General Immobilization of Ultrafine Alloyed Nanoparticles within Metal–Organic Frameworks with High Loadings for Advanced Synergetic Catalysis

Abstract

The development of a general synthesis approach for creating fine alloyed nanoparticles (NPs) in the pores of metal–organic frameworks (MOFs) shows great promise for advanced synergetic catalysis but has not been realized so far. Herein, for the first time we proposed a facile and general strategy to immobilize ultrafine alloyed NPs within the pores of an MOF by the galvanic replacement of transition-metal NPs (e.g., Cu, Co, and Ni) with noble-metal ions (e.g., Pd, Ru, and Pt) under high-intensity ultrasound irradiation. Nine types of bimetallic alloyed NPs of base and noble metals were successfully prepared and immobilized in the pores of MIL-101 as a model host, which showed highly dispersed and well-alloyed properties with average particle sizes ranging from 1.1 to 2.2 nm and high loadings of up to 10.4 wt %. Benefiting from the ultrafine particle size and high dispersity of Cu–Pd NPs and especially the positive synergy between Cu and Pd metals, the optimized Cu–Pd@MIL-101 exhibited an extremely high activity for the homocoupling reaction of phenylacetylene under unprecedented base- and additive-free conditions and room temperature, affording at least 19 times higher yield (98%) of 1,4-diphenylbuta-1,3-diyne than its monometallic counterparts. This general strategy for preparing various MOF-immobilized alloyed NPs potentially paves the way for the development of highly active metal catalysts for a variety of reactions.

Ultrathin Ni-MOF Nanobelts-Derived Composite for High Sensitive Detection of Nitrite

“…(2) They have high porosity and specific surface areas to carry metal nanoparticles; (3) Understanding catalysis requires defining the MOF structure distinctly and ensuring that the pore structure is easily tailored in order to assure that the surrounding environment of metal nanoparticles is easily identified (Mukoyoshi et al, 2015;Tang et al, 2018;Chen et al, 2019;Li Y.-P. et al, 2019).…”

Catalysis in Confined Spaces of Metal Organic Frameworks

“…Besides, readers are referred to other reports providing the encapsulation of metal NPs within the cages of MOFs and their catalytic performance in broad ranges of reactions including biomass conversion. [69][70][71][72][73]…”

“…This section describes the shape selective catalysis achieved by metal NPs encapsulated within the pores of MOFs as heterogeneous catalysts and are categorized based on NPs. Besides, readers are referred to other reports providing the encapsulation of metal NPs within the cages of MOFs and their catalytic performance in broad ranges of reactions including biomass conversion …”

Synthesis of Co0.5Mn0.1Ni0.4C2O4⋅n H2O Micropolyhedrons: Multimetal Synergy for High‐Performance Glucose Oxidation Catalysis

“…[6][7][8] Multimetal materials can alter the electronic structure of the activem etal centers and can also modulate the available catalytically active sites to enhance the catalytic performance. [9][10][11][12][13][14][15] For instance, Wu and co-workers [16] reported Fe 1Àx PtRu x nanocrystals that had improved electrocatalytic activity toward methanol, which was ascribed to a change in the electronic structure of Pt owing to synergistic effects between the metals. In addition, as reported by Hu et al, [17] PdO reduces the density of Pd electrons by doping with Co 3 O 4 ,and the formation of al arge number of oxygen vacancies in Co 3 O 4 significantly improved the electrocatalytic performance.…”

“…Materials containing multiple metallic elements are more attractive from a scientific and technical point of view than single metal materials, and these materials are expected to exhibit new synergistic properties between the metals . Multimetal materials can alter the electronic structure of the active metal centers and can also modulate the available catalytically active sites to enhance the catalytic performance . For instance, Wu and co‐workers reported Fe 1− x PtRu x nanocrystals that had improved electrocatalytic activity toward methanol, which was ascribed to a change in the electronic structure of Pt owing to synergistic effects between the metals.…”