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Ni is one of the most extensively utilized metals in industrial catalysis. For example, Ni is the catalyst of choice for the steam reforming of hydrocarbons. However, pure Ni also detrimentally catalyzes the formation of graphitic carbon, which in turn leads to coking and deactivation of the catalyst. It has been shown that alloying small amounts of a less reactive metal like Au into Ni can alleviate this issue by breaking up the larger Ni ensembles that promote coke formation. We are taking the opposite of this approach by alloying very small amounts of Ni into Cu, a catalytically less active host metal, to create single Ni atom sites. In this way our single-atom alloy approach has the potential to greatly enhance catalytic selectivity and reduce poisoning, analogous to other single-atom alloys such as PtCu and PdCu. Herein we report the atomic-scale surface structure and local geometry of low coverages of Ni deposited on a Cu(111) single crystal as determined by scanning tunneling microscopy. At 433 K, low concentrations of Ni alloy in the Cu host as a single-atom alloy in Ni-rich brims along ascending step edges. To support our STM assignments of the single-atom dispersion of Ni, reflection absorption infrared spectroscopy of CO on NiCu was performed. To access the binding strength of CO to isolated Ni sites, we used temperature-programmed desorption studies, which revealed that CO binds more weakly to single Ni atoms in Cu compared with Ni(111), indicating that NiCu single-atom alloys are promising for catalytic applications in which CO poisoning is an issue. Together, these results provide a guide for the preparation of NiCu single-atom alloy model catalysts that are predicted by theory to be promising for a number of reactions.
The reducibility of metal oxides,
when they serve as the catalyst support or are the active sites themselves,
plays an important role in heterogeneous catalytic reactions. Here
we present an integrated experimental and theoretical study that reveals
how the addition of small amounts of atomically dispersed Pt at the
metal/oxide interface dramatically enhances the reducibility of a
Cu2O thin film by H2. X-ray photoelectron spectroscopy
(XPS) and temperature-programmed desorption (TPD) results reveal that,
upon oxidation, a PtCu single-atom alloy (SAA) surface is covered
by a thin Cu2O film and is, therefore, unable to dissociate
H2. Despite this, in situ studies using
ambient-pressure (AP) XPS reveal that the presence of a small amount
of Pt under the oxide layer can, at the single-atom limit, promote
the reduction of Cu2O by H2 at room temperature.
We built two density functional theory based surface models to better
understand these experimental findings: a Cu2O/Cu(111)-like
surface oxide layer, known as the “29” oxide, in which
Pt is alloyed into the Cu(111) surface, as well as a PtCu SAA. Our
calculations suggest that the increased activity is due to the presence
of atomically dispersed Pt under the surface oxide layer, which weakens
the Cu–O bonds in its immediate vicinity, thus making the interface
between subsurface Pt and the surface oxide a nucleation site for
the formation of metallic Cu. This initial step in the reduction process
results in the presence of surface Pt atoms surrounded by metallic
Cu patches, and the Pt atoms become active in H2 dissociation,
which consequently accelerates the reduction of the oxide layer. This
work demonstrates how isolated Pt atoms at the metal/oxide interface
of a Cu-based catalyst accelerate the reduction of the oxide and,
therefore, help maintain the active, reduced state of the catalyst
under the reaction conditions.
Single-atom catalysts have attracted a great deal of attention due to their distinct reactivity and potential for cost savings. However, despite the wealth of literature in recent years, identifying the exact nature of the active sites and associated reaction mechanisms remains challenging in many cases. Herein, we take a surface science approach to understand how Rh single atoms and small clusters behave on the thin film "29" Cu 2 O grown on Cu(111). We find that in contrast to Pt, which is present solely as single atoms on the "29" Cu 2 O surface, Rh atoms and clusters coexist and each enable low-temperature CO oxidation, but via different pathways. Specifically, the single Rh atoms produce CO 2 at 444 K via a Mars van Krevelen mechanism whereas the Rh clusters can also dissociate CO, as demonstrated via isotope labeling, and liberate CO 2 at 313 K. Density functional theory (DFT) calculations quantify the energetics of these different pathways and demonstrate that only extended Rh is capable of CO dissociation. Low-temperature scanning tunneling microscopy (STM) reveals that unlike Pt atoms on the same surface, which stay atomically dispersed, the distribution of Rh structures is dependent on pretreatment conditions. DFT calculations reveal the greater tendency of Rh atoms to cluster than Pt, and STM image simulations confirm the active sites. Ambient pressure X-ray photoelectron spectroscopy studies on the same single crystal model systems demonstrate that 1% of a monolayer of Rh on the "29" Cu 2 O thin film significantly accelerates its reduction by CO at 400 K, thus confirming the ultrahigh vacuum surface science findings. Together, these results illustrate how well-defined single crystal experiments are useful in building structure−function relationships that elucidate the reactivity of different ensemble sizes with a level of detail beyond what is possible with high surface area catalysis.
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