Co−MOF‐74@Cu−MOF‐74 Derived Bifunctional Co−C@Cu−C for One‐Pot Production of 1, 4‐Diphenyl‐1, 3‐Butadiene from Phenylacetylene

Abstract

Carbon‐supported metal nanoparticles (NPs) play important roles in heterogeneous catalysis. In particular, supported bimetallic catalytic systems can be promising multifunctional catalysts for one‐pot tandem/cascade reactions, in which two or more successive independent reactions are realized in one pot. In this manuscript, we report the preparation of a carbon‐supported bimetallic CoCu catalytic system (Co−C@Cu−C), with Co NPs wrapped by carbon‐supported Cu NPs, from the pyrolysis of a core‐shell structured Co−MOF‐74@Cu−MOF‐74. The as‐obtained Co−C@Cu−C acts as a bifunctional catalyst for the transformation of phenylacetylene to 1, 4‐diphenyl‐1, 3‐butadiene in one pot, in which supported metallic Cu NPs and Co NPs are active for the coupling and hydrogenation reaction respectively. By tuning the reaction rates of the coupling and the hydrogenation in this tandem reaction over the Co−C@Cu−C via changing the reaction medium and the reducing agent, an efficient direct transformation of phenylacetylene to 1, 4‐diphenyl‐1, 3‐butadiene was realized. This work not only highlights the important role of MOFs in the preparation of multifunctional carbon supported metal NPs for heterogeneous catalysis, but also demonstrates the possibility of tuning the reaction rates of different catalytic steps in a tandem reaction to realize an efficient overall reaction.

Highly porous copper-supported magnetic nanocatalysts: made of volcanic pumice textured by cellulose and applied for the reduction of nitrobenzene derivatives

“…At the first stage, the Cu 2+ ions as the main catalytic sites are reduced to Cu 0 by sodium borohydride (NaBH 4 ) under the alkaline conditions provided by potassium carbonate (K 2 CO 3 ). 54 In stage 2, both the NB and borohydride (BH 4 − ) structures are attracted onto the catalyst surface through electronic and hydrogen bond interactions. 55 In third stage, hydridation of the NB structure is performed by the borohydride in the vicinity of the NB on the surface of the Fe 3 O 4 @VPMP/CLS–Cu particle.…”

One‐Step Synthesis of Core‐Shell‐Structured Mixed‐Metal CPO‐27(Cu,Co) and Investigations on Its Controlled Thermal Transformation

“…Furthermore, Cai et al also used the Co/Cu combination for the synthesis of a core-shell structured CPO-27 material in a two-step procedure. [10] In a similar fashion, a coreshell structured mixed-metal CPO-27 material with the metal combination Co/Ni was reported. [11] The concept of isostructural mixed-metal metal-organic framework materials, in which all metals are distributed over crystallographically equivalent framework position, is easy to realize when metals with similar properties (e.g.…”

“…An earlier report of a bimetallic CPO-27 material also claimed a core-shell distribution of both metals, but in that work, cobalt was present in the core and copper in the shell of the crystallites and, thus, opposite to our present study. [10] Since we have successfully obtained this metal-organic framework material with core-shell distribution of both metals, we also wanted to test whether the metal distribution would remain intact during the controlled thermal decomposition. Furthermore, we wanted to investigate how both metals would behave during such thermal treatments.…”

“…[15][16][17] During the transformation process, the metal centers are partially or completely reduced and the linker molecules are converted into an amorphous or graphitic carbon matrix, in which the newly formed and often highly dispersed metal particles are embedded. The thermal decomposition of monometallic as well as mixed-metal CPO-27 has been reported for applications as highly active catalyst materials [8g, 10,18] or supercapacitors [8h] .…”

Highly efficient non-noble metallic NiCu nanoalloy catalysts for hydrogenation of nitroarenes

“…3b, the Cu 2p3/2 peak at 934.1 eV could be assigned to Cu 2+ , while the main peak around 932.4 eV could be related to Cu + and/or Cu 0 species. 42,43 To distinguish Cu 0 and Cu + , auger electron spectroscopy (AES) of the Cu LMM signal (Fig. S1) was additionally recorded, indicating the stable coexistence of Cu + (573.0 eV) and Cu 0 (569.6 eV) on the surface of these catalysts.…”