensile strains in the Pd-rich sheath due to the core–sheath lattice mismatch but also distortion and twinning of the lattice, producing nonhomogeneous local strains as hotspots for the catalysis. Toward the electrochemical oxidation of biomass-derived alcohols including ethanol, ethylene glycol, and glycerol, the highly strained nanowires outperformed their less strained counterparts and reached up to 13.6, 18.2, and 11.1 A mgPd –1, respectively. This strain engineering strategy may open new avenues to highly efficient catalysts for direct alcohol fuel cells and many other applications.

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Section: Results and Discussionmentioning

confidence: 56%

Section: Introductionmentioning

confidence: 76%

Highly Strained Au–Ag–Pd Alloy Nanowires for Boosted Electrooxidation of Biomass-Derived Alcohols

Zhang

Liu

et al. 2021

Nano Lett.

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“…[ 8 ] Exchanging the initial metal ion precursor ligand with a more strongly bound ligand such as Cl – may significantly diminish the reaction rate and thereby narrow the gap in reduction potentials between the two metal ions involved in the synthesis of bimetallic NPs. [ 9 ] Second, the presence of halide ions is also expected to facilitate so‐called localized oxidative etching on NPs with defects. [ 10 ] Oxidative etching enables the formation of defect‐free single‐crystal NPs with a lower surface free energy by selectively dissolving small twinned NPs formed in the synthesis.…”

Section: Resultsmentioning

confidence: 99%

Breaking with the Principles of Coreduction to Form Stoichiometric Intermetallic PdCu Nanoparticles

et al. 2022

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surface sites. Each metal has a specific binding affinity toward the adsorbates involved in each catalytic reaction, which allows for selective tuning and optimization of catalytic processes via consideration of the incorporated metals. [1] In a binary disordered alloy, two metals randomly occupy symmetry equivalent sites in the crystal lattice, while the metals in an intermetallic structure occupy the crystallographic sites in the structure in a nonrandom arrangement at a specific atomic stoichiometry. [2] Alloys and intermetallics are known to have very different properties for catalysis. For example, intermetallic NPs composed of Pd and Cu have been observed to display superior catalytic activities in the CO 2 reduction reaction and oxygen reduction reaction over disordered face-centered cubic (fcc) alloys of the same composition, which has been attributed to changes in the electronic surface structure owing to the differences in local atomic arrangements. [3,4] In order to explore and implement the improved catalytic properties accessible in intermetallic NPs, it is crucial that the NP structure is controlled to promote only the most catalytically active structure. This degree of control can be obtained only if we understand how intermetallic NPs are formed, and which synthetic conditions dictate the resulting structure. Previous studies have indicated that the formation of intermetallic PdCu NPs proceeds through a disorder-order transformation, Intermetallic nanoparticles (NPs) have shown enhanced catalytic properties as compared to their disordered alloy counterparts. To advance their use in green energy, it is crucial to understand what controls the formation of intermetallic NPs over alloy structures. By carefully selecting the additives used in NP synthesis, it is here shown that monodisperse, intermetallic PdCuNPs can be synthesized in a controllable manner. Introducing the additives iron(III) chloride and ascorbic acid, both morphological and structural control can be achieved. Combined, these additives provide a synergetic effect resulting in precursor reduction and defect-free growth; ultimately leading to monodisperse, single-crystalline, intermetallic PdCu NPs. Using in situ X-ray total scattering, a hitherto unknown transformation pathway is reported that diverges from the commonly reported coreduction disorder-order transformation. A Cu-rich structure initially forms, which upon the incorporation of Pd(0) and atomic ordering forms intermetallic PdCu NPs. These findings underpin that formation of stoichiometric intermetallic NPs is not limited by standard reduction potential matching and coreduction mechanisms, but is instead driven by changes in the local chemistry. Ultimately, using the local chemistry as a handle to tune the NP structure might open new opportunities to expand the library of intermetallic NPs by exploiting synthesis by design.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/smtd.202200420.

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“…Pd 3 Pb nanocubes were synthesized by the co-reduction of PdBr 2 and PbBr 2 with oleylamine and oleic acid in ODE at 170 °C for 30 min. 75 Synthesis of Alloyed Pd x Sn 1 − x /C Nanocatalysts. Alloyed Pd x Sn 1 − x /C nanocatalysts with two different Pd/Sn ratios (x = 0.95 and 0.87) were prepared using a literature polyol method.…”

Section: ■ Methodsmentioning

confidence: 99%

“…In short, the relevant precursor was placed in an alumina combustion boat and was heated in a tube furnace under a N 2 atmosphere from 30 to 400 °C (or 600 °C in the case of Pd 3 Sn 2 ) at a rate of 10 °C/min and then allowed to cool to R.T. (25 °C). Pd 3 Pb nanocubes were synthesized by the co-reduction of PdBr 2 and PbBr 2 with oleylamine and oleic acid in ODE at 170 °C for 30 min …”

Section: Methodsmentioning

confidence: 99%

Azo(xy) vs Aniline Selectivity in Catalytic Nitroarene Reduction by Intermetallics: Experiments and Simulations

et al. 2021

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Intermetallic nanoparticles are promising catalysts in hydrogenation and fuel cell technologies. Much is known about the ability of intermetallic nanoparticles to selectively reduce nitro vs alkene, alcohol, or halide functional groups; less is known about their selectivity toward aniline vs azo or azoxy condensation products that result from the reduction of a nitro group alone. Because azo(xy)arenes bear promise as dyes, chemical stabilizers, and building blocks to functional materials but can be difficult to isolate, developing high surface area nanoparticle catalysts that display azo(xy) selectivity is desirable. To address this question, we studied a family of nanocrystalline group 10 metal (Pd, Pt)-and group 14 metal (Ge, Sn, Pb)-containing intermetallicsPd 2 Ge, Pd 2 Sn, Pd 3 Sn 2 , Pd 3 Pb, and PtSnin the catalytic reduction of nitroarenes. In contrast to monometallic Au, Pt, and Pd nanoparticles and ″random″ Pd x Sn 1 − x nanoalloys, which are selective for aniline, nanoparticles of atomically precise intermetallic Pd 2 Ge, Pd 2 Sn, Pd 3 Sn 2 , and PtSn prefer an indirect condensation pathway and have a high selectivity for the azo(xy) products. The only exception is Pd 3 Pb, the most active among the intermetallic nanoparticles studied here, which is instead selective for aniline. Employing a novel application of molecular dynamicsbased on machine learned potentials within a DeePMD frameworkto heterogeneous catalysis, we are able to identify key reaction species on the different types of catalysts employed, furthering our understanding of the unique selectivity of these materials. By demonstrating how intermetallic nanoparticles can be as active yet more selective than other more traditional catalysts, this work provides new physical insights and opens new opportunities in the use of these materials in other important chemical transformations and applications.

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Bromide Ions Triggered Synthesis of Noble Metal–Based Intermetallic Nanocrystals

Cited by 27 publications

References 42 publications

Highly Strained Au–Ag–Pd Alloy Nanowires for Boosted Electrooxidation of Biomass-Derived Alcohols

Highly Strained Au–Ag–Pd Alloy Nanowires for Boosted Electrooxidation of Biomass-Derived Alcohols

Breaking with the Principles of Coreduction to Form Stoichiometric Intermetallic PdCu Nanoparticles

Azo(xy) vs Aniline Selectivity in Catalytic Nitroarene Reduction by Intermetallics: Experiments and Simulations

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