Electronic Tuning of Gold Nanoparticle Active Sites for Reduction Catalysis

Electronic tuning of active sites in heterogeneous catalysis with organic ligands remains challenging since the ligands are often bound to the most active sites on the catalysts' surfaces. In this work, gold nanoparticles, which are on average less than 2 nm in diameter, are synthesized with strongly binding thiol and phosphine ligands and have measurable quantities of accessible sites on their surfaces in both cases. Triphenylphosphine (TPP) is used as the phosphine ligand, while triphenylmethyl mercaptan (TPMT) serves as the thiol ligand. Phosphines are chosen because they are electron-donating ligands when bound to Au, and thiols are selected because they are electron-withdrawing on the Au surface. X-ray photoelectron spectroscopy (XPS) results show differences in the Au 4f binding energies between the TPP- and TPMT-bound Au nanoparticles. Fourier transform infrared spectroscopy (FTIR) measurements of bound CO indicate that the TPP-bound Au nanoparticles are more electron-rich than the TPMT-bound Au nanoparticles. The number of binding sites on the surface is quantified using 2-naphthalenethiol titration experiments. It is observed that the number of binding sites on the thiol and phosphine-bound Au nanoparticles is similar in both cases. The Au nanoparticles are used for three different reactions: resazurin reduction, CO oxidation, and benzyl alcohol oxidation. For both CO oxidation and benzyl alcohol oxidation, which are performed with the ligands attached, TPP- and TPMT-bound nanoparticles are both catalytically active. However, for resazurin reduction, the TPMT-bound Au nanoparticles are not active, while the TPP-bound Au nanoparticles are catalytically active. These results illustrate that the catalytic activity can be tuned using bound organic ligands with different electronic properties for reduction reactions using Au nanoparticle catalysts.