Highly Ordered and Thermally Stable FeRh Cluster Superlattice on Graphene for Low-Temperature Catalytic CO Oxidation.

We report on bimetallic FeRh clusters with a narrow size-distribution grown on graphene on Ir(111) as a carbon-supported model catalyst to promote low-temperature catalytic CO oxidation. By combining scanning tunneling microscopy with catalytic performance measurements, we reveal that Fe-Rh interfaces are active sites for oxygen activation and CO oxidation, especially at low temperatures. Rh core Fe shell clusters not only provide the active sites for the reaction, but also thermally stabilize surface Fe atoms towards coarsening compared with pure Fe clusters. Alternate isotope-labelled CO/O2 pulse experiments show opposite trends on preferential oxidation (PROX) performance because of surface hydroxyl species formation and competitive adsorption between CO and O2 . The present results introduce a general strategy to stabilize metallic clusters and to reveal the reaction mechanisms on bimetallic structures for low-temperature catalytic CO oxidation as well as preferential oxidation.

Molecular motor crossing the frontier of classical to quantum tunneling motion.

The reliability by which molecular motor proteins convert undirected energy input into directed motion or transport has inspired the design of innumerable artificial molecular motors. We have realized and investigated an artificial molecular motor applying scanning tunneling microscopy (STM), which consists of a single acetylene (C2H2) rotor anchored to a chiral atomic cluster provided by a PdGa(111) surface that acts as a stator. By breaking spatial inversion symmetry, the stator defines the unique sense of rotation. While thermally activated motion is nondirected, inelastic electron tunneling triggers rotations, where the degree of directionality depends on the magnitude of the STM bias voltage. Below 17 K and 30-mV bias voltage, a constant rotation frequency is observed which bears the fundamental characteristics of quantum tunneling. The concomitantly high directionality, exceeding 97%, implicates the combination of quantum and nonequilibrium processes in this regime, being the hallmark of macroscopic quantum tunneling. The acetylene on PdGa(111) motor therefore pushes molecular machines to their extreme limits, not just in terms of size, but also regarding structural precision, degree of directionality, and cross-over from classical motion to quantum tunneling. This ultrasmall motor thus opens the possibility to investigate in operando effects and origins of energy dissipation during tunneling events, and, ultimately, energy harvesting at the atomic scales.

Correlation between Electronic Configuration and Magnetic Stability in Dysprosium Single Atom Magnets.

Single atom magnets offer the possibility of magnetic information storage in the most fundamental unit of matter. Identifying the parameters that control the stability of their magnetic states is crucial to design novel quantum magnets with tailored properties. Here, we use X-ray absorption spectroscopy to show that the electronic configuration of dysprosium atoms on MgO(100) thin films can be tuned by the proximity of the metal Ag(100) substrate onto which the MgO films are grown. Increasing the MgO thickness from 2.5 to 9 monolayers induces a change in the dysprosium electronic configuration from 4f9 to 4f10. Hysteresis loops indicate long magnetic lifetimes for both configurations, however, with a different field-dependent magnetic stability. Combining these measurements with scanning tunneling microscopy, density functional theory, and multiplet calculations unveils the role of the adsorption site and charge transfer to the substrate in determining the stability of quantum states in dysprosium single atom magnets.

Near-Enantiopure Trimerization of 9-Ethynylphenanthrene on a Chiral Metal Surface.

Enantioselectivity in heterogeneous catalysis strongly depends on the chirality transfer between catalyst surface and all reactants, intermediates, and the product along the reaction pathway. Herein we report the first enantioselective on-surface synthesis of molecular structures from an initial racemic mixture and without the need of enantiopure modifier molecules. The reaction consists of a trimerization via an unidentified bonding motif of prochiral 9-ethynylphenanthrene (9-EP) upon annealing to 500 K on the chiral Pd3 -terminated PdGa{111} surfaces into essentially enantiopure, homochiral 9-EP propellers. The observed behavior strongly contrasts the reaction of 9-EP on the chiral Pd1 -terminated PdGa{111} surfaces, where 9-EP monomers that are in nearly enantiopure configuration, dimerize without enantiomeric excess. Our findings demonstrate strong chiral recognition and a significant ensemble effect in the PdGa system, hence highlighting the huge potential of chiral intermetallic compounds for enantioselective synthesis and underlining the importance to control the catalytically active sites at the atomic level.

Thermal and Magnetic-Field Stability of Holmium Single-Atom Magnets.

We use spin-polarized scanning tunneling microscopy to demonstrate that Ho atoms on magnesium oxide exhibit a coercive field of more than 8 T and magnetic bistability for many minutes, both at 35 K. The first spontaneous magnetization reversal events are recorded at 45 K, for which the metastable state relaxes in an external field of 8 T. The transverse magnetic anisotropy energy is estimated from magnetic field and bias voltage dependent switching rates at 4.3 K. Our measurements constrain the possible ground state of Ho single-atom magnets to either J_{z}=7 or 8, both compatible with magnetic bistability at fields larger than 10 mT.

Uniaxial 2D Superlattice of Fe4 Molecular Magnets on Graphene.

We demonstrate that electrospray deposition enables the fabrication of highly periodic self-assembled arrays of Fe4H single molecule magnets on graphene/Ir(111). The energetic positions of molecular states are probed by means of scanning tunneling spectroscopy, showing pronounced long- and short-ranged spatial modulations, indicating the presence of both locally varying intermolecular as well as adsorption-site dependent molecule-substrate interactions. From the magnetic field dependence of the X-ray magnetic circular dichroism signal, we infer that the magnetic easy axis of each Fe4H molecule is oriented perpendicular to the sample surface and that after the deposition the value of the uniaxial anisotropy is identical to the one in bulk. Our findings therefore suggest that the observed interaction of the molecules with their surrounding does not modify the molecular magnetism, resulting in a two-dimensional array of molecular magnets that retain their bulk magnetic properties.

Intense fluorescence of Au20.

Ligand-protected Au clusters are non-bleaching fluorescence markers in bio- and medical applications. Here we show that their fluorescence can be an intrinsic property of the Au cluster itself. We find a very intense and sharp fluorescence peak located at λ=739.2 nm (1.68 eV) for Au20 clusters in a Ne matrix held at 6 K. The fluorescence reflects the Highest Occupied Molecular Orbital-Lowest Unoccupied Molecular Orbital (HOMO-LUMO) diabatic bandgap of the cluster. Au20 shows a very rich absorption fine structure reminiscent of well defined molecule-like quantum levels. These levels are resolved since Au20 has only one stable isomer (tetrahedral); therefore our sample is mono-disperse in cluster size and conformation. Density-functional theory (DFT) and time-dependent DFT calculations clarify the nature of optical absorption and predict both main absorption peaks and intrinsic fluorescence in fair agreement with experiment.

Magnetic Hysteresis in Er Trimers on Cu(111).

We report magnetic hysteresis in Er clusters on Cu(111) starting from the size of three atoms. Combining X-ray magnetic circular dichroism, scanning tunneling microscopy, and mean-field nucleation theory, we determine the size-dependent magnetic properties of the Er clusters. Er atoms and dimers are paramagnetic, and their easy magnetization axes are oriented in-plane. In contrast, trimers and bigger clusters exhibit magnetic hysteresis at 2.5 K with a relaxation time of 2 min at 0.1 T and out-of-plane easy axis. This appearance of magnetic stability for trimers coincides with their enhanced structural stability.

Superlattice of Single Atom Magnets on Graphene.

Regular arrays of single atoms with stable magnetization represent the ultimate limit of ultrahigh density storage media. Here we report a self-assembled superlattice of individual and noninteracting Dy atoms on graphene grown on Ir(111), with magnetic hysteresis up to 5.6 T and spin lifetime of 1000 s at 2.5 K. The observed magnetic stability is a consequence of the intrinsic low electron and phonon densities of graphene and the 6-fold symmetry of the adsorption site. Our array of single atom magnets has a density of 115 Tbit/inch2, defined by the periodicity of the graphene moiré pattern.

Surface aligned magnetic moments and hysteresis of an endohedral single-molecule magnet on a metal.

The interaction between the endohedral unit in the single-molecule magnet Dy_{2}ScN@C_{80} and a rhodium (111) substrate leads to alignment of the Dy 4f orbitals. The resulting orientation of the Dy_{2}ScN plane parallel to the surface is inferred from comparison of the angular anisotropy of x-ray absorption spectra and multiplet calculations in the corresponding ligand field. The x-ray magnetic circular dichroism is also angle dependent and signals strong magnetocrystalline anisotropy. This directly relates geometric and magnetic structure. Element specific magnetization curves from different coverages exhibit hysteresis at a sample temperature of ∼4 K. From the measured hysteresis curves, we estimate the zero field remanence lifetime during x-ray exposure of a submonolayer to be about 30 seconds.

Temperature-dependent self-assembly of NC-Ph5-CN molecules on Cu(111).

We present the results of temperature-dependent self-assembly of dicarbonitrile-pentaphenyl molecules (NC-Ph5-CN) on Cu(111). Our low-temperature scanning tunneling microscopy study reveals the formation of metal-organic and purely organic structures, depending on the substrate temperature during deposition (160-300 K), which determines the availability of Cu adatoms at the surface. We use tip functionalization with CO to obtain submolecular resolution and image the coordination atoms, enabling unequivocal identification of metal-coordinated nodes and purely organic ones. Moreover, we discuss the somewhat surprising structure obtained for deposition and measurement at 300 K.

Highly enantioselective adsorption of small prochiral molecules on a chiral intermetallic compound.

Intrinsically chiral surfaces of intermetallic compounds are shown to be novel materials for enantioselective processes. Their advantage is the significantly higher thermal and chemical stability, and therefore their extended application range for catalyzed chiral reactions compared to surfaces templated with chiral molecular modifiers or auxiliaries. On the Pd1 -terminated PdGa(111) surface, room-temperature adsorption of a small prochiral molecule (9-ethynylphenanthrene) leads to exceptionally high enantiomeric excess ratios of up to 98 %. Our findings highlight the great potential of intrinsically chiral intermetallic compounds for the development of novel, enantioselective catalysts that can be operated at high temperatures and potentially also in harsh chemical environments.

Reaction-induced cluster ripening and initial size-dependent reaction rates for CO oxidation on Pt(n)/TiO2(110)-(1×1).

We determined the CO oxidation rates for size-selected Ptn (n ∈ {3,7,10}) clusters deposited onto TiO2(110). In addition, we investigated the cluster morphologies and their mean sizes before and after the reaction. While the clusters are fairly stable upon annealing in ultrahigh vacuum up to 600 K, increasing the temperature while adsorbing either one of the two reactants leads to ripening already from 430 K on. This coarsening is even more pronounced when both reactants are dosed simultaneously, i.e., running the CO oxidation reaction. Since the ripening depends on the size initially deposited, there is nevertheless a size effect; the catalytic activity decreases monotonically with increasing initial cluster size.

Adsorption of small hydrocarbons on the three-fold PdGa surfaces: the road to selective hydrogenation.

Intermetallic compounds are a promising class of materials as stable and selective heterogeneous catalysts. Here, the (111) and (-1-1-1) single crystal surfaces of the PdGa intermetallic compound were studied as model catalysts with regard to the selective hydrogenation of acetylene (C2H2) to ethylene (C2H4). The distinct atomic surface structures exhibit isolated active centers of single atomic and three atomic Pd ensembles, respectively. For the two prototypal model catalyst surfaces, the adsorption sites and configurations for hydrogen (H2), acetylene, and ethylene were investigated by combining scanning tunneling microscopy, temperature-programmed desorption, and ab initio modeling. The topmost Pd surface atoms provide the preferred adsorption sites for all studied molecules. The structural difference of the Pd ensembles has a significant influence on the adsorption energy and configuration of C2H2, while the influence of the ensemble structure is weak for C2H4 and H2 adsorption. To approach the question of catalytic performance, we simulated the reaction pathways for the heterogeneous catalytic hydrogenation of acetylene on the two surfaces by means of density functional theory. Due to the geometrical separation of the Pd sites on the surfaces, the steric approach of the reactants (H and C2Hx) was found to be of importance to the energetics of the reaction. The presented study gives a direct comparison of binding properties of catalytic Pd on-top sites vs three-fold Pd hollow sites and is therefore of major relevance to the knowledge-based design of highly selective hydrogenation catalysts.

Probing Catalytic Sites and Adsorbate Spillover on Ultrathin FeO2-x Film on Ir(111) during CO Oxidation.

The spatially resolved identification of active sites on the heterogeneous catalyst surface is an essential step toward directly visualizing a catalytic reaction with atomic scale. To date, ferrous centers on platinum group metals have shown promising potential for low-temperature CO catalytic oxidation, but the temporal and spatial distribution of active sites during the reaction and how molecular-scale structures develop at the interface are not fully understood. Here, we studied the catalytic CO oxidation and the effect of co-adsorbed hydrogen on the FeO2-x/Ir(111) surface. Combining scanning tunneling microscopy (STM), isotope-labeled pulse reaction measurements, and DFT calculations, we identified both FeO2/Ir and FeO2/FeO sites as active sites with different reactivity. The trilayer O-Fe-O structure with its Moiré pattern can be fully recovered after O2 exposure, where molecular O2 dissociates at the FeO/Ir interface. Additionally, as a competitor, dissociated hydrogen migrates onto the oxide film with the formation of surface hydroxyl and water clusters down to 150 K.

Electrically driven spin resonance of 4f electrons in a single atom on a surface.

A pivotal challenge in quantum technologies lies in reconciling long coherence times with efficient manipulation of the quantum states of a system. Lanthanide atoms, with their well-localized 4f electrons, emerge as a promising solution to this dilemma if provided with a rational design for manipulation and detection. Here we construct tailored spin structures to perform electron spin resonance on a single lanthanide atom using a scanning tunneling microscope. A magnetically coupled structure made of an erbium and a titanium atom enables us to both drive the erbium's 4f electron spins and indirectly probe them through the titanium's 3d electrons. The erbium spin states exhibit an extended spin relaxation time and a higher driving efficiency compared to 3d atoms with spin ½ in similarly coupled structures. Our work provides a new approach to accessing highly protected spin states, enabling their coherent control in an all-electric fashion.

Distinction of nuclear spin states with the scanning tunneling microscope.

We demonstrate rotational excitation spectroscopy with the scanning tunneling microscope for physisorbed H(2) and its isotopes HD and D(2). The observed excitation energies are very close to the gas phase values and show the expected scaling with the moment of inertia. Since these energies are characteristic for the molecular nuclear spin states we are able to identify the para and ortho species of hydrogen and deuterium, respectively. We thereby demonstrate nuclear spin sensitivity with unprecedented spatial resolution.

Formation of fe cluster superlattice in a metal-organic quantum-box network.

We report on the self-assembly of Fe adatoms on a Cu(111) surface that is patterned by a metal-organic honeycomb network, formed by coordination of dicarbonitrile pentaphenyl molecules with Cu adatoms. Fe atoms landing on the metal surface are mobile and steered by the quantum confinement of the surface state electrons towards the center of the network hexagonal cavities. In cavities hosting more than one Fe, preferential interatomic distances are observed. The adatoms in each hexagon aggregate into a single cluster upon gentle annealing. These clusters are again centered in the cavities and their size is discerned by their distinct apparent heights.

Effect of the TiO2 reduction state on the catalytic CO oxidation on deposited size-selected Pt clusters.

The catalytic activity of deposited Pt(7) clusters has been studied as a function of the reduction state of the TiO(2)(110)-(1 × 1) support for the CO oxidation reaction. While a slightly reduced support gives rise to a high catalytic activity of the adparticles, a strongly reduced one quenches the CO oxidation. This quenching is due to thermally activated diffusion of Ti(3+) interstitials from the bulk to the surface where they deplete the oxygen adsorbed onto the clusters by the formation of TiO(x) (x ≃ 2) structures. This reaction is more rapid than the CO oxidation. The present results are of general relevance to heterogeneous catalysis on TiO(2)-supported metal clusters and for reactions involving oxygen as intermediate.

An endohedral single-molecule magnet with long relaxation times: DySc2N@C80.

The magnetism of DySc(2)N@C(80) endofullerene was studied with X-ray magnetic circular dichroism (XMCD) and a magnetometer with a superconducting quantum interference device (SQUID) down to temperatures of 2 K and in fields up to 7 T. XMCD shows hysteresis of the 4f spin and orbital moment in Dy(III) ions. SQUID magnetometry indicates hysteresis below 6 K, while thermal and nonthermal relaxation is observed. Dilution of DySc(2)N@C(80) samples with C(60) increases the zero-field 4f electron relaxation time at 2 K to several hours.