Mechanistic and Electronic Insights into a Working NiAu Single-Atom Alloy Ethanol Dehydrogenation Catalyst.

Elucidation of reaction mechanisms and the geometric and electronic structure of the active sites themselves is a challenging, yet essential task in the design of new heterogeneous catalysts. Such investigations are best implemented via a multipronged approach that comprises ambient pressure catalysis, surface science, and theory. Herein, we employ this strategy to understand the workings of NiAu single-atom alloy (SAA) catalysts for the selective nonoxidative dehydrogenation of ethanol to acetaldehyde and hydrogen. The atomic dispersion of Ni is paramount for selective ethanol to acetaldehyde conversion, and we show that even the presence of small Ni ensembles in the Au surface results in the formation of undesirable byproducts via C-C scission. Spectroscopic, kinetic, and theoretical investigations of the reaction mechanism reveal that both C-H and O-H bond cleavage steps are kinetically relevant and single Ni atoms are confirmed as the active sites. X-ray absorption spectroscopy studies allow us to follow the charge of the Ni atoms in the Au host before, under, and after a reaction cycle. Specifically, in the pristine state the Ni atoms carry a partial positive charge that increases upon coordination to the electronegative oxygen in ethanol and decreases upon desorption. This type of oxidation state cycling during reaction is similar to the behavior of single-site homogeneous catalysts. Given the unique electronic structure of many single-site catalysts, such a combined approach in which the atomic-scale catalyst structure and charge state of the single atom dopant can be monitored as a function of its reactive environment is a key step toward developing structure-function relationships that inform the design of new catalysts.

Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation.

Atomically dispersed catalysts refer to substrate-supported heterogeneous catalysts featuring one or a few active metal atoms that are separated from one another. They represent an important class of materials ranging from single-atom catalysts (SACs) and nanoparticles (NPs). While SACs and NPs have been extensively reported, catalysts featuring a few atoms with well-defined structures are poorly studied. The difficulty in synthesizing such structures has been a critical challenge. Here we report a facile photochemical method that produces catalytic centers consisting of two Ir metal cations, bridged by O and stably bound to a support. Direct evidence unambiguously supporting the dinuclear nature of the catalysts anchored on α-Fe2O3 is obtained by aberration-corrected scanning transmission electron microscopy (AC-STEM). Experimental and computational results further reveal that the threefold hollow binding sites on the OH-terminated surface of α-Fe2O3 anchor the catalysts to provide outstanding stability against detachment or aggregation. The resulting catalysts exhibit high activities toward H2O photooxidation.

Rethinking the molecular structures of WVIOx sites dispersed on titania: distinct mono-oxo configurations at 430 °C and temperature-dependent transformations.

The structural properties of the (WOx)n phase dispersed on TiO2 (P25, anatase) at surface densities of 0.5-4.5 W nm-2 (i.e. up to approximately a monolayer) were explored by using in situ Raman and FTIR spectroscopy, in situ Raman/18O exchange and Raman spectroscopy in static equilibrium at temperatures of 175-430 °C. Deciphering the temperature and coverage dependence of the spectral features under oxidative dehydration conditions showed that (i) the (WOx)n dispersed phase is heterogeneous at 430 °C consisting of two distinct mono-oxo species: Species-I with C3v-like OW(-O-)3 configuration (WO mode at 1009-1014 cm-1) and Species-II with C4v-like OW(-O-)4 configuration (WO mode at 1003-1009 cm-1); (ii) the OW(-O-)3 site is formed with first order of priority and its formation ceases after the complete consumption of the most basic hydroxyls that are titrated first, hence is abundant at low coverage (<1.5 W nm-2); (iii) the OW(-O-)4 site prevails over the OW(-O-)3 site at medium to high coverage (≥2 W nm-2) and partially occurs in associated (polymerized) coverages above 2 W nm-2; (iv) lowering the temperature in the 430 → 250 → 175 °C sequence does not affect the structural and vibrational properties of OW(-O-)3 but leads to the gradual transformation of the OW(-O-)4 site to a di-oxo (O)2W(-O-)3 site (with a symmetric stretching mode at ∼985 cm-1) and the partial association of adjacent OW(-O-)4 units. All temperature-dependent structural/configurational transformations are fully reversible in the 430-175 °C range and are interpreted at the molecular level by a mechanism involving water molecules retained at the surface that act in a reversible temperature-dependent mediative manner resulting in hydroxylation (upon cooling, e.g. to 250 °C) and dehydroxylation (upon heating, e.g. to 430 °C). The Raman spectra obtained for the hydroxyl region confirm the successive hydroxylation/dehydroxylation steps during temperature cycles (e.g. 430 → 250 → 430 °C). One can tune the speciation of the dispersed (WOx)n phase under dehydrated conditions by appropriate control of temperature and coverage.

Single-atom gold oxo-clusters prepared in alkaline solutions catalyse the heterogeneous methanol self-coupling reactions.

In an effort to obtain the maximum atom efficiency, research on heterogeneous single-atom catalysts has intensified recently. Anchoring organometallic homogeneous catalysts to surfaces creates issues with retaining mononuclearity and activity, while the several techniques developed to prepare atomically dispersed precious metals on oxide supports are usually complex. Here we report a facile one-pot synthesis of inorganometallic mononuclear gold complexes formed in alkaline solutions as robust and versatile single-atom gold catalysts. The complexes remain intact on impregnation onto supports or after drying in air to give a crystalline powder. They can be used to interrogate the nuclearity of the catalytically active gold site for reactions known to be catalysed by oxidized gold species. We show that the [Au1-Ox]- cluster directs the heterogeneous coupling of two methanol molecules to methyl formate and hydrogen with a 100% selectivity below 180 °C. The reaction is industrially important as well as the key step in methanol steam reforming on gold catalysts.