Direct detection of hot electrons produced by exothermic reactions on catalysts is an effective strategy to quantify the non-adiabatic energy transfer during the elementary steps of the surface reactions, which provides an insight of the catalytic activity.^1,2 In particular, hot electron dynamics at the surface of metal nanoparticles (NPs) with precisely controlled shape and size is a challenge as well as a key issue in the real-world catalyst system. Herein, we show a novel scheme of graphene catalytic nanodiode composed of a Pt NPs array on graphene/TiO₂ Schottky nanodiode, which allows detection of hot electron flows induced by hydrogen oxidation on Pt NPs. By analyzing the correlation between the turnover rate (catalytic activity) and hot electron current (chemicurrent) measured on the graphene catalytic nanodiodes, we demonstrate that the catalytic nanodiodes utilizing a single graphene layer for electrical connection of Pt NPs are beneficial for the detection of hot electrons due to not only atomically thin nature of graphene but also reducing the height of the potential barrier existing at the Pt NPs/graphene interface. Thereby, the graphene catalytic nanodiodes offer an effective and easy to use approach to study mechanisms of chemical energy conversion in various heterogeneous system, even including composite catalysts with carbon-based supports.

References

1. H. Lee, I. I. Nedrygailov, Y. K. Lee, C. Lee, H. Choi, J. S. Choi, C. Choi, J. Y. Park, Nano Lett. 16 (2016) 1650-1656.

2. H. Lee, I. I. Nedrygailov, C. Lee, G. A. Somorjai, J. Y. Park, Angew. Chem. Int. Ed. 54 (2015) 2340-2344.

Density functional theory and complete active space self-consistent field calculations were used to probe the thermal decomposition of alkyl radicals on the Si(100) surface. Single dimer and single row double dimer cluster models were used to mimic the Si(100) surface in the calculations, and results indicate an interdimer β-hydrogen elimination reaction is the kinetically favored thermal decomposition pathway for adsorbed alkyl radicals. This pathway occurs via a spin crossing from the initial singlet energy surface to the triplet surface mediated by spin-orbit coupling. On the triplet surface the barrier to the elimination reaction is predicted to be about 40 kJ/mol lower than on the singlet surface. Experimental thermal desorption studies of alkyl chlorides adsorbed onto the Si(100)-(2x1) surface appear to give desorption energies for alkene products that are consistent with the barriers computed for the interdimer β-hydrogen elimination spin accelerated reaction mechanism. Experimental and computational results for the adsorption/desorption energetics of several different alkyl radicals will be discussed, along with results from partial deuteration studies of adsorption of selected haloalkanes.

Specifically, alkali (Na⁺/Rb⁺) and noble gas(Ar^q+) ions were used to irradiate a Schottky diode consisting of

a thin film of Ag (~25nm) grown on an n-type Si (111) wafer. Measurements of the resultant current

through the device were performed as a function of energy, angle of incidence and velocity of the

incident ions. Energy loss of the incident energetic ions inside the metal film leads to the generation of

hot carriers that travel ballistically to the Schottky interface and are detected as a kinetically-induced

current or “kinecurrent” within the device. This kinecurrent is analogous to previous measurements of

“chemicurrent” [H. Nienhaus, Surface Science, 45, 1-78 (2002)], which were linked to the energy

delivered to a surface by exothermic reactions that could non-adiabatically couple to the electronic

structure and generate hot carriers.

When an H atom collides with a solid surface, it can transfer some of its kinetic energy into elementary excitations of the solid like phonons and electron-hole pairs. If the atom loses enough kinetic energy, it can become bound to the solid, either on the surface or in the bulk. For a metal, the availability of a continuum of low lying electronic excitations can lead to the breakdown of the adiabatic Born Oppenheimer approximation and the facile nonadiabatic excitation of electron-hole pairs (ehp). If the H atom loses sufficient energy, it can enter a bound state with the solid, either on the surface or in the bulk.

We have used a combined theoretical and experimental approach to elucidate the relative roles of adiabatic processes (phonon excitation) and nonadiabatic processes (ehp excitation) in collisions of H atoms with metals, insulators, and graphene. The experiments use photolysis to produce nearly mono-energetic beams of H atoms with energies of 1 - 3.3 eV and high resolution energy loss measurements using Rydberg atom tagging time-of-flight analysis. The theory involves calculations of classical trajectories for H atom collisions with two techniques. In the first, we calculate energies and forces on-the-fly during the course of a trajectory using density functional theory (DFT) and ab initio molecular dynamics (AIMD). In the second, we construct a full dimensional potential energy surface (PES) using a flexible functional form fit to DFT energies and bulk properties of the solid.

The measured mean energy loss for H atoms scattering from metals is large, approximately 30% of the initial energy and there is a tail in the energy loss distribution (ELD) extending to the full energy of incidence. The measured ELD is in reasonable agreement with theory only if nonadiabatic effects are included; adiabatic theory drastically underestimates the energy loss. Scattering from insulators (where ehp excitation can be excluded) shows much smaller energy loss and results consistent with adiabatic theory.

For metals, nonadiabatic effects not only dominate the energy loss process, but also change both the magnitude and mechanism for adsorption on metals. With nonadiabatic effects, the most probable pathway to adsorption is for H atoms to penetrate the surface, lose energy in the subsurface region, and then reemerge to adsorb on the surface.

*Work at UMD supported by NSF CHE 13-05892

[1] T.L. Einstein, A. Pimpinelli, D.L. González, J. Cryst. Growth 401 (2014) 627; TLE, AP, DLG, J.R. Morales-Cifuentes, J. Physics: Conf. Ser. J. Phys.: Conf. Series 640 (2015) 012024

[2] T. Potocar et al., Phys. Rev. B 83 (2011) 075423 & later work by A. Winkler et al., see [1].

[3] JRM-C, TLE, and AP, Phys. Rev. Lett. 113 (2014) 246101.

[4] R. Sathiyanarayanan, Ph.D. thesis, UMD, 2009; R. Sathiyanarayanan and TLE, preprint.

[5] A.S. DeLoach, B.R. Conrad, TLE, and D.B. Dougherty, submitted.

The involvement of Au atoms in the self-assembled methylthiolate (CH₃S) monolayers on Au(111) has been demonstrated experimentally [1], while for S and Cl, chain-like structures with no direct Au involvement were found [2,3]. We find that for S on various coinage metal surfaces, the linear S-M-S complexes (M=Cu, Ag, Au) are prevalent. A systematical theoretical study of the X-Au-X complexes, with X=S, Cl, CH₃S, and SiH₃S, has been performed using DFT and other quantum chemistry methods. Assuming equilibration of the metal substrate, the chemical potential of X are calculated and used to predict the stability of various Au-X complexes. We find good agreement between DFT and available experimental findings. Furthermore, the van del Waals interaction is shown to play a crucial role in the self-assembly of CH₃S observed in experiments [1].

[1] P. Maksymovych, O. Voznyy, D. B. Dougherty, D. C. Sorescu, J. T. Yates Jr., Prog. Surf. Sci.85, 206 (2010).

[2] V. V. Zheltov et al.Phys. Rev. B, 89, 195425 (2014).

[3] H. Walen, J. Chem. Phys.143, 014704 (2015).

We have performed density functional theory based calculations to compare the characteristics of the interface of Fe-Ag and Fe-Cr multilayers. A perfect interface lattice match between the Fe and Ag layers was obtained by rotating fcc Ag(100) layers by 45° on bcc Fe(100). On the other hand, the Fe-Cr interface could be modeled by epitaxial layers of bcc Fe(100) and Cr(100). In Fe-Ag multilayers, we find the signature peak of Fe bulk phonons (35 meV) to be completely diminished, while the low energy peaks are remarkably enhanced, in agreement with experiment [1]. In contrast, the phonon density of state in the Fe-Cr multilayers do not show any salient feature except a slight decrease in the 35 meV peak for the Fe layer at the interface, as compared to that of the middle Fe layer, again in agreement with experiment [2]. The magnetic moment of the interfacial Fe atoms is larger than that of Fe atoms in other layers, as a result of charge transfer from Fe to Ag at the interface. As compared to the middle layers, more spin-up and less spin-down states are occupied at the interface in such a way that Fe donates a large number of spin-down electrons to Ag but receives only a few spin-up electrons from the latter because of the almost fully occupied Ag d-band. This leads to rather unstable Fe-Ag interface. On the contrary, at the Fe-Cr interface, Cr can easily give and take electrons leading to smooth interfacial coupling and stable environment.

[1] B. Roldan Cuenya et al., to be published

[2] Roldan et al, Phys. Rev. B 77, 165410 (2008).

Work supported in part by DOE Grant No. DOE-DE-FG02-07ER46354