Revealing the Role of CO during CO2 Hydrogenation on Cu Surfaces with In Situ Soft X-Ray Spectroscopy.

The reactions of H2, CO2, and CO gas mixtures on the surface of Cu at 200 °C, relevant for industrial methanol synthesis, are investigated using a combination of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and atmospheric-pressure near edge X-ray absorption fine structure (AtmP-NEXAFS) spectroscopy bridging pressures from 0.1 mbar to 1 bar. We find that the order of gas dosing can critically affect the catalyst chemical state, with the Cu catalyst maintained in a metallic state when H2 is introduced prior to the addition of CO2. Only on increasing the CO2 partial pressure is CuO formation observed that coexists with metallic Cu. When only CO2 is present, the surface oxidizes to Cu2O and CuO, and the subsequent addition of H2 partially reduces the surface to Cu2O without recovering metallic Cu, consistent with a high kinetic barrier to H2 dissociation on Cu2O. The addition of CO to the gas mixture is found to play a key role in removing adsorbed oxygen that otherwise passivates the Cu surface, making metallic Cu surface sites available for CO2 activation and subsequent conversion to CH3OH. These findings are corroborated by mass spectrometry measurements, which show increased H2O formation when H2 is dosed before rather than after CO2. The importance of maintaining metallic Cu sites during the methanol synthesis reaction is thereby highlighted, with the inclusion of CO in the gas feed helping to achieve this even in the absence of ZnO as the catalyst support.

Gently does it!: in situ preparation of alkali metal-solid electrolyte interfaces for photoelectron spectroscopy.

The key charge transfer processes in electrochemical energy storage devices occur at electrode-electrolyte interfaces, which are typically buried, making it challenging to access their interfacial chemistry. In the case of Li-ion batteries, metallic Li electrodes hold promise for increasing energy and power densities and, when used in conjunction with solid electrolytes, the adverse safety implications associated with dendrite formation in organic liquid electrolytes can potentially be overcome. To better understand the stability of solid electrolytes when in contact with alkali metals and the reactions that occur, here we consider the deposition of thin (∼10 nm) alkali metal films onto solid electrolyte surfaces, where the metal is thin enough that X-ray photoelectron spectroscopy can probe the buried electrode-electrolyte interface. We highlight the importance of in situ alkali metal deposition by assessing the contaminant species that are present after glovebox handling and the use of 'inert' transfer devices. Consequently, we compare and contrast three available methods for in situ alkali-metal deposition; Li sputter deposition, Li evaporation, and Li plating induced by e- flood-gun irradiation. Studies on both a sulphide solid electrolyte (Li6PS5Cl), and a single-layer graphene probe surface reveal that the more energetic Li deposition methods, such as sputtering, can induce surface damage and interfacial mixing that are not seen with thermal evaporation. This indicates that the appropriate selection of the Li deposition method for in situ studies is required to observe representative behaviour, and the results of previous studies involving energetic deposition may warrant further evaluation.

Identifying the catalyst chemical state and adsorbed species during methanol conversion on copper using ambient pressure X-ray spectroscopies.

Methanol is a promising chemical for the safe and efficient storage of hydrogen, where methanol conversion reactions can generate a hydrogen-containing gas mixture. Understanding the chemical state of the catalyst over which these reactions occur and the interplay with the adsorbed species present is key to the design of improved catalysts and process conditions. Here we study polycrystalline Cu foils using ambient pressure X-ray spectroscopies to reveal the Cu oxidation state and identify the adsorbed species during partial oxidation (CH3OH + O2), steam reforming (CH3OH + H2O), and autothermal reforming (CH3OH + O2 + H2O) of methanol at 200 °C surface temperature and in the mbar pressure range. We find that the Cu surface remains highly metallic throughout partial oxidation and steam reforming reactions, even for oxygen-rich conditions. However, for autothermal reforming the Cu surface shows significant oxidation towards Cu2O. We rationalise this behaviour on the basis of the shift in equilibrium of the CH3OH* + O* ⇌ CH3O* + OH* reaction step caused by the addition of H2O.

Unraveling the Reaction Mechanisms of SiO Anodes for Li-Ion Batteries by Combining in Situ 7Li and ex Situ 7Li/29Si Solid-State NMR Spectroscopy.

Silicon monoxide is a promising alternative anode material due to its much higher capacity than graphite, and improved cyclability over other Si anodes. An in-depth analysis of the lithium silicide (Li xSi) phases that form during lithiation/delithiation of SiO is presented here and the results are compared with pure-Si anodes. A series of anode materials is first prepared by heating amorphous silicon monoxide (a-SiO) at different temperatures, X-ray diffraction and 29Si NMR analysis revealing that they comprise small Si domains that are surrounded by amorphous SiO2, the domain size and crystallinity growing with heat treatment. In and ex situ 7Li and 29Si solid-state NMR combined with detailed electrochemical analysis reveals that a characteristic metallic Li xSi phase is formed on lithiating a-SiO with a relatively high Li concentration of x = 3.4-3.5, which is formed/decomposed through a continuous structural evolution involving amorphous phases differing in their degree of Si-Si connectivity. This structural evolution differs from that of pure-Si electrodes where the end member, crystalline Li15Si4, is formed/decomposed through a two-phase reaction. The reaction pathway of SiO depends, however, on the size of the ordered Si domains within the pristine material. When crystalline domains of >3 nm within a SiO2 matrix are present, a phase resembling Li15Si4 forms, albeit at a higher overpotential. The continuous formation/decomposition of amorphous Li xSi phases without the hysteresis and phase change associated with the formation of c-Li15Si4, along with a partially electrochemically active SiO2/lithium silicate buffer layer, are paramount for the good cyclability of a-SiO.

Understanding Fluoroethylene Carbonate and Vinylene Carbonate Based Electrolytes for Si Anodes in Lithium Ion Batteries with NMR Spectroscopy.

Fluoroethylene carbonate (FEC) and vinylene carbonate (VC) are widely used as electrolyte additives in lithium ion batteries. Here we analyze the solid electrolyte interphase (SEI) formed on binder-free silicon nanowire (SiNW) electrodes in pure FEC or VC electrolytes containing 1 M LiPF6 by solid-state NMR with and without dynamic nuclear polarization (DNP) enhancement. We find that the polymeric SEIs formed in pure FEC or VC electrolytes consist mainly of cross-linked poly(ethylene oxide) (PEO) and aliphatic chain functionalities along with additional carbonate and carboxylate species. The formation of branched fragments is further confirmed by 13C-13C correlation NMR experiments. The presence of cross-linked PEO-type polymers in FEC and VC correlates with good capacity retention and high Coulombic efficiencies of the SiNWs. Using 29Si DNP NMR, we are able to probe the interfacial region between SEI and the Si surface for the first time with NMR spectroscopy. Organosiloxanes form upon cycling, confirming that some of the organic SEI is covalently bonded to the Si surface. We suggest that both the polymeric structure of the SEI and the nature of its adhesion to the redox-active materials are important for electrochemical performance.

In Situ Graphene Growth Dynamics on Polycrystalline Catalyst Foils.

The dynamics of graphene growth on polycrystalline Pt foils during chemical vapor deposition (CVD) are investigated using in situ scanning electron microscopy and complementary structural characterization of the catalyst with electron backscatter diffraction. A general growth model is outlined that considers precursor dissociation, mass transport, and attachment to the edge of a growing domain. We thereby analyze graphene growth dynamics at different length scales and reveal that the rate-limiting step varies throughout the process and across different regions of the catalyst surface, including different facets of an individual graphene domain. The facets that define the domain shapes lie normal to slow growth directions, which are determined by the interfacial mobility when attachment to domain edges is rate-limiting, as well as anisotropy in surface diffusion as diffusion becomes rate-limiting. Our observations and analysis thus reveal that the structure of CVD graphene films is intimately linked to that of the underlying polycrystalline catalyst, with both interfacial mobility and diffusional anisotropy depending on the presence of step edges and grain boundaries. The growth model developed serves as a general framework for understanding and optimizing the growth of 2D materials on polycrystalline catalysts.

Controlling Catalyst Bulk Reservoir Effects for Monolayer Hexagonal Boron Nitride CVD.

Highly controlled Fe-catalyzed growth of monolayer hexagonal boron nitride (h-BN) films is demonstrated by the dissolution of nitrogen into the catalyst bulk via NH3 exposure prior to the actual growth step. This "pre-filling" of the catalyst bulk reservoir allows us to control and limit the uptake of B and N species during borazine exposure and thereby to control the incubation time and h-BN growth kinetics while also limiting the contribution of uncontrolled precipitation-driven h-BN growth during cooling. Using in situ X-ray diffraction and in situ X-ray photoelectron spectroscopy combined with systematic growth calibrations, we develop an understanding and framework for engineering the catalyst bulk reservoir to optimize the growth process, which is also relevant to other 2D materials and their heterostructures.

Dissociative Carbon Dioxide Adsorption and Morphological Changes on Cu(100) and Cu(111) at Ambient Pressures.

Ambient-pressure X-ray photoelectron spectroscopy (APXPS) and high-pressure scanning tunneling microscopy (HPSTM) were used to study the structure and chemistry of model Cu(100) and Cu(111) catalyst surfaces in the adsorption and dissociation of CO2. It was found that the (100) face is more active in dissociating CO2 than the (111) face. Atomic oxygen formed after the dissociation of CO2 poisons the surface by blocking further adsorption of CO2. This "self-poisoning" mechanism explains the need to mix CO into the industrial feed for methanol production from CO2, as it scavenges the chemisorbed O. The HPSTM images show that the (100) surface breaks up into nanoclusters in the presence of CO2 at 20 Torr and above, producing active kink and step sites. If the surface is precovered with atomic oxygen, no such nanoclustering occurs.

Influence of Dissolved O2 in Organic Solvents on CuOEP Supramolecular Self-Assembly on Graphite.

The supramolecular self-assembly of copper(II) octaethylporphyrin (CuOEP) and octaethylporphyrin (H2OEP) on graphitic surfaces immersed in organic solvents (dichlorobenzene, dodecane) is studied using scanning tunneling microscopy (STM) and Raman spectroscopy. STM reveals that the self-assembled structure of CuOEP in 1,2-dichlorobenzene is significantly altered by dissolved oxygen within the solvent. Raman spectroscopy reveals that the presence of the oxygen alters the molecule-substrate interaction, which is attributed to the adsorption of oxygen on the Cu center of the CuOEP, which is facilitated by electron transfer from the graphitic surface. Such oxygen-induced changes are not observed for H2OEP, indicating that the metal center of CuOEP plays a critical role. When the solvent is dodecane, we find that solvation effects dominate. CuOEP adsorbed on graphitic surfaces provides a model system relevant to the study of the transport and activation of oxygen by enzymes and other complexes.