Plasmon Catalysis on Bimetallic Surface—Selective Hydrogenation of Alkynes to Alkanes or Alkenes

Abstract

Utilization of plasmonics as a driving tool for chemical transformation triggering enables to achieve unprecedented results regarding photochemical conversion efficiency and chemical selectivity regulation. In this study, the bimetallic surface plasmon-polariton-supported grating is proposed as an effective background for plasmon-induced hydrogenation of alkynyl groups of absolute chemoselectivity. The periodical bimetallic structure consists of spatially modulated gold layers, covered with the nanometer-thick platinum layer. The alkyne bonds are covalently attached to the surface of the catalytic system through covalent grafting of the bimetallic surface with 4-ethynylbenzenediazonium tosylate, with triple bonds separated from the platinum layer by the benzene rings. The proposed bimetallic structure enables selective hydrogenation of alkyne bonds to alkenyl or alkyl moieties using cyclohexene as a hydrogen source. The selectivity of hydrogenation can be controlled by changing the structure parameters, for example, the thickness of the upper platinum layer.

New Variants of Nitroxide Mediated Polymerization

“…The exact mechanism of the interaction of plasmon with organic molecules is still questionable and has been discussed extensively recent years [ 88 , 89 ]. Anyway, now we can certainly confirm that plasmonic energy significantly enhances the rate of the reaction and provides an alternative method for the activation of chemical transformations, such as Pd-catalyzed cross-coupling reactions [ 90 , 91 ], hydrogenations [ 92 , 93 , 94 ], cycloadditions [ 95 , 96 ], oxidative reactions [ 97 , 98 ].…”

Kinetics of Plasmon-Driven Hydrosilylation of Silicon Surfaces: Photogenerated Charges Drive Silicon- Carbon Bond Formation

“…[1][2][3][4] The combination of plasmonics and surface chemistry is an emerging research area, with a wide range of promising applications that includes sensing, photovoltaics, catalysis, imaging, and nanomedicine, among others. [5][6][7][8][9] Localized surface plasmon resonance (LSPR) in metallic nanostructures is a well established as the platform for surface enhanced Raman spectroscopy (SERS), and has seen increasing interest as a driver of highly localized surface chemistry, as described beautifully in a recent review. 10 Depending on the size and other properties of the metallic nanostructures, illumination with the resonant optical wavelength to excite LSPR modes can be used to drive surface chemical reactions.…”

Aqueous phase semihydrogenation of alkynes over Ni–Fe bimetallic catalysts

“…5,6 However, due to various disadvantages of the Lindlar catalyst (use of excess ligand and harmful Pb as a promoter), over the past decades, many catalysts have been developed based on monometallic Pd, [7][8][9][10] Au, [11][12][13] Ru, 14 Rh, 15 Ni, [16][17][18][19][20][21][22][23][24][25] Co, 26 Fe, 27 and Cu (ref. 28 and 29) as well as bimetallic Pd-Ag, 30 Pd-Au, 31 Pd-Ru, 32 Au-Pt, 33 Pd-Cu, 34 Pd-Ga, 35 Rh-Co, 36 Rh-Ni, 37 Co-Pt, 38 Ni-Cu, 39 Ni-Fe, 40,41 Cu-Fe, 41 Ni-Ga (ref. 42 and 43) and trimetallic Cu-Ni-Fe (ref.…”

“…In this direction, particularly, exploration of bimetallic nanoparticles have gained tremendous attention for the selective hydrogenation of alkynes as compared to monometallic catalysts, because they exhibit superior chemical and physical properties. [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] For example, very recently Li et al have reported Pd@Au-Pd alloy surface nanocubes for semihydrogenation of alkynes to alkenes (alkene/alkane; 91/9) using a hydrogen balloon in toluene at room temperature. 31 Similarly, Lu et al also reported bimetallic Pd-Pb alloy octahedral nanocrystal based catalysts for the semihydrogenation of alkynes.…”

“…45 Lyutakov et al also explored bimetallic Au/Pt heterostructures for the selective hydrogenation of alkyne bonds, of 4-ethynylphenyl groups covalently grafted on the catalyst surface, to alkenyl or alkyl moieties using cyclohexene as a hydrogen source. 33 The Au supported surface plasmon polaritons (SPPs) activate the hydrogenation of alkynes, while the thickness of the Pt layer tunes the alkenyl vs. alkyl selectivity. 33 The RhNi@MOF-74 alloy catalyst also exhibited appreciably good activity for the semihydrogenation of alkynes to Z-alkenes.…”