Ni₂P Nanoalloy as an Air‐Stable and Versatile Hydrogenation Catalyst in Water: P‐Alloying Strategy for Designing Smart Catalysts

Abstract

Non‐noble metal‐based hydrogenation catalysts have limited practical applications because they exhibit low activity, require harsh reaction conditions, and are unstable in air. To overcome these limitations, herein we propose the alloying of non‐noble metal nanoparticles with phosphorus as a promising strategy for developing smart catalysts that exhibit both excellent activity and air stability. We synthesized a novel nickel phosphide nanoalloy (nano‐Ni2P) with coordinatively unsaturated Ni active sites. Unlike conventional air‐unstable non‐noble metal catalysts, nano‐Ni2P retained its metallic nature in air, and exhibited a high activity for the hydrogenation of various substrates with polar functional groups, such as aldehydes, ketones, nitriles, and nitroarenes to the desired products in excellent yields in water. Furthermore, the used nano‐Ni2P catalyst was easy to handle in air and could be reused without pretreatment, providing a simple and clean catalyst system for general hydrogenation reactions.

Support-Boosted Nickel Phosphide Nanoalloy Catalysis in the Selective Hydrogenation of Maltose to Maltitol

“…This stability enables easy catalyst handling and eliminates the need for high-temperature treatment with H 2 to reduce non-noble metals before use. Furthermore, these catalysts showed high activity in versatile hydrogenation reactions of aldehydes, sulfoxides, ketones, nitroarenes, and nitriles. − Further functionalization of metal phosphide nanoalloys is expected to open up an exciting research field on metal phosphide catalysis. In particular, although supports are known to greatly affect the catalytic performance, metal–support interactions and support-boosted metal phosphide catalysis remain unexplored.…”

Mild and Efficient Heterogeneous Hydrogenation of Nitroarenes Facilitated by a Pyrolytically Activated Dinuclear Ni(II)-Ce(III) Diimine Complex

“…A recent publication on a thermally activated, PPh 3 -functionalized cobalt corrole that proved very effective in the heterogeneous nitroarene-to-aniline hydrogenation expanded the application range of this versatile macrocyclic compound class ( Figure 1 b) [ 86 ]. As was to be expected, the extra axial phosphine ligand permitted a brisk access to N , P -co-doped solid catalysts in which the incorporated P atoms significantly improved the redox properties of the material [ 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 , 96 , 97 , 98 , 99 , 100 , 101 , 102 , 103 , 104 , 105 , 106 ].…”

Efficient D‐Xylose Hydrogenation to D‐Xylitol over a Hydrotalcite‐Supported Nickel Phosphide Nanoparticle Catalyst

“…The high catalytic performance of nano-Ni 2 P/HT may be due to the cooperative catalysis by nano-Ni 2 P and HT, which activate H 2 and the C=O moiety of D-xylose, respectively. [35,38,39] Subsequently, the catalytic activity of nano-Ni 2 P/HT in the hydrogenation of D-xylose was compared with those of conventional Ni catalysts. Ni/HT and its H 2 -treated Ni/HT-Red were investigated as model catalysts for NiO x and Ni(0) nanoparticles, respectively (Table 1, entries 12 and 13).…”

“…Nevertheless, we recently developed supported non-precious metal phosphide nanoparticles for use in diverse hydrogenation reactions. [31][32][33][34][35][36][37] In particular, hydrotalcite (HT: Mg 6 Al 2 CO 3 (OH) 16 • 4(H 2 O))-supported nickel phosphide nanoparticles (nano-Ni 2 P/HT) served as a highly active, air-stable, and reusable catalyst for the hydrogenation of D-glucose and maltose to the corresponding sugar alcohols. [38,39] In this context, the combination of nano-Ni 2 P and HT played a key role in the high catalytic performance, where nano-Ni 2 P activates H 2 , while HT acts as an electron donor to Ni and as an activator of the sugar C=O moiety, thereby facilitating the hydrogenation reaction.…”