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Catalyst passivation through carbon poisoning is a common and costly problem as it reduces the lifetime and performance of the catalyst. Adding oxygen to the feed stream could reduce poisoning but may also affect the activity negatively. We have studied the dehydrogenation, decomposition, and desorption of naphthalene co-adsorbed with oxygen on Ni(111) by combining temperature-programmed desorption (TPD), sum frequency generation spectroscopy (SFG), photoelectron spectroscopy (PES), and density functional theory (DFT). Chemisorbed oxygen reduces the sticking of naphthalene and shifts H2 production and desorption to higher temperatures by blocking active Ni sites. Oxygen increases the production of CO and reduces carbon residues on the surface. Chemisorbed oxygen is readily removed when naphthalene is decomposed. Oxide passivates the surface and reduces the sticking coefficient. But it also increases the production of CO dramatically and reduces the carbon residues. Ni2O3 is more active than NiO., QC 20240322

There are several difficulties when experimentally determined reaction mechanisms are applied from model systems to real catalysis. Besides the infamous pressure and material gaps, it is sometimes necessary to consider impurities in the real reactant feedstock that can act as promoters or catalyst poisons and alter the reaction path. In this study, the effect of sulfur on the dehydrogenation of naphthalene on Ni(111) is investigated by using X-ray photoelectron spectroscopy and scanning tunneling microscopy. Sulfur induces a (5√3 × 2) surface reconstruction, as previously reported in the literature. The sulfur does not have a strong effect on the dehydrogenation temperature of naphthalene. However, the presence of sulfur leads to a preferred formation of carbidic over graphitic carbon and a strong inhibition of carbon diffusion into the nickel bulk, which is one of the steps of destructive whisker carbon formation described in the catalysis literature.

There are several difficulties when experimentally determined reaction mechanisms are applied from model systems to real catalysis. Besides the infamous pressure and material gaps, it is sometimes necessary to consider impurities in the real reactant feedstock that can act as promoters or catalyst poisons and alter the reaction path. In this study, the effect of sulfur on the dehydrogenation of naphthalene on Ni(111) is investigated by using X-ray photoelectron spectroscopy and scanning tunneling microscopy. Sulfur induces a (5 root 3 x 2) surface reconstruction, as previously reported in the literature. The sulfur does not have a strong effect on the dehydrogenation temperature of naphthalene. However, the presence of sulfur leads to a preferred formation of carbidic over graphitic carbon and a strong inhibition of carbon diffusion into the nickel bulk, which is one of the steps of destructive whisker carbon formation described in the catalysis literature., QC 20240216

Single-atom catalysts (SACs) consist of a low coverage of isolated metal atoms dispersed on a metal substrate, called single-atom alloys (SAAs), or alternatively single metal atoms coordinated to oxygen atoms on an oxide support. We present the synthesis of a new type of Co1Cu SAC centers on a Cu2O(111) support by means of a site-selective atomic layer deposition technique. Isolated metallic Co atoms selectively coordinate to the native oxygen vacancy sites (Cu sites) of the reconstructed Cu2O(111) surface, forming a Co1Cu SAA with no direct Co- Ox bonds. The centers, here referred to as Co1Cu hybrid SACs, are found to stabilize the active Cu+ sites of the low-cost Cu2O catalyst that otherwise is prone to deactivation under reaction conditions. The stability of the Cu2O(111) surface was investigated by synchrotron radiation-based ambient-pressure X-ray photoelectron spectroscopy under reducing CO environment. The structure and reduction reaction are modeled by density functional theory calculations, in good agreement with experimental results., QC 20220630

Single-atom catalysts (SACs) consist of a low coverage of isolated metal atoms dispersed on a metal substrate, called single-atom alloys (SAAs), or alternatively single metal atoms coordinated to oxygen atoms on an oxide support. We present the synthesis of a new type of Co1Cu SAC centers on a Cu2O(111) support by means of a site-selective atomic layer deposition technique. Isolated metallic Co atoms selectively coordinate to the native oxygen vacancy sites (Cu sites) of the reconstructed Cu2O(111) surface, forming a Co1Cu SAA with no direct Co- Ox bonds. The centers, here referred to as Co1Cu hybrid SACs, are found to stabilize the active Cu+ sites of the low-cost Cu2O catalyst that otherwise is prone to deactivation under reaction conditions. The stability of the Cu2O(111) surface was investigated by synchrotron radiation-based ambient-pressure X-ray photoelectron spectroscopy under reducing CO environment. The structure and reduction reaction are modeled by density functional theory calculations, in good agreement with experimental results., This work was funded by the Ministry of Science and Technology of China (no. 2017YFA0204904), the Swedish Research Council (VR), the Knut och Alice Wallenbergs stiftelse, and STINT Joint China-Sweden Mobility program. H.T. acknowledges the financial support from the Ragnar Holm foundation, and C.W. acknowledges the financial support from Trygger's foundation. The computational resources were provided by the supercomputing system in the Supercomputing Center of University of Science and Technology of China. The MAX IV staff is gratefully acknowledged for their support on beamlines HIPPIE and SPECIES. Research conducted at MAX IV, a Swedish national user facility, is supported by the Swedish Research Council under contract 2018-07152, the Swedish Governmental Agency for Innovation Systems under contract 2018-04969, and Formas under contract 2019-02496. S.K. thanks TARLA for collaborative research effort.

Ethanol dehydrogenation on metal oxides such as Cu2O is an important reaction for the production of renewable energy by fuel cells both via the production of H-2 fuel and via application in direct alcohol fuel cells. To better understand this reaction, we studied the adsorption, dissociation, and desorption of ethanol on Cu2O(111) and (100) surfaces using high-resolution photoelectron spectroscopy, vibrational sum-frequency generation spectroscopy, and temperature-programmed desorption accompanied by density functional theory calculations. On Cu-2(100), the first layer consists primarily of dissociatively adsorbed ethoxy. Second and third layers of ethanol physisorb at low temperatures and desorb below 200 K. On the Cu2O(111) surface, adsorption is mixed as ethoxy, ethanol, and the products following C-C cleavage, CHx, and OCHx, are found in the first layer. Upon heating, products following both C-C and C-O bond breaking are observed on both surfaces and continued heating accentuates molecular cracking. C-O cleavage occurs more on the (100) surface, whereas on the Cu2O(111) surface, C-C cleavage dominates and occurs at lower temperatures than those for the (100) surface. The increased ability of Cu2O(111) to crack ethanol is explained by the varied surface structure including surface oxygen, electron-rich O vacancies, and Cu., QC 20220201

In order to be able to design novel catalytic processes more efficiently, detailed understanding of the catalyst-reactant interaction and the dynamics of the microscopic reaction steps is needed. The present thesis aims to contribute to the fundamental understanding of catalyst reactant systems by means of experiments using model systems in Ultra High Vacuum (UHV). The main body of work involves femtochemistry/mass spectrometry measurements as well as sum-frequency generation (SFG) measurements, which both make use of a femtosecond laser and a UHV sample environment. The results of two experimental investigations within the field of surface science are presented. The first paper concerns CO oxidation on ruthenium (0001) and in particular the energy transfer from substrate to adsorbates upon laser excitation. For these experiments laser-induced desorption was performed. We were able to control the branching ratios of competing mechanisms and understand the role of non-thermal electrons in the mechanisms. The second project aims to understand the adsorption and dehydrogenation of methanol on cuprous oxide (Cu2O) which is complicated by the fact that the cuprous oxide surface reconstructs differently under different conditions. The results presented in this part were acquired using mainly X-ray Photoelectron Spectroscopy and SFG. We were able to understand the restructuring of the Cu2O surface and to show that methanol adsorbs molecularly on Cu2O(111) instead of dissociatively as a methoxy and hydrogen species as it does on Cu2O(100).

Adsorption and desorption of methanol on the (111) and (100) surfaces of Cu2O have been studied using high-resolution photoelectron spectroscopy in the temperature range 120–620 K, in combination with density functional theorycalculations and sum frequency generation spectroscopy. The bare (100) surfaceexhibits a (3,0; 1,1) reconstruction but restructures during the adsorption process into a Cu-dimer geometry stabilized by methoxy and hydrogen binding in Cu-bridge sites. During the restructuring process, oxygen atoms from the bulk that can host hydrogen appear on the surface. Heating transforms methoxy to formaldehyde, but further dehydrogenation is limited by the stability of the surface and the limited access to surface oxygen. The (√3 × √3)R30°-reconstructed (111) surface is based on ordered surface oxygen and copper ions and vacancies, which offers a palette of adsorption and reaction sites. Already at 140 K, a mixed layer of methoxy, formaldehyde, and CHxOy is formed. Heating to room temperature leaves OCH and CHx. Thus both CH-bond breaking and CO-scission are active on this surface at low temperature. The higher ability to dehydrogenate methanol on (111) compared to (100) is explained by the multitude of adsorption sites and, in particular, the availability of surfaceoxygen., QC 20170816

An attractive solution to mitigate tars and also to decompose lighter hydrocarbons in biomass gasification is secondary catalytic reforming, converting hydrocarbons to useful permanent gases. Albeit that it has been in use for a long time in fossil feedstock catalytic steam reforming, understanding of the catalytic processes is still limited. Naphthalene is typically present in the biomass gasification gas and to further understand the elementary steps of naphthalene transformation, we investigated the temperature dependent naphthalene adsorption, dehydrogenation and passivation on Ni(111). TPD (temperature-programmed desorption) and STM (scanning tunneling microscopy) in ultrahigh vacuum environment from 110 K up to 780 K, combined with DFT (density functional theory) were used in the study. Room temperature adsorption results in a flat naphthalene monolayer. DFT favors the dibridge[7] geometry but the potential energy surface is rather smooth and other adsorption geometries may coexist. DFT also reveals a pronounced dearomatization and charge transfer from the adsorbed molecule into the nickel surface. Dehydrogenation occurs in two steps, with two desorption peaks at approximately 450 and 600 K. The first step is due to partial dehydrogenation generating active hydrocarbon species that at higher temperatures migrates over the surface forming graphene. The graphene formation is accompanied by desorption of hydrogen in the high temperature TPD peak. The formation of graphene effectively passivates the surface both for hydrogen adsorption and naphthalene dissociation. In conclusion, the obtained results on the model naphthalene and Ni(111) system, provides insight into elementary steps of naphthalene adsorption, dehydrogenation, and carbon passivation, which may serve as a good starting point for rational design, development and optimization of the Ni catalyst surface, as well as process conditions, for the aromatic hydrocarbon reforming process.

We studied CO oxidation on Ru(0001) induced by 400 nm and 800 nm femtosecond laser pulses where we find a branching ratio between CO oxidation and desorption of 1: 9 and 1: 31, respectively, showing higher selectivity towards CO oxidation for the shorter wavelength excitation. Activation energies computed with density functional theory show discrepancies with values extracted from the experiments, indicating both a mixture between different adsorbed phases and importance of non-adiabatic effects on the effective barrier for oxidation. We simulated the reactions using kinetic modeling based on the two-temperature model of laser-induced energy transfer in the substrate combined with a friction model for the coupling to adsorbate vibrations. This model gives an overall good agreement with experiment except for the substantial difference in yield ratio between CO oxidation and desorption at 400 nm and 800 nm. However, including also the initial, non-thermal effect of electrons transiently excited into antibonding states of the O-Ru bond yielded good agreement with all experimental results.

An attractive solution to mitigate tars and also to decompose lighter hydrocarbons in biomass gasification is secondary catalytic reforming, converting hydrocarbons to useful permanent gases. Albeit in use for long time in fossil feedstock catalytic steam reforming, the understanding of the catalytic processes is still limited. Naphthalene is typically present in the biomass gasification gas and to further understand the elementary steps of naphthalene transformation, we investigated the temperature dependent naphthalene adsorption, dehydrogenation and passivation on Ni(111). TPD (temperature programmed desorption) and STM (scanning tunneling microscopy) in ultra-high vacuum environment from 110 K up to 780 K, combined with DFT (density functional theory) were used in the study. Room temperature adsorption results in a flat naphthalene monolayer. DFT favors the di-bridge[7] geometry but the potential energy surface is rather smooth. DFT also reveals a pronounced dearomatization and charge transfer from the adsorbed molecule into the nickel surface. Dehydrogenation occurs in two steps, with two desorption peaks at approximately 450 K and 600 K. The first step is due to partial dehydrogenation generating active hydrocarbon species that at higher temperatures migrates over the surface forming graphene. The graphene formation is accompanied by desorption of hydrogen in the high temperature TPD peak. The formation of graphene effectively passivates the surface both for hydrogen adsorption and naphthalene dissociation. In conclusion, the obtained results on the model naphthalene and Ni(111) system, provides insight into elementary steps of naphthalene adsorption, dehydrogenation and carbon passivation, which may serve as a good starting point for rational design, development and optimization of the Ni catalyst surface, as well as process conditions, for the aromatic hydrocarbon reforming process., QC 20170830