Production of 2,5-furandicarboxylic acid (FDCA, a platform chemical for the chemical industry in the future) by the selective aerobic oxidation of 5-hydroxymethyl-furfural is a crucial component to enable the FDCA production from sugars. The challenge is to achieve a high FDCA yield at low temperatures. Here, we report a catalyst composed of alloyed nanoparticles (containing 1.5 wt % Ag and 1.5 wt % Pd) supported on CeO2 nanofibers, which achieved an excellent FDCA yield (93%) at 20 °C. Interesting observations include yield deterioration at higher reaction temperatures; water is the source of the oxygen atom(s) added to the oxidized intermediates and product, while O2 molecules adsorbed onto the catalyst scavenge electrons, yielding OH• radicals from OH– ions in the reaction system to drive the oxidation. At 20 °C, we avoid side reactions, but there is no external energy provided for overcoming the activation barriers. The barriers for activating the alcohol groups are significant. We find that the appropriate chemisorption on the catalyst is critical for a high FDCA yield. By tuning the Ag/Pd ratio, we attained the most catalytically active sites, bimetallic surface sites, at the boundaries between Ag and Pd clusters. The chemisorption at these sites is strong enough to cause the selective oxidation of both the aldehyde and alcohol groups in HMF at 20 °C, avoiding side reactions at high temperatures. The knowledge acquired from this study is expected to have implications for other catalytic systems where competitive reactions proceed.

Surface‐plasmon‐mediated phenylacetylide intermediate transfer from the Cu to the Pd surface affords a novel mechanism for transmetalation, enabling wavelength‐tunable cross‐coupling and homo‐coupling reaction pathway control. C−C bond forming Sonogashira coupling and Glaser coupling reactions in O2 atmosphere are efficiently driven by visible light over heterogeneous Cu and Pd nanoparticles as a mixed catalyst without base or other additives. The reaction pathway can be controlled by switching the excitation wavelength. Shorter wavelengths (400–500 nm) give the Glaser homo‐coupling diyne, whereas longer wavelength irradiation (500–940 nm) significantly increases the degree of cross‐coupling Sonogashira coupling products. The ratio of the activated intermediates of alkyne to the iodobenzene is wavelength dependent and this regulates transmetalation. This wavelength‐tunable reaction pathway is a novel way to optimize the product selectivity in important organic syntheses.

Selective activation of the C(sp3)−H bond is an important process in organic synthesis, where efficiently activating a specific C(sp3)−H bond without causing side reactions remains one of chemistry's great challenges. Here we report that illuminated plasmonic silver metal nanoparticles (NPs) can abstract hydrogen from the C(sp3)−H bond of the Cα atom of an alkyl aryl ether β‐O‐4 linkage. The intense electromagnetic near‐field generated at the illuminated plasmonic NPs promotes chemisorption of the β‐O‐4 compound and the transfer of photo‐generated hot electrons from the NPs to the adsorbed molecules leads to hydrogen abstraction and direct cleavage of the unreactive ether Cβ−O bond under moderate reaction conditions (≈90 °C). The plasmon‐driven process has certain exceptional features: enabling hydrogen abstraction from a specific C(sp3)−H bond, along with precise scission of the targeted C−O bond to form aromatic compounds containing unsaturated, substituted groups in excellent yields.

Selective activation of the C(sp 3 )À H bond is an important process in organic synthesis, where efficiently activating a specific C(sp 3 )À H bond without causing side reactions remains one of chemistry's great challenges. Here we report that illuminated plasmonic silver metal nanoparticles (NPs) can abstract hydrogen from the C(sp 3 )À H bond of the C α atom of an alkyl aryl ether β-O-4 linkage. The intense electromagnetic nearfield generated at the illuminated plasmonic NPs promotes chemisorption of the β-O-4 compound and the transfer of photo-generated hot electrons from the NPs to the adsorbed molecules leads to hydrogen abstraction and direct cleavage of the unreactive ether C β À O bond under moderate reaction conditions ( � 90 °C). The plasmon-driven process has certain exceptional features: enabling hydrogen abstraction from a specific C(sp 3 )À H bond, along with precise scission of the targeted CÀ O bond to form aromatic compounds containing unsaturated, substituted groups in excellent yields.

Surface‐plasmon‐mediated phenylacetylide intermediate transfer from the Cu to the Pd surface affords a novel mechanism for transmetalation, enabling wavelength‐tunable cross‐coupling and homo‐coupling reaction pathway control. C−C bond forming Sonogashira coupling and Glaser coupling reactions in O2 atmosphere are efficiently driven by visible light over heterogeneous Cu and Pd nanoparticles as a mixed catalyst without base or other additives. The reaction pathway can be controlled by switching the excitation wavelength. Shorter wavelengths (400–500 nm) give the Glaser homo‐coupling diyne, whereas longer wavelength irradiation (500–940 nm) significantly increases the degree of cross‐coupling Sonogashira coupling products. The ratio of the activated intermediates of alkyne to the iodobenzene is wavelength dependent and this regulates transmetalation. This wavelength‐tunable reaction pathway is a novel way to optimize the product selectivity in important organic syntheses.