The Chemical Properties of Hydrogen Atoms Adsorbed on M0‐Nanoparticles Suspended in Aqueous Solutions: The Case of Ag0‐NPs and Au0‐NPs Reduced by BD4−

Sermiagin, Alina; Meyerstein, Dan; Bar‐Ziv, Ronen; Zidki, Tomer

doi:10.1002/anie.201809302

Cited by 19 publications

(33 citation statements)

References 51 publications

(120 reference statements)

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“…The reduction of 4‐NP occurs by transferring electrons/hydrides/hydrogens from the donor BH 4 − to the acceptor NPs, and to the substrate 4‐NP after their adsorption/migration on the surface of the NPs. Recently, we demonstrated that with catalytic HER in the presence of M−NPs at high [BH 4 − ] levels as the reducing agent, H 2 is formed through the hydride pathway (Heyrovsky mechanism, Reaction 1) and that the Heyrovsky mechanism takes place to a greater extent on Ag NPs in comparison with Au NPs . This mechanism can be correlated to this work since the [BH 4 − ] used is high, and Ag NPs exhibit higher catalytic activity than Au NPs (Figures and S6).…”

Section: Resultssupporting

confidence: 73%

“…Recently, we demonstrated that with catalytic HER in the presence of MÀ NPs at high [BH 4 À ] levels as the reducing agent, H 2 is formed through the hydride pathway (Heyrovsky mechanism, Reaction 1) and that the Heyrovsky mechanism takes place to a greater extent on Ag NPs in comparison with Au NPs. [61] This mechanism can be correlated to this work since the [BH 4 À ] used is high, and Ag NPs exhibit higher catalytic activity than Au NPs (Figures 4 and S6). The fact that AgÀ Pt (9 : 1) alloy NPs are excellent catalysts for 4-NP reduction suggests that the catalyst holds electrons on its surface to form hydrides.…”

Section: Catalytic Study Of 4-nitrophenol Reductionsupporting

confidence: 72%

“…The MNP and BMNP suspensions were prepared at room temperature according to Creighton's procedure, modified by Zidki et al . using different precursor salts for the required NPs (Ag 2 SO 4 , HAuCl 4, and K 2 PtCl 6 for Ag, Au, and Pt MNPs, respectively).…”

Section: Methodsmentioning

confidence: 99%

“…[62,63] The mean particle size diameter of Ag, Au, and Pt NPs prepared under identical procedures were reported to be 3.8, 4.4, and 3.2 nm, respectively. [61,62] Figure 1 (a-c) shows HR-TEM micrographs of the AgÀ Pt (5 : 2) NPs at different magnifications, which appear as chains of spheres attached to each other. Figure 1d shows their particle size histogram displaying an average diameter of 4.1 � 0.4 nm, counted out of 120 NPs from the micrographs.…”

Section: Catalytic Reduction Of 4-nitrophenolmentioning

confidence: 99%

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On the Remarkable Performance of Silver‐based Alloy Nanoparticles in 4‐Nitrophenol Catalytic Reduction

Varshney

Bar‐Ziv²,

Zidki

2020

ChemCatChem

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Elimination of nitro groups from the toxic aromatic nitro compounds is of great environmental importance. A catalytic study of the 4-nitrophenol reduction on the surface of metallic and alloy nanoparticles is presented. The silver-based catalysts, with low amounts of platinum (10 % Pt), exhibit excellent catalytic activity without an induction-time, which fulfills both the performance and cost requirements for the catalytic reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH 4. The apparent rate constant of 59 × 10 À 3 s À 1 and an extremely high activity parameter value of 13,600 s À 1 g À 1 are reported for the first time. This mechanistic study suggests that hydrides are the active species for 4-nitrophenol reduction, and that the composition of the alloy can affect the reactivity and competition with the hydrogen evolution reaction. Our work opens future possibilities for the optimal design of efficient and low-cost catalysts for redox processes and neutralization of organic pollutants.

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Section: Resultssupporting

confidence: 73%

Section: Catalytic Study Of 4-nitrophenol Reductionsupporting

confidence: 72%

Section: Methodsmentioning

confidence: 99%

Section: Catalytic Reduction Of 4-nitrophenolmentioning

confidence: 99%

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On the Remarkable Performance of Silver‐based Alloy Nanoparticles in 4‐Nitrophenol Catalytic Reduction

Varshney

Bar‐Ziv²,

Zidki

2020

ChemCatChem

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“…Valuable mechanistic proposals have been published for the NP‐catalyzed hydrogen evolution from borohydride salts under various conditions, emphasizing the crucial role of the NP and NP−H bonds formation and evolution ,. Some proposals suggested oxidative addition [82 ] of a B−H bond to transfer a hydrogen atom onto the MNP and leave the negative charge onto the boron atom followed by electron transfer that may be subsequently used in further steps.…”

Section: Resultsmentioning

confidence: 99%

Efficient “Click”‐Dendrimer‐Supported Synergistic Bimetallic Nanocatalysis for Hydrogen Evolution by Sodium Borohydride Hydrolysis

et al. 2019

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Hydrogen is efficiently generated upon "click" dendrimersupported catalysis of NaBH 4 hydrolysis by a series mono-and bimetallic nanoparticles (NPs) of the late transition metals. Among the monometallic NPs, PtNPs show the best performances, Co being the best first-raw transition metal. A remarkable synergy between Pt and Co in Pt/CoNP@dendrimer is also disclosed, compared with various other bimetallic NP catalysts, achieving a TOF of 303 mol H2 · mol catal.À 1 · min À 1 when the ratio of Pt to Co is 1 : 1. In the presence of NaOH, the catalytic activity is boosted for all monometallic NPs except PtNPs, but NaOH exerted a negative influence on the bimetallic NP catalysts. The kinetic studies with the catalyst Pt 1 Co 1 NP@dendrimer involve in particular a primary kinetic isotope effect k D /k H = 3.41 obtained for the hydrolysis reaction with D 2 O, suggesting that OÀ H bond cleavage of water is involved in the rate-determining step, and an overall reaction mechanism is proposed.

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The Role of Common Alcoholic Sacrificial Agents in Photocatalysis: Is It Always Trivial?

Sathiyan

Bar‐Ziv²,

Marks

et al. 2021

Chemistry A European J

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Photocatalytic hydrogen production is proposed as a sustainable energy source. Simultaneous reduction and oxidation of water is a complex multistep reaction with high overpotential. Photocatalytic processes involving semiconductors transfer electrons from the valence band to the conduction band. Sacrificial substrates that react with the photochemically formed holes in the valence band are often used to study the mechanism of H 2 production, as they scavenge the holes and hinder charge carrier recombination (electron-hole pairs). Here, we show that the desired sacrificial agent is one forming a radical that is a fairly strong reducing agent, and whose oxidized form is not a good electron acceptor that might suppress the hydrogen evolution reaction (HER). In an acidic medium, methanol was found to fulfill both these requirements better than ethanol and propan-2-ol in the TiO 2 -(M 0 -NPs) (M = Au or Pt) system, whereas in an alkaline medium, the alcohols exhibit a reverse order of activity. Moreover, we report that CH 2 (OH) 2 is by far the most efficient sacrificial agent in a nontrivial mechanism in acidic media. Our study provides general guidelines for choosing an appropriate sacrificial substrate and helps to explain the variance in the performance of alcohol scavenger-based photocatalytic systems.

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The Chemical Properties of Hydrogen Atoms Adsorbed on M⁰‐Nanoparticles Suspended in Aqueous Solutions: The Case of Ag⁰‐NPs and Au⁰‐NPs Reduced by BD₄⁻

Cited by 19 publications

References 51 publications

On the Remarkable Performance of Silver‐based Alloy Nanoparticles in 4‐Nitrophenol Catalytic Reduction

On the Remarkable Performance of Silver‐based Alloy Nanoparticles in 4‐Nitrophenol Catalytic Reduction

Efficient “Click”‐Dendrimer‐Supported Synergistic Bimetallic Nanocatalysis for Hydrogen Evolution by Sodium Borohydride Hydrolysis

The Role of Common Alcoholic Sacrificial Agents in Photocatalysis: Is It Always Trivial?

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