Distinct Site Motifs Activate O and H on Supported Au Nanoparticles in Liquid Water

Overview

Journal ACS Catal

Publisher American Chemical Society

Date 2024 Mar 7

PMID 38449529

Authors

Jason S Adams

Haoyu Chen

Tomas Ricciardulli

Sucharita Vijayaraghavan

Abinaya Sampath

David W Flaherty

Affiliations

Soon will be listed here.

Abstract

Au nanoparticles catalyze the activation and conversion of small molecules with rates and kinetic barriers that depend on the dimensions of the nanoparticle, composition of the support, and presence of catalytically culpable water molecules that solvate these interfaces. Here, molecular interpretations of steady-state rate measurements, kinetic isotope effects, and structural characterizations reveal how the interface of Au nanoparticles, liquid water, and metal oxide supports mediate the kinetically relevant activation of H and sequential reduction of O-derived intermediates during the formation of HO and HO. Rates of H consumption are 10-100 fold greater on Au nanoparticles supported on metal oxides (e.g., titania) compared to more inert and hydrophobic materials (carbon, boron nitride). Similarly, Au nanoparticles on reducible and Lewis acidic supports (e.g., lanthana) bind dioxygen intermediates more strongly and present lower barriers (<22 kJ mol) for O-O bond dissociation than inert interfaces formed with silica (>70 kJ mol). Selectivities for HO formation increase significantly as the diameters of the Au nanoparticles increase because differences in nanoparticle size change the relative fractions of exposed sites that exist at Au-support interfaces. In contrast, site-normalized rates and barriers for H activation depend weakly on the size of Au nanoparticles and the associated differences in active site motifs. These findings suggest that HO aids the activation of H at sites present across all surface Au atoms when nanoparticles are solvated by water. However, molecular O preferentially binds and dissociates at Au-support interfaces, leading to greater structure sensitivity for barriers of O-O dissociation across different support identities and sizes of Au nanoparticles. These insights differ from prior knowledge from studies of gas-phase reactions of H and O upon Au nanoparticle catalysts within dilute vapor pressures of water (10 to 0.1 kPa HO), in which catalysis occurs at the perimeter of the Au-support interface. In contrast, contacting Au catalysts with liquid water (55.5 M HO) expands catalysis to all surface Au atoms and enables appreciable HO formation.

References

Du X, Huang Y, Pan X, Han B, Su Y, Jiang Q . Size-dependent strong metal-support interaction in TiO supported Au nanocatalysts. Nat Commun. 2020; 11(1):5811. PMC: 7669859. DOI: 10.1038/s41467-020-19484-4. View

Takale B, Bao M, Yamamoto Y . Gold nanoparticle (AuNPs) and gold nanopore (AuNPore) catalysts in organic synthesis. Org Biomol Chem. 2014; 12(13):2005-27. DOI: 10.1039/c3ob42207k. View

Sankar M, He Q, Engel R, Sainna M, Logsdail A, Roldan A . Role of the Support in Gold-Containing Nanoparticles as Heterogeneous Catalysts. Chem Rev. 2020; 120(8):3890-3938. PMC: 7181275. DOI: 10.1021/acs.chemrev.9b00662. View

Shekhar M, Wang J, Lee W, Williams W, Kim S, Stach E . Size and support effects for the water-gas shift catalysis over gold nanoparticles supported on model Al2O3 and TiO2. J Am Chem Soc. 2012; 134(10):4700-8. DOI: 10.1021/ja210083d. View

Musumeci F, Pollack G . Influence of water on the work function of certain metals. Chem Phys Lett. 2012; 536:65-67. PMC: 3359016. DOI: 10.1016/j.cplett.2012.03.094. View

Delannoy L, El Hassan N, Musi A, Le To N, Krafft J, Louis C . Preparation of supported gold nanoparticles by a modified incipient wetness impregnation method. J Phys Chem B. 2006; 110(45):22471-8. DOI: 10.1021/jp062130l. View

Huynh M, Meyer T . Proton-coupled electron transfer. Chem Rev. 2007; 107(11):5004-64. PMC: 3449329. DOI: 10.1021/cr0500030. View

Tse E, Varnell J, Hoang T, Gewirth A . Elucidating Proton Involvement in the Rate-Determining Step for Pt/Pd-Based and Non-Precious-Metal Oxygen Reduction Reaction Catalysts Using the Kinetic Isotope Effect. J Phys Chem Lett. 2016; 7(18):3542-7. DOI: 10.1021/acs.jpclett.6b01235. View

Noujima A, Mitsudome T, Mizugaki T, Jitsukawa K, Kaneda K . Unique catalysis of gold nanoparticles in the chemoselective hydrogenolysis with H2: cooperative effect between small gold nanoparticles and a basic support. Chem Commun (Camb). 2012; 48(53):6723-5. DOI: 10.1039/c2cc32850j. View

10.

Kim T, Gong J, Ojifinni R, White J, Mullins C . Water activated by atomic oxygen on Au(111) to oxidize CO at low temperatures. J Am Chem Soc. 2006; 128(19):6282-3. DOI: 10.1021/ja058263m. View

11.

Valden , Lai , GOODMAN . Onset of catalytic activity of gold clusters on titania with the appearance of nonmetallic properties . Science. 1998; 281(5383):1647-50. DOI: 10.1126/science.281.5383.1647. View

12.

Molina L, Hammer B . Active role of oxide support during CO oxidation at Au/MgO. Phys Rev Lett. 2003; 90(20):206102. DOI: 10.1103/PhysRevLett.90.206102. View

13.

Wilson N, Flaherty D . Mechanism for the Direct Synthesis of H2O2 on Pd Clusters: Heterolytic Reaction Pathways at the Liquid-Solid Interface. J Am Chem Soc. 2015; 138(2):574-86. DOI: 10.1021/jacs.5b10669. View

14.

Meier D, Goodman D . The influence of metal cluster size on adsorption energies: CO adsorbed on Au clusters supported on TiO2. J Am Chem Soc. 2004; 126(6):1892-9. DOI: 10.1021/ja030359y. View

15.

Whittaker T, Kumar K, Peterson C, Pollock M, Grabow L, Chandler B . H Oxidation over Supported Au Nanoparticle Catalysts: Evidence for Heterolytic H Activation at the Metal-Support Interface. J Am Chem Soc. 2018; 140(48):16469-16487. DOI: 10.1021/jacs.8b04991. View

16.

Green I, Tang W, Neurock M, Yates Jr J . Insights into catalytic oxidation at the Au/TiO(2) dual perimeter sites. Acc Chem Res. 2013; 47(3):805-15. DOI: 10.1021/ar400196f. View

17.

Mullen G, Mullins C . Chemistry. Water's place in Au catalysis. Science. 2014; 345(6204):1564-5. DOI: 10.1126/science.1259527. View

18.

Date M, Okumura M, Tsubota S, Haruta M . Vital role of moisture in the catalytic activity of supported gold nanoparticles. Angew Chem Int Ed Engl. 2004; 43(16):2129-32. DOI: 10.1002/anie.200453796. View

19.

Saavedra J, Doan H, Pursell C, Grabow L, Chandler B . The critical role of water at the gold-titania interface in catalytic CO oxidation. Science. 2014; 345(6204):1599-602. DOI: 10.1126/science.1256018. View

20.

Corma A, Garcia H . Supported gold nanoparticles as catalysts for organic reactions. Chem Soc Rev. 2008; 37(9):2096-126. DOI: 10.1039/b707314n. View