Cu/Ni-NiO_x Nanoparticles Distributed on Graphene as Catalysts for the Methanolysis of Ammonia Borane to Produce Hydrogen

Abstract

Ultrasmall Cu/Ni-NiO x nanoparticles (NPs) had been successfully prepared by attaching and growing Ni-NiO x NPs on the surface of Cu NPs and then uniformly dispersed onto graphene (G) surface. High-angle annular dark-field–scanning transmission electron microscopy (HAADF-STEM) characterization confirmed that Ni-NiO x NPs were uniformly distributed on the surface of Cu NPs. The catalytic methanolysis of ammonia borane (AB) proved that Cu/Ni-NiO x NPs possessed high catalytic hydrogen (H2) evolution activity, and the highest turnover frequency (TOF) was 17.72 mol H2·mol–1 Cu·min–1. Comparative experiments revealed that the high catalytic activity originated from the abundant catalytic active sites of Cu/Ni-NiO x NPs. The attachment of Ni-NiO x on the surface of Cu NPs that dispersed on G (G-Cu/Ni-NiO x ) can not only effectively improve the antioxidative performance of Cu NPs under ambient conditions but also promote the methanolysis of AB to produce H2.

Review on Hydrogen Production from Catalytic Ammonia Borane Methanolysis: Advances and Perspectives

“…In order to further improve the catalytic activity of non-noble-metal catalysts, some researchers use nonmetallic elements to regulate non-noble-metal alloys, the electron-acceptor effect is formed between nonmetals and metals, and the catalytic activity is improved by regulating the catalytic activity site of the catalyst. , Kalidindi et al synthesized Co–Co 2 B Ni–Ni 3 B and Co–Ni–B nanocomposites by the reduction of Co 2+ and Ni 2+ ions, the comparison of the rate constants shows the effect of the catalyst following this order: Co–Ni–B > Co–Co 2 B > Ni–Ni 3 B. Zhang et al synthesized a series of Co–B amorphous alloys by liquid phase reduction method, a series of catalysts Co x B 1– x ( x = 0.25, 0.50, 0.75) is synthesized by tuning the n (Co 2+ )/ n (BH 4 – ) to catalyze AB methanolysis for hydrogen production, and the results show that the catalytic activity follows this order: Co 0.75 B 0. 25 > Co 0.50 B 0.50 > Co 0.25 B 0.75 , shown in Figure .…”

Methanolysis of ammonia borane using binder‐free hierarchical Co@Ni metal‐organic framework nanocolumn arrays catalyst for hydrogen generation

“…It is also highly soluble in water (33.6 g/100 mL) at room temperature. [5][6][7] Further, AB can quickly release a huge quantity of hydrogen during the Dharman Ranjith Kumar and Samikannu Prabu equal contribution to this work. hydrolytic process in the presence of nanocatalysts.…”

“…13 Zheng et al reported that Cu/Ni-NiO x nanoparticles on graphene sheets for AB methonalysis and the nanoparticles possessed higher catalytic hydrogen generation with 17.72 mol H 2 .mol À1 (TOF). 6 Konus et al prepared TiO 2 -supported Ru (0) nanoparticles by in situ reduction process and performed hydrogen production from the AB hydrolysis with a TOF value of 200 min À1 at room temperature. 14 Karatas et al developed Rh (0) nanoparticles on MXene and the catalysts show significant catalytic performance in the hydrogen production with 288.4 min À1 TOF value at room temperature.…”

“…AB is more stable under ambient conditions and also a higher stoichiometric content of hydrogen (19.6 wt%). It is also highly soluble in water (33.6 g/100 mL) at room temperature 5‐7 . Further, AB can quickly release a huge quantity of hydrogen during the hydrolytic process in the presence of nanocatalysts.…”

“…Tong et al developed CuAg alloy for plasma‐enhanced AB methanolysis and exhibited higher hydrogen production (17.1 μmol min −1 ) under light irradiation 13 . Zheng et al reported that Cu/Ni‐NiO x nanoparticles on graphene sheets for AB methonalysis and the nanoparticles possessed higher catalytic hydrogen generation with 17.72 mol H 2 .mol −1 (TOF) 6 . Konus et al prepared TiO 2 ‐supported Ru (0) nanoparticles by in situ reduction process and performed hydrogen production from the AB hydrolysis with a TOF value of 200 min −1 at room temperature 14 .…”