Enhancement in Aerobic Alcohol Oxidation Catalysis of Au₂₅ Clusters by Single Pd Atom Doping

Abstract

Au 25 and Pd 1 Au 24 clusters on multiwalled carbon nanotubes were developed via adsorption of Au 25 (SC 12 H 25 ) 18 and Pd 1 Au 24 (SC 12 H 25 ) 18 , respectively, on the nanotubes, followed by calcination. Comparison of their catalysis for the aerobic oxidation of benzyl alcohol showed that single Pd atom doping significantly improved the catalytic performance of Au 25 for the first time.

Understanding the synergistic effects of gold bimetallic catalysts

“…The synergistic effect between the isolated single atom and the host cluster has also been found in other reactions, such as acetoxylation of ethylene to vinyl acetate [116], selective oxidation of glycerol to glyceric acid [117], aerobic oxidation of alcohols [118], and electrocatalytic production of H 2 O 2 [119]. In these reactions, the role of single atoms of impurity is to limit the byproduct formation, thus improving the selectivity toward the desired reaction pathway and the stability against being poisoned by byproducts.…”

Catalysis by gold: New insights into the support effect

“…4, and found that the gold atoms on top of palladium nanoclusters were highly active for aerobic glucose oxidation. Au was recognized as supported on Pd, which is an inverse example compared with the single Pd atom doped Au 25 cluster [94]. Au was shown to be negatively charged, which indicated that the electron transfer from Pd to Au.…”

Active metal (cadmium) doping enhanced the stability of inert metal (gold) nanocluster under O2 atmosphere and the catalysis activity of benzyl alcohol oxidation

“…By doping these small homogold nanoclusters with even single atom, many new physical and chemical properties are expressed [6][7][8][9][10]. In the past few years, significant advances have been made in the synthesis and property studies of these doping nanoclusters [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21].…”

“…By doping these small homogold nanoclusters with even single atom, many new physical and chemical properties are expressed [6][7][8][9][10]. In the past few years, significant advances have been made in the synthesis and property studies of these doping nanoclusters [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21]. Among homogold nanoclusters, Au 25 (SR) 18 nanocluster has been well studied due to its stable structure among three different charges (−1/0/+1) [22][23][24][25][26], which led to the exploration of a wide range of catalytic pathways facilitated by Au 25 for organic reactions, such as oxidation [27][28][29], hydrogenation [30][31][32], electronic transfer reactions [26,33], and electrocatalysis [34,35].…”

“…Among homogold nanoclusters, Au 25 (SR) 18 nanocluster has been well studied due to its stable structure among three different charges (−1/0/+1) [22][23][24][25][26], which led to the exploration of a wide range of catalytic pathways facilitated by Au 25 for organic reactions, such as oxidation [27][28][29], hydrogenation [30][31][32], electronic transfer reactions [26,33], and electrocatalysis [34,35]. Recent research implies that doping foreign atoms into this 25 noble metal system can largely affect the stability and the catalytic activity compared to the homogold counterpart [7][8][9][10][17][18][19]. Compared with these inert metal doped (M-Au) 25 (M=Pt/Pd/Cu/Ag) nanoclusters, the research on highly active metal (such as Cd) being used to dope into the nanocluster was rarely studied.…”