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Improved ethanol electrooxidation performance by shortening Pd-Ni active site distance in Pd-Ni-P nanocatalysts.

ABSTRACT: Incorporating oxophilic metals into noble metal-based catalysts represents an emerging strategy to improve the catalytic performance of electrocatalysts in fuel cells. However, effects of the distance between the noble metal and oxophilic metal active sites on the catalytic performance have rarely been investigated. Herein, we report on ultrasmall (∼5 nm) Pd-Ni-P ternary nanoparticles for ethanol electrooxidation. The activity is improved up to 4.95 A per mg_Pd, which is 6.88 times higher than commercial Pd/C (0.72 A per mg_Pd), by shortening the distance between Pd and Ni active sites, achieved through shape transformation from Pd/Ni-P heterodimers into Pd-Ni-P nanoparticles and tuning the Ni/Pd atomic ratio to 1:1. Density functional theory calculations reveal that the improved activity and stability stems from the promoted production of free OH radicals (on Ni active sites) which facilitate the oxidative removal of carbonaceous poison and combination with CH₃CO radicals on adjacent Pd active sites.

SUBMITTER: Chen L

PROVIDER: S-EPMC5234093 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Hierarchical Pd-Sn alloy nanosheet dendrites: an economical and highly active catalyst for ethanol electrooxidation.

Project description:Hierarchical alloy nanosheet dendrites (ANSDs) are highly favorable for superior catalytic performance and efficient utilization of catalyst because of the special characteristics of alloys, nanosheets, and dendritic nanostructures. In this paper, we demonstrate for the first time a facile and efficient electrodeposition approach for the controllable synthesis of Pd-Sn ANSDs with high surface area. These synthesized Pd-Sn ANSDs exhibit high electrocatalytic activity and superior long-term cycle stability toward ethanol oxidation in alkaline media. The enhanced electrocataytic activity of Pd-Sn ANSDs may be attributed to Pd-Sn alloys, nanosheet dendrite induced promotional effect, large number of active sites on dendrite surface, large surface area, and good electrical contact with the base electrode. Because of the simple implement and high flexibility, the proposed approach can be considered as a general and powerful strategy to synthesize the alloy electrocatalysts with high surface areas and open dendritic nanostructures.

| S-EPMC3563035 | biostudies-literature

Ni(OH)2 Decorated Pt-Cu Octahedra for Ethanol Electrooxidation Reaction.

Project description:Here we report the synthesis of 9 nm Ni(OH)2 decorated Pt-Cu octahedra (Ni(OH)2-PtCu) in one-pot synthesis for ethanol oxidation reaction (EOR) electrocatalysis in acidic electrolyte. To prepare Ni(OH)2-PtCu octahedra, CO gas was directly introduced in a reaction process as selective capping agents on the PtCu(111) facet. Ni(OH)2 was naturally deposited on the Pt-Cu octahedra during the synthesis. Carbon supported Ni(OH)2-PtCu (Ni(OH)2-PtCu/C) as an EOR catalyst showed enhanced CO tolerance due to the existence of oxophilic Ni(OH)2 on the surface of Pt-Cu, facilitating water dissolution to produce OH adsorption and to promote complete CO oxidation to CO2. In addition, Pt-Cu alloy composition also showed improvement of CO tolerance because of modified d-band structure of the Pt atoms, thereby weakening the binding strength of CO on the catalysts. Therefore, the Ni(OH)2-PtCu/C showed enhanced EOR activity and durability compared to the Pt-Cu octahedra and commercial Pt/C counterparts.

| S-EPMC6733919 | biostudies-literature

Ultrathin layered double hydroxide nanosheets with Ni(III) active species obtained by exfoliation for highly efficient ethanol electrooxidation.

Project description:The development of non-precious metal electrocatalysts for renewable energy conversion and storage is compelling but greatly challenging due to low activity of the existing catalysts. Herein, the ultrathin NiAl-layered double hydroxide nanosheets (NiAl-LDH-NSs) are prepared by simple liquid-exfoliation of bulk NiAl-LDHs and first used as ethanol electrooxidation catalysts. The ultrathin two-dimensional (2D) structure ensures that the LDH nanosheets expose a greater number of active sites. More importantly, much Ni(III) active species (NiOOH) in the ultrathin nanosheets are formed by the exfoliation process, which play an authentic catalytic role in the ethanol oxidation reaction (EOR). The presence of NiOOH remarkably improves the reactivity and electrical conductivity of LDH nanosheets. These synergistic effects lead to strikingly more than 30 times enhanced EOR activity of NiAl-LDH-NSs compared to bulk NiAl-LDHs. The obtained electrocatalytic activity is also much better than those of most Ni- and LDH-based EOR catalysts reported to date. In addition, the ultrathin NiAl-LDH-NS electrocatalyst also exhibits good long-term stability (maintain 81.8% of the original value after 10000 s). This study not only provides a highly competitive EOR catalyst, but also opens new avenues toward the design of highly efficient electrode materials that have various potential applications in supercapacitor, Ni-MH battery and other electrocatalytic systems.

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| S-EPMC3943891 | biostudies-literature

Modulation of the electronic structure and the Ni-Fe distance in heterobimetallic models for the active site in [NiFe]hydrogenase.

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| S-EPMC1317917 | biostudies-literature

Pt/Ni(OH)<sub>2</sub>-NiOOH/Pd multi-walled hollow nanorod arrays as superior electrocatalysts for formic acid electrooxidation.

Project description:The catalytic activity and durability are crucial for the development of high-performance electrocatalysts. To design electrocatalysts with excellent electroactivity and durability, the structure and composition are two important guiding principles. In this work, novel Pt/Ni(OH)2-NiOOH/Pd multi-walled hollow nanorod arrays (MHNRAs) are successfully synthesized. The unique MHNRAs provide fast transport and short diffusion paths for electroactive species and high utilization rate of catalysts. Because of the special surface and synergistic effects, the Pt/Ni(OH)2-NiOOH/Pd MHNRA electrocatalysts exhibit high catalytic activity, high durability and superior CO poisoning tolerance for the electrooxidation of formic acid in comparison with Pt@Pd MHNRAs, commercial Pt/C, Pd/C and PtRu/C catalysts.

| S-EPMC5510012 | biostudies-literature

Models of the Ni-L and Ni-SIa States of the [NiFe]-Hydrogenase Active Site.

Project description:A new class of synthetic models for the active site of [NiFe]-hydrogenases are described. The Ni(I/II)(SCys)2 and Fe(II)(CN)2CO sites are represented with (RC5H4)Ni(I/II) and Fe(II)(diphos)(CO) modules, where diphos = 1,2-C2H4(PPh2)2(dppe) or cis-1,2-C2H2(PPh2)2(dppv). The two bridging thiolate ligands are represented by CH2(CH2S)2(2-) (pdt(2-)), Me2C(CH2S)2(2-) (Me2pdt(2-)), and (C6H5S)2(2-). The reaction of Fe(pdt)(CO)2(dppe) and [(C5H5)3Ni2]BF4 affords [(C5H5)Ni(pdt)Fe(dppe)(CO)]BF4 ([1a]BF4). Monocarbonyl [1a]BF4 features an S = 0 Ni(II)Fe(II) center with five-coordinated iron, as proposed for the Ni-SIa state of the enzyme. One-electron reduction of [1a](+) affords the S = 1/2 derivative [1a](0), which, according to density functional theory (DFT) calculations and electron paramagnetic resonance and Mössbauer spectroscopies, is best described as a Ni(I)Fe(II) compound. The Ni(I)Fe(II) assignment matches that for the Ni-L state in [NiFe]-hydrogenase, unlike recently reported Ni(II)Fe(I)-based models. Compound [1a](0) reacts with strong acids to liberate 0.5 equiv of H2 and regenerate [1a](+), indicating that H2 evolution is catalyzed by [1a](0). DFT calculations were used to investigate the pathway for H2 evolution and revealed that the mechanism can proceed through two isomers of [1a](0) that differ in the stereochemistry of the Fe(dppe)CO center. Calculations suggest that protonation of [1a](0) (both isomers) affords Ni(III)-H-Fe(II) intermediates, which represent mimics of the Ni-C state of the enzyme.

| S-EPMC4807737 | biostudies-literature

Distance Effect of Ni-Pt Dual Sites for Active Hydrogen Transfer in Tandem Reaction.

Project description:Unveiling the distance effect between different sites in multifunctional catalysts remains a major challenge. Herein, we investigate the distance effect by constructing a dual-site distance-controlled tandem catalyst with a five-layered TiO2/Pt/TiO2/Ni/TiO2 tubular nanostructure by template-assisted atomic layer deposition. In this catalyst, the Ni and Pt sites are separated by a porous TiO2 interlayer, and the distance between them can be precisely controlled on the subnanometer scale by altering the thickness of the interlayer, while the inner and outer porous TiO2 layers are designed for structural stability. The catalyst exhibits superior performance for the tandem hydrazine hydrate decomposition to hydrogen and subsequent nitrobenzene hydrogenation when the Ni and Pt site distance is on the subnanometer level. The performance increases with the decrease of the distance and is better than the catalyst without the TiO2 interlayer. Isotopic and kinetic experiments reveal that the distance effect controls the transfer of active hydrogen, which is the rate-determining step of the tandem reaction in a water solvent. Reduced Ti species with oxygen vacancies on the TiO2 interlayer provide the active sites for hydrogen transfer with -Ti-OH surface intermediates via the continuous chemisorption/desorption of water. A smaller distance induces the generation of more active sites for hydrogen transfer and thus higher efficiency in the synergy of Ni and Pt sites. Our work provides new insight for the distance effect of different active sites and the mechanism of intermediate transfer in tandem reactions.

| S-EPMC8454767 | biostudies-literature

Site-selective electrooxidation of methylarenes to aromatic acetals.

Project description:Aldehyde is one of most synthetically versatile functional groups and can participate in numerous chemical transformations. While a variety of simple aromatic aldehydes are commercially available, those with a more complex substitution pattern are often difficult to obtain. Benzylic oxygenation of methylarenes is a highly attractive method for aldehyde synthesis as the starting materials are easy to obtain and handle. However, regioselective oxidation of functionalized methylarenes, especially those that contain heterocyclic moieties, to aromatic aldehydes remains a significant challenge. Here we show an efficient electrochemical method that achieves site-selective electrooxidation of methyl benzoheterocycles to aromatic acetals without using chemical oxidants or transition-metal catalysts. The acetals can be converted to the corresponding aldehydes through hydrolysis in one-pot or in a separate step. The synthetic utility of our method is highlighted by its application to the efficient preparation of the antihypertensive drug telmisartan.

| S-EPMC7264330 | biostudies-literature

Facile Synthesis of Pd@PtM (<i>M</i> = Rh, Ni, Pd, Cu) Multimetallic Nanorings as Efficient Catalysts for Ethanol Oxidation Reaction.

Project description:Pt-based multimetallic nanorings with a hollow structure are attractive as advanced catalysts due to their fantastic structure feature. However, the general method for the synthesis of such unique nanostructures is still lack. Here we report the synthesis of Pd@PtM (M = Rh, Ni, Pd, Cu) multimetallic nanorings by selective epitaxial growth of Pt alloyed shells on the periphery of Pd nanoplates in combination with oxidative etching of partial Pd in the interior. In situ generation of CO and benzoic acid arising from interfacial catalytic reactions between Pd nanoplates and benzaldehyde are critical to achieve high-quality Pt-based multimetallic nanorings. Specifically, the in-situ generated CO promotes the formation of Pt alloyed shells and their epitaxial growth on Pd nanoplates. In addition, the as-formed benzoic acid and residual oxygen are responsible for selective oxidative etching of partial Pd in the interior. When evaluated as electrocatalysts, the Pd@PtRh nanorings exhibit remarkably enhanced activity and stability for ethanol oxidation reaction (EOR) compared to the Pd@PtRh nanoplates and commercial Pt/C due to their hollow nanostructures.

| S-EPMC8170318 | biostudies-literature

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