CuNi NPs supported on MIL-101 as highly active catalysts for the hydrolysis of ammonia borane

Gao, Dingshan; Zhang, Yuhong; Zhou, Liqun; Yang, Kunzhou

doi:10.1016/j.apsusc.2017.08.167

Cited by 53 publications

(28 citation statements)

References 37 publications

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“… 30,42 In some reports, metal leaching may have also led to the decline in the catalytic activity. 43 Generally, metal leaching depends upon the reaction medium (pH, oxidation potential, and chelating properties of the metal) and the bulk and surface properties of the metal. 44 Moreover, if the Ru nanoparticles detached from the support, they can easily aggregate in solution, thus resulting in decreased catalytic activity.…”

Section: Resultsmentioning

confidence: 99%

Amine-functionalized MIL-53(Al) with embedded ruthenium nanoparticles as a highly efficient catalyst for the hydrolytic dehydrogenation of ammonia borane

2018

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Well-dispersed ruthenium nanoparticles (Ru NPs) are immobilized within the pores of amine-functionalized MIL-53 via an in situ impregnation-reduction method. The resulting Ru/MIL-53(Al)-NH 2 catalyst exhibits superior catalytic performance for the dehydrogenation of ammonia borane (AB) at ambient temperature relative to the Ru/MIL-53(Al) catalyst; it has a turnover frequency (TOF) of 287 mol H 2 min À1 (mol Ru) À1and an activation energy (E a ) of 30.5 kJ mol À1 . The amine groups present in the MIL-53(Al)-NH 2 framework facilitate the formation and stabilization of ultra-small Ru NPs by preventing their aggregation. Additionally, the Ru/MIL-53(Al)-NH 2 catalyst exhibits satisfactory durability and reusability:72.4% and 86.3% of the initial catalytic activity was maintained after the fifth successive cycle of the hydrolytic dehydrogenation of AB in the two respective tests.

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Section: Resultsmentioning

confidence: 99%

Amine-functionalized MIL-53(Al) with embedded ruthenium nanoparticles as a highly efficient catalyst for the hydrolytic dehydrogenation of ammonia borane

2018

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“…On the one hand, as mentioned above, Cu can facilitate the formation of metal Co. Besides, the chemical properties and surface electronic structure of the final active species can be modified by introducing Cu into the catalyst, which is conducive to fast hydrogen release. In addition, as discussed above, the BET surface area of Co x Cu 1− x Co 2 O 4 @Co y Cu 1− y Co 2 O 4 is larger than that of Co 3 O 4 @Co 3 O 4 .…”

Section: Comparison Of Tof Values For Some Non‐precious Metal Catalystsmentioning

confidence: 99%

A Simple and Scalable Route to Synthesize Co_xCu₁₋_xCo₂O₄@Co_yCu₁₋_yCo₂O₄ Yolk–Shell Microspheres, A High‐Performance Catalyst to Hydrolyze Ammonia Borane for Hydrogen Production

Lin

et al. 2019

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Yolk–shell structured micro/nano‐sized materials have broad and important applications in different areas due to their unique spatial configurations. In this study, yolk–shell structured Co3O4@Co3O4 is prepared using a simple and scalable hydrothermal reaction, followed by a calcination process. Then, CoxCu1−xCo2O4@CoyCu1−yCo2O4 microspheres are synthesized via adsorption and calcination processes using the as‐prepared Co3O4@Co3O4 as the precursor. A possible formation mechanism of the yolk–shell structures is proposed based on the characterization results, which is different from those of yolk–shell structures in previous study. For the first time, the catalytic activity of yolk–shell structured catalysts in ammonia borane (AB) hydrolysis is studied. It is discovered that the yolk–shell structured CoxCu1−xCo2O4@CoyCu1−yCo2O4 microspheres exhibit high performance with a turnover frequency (TOF) of 81.8 molhydrogen min−1 molcat−1. This is one of the highest TOF values reported for a noble‐metal‐free catalyst in the literature. Additionally, the yolk–shell structured CoxCu1−xCo2O4@CoyCu1−yCo2O4 microspheres are highly stable and reusable. These yolk–shell structured CoxCu1−xCo2O4@CoyCu1−yCo2O4 microsphere is a promising catalyst candidate in AB hydrolysis considering the excellent catalytic behavior and low cost.

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“…Hydrogen, as a clean renewable energy, has attracted much attention to meet the growing demand for transportation and electronic devices. − However, efficient storage and safe delivery of hydrogen remain a great challenge. − Recently, ammonia borane (AB) has been extensively studied as a chemical hydrogen storage medium due to its nontoxicity, high hydrogen density (19.6 wt %), safe storage, high solubility in water and low-temperature dehydrogenation behavior. − When the suitable heterogeneous metal-based catalysts are applied, hydrolysis of one AB molecule can produce three H 2 molecules rapidly. − However, the efficient operation of this reaction still relies on high energy input and precious-metal catalysts. Therefore, it is desirable to develop new catalytic reaction systems by using non-noble metal catalysts and renewable solar light-driven means.…”

Section: Introductionmentioning

confidence: 99%

Visible-Light-Driven Multichannel Regulation of Local Electron Density to Accelerate Activation of O–H and B–H Bonds for Ammonia Borane Hydrolysis

Zhang

Liu

et al. 2020

ACS Catal.

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Regulating electron density at the active site by integrating contributions from multiple channels is an effective strategy to accelerate the reaction rate. Herein, the hydrolysis of ammonia borane (AB) is systematically studied on the NiCu alloy-loaded carbon nitride nanosheets (Ni x Cu y /CNS). The TOF of AB hydrolysis for NiCu/CNS catalyst under visible light irradiation was nearly 3.5 times higher than that in the dark. Photoelectrochemical characterizations indicate that the improved photocatalytic activities originate from a combination of alloying effect, Mott–Schottky junction at the metal–semiconductor interface as well as the localized surface plasmon resonance induced under the visible light irradiation, which synergistically increase the local electron density at the active Ni sites. More importantly, the infrared spectra and isotope labeling-mass spectrometry methods were used to establish the source of hydrogen and unravel the reaction mechanism. It is suggested that the cleavages of B–H and O–H bonds are the initial steps of AB hydrolysis, which lead to the formation of intermediates M–H– (metal and electronegative H– from −BH3) and M–H+ (metal and electropositive H+ from H2O), respectively. The H2 molecule could form through three main paths as (1) two H atoms from −BH3, (2) two H atoms from H2O, and (3) one H atom from −BH3 and another from H2O. Results of density functional theory (DFT) calculations are consistent with the formation of electron-rich Ni sites in the NiCu, and the activation of H2O is a rate-limiting step (RLS). Redistribution of electrons in NiCu significantly enhances the adsorption of AB, the activation of H2O molecules, and the associative desorption of H adatoms as well, which effectively promote the cleavage of B–H and O–H bonds and release of H2. This work gives a systematic mechanistic study on photocatalytic AB hydrolysis involving multichannel electron-transfer pathways, which will provide a powerful guidance for the rational design of active catalysts for AB hydrolysis through multipronged effects.

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CuNi NPs supported on MIL-101 as highly active catalysts for the hydrolysis of ammonia borane

Cited by 53 publications

References 37 publications

Amine-functionalized MIL-53(Al) with embedded ruthenium nanoparticles as a highly efficient catalyst for the hydrolytic dehydrogenation of ammonia borane

Amine-functionalized MIL-53(Al) with embedded ruthenium nanoparticles as a highly efficient catalyst for the hydrolytic dehydrogenation of ammonia borane

A Simple and Scalable Route to Synthesize Co_xCu₁₋_xCo₂O₄@Co_yCu₁₋_yCo₂O₄ Yolk–Shell Microspheres, A High‐Performance Catalyst to Hydrolyze Ammonia Borane for Hydrogen Production

Visible-Light-Driven Multichannel Regulation of Local Electron Density to Accelerate Activation of O–H and B–H Bonds for Ammonia Borane Hydrolysis

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CuNi NPs supported on MIL-101 as highly active catalysts for the hydrolysis of ammonia borane

Cited by 53 publications

References 37 publications

Amine-functionalized MIL-53(Al) with embedded ruthenium nanoparticles as a highly efficient catalyst for the hydrolytic dehydrogenation of ammonia borane

Amine-functionalized MIL-53(Al) with embedded ruthenium nanoparticles as a highly efficient catalyst for the hydrolytic dehydrogenation of ammonia borane

A Simple and Scalable Route to Synthesize CoxCu1−xCo2O4@CoyCu1−yCo2O4 Yolk–Shell Microspheres, A High‐Performance Catalyst to Hydrolyze Ammonia Borane for Hydrogen Production

Visible-Light-Driven Multichannel Regulation of Local Electron Density to Accelerate Activation of O–H and B–H Bonds for Ammonia Borane Hydrolysis

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A Simple and Scalable Route to Synthesize Co_xCu₁₋_xCo₂O₄@Co_yCu₁₋_yCo₂O₄ Yolk–Shell Microspheres, A High‐Performance Catalyst to Hydrolyze Ammonia Borane for Hydrogen Production