Adsorption and interaction of ethylene on RuO2(110) surfaces

Ethylene (C2H4) adsorbed on the stoichiometric and oxygen-rich RuO2(110) surfaces, exposing coordinatively unsaturated Ru-cus and O-cus atoms, is investigated by applying high-resolution electron energy-loss spectroscopy and thermal desorption spectroscopy in combination with isotope labeling experiments. On the stoichiometric RuO2(110) surface C2H4 adsorbs and desorbs molecularly. In contrast, on the oxygen-rich RuO2(110) surface ethylene adsorbs molecularly at 85 K and is completely oxidized through interaction with O-cus and O-bridge upon annealing to 500 K. The first couple of reactions are observed at 200 K taking place on Ru-cus: A change from pi- to sigma-bonding, formation of -C=O and -C-O groups, and dehydrogenation giving rise to H2O adsorbed at Ru-cus. Maximum reaction rate is reached for C2H4 chemisorbed at Ru-cus with O-cus neighbors on each side. A model for the first couple of reactions is sketched. For the final combustion, C2H4 reacts both with O-cus and O-bridge. Ethylene oxide is not detected under any circumstance.     

Adsorption of platinum on the stoichiometric RuO2(110) surface

Density functional theory was used to calculate the geometries and electronic structures of Pt adsorption on the stoichiometric RuO(2)(110) surface at different coverages. The calculated results revealed that the Pt atoms strongly adsorb on RuO(2), and two-dimensional growth up to 1.25 ML deposition is energetically favorable. At low coverage, the binding between Pt and RuO(2) is very strong, accompanied by a significant transfer of electron density from Pt to the support and a large downshift of the d-band compared to that of the unsupported Pt. At high coverage, a weak interaction of RuO(2) with the Pt cluster is observed, and the electronic structure of Pt is only slightly modified with respect to that of the unsupported material. Our results suggest that among the systems investigated, the RuO(2)-supported Pt at a coverage of 1 ML may become one of the best alternatives to pure Pt as a catalyst because it combines a high stability and a moderate activity similar to Pt.     

Catalytic oxidation of ammonia on RuO2(110) surfaces: mechanism and selectivity

The selective oxidation of ammonia to either N2 or NO on RuO2(110) single-crystal surfaces was investigated by a combination of vibrational spectroscopy (HREELS), thermal desorption spectroscopy (TDS) and steady-state rate measurements under continuous flow conditions. The stoichiometric RuO2(110) surface exposes coordinatively unsaturated (cus) Ru atoms onto which adsorption of NH3 (NH3-cus) or dissociative adsorption of oxygen (O-cus) may occur. In the absence of O-cus, ammonia desorbs completely thermally without any reaction. However, interaction between NH3-cus and O-cus starts already at 90 K by hydrogen abstraction and hydrogenation to OH-cus, leading eventually to N-cus and H2O. The N-cus species recombine either with each other to N2 or with neighboring O-cus leading to strongly held NO-cus which desorbs around 500 K. The latter reaction is favored by higher concentrations of O-cus. Under steady-state flow condition with constant NH3 partial pressure and varying O2 pressure, the rate for N2 formation takes off first, passes through a maximum and then decreases again, whereas that for NO production exhibits an S-shape and rises continuously. In this way at 530 K almost 100% selectivity for NO formation (with fairly high reaction probability for NH3) is reached.     

Inhibition of CO oxidation on RuO2(110) by adsorbed H2O molecules

Catalytic CO oxidation on the RuO(2)(110) surface was studied at 300 K by scanning tunneling microscopy (STM), high-resolution electron-energy-loss spectroscopy (HREELS), and thermal desorption spectroscopy (TDS). Upon repeatedly exposing the surface to several 10 L of CO and O(2) at 300 K, STM shows that unreactive features accumulate with each CO and O(2) titration run. HREELS and TDS show formation of increasing amounts of H(2)O, retarded formation of O-cus atoms and incomplete removal of CO-bridge molecules during O(2) dosing, and a changing ratio of single- and double-bonded CO-bridge molecules. It is concluded that H(2)O (presumably from the residual gas) is accumulating at the Ru-cus sites thus blocking them, so that the dissociative adsorption of oxygen is prevented and the CO oxidation reaction is suppressed. Some 10% CO- bridge remains on the surface even during oxygen exposure. Consistent with this interpretation, deactivation of the surface is suppressed at 350 K, at the onset of H(2)O desorption.     

Interaction of hydrogen with RuO2(110) surfaces: activity differences between various oxygen species

The interaction of hydrogen with RuO(2)(110) surfaces was studied by means of thermal desorption and vibration spectroscopies. The stoichiometric surface exposes two types of coordinatively unsaturated atoms: double-bonded O-bridge and five-fold-bonded Ru-cus, while at the O-rich surface the Ru-cus atoms are covered with single-bonded O-cus. On the stoichiometric RuO(2)(110) surface at 90 K, H(2) either adsorbs molecularly on Ru-cus sites or dissociates and forms with O-bridge an H(2)O-like surface group. If, in addition, also O-cus is present at the surface, hydrogen interacts exclusively with this species forming H(2)O-cus. This demonstrates that hydrogen reacts much more readily with O-cus than with O-bridge as expected from the reduced bond order and smaller binding energy of O-cus. It is furthermore shown that at surface temperatures below 90 K free coordinatively unsaturated Ru-cus sites are needed to activate the incoming H(2) molecules prior to any reaction with O-cus or O-bridge. Generally, Ru-cus sites play a key role for reactions of a number of molecules at the RuO(2)(110) surface. These findings are supported by recent DFT-based calculations but are at variance with other reports.     

Surface and electrocatalytic properties of well-defined and vicinal RuO2 single crystal faces

The kinetics of Cl₂ evolution from concentrated NaCl solutions on the (110) and (230) faces of RuO₂ single crystals has been investigated by determining the Tafel slope, the stoichiometric number and the reaction orders with respect to Cl^– and H⁺. The experimental parameters suggest that the mechanism is presumably similar to that put forward earlier by Krishtalik [51] for RuO₂ layers, but a step common to oxygen evolution, like the case of polycrystalline samples, is present only with the (230) face. Reasons for this difference and for the apparent lower activity of the (110) face with respect to the (230) are discussed. A detailed analysis of the surface behavior of the two faces in Cl^– free acid and alkaline solutions has also been carried out by cyclic voltammetry.Dedicated to Professor G. Horanyi on the occasion of his 70th birthday     

Theoretical investigation on RuO2 nanoclusters adsorbed on TiO2 rutile (110) and anatase (101) surfaces

Minimizing the energy of an $N$ -electron system as a functional of a two-electron reduced density matrix (2-RDM), constrained by necessary $N$ -representability conditions (conditions for the 2-RDM to represent an ensemble $N$ -electron quantum system), yields a rigorous lower bound to the ground-state energy in contrast to variational wave function methods. We characterize the performance of two sets of approximate constraints, (2,2)-positivity (DQG) and approximate (2,3)-positivity (DQGT) conditions, at capturing correlation in one-dimensional and quasi-one-dimensional (ladder) Hubbard models. We find that, while both the DQG and DQGT conditions capture both the weak and strong correlation limits, the more stringent DQGT conditions improve the ground-state energies, the natural occupation numbers, the pair correlation function, the effective hopping, and the connected (cumulant) part of the 2-RDM. We observe that the DQGT conditions are effective at capturing strong electron correlation effects in both one- and quasi-one-dimensional lattices for both half filling and less-than-half filling.     

Dynamic response of chlorine atoms on a RuO(2)(110) model catalyst surface

The dynamic behavior of surface accommodated chlorine atoms on RuO(2)(110) was studied by a variety of experimental methods including high resolution core level shift, thermal desorption-, and in situ infrared spectroscopy as well as in situ surface X-ray diffraction in combination with state-of-the-art density functional theory calculations. On the chlorinated RuO(2)(110) surface the undercoordinated oxygen atoms have been selectively replaced by chlorine. These strongly bound surface chlorine atoms shift from bridging to on-top sites when the sample is annealed in oxygen, while the reverse shift of Cl from on-top into bridge positions is observed during CO exposure; the vacant bridge position is then occupied by either chlorine or CO. For the CO oxidation reaction over chlorinated RuO(2)(110), the reactant induced site switching of chlorine causes a site-blocking of the catalytically active one-fold coordinatively unsaturated (1f-cus) Ru sites. This site blocking reduces the number of active sites and, even more important, on-top Cl blocks the free migration of the adsorbed reactants along the one-dimensional 1f-cus Ru rows, thus leading to a loss of catalytic activity.     

Mechanism and Tafel lines of electro-oxidation of water to oxygen on RuO2(110)

How to efficiently oxidize H(2)O to O(2) (H(2)O → 1/2O(2) + 2H(+) + 2e(-)) is a great challenge for electrochemical/photo water splitting owing to the high overpotential and catalyst corrosion. Here extensive periodic first-principles calculations integrated with modified-Poisson-Boltzmann electrostatics are utilized to reveal the physical origin of the high overpotential of the electrocatalytic oxygen evolution reaction (OER) on RuO(2)(110). By determining the surface phase diagram, exploring the possible reaction channels, and computing the Tafel lines, we are able to elucidate some long-standing puzzles on the OER kinetics from the atomic level. We show that OER occurs directly on an O-terminated surface phase above 1.58 V vs NHE, but indirectly on a OH/O mixed phase below 1.58 V by converting first the OH/O mixed phase to the O-terminated phase locally. The rate-determining step of OER involves an unusual water oxidation reaction following a Eley-Rideal-like mechanism, where a water molecule from solution breaks its OH bond over surface Os with concurrent new O-OH bond formation. The free energy barrier is 0.74 eV at 1.58 V, and it decreases linearly with the increase of potential above 1.58 V (a slope of 0.56). In contrast, the traditionally regarded surface oxygen coupling reaction with a Langmuir-Hinshelwood mechanism is energetically less favored and its barrier is weakly affected by the potential. Fundamentally, we show that the empirical linear barrier~potential relation is caused by the linear structural response of the solvated transition state to the change of potential. Finally, the general strategy for finding better OER anode is also presented.     

Unusual process of water formation on RuO2(110) by hydrogen exposure at room temperature

The reduction mechanism of the RuO(2)(110) surface by molecular hydrogen exposure is unraveled to an unprecedented level by a combination of temperature programmed reaction, scanning tunneling microscopy, high-resolution core level shift spectroscopy, and density functional theory calculations. We demonstrate that even at room temperature hydrogen exposure to the RuO(2)(110) surface leads to the formation of water. In a two-step process, hydrogen saturates first the bridging oxygen atoms to form (O(br)-H) species and subsequently part of these O(br)-H groups move to the undercoordinated Ru atoms where they form adsorbed water. This latter process is driven by thermodynamics leaving vacancies in the bridging O rows.     

氧化锡表面的原子簇模型计算

Cluster models of SnO2(110) face and oxygen vacancies and oxygen adsorption on its surface have been calculated by EHMO method. The results show that a tin atom with a coordination number of four is the adsorption center, because the total energy of cluster model becomes lower when an oxygen atom adsorpts on the tin atom with a coordination number of four. The tin atom with this coordination number gains and loses electrons more easily than tin atoms with a coordination number of five. All tin atoms in the cluster of SnO2(110) face are Sn4+.     

First-principles study of the magnetic exchange forces between the RuO2(110) surface and Fe tip

Magnetic exchange force microscopy (MExFM) is an important experimental technique for mapping the magnetic structure of surfaces with atomic resolution relying on the spin-dependent short-range exchange interaction between a magnetic tip and a magnetic surface. RuO₂ is a significant compound with applications in heterogeneous catalysis and electrocatalysis. It has been characterized recently as an antiferromagnetic (AFM) material, and its magnetism has been predicted somewhat surprisingly to play an important role in its catalytic properties. In the current study, we explore theoretically whether MExFM can visualize the magnetic surface structure of RuO₂. We use density functional theory (DFT) calculations to extract the exchange interactions between a ferromagnetic Fe tip interacting with an AFM RuO₂(110) surface, as a function of tip-surface distance and the position of the tip over the surface. Mimicking the MExFM experiment, these data are then used to calculate the normalized frequency shift of an oscillating cantilever tip versus the minimum tip-surface distance, and construct corrugation height line profiles. It is found that the exchange interaction between tip and surface is strongest for a parallel configuration of the spins of the tip and of the surface; it is weakest for an anti-parallel orientation. In a corrugation profile, this gives rise to a sizable height difference of 25 pm between the spin-up and spin-down Ru atoms in the RuO₂(110) surface at a normalized frequency shift =−10.12 fNm^1/2. The O atoms in the surface are not or hardly visible in the corrugation profile.     

Ethanol photo-oxidation on a rutile TiO2(110) single crystal surface

The reaction of ethanol has been studied on the surface of rutile TiO(2)(110) by Temperature Programmed Desorption (TPD), online mass spectrometry under UV excitation and photoelectron spectroscopy while the adsorption energies of the molecular and dissociative modes of ethanol were computed using the DFT/GGA method. The most stable configuration is the dissociative adsorption in line with experimental results at room temperature. At 0.5 ML coverage the adsorption energy was found equal to 80 kJ mol(-1) for the dissociative mode (ethoxide, CH(3)CH(2)O(a) + H(a)) followed by the molecular mode (67 kJ mol(-1)). The orientation of the ethoxides along the [001] or [110] direction had minor effect on the adsorption energy although affected differently the Ti and O surface atomic positions. TPD after ethanol adsorption at 300 K indicated two main reactions: dehydration to ethylene and dehydrogenation to acetaldehyde. Pre-dosing the surface with ethanol at 300 K followed by exposure to UV resulted in the formation of acetaldehyde and hydrogen. The amount of acetaldehyde could be directly linked to the presence of gas phase O(2) in the vacuum chamber. The order of this photo-catalytic reaction with respect to O(2) was found to be 0.5. Part of acetaldehyde further reacted with O(2) under UV excitation to give surface acetate species. Because the rate of photo-oxidation of acetates (acetic acid) was slower than that of ethoxides (ethanol), the surface ended up by being covered with large amounts of acetates. A reaction mechanism for acetaldehyde, hydrogen and acetate formation under UV excitation is proposed.     

STM study of glycine on TiO2(110) single crystal surfaces

The adsorption of glycine (NH2CH2COOH) was examined by scanning tunneling microscopy (STM) on TiO2(110) surfaces at room temperature. A (2x1) ordered overlayer was observed on the TiO2(110)-(1x1) surface. The adsorption of acetic acid and propanoic acid was also investigated on this surface and their STM images were quite similar to that of glycine. Since acetate and propanoate are formed by dissociative adsorption of these acids on TiO2(110), it is proposed that glycine adsorbs in the same way to form a glycinate. The amino group in the glycinate adlayer structurally analogous to those formed from aliphatic carboxylic acids would be extended away from the surface and potentially free to participate in additional reactions. The underlying structure of the TiO2 surface is important in determining the structure of the glycinate adlayer; no ordering of these adsorbates was observed on the TiO2(110)-(1x2) surface.     

Theoretical Study of Cr Doped into TiO2（110） Surface

1 INTRODUCTION TiO2 is an excellent photocatalyst for decom- posing organic pollution[1]. TiO2 can only adsorb the short wavelengh light (λ < 387 nm), namely, ultra- violet radiation because its band-gap is 3.12 eV. Since ultraviolet radiation only occupies 4～6 percent of solar light, the efficient of solar energy is poor. Therefore, the study is now focused on photocata- lysis in visual light. Anpo’s[2] experimental result indicates that doping Cr and V into TiO2 can pro- mote its…     

The role of weakly bound on-top oxygen in the catalytic CO oxidation reaction over RuO2(110)

RuO(2)-based catalysts are much more active in the oxidation of CO than related metallic Ru catalysts. This high catalytic activity (or low activation barrier) is attributed to the weak oxygen surface bonding of bridging O atoms on RuO(2)(110) in comparison with the strongly chemisorbed oxygen on Ru(0001). Since the RuO(2)(110) surface is able to stabilize an even more weakly bound on-top oxygen species, one would anticipate that the catalytic activity will increase further under oxidizing conditions. We will show that this view is far too simple to explain our temperature-programmed reaction experiments, employing isotope labeling of the potentially active surface oxygen species on RuO(2)(110). Rather, both surface O species on RuO(2)(110) reveal similar activities in oxidizing CO.