Trace Thiol Moieties in the Ligand Layer Induce Superior Catalytic Gold Nanoclusters

We here show that the typical poison of thiols, if below a certain level, promotes rather than suppresses the catalytic activity of gold nanoclusters (AuNCs). A few thiol groups functionalized hyperbranched polyethylenimine (PEI, M_n = 2000 Da) patched on a mesoporous polymeric bead aid the direct synthesis of AuNCs. The nucleation efficiency of AuNC is 93-fold favored at a level of 2 thiols per PEI (0.04 equiv of the amino units) than that by neat PEI, and AuNCs (1.3 nm) are obtained up to a gold load of 6.3% on the support. Unexpectedly, the catalytic activity of AuNCs is favored by the thiol up to 2 thiols per PEI, as evaluated from the surface-normalized rate constant of the model reaction of 4-nitrophenol-reduction. The catalytic promotion by thiols probably stems from optimized electron density on AuNC. If the residual NH groups of PEI were further fully treated with glycidyltrimethylammonium chloride, the catalytic activity is again enhanced, where the accelerated mass transfer is responsible for the promotion. Overall, the catalytic activity reaches an unprecedented value (metal-normalized rate constant k_c = 29.4 L mmol^-1 s^-1 and turnover frequency = 1623 h^-1, as evaluated with the model reaction of 4-nitrophenol reduction) ever reported for supported AuNCs. Our results suggest that orthogonal ligand optimization is an effective manner of triggering the release of the catalytic potential of AuNCs, among which thiol is unique.