Intermetallic ZrPd₃-Embedded Nanoporous ZrC as an Efficient and Stable Catalyst of the Suzuki Cross-Coupling Reaction

Abstract

The Suzuki cross-coupling reaction, which is generally catalyzed by Pd-based materials, is a practical approach to create C–C bonds. Although heterogeneous catalysts, including metal-loaded and intermetallic catalysts, afford simple reaction conditions and catalyst reusability, it is challenging to achieve high catalytic activity, durability, and Pd-atom economy together in a single catalyst. Herein, we report the successful preparation of Pd–ZrC, a Pd-based catalyst with the described desirable features. In it, a-few-nanometer-sized nanoparticles of intermetallic ZrPd3 are uniformly dispersed on the surface of nanoporous ZrC with a surface area of 340–450 m2 g–1. As a result of the presence of electron-rich Pd sites and the material’s strong electron-donating ability, Pd–ZrC achieved high catalytic performance in Suzuki cross-coupling reactions at room temperature. Because a low Pd content (1 wt %) is sufficient to produce highly catalytically active Pd–ZrC, this material represents a great improvement in terms of Pd-atom economy over previously reported catalysts. Moreover, no catalytic degradation was noted over up to the presented 15 reaction cycles as the active Pd sites were stabilized in the ZrPd3 lattice. These results indicate that Pd–ZrC has the advantages of both metal-loaded and intermetallic catalysts, providing an approach to enhance the degree of freedom for designing heterogeneous catalysts.

Crystal phase-selective synthesis of intermetallic palladium borides and their phase-regulated (electro)catalytic properties

“…S12-S14 †). 23 These results identify the crucial role of the interstitial boron atom in the structural stability of Pd 2 B. The XRD pattern and HRTEM image of Pd 2 B were unchanged after the catalytic reaction, suggesting that Pd 2 B possessed an excellent structure stability (Fig.…”

“…The apparent activation energy (E a ) is an important parameter to evaluate the kinetics of the Suzuki coupling reaction over these catalysts. 23 As shown in Fig. 3c and S10, † the apparent E a of the Suzuki coupling reaction has a decreasing trend: Pd 2 B (37.5 kJ mol −1 ), Pd 5 B 2 (63.2 kJ mol −1 ), Pd 6 B (67.9 kJ mol −1 ), and Pd (84.2 kJ mol −1 ).…”

Catalysis of Alloys: Classification, Principles, and Design for a Variety of Materials and Reactions

“…Therefore, bulk powder synthesized by arc melting is generally used instead of supported nanoparticles. Recently, Hosono et al synthesized a nanoparticulate ZrPd 3 IMC using a ZrC support and discovered its excellent catalytic performance and stability in Suzuki–Miyaura cross-coupling . The nanoporous structure of ZrC NPs with a high surface area yieled uniformly dispersed ZrPd 3 nanoparticles (mainly 2–4 nm).…”

Insight into rare-earth-incorporated catalysts: The chance for a more efficient ammonia synthesis

“…As shown in Figs. 12(a [75,76], LaScSi [77], LaCu 0.67 Si 1.33 [78], Y 3 Pd 2 [79], and ZrPd 3 [80]) and their applications as catalysts/supports for diverse reactions [81], in which the NH 3 synthesis was the most focused one (Table 1, Entries 33-37).…”