Homogeneous Distribution of Pt₁₆(C₄O₄SH₅)₂₆ Clusters in ZIF-67 for Efficient Hydrogen Generation and Oxygen Reduction

Abstract

In recent years, based on the high catalytic activities of metal nanoclusters (MNCs) and the unique porous structure of metal–organic frameworks (MOFs), much work has focused on MOF-confined small MNCs for catalysis applications. However, the commonly used “ship-in-boat” approach is unfeasible for precisely controlling the size and composition of the formed MNCs and meanwhile often causes structural distortion/degradation. On the other hand, the “bottle-around-ship” method usually has the disadvantages that MOFs show uncontrollable self-nucleation outside the MNCs and the stabilizers on the surface of MNCs may greatly reduce their catalytic activities. In this work, monodispersed Pt16(C4O4SH5)26 clusters (Pt16(MSA)26) were first prepared and used as a precursor for the synthesis of Pt­(MSA)@ZIF-67 via the typical Co-carboxylate type of linkage at the interface under ambient atmosphere. After encapsulating the Pt clusters in ZIF-67, the protecting ligands were removed under 300 °C to get surface-clean Pt16 clusters confined in ZIF-67 (Pt@ZIF-67). The obtained Pt@ZIF-67 exhibited high catalytic activity for the hydrolysis of ammonia borane that was superior to that of most of the reported noble-metal catalysts. Meanwhile, by annealing the Pt­(MSA)@ZIF-67 at 800 °C to form highly conductive graphitic carbon-coated Pt NCs and Co nanoparticles (NPs) (Pt/Co@NC), the obtained composite showed high catalytic activity for the oxygen reduction reaction (ORR). The formed Pt/Co@NC showed 9.6 times higher ORR mass activity (at 0.8 V) than Pt/C. This work provides a strategy to fabricate highly dispersed and stable metal clusters confined in the porous matrix for catalysis and shows that highly porous MOFs have promising catalysis applications by combining them with other active components.

Atomically Precise Cun(n=3, 6 and 11) Nanocatalysts for Alkyne‐Haloalkane‐Amine (AHA) Coupling Reaction

“…[30] Chen and colleagues encapsulated monodisperse Pt 16 (C 4 O 4 SH 5 ) 26 NCs in ZIF-67 and removed ligands to obtain Pt@ZIF-67. [31] The prepared catalyst exhibited high catalytic activity for the hydrolysis of ammonia borane that was superior to that of catalysts previously reported. In recent years, Cu catalysts have been widely used in the field of catalysis and show good performance.…”

“…Li and co‐workers designed Pd 3 Cl NCs for the Suzuki‐Miyaura C−C cross‐coupling, which shows excellent catalytic activity [30] . Chen and colleagues encapsulated monodisperse Pt 16 (C 4 O 4 SH 5 ) 26 NCs in ZIF‐67 and removed ligands to obtain Pt@ZIF‐67 [31] . The prepared catalyst exhibited high catalytic activity for the hydrolysis of ammonia borane that was superior to that of catalysts previously reported.…”

Ultrafine platinum nanoparticles supported on N,S-codoped porous carbon nanofibers as efficient multifunctional materials for noticeable oxygen reduction reaction and water splitting performance

“…1–6 The sluggish kinetics of catalysts in the oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are known to govern their performance in energy utilization and power output. 7–14 Generally, platinum (Pt) on carbon materials has been widely used for ORR, 15–17 OER, 18–20 HER, 21–23 and hydrogen storage. 24–29 However, these catalysts require relatively large surface area, high electrical conductivity of carbon materials, and high loading density and uniform dispersion of platinum nanoparticles (NPs).…”

Metal‐Organic‐Framework‐derived Co Nanoparticles Embedded in P, N‐Dual‐doped Porous Carbon/rGO Catalyst for Water Splitting and Oxygen Reduction

“…[16] It is hard to achieve excellent electrochemical performance with these catalysts because that the kinetics of OER and oxygen reduction reaction (ORR) are slow. [17][18][19][20] Researches have shown that carbon materials have great potential for developing high-performance, low-cost catalysts by co-doping metallic and non-metallic heteroatoms. [21][22][23][24] Notably, metal(Co)À NÀ C has emerged as a promising candidate for researchers due to its low cost and high catalytic activity.…”

“…So far, researchers devote themselves to explore non‐noble metal oxides, non‐noble metal heteroatoms doped with carbon and so on to improve their catalytic performance [16] . It is hard to achieve excellent electrochemical performance with these catalysts because that the kinetics of OER and oxygen reduction reaction (ORR) are slow [17–20] . Researches have shown that carbon materials have great potential for developing high‐performance, low‐cost catalysts by co‐doping metallic and non‐metallic heteroatoms [21–24] .…”