Surfactant-aided synthesis of RhCo nanoclusters as highly effective and recyclable catalysts for the hydrolysis of methylamine borane and dimethylamine borane

Tunç, Nihat; Rakap, Murat

doi:10.1039/d0cy01472a

Cited by 16 publications

(4 citation statements)

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“…In addition, the catalytic activity of the Pt 0.7 Ni 0.3 /CNS nanohybrid with other reported catalytic systems for H 2 generation from dimethylamineborane hydrolysis is also compared in Table . − As a result, the comparison had further confirmed that Pt 0.7 Ni 0.3 /CNS exhibited the highest TOF of 16,607 h –1 at 0.3 M NaOH, which exceeded the other reported catalytic systems, in H 2 generation from dimethylamineborane hydrolysis.…”

Section: Resultsmentioning

confidence: 83%

Bimetallic PtNi Nanoclusters Supported on Carbon Nanospheres as Catalysts for H₂ Production from Dimethylamineborane Hydrolysis

Huang

Tian

et al. 2022

ACS Appl. Nano Mater.

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Although remarkable advances are achieved in the development of novel and high-efficiency catalytic systems for H2 production from the decomposition of dimethylamineborane in neat organic media, there are few available reports on H2 production upon dimethylamineborane hydrolysis. Hence, it is still of high importance to design and develop efficient and highly selective catalysts for H2 production upon dimethylamineborane hydrolysis. Herein, we have first designed and synthesized a series of carbon nanosphere (CNS)-supported PtNi bimetallic nanohybrids (PtNi/CNS), by immobilization of nearly monodispersed PtNi bimetallic nanoparticles at the surface of CNSs, for the highly selective and efficient H2 production from dimethylamineborane hydrolysis. Among them, the optional Pt0.7Ni0.3/CNS nanohybrid exhibits the highest turnover frequency of 16,607 h–1, which exceeded most reported catalytic systems, in the H2 generation from dimethylamineborane hydrolysis at 30 °C under 0.3 M NaOH due to the superior synergistic effect. The activation energy (E a) of Pt0.7Ni0.3/CNS-catalyzed dimethylamineborane hydrolysis is calculated to be 31.1 kJ/mol. Interestingly, the large kinetic isotope effect of 2.76 with D2O verified that the breaking of a water O–H bond is the rate-controlling step of dimethylamineborane hydrolysis. This work presents a new, efficient, and durable Pt-based nanocatalyst for H2 production from dimethylamineborane hydrolysis.

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Section: Resultsmentioning

confidence: 83%

Bimetallic PtNi Nanoclusters Supported on Carbon Nanospheres as Catalysts for H₂ Production from Dimethylamineborane Hydrolysis

Huang

Tian

et al. 2022

ACS Appl. Nano Mater.

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“…Meanwhile, their logarithmic plots of H 2 (ln TOF) and AB concentration (ln [AB]) are nearly horizontal, indicating zeroorder kinetics with respect to AB concentrations (Figure 4c). 20,37 This rules out the cleavage of B−N and B−H bonds as the rate-determining step, when the above samples are used as catalysts. In contrast, the rates of H 2 production are obviously accelerated with the increasing catalyst (Rh) concentrations (Figure 4b).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Ultrafine RhNi Nanocatalysts Confined in Hollow Mesoporous Carbons for a Highly Efficient Hydrogen Production from Ammonia Borane

Ren

Chen

et al. 2021

Inorg. Chem.

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Ammonia borane (AB) has received growing research interest as one of the most promising hydrogen-storage carrier materials. However, fast dehydrogenation of AB is still limited by sluggish catalytic kinetics over current catalysts. Herein, highly uniform and ultrafine bimetallic RhNi alloy nanoclusters encapsulated within nitrogen-functionalized hollow mesoporous carbons (defined as RhNi@NHMCs) are developed as highly active, durable, and selective nanocatalysts for fast hydrolysis of AB under mild conditions. Remarkable activity with a high turnover frequency (TOF) of 1294 mol H 2 mol Rh −1 min −1 and low activation energy (E a ) of 18.6 kJ mol −1 is observed at room temperature, surpassing the previous Rh-based catalysts. The detailed mechanism studies reveal that when catalyzed by RhNi@NHMCs, a covalently stable O−H bond by H 2 O first cleaves in electropositive H* and further attacks B−H bond of AB to stoichiometrically produce 3 equiv of H 2 , whose catalytic kinetics is restricted by the oxidation cleavage of the O−H bond. Compositional and structural features of RhNi@NHMCs result in synergic electronic, functional, and support add-in advantages, kinetically accelerating the cleavage of the attacked H 2 O (O−H bond) and remarkably promoting the catalytic hydrolysis of AB accordingly. This present work represents a new and effective strategy for exploring high-performance supported metal-based alloy nanoclusters for (electro)catalysis.

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“…[5] However, the formation of some volatile side products such as ammonia, borazine, or diborane in the dehydrogenation of AB limits its employment in the on-board systems since they are poisonous for the fuel cells. [6,7,8] In this context, carbon derivatives of AB including methylamine borane (BH 3 NH 2 CH 3 , MeAB), [9,10] dimethylamine borane (BH 3 NH(CH 3 ) 2 , DMAB), [11] hydrazine borane (BH 3 N 2 H 4, HB), [12,13] and ethane 1,2-diamine borane ((BH 3 NH 2 CH 2 ) 2 , EDAB) [14,15] are regarded as very promising candidates.…”

Section: Introductionmentioning

confidence: 99%

Nanoceria‐Supported Ru‐Based Nanoparticles as Highly Efficient Catalysts for Hydrolysis of Ethane 1,2‐Diamine Borane

Tunç

Rakap

2022

ChemistrySelect

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Here, the first ever preparation of some series of nanoceria‐supported Ru‐based nanoparticles with different compositions (RuxM100‐x@NC, M: Co, Ni, Pd) and their use as highly active catalysts to liberate hydrogen gas from hydrolysis of ethane 1,2‐diamine borane (EDAB) is reported. For the preparation of totally fifteen RuxM100‐x@NC nanoparticles with different compositions, the related metal cations are first supported on nanoceria surfaces by wet impregnation method in aqueous solution. Then, Ru3+‐M2+‐exchanged nanoceria samples are synchronously reduced during hydrolysis reaction of EDAB to form corresponding RuxM100x@NC nanoparticles meanwhile the formed nanoparticles catalyze the same reaction. RuxM100x@NC nanoparticles are identified by inductively coupled plasma‐optical emission spectroscopy (ICP‐OES), powder X‐ray diffraction (PXRD), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), and BET surface area techniques. They provide quiet high catalytic activities in the hydrolysis reaction of EDAB. Among them, Ru20Pd80@NC nanoparticles are by far the best one up to date with a TOF value of 608.49 min−1 at 25 °C.

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Surfactant-aided synthesis of RhCo nanoclusters as highly effective and recyclable catalysts for the hydrolysis of methylamine borane and dimethylamine borane

Abstract: In the present study, the first ever and easy surfactant-aided synthesis of hexadecyltrimethyl ammonium bromide-stabilized RhCo nanoclusters (Rh0.63Co0.37@CTAB) and their employment as highly efficient, relatively cost-saver, and recyclable catalysts to...

Cited by 16 publications

References 59 publications

Bimetallic PtNi Nanoclusters Supported on Carbon Nanospheres as Catalysts for H₂ Production from Dimethylamineborane Hydrolysis

Bimetallic PtNi Nanoclusters Supported on Carbon Nanospheres as Catalysts for H₂ Production from Dimethylamineborane Hydrolysis

Ultrafine RhNi Nanocatalysts Confined in Hollow Mesoporous Carbons for a Highly Efficient Hydrogen Production from Ammonia Borane

Nanoceria‐Supported Ru‐Based Nanoparticles as Highly Efficient Catalysts for Hydrolysis of Ethane 1,2‐Diamine Borane

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Surfactant-aided synthesis of RhCo nanoclusters as highly effective and recyclable catalysts for the hydrolysis of methylamine borane and dimethylamine borane

Abstract: In the present study, the first ever and easy surfactant-aided synthesis of hexadecyltrimethyl ammonium bromide-stabilized RhCo nanoclusters (Rh0.63Co0.37@CTAB) and their employment as highly efficient, relatively cost-saver, and recyclable catalysts to...

Cited by 16 publications

References 59 publications

Bimetallic PtNi Nanoclusters Supported on Carbon Nanospheres as Catalysts for H2 Production from Dimethylamineborane Hydrolysis

Bimetallic PtNi Nanoclusters Supported on Carbon Nanospheres as Catalysts for H2 Production from Dimethylamineborane Hydrolysis

Ultrafine RhNi Nanocatalysts Confined in Hollow Mesoporous Carbons for a Highly Efficient Hydrogen Production from Ammonia Borane

Nanoceria‐Supported Ru‐Based Nanoparticles as Highly Efficient Catalysts for Hydrolysis of Ethane 1,2‐Diamine Borane

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Bimetallic PtNi Nanoclusters Supported on Carbon Nanospheres as Catalysts for H₂ Production from Dimethylamineborane Hydrolysis

Bimetallic PtNi Nanoclusters Supported on Carbon Nanospheres as Catalysts for H₂ Production from Dimethylamineborane Hydrolysis