Catalytic dehydrogenation of natural terpenes via CuPd alloy nanoparticles generated on mesoporous graphitic carbon nitride

Abstract

A facile wet‐chemical protocol for the synthesis of bimetallic CuPd alloy nanoparticles (NPs) anchored on mesoporous graphitic carbon nitride (m‐gCN), serving as both stabilizer and support material, was presented herein. The presented protocol allowed to synthesize nearly monodisperse CuPd alloy NPs with an average particle size of 3.9 ± 0.9 nm without use of any additional surfactants and to prepare CuPd/m‐gCN nanocatalysts with different Cu/Pd compositions (Cu25Pd75/m‐gCN, Cu35Pd65/m‐gCN, Cu16Pd74/m‐gCN, Cu32Pd68/m‐gCN, Cu10Pd90/m‐gCN, and Cu50Pd50/m‐gCN). After the detailed characterization of CuPd/m‐gCN nanocatalysts, they were utilized as catalysts in the dehydrogenation of terpenes. Among all tested nanocatalysts, Cu50Pd50/m‐gCN showed the highest activity in terms of the product yields within the same reaction time. Various parameters influencing the catalytic activity of Cu50Pd50/m‐gCN were studied using himachalene as a model substrate and the optimum conditions were determined. Under the optimized reaction conditions, the catalytic application of Cu50Pd50/m‐gCN nanocatalysts was extended to nine different terpenes and the corresponding products were obtained in high conversion yields (>90%) under mild conditions. A reusability test showed that Cu50Pd50/m‐gCN nanocatalysts can be re‐used up to four cycles without significant loss in their initial activity.

Exploring the Potential of Copper Palladium Nanocube Electrocatalysts for Enhancing the Overall Water Splitting Performance

“…The high-resolution Pd 3d spectra (Figure b) were deconvoluted into different fragments, and the peak observed at a binding energy of 335.4 eV corresponds to Pd 0 and 336.62 and 341.82 eV correspond to Pd 2+ . To elaborate, in the high-resolution XPS spectrum of Pd 3d, the two peaks were observed at 336.03 and 341.6 eV, where Δ = 5.3 ± 0.2 eV is the spin orbit component, which shows the slight shift toward higher binding energies compared to the metallic Pd indicating the loss of electrons in Pd. − The core level Cu 2p spectra (Figure c), the binding energy at 934.16 and 954.06 eV indicate the formation of metallic copper along with the Cu 2+ state in the 932 eV. The deconvoluted O 1s spectra (Figure d) at binding energies of 529, 530, and 531 eV correspond to M–O, M–O–M, and M–OH, clearly confirms the formation of CuPd catalyst.…”

Black Phosphorus Quantum Dots/Carbon Nitride-Reduced Graphene Oxide Ternary Heterojunction as a Multifunctional Metal-Free Photocatalyst for Photooxidation Reactions

“…There will be an effective contribution of CN to the binary heterojunction with regard to further stabilization and improvement of redox capacity due to strong sp 2 -hybridized C and N bonds and a band gap of 2.7 eV, respectively. 11,24,25 As a result of establishing a heterojunction with these materials (BPQDs, rGO, and CN), a function-oriented photocatalyst can be constructed for both bond formation and bond cleavage in organic transformations. Such a cooperative photocatalyst system could be designed in a way to generate essential radical intermediates for building complex organic molecules while enabling indispensable reactive oxygen species (ROS) for the degradation of pollutants in water.…”

“…In this regard, carbon nitride (CN) as a third component might have a transformative impact on the BPQDs-rGO-based targeted heterojunction photocatalyst. There will be an effective contribution of CN to the binary heterojunction with regard to further stabilization and improvement of redox capacity due to strong sp 2 -hybridized C and N bonds and a band gap of 2.7 eV, respectively. ,, As a result of establishing a heterojunction with these materials (BPQDs, rGO, and CN), a function-oriented photocatalyst can be constructed for both bond formation and bond cleavage in organic transformations. Such a cooperative photocatalyst system could be designed in a way to generate essential radical intermediates for building complex organic molecules while enabling indispensable reactive oxygen species (ROS) for the degradation of pollutants in water. , Considering the importance of these applications, the scope of a photocatalyst is a piece of valuable information to determine a point whether a substrate transforms into the desired compound.…”