Nanostructured Ni₂P as a Robust Catalyst for the Hydrolytic Dehydrogenation of Ammonia–Borane

Abstract

Ammonia-borane (AB) is ap romising chemical hydrogen-storage material. However,the development of realtime,e fficient, controllable,a nd safe methods for hydrogen release under mild conditions is ac hallenge in the large-scale use of hydrogen as al ong-term solution for future energy security.An ew class of low-cost catalytic system is presented that uses nanostructured Ni 2 Pa sc atalyst, which exhibits excellent catalytic activity and high sustainability toward hydrolysis of ammonia-borane with the initial turnover frequency of 40.4 mol (H2) mol (Ni2P) À1 min À1 under air atmosphere and at ambient temperature.T his value is higher than those reported for noble-metal-free catalysts,and the obtained Arrhenius activation energy (E a = 44.6 kJ mol À1 )f or the hydrolysis reaction is comparable to Ru-based bimetallic catalysts.Ac learly mechanistic analysis of the hydrolytic reaction of AB based on experimental results and ad ensity functional theory calculation is presented.

Electrons and Hydroxyl Radicals Synergistically Boost the Catalytic Hydrogen Evolution from Ammonia Borane over Single Nickel Phosphides under Visible Light Irradiation

“…The peaks at 853.0, 852.7 and 852.4 eV were assigned to the positive charge Ni δ + for Ni 2 P, Ni 12 P 5 and Ni 3 P, respectively. [22,41,42] The value of δ was δ(Ni 2 P) > δ(Ni 12 P 5 ) > δ(Ni 3 P). The peaks at 855.9, 856.0 and 855.9 eV were consistent to the Ni 2 + for Ni 2 P, Ni 12 P 5 and Ni 3 P, [43] respectively, due to the surface oxidation.…”

“…[8][9][10][11][12][13][14][15][16][17][18] However, their activities still remain low compared with the noble metal catalysts. [19][20][21][22][23][24][25][26][27] Thus, it is highly desirable to explore new catalytic systems using low-cost and efficient catalysts for hydrogen evolution.…”

“…Up to now, a variety of catalysts based on non‐noble metals such as Ni and Co have been explored for the hydrogen evolution from NH 3 BH 3 (NH 3 BH 3 +2H 2 O→NH 4 BO 2 +3H 2 ), which is a thermodynamics‐controlled process . However, their activities still remain low compared with the noble metal catalysts . Thus, it is highly desirable to explore new catalytic systems using low‐cost and efficient catalysts for hydrogen evolution.…”

Bimetallic Phosphide (Ni,Cu)2P Nanoparticles by Inward Phosphorus Migration and Outward Copper Migration

“…Two borderline scenarios of phosphorus insertion into core-shell Cu-Ni nanoparticle. (i) Preference of phosphorus towards one of the metalsTo obtain a fully crystallized product, as-synthesized Cu 0.25 Ni 0.75 nanoparticles were reacted directly after synthesis (no further purification) with a solution of P 4 in toluene at 250 °C for 2 h. Toluene was evaporated in vacuo before heating to avoid reflux at the reaction temperature 31. P NMR spectrum of the supernatant after centrifugation shows that P 4 was completely consumed (ESI Figure S7b).…”

In Situ Synthesis of NiCoP Nanoparticles Supported on Reduced Graphene Oxide for the Catalytic Hydrolysis of Ammonia Borane

“…[32] Fu and co-workers reported the synthesis of nanostructured Ni 2 P by reacting Ni(OH) 2 powders with NaH 2 PO 2 at high temperature in argon and its catalytic performance toward hydrolysis of AB. [33] Our group reported the synthesis of RhNiP catalyst and its superior catalytic performance toward hydrogen generation from alkaline solution of hydrazine, [34] as well as CoBP NPs supported on three-dimensional nitrogen-doped graphene hydrogel and its catalytic performance toward hydrolysis of ammonia borane at room temperature. [35] Despite great efforts have been made on developing monometallic transition metal phosphides towards hydrogen generation from hydrogen storage materials, to the best of our knowledge, bimetallic phosphide-based catalyst for hydrolysis of AB has been rarely reported.…”